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The crystal structure of the new double CuII complex salt, [Cu(L)(H2O)2][Cu(L)]Br4·2H2O (L = 3,14-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]docosane, C22H44N4) has been determined using synchrotron radiation. The asymmetric unit contains one half of a [Cu(L)(H2O)2]2+ cation, one half of a [Cu(L)]2+ cation (both completed by crystallographic inversion symmetry), two bromide anions and one water solvent molecule. The CuII atom in the first complex exists in a tetragonally distorted octahedral environment with the four N atoms of the macrocyclic ligand in equatorial and two aqua ligands in axial positions, whereas the CuII atom in the second complex exists in a square-planar environment defined by the four nitrogen atoms of the macrocyclic ligand. The two macrocyclic rings adopt the most stable trans-III configuration with normal Cu—N bond lengths from 2.016 (3) to 2.055 (3) Å and an axial Cu—O bond length of 2.658 (4) Å. The crystal structure is stabilized by intermolecular hydrogen bonds involving the macrocycle N—H or C—H groups and the O—H groups of water molecules as donor groups, and the O atoms of water molecules and bromide anions as acceptor groups, giving rise to a one-dimensional network extending parallel to [100].

The crystal structure of the title salt, C20H42N42+·2ClO4−, has been determined using synchrotron radiation at 220 (2) K. The structure determination reveals that protonation has occurred at diagonally opposite amine N atoms. The asymmetric unit comprises one half of the organic dication, which lies about a center of inversion, and one perchlorate anion. The macrocyclic dication adopts the most stable endodentate trans-III conformation. The crystal structure is stabilized by intramolecular N—H...N, and intermolecular N—H...O and C–H...O hydrogen bonds involving the macrocycle N—H and C—H groups as donors and the O atoms of perchlorate anions as acceptors, giving rise to a three-dimensional network.

The crystal structure of the novel hydrated CuII salt, [Cu(L)(H2O)2]Cl2·4H2O (L = 3,14-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]docosane, C22H44N4) has been determined using synchrotron radiation. The asymmetric unit contains one half of the [Cu(L)(H2O)2]2+ cation (completed by crystallographic inversion symmetry), one chloride anion and two lattice water molecules. The copper(II) atom exists in a tetragonally distorted octahedral environment with the four N atoms of the macrocyclic ligand in equatorial and two O atoms from water molecules in axial positions. The latter exhibit a long axial Cu—O bond length of 2.7866 (16) Å due to the Jahn–Teller distortion. The macrocyclic ring adopts a stable trans-III conformation with typical Cu—N bond lengths of 2.0240 (11) and 2.0441 (3) Å. The complex is stabilized by hydrogen bonds formed between the O atoms of coordinated water molecules and the NH groups as donors, and chloride anions as acceptors. The chloride anions are further connected to the lattice water solvent molecules through O—H...Cl hydrogen bonds, giving rise to a three-dimensional network structure.

The crystal structure of the title complex, cis-[Cr(NCS)2(cyclam)]Br (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4), has been determined from synchrotron X-ray data. The asymmetric unit contains one [Cr(NCS)2(cyclam)]+ cation and one bromide anion. The CrIII ion of the complex cation is coordinated by the four N atoms of the cyclam ligand and by two N-coordinating NCS groups in a cis arrangement, displaying a distorted octahedral coordination sphere. The Cr—N(cyclam) bond lengths are in the range 2.075 (3) to 2.081 (3) Å while the average Cr—N(NCS) bond length is 1.996 (16) Å. The macrocyclic cyclam moiety adopts the most stable cis-V conformation. The crystal structure is stabilized by intermolecular hydrogen bonds involving the cyclam N—H groups as donor groups, and the bromide anion and the S atom of one of the NCS ligands as acceptor groups.

The crystal structure of the hydrated title salt, C22H48N44+·4Cl−·4H2O (C22H48N4 = H4L = 3,14-diethyl-2,6,13,17-tetraazoniatricyclo[16.4.0.07,12]docosane), has been determined using synchrotron radiation at 220 K. The structure determination reveals that protonation has occurred at all four amine N atoms. The asymmetric unit comprises one half of the macrocyclic cation (completed by crystallographic inversion symmetry), two chloride anions and two water molecules. The macrocyclic ring of the tetracation adopts an exodentate (3,4,3,4)-D conformation. The crystal structure is stabilized by intermolecular hydrogen bonds involving the macrocycle N—H groups and water O—H groups as donors, and the O atoms of the water molecules and chloride anions as acceptors, giving rise to a three-dimensional network.

The structure of the title compound, [CrCl2(C10H24N4)][Cr(HCONH2)2(C10H24N4)][ZnCl4]2 (C10H24N4 = 1,4,8,11-tetraazacyclotetradecane, cyclam; HCONH2 = formamide, fa), has been determined from synchrotron X-ray data. The asymmetric unit contains two independent halves of the [CrCl2(cyclam)]+ and [Cr(fa)(cyclam)]3+ cations, and one tetrachloridozincate anion. In each complex cation, the CrIII ion is coordinated by the four N atoms of the cyclam ligand in the equatorial plane and two Cl ligands or two O-bonded formamide molecules in a trans axial arrangement, displaying a distorted octahedral geometry with crystallographic inversion symmetry. The Cr—N(cyclam) bond lengths are in the range 2.061 (2) to 2.074 (2) Å, while the Cr—Cl and Cr—O(fa) bond distances are 2.3194 (7) and 1.9953 (19) Å, respectively. The macrocyclic cyclam moieties adopt the centrosymmetric trans-III conformation with six- and five-membered chelate rings in chair and gauche conformations. The crystal structure is stabilized by intermolecular hydrogen bonds involving the NH or CH groups of cyclam and the NH2 group of coordinated formamide as donors, and Cl atoms of the ZnCl42− anion as acceptors.

The crystal structure of title compound, (C14H36N4)[CrO3Cl]2Cl2, has been determined by synchrotron radiation X-ray crystallography at 220 K. The macrocyclic cation lies across a crystallographic inversion center and hence the asymmetric unit contains one half of the organic cation, one chlorochromate anion and one chloride anion. Both the Cl− anion and chlorochromate Cl atom are involved in hydrogen bonding. In the crystal, hydrogen bonds involving the 1,4,8,11-tetramethyl-1,4,8,11-tetraazoniacyclotetradecane (TMC) N—H groups and C—H groups as donor groups and three O atoms of the chlorochromate and the chloride anion as acceptor groups link the components, giving rise to a three-dimensional network.

The crystal structure of title salt, C22H46N42+·2NO3−·2H2O, has been determined using synchrotron radiation at 220 K. The structure determination reveals that protonation has occurred at diagonally opposite amine N atoms. The asymmetric unit contains half a centrosymmetric dication, one nitrate anion and one water molecule. The molecular dication, C22H46N42+, together with the nitrate anion and hydrate water molecule are involved in an extensive range of hydrogen bonds. The molecule is stabilized, as is the conformation of the dication, by forming intermolecular N—H...O, O—H...O, together with intramolecular N—H...N hydrogen bonds.

The structure of the title compound, [Cr(tacn)2]2[ZnCl4]3·H2O (tacn is 1,4,7-triazacyclononane; C6H15N3), has been determined from synchrotron X-ray data. Each CrIII cation is coordinated by the six N atoms from the two tacn ligands, displaying a distorted octahedral geometry. Three distorted tetrahedral [ZnCl4]2− anions and one lattice water molecule lie outside this coordination sphere. The Cr—N bond lengths are in the range 2.0621 (11) to 2.0851 (12) Å, while the mean inner N—Cr—N bond angle is 82.51 (5)°. The crystal packing is stabilized by hydrogen-bonding interactions with the N—H groups of the tacn ligands and the water O—H groups acting as donors, and the O atoms of the water molecules and Cl atoms of the [ZnCl4]2− anions as acceptors. Overall these contacts lead to the formation of a three-dimensional network.

The asymmetric unit of the title compound, [Ag(C24H46N6O2)](NO3)2 [C24H46N6O2 is (5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]docosane-2,13-diyl)diacetamide, L], consists of one independent half of the [Ag(C24H46N6O2)]2+ cation and one nitrate anion. The Ag atom, lying on an inversion centre, has a square-planar geometry and the complex adopts a stable trans-III conformation. Interestingly, the two O atoms of the pendant acetamide groups are not coordinated to the AgII ion. The longer distance of 2.227 (2) Å for Ag—N(tertiary) compared to 2.134 (2) Å for Ag—N(secondary) may be due to the effects of the attached acetamide group on the tertiary N atom. Two nitrate anions are very weakly bound to the AgII ion in the axial sites and are further connected to the ligand of the cation by N—H...O hydrogen bonds. The crystal packing is stabilized by hydrogen-bonding interactions among the N—H donor groups of the macrocycle and its actetamide substituents, and the O atoms of the nitrate anions and of an acetamide group as the acceptor atoms.

The asymmetric unit of the title compound, Ag[Cr(C11H14N2O8)]·3H2O, contains one [Cr(1,3-pdta)]− anion [1,3-pdta is (propane-1,3-diyldinitrilo)tetraacetate], one Ag+ cation and three water molecules. The Cr3+ ion is coordinated to the four O and two N atoms of the 1,3-pdta ligand, displaying a distorted octahedral geometry. The mean Cr—N and Cr—O bond lengths are 2.0727 (17) and 1.9608 (15) Å, respectively. The conformations of the chelate rings were found to be envelope for the glycinates and twist-boat for the six-membered diamine (T) ring. The Ag+ cation is surrounded by six O atoms from three non-coordinated carbonyl O atoms of neighbouring 1,3-pdta groups and three water molecules. The crystal structure is stabilized by intermolecular hydrogen bonding involving the water O—H group as donor and the carboxyl O atom as acceptor.

The asymmetric unit of the hydrated title salt, (C10H28N4)[Cr2O7]2·H2O [C10H28N4 = H4(cyclam) = 1,4,8,11-tetraazoniacyclotetradecane], contains two half-cations (both completed by crystallographic inversion symmetry), two dichromate anions and one water molecule. The two [CrO7]2− anions exhibit a nearly staggered conformation, with bridging angles of 133.37 (11) and 136.28 (12)°. The distortions of the dichromate anions are due to their participation in hydrogen-bonding interactions with the water molecule and the cations. Intermolecular hydrogen bonds involving the cyclam N—H groups and water O—H groups as donor groups, and the O atoms of the dichromate anions as acceptor groups give rise to a three-dimensional network.

The asymmetric unit of the title compound, [Cr(C2O4)(C10H24N4)]2[Cr2O7]·8H2O (C10H24N4 = 1,4,8,11-tetraazacyclotetradecane, cyclam; C2O4 = oxalate, ox) contains one [Cr(ox)(cyclam)]+ cation, one half of a dichromate anion that lies about an inversion centre so that the bridging O atom is equally disordered over two positions, and four water molecules. The terminal O atoms of the dichromate anion are also disordered over two positions with a refined occupancy ratio 0.586 (6):0.414 (6). The CrIII ion is coordinated by the four N atoms of the cyclam ligand and one bidentate oxalato ligand in a cis arrangement, resulting in a distorted octahedral geometry. The Cr—N(cyclam) bond lengths are in the range 2.069 (2)–2.086 (2) Å, while the average Cr—O(ox) bond length is 1.936 Å. The macrocyclic cyclam moiety adopts the cis-V conformation. The dichromate anion has a staggered conformation. The crystal structure is stabilized by intermolecular hydrogen bonds involving the cyclam N—H groups and water O—H groups as donors, and the O atoms of oxalate ligand, water molecules and the Cr2O72− anion as acceptors, giving rise to a three-dimensional network.

The structure of the complex salt, cis-[Cr(NCS)2(cyclam)]2[Cr2O7]·H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4), has been determined from synchrotron data. The asymmetric unit comprises of one [Cr(NCS)2(cyclam)]+ cation, one half of a Cr2O72− anion (completed by inversion symmetry) and one half of a water molecule (completed by twofold rotation symmetry). The CrIII ion is coordinated by the four cyclam N atoms and by two N atoms of cis-arranged thiocyanate anions, displaying a distorted octahedral coordination sphere. The Cr—N(cyclam) bond lengths are in the range 2.080 (2) to 2.097 (2) Å while the average Cr—N(NCS) bond length is 1.985 (4) Å. The macrocyclic cyclam moiety adopts the cis-V conformation. The bridging O atom of the dichromate anion is disordered around an inversion centre, leading to a bending of the Cr—O—Cr bridging angle [157.7 (3)°]; the anion has a staggered conformation. The crystal structure is stabilized by intermolecular hydrogen bonds involving the cyclam N—H groups and water O—H groups as donor groups, and the O atoms of the Cr2O72− anion and water molecules as acceptor groups, giving rise to a three-dimensional network.

In the asymmetric unit of the title compound, [CrCl2(C10H24N4)][Cr(C2O4)(C10H24N4)](ClO4)2 (C10H24N4 = 1,4,8,11-tetraazacyclotetradecane, cyclam; C2O4 = oxalate, ox), there are two independent halves of the [CrCl2(cyclam)]+ and [Cr(ox)(cyclam)]+ cations, and one perchlorate anion. In the complex cations, which are completed by application of twofold rotation symmetry, the CrIII ions are coordinated by the four N atoms of a cyclam ligand, and by two chloride ions or one oxalate bidentate ligand in a cis arrangement, displaying an overall distorted octahedral coordination environment. The Cr—N(cyclam) bond lengths are in the range of 2.075 (5) to 2.096 (4) Å while the Cr—Cl and Cr—O(ox) bond lengths are 2.3358 (14) and 1.956 (4) Å, respectively. Both cyclam moieties adopt the cis-V conformation. The slightly distorted tetrahedral ClO4− anion remains outside the coordination sphere. The supramolecular architecture includes N—H...O and N—H...Cl hydrogen bonding between cyclam NH donor groups, O atoms of the oxalate ligand or ClO4− anions and one Cl ligand as acceptors, leading to a three-dimensional network structure.

The structure of the title compound, [CrCl2(tn)2]2[Cr2O7] (tn = propane-1,3-diamine; C3H10N2), has been determined from synchrotron data. The asymmetric unit contains one CrIII complex cation and half a [Cr2O7]2− anion. In the complex cation, the CrIII ion is coordinated by the four N atoms of two propane-1,3-diamine (tn) ligands in the equatorial plane and by two Cl atoms in a trans configuration, displaying a distorted octahedral coordination sphere. The two six-membered rings in the complex cation have an anti chair–chair conformation with respect to each other. The mean Cr—N(tn) and Cr—Cl bond lengths are 2.09 (1) and 2.320 (2) Å, respectively. The slightly bent dichromate anion is disordered over two sets of sites (occupancy ratio = 0.7:0.3) and has a staggered conformation. The crystal structure is stabilized by intermolecular hydrogen bonds involving the NH2 groups of the tn ligands as donors and the O atoms of the [Cr2O7]2− anion and chlorido ligands as acceptors.

The crystal structure of the title salt, C20H44N44+·4Cl−·4H2O, has been determined using synchrotron radiation at 220 K. The structure determination reveals that protonation has occurred at all four amine N atoms. The asymmetric unit contains one half-cation (completed by crystallographic inversion symmetry), two chloride anions and two water molecules. There are two molecules in the unit cell. The Cl− anions and hydrate molecules are involved in hydrogen bonding. The crystal structure is stabilized by intermolecular hydrogen bonds involving the macrocycle N—H groups and water O—H groups as donors and the O atoms of the water molecules and the Cl− anions as acceptors, giving rise to a three-dimensional network.

The structure of the title compound, [(NH4)0.8K0.2][Cr(C5H7NO4)2] (C5H7NO4 is methyliminodiacetate; mida), has been determined from synchrotron data. The CrIII atom is located on a centre of symmetry and is coordinated by two N atoms and four O atoms of two facially arranged tridentate mida ligands, displaying a slightly distorted octahedral coordination environment. The Cr—N and mean Cr—O bond lengths are 2.0792 (14) and 1.958 (14) Å, respectively. The cation site is located on a twofold rotation axis and shows occupational disorder, being occupied by ammonium and potassium cations in a 0.8:0.2 ratio. In the crystal, intermolecular hydrogen bonds involving the N—H groups of the ammonium cation as donor and the two non-coordinating O atoms of the carboxylate group as acceptor groups consolidate the three-dimensional packing.

The structure of the title double salt, [Cr(rac-chxn)3][ZnCl4]Cl·3H2O (chxn is trans-1,2-cyclohexanediamine; C6H14N2), has been determined from synchrotron data. The CrIII ion is coordinated by six N atoms of three chelating chxn ligands, displaying a slightly distorted octahedral coordination environment. The distorted tetrahedral [ZnCl4]2− anion, the isolated Cl− anion and three lattice water molecules remain outside the coordination sphere. The Cr—N(chxn) bond lengths are in a narrow range between 2.0737 (12) and 2.0928 (12) Å; the mean N—Cr—N bite angle is 82.1 (4)°. The crystal packing is stabilized by hydrogen-bonding interactions between the amino groups of the chxn ligands and the water molecules as donor groups, and O atoms of the water molecules, chloride anions and Cl atoms of the [ZnCl4]2− anions as acceptor groups, leading to the formation of a three-dimensional network. The [ZnCl4]2− anion is disordered over two sets of sites with an occupancy ratio of 0.94:0.06.

The asymmetric unit of the title complex salt, [Cr(C10H24N4)(NH3)2][ZnCl4]Cl·H2O, is comprised of four halves of the CrIII complex cations (the counterparts being generated by application of inversion symmetry), two tetrachloridozincate anions, two chloride anions and two water molecules. Each CrIII ion is coordinated by the four N atoms of the cyclam (1,4,8,11-tetraazacyclotetradecane) ligand in the equatorial plane and by two N atoms of ammine ligands in axial positions, displaying an overall distorted octahedral coordination environment. The Cr—N(cyclam) bond lengths range from 2.0501 (15) to 2.0615 (15) Å, while the Cr—(NH3) bond lengths range from 2.0976 (13) to 2.1062 (13) Å. The macrocyclic cyclam moieties adopt the trans-III conformation with six- and five-membered chelate rings in chair and gauche conformations. The [ZnCl4]2− anions have a slightly distorted tetrahedral shape. In the crystal, the Cl− anions link the complex cations, as well as the solvent water molecules, through N—H...Cl and O—H...Cl hydrogen-bonding interactions. The supramolecular set-up also includes N—H...Cl, C—H...Cl, N—H...O and O—H...Cl hydrogen bonding between N—H or C—H groups of cyclam, ammine N—H and water O—H donor groups, and O atoms of the water molecules, Cl− anions or Cl atoms of the [ZnCl4]2− anions as acceptors, leading to a three-dimensional network structure.

The structure of the title complex, [CrCl2(2,3,2-tet)]ClO4 (2,3,2-tet is 1,4,8,11-tetraazaundecane, C7H20N4), has been determined from synchrotron data. The CrIII ion is coordinated by the four N atoms of the 1,4,8,11-tetraazaundecane ligand in the equatorial plane and two chloride ions in an axial arrangement, displaying a slightly distorted octahedral coordination environment. The two H atoms of the secondary amines are grouped on the same side of the equatorial N4 plane (meso-RS conformation). The Cr—N bond lengths range from 2.069 (2) to 2.084 (2) Å, while the mean Cr—Cl bond length is 2.325 (2) Å. The crystal structure is stabilized by intermolecular hydrogen-bonding interactions between the primary and secondary amine groups of the 2,3,2-tet ligands, the Cl ligands and the O atoms of the perchlorate counter-anion, forming corrugated layers parallel to (010).

The title bromide salt, [Cr{CO(NH2)2}6](Cr2O7)Br·H2O, is isotypic to the corresponding chloride salt. Within the complex cation, the CrIII atom is coordinated by six O atoms of six urea ligands, displaying a slightly distorted octahedral coordination environment. The Cr—O bond lengths involving the urea ligands are in the range 1.9534 (13)–1.9776 (12) Å. The Cr2O72− anion has a nearly staggered conformation, with a bridging angle of 130.26 (10)°. The individual components are arranged in rows extending parallel to [100]. The Br− anion links the complex cation, as well as the solvent water molecule, through N—H...Br and O—H...Br hydrogen-bonding interactions. The supramolecular architecture also includes N—H...O and O—H...O hydrogen bonding between urea N—H and water O—H donor groups and the O atoms of the Cr2O72− anion as acceptor atoms, leading to a three-dimensional network structure.

The structure of the title compound, cis-[CrCl(cycb)(H2O)][ZnCl4]·3H2O (cycb is rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; C16H36N4), has been determined from synchrotron data. In the complex cation, the CrIII ion is bound by four N atoms from the tetradentate cycb ligand, a chloride ion and one water molecule in a cis arrangement, displaying a distorted octahedral coordination geometry. The distorted tetrahedral [ZnCl4]2− anion and three additional water molecules remain outside the coordination sphere. The Cr—N(cycb) bond lengths are in the range of 2.0837 (14) to 2.1399 (12) Å while the Cr—Cl and Cr—(OH2) bond lengths are 2.2940 (8) and 2.0082 (13) Å, respectively. The crystal packing is stabilized by hydrogen-bonding interactions between the N—H groups of the macrocyclic ligand, the O—H groups of the water molecules and the Cl atoms of the tetrachloridozincate anion, leading to the formation of a three-dimensional network.

The structure of the title compound, C21H40N4·2H2O, has been determined from synchrotron X-ray radiation data. The asymmetric unit comprises one 12-membered macropolycycle and two lattice water molecules. The macropolycycle contains two cyclohexane rings and one 1,3-diazacyclohexane ring, all in chair conformations. The C—N and C—C bond lengths are in the ranges 1.4526 (16)–1.4786 (17) and 1.517 (2)–1.5414 (17) Å, respectively. One intramolecular N—H...N hydrogen bond helps to stabilize the molecular conformation while medium-strength intermolecular N—H...O, O—H...N and O—H...O hydrogen bonds involving the lattice water molecules connect the components into a three-dimensional network.

The structure of the title hybrid compound, (C6H16N2)[CrO4], has been determined from synchrotron data. The organic cation adopts a chair conformation. The inorganic CrO42− anion is slightly distorted owing to its involvement in N—H...O hydrogen-bonding interactions with neighbouring trans-cyclohexane-1,2-diammonium cations, whereby the two Cr—O bonds to the O atoms acting as acceptor atoms for two hydrogen bonds are slightly longer than the other two Cr—O bonds for which only one acceptor interaction per O atom is observed. In the crystal, cations and anions are packed into layers parallel to (001), held together through the aforementioned N—H...O hydrogen bonds.

The structure of the title compound, [Cr(NCS)2(C2H8N2)2]ClO4, has been determined from synchroton data. The asymmetric unit consists of one half of a centrosymmetric CrIII complex cation and half of a perchlorate anion with the Cl atom on a twofold rotation axis. The CrIII ion is coordinated by the four N atoms of two ethane-1,2-diamine (en) ligands in the equatorial plane and two N-bound thiocyanate (NCS−) anions in a trans-axial arrangement, displaying a slightly distorted octahedral geometry with crystallographic inversion symmetry. The Cr—N(en) bond lengths are in the range 2.053 (16)–2.09 (2) Å, while the Cr—N(thiocyanate) bond length is 1.983 (2) Å. The five-membered en rings are disordered over two sites, with occupancy ratios of 0.522 (16):0.478 (16). Each ClO4− anion is disordered over two sites with equal occupancy. The crystal structure is stabilized by intermolecular hydrogen bonds involving the en NH2 groups as donors and perchlorate O and thiocyanate S atoms as acceptors.

The structure of the title compound, [Cr(NCS)2(cyclam)]2[ZnCl4] (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4), has been determined from synchrotron data. The asymmetric unit contains two independent halves of the CrIII complex cations and half of a tetrachloridozincate anion. In each complex cation, the CrIII atom is coordinated by the four N atoms of the cyclam ligand in the equatorial plane and by two N-bound NCS− anions in a trans axial arrangement, displaying a distorted octahedral geometry with crystallographic inversion symmetry. The mean Cr—N(cyclam) and Cr—N(NCS) bond lengths are 2.065 (4) and 1.995 (6) Å, respectively. The macrocyclic cyclam moieties adopt centrosymmetric trans-III configurations with six- and five-membered chelate rings in chair and gauche configurations, respectively. The [ZnCl4]2− anion, which lies about a twofold rotation axis, has a slightly distorted tetrahedral geometry. The crystal packing is stabilized by hydrogen-bonding interactions between the N—H groups of the cyclam ligands, the S atoms of the NCS− groups and the Cl− ligands of the anion.

The structure of the title compound, [Cr(NCS)2(C2H8N2)2]2[ZnCl4], has been determined from synchrotron data. In the asymmetric unit, there are four independent halves of the CrIII complex cations, each of which lies on an inversion centre, and one tetrachloridozincate anion in a general position. The CrIII atoms are coordinated by the four N atoms of two ethane-1,2-diamine (en) ligands in the equatorial plane and two N-bound NCS− anions in a trans arrangement, displaying a slightly distorted octahedral geometry with crystallographic inversion symmetry. The Cr—N(en) and Cr—N(NCS) bond lengths range from 2.0653 (10) to 2.0837 (10) Å and from 1.9811 (10) to 1.9890 (10) Å, respectively. The five-membered metalla-rings are in stable gauche conformations. The [ZnCl4]2− anion has a distorted tetrahedral geometry. The crystal structure is stabilized by intermolecular hydrogen bonds involving the en NH2 or CH2 groups as donors and chloride ligands of the anion and S atoms of NCS− ligands as acceptors.

In the asymmetric unit of the title compound, [CrF2(C5H5N)4][ZnCl3(C5H5N)]·H2O, there are two independent complex cations, one trichlorido(pyridine-κN)zincate anion and one solvent water molecule. The cations lie on inversion centers. The CrIII ions are coordinated by four pyridine (py) N atoms in the equatorial plane and two F atoms in a trans axial arrangement, displaying a slightly distorted octahedral geometry. The Cr—N(py) bond lengths are in the range 2.0873 (14) to 2.0926 (17) Å while the Cr—F bond lengths are 1.8609 (10) and 1.8645 (10) Å. The [ZnCl3(C5H5N)]− anion has a distorted tetrahedral geometry. The Cl atoms of the anion were refined as disordered over two sets of sites in a 0.631 (9):0.369 (9) ratio. In the crystal, two anions and two water molecules are linked via O—H...Cl hydrogen bonds, forming centrosymmetric aggregates. In addition, weak C—H...Cl, C—H...π and π–π stacking interactions [centroid–centroid distances = 3.712 (2) and 3.780 (2)Å] link the components of the structure into a three-dimensional network.

The structure of the title salt, [CrCl(C10H8N2)2(H2O)][ZnCl4], has been determined from synchrotron data. The CrIII ion is coordinated by four N atoms from two 2,2′-bipyridine (bipy) ligands, one O atom from a water molecule and a chloride anion in a cis arrangement, displaying a distorted octahedral geometry. The tetrahedral [ZnCl4]2− anion is slightly distorted owing to its involvement in O—H...Cl hydrogen bonding with the coordinating water molecule. The Cr—N(bipy) bond lengths are in the range 2.0485 (13)–2.0632 (12) Å, while the Cr—Cl and Cr—(OH2) bond lengths are 2.2732 (6) and 1.9876 (12) Å, respectively. In the crystal, molecules are stacked along the a axis.

The structure of the title compound, [CrCl(C12H8N2)2(H2O)][ZnCl4]·H2O, has been determined from synchrotron data. The CrIII ion is bonded to four N atoms from two 1,10-phenanthroline (phen) ligands, one water molecule and a Cl atom in a cis arrangement, displaying an overall distorted octahedral coordination environment. The Cr—N(phen) bond lengths are in the range of 2.0495 (18) to 2.0831 (18) Å, while the Cr—Cl and Cr—(OH2) bond lengths are 2.2734 (7) and 1.9986 (17) Å, respectively. The tetrahedral [ZnCl4]2− anion is slightly distorted owing to its involvement in O—H...Cl hydrogen bonding with coordinating and non-coordinating water molecules. The two types of water molecules also interact through O—H...O hydrogen bonds. The observed hydrogen-bonding pattern leads to the formation of a three-dimensional network structure.

The structure of the title compound, (NH4)[Cr(pydc)2] (pydc is pyridine-2,6-dicarboxylate, C7H3NO4), has been determined from synchrotron data. The CrIII ion and the N atom of the ammonium cation are located on a crystallographic fourfold rotoinversion axis (-4). The CrIII cation is coordinated by four O atoms and the two N atoms of two meridional pydc ligands, displaying a distorted octahedral geometry. The Cr—N and Cr—O bond lengths are 1.9727 (15) and 1.9889 (9) Å, respectively. The crystal structure is stabilized by intermolecular hydrogen bonds involving the N–H groups of the ammonium cation and pyridine C–H groups as donors and the non-coordinating carbonyl O atoms as acceptors.

The title salt, Na[CrF2(C5H5N)4]2[ZnCl4]ClO4, consists of two cationic CrIII complexes, an Na+ cation, one [ZnCl4]2− anion and one ClO4− anion. The CrIII atoms are coordinated by four pyridine (py) N atoms and two F atoms in a trans arrangement, displaying a distorted octahedral geometry. The mean Cr—N(py) and Cr—F bond lengths are 2.086 (8) and 1.864 (14) Å, respectively. The [ZnCl4]2− anion has a distorted tetrahedral geometry. The most notable feature of the crystal packing is the formation of weak pyridine–perchlorate C—H...O hydrogen bonds, resulting in supramolecular chains along the b-axis direction. The perchlorate anion was disordered over two sets of sites in a 0.868 (3):0.132 (3) ratio.