catena‐Poly­[[tetrakis(2‐allyl­tetrazole‐κN4)‐tetra‐μ‐chloro‐tricopper(II)]‐di‐μ‐chloro]

In the crystal structure of the title compound, [Cu₃Cl₆(C₄H₆N₄)₄]_n, there are three Cu atoms, six Cl atoms and four 2‐allyl­tetrazole ligands in the asymmetric unit. The polyhedron of one Cu atom adopts a flattened octahedral geometry, with two 2‐allyl­tetrazole ligands in the axial positions [Cu—N4 = 1.990 (2) and 1.991 (2) Å] and four Cl atoms in the equatorial positions [Cu—Cl = 2.4331 (9)–2.5426 (9) Å]. The polyhedra of the other two Cu atoms have a square‐pyramidal geometry, with three basal sites occupied by Cl atoms [Cu—Cl = 2.2487 (9)–2.3163 (8) and 2.2569 (9)–2.3034 (9) Å] and one basal site occupied by a 2‐allyl­tetrazole ligand [Cu—N4 = 2.028 (2) and 2.013 (2) Å]. A Cl atom lies in the apical position of either pyramid [Cu—Cl = 2.8360 (10) and 2.8046 (9) Å]. The possibility of including the tetrazole N3 atoms in the coordination sphere of the two Cu atoms is discussed. Neighbouring copper polyhedra share their edges with Cl atoms to form one‐dimensional polymeric chains running along the a axis.     

The layered structure of poly­[[di‐μ‐chloro‐bis­[chloro(2‐ethyl­tetrazole‐κN4)copper(II)]]‐di‐μ‐2‐ethyl­tetrazole‐κ2N1:N4]

In the polymeric title complex, [CuCl₂(C₃H₆N₄)₂]_n, there are two ligands in the asymmetric unit. The Cu atom adopts an elongated octahedral geometry, with two 2‐ethyl­tetrazole ligands [Cu—N = 2.0037 (16) and 2.0136 (16) Å] and two Cl atoms [Cu—Cl = 2.2595 (6) and 2.2796 (6) Å] in equatorial positions. A Cl atom and a symmetry‐related 2‐ethyl­tetrazole mol­ecule [Cu—Cl = 2.8845 (8) Å and Cu—N = 2.851 (2) Å] lie in the axial positions of the octahedron. One of the two 2‐­ethyltetrazole ligands of the asymmetric unit exhibits bidentate binding to two Cu atoms through two N atoms of the tetrazole ring, whereas the other ligand is coordinated in a monodentate fashion via one tetrazole N atom. The Cu‐atom octahedra form dimer entities by sharing edges with equatorial and axial Cl atoms. The dimers are linked together through the 2‐ethyl­tetrazole ligands to form one‐dimensional polymeric zigzag chains extending along the b axis. The chains are connected into infinite layers parallel to the (10) plane via the 2‐ethyl­tetrazole ligands.     

catena‐Poly­[[bis­[μ‐1,2‐bis(1‐methyl­tetrazol‐5‐yl)­ethane‐κ2N4:N4′]bis[chloro­copper(II)]]‐di‐μ‐chloro]

In the title compound, [Cu₂Cl₄(C₆H₁₀N₈)₂]_n, the ligand has C₂ symmetry, and the Cu and Cl atoms lie on a mirror plane. The coordination polyhedron of the Cu atom is a distorted square pyramid, with the basal positions occupied by two N atoms from two different ligands [Cu—N = 2.0407 (18) Å] and by the two Cl atoms [Cu—Cl = 2.2705 (8) and 2.2499 (9) Å], and the apical position occupied by a Cl atom [Cu—Cl = 2.8154 (9) Å] that belongs to the basal plane of a neighbouring Cu atom. The [CuCl₂(C₆H₁₀N₈)]₂ units form infinite chains extending along the a axis via the Cl atoms. Intermolecular C—H⃛Cl contacts [C⃛Cl = 3.484 (2) Å] are also present in the chains. The chains are linked together by intermolecular C—H⃛N interactions [C⃛N = 3.314 (3) Å].     

catena‐Poly­[[[cis‐bis(1‐phenyl­tetra­zole‐κN4)copper(II)]‐di‐μ‐chloro] hemi(1‐phenyl­tetrazole)]

The title compound, {[CuCl₂(PhTz)₂]·0.5PhTz}_n (PhTz is 1‐­phenyl­tetrazole, C₇H₆N₄), has a polymeric structure, with uncoordinated disordered PhTz mol­ecules in the cavities. The coordination polyhedron of the Cu atom is a highly elongated octahedron. The equatorial positions are occupied by two Cl atoms [Cu—Cl = 2.2687 (9) and 2.2803 (7) Å] and two N atoms of the PhTz ligands [Cu—N = 2.0131 (19) and 2.0317 (18) Å]. The more distant axial positions are occupied by two Cl atoms [Cu—Cl = 3.0307 (12) and 2.8768 (11) Å] that lie in the equatorial planes of two neighbouring Cu octahedra. The [CuCl₂(PhTz)₂] units are linked by Cu—Cl bridges into infinite chains extending parallel to the a axis. The chains are linked into two‐dimensional networks by intermolecular C—H⋯N interactions between the phenyl and tetrazole fragments, and by face‐to‐face π–π interactions between symmetry‐related phenyl rings. These two‐dimensional networks, which lie parallel to the ac plane, are connected by intermolecular π–π stacking interactions between phenyl rings, thus forming a three‐dimensional network.     

A novel one‐dimensional complex: catena‐poly­[[manganese(III)‐di‐μ‐2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolato‐κ2O1,N:κO2;κO2:κ2O1] chloride]

In the title one‐dimensional complex, {[Mn^III(C₉H₁₀NO₂)₂]Cl}_n, the Schiff base ligand 2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolate (Hsae⁻) functions as both a bridging and a chelating ligand. The Mn^III ion is six‐coordinated by two N and four O atoms from four different Hsae⁻ ligands, yielding a distorted MnO₄N₂ octahedral environment. Each [Mn^III(Hsae)₂]⁺ cationic unit has the Mn atom on an inversion centre and each [Mn^III(Hsae)₂]⁺ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae⁻ rings.     

Tetra­kis(μ2‐1,8‐naphthyridine)‐1:2κ4N:N′;3:4κ4N:N′‐bis­(μ2‐salicylato)‐1:4κ2O:O′;2:3κ2O:O′‐tetrakis­(salicylic acid)‐1κO,2κO,3κO,4κO‐tetra­silver(I)(4 Ag—Ag)

The title complex, [Ag₄(C₇H₅O₃)₂(C₈H₆N₂)₄(C₇H₆O₃)₄], lies about an inversion centre and has a unique tetra­nuclear structure consisting of four Ag^I atoms bridged by four N atoms from two 1,8‐naphthyridine (napy) ligands to form an N:N′‐bridge and four O atoms from two salicylate (SA) ligands to form an O:O′‐bridge. The Ag atoms have distorted octa­hedral coordination geometry. The centrosymmetric Ag₄ ring has Ag—Ag separations of 2.772 (2) and 3.127 (2) Å, and Ag—Ag—Ag angles of 107.70 (4) and 72.30 (4)°. All SA hydroxy groups take part in intra­molecular O—H⋯O hydrogen bonding. In the crystal packing, the napy rings are oriented parallel and overlap one another. These π–π inter­actions, together with weak inter­molecular C—H⋯O contacts, stabilize the crystal structure.     

catena‐Poly[[bis(cis‐1‐tert‐butyltetrazole‐κN4)copper(II)]‐di‐μ‐chloro]

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1‐alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N‐4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry‐related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.     

Bis[μ‐4‐(ethylammoniomethyl)‐3,5‐dimethylpyrazolato‐κ2N1:N2]bis[(η4‐1,5‐cyclooctadiene)rhodium(I)] dichloride dichloromethane methanol solvate

In the title compound, [Rh₂(C₈H₁₅N₃)₂(C₈H₁₂)₂]Cl₂·CH₂Cl₂·CH₃OH, the dinuclear Rh^I complex has C₂ symmetry and the two pyrazolato ligands act as μ‐bridges. The coordination of each Rh^I cation is completed by one cyclo­octa­diene (COD) ligand. It is shown that the average Rh—C(COD) distance is linearly dependent on the Rh—N(pyrazole) distance in this type of compound, and this is ascribed to the steric hindrance produced by the packing.     

catena‐Poly[[[(oxamide dioxime‐κ2N,N′)copper(II)]‐μ‐l‐tartrato‐κ4O1,O2:O3,O4] tetrahydrate]: a chiral nanochannel framework hosting solvent water molecules

The crystal structure of the title compound, {[Cu(C₄H₄O₆)(C₂H₆N₄O₂)]·4H₂O}_n, contains the central Cu^II cation in a distorted octahedral coordination, symmetrically chelated by the two imine N atoms of a neutral oxamide dioxime (H₂oxado) ligand [Cu—N = 1.9829 (16) Å] and unsymmetrically bis‐chelated by two halves of the l ‐(+)‐tartrate(2−) (tart) ligands, each half being linked to the Cu^II cation via the deprotonated carboxylate group and protonated hydroxy group [Cu—O = 1.9356 (14) and 2.4674 (13) Å, respectively]. The extended asymmetric unit is defined by twofold axes, one passing through the Cu^II cation and the centre of the oxamide dioxime (H₂oxado) ligand and the another two (symmetry related) bisecting the central C—C bonds of the tartrate ions. The structure is chiral, consisting of enantiomeric linear‐chain polymers oriented along [001], with virtual monomeric {Cu(tart_0.5)₂(H₂oxado)} repeat units and with the chains interleaved face‐to‐face into `twin pillars'. Nanochannels exist, running parallel to the c axis and bisecting a and b, which host `double strings' of solvent water molecules. Extensive hydrogen bonding (O—H...O and N—H...O) between the chains and solvent water molecules, together with extended π–σ interactions, consolidate the bulk crystal structure.     

catena‐Poly­[[di­chlorozinc(II)]‐μ‐1,3‐di‐4‐pyridyl­propane‐κ2N:N′]

The title compound, [ZnCl₂(bpp)]_n (where bpp is 1,3‐di‐4‐pyridyl­propane, C₁₃H₁₄N₂), has been prepared by the hydro­thermal reaction of ZnCl₂ and bpp at 433 K. The Zn, Cl and central propyl C atom lie on the mirrors of the P2₁/m space group. The molecular structure shows a weave‐like polymeric chain. Each Zn atom is coordinated by two N atoms and two Cl atoms in a distorted tetrahedral geometry, with the Zn—N distance being 2.055 (5) Å and the Zn—Cl distances being 2.239 (3) and 2.247 (2) Å.     

Poly[[diaquabis[μ2‐2‐(4‐pyridinio)propane‐1,3‐dionato‐κ2O:O′]cobalt(II)] dinitrate]

The title compound, {[Co(C₈H₇NO₂)₂(H₂O)₂](NO₃)₂}_n, is the first d‐metal ion complex involving bidentate bridging of a β‐dialdehyde group. The Co²⁺ ion is situated on an inversion centre and adopts an octahedral coordination with four equatorial aldehyde O atoms [Co—O = 2.0910 (14) and 2.1083 (14) Å] and two axial aqua ligands [Co—O = 2.0631 (13) Å]. The title compound has a two‐dimensional square‐grid framework structure supported by propane‐1,3‐dionate O:O′‐bridges between the metal ions. The organic ligand itself possesses a zwitterionic structure, involving conjugated anionic propane‐1,3‐dionate and cationic pyridinium fragments. Hydrogen bonding between coordinated water molecules, the pyridinium NH group and the nitrate anions [O...O = 2.749 (2) and 2.766 (3) Å, and N...O = 2.864 (3) Å] is essential for the crystal packing.     

Di‐μ‐chlorido‐bis[dichloridobis(methylamido‐κN)bis(methylamine‐κN)titanium(IV)]

The title compound, [Ti₂Cl₆(C₂H₆N)₂(C₂H₇N)₂], is a binuclear octahedral complex lying about an inversion centre. There are four different chloride environments, two terminal [Ti—Cl = 2.2847 (5) and 2.3371 (5) Å] and two bridging [Ti—Cl = 2.4414 (5) and 2.6759 (5) Å], with the Ti—Cl distances being strongly influenced by both the ligand trans to the chloride and whether or not the chloride anion is bridging between the two Ti^IV centres. The compound forms a two‐dimensional network in the solid state, with weak intermolecular C—H...Cl interactions giving rise to a planar network in the (10) plane.     

[2‐(2‐Pyridyl)‐1H‐benzimidazole‐κ2N2,N3]bis(p‐toluato‐κ2O,O′)manganese(II)

In the title compound, [Mn(C₈H₇O₂)₂(C₁₂H₉N₃)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2‐(2‐pyridyl)benzimidazole ligand [Mn—N = 2.1954 (13) and 2.2595 (14) Å] and two p‐toluate ligands [Mn—O = 2.1559 (13)–2.2748 (14) Å]. It displays a severely distorted octahedral geometry, with cis angles ranging from 58.87 (4) to 106.49 (5)°. Intermolecular C—H...O hydrogen bonds between the p‐toluate ligands link the molecules into infinite chains, and every two neighbouring chains are further coupled by N—H...O and C—H...O hydrogen bonds between the 2‐(2‐pyridyl)benzimidazole and p‐toluate ligands, leading to an infinite ribbon‐like double‐chain packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and possible C—H...π interactions, as well as stacking interactions involving the 2‐(2‐pyridyl)benzimidazole ligands.     

catena‐Poly[[[tetrakis(μ‐acetato‐κ2O:O′)dirhodium(II)]‐μ‐[1,3‐bis(dimethylamino)propan‐2‐ol‐κ2N:N′]] tetrahydrofuran hemisolvate]

In the structure of the title compound, {[Rh₂(C₂H₃O₂)₄(C₇H₁₈N₂O)]·0.5C₄H₈O}_n or {[Rh₂(O₂CMe)₄(Hbdmap)]·0.5C₄H₈O}_n, where Hbdmap is 1,3‐bis­(dimethyl­amino)propan‐2‐ol, each Hbdmap ligand is coordinated to two [Rh₂(O₂CMe)₄] units by two N atoms, resulting in a polymeric chain structure. The observed coordination mode of the Hbdmap mol­ecule is unprecedented.     

Poly­[iron(II)‐di‐μ‐imidazole‐4,5‐di­carboxyl­ato‐κ3N3,O4:O5]

In the title compound, [Fe(C₅H₃N₂O₄)₂]_n, each Fe atom lies on a centre of symmetry, in an octahedral coordination environment consisting of two chelate rings [Fe—N = 2.154 (3) Å and Fe—O = 2.180 (3) Å] and two carboxyl­ate O atoms [Fe—O = 2.111 (2) Å] from imidazole‐4,5‐di­carboxyl­ate ligands. Extensive hydrogen‐bonding interactions exist between layers constructed of Fe₄ squares, forming tunnels along the a axis with large voids.     

Bis(methanol‐κO)dioxido[3,3′‐(1H‐1,2,4‐triazole‐3,5‐diyl)diphenolato‐κ3O,N4,O′]uranium(VI) methanol monosolvate

The structure of the title compound, [U(C₁₄H₉N₃O₂)O₂(CH₃OH)₂]·CH₃OH, is the first to be reported for an actinide complex including triazole ligands. The U^VI atom exhibits a pentagonal–bipyramidal NO₆ coordination environment, involving two axial oxide ligands [U=O = 1.766 (3) and 1.789 (3) Å], four equatorial O atoms [U—O = 2.269 (3)–2.448 (3) Å] from the ligand and the two coordinated methanol molecules, and one equatorial N atom [U—N = 2.513 (4) Å] from the ligand. In the crystal structure, the complex molecules are linked via intermolecular N—H...O and O—H...O hydrogen bonds to form a two‐dimensional structure.     

catena‐Poly[[μ‐hexa­nedioato‐1κO1:2κO6‐bis­[aqua­(5‐carboxy­penta­noato‐κO)copper(II)]]‐di‐μ‐4,4′‐bipyridine‐1κN:1′κN′;2κN:2′κN′]

In the title compound, [Cu₂(C₆H₈O₄)(C₆H₉O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]_n, the square‐pyramidally coordinated Cu atoms are bridged by both 4,4‐bipyridine and adipate ligands into ladder‐­like chains, with exo‐orientated 5‐carboxypentan­oate ligands pendant from both side rails. Half of the adipate ligand is related to the other half by inversion symmetry. Inter­chain O—H⋯O hydrogen bonds from the aqua ligands to the carbonyl O atoms of the 5‐carboxy­penta­noate ligands are responsible for the formation of two‐dimensional grid‐like (4,4)‐networks, which complete a twofold inter­penetration.     

Bis(7‐amino‐1,3‐benzothiazole‐κN3)dichlorozinc(II)

The title complex, [ZnCl₂(C₇H₆N₂S)₂], contains a Zn centre with a distorted tetrahedral coordination sphere, involving two Cl⁻ ligands and two endocyclic N atoms from the thia­zole moiety [Zn—Cl = 2.2284 (7) and 2.2236 (7) Å, and Zn—N = 2.081 (2) and 2.041 (2) Å]. The interplanar angle between the two ligands is 79.32 (6)°. The amino groups participate in intermolecular N—H⋯Cl hydrogen bonds, with N⋯Cl distances in the range 3.463 (2)–3.519 (2) Å.     

catena‐Poly­[[di­aqua­cadmium(II)]‐μ‐5‐carboxyimidazole‐4‐carboxylato‐κ4N1,O5:O4,N3]

A new cadmium coordination polymer, [Cd(C₅H₂N₂O₄)(H₂O)₂]_n, possesses a one‐dimensional zigzag chain structure built from Cd^II centers bridged sequentially by pairs of O and N atoms of the 5‐carboxyimidazole‐4‐carboxylate ligand. The Cd^II center is in a distorted octahedral geometry, being coordinated by two O atoms from two coordinated water mol­ecules [Cd—O = 2.322 (7) and 2.364 (7) Å], and by two N atoms [Cd—N = 2.222 (6) and 2.232 (6) Å] and two carboxyl O atoms [Cd—O = 2.383 (6) and 2.414 (6) Å] from two 5‐carboxyimidazole‐4‐carboxylate ligands.     

A new adamantanecarboxylate coordination polymer: poly[[(μ3‐adamantane‐1,3‐dicarboxylato)aquadioxidouranium(VI)] monohydrate]

The title compound, {[U(C₁₂H₁₄O₄)O₂(H₂O)]·H₂O}_n, is the first actinide complex featuring adamantanecarboxylate ligands. The metal ion possesses a pentagonal–bipyramidal UO₇ coordination involving two axial oxide ligands [U—O = 1.732 (5) and 1.764 (5) Å] and five equatorial O atoms [U—O = 2.259 (5)–2.494 (4) Å] of aqua and carboxylate ligands. The latter display pseudo‐chelating and bridging coordination modes of the carboxylate groups that are responsible for the generation of the centrosymmetric discrete uranium–carboxylate [UO₂(μ‐RCOO)₂UO₂] dimers [U...U = 5.5130 (5) Å] and their connection into one‐dimensional chains. Hydrogen bonding involving two coordinated and two solvent water molecules [O...O = 2.719 (7)–2.872 (7) Å] yields centrosymmetric (H₂O)₄ ensembles and provides noncovalent linkage between the coordination chains to generate a three‐dimensional network structure.