catena‐Poly[potassium [copper(II)‐μ‐isothiocyanato‐μ‐N‐salicylidene‐β‐alaninato(2–)]]

The title polymeric compound, catena‐poly­[dipotassium [bis­[μ‐N‐salicyl­idene‐β‐alaninato(2−)]‐κ⁴O,N,O′:O′′;κ⁴O′′:O,N,O′‐dicopper(II)]‐di‐μ‐iso­thio­cyanato‐κ²N:S;κ²S:N], {K[Cu(NCS)(C₁₀H₉NO₃)]}_n, consists of [iso­thio­cyanato(N‐salicyl­idene‐β‐alaninato)copper(II)]⁻ anions connected through the two three‐atom thio­cyanate (μ‐NCS) and the two anti,anti‐μ‐­carboxyl­ate bridges into infinite one‐dimensional polymeric anions, with coulombically interacting K⁺ counter‐ions with coordination number 7 constrained between the chains. The Cu^II atoms adopt a distorted tetragonal–bipyramidal coordination, with three donor atoms of the tridentate Schiff base and one N atom of the bridging μ‐NCS ligand in the basal plane. The first axial position is occupied by a thio­cyanate S atom of a symmetry‐related μ‐NCS ligand at an apical distance of 2.9770 (8) Å, and the second position is occupied by an O atom of a bridging carboxyl­ate group from an adjacent coordination unit at a distance of 2.639 (2) Å.     

[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[[[2,4‐dichloro‐6‐(pyridin‐2‐ylmethyl­iminomethyl)phenolato]copper(II)]‐μ‐thio­cyanato]

The title complex, [Cu(C₁₃H₉Cl₂N₂O)(NCS)]_n, is a novel thio­cyanate‐bridged polynuclear copper(II) compound. The Cu^II atom is five‐coordinated in a square‐pyramidal configuration, with one O and two N atoms of one Schiff base ligand and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the axial position. The [2,4‐dichloro‐6‐(pyridin‐2‐ylmethyl­imino­methyl)­phenolato]­copper(II) moieties are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis.     

[Di‐2‐pyridyl ketone N4,N4‐(butane‐1,4‐di­yl)­thio­semi­carbazonato‐κ3N,N′,S]­di­oxo­vanadium(V)

The V^V atom in the title complex, [V(C₁₆H₁₆N₅S)O₂], is five‐coordinate in a highly distorted square‐pyramidal geometry, with the pyridyl N, the azomethine N and the thiol­ate S atoms of the di‐2‐pyridyl ketone N⁴,N⁴‐(butane‐1,4‐di­yl)­thio­semi­carbazone ligand and one oxo ligand occupying the basal coordination positions, while the second oxo ligand occupies the apical position. The mol­ecules are inter­connected by weak inter­molecular inter­actions, mainly of the C—H⋯O type, involving the oxo atoms.     

Chlorotris(N,N′‐dicyclohexylthiourea‐S)tellurium(II) chloride,a tellurium complex with a TeClS3 coordination sphere

During the synthesis of a series of square‐planar [TeCl₂(stu)₂] complexes, where stu represents bulky di‐ or tetrasubstituted thio­ureas, the title compound, [TeCl{(C₆H₁₁NH)₂CS}₃]Cl or C₃₉H₇₂ClN₆S₃Te⁺·Cl^?, was the unexpected result when stu was N,N′‐di­cyclo­hexyl­thio­urea. The complex is square planar, with Te—S distances of 2.5803 (4), 2.6211 (4) and 2.8214 (4) Å, and a Te—Cl distance of 2.6485 (4) Å, indicating a small trans influence of the thio­urea ligand.     

(Z)‐3‐(1H‐Indol‐3‐yl)‐2‐(3‐thienyl)­acrylo­nitrile and (Z)‐3‐[1‐(4‐tert‐butyl­benzyl)‐1H‐indol‐3‐yl]‐2‐(3‐thienyl)­acrylo­nitrile

(Z)‐3‐(1H‐Indol‐3‐yl)‐2‐(3‐thienyl)­acrylo­nitrile, C₁₅H₁₀N₂S, (I), and (Z)‐3‐[1‐(4‐tert‐butyl­benzyl)‐1H‐indol‐3‐yl]‐2‐(3‐thienyl)­acrylo­nitrile, C₂₆H₂₄N₂S, (II), were prepared by base‐catalyzed reactions of the corresponding indole‐3‐carbox­aldehyde with thio­phene‐3‐aceto­nitrile. ¹H/¹³C NMR spectral data and X‐ray crystal structures of compounds (I) and (II) are presented. The olefinic bond connecting the indole and thio­phene moieties has Z geometry in both cases, and the mol­ecules crystallize in space groups P2₁/c and C2/c for (I) and (II), respectively. Slight thienyl ring‐flip disorder (ca 5.6%) was observed and modeled for (I).     

A novel three‐dimensional cadmium(II) coordination polymer incorporating 1,4‐bis­(1,2,4‐triazol‐1‐ylmethyl)­benzene and thio­cyanate

In the title complex, poly[cadmium(II)‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene‐di‐μ₂‐thio­cyanato], [Cd(NCS)₂(C₁₂H₁₂N₆)]_n, the Cd^II atom lies on an inversion centre in a distorted octa­hedral environment. Four N atoms from the thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands occupy the equatorial positions, and two S atoms from symmetry‐related thio­cyanate ligands occupy the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cd^II atoms into two‐dimensional sheets containing novel 16‐membered [Cd₄(μ‐NCS‐N:S)₄] rings. The bbtz ligands further link these two‐dimensional sheets into an unprecedented covalent three‐dimensional network for the cadmium–thio­cyanate system.     

catena‐Poly[[bis­[μ‐2,4‐dichloro‐6‐(2‐pyridyl­methyl­imino­meth­yl)phenolato]dicadmium(II)]‐di‐μ‐thiocyanato]

The title complex, [Cd₂(C₁₃H₉Cl₂N₂O)₂(NCS)₂]_n, is a novel thio­cyanate‐bridged polynuclear cadmium(II) compound. The Cd^II atom is six‐coordinated in a distorted octa­hedral configuration, with one O and two N atoms of one Schiff base mol­ecule and one terminal S atom of a bridging thio­cyanate ligand defining the equatorial plane, and one terminal N atom of another bridging thio­cyanate ligand and one O atom of another Schiff base mol­ecule occupying axial positions. Adjacent inversion‐related [2,4‐dichloro‐6‐(2‐pyridylmethyl­imino­meth­yl)phenolato]cadmium(II) moieties utilize bridging phenolate and thio­cyanate groups to form polymeric chains running along the b axis.     

catena‐Poly­[[[bis(N,N′‐di­phenyl­thio­urea)­cadmium(II)]‐di‐μ‐thio­cyanato] dihydrate]

Bridging by the two thio­cyanato groups in centrosymmetric six‐coordinate bis­(thio­cyanato)­bis­(di­phenyl­thio­urea)­cad­mium(II) dihydrate leads tothe formation of eight‐membered [Cd—SCN→Cd—SCN→] rings that are linked at the metal atom to furnish chains running parallel to the a axis, i.e {[Cd(NCS)₂(C₁₃H₁₂N₂S)₂]·2H₂O}_n.     

A novel three‐dimensional copper(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmeth­yl)benzene and thio­cyanate

In the title complex, poly[copper(II)‐di‐μ₂‐thio­cyanato‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene], [Cu(NCS)₂(C₁₂H₁₂N₆)]_n, the Cu^II atom lies on an inversion centre in a tetra­gonally distorted octa­hedral environment. Four N atoms from thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands fill the equatorial positions, and S atoms from symmetry‐related thio­cyanate ligands fill the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cu^II atoms into two‐dimensional sheets containing an unprecedented 16‐membered [Cu₄(μ‐NCS‐N:S)₄] ring. The bbtz ligands further link the two‐dimensional sheets into a three‐dimensional network.     

A host–guest complex of di­aqua­bis­[1‐hydroxy‐2(1H)‐pyridine­thionato‐O,S]­magnesium(II) and 2,2′‐di­thio­bis­(pyridine N‐oxide)

The title compound, [Mg(C₅H₄NOS)₂(H₂O)₂]·C₁₀H₈N₂O₂S₂, is a two‐component host–guest material. The 2,2′‐di­thio­bis(pyridine N‐oxide) molecule has crystallographic twofold symmetry. The metal complex lies on an inversion centre and associates via C—H?S interactions into chains which thread the 2,2′‐di­thio­bis­(pyridine N‐oxide) lattice in perpendicular directions. Hydro­gen bonds exist between the water mol­ecules of the di­aqua­magnesium units and the N—O groups of the host lattice.     

Tris(3,5‐di­methyl‐1H‐pyrazole‐1‐thio­carboxamidato‐κ2N2,N)­cobalt(III)

In the crystal structure of the title complex, [Co(C₆H₈N₃S)₃], the Co^III atom is octahedrally coordinated by three monodeprotonated bidentate 3,5‐di­methyl‐1H‐pyrazole‐1‐thio­carbox­amide ligands with two thio­carbox­amide N atoms in axial positions. The asymmetric unit contains two mol­ecules (A and B) and these mol­ecules are arranged in chains in an alternating fashion connected by N—H⋯S interactions.     

Two N‐substituted 3,5‐diphenyl‐2‐pyrazoline‐1‐thiocarboxamides

The structures of N‐ethyl‐3‐(4‐fluoro­phen­yl)‐5‐(4‐methoxy­phen­yl)‐2‐pyrazoline‐1‐thio­carboxamide, C₁₉H₂₀FN₃OS, (I), and 3‐(4‐fluoro­phen­yl)‐N‐methyl‐5‐(4‐methyl­phen­yl)‐2‐pyrazoline‐1‐thio­carboxamide, C₁₈H₁₈FN₃S, (II), have similar geometric parameters. The meth­oxy/methyl‐substituted phenyl groups are almost perpendicular to the pyrazoline (pyraz) ring [inter­planar angles of 89.29 (8) and 80.39 (10)° for (I) and (II), respectively], which is coplanar with the fluoro­phenyl ring [inter­planar angles of 5.72 (9) and 10.48 (10)°]. The pyrazoline ring approximates an envelope conformation in both structures, with the two‐coordinate N atom involved in an intra­molecular N—H⋯N_pyraz inter­action. In (I), N—H⋯O and C—H⋯S inter­molecular hydrogen bonds are the primary inter­actions, whereas in (II), there are no intermolecular hydrogen bonds.     

{3,3′‐[2,2′‐(Ethylenedioxy)dibenzyl­idene]bis(S‐methyl dithiocarbazate)}­nickel(II)

The tetradentate N₂S₂ Schiff base ligand 3,3′‐[2,2′‐(ethyl­ene­di­oxy)di­benzyl­idene]­bis­(S‐methyl di­thio­car­ba­zate) (H₂L), prepared by the condensation of S‐methyl di­thio­carb­aza­te with 1,4‐bis(2‐formyl­phenyl)‐1,4‐dioxa­butane in a 1:2 molar ratio, reacts with nickel acetate to form the title neutral metal complex, [Ni(C₂₀H₂₀N₄O₂S₄)]. The X‐ray structure of the complex shows a distorted square‐planar geometry around the Ni atom. The monomeric units are weakly associated into dimers via a long Ni?S interaction [3.569 (1) Å]. These dimeric units are then linked by C—H?S intermolecular contacts to form a polymeric chain 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.     

Bis(1,10‐phenanthroline)(thio­sulfato)­manganese(II) methanol solvate and catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phenanthroline)­manganese(II)]‐μ‐thio­sulfato]

The structure of bis(1,10‐phenanthroline‐κ²N,N′)(thio­sulfato‐κ²O:S)­manganese(II) methanol solvate, [Mn(S₂O₃)(C₁₂H₈N₂)₂]·CH₃OH, is made up of Mn²⁺ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O‐chelating thio­sulfate anion, forming monomeric entities. The structure of catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phen­anthro­line‐κ²N,N′)­manganese(II)]‐μ‐thio­sulfato‐κ²O:S], [Mn(S₂O₃)(C₁₄H₁₂N₂)(H₂O)₂]_n, is polymeric, consisting of Mn(dmph)(H₂O)₂ units (dmph is 2,9‐di­methyl‐1,10‐phenanthroline) linked by thio­sulfate anions acting in an S,O‐chelating manner.     

Transition metal complexes with thiosemicarbazide‐based ligands. XLIV. Aqua(3‐hydroxy‐5‐hydroxymethyl‐2‐methylpyridine‐4‐carboxaldehyde 3‐­methylisothiosemicarbazone‐κ3O,N1,N4)nitratocopper(II) nitrate

The title complex, [Cu(NO₃)(C₁₀H₁₄N₄O₂S)(H₂O)](NO₃), is the first metal complex with a Schiff base derived from iso­thio­semicarbazide and pyridoxal (pyridoxal is 3‐hydroxy‐5‐­hydroxy­methyl‐2‐methyl­pyridine‐4‐carbox­aldehyde). The Cu^II environment is a square pyramid, the equatorial plane of which is formed by the tridentate ONN‐coordinated iso­thio­semicarbazone and one water mol­ecule, while the nitrate ligand is in the apical position. The existence of numerous strong intermolecular hydrogen bonds, and weak C—H?O and C—H?π interactions, leads to a three‐dimensional supramolecular structure.     

1,2‐Di­cyano‐1,2‐bis­(imidazolidine‐2‐thione)­digold(I) and 2,2‐di­cyano‐1,1‐bis­(di­methyl­thio­urea)­digold(I)

Gold(I) cyanide forms complexes with imidazolidine‐2‐thione (etu) and di­methyl­thio­urea (dmtu) with the formula [Au₂(CN)₂L₂], i.e. the title complexes di­cyano‐1κC,2κC‐bis(imidazolidine‐2‐thione)‐1κS,2κS‐digold(I)(Au—Au), [Au₂(CN)₂(C₃H₆N₂S)₂], and di­cyano‐1κ²C‐bis(N,N′‐di­methyl­thio­urea)‐2κ²S‐digold(I)(Au—Au), [Au₂(CN)₂(C₃H₈N₂S)₂]. In the etu complex, two approximately linear (etu)AuCN groups are held together by a weak homopolar Au—Au bond [3.117 (1) Å], with a torsion angle of 61 (3)° between the two groups. In the dmtu complex, an approximately linear Au(dmtu)₂ group is bound to an approximately linear Au(CN)₂ group by a weak heteropolar Au—Au bond [3.091 (1) Å], with a torsion angle of 83 (5)° between the two groups.     

Dipotassium di‐μ‐iso­thio­cyanato‐κ4N:S‐bis­[(N‐salicyl­idene‐dl‐valinato‐κ3O,N,O′)­cuprate(II)]

The title compound, K₂[Cu₂(NCS)₂(C₁₂H₁₃NO₃)₂], consists of two K⁺ cations and (N‐salicyl­idene‐d ‐valinato)­cop­per(II) and (N‐salicyl­idene‐l ‐valinato)cop­per(II) coordination units con­nected through three‐atom thio­cyanate (μ‐NCS) bridges into a centrosymmetric dianion. The Cu^II atom adopts a square‐pyramidal coordination, with three donor atoms of the tridentate Schiff base and one N atom of the bridging ligand (μ‐NCS) in the basal plane. The axial position is occupied by the thio­cyanate S atom of a symmetry‐related ligand at an apical distance of 2.9332 (10) Å. Coulombic interactions between six‐coordinated K⁺ ions and the heteroatoms of neighbouring dimeric anions leads to the formation of one‐dimensional chains of mol­ecules parallel to [010]. The superposition of the normals of the pyramidal base planes in a direction close to [001] indicates possible π–π interactions between neighbouring units.     

A novel thio­cyanate‐bridged one‐dimensional chain complex: [Cu(NCS)2(Hambi)] (Hambi is 2‐amino­methyl‐1H‐benz­imidazole)

Using 2‐amino­methyl‐1H‐benz­imidazole as the ligand, a new thio­cyanate‐bridged copper(II) complex, namely bis(2‐aminomethyl‐1H‐benz­imidazole‐κ²N²,N³)­di­thio­cyanato­copper(II),[Cu(NCS)₂(C₈H₉N₃)], has been synthesized and structurally characterized. The Cu atom is five‐coordinated and exhibits a distorted square‐pyramidal geometry. The thio­cyanate ions (NCS⁻) act as either bridging or terminal ligands. The bridging NCS⁻ ligands connect neighboring Cu atoms, constructing chains, while the terminal NCS⁻ ligands form hydrogen bonds with amine H atoms, leading to a complicated network.