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Only two 4-halo-1H-pyrazole crystal structures are known to date (chloro and bromo, the structure of 4-iodo-1H-pyrazole has not been reported yet). The triclinic structure of 4-fluoro-1H-pyrazole, C3H3FN2 (P\overline{1}), reported here is not isomorphous with those of the chloro and bromo analogues (which are isomorphous, orthorhombic Pnma). To avoid sublimation during the measurement, diffraction data were collected at 150 K. Two crystallographically unique 4-fluoro-1H-pyrazole moieties linked by an N—H...N hydrogen bond are found in the asymmetric unit. Unlike the trimeric supramolecular motifs found in the structures of the chloro and bromo analogues, 4-fluoro-1H-pyrazole forms one-dimensional chains by intermolecular hydrogen bonding in the crystal.

The synthesis and structures of dinuclear palladium complexes with 1,3-benzimidazolidine-2-thione (bzimtH) and 1,3-imidazoline-2-thione (imtH) are reported, namely, bis(μ-1H-benzimidazole-2-thiolato)-κ2 N 3:S;κ2 S:N 3-bis[cyanido(triphenylphosphine-κP)palladium(II)], [Pd2(C7H5N2S)2(CN)2(C18H15P)2] or [Pd2(μ-N,S-bzimtH)2(CN)2(PPh3)2] (1), and bis(μ-1H-imidazole-2-thiolato)-κ2 N 3:S;κ2 S:N 3-bis[cyanido(triphenylphosphine-κP)palladium(II)] acetonitrile 0.58-solvate, [Pd2(C3H3N2S)2(CN)2(C18H15P)2]·0.58C2H3N or [Pd2(μ-N,S-imtH)2(CN)2(PPh3)2]·0.58C2H3N (2). The compound [Pd2(μ-N,S-bzimtH)2(CN)2(PPh3)2] is located on a crystallographic twofold axis while [Pd2(μ-N,S-imtH)2(CN)2(PPh3)2]. 0.58(C2H3N) contains two partially occupied acetonitrile solvent molecules with occupancies of 0.25 and 0.33. In both of these compounds, the anionic bzimtH− and imtH− ligands coordinate through N,S-donor atoms in a bridging mode, covering four coordination sites of two metal centers and other two sites are occupied by two PPh3 ligand molecules. Finally, the remaining two sites of two metal centers are occupied by cyano groups, abstracted by the metals from the solvent during reaction. In the packing of the 1,3-benzimidazolidine- 2-thione and 1,3-imidazoline-2-thione complexes, there are intramolecular π–π interactions involving the thione moiety as well as an N—H...N hydrogen bond linking the thione and cyano ligands. In addition, in 2, as well as the π–π interaction involving the thione moieties, there is an additional π–π interaction involving one of the thione moieties and an adjacent phenyl ring from the triphenylphosphine ligand. There are also C—H...N interactions between the imidazoline rings and the acetonitrile N atoms.

The synthesis and single-crystal X-ray structure for tetraaquatetrakis(μ-2-propylvalerato)tetrakis(μ4-salicylhydroximato)dysprosiumtetramanganesesodium dimethylformamide tetrasolvate, [DyMn4Na(C7H4NO3)4(C8H15O2)4(H2O)4]·4C3H7NO or DyNa(2-PV)4[12-MCMnIII Nshi-4](H2O)4·4DMF, 1, where MC is metallacrown, shi3− is salicylhydroximate, 2-PV is 2-propylvalerate, and DMF is N,N-dimethylformamide, is reported. The slightly domed metallamacrocycle contains four ring MnIII ions and four shi3− ligands that generate an [MnIII—N—O] repeat unit that recurs four times. The ring MnIII ions are five-coordinate with a square-pyramidal shape. Furthermore, the metallacrown binds both a DyIII ion and a Na+ ion in the central cavity. The central ions are located on opposite faces of the cavity with the DyIII ion located on the convex side of the MC and the Na+ ion located on the concave side. Each central ion is eight-coordinate although they possess different geometries. The DyIII ion has a square-antiprismatic shape, while the Na+ ion has an extremely distorted biaugmented trigonal–prismatic shape. The four 2-propylvalerate anions help to tether the DyIII to the MC cavity by forming bridges between the DyIII ion and each ring MnIII ion. Moreover, the interstitial DMF molecules are hydrogen bonded to the water molecules that complete the coordination environment of the Na+ ion. The metallacrown framework (excluding the DyIII and Na+ ions), the bridging 2-propylvalerate, and the interstitial DMF molecule experience whole-molecule disorder due to the rotational orientation of the metallamacrocycle. Additionally, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional orientations, and the main moiety interstitial DMF molecule is disordered over one additional orientation. The main moiety of the metallacrown framework refined to 0.9030 (14), while the minor B-moiety refined to 0.0971 (14). The main moiety alkyl chain of the 2-propylvalerate refined to 0.287 (3): 0.309 (3): 0.307 (3), and the minor B-moiety alkyl chain refined to 0.0971 (14). Lastly, the main moiety interstitial DMF refined to 0.549 (3): 0.354 (3), and the minor B-moiety DMF refined to 0.0971 (14).

Both trans and cis iron–CTMC complexes, namely, trans-dichlorido[(5SR,7RS,12RS,14SR)-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecane]iron(III) tetrachloridoferrate, [Fe(C14H32N4)Cl2][FeCl4] (1a), the analogous chloride methanol monosolvate, [Fe(C14H32N4)Cl2]Cl·CH3OH (1b), and cis-dichlorido[(5SR,7RS,12SR,14RS)-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecane]iron(III) chloride, [Fe(C14H32N4)Cl2]Cl (2), were successfully synthesized and structurally characterized using X-ray diffraction. The coordination geometry of the macrocycle is dependent on the stereoisomerism of CTMC. The packing of these complexes appears to be strongly influenced by extensive hydrogen-bonding interactions, which are in turn determined by the nature of the counter-anions (1a versus 1b) and/or the coordination geometry of the macrocycle (1a/1b versus 2). These observations are extended to related ferric cis- and trans-dichloro macrocyclic complexes.

The synthesis and crystal structure for the title compound, hexaaquahexakis(μ-2-hydroxybenzenecarbohydroxamato)bis(2-hydroxybenzenecarbohydroxamato)tetraindium(III) tetranitrate 8.57-hydrate + unknown solvent, [In4(H2shi)8(H2O)6](NO3)4·8.57H2O·solvent, where H2shi− is salicylhydroximate (C7H5NO3), are reported. The complex cation of the structure, [In4(H2shi)8(H2O)6]4+, is a dimer with a step-like topology and possesses an inversion center that relates each [In2(H2shi)4(H2O)3]2+ side of the complex cation. Each InIII ion is seven-coordinate with a pentagonal–bipyramidal geometry, and the salicylhydroximate ligands have a 1− charge as only the oxime oxygen of the ligand is deprotonated. Four interstitial nitrate anions maintain the charge balance of the compound. One of the nitrate anions (and its symmetry equivalent) is disordered over two different orientations with an occupancy ratio of 0.557 (7) to 0.443 (7). The interstitial solvent water molecules show substantial disorder. Approximately 8.57 water molecules per formula unit were refined as disordered and partially occupied, while a suitable model could not be devised for the other extensively disordered solvent molecules (water and possibly methanol as this was the synthesis solvent). Thus, these latter solvent molecules were instead treated with the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9–18.] as implemented in the program PLATON, and the procedure corrected for 151 electrons within solvent-accessible voids of 367 Å3.

The title chlorin, 2PhH2 , hydrogen-bonded to dimethylaminopyridine (DMAP), C44H32N4O2·C7H10N2, and its corresponding zinc(II) complex, 2PhZn, axially coordinated to ethylenediamine (EDA), [Zn(C44H30N4O2)]·C2H8N2, were isolated and crystallized by adventitious reduction of the corresponding osmate esters by DMAP and EDA, respectively. Known since 1996 and, inter alia, used for the preparation of a wide range of (planar and non-planar) chlorin analogues (so-called pyrrole-modified porphyrins), their conformational analyses in the solid state are important benchmarks. Both macrocycles are only modestly distorted from planarity and both are slightly more non-planar than the corresponding dimethoxy-derivative, but less planar than a free-base meso-pentafluorophenyl-based osmate ester. NSD analyses provide quantitative and qualitative analyses of the distortion modes. One origin of the non-planarity is presumably the avoidance of the eclipsed configuration of the two vic–cis diols on the pyrroline moiety; the resulting deformation of the pyrroline translates in some cases into the macrocycle. The structure of 2PhH2 features voids making up ca 26% of the unit-cell volume filled with highly disordered solvate molecules (chloroform and hexanes). 2PhZn crystallized with a 13.6 (4)% occupied solvate methanol molecule.

Bis(benzene-1,2-diolato-κ2 O,O′)bis(dimethyl sulfoxide-κO)titanium(IV), [Ti(C6H4O2)2(C2H6OS)2], crystallizes with two crystallographically independent molecules in the space group P21/c emulating orthorhombic Pbca symmetry (β = 90.0445 (9)°]. The two molecules are related by pseudo-glide symmetry, broken by modulation of each one catecholate and dimethyl sulfoxide (DMSO) ligand. Twinning by pseudomerohedry was observed [twin ratio 0.5499 (7):0.4401 (7)]. Complex 3 was obtained by heating of diprotonated titanium tris-catecholate precursor 2H in DMSO, by formal displacement of a catechol molecule by two DMSO molecules. Complex 3 is just the second heteroleptic, mono-nuclear, neutral bis-catecholate complex with TiO6 metal coordination, the only other one being its bis-DMF analogue 6. The two molecules of 3 exhibit a distorted octahedral geometry. The geometry and distortions from ideal symmetry of 3 are discussed and compared to 6 and to cationic tris-catecholate titanium complexes.

Syntheses are described for the blue/purple complexes of cobalt(II) chloride with the tetradentate ligands 1,4-bis[2-(pyridin-2-yl)ethyl]piperazine (Ppz), 1,4-bis[2-(pyridin-2-yl)ethyl]homopiperazine (Phpz), trans-2,5-dimethyl-1,4-bis[2-(pyridin-2-yl)ethyl]piperazine (Pdmpz) and tridentate 4-methyl-1-[2-(pyridin-2-yl)ethyl]homopiperazine (Pmhpz). The CoCl2 complexes with Ppz, namely, {μ-1,4-bis[2-(pyridin-2-yl)ethyl]piperazine}bis[dichloridocobalt(II)], [Co2Cl4(C18H24N4)] or Co2(Ppz)Cl4, and Pdmpz (structure not reported as X-ray quality crystals were not obtained), are shown to be dinuclear, with the ligands bridging the two tetrahedrally coordinated CoCl2 units. Co2(Ppz)Cl4 and {dichlorido{4-methyl-1-[2-(pyridin-2-yl)ethyl]-1,4-diazacycloheptane}cobalt(II) [CoCl2(C13H21N3)] or Co(Pmhpz)Cl2, crystallize in the monoclinic space group P21/n, while crystals of the pentacoordinate monochloro chelate 1,4-bis[2-(pyridin-2-yl)ethyl]piperazine}chloridocobalt(II) perchlorate, [CoCl(C18H24N4)]ClO4 or [Co(Ppz)Cl]ClO4, are also monoclinic (P21). The complex {1,4-bis[2-(pyridin-2-yl)ethyl]-1,4-diazacycloheptane}dichloridocobalt(II) [CoCl2(C19H26N4)] or Co(Phpz)Cl2 (P\overline{1}) is mononuclear, with a pentacoordinated CoII ion, and entails a Phpz ligand acting in a tridentate fashion, with one of the pyridyl moieties dangling and non-coordinated; its displacement by Cl− is attributed to the solvophobicity of Cl− toward MeOH. The pentacoordinate Co atoms in Co(Phpz)Cl2, [Co(Ppz)Cl]+ and Co(Pmhpz)Cl2 have substantial trigonal–bipyramidal character in their stereochemistry. Visible- and near-infrared-region electronic spectra are used to differentiate the two types of coordination spheres. TDDFT calculations suggest that the visible/NIR region transitions contain contributions from MLCT and LMCT character, as well as their expected d–d nature. For Co(Pmhpz)Cl2 and Co(Phpz)Cl2, variable-temperature magnetic susceptibility data were obtained, and the observed decreases in moment with decreasing temperature were modelled with a zero-field-splitting approach, the D values being +28 and +39 cm−1, respectively, with the S = 1/2 state at lower energy.

The title compound, [Eu(C9H10BN6)(C19H15O2)2(C3H7NO)] or [TpEu(Anthracac)2(DMF)], was synthesized by reaction of a tris(pyrazolyl)borate (Tp−) Eu3+ complex with 3-(anthracen-9-yl)pentane-2,4-dione (HAnthracac) in the presence of triethylamine. In the title compound, Eu3+ is located in an octavertex square-pyramidal coordination environment. In the two Anthracac− ligands, the anthracene and nearly planar acetylacetonate fragments are almost orthogonal. Neighboring molecules of TpEu(Anthracac)2(DMF) are connected in the crystal by intermolecular van der Waals interactions, while π-stacking interactions are limited to the edges of two anthracene rings.

The solid and solution-state structures of a series of lipid-inspired ionic liquids are correlated. X-ray crystallography is combined with UV-vis spectroscopy to gain a deep understanding of the interactions present in both phases.

An X-ray structural analysis revealed that the salts of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), N-methylphenothiazine (MPTZ), and octamethylbiphenylene (OMB), with dodecamethyl- or hexabromo-substituted carbadodecaborate anions, comprise layers of the (partially) oxidized organic donors separated by sheets of the bulky counter-ions. The cationic layers comprise either well-separated TMPD+ or MPTZ+ cation radicals or π-stacks of partially oxidized OMB moieties consisting of more or less distinct (OMB)2+ units. Quantum mechanical calculations revealed that the formation of essentially isolated cation-radical or π-bonded associations in the salts with these weakly coordinating anions is correlated with the strength of the multicenter π-bonding between cation radicals. This pancake bonding is determined by the balance of the electrostatic repulsion between cationic counterparts and attractive dispersion and weakly covalent interactions.

Pancake bonding between partially oxidized tetramethyltetrathiafulvalene (TMTTF) moieties was examined via X-ray structural, spectral, and magnetic susceptibility measurements of the salts comprisi...

Two crystals incorporating the thiamine·HCl cation and the fluorinated anion 1,3-disulfonylhexafluoropropyleneimide have been characterized via single-crystal X-ray diffraction. The host-guest interactions of thiamine with the anions are analyzed and characterized using Hirshfeld surface analysis. The cations in both structures form a dimer in the solid-state via reciprocal hydrogen bonding through the amine and hydroxyl moieties. Additional investigation into the interactions responsible for dimer formation found that the sulfur atom in the thiazolium ring interacting with several hydrogen atoms to form stabilizing interactions. These interactions in the dimer are further analyzed using reduced density gradient analysis and the results are correlated to the fingerprint plots derived from the Hirshfeld surfaces. Moreover, specific interactions are observed from the cyclical anions, with both the fluorine and sulfonyl oxygen atoms participating in bridging interactions, displaying the diverse host-guest properties of thiamine.

Two crystallographically independent mol­ecules are present in the asymmetric unit. O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds form rings and chains and π–π stacks further connect mol­ecules in the crystal., Two crystallographically independent mol­ecules are present in the asymmetric unit of the title compound, C14H11NO2, with virtually identical geometries. The carbazole units are planar. The hy­droxy group at position 1, carbaldehyde group at position 2, and methyl group at position 8 (with the exception of two H atoms) are coplanar with the attached benzene rings. The dihedral angle between the two benzene rings is 2.20 (9)° in mol­ecule A and 2.01 (9)° in mol­ecule B. The pyrrole ring makes dihedral angles of 0.82 (10) and 1.40 (10)° [0.84 (10) and 1.18 (10)° in mol­ecule B] with the (–CH3)-substituted and (–OH and –CHO) substituted benzene rings, respectively. The mol­ecular structure is stabilized by the intra­molecular O—H⋯O hydrogen bonds, while the crystal structure features N—H⋯O and C—H⋯O hydrogen bonds. A range of π–π contacts further stabilizes the crystal structure.

A series of 11 compounds, including alkali (Li, Na, K, Rb, Cs) and alkaline-earth (Mg, Ca, Sr, Ba) coordination polymers, transition-metal (Cu, Cd) complexes, and the ammonium salt of 3,5-dimethylp...

Two polymorphs of a benzoxadiazole derivative were examined to determine the interactions leading to the formation of two distinct crystalline forms. Hirshfeld surface analysis was used to establish and contrast the interactions in the two samples. Fingerprints derived from the surface analysis were used to distinguish and lead the analysis in discovering the different interactions in the two crystals. π interactions, specifically, π-hole interactions with a nitro moiety, were found to play an important role in the formation of the crystal structure. Further, carbonyl interactions and π-stacking contribute to the overall relative stability of the different conformational polymorphs. Calculated energy frameworks were used to help visualize the interactions between molecules in the crystal structure, supported by an understanding of the individual interactions. The experimental data were supplemented with theoretical studies to establish a through understanding of these heterocyclic systems.

The single-crystal structures of several maleate salt of bedaquiline, a drug used for the treatment of drug-resistant tuberculosis (TB), are described., Bedaquiline is one of two important new drugs for the treatment of drug-resistant tuberculosis (TB). It is marketed in the US as its fumarate salt, but only a few salts of bedaquiline have been structurally described so far. We present here five crystal structures of bedaquilinium maleate {systematic name: [4-(6-bromo-2-meth­oxy­quinolin-3-yl)-3-hy­droxy-3-(naphthalen-1-yl)-4-phenyl­but­yl]di­methyl­aza­nium 3-carb­oxy­prop-2-enoate}, C32H32BrN2O2 +·C4H3O4 −, namely, a hemihydrate, a tetra­hydro­furan (THF) solvate, a mixed acetone/hexane solvate, an ethyl acetate solvate, and a solvate-free structure obtained from the acetone/hexane solvate by in situ single-crystal-to-single-crystal desolvation. All salts exhibit a 1:1 cation-to-anion ratio, with the anion present as monoanionic hydro­maleate and a singly protonated bedaquilinium cation. The maleate exhibits the strong intra­molecular hydrogen bond typical for cis-di­carb­oxy­lic acid anions. The conformations of the cations and packing inter­actions in the maleate salts are compared to those of free base bedaquiline and other bedaquilinium salts.

A series of heterotrimetallic manganese-lanthanide-sodium dimer metallacrowns has been synthesized and characterized by single-crystal X-ray analysis: {LnNa[12-MCMn(III)N(shi)-4]}2(iph)4, where LnIII = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14), and Y (15); MC is metallacrown; shi3− is salicylhydroximate; and iph2− is isophthalate. The manganese(III) ions and shi3− ligands generate the 12-MC-4 framework with one LnIII and Na+ ion bound to each [12-MCMn(III)N(shi)-4] on opposite sides of the central MC cavity. The carboxylate groups of the isophthalate ligands bridge between the central LnIII ion and each ring MnIII ion, and the meta-arrangement of the carboxylate groups joins two LnNa[12-MCMn(III)N(shi)-4] units together to form the dimer through the LnIII ions, which reside on the interior of the molecule. The identity of the central LnIII ion slightly impacts the size the [12-MCMn(III)N(shi)-4] framework. As the crystal radius of the LnIII ion increases from LuIII (1.02 A) to LaIII (1.19 A), the 12-MC-4 framework expands to accommodate the larger LnIII ion as the MC cavity increases in size (0.53 A for LuIII to 0.58 A for LaIII) and the average cross cavity MnIII-MnIII and oxime oxygen-oxime oxygen distances also increase (MnIII-MnIII distances: 6.48 A for LuIII to 6.52 A for LaIII; Ooxime-Ooxime distances: 3.66 A for LuIII to 3.75 A for LaIII). In addition, the larger LnIII ions reside further from the MC cavity as indicated by the LnIII-oxime oxygen mean plane (OoxMP) distance. The LnIII-OoxMP distance steadily decreases from LaIII (1.7527(12) A) to LuIII (1.5575(15) A). The complex {LaNa[12-MCMn(III)N(shi)-4]}2(iph)4(DMF)6(H2O)2 is a dimer of [12-MC-4] molecules linked by four isophthalate anions

The metallacrown compound, NiII(OAc)2[12-MCMn(III)N(shi)-4](CH3OH)6·2CH3OH·H2O, where MC is metallacrown, shi3− is salicyl­hydroximate, and −OAc is acetate, has an overall square shape that captures an NiII ion in a central cavity while the ring of the metallamacrocycle contains four MnIII ions. Two acetate anions, which are located on opposite faces of the MC, form bridges between the central NiII ion and two of the ring MnIII ions., The synthesis and crystal structure of the title compound [systematic name: di-μ-acetato-tetra­kis­(μ4-N,2-dioxido­benzene-1-carboximidato)hexa­methano­ltetra­manganese(III)nickel(II) methanol disolvate monohydrate], [Mn4Ni(C7H4NO3)4(C2H3O2)2(CH4O)6]·2CH4O·H2O or Ni(OAc)2[12-MCMn(III)N(shi)-4](CH3OH)6·2CH3OH·H2O, where MC is metallacrown, −OAc is acetate, and shi3− is salicyl­hydroximate, are reported. The macrocyclic metallacrown is positioned on an inversion center located on the NiII ion that resides in the central MC cavity. The macrocycle consists of an MnIII–N–O repeat unit that recurs four times to generate an overall square-shaped mol­ecule. Both the NiII and MnIII ions are six-coordinate with an octa­hedral geometry. In addition, the MnIII ions possess an elongated Jahn–Teller distortion along the z-axis of the coordination environment. The inter­stitial water mol­ecule is slightly offset from and disordered about an inversion center.

The single-crystal structures of three salts of bedaquiline, a drug used for the treatment of drug-resistant tuberculosis (TB), are described., Bedaquiline [systematic name: 1-(6-bromo-2-meth­oxy­quinolin-3-yl)-4-(di­methyl­amino)-2-(naphthalen-1-yl)-1-phenyl­butan-2-ol, C32H31BrN2O2] is one of two important new drugs for the treatment of drug-resistant tuberculosis (TB). It is marketed in the US as its fumarate salt {systematic name: [4-(6-bromo-2-meth­oxy­quinolin-3-yl)-3-hy­droxy-3-(naphthalen-1-yl)-4-phenyl­but­yl]di­methyl­aza­nium 3-carb­oxy­prop-2-enoate, C32H32BrN2O2 +·C4H3O4 −}, and about a dozen other salts of bedaquiline have been described in patent literature, but none have so far been structurally described. In a first communication, we present the crystal structure of bedaquilinium fumarate and of two new benzoate salts, as well as that of a degradation product of the reaction of bedaquilinium fumarate with sodium ethoxide, 3-benzyl-6-bromo-2-meth­oxy­quinoline, C17H14BrNO. The fumarate and benzoate salts both feature cations monoprotonated at the di­methyl­amino group. The much less basic quinoline N atom remains unprotonated. Both salts feature a 1:1 cation-to-anion ratio, with the fumarate being present as monoanionic hydro­fumarate. The conformations of the cations are com­pared to that of free base bedaquiline and with each other. The flexible backbone of the bedaquiline structure leads to a landscape of conformations with little commonalities between the bedaquiline entities in the various structures. The conformations are distinctively different for the two independent mol­ecules of the free base, the two independent mol­ecules of the hydro­fumarate salt, and the one unique cation of the benzoate salt. Packing of the salts is dominated by hydrogen bonding. Hydrogen-bonding motifs, as well as the larger hydrogen-bonded entities within the salts, are quite similar for the salts, despite the vastly differing conformations of the cations, and both the hydro­fumarate and the benzoate structure feature chains of hydrogen-bonded anions that are surrounded by and hydrogen bonded to the larger bedaquilinium cations, leading to infinite broad ribbons of anions, cations, and (for the benzoate salt) water mol­ecules. The benzoate salt was isolated in two forms: as a 1.17-hydrate (C32H32BrN2O2 +·C7H5O2 −·1.166H2O), obtained from acetone or propanol solution, with one fully occupied water mol­ecule tightly integrated into the hydrogen-bonding network of anions and cations, and one partially occupied water mol­ecule [refined occupancy 16.6 (7)%], only loosely hydrogen bonded to the quinoline N atom. The second form is an aceto­nitrile solvate (C32H32BrN2O2 +·C7H5O2 −·0.742CH3CN·H2O), in which the partially occupied water mol­ecule is replaced by a 74.2 (7)%-occupied aceto­nitrile mol­ecule. The partial occupancy induces disorder for the benzoate phenyl ring. The aceto­nitrile solvate is unstable in atmosphere and converts into a form not distinguishable by powder XRD from the 1.17-hydrate.

Two series of aluminum-lanthanide-sodium 12-metallacrown-4 compounds have been synthesized and characterized by single-crystal X-ray analysis. For the individual LnNa(ben)4[12-MCAl(III)N(shi)-4] molecules, where LnIII = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), Lu (9), and Y (10), ben− is benzoate, MC is metallacrown, and shi3− is salicylhydroximate, two independent molecules are present in each unit cell. The aluminum(III) ions and shi3− ligands comprise the MC framework, while the LnIII and Na+ ions bind opposite of each other across the central MC cavity. The benzoate anions serve to tether the LnIII ion to the MC framework. When benzoate is replaced with the dicarboxylate anion isophthalate (iph2−), two [12-MCAl(III)N(shi)-4] units are connected to form a dimer of MCs: {LnNa[12-MCAl(III)N(shi)-4]}2(iph)4, where LnIII = Eu (11), Gd (12), Tb (13), Dy (14), Ho (15), Ho (16), Er (17), Yb (18), and Lu (19). As in 1–10, the aluminum(III) ions and shi3− ligands produce the MC frameworks, and one LnIII ion binds to each central MC cavity. However, there are two binding modes for the sodium ions. For 12–15 and 18, the sodium ions bind to the central MC cavity opposite of the LnIII ions as in 1–10. For 11, 16, 17, and 19, the sodium ions bind to the side of the MC framework by bonding to the phenolate and carboxylate oxygen atoms of two shi3− ligands and to the carboxylate oxygen atom of an iph2− ligand. In these structures, the MC cavity is vacant opposite of the LnIII ions. The substitution of isophthalate for benzoate does not significantly alter the [12-MCAl(III)N(shi)-4] framework as the size of the central MC cavity is not significantly different between analogous lanthanide individual and dimer MCs. However, the identity of the central LnIII ion does determine how close the LnIII ion can approach the mean plane of the oxime oxygen atoms (OoxMP) of the MC cavity. As the ion radius of the central LnIII ion decreases, the LnIII ion is able to more closely approach the OoxMP. For the individual MCs 1–10, the EuIII of 1 is the farthest away from the OoxMP (1.55 A) and this value steadily decreases to 1.44 A for the LuIII ion of 9. This same trend is true for the dimer MCs as the EuIII ion of 11 is 1.45 A from the OoxMP and the LuIII ion of 19 is 1.36 A from the OoxMP. Though the location of the sodium ions in the dimer MCs does influence the LnIII-OoxMP distance as the absence of the sodium ion in the MC cavity allows the LnIII ion to approach the MC cavity even closer. In 15 a sodium ion is opposite the HoIII ion and the HoIII-OoxMP distance is 1.47 A, while in 16 the sodium ion is bound to the side of the MC and the HoIII-OoxMP distance is 1.40 A. The complex GdNa[12-MCAl(III)N(shi)-4]}2(iph)4(DMF)2(H2O)8 is a dimer of [12-MC-4] molecules linked by four isophthalate anions.

The two [3.3.1] metallacryptate complexes [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]·H2O·4DMF, 1, and [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8.5]2·6.335DMF, 2, where shi3− is salicyl­hydroximate and DMF is N,N-di­methyl­formamide, both consist of an aluminium-based metallacryptand. In 1 and 2, the metallacryptand encapsulates a dysprosium(III) ion in the central cavity, and the resulting metallacryptates are connected to each other to generate a two-dimensional sheet., The two [3.3.1] metallacryptate complexes, namely, poly[[μ3-acetato-hexa­kis­(μ-N,N-di­methyl­formamide)­bis­(N,N-di­methyl­formamide)bis­[salicyl­hydroxi­mato(2−)]hepta­kis­[salicyl­hydrox­im­ato(3−)]hexa­aluminium(III)dysprosium(III)penta­sodium(I)] N,N-di­methyl­formamide tetra­solvate monohydrate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]·4DMF·H2O or {[DyAl6Na5(C7H5NO3)2(C7H4NO3)7(C2H3O2)(C3H7NO)8]·4C3H7NO·H2O}n, 1, and poly[[di-μ4-acetato-nona­kis­(μ-N,N-di­methyl­form­amide)­octa­kis­(N,N-di­methyl­formamide)tetra­kis­[sali­cyl­hydroximato(2-)]tetra­deca­kis­[salicyl­hydroximato(3−)]dodeca­aluminium(III)didysprosium(III)deca­sodium(I)] N,N-di­methyl­form­amide 6.335-solvate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8.5]2·6.335DMF or {[Dy2Al12Na10(C7H5NO3)4(C7H4NO3)14(C2H3O2)2(C3H7NO)17]·6.335C3H7NO}n, 2, where shi3− is salicyl­hydroximate and DMF is N,N-di­methyl­formamide, both consist of an aluminium-based metallacryptand. In 1 and 2, the metallacryptand encapsulates a dysprosium(III) ion in the central cavity, and the resulting metallacryptates are connected to each other via sodium-DMF linkages to generate a two-dimensional sheet. The metallacryptates of 1 and 2 are the three-dimensional analogues of metallacrowns as the metallacryptates contain a metal–nitro­gen–oxygen cyclic repeat unit throughout the complexes. For 1 the building block of the two-dimensional sheet is comprised of only one type of metallacryptate, which is connected to four neighboring metallacryptates via four sodium–DMF linkages. In 2, the building block is a dimeric unit of two metallacryptates. Each dimeric metallacryptate unit is connected to four other dimeric units via six sodium–DMF linkages. The two metallacryptates of each dimeric unit can be considered enanti­omers of each other. In both 1 and 2, chirality is imparted to the metallacryptate due to the Λ and Δ propeller configurations of the four octa­hedral aluminium ions of the metallacryptand shell.

The title morpholinochlorin, C46H16F20N4O3, was crystallized from hexane/methylene chloride as its 0.44 methylene chloride solvate, C46H16F20N4O3·0.44CH2Cl2. The morpholinochlorin was synthesized by stepwise oxygen insertion into a porphyrin using a `breaking and mending strategy': NaIO4-induced diol cleavage of the corresponding 2,3-dihydroxychlorin with in situ methanol-induced, acid-catalyzed intramolecular ring closure of the intermediate secochlorins bisaldehyde. Formally, one of the pyrrolic building blocks was thus replaced by a 2,3-dimethoxymorpholine moiety. Like other morpholinochlorins, the macrocycle of the title compound adopts a ruffled conformation, and the modulation of the porphyrinic π-system chromophore induces a red-shift of its optical spectrum compared to its corresponding chlorin analog. Packing in the crystal is governed by interactions involving the fluorine atoms of the pentafluorophenyl substituents, dominated by C—H...F interactions, and augmented by short fluorine...fluorine contacts, C—F...π interactions, and one severely slipped π-stacking interaction between two pentafluorophenyl rings. The solvate methylene chloride molecule is disordered over two independent positions around an inversion center with occupancies of two × 0.241 (5) and two × 0.199 (4), for a total site occupancy of 88%.

The metallacrown complexes DyIIINa(3-OHben)4[12-MCMn(III)N(shi)-4](H2O)4·10DMA, 1, and DyIIINa(4-OHben)4[12-MCMn(III)N(shi)-4](H2O)4·4DMF, 2, where MC is metallacrown, shi3− is salicyl­hydroximate, 3-OHben is 3-hy­droxy­benzoate, DMA is N,N-di­methyl­acetamide, 4-OHben is 4-hy­droxy­benzoate, and DMF is N,N-di­methyl­formamide, consist of a macrocyclic mol­ecule with an [MnIII—N—O] repeat unit. For both 1 and 2, a DyIII ion is captured on the convex side of the central cavity, while a Na+ ion is captured on the concave side of the cavity. Four 3-hy­droxy­benzoate or 4-hy­droxy­benzoate anions bridge between the ring MnIII ions and the central DyIII ion., The syntheses and crystal structures for the compounds tetra-μ-aqua-­tetra­kis­{2-[aza­nid­yl­ene(oxido)meth­yl]phenolato}tetra­kis­(μ2-3-hy­droxy­benzoato)dys­pro­s­ium(III)­tetra­manganese(III)sodium(I) N,N-di­methyl­acetamide deca­solvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]·10C4H9NO or [DyIIINa(4-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·10DMA, 1, and tetra-μ-aqua-­tetra­kis­{2-[aza­nid­yl­ene(oxido)meth­yl]phenolato}tetra­kis­(μ2-3-hy­droxy­benzoato)dys­pros­ium(III)tetra­manganese(III)sodium(I) N,N-di­methylformamide tetra­solvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]·4C3H7NO or [DyIIINa(3-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·4DMF, 2, and where MC is metallacrown, shi3− is salicyl­hydroximate, 3-OHben is 3-hy­droxy­benzoate, DMA is N,N-di­methyl­acetamide, 4-OHben is 4-hy­droxy­benzoate, and DMF is N,N-di­methyl­formamide, are reported. For both 1 and 2, the macrocyclic metallacrown consists of an [MnIII—N—O] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a DyIII ion on the convex side of the metallacrown and an Na+ ion the concave side. The MnIII ions are six-coordinate with an elongated tetra­gonally distorted octa­hedral geometry. Both the DyIII and Na+ ions are eight-coordinate. The DyIII ions possess a square-anti­prismatic geometry, while the Na+ ions have a distorted biaugmented trigonal–prismatic geometry. Four 3-hy­droxy­benzoate or 4-hy­droxy­benzoate ligands bridge each MnIII ion to the central DyIII ion. For 1, whole-mol­ecule disorder is observed for the main mol­ecule, excluding only the DyIII and Na+ ions, and the occupancy ratio refined to 0.8018 (14):0.1982 (14). Three DMA mol­ecules were refined as disordered with two in general positions by an approximate 180° rotation and the third disordered twice by general disorder as well as by an exact 180° rotation about a twofold axis that bis­ects it. The occupancy ratios refined to 0.496 (8):0.504 (8), 0.608 (9):0.392 (9), and 2×0.275 (7):2×0.225 (7), respectively. For 2, segments of the metallacrown are disordered including the DyIII ion, one of the Mn ions, two of the Mn-bound 4-hy­droxy­benzoate ligands, the Mn-bridging salicyl­hydroximate ligand, and portions of the remaining three shi3− ligands. The occupancy ratio for the metallacrown disorder refined to 0.849 (9):0.151 (9). Two DMF solvent mol­ecules are also disordered, each over two orientations. The disorder ratios refined to 0.64 (3):0.36 (3) and to 0.51 (2):0.49 (2), respectively. For 2, the crystal under investigation was refined as a non-merohedric twin by a 90° rotation around the real a axis [twin ratio 0.9182 (8):0.0818 (8)].

Alterations to synthetic conditions either by varying stochiometric ratios of the reactants or solvent choice yield two new metallacrowns (MCs): Mn(Hsal)2[12-MCMnIII(N)shi-4](DMF)6·4DMF, 1, where −Hsal is salicylate, shi3− salicylhydroximate, and DMF is N,N-dimethylformamide, and {Na2(OAc)2[12-MCMnIII(N)shi-4](MeOH)4(H2O)22MeOH}n, 2, where −OAc is acetate and MeOH is methanol. Compound 1 crystallizes in the monoclinic space group C2/c with a = 19.0264 (6) A, b = 23.1440 (8) A, c = 18.6704 (5) A, α = 90°, β = 90.3600 (10)°, γ = 90°, V = 8221.3 (4) A3, and Z = 4. Compound 2 crystallizes in the triclinic space group P $$\stackrel{-}{1}$$ with a = 7.8995 (7) A, b = 11.2374 (10) A, c = 14.5559 (13) A, α = 112.535 (3)°, β = 91.987 (3)°, γ = 98.558 (3)°, V = 1174.22 (18) A3, and Z = 1. Compound 1 is a discrete metallacrown molecule that contains four ring MnIII ions and a MnII ion captured in the metallacrown central cavity. The MnII ion is tethered to the metallacrown via two salicylate bridges that also bridge to the ring MnIII ions. Compound 2 is a one-dimensional chain of metallacrowns. The metallacrown consists of four ring MnIII ions and two sodium ions which are bound on opposite faces of the metallacrown cavity. Each di-sodium metallacrown is then linked to neighboring metallacrowns through acetate anion bridges to form a one-dimensional chain. The complex Na2(OAc)2[12-MCMnIII(N)shi-4](MeOH)4(H2O)2·2MeOH forms a one-dimensional chain of metallacrowns by linking together neighboring metallacrowns through acetate anion bridges.

Similar synthetic schemes yield two different metallacrown (MC) complexes: bis(μ-3-chlorobenzoato)hexakis(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)tetramanganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1, and tetra-μ-aqua-tris(μ-3-chlorobenzoato)(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)pentamanganese(III)sodium(I) dimethylformamide tetrasolvate 0.72-hydrate, [Mn5Na(C7H4ClO2)3(C7H4NO3)4(C3H7NO)(H2O)4]·4C3H7NO·0.718H2O or MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O, 2, where shi3− is salicylhydroximate and DMF is N,N-dimethylformamide. Both complexes have the same framework consisting of four MnIII ions in the MC ring and four shi3− ligands, resulting in an overall square-shaped molecule. The MnIII ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 1 is nearly planar, and the MC binds two Na+ ions on opposite faces of the MC central cavity. The 3-chlorobenzoate anions also bind on opposite faces of the MC and form bridges between the central Na+ ions and the ring MnIII ions. For 1 the metallacrown molecule, except for the central Na+ ion, exhibits whole molecule disorder over two sets of sites. Both moieties are centrosymmetric and are related to each other by a pseudo-mirror operation with opposite sense of rotation around the Na...Na axis. The occupancy ratio of the main disorder of the metallacrown molecules and 3-chlorobenzoate anions refined to 0.9276 (9):0.0724 (9). The structure of 2 is slightly domed, and the MC binds both an MnII ion and an Na+ ion in the MC central cavity. The MnII ion is located on the convex side of the MC, while the Na+ ion binds to the concave side. Complex 2 represents the first instance of a [12-MCMn(III)N(shi)-4] molecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chlorobenzoate anions bind on the convex side of the MC and connect the MnII ion to three of the ring MnIII ions.

The title compound, [Mn(C3H7NO)4(H2O)2][Cu5(C7H4NO3)4]·C3H7NO or cis-[Mn(H2O)2(DMF)4]{Cu[12-MCCu(II)N(shi)-4]}·DMF, where MC is metallacrown, shi3− is salicylhydroximate, and DMF is N,N-dimethylformamide, crystallizes in the monoclinic space group P21/n. Two crystallographically independent metallacrown anions are present in the structure, and both anions exhibit minor main molecule disorder by an approximate (non-crystallographic) 180° rotation with occupancy ratios of 0.9010 (9) to 0.0990 (9) for one anion and 0.9497 (8) to 0.0503 (8) for the other. Each pentacopper(II) metallacrown contains four CuII ions in the MC ring and a CuII ion captured in the central cavity. Each CuII ion is four-coordinate with a square-planar geometry. The anionic {Cu[12-MCCu(II)N(shi)-4]}2− is charged-balanced by the presence of a cis-[Mn(H2O)2(DMF)4]2+ cation located in the lattice. In addition, the octahedral MnII counter-cation is hydrogen bonded to both MC anions via the coordinated water molecules of the MnII ion. The water molecules form hydrogen bonds with the phenolate and carbonyl oxygen atoms of the shi3− ligands of the MCs.

Carbon-bound halogen atoms (iodine, bromine, chlorine and occasionally fluorine) are known to act as electron acceptors and form interactions with different species capable of acting as electron do...

Extended inorganic hybrids are highly tunable, with changes in the identity of each component giving rise to a variety of different architectures and symmetries. Lead oxide carboxylates are a family of extended inorganic hybrids in which inorganic substructures based on edge-sharing Pb4O tetrahedra are further coordinated by carboxylate ligands. It has previously been shown that the dimensionality of these compounds correlates with the noncoordinating to coordinating volume ratio of the organic ligand. Here, we present five novel lead oxide carboxylates – two with isomeric naphthoate ligands and three with isomeric biphenylcarboxylate ligands – in order to address the role of ligand geometry in directing the spatial arrangement and symmetry of inorganic motifs in these compounds. The compounds have been characterized by single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and elemental analysis. In these compounds, the spatial arrangement of helical inorganic chains is controlled by the extent to which ligands on a given chain fill space immediately surrounding that chain. Noncovalent interaction index calculations have been undertaken for the naphthoate compounds in order to visualize the role of aromatic-aromatic interactions in stabilizing the structures. The structural patterns found here may be applicable to other hybrid systems containing one-dimensional, extended inorganic substructures.

Substituted triazines are a class of compounds utilized for scavenging and sequestering hydrogen sulfide in oil and gas production operations. The reaction of one of these triazines under field conditions resulted in the formation of the title compound, 2-(1,3,5-dithiazinan-5-yl)ethanol, C5H11NOS2, or MEA-dithiazine. Polymorphic form I, in space group I41/a, was first reported in 2004 and its extended structure displays one-dimensional, helical strands connected through O—H...O hydrogen bonds. We describe here the form II polymorph of the title compound, which crystallizes in the orthorhombic space group Pbca as centrosymmetric dimers through pairwise O—H...N hydrogen bonds from the hydroxyl moiety to the nitrogen atom of an adjacent molecule.

We report a curious porous molecular crystal that is devoid of the common traits of related systems. Namely, the molecule does not rely on directional hydrogen bonds to enforce open packing, and it...

The mechanism of formation of metal–organic frameworks (MOFs) is an emerging field, where each new discovery propels the field forward. Often, studies focus on studying nucleation events with advan...

Phenytoin sodium, a salt of 5,5-diphenylimidazolidine-2,4-dione, or phenytoin, is commercially available in various dosage forms for its anti-epileptic properties to treat and prevent seizures. The title compound, poly[aquatris(μ3-4,4-diphenyl-2,5-dioxoimidazolidin-1-ido)trimethanoltrisodium(I)], [Na3(C15H11N2O2)3(CH4O)3(H2O)1.08] n , a methanol solvate and hydrate of phenytoin sodium, forms a modulated crystal structure that consists of a supercell made up of three close-to-identical repeat units. Each of the basic fragments consists of one phenytoin anion, a sodium cation, and either a methanol, or a methanol and a water molecule coordinated to the sodium ion, yielding a formula unit of Na(C15H11N2O2)(CH3OH) x (H2O) y for each of the three segments (x, y = 0 or 1; x + y = 1 or 2). Modulation along the b axis is introduced due to the presence or absence of water or methanol molecules at sodium and by the alternating torsion angles of one of the two phenytoin phenyl rings. Individual segments within the asymmetric unit are linked by covalent Na—O and Na—N bonds, with each sodium ion coordinated to one anionic amide N atom and three keto O atoms. The Na—N and one of the Na—O bonds connect (C15H11N2O2)·Na units along the modulation direction, creating an infinite [(C15H11N2O2)·Na]_{\infty} chain that is further stabilized by intramolecular N—H...O hydrogen bonding parallel to [010]. The second Na—O bond connects this chain with a symmetry-equivalent copy of itself created by a screw-axis operation, yielding double strands of [(C15H11N2O2)·Na]_{\infty} chains. Two of these double strands, propagating in opposite directions, constitute the content of the unit cell. Neighboring double strands are connected with each other to form layers perpendicular to the a axis, tethered together via O—H...O hydrogen bonds involving the water and methanol molecules. In addition to modulation, each of the repeat units also exhibits disorder of the modulated segments. Phenyl rings of each repeat unit are rotationally disordered, and sodium-coordinated methanol and water molecules are also positionally disordered and/or partially occupied. The solvated structure reported here, while not matching the patterns reported for any of the known forms of phenytoin sodium, does provide a first insight into the complications and complexities involved in resolving the structure of anhydrous phenytoin sodium.

The crystal structure of a palladium(II) coordination compound features the same ligand bound to the metal center in both a κ2 and κ3 fashion., Bidentate and tridentate coordination of a 2,4-di-tert-butyl-substituted bridging amine bis­(phenolate) ligand to a palladium(II) center are observed within the same crystal structure, namely di­chlorido­({6,6′-[(ethane-1,2-diylbis(methyl­aza­nedi­yl)]bis­(methyl­ene)}bis­(2,4-di-tert-butyl­phenol))palladium(II) chlorido­(2,4-di-tert-butyl-6-{[(2-{[(3,5-di-tert-butyl-2-hy­droxy­phen­yl)meth­yl](meth­yl)amino}­eth­yl)(meth­yl)amino]­meth­yl}phenolato)palladium(II) methanol 1.685-solvate 0.315-hydrate, [PdCl2(C34H56N2O2)][PdCl(C34H55N2O2)]·1.685CH3OH·0.315H2O. Both complexes exhibit a square-planar geometry, with unbound phenol moieties participating in inter­molecular hydrogen bonding with co-crystallized water and methanol. The presence of both κ2 and κ3 coordination modes arising from the same solution suggest a dynamic process in which phenol donors may coordinate or dissociate from the metal center, and offers insight into catalyst speciation throughout Pd-mediated processes. The unit cell contains di­chlorido­({6,6′-[(ethane-1,2-diylbis(methyl­aza­nedi­yl)]bis­(methyl­ene)}bis­(2,4-di-tert-butyl­phenol))palladium(II), {(L 2)PdCl2}, and chlorido­(2,4-di-tert-butyl-6-{[(2-{[(3,5-di-tert-butyl-2-hy­droxy­phen­yl)meth­yl](methyl)amino}eth­yl)(meth­yl)amino]­meth­yl}phenolato)palladium(II), {(L 2 X)PdCl}, mol­ecules as well as fractional water and methanol solvent mol­ecules.

Three new isotypic heteropolynuclear complexes, namely pentaaquacarbonatopentakis(glycinehydroxamato)nitratopentacopper(II)lanthanide(III) x-hydrate, [LnCu5(GlyHA)5(CO3)(NO3)(H2O)5]·xH2O (GlyHA2− is glycinehydroxamate, N-hydroxyglycinamidate or aminoacetohydroxamate, C2H4N2O2 2−), with lanthanide(III) (Ln III) = gadolinium (Gd, 1, x = 3.5), dysprosium (Dy, 2, x = 3.28) and holmium (Ho, 3, x = 3.445), within a 15-metallacrown-5 class were obtained on reaction of lanthanide(III) nitrate, copper(II) acetate and sodium glycinehydroxamate. Complexes 1–3 contain five copper(II) ions and five bridging GlyHA2− anions, forming a [CuGlyHA]5 metallamacrocyclic core. The Ln III ions are coordinated to the metallamacrocycle through five O-donor hydroxamates. The electroneutrality of complexes 1–3 is achieved by a bidentate carbonate anion coordinated to the Ln III ion and a monodentate nitrate anion coordinated apically to one of the copper(II) ions of the metallamacrocycle. The lattice parameters of complexes 1–3 are similar to those previously reported for an EuIII–CuII 15-metallacrown-5 complex with glycinehydroxamate of proposed composition [EuCu5(GlyHA)5(OH)(NO3)2(H2O)4]·3.5H2O [Stemmler et al. (1999). Inorg. Chem. 38, 2807–2817]. High-quality X-ray data obtained for 1–3 have allowed a re-evaluation of the X-ray data solution proposed earlier for the EuCu5 complex and suggest that the formula is actually [EuCu5(GlyHA)5(CO3)(NO3)(H2O)5]·3.5H2O.

The discovery of new inorganic building units for metal–organic framework (MOF) synthesis remains challenging. We hypothesized that incorporation of X-type halogen capping ligands on indium-building units would yield a series of previously unknown frameworks and the placement of the halogen could lead to framework isomerism. Herein we report the synthesis of three new MOFs; two (YCM-31 and YCM-32) contain an [In(CO2R)3Cl]− secondary building unit (SBU) and are framework isomers of each other. A third new MOF, ZJU-28′, contains an [In(CO2R)4]− SBU and is a framework isomer of the known MOF ZJU-28. The conditions to control the syntheses of these isomers through ammonium-cation templation, along with the rationale for their formation are discussed.

Exploration of the NH4VO3/Na2TeO3/2,4,6-triaminopyrimidine/H2O system yielded the formation of two new phases, [C4H8N5][VO3] and [C4H8N5]2[V2Te2O10]. Phase selection in this system is largely dictated by the tellurium concentration during reaction. Differences in the [V2Te2O10]n2n− layer topologies in [C4H8N5]2[V2Te2O10] and two related phases, [C6H16N2][V2Te2O10] and [C5H14N2][V2Te2O10] were probed using noncovalent interaction energy ratios. These ratios allow for one to directly visualize and quantify differences in intermolecular interaction strengths between compounds. The presence or absence of π - π stacking interactions between organic ammonium cations in [C4H8N5]2[V2Te2O10] and two related phases, [C6H16N2][V2Te2O10] and [C5H14N2][V2Te2O10] is the source of layer connectivity differences. These π - π interactions between 2,4,6-triaminopyrimidinium cations in [C4H8N5]2[V2Te2O10] dictate their orientations between [V2Te2O10]n2n− layers, and direct the locations of hydrogen-bonding interactions. Effects associated with reactant concentrations, charge density matching and intermolecular interactions were probed using composition space analyses, Iterative Hirshfeld partial atomic charge, molecular surface area calculations and noncovalent interaction index calculations, respectively.

CMA (calcium magnesium acetate) road deicers have gained popularity in recent years as an environmentally friendly alternative to traditional rock salt, and as an industrial adsorbent for removing H2S and other odorous acid gases from gas streams. Despite its increasing commercial use, its exact composition and crystalline structure remained unknown, with subsequent problems in evaluating properties of commercial CMA. Various synthetic routes towards formation of crystalline calcium magnesium acetates were investigated. From aqueous solutions preferential formation of calcium monohydrates or calcium monohydrate acetic acid solvates is observed. Crystals of genuine mixed metal calcium-magnesium acetate were obtained from hot glacial acetic acid. Material suitable for analysis by single crystal X-ray diffraction, SC-XRD, was obtained by slight reduction of solvent volume at 80 °C for several hours. CMA crystallizes in the orthorhombic space group Pnma with a formula of Mg2Ca(OAc)6 (OAc = acetate anion), with a magnesium to calcium ratio of two to one. Under the same conditions, but in the absence of magnesium, the acetic acid solvate of calcium acetate, Ca(OAc)2(HOAc), is obtained, which is also described. Multicrystalline XRD and EDS analysis data of ground CMA samples match those of commercial CMA. Single crystal structural analysis finds an unusually large unoccupied void space of 9.4% of the unit cell volume. Thermal gravimetric analysis, TGA, gives an upper limit of one water molecule per formula unit of CMA, leaving the void space at least partially unoccupied. This helps to better understand CMAs unusually low density, which had been an issue when used as a commercial road deicer, having been described as being easily blown off road surfaces when applied in crystalline or powder form.

Analysis of two crystal structures of lithium bis(pentafluoroethanesulfonyl)imide is presented. Two orientations of the anion, that is a cis and trans orientation, are observed. Both structures exhibit unique interactions leading to the formation of discrete fluorous domains in the solid-state. A notable difference in the F···F interactions is seen when contrasting the two orientations wherein the trans geometry has a higher percentage of fluorine interactions than the cis orientation. The inclusion of water molecules in one of the structures also leads to the formation of a polar domain formed through a series of cyclical hydrogen bonding rings. The two structures allow for a detailed examination of the bond distances and angles involved in the formation of the two structures. Analysis of the void space in the two structures leads to the observation that the trans conformation exhibits notably higher void space as compared with the cis orientation. Hirshfeld surface analysis is used to help rationalize the interactions leading to unique changes in geometries and structure.

The wide-range variation of the strength of halogen bonds (XB) not only facilitates a variety of applications of this interaction, but it also allows examining the relation (and interconversion) between supramolecular and covalent bonding. Herein, the Br&hellip, Cl halogen bonding in a series of complexes of bromosubstituted electrophiles (R-Br) with chloride anions were examined via X-ray crystallographic and computational methods. Six co-crystals showing such bonding were prepared by evaporation of solutions of R-Br and tetra-n-propylammonium chloride or using Cl&minus, anions released in the nucleophilic reaction of 1,4-diazabicyclo[2.2.2]octane with dichloromethane in the presence of R-Br. The co-crystal comprised networks formed by 3:3 or 2:2 halogen bonding between R-Br and Cl&minus, with the XB lengths varying from 3.0 &Aring, to 3.25 &Aring, Analysis of the crystallographic database revealed examples of associations with substantially longer and shorter Br&hellip, Cl separations. DFT computations of an extended series of R&ndash, Br&hellip, Cl&minus, complexes confirmed that the judicious choice of brominated electrophile allows varying halogen Br&hellip, Cl bond strength and length gradually from the values common for the weak intermolecular complexes to that approaching a fully developed covalent bond. This continuity of halogen bond strength in the experimental (solid-state) and calculated associations indicates a fundamental link between the covalent and supramolecular bonding.

The three [3.3.1] metallacryptate complexes [Hpy]2[GdAl6(H2shi)2(shi)7(py)1.855(H2O)2]·7.396py·H2O, 1, [Hpy]2[DyAl6(H2shi)2(shi)7(py)1.891(H2O)2]·7.429py·H2O, 2, and [Hpy]2[YbAl6(H2shi)2(shi)7(py)1.818(H2O)2]·7.386py·H2O, 3, where Hpy+ is pyridinium, shi3− is salicyl­hydroximate, and py is pyridine, consist of an aluminium-based metallacryptand that captures an Ln III ion in the central cavity. The metallacryptand portions are comprised of an Al—N—O repeat unit; thus, they can be considered three-dimensional metallacrowns. The encapsulated Ln III ions are nine-coordinate with a spherical capped-square-anti­prism geometry, while the six AlIII ions are all octa­hedral. Four of the AlIII ions are chiral centers with 2 Δ and 2 Λ stereoconfigurations. The remaining two AlIII ions have trans chelate rings from two different shi3− ligands., The three isomorphous [3.3.1] metallacryptate complexes bis­(pyridinium) di­aqua­dipyridine­hexa­kis­[μ3-salicyl­hydroximato(3−)]bis­[μ2-salicyl­hydroxim­ato(1−)]hexa­aluminiumgadolinium–pyridine–water (1/7.396/1), (C5H6N)2[GdAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.396C5H5N·H2O or [Hpy]2[GdAl6(H2shi)2(shi)7(py)1.855(H2O)2]·7.396py·H2O, 1, bis­(pyridinium) di­aqua­dipyridine­hexa­kis­[μ3-salicyl­hydroximato(3−)]bis­[μ2-salicyl­hydroxim­ato(1−)]hexa­aluminiumdysprosium–pyridine–water (1/7.429/1), (C5H6N)2[DyAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.429C5H5N·H2O or [Hpy]2[DyAl6(H2shi)2(shi)7(py)1.891(H2O)2]·7.429py·H2O, 2, and bis­(pyrid­in­ium) di­aqua­dipyridine­hexa­kis­[μ3-salicyl­hydroximato(3−)]bis­[μ2-salicyl­hydrox­imato(1−)]hexa­aluminiumytterbium–pyridine–water (1/7.386/1), (C5H6N)2[YbAl6(C7H6NO3)2(C7H4NO3)7(C5H5N)1.855(H2O)2]·7.429C5H5N·H2O or [Hpy]2[YbAl6(H2shi)2(shi)7(py)1.818(H2O)2]·7.386py·H2O, 3, where Hpy+ is pyridinium, shi3− is salicyl­hydroximate, and py is pyridine, consist of an aluminium-based metallacryptand that captures an Ln III ion in the central cavity. The metallacryptand portions are comprised of an Al—N—O repeat unit; thus, they can be considered three-dimensional metallacrowns. The encapsulated Ln III ions are nine-coordinate with a spherical capped-square-anti­prism geometry, while the six AlIII ions are all octa­hedral. Four of the AlIII ions are chiral centers with 2 Δ and 2 Λ stereoconfigurations. The remaining two AlIII ions have trans chelate rings from two different shi3− ligands. For 1–3, a section of the main mol­ecule is disordered induced by the presence or absence of a pyridine ligand coordinated to one of the AlIII ions. In the absence of the pyridine moiety, an H2shi− ligand moves into the space otherwise occupied by the pyridine and the phenol oxygen atom coordinates to the AlIII ion. The movement of the H2shi− ligand induces movement for the Ln III ion, for another AlIII ion that also binds the same H2shi− ligand, and for one of the shi3− ligands coordinated to the latter AlIII ion. For 1–3 the occupancy ratio of the metallacryptand portions refined to 0.8550 (13):0.1450 (13), to 0.8909 (13):0.1091 (13), and to 0.8181 (14):0.1819 (14), respectively.

Treatment of the ortho-triazacyclophane 1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-triene [(C6H5)3(NH)(NCH3)2, L1] with Fe[N(SiMe3)2]2 yields the dimeric iron(II) complex bis(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)bis[(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)iron(II)], [Fe(C20H18N3)4] or Fe2(L1)4 (9). Dissolution of 9 in tetrahydrofuran (THF) results in solvation by two THF ligands and the formation of a simpler monoiron complex, namely bis(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido-κN 7)bis(tetrahydrofuran-κO)iron(II), [Fe(C20H18N3)2(C4H8O)2] or (L1)2Fe(THF)2 (10). The reaction is reversible and 10 reverts in vacuo to diiron complex 9. In the structures of both 9 and 10, the monoanionic triazacyclophane ligand L1− is observed in only the less-symmetric saddle conformation. No bowl-shaped crown conformers are observed in the solid state, thus preventing chelating κ3-coordination to the metal as had been proposed earlier based on density functional theory (DFT) calculations. Instead, the L1− ligands are bound in either a η2-chelating fashion through the amide and one amine donor (for one of the four ligands of 9), or solely through their amide N atoms in an even simpler monodentate η1-coordination mode. Density functional calculations on dimer 9 revealed nearly full cationic charges on each Fe atom and no bonding interaction between the two metal centers, consistent with the relatively long Fe...Fe distance of 2.912 (1) Å observed in the solid state.

Reaction of copper(II) nitrate with pivaloylhydroxamic acid yielded the title compound, [Cu(pivHA)2] (where pivHA− is pivaloyl hydroxamate, C5H10NO2). The centrosymmetric mononuclear complex consists of a CuII ion, which is located on a center of inversion, with two coordinated pivaloyl hydroxamate monoanions. The CuII ion has a square-planar coordination environment consisting of four O atoms – two carbonyl O atoms and two hydroxamate O atoms from two hydroxamate pivHA− ligands. The pivHA− anions are coordinated to copper(II) in a trans-mode, forming two five-membered O,O′-chelate rings.