trans‐Bis­(diethano­lamine)­bis­(iso­thio­cyanato)­nickel(II)

In the neutral title complex, trans‐bis(2,2′‐imino­di­ethanol‐N,O)­bis­(iso­thio­cyanato)­nickel(II), [Ni(NCS)₂(C₄H₁₁NO₂)₂], the iso­thio­cyanate ions and the di­ethanol­amine mol­ecules act as mono­dentate and bi­dentate ligands, respectively. The Ni^II ion exhibits a distorted octahedral configuration with crystallographically imposed inversion symmetry and N_NCS—Ni—N_amine and N_NCS—Ni—O_amine bond angles of 88.78 (10) and 89.44 (10)°, respectively. The Ni—N bond distances are in the range 2.069 (3)–2.096 (2) Å. The mol­ecules are linked by hydrogen bonds to form a three‐dimensional infinite lattice.     

Comparative X‐ray study of three nickel(II)–thio­cyanate compounds

Three cis nickel–di­thio­cyanate (SCN) complexes with different N,N′‐bidentate bases have been prepared and their crystal structures determined: bis(2,2′‐bi­pyridine‐N,N′)­bis­(thio­cyan‐­ato‐N)­nickel(II), [Ni(SCN)₂­(C₁₀H₈N₂)₂], bis(1,10‐phen­anthroline‐N,N′)­bis­(thio­cyanato‐N)­nickel(II), [Ni(SCN)₂­(C₁₂H₈N₂)₂], and bis(2,9‐di­methyl‐1,10‐phenanthroline‐N,N′)­bis­(thiocyanato‐N)nickel(II) mono­hydrate, [Ni(SCN)₂­(C₁₂H₈N₂)₂]·H₂O. Distortions due to ligand size are discussed.     

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 one‐dimensional ladder‐like coordination polymer derived from chains formed via hydrogen bonds: catena‐poly­[[aqua­di­pyridine­nickel(II)]‐μ‐2,2′‐di­thio­dibenzoato‐κ3O,O′:O′′]

The title one‐dimensional chain nickel(II)–di­sulfide complex, [Ni(C₁₄H₈O₄S₂)(C₅H₅N)₂(H₂O)]_n, has each Ni^II cation coordinated by two N atoms from two pyridine ligands, three carboxyl­ate O atoms from two different di­thio­dibenzoate ligands and one O atom from a coordinated water mol­ecule, in a distorted octahedral coordination geometry. Each di­thio­dibenzoate ion links two Ni^II cations through its carboxyl­ate O atoms, making the structure polymeric. Hydro­gen‐bond interactions between two shoulder‐to‐shoulder chains lead to the formation of a ladder‐like structure.     

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.     

Transition metal complexes with thio­semicarbazide‐based ligands. XV. A square‐pyramidal NiII complex with an asymmetric coordination of 2,6‐di­acetyl­pyridine bis(S‐methyl­iso­thio­semicarbazone)

The title compound, [di­acetyl­pyridine bis(S‐methyl­iso­thio­semicarbazonato)]­iodo­nickel(II), [Ni(C₁₃H₁₈N₇S₂)I], is the first example of a complex involving the ²N coordination of the iso­thio­semicarbazide moiety. 2,6‐Di­acetyl­pyridine bis(S‐methyl­iso­thio­semicarbazone), as a potentially pentadentate ligand (N₅), is coordinated as a tetradentate species, whereby one (deprotonated) iso­thio­semicarbazide moiety is coordinated in the usual way (¹N⁴N), but the other (neutral) is bonded via the ²N atom only, the fourth ligator being the pyridine nitro­gen. The difference in coordination mode of the iso­thio­semicarbazide moiety is reflected in the ¹N—²N bond lengths of 1.359 (4) and 1.379 (3) Å in the deprotonated and undeprotonated moieties, respectively. The structure contains three fused chelate rings in a 5:5:6 arrangement. The six‐membered ring has a non‐planar conformation.     

Bis­[1‐(p‐chloro­phenyl)‐5‐iso­propyl­biguanide‐κ2N2,N4]­nickel(II) dichloride di­methyl­form­amide solvate

The asymmetric unit of the title compound, [Ni(C₁₁H₁₆ClN₅)₂]Cl₂·C₃H₇NO, contains one monomeric nickel(II) com­plex cation, two Cl⁻ anions and one di­methyl­form­amide sol­vent mol­ecule. The Ni atom is coordinated to each of two 1‐­(p‐chloro­phenyl)‐5‐iso­propyl­biguanide (proguanil) ligands via two N atoms. The complex exhibits a square‐planar coordination, with the Ni atom lying 0.021 (2) Å out of the basal plane. The crystal packing is characterized by several hydrogen bonds.     

Di­aqua­bis(4,5‐di­hydro‐1,2,4‐triazolo[1,5‐a]­pyrimidin‐5‐one‐N3)bis­(thiocyanato‐N)­nickel(II)

The title compound, [Ni(NCS)₂(C₅H₄N₄O)₂(H₂O)₂], crystallizes in the triclinic space group P. The molecular unit contains two neutral mol­ecules of 4,5‐di­hydro‐1,2,4‐triazolo[1,5‐a]­pyrimidin‐5‐one (5HtpO) coordinated through the N atom in position 3, two thio­cyanate ligands coordinated through their N atoms and two water mol­ecules completing an octahedral environment around the Ni^II ion, which lies on a centre of inversion. The structure is stabilized by hydrogen bonding. Distances in the coordination sphere are Ni—N3(5HtpO) 2.132 (2), Ni—O(water) 2.085 (2) and Ni—N(thio­cyanato) 2.040 (2) Å.     

A three‐dimensional network of cadmium

The title complex, poly­[bis­[N‐(2‐amino­ethyl)‐N‐methyl‐1,2‐ethane­di­amine]­hexa‐μ‐thio­cyanato‐tricadmium(II) monohydrate], [Cd₃(NCS)₆(medien)₂]_n·nH₂O [medien is N,N‐bis(2‐amino­ethyl)­methyl­amine, C₅H₁₆N₃], adopts a three‐dimensional inorganic polymeric network structure. Two cadmium centres (Cd1 and Cd2) are linked to each other via thio­cyanate bridges. The environment of the Cd1 atom involves only S atoms, making it soft, whereas the environment of the Cd2 atom involves only N atoms, making it hard.     

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.     

One‐dimensional polymeric chain structure of bis­(aniline)­di­thio­cyanato­cadmium(II)

In the title compound, catena‐poly­[[bis­(aniline‐N)cadmium(II)]‐di‐μ‐thio­cyanato‐S:N;N:S], [Cd­(SCN)₂­(C₆H₇N)₂], the Cd^II atom lies on an inversion centre and is in a distorted octahedral geometry. The coordination sphere contains two thio­cyanate (SCN) S atoms, two iso­thio­cyanate (NCS) N atoms and two aniline N atoms. The six‐coordinated Cd atoms run parallel to the b axis and are doubly bridged with neighbouring Cd atoms by SCN and NCS ligands. Thus, this complex has a one‐dimensional coordination polymeric chain structure in which the aniline ligand is in the trans conformation.     

Bis(1,10‐phenanthroline‐N,N′)(thiosulfato‐O,S)­nickel(II)–water–methanol (1/0.92/1.4) and bis(2,2′‐bi­pyridyl‐N,N′)(thiosulfato‐O,S)nickel(II)–water–methanol (1/2/0.55)

The title compounds, [Ni(S₂O₃)­(C₁₂H₈N₂)₂]·­0.92H₂O·­1.4CH₄O and [Ni(S₂O₃)­(C₁₀H₈N₂)₂]·­2H₂O·­0.55CH₄O, are monomeric, containing nickel(II) in a distorted octahedral coordination environment provided by the four N atoms of two bidentate bipy or phen groups and one S and one O atom from a chelating thio­sulfate anion. The crystals are highly unstable outside their mother liquors and are stabilized in solution by a not fully determined number of water and methanol solvate mol­ecules. The phenanthroline structure includes two independent moieties related by a non‐crystallographic inversion center. The thio­sulfate anions display the usual S—O lengthening found when the anion acts in a bidentate mode.     

Cobalt(II) and nickel(II) complexes of isoquinoline‐1‐carboxylate

trans‐Di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­cobalt(II) dihydrate, [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, and trans‐di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­nickel(II) dihydrate, [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, contain the same isoquinoline ligand, with both metal atoms residing on a centre of symmetry and having the same distorted octahedral coordination. In the former complex, the Co—O(water) bond length in the axial direction is 2.167 (2) Å, which is longer than the Co—O(carboxylate) and Co—N bond lengths in the equatorial plane [2.055 (2) and 2.096 (2) Å, respectively]. In the latter complex, the corresponding bond lengths for Ni—O(water), Ni—O(carboxylate) and Ni—N are 2.127 (2), 2.036 (2) and 2.039 (3) Å, respectively. Both crystals are stabilized by similar stacking interactions of the ligand, and also by hydrogen bonds between the hydrate and coordinated water molecules.     

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.     

Four cytotoxic N4‐substituted thiosemicarbazones derived from 2‐hydroxynaphthalene‐1‐carboxaldehyde

The X‐ray crystal structures are reported of four novel and potentially O,N,S‐tridentate donor ligands that demonstrate antitumour activity. These ligands are 1‐[(4‐methyl­thio­semicarbazono)methyl]‐2‐naphthol, C₁₃H₁₃N₃OS, (III), 1‐[(4‐ethylthio­semicarbazono)­methyl]‐2‐naphthol, C₁₄H₁₅N₃OS, (IV), 1‐[(4‐phenyl­thio­semicarbazono)­methyl]‐2‐naphthol, C₁₈H₁₅N₃OS, (V), and 1‐[(4,4‐di­methyl­thio­semicarbazono)­methyl]‐2‐naphthol di­methyl sulfoxide solvate, C₁₄H₁₅N₃OS·C₂H₆OS, (VI). These chelators are N4‐substituted thio­semicarbazones, each based on the same parent aldehyde, namely 2‐­zhydroxynaphthalene‐1‐carboxaldehyde isonicotinoylhydrazone. Conformational variations within this series are discussed in relation to the optimum conformation for metal‐ion binding.     

A three‐dimensional inorganic/organic hybrid material, [Ni2(4,4′‐bipy)3(H2O)2V4O12]·2.5H2O

The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni₂­(V₂O₆)₂­(C₁₀H₈N₂)₃­(H₂O)₂]·­2.5H₂O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V₂O₆], [Ni­(4,4′‐bipy)₄O₂] and [Ni­(H₂O)₂­(4,4′‐bipy)₂O₂] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.     

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.     

{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.     

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.     

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.