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[[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.     

Hexa‐μ2‐chloro‐μ4‐oxo‐tetrakis[(2‐ethyl­tetrazole‐κN4)copper(II)]

In the title molecular complex, [Cu₄Cl₆O(2‐EtTz)₄], where 2‐EtTz is 2‐ethyl­tetrazole (C₃H₆N₄), the central O atom is located on the symmetry site and is tetrahedrally coordinated to four Cu atoms, with Cu—O distances of 1.8966 (4) Å. A very slight distortion of Cu₄O from a regular tetrahedron is observed [two Cu—O—Cu angles are 108.76 (3)° and four others are 109.828 (13)°]. Each Cu atom is connected to three others via the Cl atoms, forming a slightly distorted Cl octahedron around the O atom, with O⋯Cl distances of 2.9265 (7) Å for Cl atoms lying on the twofold axis and 2.9441 (13) Å for those in general positions. The Cu atom has a distorted trigonal–bipyramidal environment, with three Cl atoms in the equatorial plane, and with the N atom of the 2‐ethyl­tetrazole ligand and the μ₄‐O atom in axial positions. The Cu atom is displaced out of the equatorial plane by ca 0.91 Å towards the coordinated N atom of the 2‐­ethyl­tetrazole ligand.     

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.     

A 1:2 complex of mercury(II) chloride with 1,3‐imidazole‐2‐thione

The Hg atom in the title monomeric complex, di­chloro­bis(3‐imidazolium‐2‐thiol­ato‐S)­mercury(II), [HgCl₂(C₃H₄N₂S)₂], is four‐coordinate having an irregular tetrahedral geometry composed of two Cl atoms [Hg—Cl 2.622 (2) and 2.663 (2) Å] and two thione S atoms [Hg—S 2.445 (2) and 2.462 (2) Å]. The monodentate thione ligand adopts a zwitterionic form and exists as the 3‐imidazolium‐2‐thiol­ate ion. The bond angle S1—Hg—S2 of 130.87 (8)° has the greatest deviation from ideal tetrahedral geometry. Intermolecular hydrogen bonds between two of the four N—H groups and one of the Cl atoms [3.232 (8) and 3.238 (7) Å] stabilize the crystal structure, while the other two N—H groups contribute through the formation of N—H?Cl intramolecular hydrogen bonds with the other Cl atom [3.121 (7) and 3.188 (7) Å].     

Dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]zinc(II) and di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}

The Zn atom in dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)­methane]zinc(II), [ZnCl₂(C₁₁H₁₆N₄)], (I), is tetra­hedrally coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand and two terminal Cl atoms. The mol­ecule has no crystallographic symmetry. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazol­yl)methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to yield inter­molecular C—H⋯Cl contacts, thereby forming a one‐dimensional zigzag chain extending along the b axis. On the other hand, in di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}, [Cd₂Cl₄(C₁₁H₁₆N₄)₂], (II), each of the two crystallographically equivalent Cd atoms is penta­coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand, and by one terminal and two bridging Cl⁻ anions. The mol­ecule has a crystallographic centre of symmetry located at the mid‐point of the Cd⋯Cd line. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazolyl)­methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to produce pairwise inter­molecular C—H⋯Cl contacts, thereby affording chains of mol­ecules running along the c axis.     

Dichloro­(O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid‐κ2N,N′)copper(II)

In the title compound, [CuCl₂(C₉H₁₂N₂O)], the Cu^II atom is coordinated by two Cl⁻ anions and two N atoms of one O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid mol­ecule in a slightly distorted square‐planar geometry, with Cu—N distances of 2.0483 (17) and 1.9404 (18) Å, and Cu—Cl distances of 2.2805 (10) and 2.2275 (14) Å. In addition, each Cu^II atom is connected by one Cl⁻ anion and the Cu^II atom from a neighbouring mol­ecule, with Cu⋯Cl and Cu⋯Cu distances of 2.9098 (13) and 3.4022 (12) Å, respectively, and, therefore, a centrosymmetric dimer is formed. Adjacent mol­ecular dimers are connected by π–π stacking inter­actions between pyridine rings to form a zigzag mol­ecular chain. The mol­ecular chains are also enforced by N—H⋯Cl and C—H⋯Cl inter­actions.     

catena‐Poly[[diiodo­zinc(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′]

The title compound, [ZnI₂(bipy)]_n (bipy is 4,4′‐bipyridine, C₁₀H₈N₂), has been prepared by the hydro­thermal reaction of ZnI₂ and bipy at 433 K. Each Zn atom is coordinated by two N atoms from two different bipy ligands and by two I atoms in a distorted tetra­hedral geometry, with Zn—N distances ranging from 2.068 (7) to 2.101 (8) Å and Zn—I distances ranging from 2.5471 (13) to 2.5673 (13) Å. The mol­ecular structure features a zigzag polymeric chain. Face‐to‐face π–π stacking inter­actions between adjacent bipy ligands stabilize the structure.     

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.     

Dichloro{N‐[3‐(η5‐cyclopentadienyl)propyl]‐4‐toluenesulfonamido‐κ2N,O}titanium(IV)

The title compound, [Ti(C₁₅H₁₇NO₂S)Cl₂], has a Ti atom bound to the N and O atoms of a p‐toluene­sulfon­amide ligand, which is tethered by a three‐carbon chain to a η⁵‐cyclo­penta­dienyl group. The distorted square‐pyramidal geometry is completed by two Cl atoms. The Ti—N bond length of 2.0375 (13) Å is longer than that in related compounds, the N atom having asymmetric trigonal–planar geometry. Conformational strain relief is noted when compared with ethyl‐tethered compounds.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

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.     

Low‐dimensional compounds containing cyano groups. II. catena‐Poly[[(2,2′‐bipyridine‐κ2N:N′)(dicyanamido‐κN)copper(II)]‐μ‐dicyanamido‐κ2N:N′]

The crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₀H₈N₂)]_n, is formed by neutral zigzag chains of the [–NC–N–CN–Cu{(bpy)N(CN)₂}–NC–N–CN–] type run­ning along the c axis (bpy is 2,2′‐bi­pyridine). The Cu atoms in the chains are pentacoordinated in the form of a distorted tetragonal pyramid, with a CuN₅ chromophore. The coordination sites are occupied by two N atoms of one bpy mol­ecule in the basal plane [Cu—N 2.018 (4) and 2.025 (2) Å] and by three terminal N atoms of two dicyan­amide ligands. One of the dicyan­amide ligands is coordinated in a monodentate fashion through a nitrile N atom in the basal plane [Cu—N 1.963 (4) Å]. The second acts as an end‐to‐end bridging ligand to a neighbouring Cu atom and is coordinated by one nitrile N atom in the basal plane [Cu—N 2.001 (2) Å], while the second nitrile N atom occupies the apical position [Cu—N 2.159 (2) Å] and originates from the bridge connecting another Cu atom. The shortest intrachain Cu?Cu distance is 8.212 (1) Å, as a consequence of the large bridging ligand, whereas the minimum interchain distance between Cu atoms is only 5.77 (7) Å, because of the interdigitation of the chains.     

Di‐μ‐chloro‐bis­{bis­[2,5‐bis­(4‐methoxy­phenyl)‐1,3,4‐oxadiazole‐κ2C2′,N]iridium(III)] dichloro­methane disolvate

In the title compound, [Ir₂(C₁₆H₁₃N₂O₃)₄Cl₂]·2CH₂Cl₂, the two Ir atoms, 3.7075 (6) Å apart, are bridged by two Cl atoms which straddle a twofold axis of rotation through the two Ir atoms. Each Ir centre resides in a distorted octa­hedral environment completed by two chelating 2,5‐bis­(4‐methoxy­phenyl)‐1,3,4‐oxadiazole ligands, with trans‐N—N and cis‐C—C dispositions. In the stacking structure, there are two types of hydrogen bonds, involving the meth­oxy substitutent, an N atom of the oxadiazole ring and the dichloro­methane solvent mol­ecules.     

Dichloro­[(6R,7S,8S,14S)‐(–)‐sparteine‐κ2N,N′]mercury(II)

In the title compound, [HgCl₂(C₁₅H₂₆N₂)], the chiral alkaloid (6R,7S,8S,14S)‐(−)‐l ‐sparteine acts as a bident­ate ligand, with two Cl⁻ ligands occupying the remaining coordination sites, producing a distorted tetra­hedron. The N—Hg—N plane is twisted by 81.1 (2)° from the Cl—Hg—Cl plane. The mid‐point of the N⋯N line does not lie exactly on the Cl—Hg—Cl plane but is tilted towards one of the N atoms by 0.346 Å. Similarly, the mid‐point of the Cl⋯Cl line is tilted toward one of the Cl atoms by 0.163 Å. The packing structure shows that the complex is stabilized by two inter­atomic Cl⋯H contacts involving both Cl atoms and the methyl­ene or methine H atoms of the (−)‐sparteine ligand.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

(2,2′‐Biquinoline‐κ2N,N′)dichloropalladium(II), ‐copper(II) and ‐zinc(II)

In the three title complexes, namely (2,2′‐biquinoline‐κ²N,N′)dichloro­palladium(II), [PdCl₂(C₁₈H₁₂N₂)], (I), and the corresponding copper(II), [CuCl₂(C₁₈H₁₂N₂)], (II), and zinc(II) complexes, [ZnCl₂(C₁₈H₁₂N₂)], (III), each metal atom is four‐coordinate and bonded by two N atoms of a 2,2′‐biquinoline molecule and two Cl atoms. The Pd^II atom has a distorted cis‐square‐planar coordination geometry, whereas the Cu^II and Zn^II atoms both have a distorted tetra­hedral geometry. The dihedral angles between the N—M—N and Cl—M—Cl planes are 14.53 (13), 65.42 (15) and 85.19 (9)° for (I), (II) and (III), respectively. The structure of (II) has twofold imposed symmetry.     

Polymeric (3‐amino‐2‐chloropyridine)nitratosilver(I)

In the title compound {alternative name: poly­[silver(I)‐μ‐(3‐­amino‐2‐chloro­pyridine)‐μ‐nitr­ato]}, [Ag(NO₃)(C₅H₅ClN₂)]_n the Ag^I atom is in an irregular AgN₂O₃ geometry, surrounded by one pyridyl N atom [Ag—N 2.283 (5) Å], one amine N atom [Ag—N 2.364 (6) Å] and three O atoms from different nitrate ions [Ag—O 2.510 (6)–2.707 (6) Å]. The Ag ions are bridged by the 3‐amino‐2‐chloro­pyridine ligands into helical chains. Adjacent uniform chiral chains are further interlinked through the NO₃ bridges into an interesting two‐dimensional coordination network in the solid.     

Dichloro­[(1E,1′E)‐1,1′‐(pyridine‐2,6‐diyl)diethanone bis­(O‐methyl­oxime)‐κ3N1,N2,N6]copper(II)

In the title compound, [CuCl₂(C₁₁H₁₅N₃O₂)], the Cu^II ion is five‐coordinated in a strongly distorted trigonal–bipyramidal arrangement, with the two methyl­oxime N atoms located in the apical positions, and the pyridine N and the Cl atoms located in the basal plane. The two axial Cu—N distances are almost equal (mean 2.098 Å) and are substantially longer than the equatorial Cu—N bond [1.9757 (15) Å]. It is observed that the N(oxime)—M—N(pyridine) bond angle for five‐membered chelate rings of 2,6‐diacetyl­pyridine dioxime complexes is inversely related to the magnitude of the M—N(pyridine) bond. The structure is stabilized by intra‐ and inter­molecular C—H⋯Cl hydrogen bonds which involve the methyl H atoms, except for one of the two acetyl­methyl groups.