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.     

N‐Ethylpyridinium bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)nickelate

The title compound, (C₇H₁₀N)[Ni(C₃S₅)₂] or (Etpy)[Ni(dmit)₂] (where Etpy is the N‐ethyl­pyridinium cation, C₇H₁₀N⁺, and dmit is the 2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ate dianion, C₃S₅²⁻), crystallizes in the P space group with two mol­ecules in the asymmetric unit. The [Ni(dmit)₂]⁻ monoanion has a planar D_2h conformation, with the central Ni atom and the four coordinated S atoms forming an NiS₄ square plane. The six‐membered ring of the Etpy cation also shows good planarity, as expected. There are two main types of disorder in the two Etpy cations. Several short intermolecular interactions are present, such as S⋯S, Ni⋯S and Ni⋯Ni, which help to form the enhanced three‐dimensional structure of the crystal.     

catena‐Poly[bis[(η2‐1‐allyl‐3‐aminopyridinium)copper(I)]‐di‐μ‐chloro‐copper(I)‐di‐μ‐chloro‐copper(I)‐di‐μ‐chloro]

Crystals of the title π‐complex, [Cu₄Cl₆(C₈H₁₁N₂)₂]_n, were obtained by means of alternating‐current electrochemical synthesis. The structure consists of infinite copper–chlorine chains to which 1‐allyl‐3‐amino­pyridinium moieties are attached via a η² Cu—(C=C) interaction. The two independent Cu atoms have distinct coordination environments. One is three‐coordinate, surrounded by two chloro ligands and the olefinic bond, whereas the second copper center is surrounded by a tetrahedral arrangement of four Cl atoms. The lower basicity of 3‐amino­pyridine as compared with 2‐ and 4‐amino­pyridine lowers the capacity of the organic ligand for donating to N—H⋯Cl hydrogen bonds and results in the formation of a large inorganic fragment.     

μ‐Aqua‐penta­aqua­[μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine]­chloro­dinickel(II) trichloride trihydrate

The title compound, μ‐aqua‐1:2κ²O‐penta­aqua‐1κ²O,2κ³O‐μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine‐1κ²N¹,N⁶:2κ²N²,N³‐chloro‐1κCl‐dinickel(II) trichloride trihydrate, [Ni₂Cl(C₁₆H₁₄­N₄)(H₂O)₆]Cl₃·3H₂O, consists of two Ni^II atoms, a 3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six‐membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) Å. The crystal structure is stabilized by an intra‐ and intermolecular hydrogen‐bonding scheme involving water–water and water–chlorine interactions.     

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].     

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[[[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.     

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.     

An X‐ray powder investigation of catena‐poly[copper(II)‐di‐μ‐chloro‐κ41:2Cl‐μ‐1,5‐dimethyl‐1H‐tetra­zole‐κ2N3:N4]

The crystal structure of the polymeric title complex, [CuCl₂(C₃H₆N₄)]_n, has been solved from laboratory X‐ray powder diffraction data collected at room temperature. The structural model obtained was refined with the Rietveld method using geometric soft restraints. There are two Cu atoms, two Cl atoms and one 1,5‐dimethyl­tetra­zole ligand in the asymmetric unit. Both Cu atoms lie on inversion centres and adopt essentially elongated octa­hedral coordination. Within the octa­hedra, the elongated axial positions are occupied by Cl atoms, while two Cl and two N atoms (N3 and N4 of the tetra­zole ring) are in equatorial sites. Each Cl atom forms an asymmetric bridge between neighbouring Cu atoms, which are also bridged via the N3—N4 bond of the tetra­zole ring. These bridges result in the formation of polymeric chains, running along the a axis, with weak C—H⋯Cl hydrogen bonds crosslinking the chains.     

Bis(acesulfamato‐κ2O4,N)bis­(3‐methyl­pyridine)copper(II)

In the crystal structure of the title compound {systematic name: bis­[6‐methyl‐1,2,3‐oxa­thia­zin‐4(3H)‐one 2,2‐dioxide(1−)‐κ²N³,O⁴]bis­(3‐meth­yl­pyridine)copper(II)}, [Cu(C₄H₄NO₄S)₂(C₆H₇N)₂], the Cu^II centre resides on a centre of symmetry and has an octa­hedral geometry that is distorted both by the presence of four‐membered chelate rings and because of the Jahn–Teller effect. The equatorial plane is formed by the N atoms of two methyl­pyridine ligands and by the more basic O atoms of the acesulfamate ligands, while the weakly basic N atoms of these ligands are in elongated axial positions with a misdirected valence. The crystal is stabilized by two inter­molecular C—H⋯O inter­actions involving the methyl and CH groups, and the sulfonyl O atoms of the acesulfamate group.     

Diaqua­bis[5‐(pyrazin‐2‐yl‐κN1)‐1H‐tetra­zolato‐κN1]manganese(II) and diaqua­bis[5‐(pyrazin‐2‐yl‐κN1)‐1H‐tetra­zolato‐κN1]zinc(II)

The two new title complexes, [Mn(C₅H₃N₆)₂(H₂O)₂] and [Zn(C₅H₃N₆)₂(H₂O)₂], are isomorphous. In both compounds, the metal atom is located on an inversion center and is coordinated by four N atoms from two 5‐(pyrazin‐2‐yl)‐1H‐tetra­zolate anions in the basal plane and by two O atoms of water ligands in the apical positions to form a distorted octa­hedral geometry. Inter­molecular hydrogen‐bond inter­actions between the uncoordinated N atoms of the tetra­zolate anions and the H atoms of the water mol­ecules lead to the formation of a three‐dimensional network.     

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 mononuclear cobalt(II) complex CoII(DMBDIZ)2(NCS)2, where DMBDIZ is 2,6‐di­methyl­benzo[1,2‐d:4,5‐d′]­di­imidazole

In the title mononuclear cobalt complex, bis(2,6‐di­methyl‐1H,7H‐benzo­[1,2‐d:4,5‐d′]­di­imidazole‐κN³)­bis­(thio­cyanato‐κN)cobalt(II), [Co^II(NCS)₂(DMBDIZ)₂] or [Co(NCS)₂(C₁₀H₁₀N₄)₂], the cobalt(II) ion is coordinated to four N atoms, from two thio­cyanate anions and two DMBDIZ ligands, in a distorted tetrahedral geometry. In the DMBDIZ ligand, the two imine N atoms are positioned cis with respect to one another. The crystal packing of the complex is dominated by both hydrogen bonding, involving two N—H?N and two N—H?S interactions, and aromatic π–π stacking.     

[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[[tri‐n‐butyl­tin]‐μ‐N‐(1‐naphthyl)­maleamato]

The crystal structure of catena‐poly­[[tri‐n‐butyl­tin]‐μ‐3‐(1‐naph­thyl­amino­carbonyl)­acrylato‐κ²O¹:O³], [Sn(C₄H₉)₃(C₁₄H₁₀NO₃)]_n, is composed of polymeric chains wherein the metal center exhibits a distorted trigonal‐bipyramidal geometry, with three n‐butyl groups defining the trigonal plane [mean Sn—C 2.133 (7) Å] and the axial positions being occupied by the carboxyl­ate O atoms of two different N‐(1‐naphthyl)­maleamate ligands with inequivalent Sn—O distances [2.167 (4) and 2.457 (4) Å]. The N‐(1‐naphthyl)­maleamate fragment forms an essentially planar seven‐membered ring involving an intramolecular N—H?O hydrogen bond.     

Tetrakis(2‐amino‐5‐methyl‐1,3,4‐thia­diazo­le‐N3)­chloro­copper(II) chloride monohydrate and tetrakis(2‐amino‐5‐ethyl‐1,3,4‐thia­diazo­le‐N3)­chlorocopper(II) chloride

The structures of the title compounds, [CuCl(C₃H₅N₃S)₄]Cl·H₂O, (I), and [CuCl(C₄H₇N₃S)₄]Cl, (II), comprise square‐pyramidal Cu centres with four N‐bound organic ligands filling the base positions, a Cl atom in the apical position and a Cl^? as a free counter‐ion. The cation and free chloride ion in (II) have fourfold crystallographic symmetry. Hydro­gen‐bonding associations from the 2‐amino H atoms dominate both structures, with the principal acceptors being the chlorides, although in (I), the N4 atoms are also involved. Furthermore, (I) is a hydrate, with the water mol­ecule participating in the hydrogen‐bonding network.     

(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.     

trans‐Di­aqua­bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato‐κ2N3,O4)­cobalt(II) 4,4′‐bi­pyridine solvate

In the title compound, [Co(C₅H₃N₂O₄)₂(H₂O)₂]·C₁₀H₈N₂, the Co atom is trans‐coordinated by two pairs of N and O atoms from two monoanionic 4,5‐di­carboxy­imidazole ligands, and by two O atoms from two coordinated water mol­ecules, in a distorted octahedral geometry. The 4,4′‐bi­pyridine solvent molecule is not involved in coordination but is linked by an N—H⋯N hydrogen bond to the neutral [Co(C₅H₃N₂O₄)₂(H₂O)₂] mol­ecule. Both mol­ecules are located on inversion centers. The crystal packing is stabilized by N—H⋯N and O—H⋯O hydrogen bonds, which produce a three‐dimensional hydrogen‐bonded network. Offset π–π stacking interactions between the pyridine rings of adjacent 4,4′‐bi­pyridine molecules were observed, with a face‐to‐face distance of 3.345 (1) Å.     

A ruthenium(II) complex with p‐cymene and (S)‐2‐(anilinomethyl)pyrrolidine

The title compound, [(S)‐2‐(anilino­methyl)­pyrrolidine‐N,N′]‐chloro(η⁶‐para‐cymene)­ruthenium(II) chloride, [RuCl‐(C₁₀H₁₄)(C₁₁H₁₆N₂)]Cl, has been synthesized by the reaction of [RuCl₂(p‐cymene)]₂ (p‐cymene is para‐iso­propyl­toluene) with (S)‐2‐(anilinomethyl)­pyrrolidine in triethyl­amine/2‐propanol. The Ru atom is in a pseudo‐tetrahedral environment coordinated by a chloride ligand, the aromatic hydro­carbon is linked in a η⁶ manner and the amine is linked via its two N atoms. The chloride anion is involved in hydrogen bonding with the di­amine moieties through N—H?Cl interactions, with N?Cl distances of 3.273 (4) and 3.352 (4) Å.     

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.