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[[[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.     

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 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 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.     

catena‐Poly[[bis(nicotinamide‐κN1)copper(I)]‐μ‐thiocyanato‐κ2N:S]

The Cu^I cations in the title compound, [Cu(NCS)(C₆H₆N₂O)₂]_n, are coordinated by N atoms from each of two mirror‐related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry‐related thio­cyanate ligand, within a slightly distorted tetrahedron. The Cu^I cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The Cu^I cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three‐dimensional structure.     

[2,6‐Bis(3,5‐di­methyl­pyrazol‐1‐yl­methyl‐κN2)­pyridine‐κN]bis­(thiocyanato‐N)copper(II)

The title compound, [Cu(NCS)₂(C₁₇H₂₁N₅)], displays a distorted square‐pyramidal coordination geometry, where the basal plane is defined by the tridentate ligand and by one of the thio­cyanate ions. The apical position is occupied by the other thio­cyanate ion.     

trans‐Bis(3,5‐di­aza‐1‐azonia‐7‐phosphaadamantane‐κP)­bis­(thiocyanato‐κS)­palladium(II) bis­(thio­cyanate)

The crystal structure of the title compound, trans‐[Pd(NCS)₂(C₆H₁₃N₃P)₂](NCS)₂, is one of the few pal­ladium(II) complexes containing two protonated water‐soluble 1,3,5‐tri­aza‐7‐phos­pha­adamantane (PTA) ligands re­ported to date. The compound displays a distorted square‐planar geometry, with the Pd atom on an inversion centre and with the S atoms of the thio­cyanate counter‐ions occupying the axial positions above and below the equatorial plane described by the phosphine and thio­cyanate ligands. Geometric parameters for the formal coordination polyhedron include a Pd—P distance of 2.2940 (8) Å, a Pd—S distance of 2.3509 (8) Å and a P—Pd—S angle of 89.45 (3)°. The effective cone angle for the PTA ligands was calculated as 114.5°.     

A cobalt(III) compound of a 13‐membered cyclic tetra­amine: trans‐(12,12‐dimethyl‐1,4,7,10‐tetra­aza­cyclo­tetra­decane)diisothio­cyanato­cobalt(III) tetra­isothio­cyanato­zinc(II) ethanol solvate

The title compound, [Co(NCS)₂(C₁₁H₂₆N₄)]₂[Zn(NCS)₄]·C₂H₅OH, has two similar cations with the Co^III atom coordinated in a planar fashion by the 13‐membered cyclic tetra­amine, in the 1R,4S,7R,10S configuration, and with trans isothio­cyanate ligands. The six‐membered chelate ring is in a chair conformation, with one axially and one equatorially oriented methyl substituent [mean Co—N = 1.948 (2) Å]. The `opposite' chelate ring (N<sup>4</sup> and N<sup>7</sup>) is in an eclipsed conformation [mean Co—N = 1.928 (2) Å], and the `side' chelate rings have gauche conformations. The mean Co—N_NCS distance is 1.928 (2) Å. Both cations have one Co—N—C group nearly linear and the other appreciably bent, with mean Co—N—C angles of 178.7 (1) and 160.4 (1)°, respectively. The [Zn(NCS)₄]²⁻ anion is approximately tetra­hedral, with Zn—N = 1.951 (1)–1.986 (1) Å, N—Zn—N = 104.5 (1)–111.9 (1)° and Zn—N—C = 152.5 (1)–179.4 (1)°. One NH group is hydrogen bonded to the ethanol O atom and the other NH groups are bonded to thio­cyanate S atoms, forming a network.     

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.     

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.     

catena‐Poly­[1,4‐diazo­niabicyclo­[2.2.2]­octane [silver(I)‐tri‐μ‐thio­cyanato‐κ6S:S]]

The title compound, {(C₆H₁₄N₂)[Ag(NCS)₃]}_n, is a polymeric silver(I) complex. The Ag^I atom is hexacoordinated by the S atoms of six thio­cyanate anions, with each thio­cyanate S atom acting in a bridging mode to link the Ag atoms together. The unique Ag^I atom lies at a cell origin and has crystallo­graphically imposed symmetry. The diazonia[2.2.2]octane molecule lies about a site with imposed symmetry with the unique N atom on a threefold axis. The S and N atoms of the thio­cyanate ligands sit on a mirror plane and a threefold axis, respectively. The crystal structure consists of one‐dimensional chains, which are stabilized by N—H⋯N hydrogen bonds to form a three‐dimensional network.     

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.     

catena‐Poly[[[N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐azido] and catena‐poly[[[N,N′‐bis(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐thio­cyanato]

The two title complexes, catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐azido], [Co(C₁₇H₁₆N₂O₂)(N₃)]_n, (I), and catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐thio­cyanato], [Co(C₁₇H₁₆N₂O₂)(NCS)]_n, (II), are isomorphous polynuclear cobalt(III) compounds. In both structures, the Co^III atom is six‐coordinated in an octa­hedral configuration by two N atoms and two O atoms of one Schiff base, and two terminal N or S atoms from two bridging ligands. The [N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III) moieties are linked by the bridging ligands, viz. azide in (I) and thio­cyanate in (II), giving zigzag polymeric chains with backbones of the type [–Co—N—N—N—Co]_n in (I) or [–Co—N—C—S—Co]_n in (II) running along the c axis.     

catena‐Poly­[[bis­(thio­cyanato‐κN)cadmium(II)]‐di‐μ‐thio­urea‐κ4S:S]

The Cd^II ion in the title complex, [Cd(SCN)₂{SC(NH₂)₂}₂]_∞, is situated at a centre of symmetry, and is bound to two N atoms belonging to thio­cyanate groups and to four S atoms of bridging thio­urea ligands. The structure consists of infinite chains of slightly distorted edge‐shared Cd‐centred octahedra. The bridging S atoms of two thio­urea ligands comprise the common edge. Some thermal properties are described.     

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.     

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.     

[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.     

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.