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Reaction of Ph2SnCl2 with 1,3-bis(3,5-dimethylpyrazol-1-yl)-2-propanol (L) in a 1:1 ratio yields L(SnPh2Cl2)2 adduct, which partly hydrolyzes to the title complex (C25H31Cl3N4OSn, Mr = 628.58) during crystal growing in the air. The title complex is of monoclinic, space group P21/n with a = 9.0338(9), b = 17.890(1), c = 17.340(1) Å, β = 95.533(1)o, V = 2798.9(5) Å3, Z = 4, Dc = 1.492 Mg/m3, λ(Mo Kα) = 0.71073 Å, μ = 1.224 mm−1, F(000) = 1272, R = 0.023, wR = 0.054 for 4212 observed reflections with I ≥ 2σ( I). The crystal structure indicates that there is no direct interaction between the pyrazolyl ligand and the tin atom, but this complex forms a supramolecular structure through weak intermolecular C–H⋯Cl and O–H⋯Cl hydrogen bonds. Reaction of Ph2SnCl2 with 1,3-bis(3,5-dimethylpyrazol-1-yl)-2-propanol (L) in a 1:1 ratio yields L(SnPh2Cl2)2 adduct, which partly hydrolyzes to (PzCH2CHOHCH2PzH)·(Ph2SnCl3) (Pz = 3,5-dimethylpyrazol-1-yl) during crystal growing in the air. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Co-crystallization of a versatile building module 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4-bpt) with isophthalic acid (H2ip) and its 5-substituted derivatives R–H2ip (R = –NH2, –SO3H, and –CO2H) affords a series of supramolecular solids 1–5. All compounds have been characterized by IR, microanalysis, and powder X-ray diffraction, and their thermal stability has been investigated by TG-DTA technique. Single crystal X-ray diffraction reveals that compounds 1and 2with the formula [(H2ip)·(4-bpt)] exhibit polymorphism, which can be isolated viaa similar synthetic procedure without or with the metal ion as structure-directing reagent, and display distinct hydrogen-bonding assemblies of 3-D and double-layer networks, respectively. Multifarious 3-D supramolecular architectures are observed for compounds [(NH2–H2ip)·(4-bpt)] (3), [(SO3–H2ip)−·(H-4-bpt)+]·2H2O (4), and [(CO2H–H2ip)·(4-bpt)]·2H2O (5), in which the substituent groups of isophthalic acid are involved in different hydrogen-bonding interactions. The results clearly display the substituent effect on the structural assembly of organic co-crystals, which will be significant in the rational design and construction of such crystalline materials with specific hydrogen-bonding networks. [ABSTRACT FROM AUTHOR]

Two new flexible dipyridyl building blocks, N,N‘-bis(4-picolinoyl)hydrazine (4-bph) and its N-orientation isomer N,N‘-bis(3-picolinoyl)hydrazine (3-bph), have been synthesized as versatile cocrystallizing agents and introduced into the reactions with pyromellitic acid (H4BTA) and fumaric acid (H2Fa). Hydrogen-bonded directed assemblies of two hydrates of bphs and four binary cocrystals were validated by single-crystal X-ray diffraction analysis. With the presence of the reliable hydrogen-bonding donor/acceptor(s) of bph, the crystalline lattices of 4-bph·2H2O (1) and 3-bph·2H2O (4) are managed by N−H···Owaterand O−H···Ocarbonylto afford one-dimensional (1D) arrays, which are further extended to distinct three-dimensional (3D) (for 1) and two-dimensional (2D) (for 4) networks via O−H···Npyridylinteractions. While for the concomitant polymorphs (H2BTA)·(H2-4-bph) (2and 3), charge-assistant bifurcated N−H···O bonds do favor 1D acid−base hydrogen-bonding tapes, which are interlinked to result in a 2D layer in 2and a 3D network in 3through the competition of O−H···Ocarboxyland O−H···Ocarbonylforces. (H3BTA)2·(H2-3-bph)·4H2O (5) is also a charge-transfer organic salt with a 2D bilayered array. Proton transfer from weak H2Fa to 3-bph is not observed, and this leads to the formation of a binary neutral cocrystal (H2Fa)·(3-bph) (6), in which the 2D undulating herringbone pattern is constructed via the expected carboxylpyridyl heterosynthon and amide−amide homosynthon. [ABSTRACT FROM AUTHOR]

A bent dipyridyl compound, 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo), was employed to crystallize with 1,4-cyclohexanedicarboxylic acid (H2chdc), hydroquinone, citric acid (H4ca·H2O), barbituric acid, and ferrocene dicarboxylic acid (H2Fc) under general conditions, affording binary cocrystals [(H2chdc)·(4-bpo)] (1), [(hydroquinone)·(4-bpo)2] (2), [(H4ca)·(4-bpo)] (3), [(barbituric acid)·(4-bpo)] (4), and [(HFc)·(H-4-bpo)] (5) in high yield. X-ray single-crystal structures of these compounds reveal that a supramolecular synthon [%@mt;sys@%R%@sx@%2%@be@%2%@sxx@%%@mx@%(7)] containing classical O−H···N and weak C−H···O interactions, usually observed in organic cocrystals of carboxylic acid and heterocyclic base, is again involved in constructing the hydrogen-bonding networks of 1, 3, and 5. Its ionic analogous synthon [consisting of strong N−H···O and weak C−H···O/C%@mt;sys@%R%@sx@%2%@be@%2%@sxx@%%@mx@%(7)] also appears in the partly charge-transfer salt 5. For 2, only hydroxyl of the hydroquinone component can act as the hydrogen-bonding contributor, giving a strong O−H···N bond with 4-bpo. Multiple hydrogen-bonded donating/accepting sites in compound 3 saline 86.3 +/- 34.3 nmol/L per milligram of tissue per hour;4, another heterosynthon ring [containing strong N−H···N and weak C−H···O/C%@mt;sys@%R%@sx@%2%@be@%2%@sxx@%%@mx@%(7)] is formed due to the presence of the imide functional group. As a consequence, robust hydrogen-bonding interactions in these compounds afford diverse 2-D waved or planar layers (1 or 4), 1-D extended tape (2), 3-D net (3), and 1-D molecular-box type (5) supramolecular architectures. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss. [ABSTRACT FROM AUTHOR]

Assembly of pamoic acid (H2PA) with piperazine (PIPO) or 4,4′-bipyridyl (BIPY) results in two distinct supramolecular complexes [(PA)·(H2PIPO)]·3H2O (1) and [(H2PA)·(BIPY)] (2). The former displays triple-helix host arrays via charge-assisted N+−H···O−interactions with the inclusion of helical water chains, whereas the latter represents the first cocrystal of pamoic acid sustaining by the familiar carboxyl-pyridyl H-bonding synthons. Notably, the structure of 1can be dehydrated/rehydrated with retention of crystallinity. [ABSTRACT FROM AUTHOR]

The combination of biphenyl-4,4′-dicarboxylic acid (H2bpa) and the bent dipyridyl base 2,5-di-4-pyridyl-1,3,4-oxadiazole (4-bpo) in a 1:1 molar ratio leads to the formation of the mol­ecular cocrystal (H2bpa)·(4-bpo) or C14H10O4·C12H8N4O. The asymmetric unit contains one-half of an H2bpa unit lying across a centre of inversion and one-half of a 4-bpo mol­ecule lying across a twofold rotation axis. Inter­molecular O—H⋯N inter­actions connect the acid and base mol­ecules to form a one-dimensional zigzag chain. Through further weak C—H⋯O hydrogen bonds between adjacent chains, a two-dimensional sheet-like supramolecular network is afforded. As an extended analogue of terephthalic acid (H2tp), the backbone geometry of H2bpa has an evident influence on the hydrogen-bonding pattern of the title cocrystal compared with that of (H2tp)·(4-bpo). [ABSTRACT FROM AUTHOR]

The mol­ecular structure of the neutral mononuclear title complex, [Mn(NCS)2(C12H8N4O)2(H2O)2], is centrosymmetric; the MnII atom lies on an inversion center and is six-coordinate (MnN4O2), with an octa­hedral geometry comprising two trans monodentate 2,5-di-3-pyrid­yl-1,3,4-oxadiazole ligands, two thio­cyanate ligands and two bound water mol­ecules. Inter­molecular O—H⋯N hydrogen bonds between these monomeric units result in two-dimensional supramolecular layers with a parallel arrangement, which are stabilized by intra­layer aromatic stacking and further extended to a three-dimensional network via inter­layer weak C—H⋯S inter­actions. [ABSTRACT FROM AUTHOR]

In the crystal structure of the title complex, [Cu(bda)(bipy)2]·4H2O [H2bda = ( p-phenyl­ene­dioxy)­di­acetic acid or benzene-1,4-dioxy­acetic acid (C10H10O6) and bipy = 2,2′-bi­pyridine (C10H8N2)], the CuII centre is pentacoordinated, with a square-pyramidal geometry comprising four N atoms from two chelating bipy ligands and one carboxyl­ate O atom of the bda ligand. The other three uncoordinated carboxyl­ate O atoms of the bda ligand act as the acceptors of four O—H⋯O hydrogen bonds from the water molecules, among which another four O—H⋯O hydrogen-bonding interactions are also observed, resulting in a two-dimensional supramolecular pattern. [ABSTRACT FROM AUTHOR]

Examines the three-dimensional hydrogen-bonding supramolecular architecture of 2-(3-pyridinio)-5-(3-pyridyl)-1,2,3-oxadiazole perchlorate. Capacity of protonated cation in adopting a cis-I conformation and planar geometry; Role of each perchlorate anion; Interaction of hydrogen bonds in between the protonated cations.

Examines the crystal structure of the organic compound 5-Nitro-2,3-bis(2-pyridyl)quinoxaline. Hydrogen bonding in the compound; Crystallization system of the compound; Arrangements of pyridyl rings in the compound.

Co-crystallization of hemimellitic acid (benzene-1,2,3-tricarboxylic acid) dihydrate (H3HMA·2H2O) with 4,4′-bipyridine (4,4′-bpy) affords the 1:1 co-crystal benzene-1,2,3-tricarboxylic acid–4,4′-bipyridine (1/1), H3HMA·4,4′-bpy or C9H6O6·C10H8N2. Strong O—H⋯O hydrogen bonds connect the acid mol­ecules to form a one-dimensional zigzag chain, around which the 4,4′-bpy components are fixed as arms via O—H⋯N inter­actions, resulting in a ladder motif. Through weak C—H⋯O non-covalent forces, the resulting acid layers are extended into a three-dimensional pillar-layered architecture supported by rod-like 4,4′-bpy components. The influence on hydrogen-bonding models is also discussed, with the discovery of an unexpected inter­action motif that does not follow the routine hydrogen-bonded hierarchical rule in the construction of an acid–base co-crystal. [ABSTRACT FROM AUTHOR]

A series of CdIIcoordination polymers have been designed and hydrothermally synthesized by using a bent dipyridyl tecton 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and R-isophthalic acids (H2ip-R; R = –H, –CH3, –OCH3, –tBu, –OH, and –NO2), which exhibit diverse 1D and 2D polymeric coordination networks. The results demonstrate that the substituent effect of R-isophthalates does play a decisive role in directing the structural assemblies of this system, in which secondary interactions such as H-bonding and ππ stacking are generally observed to extend the coordination motifs. Notably, the 3-bpo building block shows adaptable conformations (cisoid-I, cisoid-II, and transoid) to facilitate the structural diversity of these complexes. Solid state properties such as thermal stability and fluorescence for these crystalline materials will also be presented. [ABSTRACT FROM AUTHOR]

Chlorine, bromine and iodine substituted derivatives of 5,5′-bisdiazo-dipyrromethane have been synthesized and their crystal structures were studied by X-ray crystallography. In the three structures, the 5,5′-bisdiazo-dipyrromethanes form interlocked dimers through quadruple N–HN hydrogen bonds. The halogenπ synthons also provide a significant contribution to the resulting supramolecular motifs. [ABSTRACT FROM AUTHOR]

In the title neutral mononuclear complex, [Cd(H2IDC)2(H2O)3]·H2O (H2IDC is the 4-carb­oxy-1 H-imidazole-5-carboxyl­ate anion, C5H3N2O4), the CdII atom is trans-coordinated by two H2IDC ligands and three aqua mol­ecules, displaying a distorted trigonal-bipyrimidal geometry. Inter­estingly, H2IDC coordinates in an N-monodentate fashion to the central CdII atom, which is unprecedented. A three-dimensional supramolecular network is generated through N—H⋯O and O—H⋯O hydrogen bonds. [ABSTRACT FROM AUTHOR]

The mol­ecular structure of the neutral mononuclear complex [Fe(NCS)2(3-bpo)2(H2O)2], in which 3-bpo denotes 2,5-di-3-pyrid­yl-1,3,4-oxadiazole (C12H8N4O), is centrosymmetric, with FeII located on an inversion center. This complex is octa­hedral, and the FeII atom is trans coordinated by two monodentate NSC− ligands, two monodentate 3-bpo ligands and two water mol­ecules. Each complex is linked to four others, forming a (011) sheet, by O—H⋯N hydrogen bonding. Weak C—H⋯S inter­actions link each (011) sheet to the two adjacent sheets, hence forming a three-dimensional array. There is also some slipped π stacking within each sheet. [ABSTRACT FROM AUTHOR]

A new polymorph of 2,5-bis­(4-pyrid­yl)-1,3,4-thia­diazole, C12H8N4S, obtained under hydro­thermal conditions, is described. In this structure, the two terminal pyrid­yl groups are inclined to the central thia­diazole ring with dihedral angles of 6.47 (2) and 29.95 (5)°, and the dihedral angle between the pyrid­yl ring planes is 23.65 (6)°. An inter­molecular C—H⋯N weak inter­action is observed. The structural differences of two polymorphs of 2,5-bis­(4-pyrid­yl)-1,3,4-thia­diazole are also discussed. [ABSTRACT FROM AUTHOR]

Two chiral d10metallosupramolecular systems based on an achiral fluorinated Schiff-base ligand have been prepared and characterized. The ZnIIcomplex 1reveals 21helical coordination chains with the inclusion of rare water chains of opposite helix in the perpendicular channels, whereas the CdIIcomplex 2displays the homochiral 1D coordination motifs with 31symmetry and a 3D supramolecular architecture built by C–H···F interactions. [ABSTRACT FROM AUTHOR]

Seven Zn(II) and Cd(II) coordination polymers, formulated as {[Zn2(5-Br-ip)2(bpy)(H2O)]·2H2O}n(1), {[Zn(5-Br-ip)(bpa)(H2O)]}n(2), {[Cd(5-Br-ip)(bpp)(H2O)]}n(3), {[Zn(5-Br-ip)(bpe)]}n(4), {[Zn2(4-Br-ip)2(bpy)]·H2O}n(5), {[Zn(4-Br-ip)(bpa)(H2O)]}n(6), and {[Cd(4-Br-ip)(bpp)]}n(7), were prepared by hydrothermal reactions based on 4-bromo- or 5-bromoisophthalic acid (4-Br-H2ip or 5-Br-H2ip) and different dipyridyl-type coligands 4,4′-bipyridyl (bpy), 1,2-bi(4-pyridyl)ethane (bpa), 1,3-di(4-pyridyl)propane (bpp), and 1,2-di(4-pyridyl)ethene (bpe). All complexes 1−7were characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. Complex 1is a 2D (6,3) coordination network and further assembled into a 3D framework via π−π stacking interactions. Complex 2shows a 1D coordination array and further forms a 2D supramolecular network via H-bonding interactions. Complex 3has a 2-fold interpenetrating 3D diamond framework. Complex 4is a 3-fold interpenetrating 3D network with CdSO4topology, constructed from alternately left- and right-handed helical arrays. Complex 5has a 3D (3,4)-connected network with (4·82)(4·82·103) topology. Complex 6features a 1D coordination chain and further forms a 2D helical supramolecular pattern by H-bonding. Complex 7exhibits a (3,5)-connected 2D layer with the Schläfli symbol of (42·6) (42·67·8). The results reveal that the diverse coordination networks of 1−7can be adjusted by the different dispositions of the -Br substituent of isophthalate building blocks, as well as the metal ions and the dipyridyl coligands. Moreover, the luminescent properties of the complexes have been investigated. [ABSTRACT FROM AUTHOR]

A survey of the Cambridge Structural Database (CSD) indicates that 79% of complexes that contain both imidazole and carboxyl groups generate imidazolium-carboxylate supramolecular heterosynthons rather than carboxyl or imidazole supramolecular homosynthons. In the absence of other competing factors, the occurrence of such heterosynthons is increased to 100%. This observation is further supported by the crystal structures of seven new complexes that contain tris(2-benzimidazylmethyl)amine (TBMA) and a variety of carboxylic acids, including benzoic acid (HBA), p-methoxybenzoic acid (HPMBA), phthalic acid (H2PA), terephthalic acid (H2TPA), isophthalic acid (H2PIA), trimesic acid (H3TMA), and pyromellitic acid (H4PMA). In all seven complexes, (H2TBMA)·(BA)2·DMF (1), (HTBMA)·(PMBA)·(TBMA)·(HPMBA)2·2DMF·H2O (2), (HTBMA)·(H2TBMA)·(HPA)·(PA)·3DMF·H2O (3), (HTBMA)2·(TPA)·2DMF (4), (HTBMA)2·(PIA)·2DMF (5), (H2TBMA)·(HTMA)·0.5DMF·H2O (6), and (HTBMA)2·(H2PMA)·2DMF·H2O (7), proton transfer occurs from acid to aromatic nitrogen of benzimidazole (partial proton transfer for 3, 6, and 7). Analysis of the H-bonding synthons and their effect on crystal packing is also presented in the context of crystal engineering and host−guest chemistry. In the structure of 1, discrete acid/base hexamers are formed via synthons III, V, and VI, while in 2−5, self-recognition via synthons IV, V, and VIresults in one-dimensional (1-D) chains, and these structures are extended to high-dimensional architectures (two-dimensional (2-D) structures in 3and three-dimensional (3-D) structures in 2, 4, and 5) via additional C−H···O, C−H···π and π···π interactions. Interestingly, salts 6and 7display the 3-D supramolecular networks via synthons III, IV, V, and VI, which have 1-D channels that are occupied by DMF guests. [ABSTRACT FROM AUTHOR]

A family of new coordination polymers based on a V-shaped flexible dicarboxyl building block 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) and familiar metal ions (MnII, CoII, NiII, CuII, ZnII, and AgI) have been prepared and structurally characterized. Their thermal stability and solid state luminescent properties of the ZnIIand AgIcomplexes have also been investigated. Single-crystal X-ray diffraction analysis reveals a significant structural diversity of these coordination frameworks, such as the 1-D zigzag chain, 2-fold interpenetrating layer composed of 21helical arrays, and 3-D open network with 42helicity and pcutopology based on the rod-shaped secondary building units (SBUs). Additionally, hydrogen bonding interactions are found in these structures to further extend or stabilize the coordination motifs. A comprehensive analysis of the coordination systems based on this dicarboxyl tecton also demonstrates that it is an excellent candidate for the design and construction of multiform metal–organic frameworks (especially helical arrays), which can be dominated by metal ions and/or synthetic conditions. [ABSTRACT FROM AUTHOR]