Bis(thio­carbohydrazide)dithio­cyanato­iron(II)

In the title compound, [Fe^II(NCS)₂(CH₆N₄S)₂], the Fe^II cation is surrounded by two S atoms and two N atoms from thio­carbohydrazide groups and by two N atoms from thio­cyanate groups. The geometry around the Fe^II cation, which is located on a center of inversion, is distorted octa­hedral. The thio­carbohydrazide mol­ecule assumes a cis–trans conformation, which is reinforced by an N—H⋯N hydrogen bond. Mol­ecules of the title compound are connected via inter­molecular N—H⋯S and N—H⋯N hydrogen bonds to form a three‐dimensional network structure.     

A novel dimeric zinc(II) complex: bis­[μ‐1,2‐bis­(1H‐1,2,4‐triazol‐1‐yl)­ethane‐κ2N4:N4′]­bis­[diisothio­cyanato­zinc(II)]

The coordination geometry of the Zn^II atom in the title complex, [Zn₂(NCS)₄(C₆H₈N₆)₂], is that of a distorted tetra­hedron, in which the Zn^II atom is coordinated by four N atoms from the triazole rings of two symmetry‐related 1,2‐bis­(1,2,4‐triazol‐1‐yl)ethane ligands and two thio­cyanate ligands. Two Zn^II atoms are bridged by two organic ligands to form a dimer. The dimer lies about an inversion center.     

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.     

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.     

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.     

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.     

Tetrakis(2,2′‐bipyridine‐κ2N,N′)­tetrakis(μ‐salicyl­ato‐κ3O,O′:O′′)‐quadro‐tetrazinc(II) decahydrate

The title compound, [Zn₄(C₇H₄O₃)₄(C₁₀H₈N₂)₄]·10H₂O, crystallizes as a centrosymmetric tetranuclear cyclic complex containing four Zn^II atoms bridged by four carboxyl­ate groups from salicyl­ate ligands, with a syn–anti configuration. Each Zn^II atom has a distorted trigonal–bipyramidal coordination geometry, formed by two N atoms of a 2,2′‐bipyridine ligand and three O atoms from two salicyl­ate ligands. The complex is stabilized by intramolecular π–π interactions between pairs of bi­pyridine rings and a 16‐membered gear‐wheel‐shaped cyclic framework. The hydrogen‐bonding network is formed via the water mol­ecules.     

A novel 8‐carboxyindeno[1,2‐b]quinoxalin‐11‐one thio­semi­carbazone zinc(II) Schiff base complex

In the novel title binuclear zinc(II) Schiff base complex, bis­(μ‐11‐thio­semicarbazonoindeno[1,2‐b]quinoxaline‐8‐carboxylato)bis­[(dimethyl sulfoxide)zinc(II)] dimethyl sulfoxide tri­solvate, [Zn₂(C₁₇H₉N₅O₂S)₂(C₂H₆OS)₂]·3C₂H₆OS, each Zn^II atom is five‐coordinated and situated in a distorted square‐pyramidal environment, coordinated by two L²⁻ ligands and one dimethyl sulfoxide mol­ecule. Each L²⁻ ligand, which coordinates to two Zn^II atoms, has two parts. One part, acting in a tridentate chelating mode, coordinates to one Zn^II atom through two N atoms and one S atom, while another part coordinates to another Zn^II atom through a monodentate carboxylate group. The whole complex has a dimeric structure. The coordination mode of the nearly planar L²⁻ ligand is quite different from the most common mode for Schiff bases.     

catena‐Poly[[{4‐bromo‐2‐[2‐(di­methyl­amino)­ethyl­imino­meth­yl]­phenolato}­copper(II)]‐μ‐thio­cyanato]

The title complex, [Cu(C₁₁H₁₄BrN₂O)(NCS)]_n, is an inter­esting thio­cyanate‐bridged polynuclear copper(II) compound, which crystallizes with two independent mol­ecules in the asymmetric unit. Each Cu^II atom is five‐coordinate 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 apical position. The {4‐bromo‐2‐[2‐(dimethyl­amino)ethyl­imino­meth­yl]phenolato}copper(II) units are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis. There are weak inter­molecular C—H⋯O and C—H⋯S hydrogen bonds between the chains in the crystal structure.     

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.     

(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.     

(μ‐C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐N‐acetato‐1κ5N,N′,N′′,N′′′,O:2κO′)­tetra­chloro‐1κCl,2κ3Cl‐cobalt(III)­zinc(II)

The crystal structure of the title compound, [CoCl(C₁₈H₃₇N₄O₂){ZnCl₃}], has been determined by X‐ray diffraction.C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclotetradecane‐N‐acetate acts as a bridging ligand to coodinate with Co^III and Zn^II ions. The Co^III ion is six‐coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The Zn^II ion is four‐coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.     

Intramolecular hydrogen‐bond‐directed coordination: trans‐bis(N‐benzoyl‐N′‐propyl­thio­urea‐κS)di­iodo­platinum(II) and trans‐bis(N‐benzoyl‐N′‐propyl­thio­urea‐κS)di­bromo­platinum(II)

In the title compounds, trans‐[PtI₂(C₁₁H₁₄N₂OS)₂], (I), and trans‐[PtBr₂(C₁₁H₁₄N₂OS)₂], (II), respectively, intramolecular N—H⋯O (propyl­amine side) hydrogen bonds in the potentially bidentate thio­urea ligands lock the carbonyl O atoms into six‐membered rings, determining the S‐mono­dentate mode of coordination of these ligands. Intramolecular N—H⋯X (X is I or Br) interactions (benzoyl­amine side) lead to slight distortions of the Pt^II coordination spheres from ideal square‐planar geometry. The Pt^II ion is located on an inversion centre in both structures.     

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.     

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.     

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.     

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.     

Di‐μ‐acetato‐bis­[(2‐acetyl­pyridine thio­semicarbazonato)zinc(II)]

The title compound, [Zn₂(C₂H₃O₂)₂(C₈H₉N₄S)₂], is a centrosymmetric dinuclear mol­ecule with two acetate bridging ligands in a syn–syn arrangement. The Zn^II atom is five‐coordinated in a trigonal–bipyramidal configuration by three thio­semicarbazone atoms (two N and one S) and by an O atom from each of the two acetate groups.     

A novel thio­cyanate‐bridged dinuclear cadmium(II) complex: di‐μ‐thio­cyanato‐bis­((methanol){4‐nitro‐2‐[2‐(dimethyl­amino)ethyl­imino­meth­yl]phenolato}cadmium(II))

The title complex, [Cd₂(C₁₁H₁₄N₃O₃)₂(NCS)₂(CH₄O)₂], is an inter­esting thio­cyanate‐bridged dinuclear cadmium(II) compound. It is located on a crystallographic inversion center. The Cd^II atom is six‐coordinated in an octa­hedral configuration by one O and two N atoms of one Schiff base ligand and by the terminal N atom of a bridging thio­cyanate ligand, defining the basal plane, and by the terminal S atom of another bridging thio­cyanate ligand and by the O atom of a coordi­nated methanol mol­ecule, occupying the axial positions. The mol­ecules are linked through inter­molecular O—H⋯O hydrogen bonds, forming chains running along the b axis.     

Di‐μ‐acetato‐bis­{[2,4‐dichloro‐6‐(2‐pyridylmethyl­imino­meth­yl)­phenol­ato]zinc(II)} and di‐μ‐thio­cyanato‐bis­{[2,4‐dichloro‐6‐(2‐pyridylmethyl­imino­meth­yl)phenolato]copper(II)}

The two title complexes, [Zn₂(C₁₃H₉Cl₂N₂O)₂(C₂H₃O₂)₂], (I), and [Cu₂(C₁₃H₉Cl₂N₂O)₂(NCS)₂], (II), are dinuclear Schiff base compounds. Both mol­ecules are located on crystallographic centres of inversion. In (I), the Zn^II atom is five‐coordinated in a trigonal–bipyramidal coordination, with one imine N atom of one Schiff base and two acetate O atoms defining the basal plane, and one O atom and one pyridine N atom of the Schiff base occupying the axial positions, while in (II), the Cu^II atom is five‐coordinated in a square‐pyramidal coordination, with one O and two N atoms of one Schiff base 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 apical position. The different bridging ligands lead to the different coordinations of the complexes.