Synthesis, crystal structure and properties of -poly[[bis-(4-methyl-pyridine-κ)cobalt(II)]-di-μ-thio-cyanato-κ :;κ :], which shows a rare coordination geometry.

Reaction of Co(NCS) with 4-methyl-pyridine in water leads to the formation of single crystals of the title compound, [Co(NCS)(CHN)] . The asymmetric unit consists of two crystallographically independent thio-cyanate anions and two crystallographically independent 4-methyl-pyridine coligands in general positions, as well as of two different Co cations, of which one is located on a twofold rotational axis, whereas the second occupies a center of inversion. The methyl H atoms in both 4-methyl-pyridine ligands are disordered and were refined using a split model.

Synthesis, crystal structure and thermal decomposition pathway of bis-(iso-seleno-cyanato-κ)tetra-kis-(pyridine-κ)manganese(II).

The reaction of MnCl·2HO with KSeCN and pyridine in water leads to the formation of the title complex, [Mn(NCSe)(CHN)], which is isotypic to its Fe, Co, Ni, Zn and Cd analogues. In its crystal structure, discrete complexes are observed that are located on centres of inversion. The Mn cations are octa-hedrally coordinated by four pyridine coligands and two seleno-cyanate anions that coordinate the N atom to the metal centres to generate -MnN(s)N(p) octa-hedra (s = seleno-cyanate and p = pyridine).

Synthesis, crystal structure and properties of bis-(iso-seleno-cyanato-κ)tetra-kis-(pyridine-κ)nickel(II).

The reaction of nickel chloride hexa-hydrate with potassium seleno-cyanate and pyridine in water leads to the formation of crystals of the title complex, [Ni(NCSe)(CHN)], which were characterized by single-crystal X-ray diffraction. Its crystal structure consists of discrete complexes, located on centers of inversion, in which the Ni cations are sixfold coordinated by two terminal N-bonded seleno-cyanate anions and four pyridine ligands within a slightly distorted octa-hedral coordination. In the crystal, the complexes are connected by weak C-H⋯Se inter-actions.

Crystal structure of tris-(hydroxyl-ammonium) orthophosphate.

The crystal structure of the title salt, ([H3NOH](+))3·[PO4](3-), consists of discrete hydroxyl-ammonium cations and ortho-phos-phate anions. The atoms of the cation occupy general positions, whereas the anion is located on a threefold rotation axis that runs through the phospho-rus atom and one of the phosphate O atoms. In the crystal structure, cations and anions are linked by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds into a three-dimensional network.

catena-Poly[[bis-(3-acetyl-pyridine-κN)cadmium]-di-μ-seleno-cyanato-κ(2)N:Se;κ(2)Se:N].

In the crystal structure of the title compound, [Cd(NCSe)(2)(C(7)H(7)NO)(2)](n), the Cd(2+) cation is coordinated by two 3-acetyl-pyridine ligands and four μ-1,3-bridging seleno-cyanate anions within a slightly distorted CdN(4)Se(2) octa-hedron. The asymmetric units consists of one Cd(2+) cation, which is situated on a center of inversion, as well as one seleno-cyanate anion and one 3-acetyl-pyridine ligand in general positions. The metal cations are μ-1,3-bridged via the seleno-cyanate anions into chains along the a axis.

Bis(3-acetyl-pyridine-κN)diaqua-bis-(seleno-cyanato-κN)cobalt(II).

In the crystal structure of the title compound, [Co(NCSe)(2)(C(7)H(7)NO)(2)(H(2)O)(2)], the Co(2+) cation is coordinated by two seleno-cyanate anions, two 3-acetyl-pyridine ligands and two water mol-ecules within a slightly distorted CoN(4)O(2) octa-hedron. The asymmetric unit consists of one Co(2+) cation, which is located on a center of inversion, as well as one seleno-cyanate anion, one 3-acetyl-pyridine ligand and one water mol-ecule in general positions. Whereas one of the water H atoms makes a classical O-H⋯O hydrogen bond, the other shows a O-H⋯Se inter-action.

Bis(3-acetyl-pyridine-κN)bis-(methanol-κO)bis-(thio-cyanato-κN)nickel(II).

In the crystal structure of the title compound, [Ni(NCS)(2)(C(7)H(7)NO)(2)(CH(3)OH)(2)], the Ni(2+) cations are coordinated by two thio-cyanate anions, two 3-acetyl-pyridine ligands and two methanol mol-ecules within slightly distorted NiN(4)O(2) octa-hedra. The asymmetric unit consists of one Ni(2+) cation, which is located on a center of inversion, as well as one thio-cyanate anion, one 3-acetyl-pyridine ligand and one methanol mol-ecule in general positions. The discrete complexes are linked by two pairs of O-H⋯O hydrogen bonds between the hy-droxy H atom and the acetyl O atom into chains along the b axis.

Metamagnetism and single-chain magnetic behavior in a homospin one-dimensional iron(II) coordination polymer.

Reaction of FeCl(2)·4H(2)O with KNCSe and pyridine in ethanol leads to the formation of the discrete complex [Fe(NCSe)(2)(pyridine)(4)] (1) in which the Fe(II) cations are coordinated by two N-terminal-bonded selenocyanato anions and four pyridine co-ligands. Thermal treatment of compound 1 enforces the removal of half of the co-ligands leading to the formation of a ligand-deficient (lacking on neutral co-ligands) intermediate of composition [Fe(NCSe)(2)(pyridine)(2)](n) (2) to which we have found no access in the liquid phase. Compound 2 is obtained only as a microcrystalline powder, but it is isotypic to [Cd(NCSe)(2)(pyridine)(2)](n) and therefore, its structure was determined by Rietveld refinement.

Tetra-kis(3-cyano-pyridine-κN)bis-(thio-cyanato-κN)cobalt(II) 1,4-dioxane disolvate.

In the crystal structure of the title compound, {[Co(NCS)(2)(C(6)H(4)N(2))(4)]·2C(4)H(8)O(2)}, the Co(II) cations are octa-hedrally coordinated by two terminal N-bonded thio-cyanate anions and four N-bonded 3-cyano-pyridine ligands. The asymmetric unit consists of one Co(II) cation, which is located on a special position with site symmetry 2/m, one thio-cyanate anion and one dioxane mol-ecule, located on a crystallographic mirror plane, as well as one 3-cyano-pyridine ligand in a general position. The crystal structure consists of discrete complexes of [Co(NCS)(2)(3-cyano-pyridine)(4)], as well as two non-coordinating 1,4-dioxane solvent mol-ecules which are disordered due to symmetry.

[Bis(3-amino-prop-yl)amine-κN,N',N'']bis-(thio-cyanato-κN)cobalt(II).

The asymmetric unit of the title compound, [Co(NCS)(2)(C(6)H(17)N(3))], consists of one Co(2+) cation, two thio-cyanate anions and one bis-(3-amino-prop-yl)amine ligand, all in general positions. The cobalt cation is coordinated by five N atoms of two terminal N-bonded thio-cyanate anions and one bis-(3-amino-prop-yl)amine ligand, defining a slightly distorted square-pyramidal coordination polyhedron. The mol-ecules are held together in the crystal by weak N-H⋯S inter-actions.

New cadmium thio- and selenocyanato coordination compounds: structural snapshots on the reaction pathway to more condensed anionic networks.

In this contribution several new coordination compounds on the basis of cadmium(II) thio- and selenocyanate with pyrimidine as co-ligand were prepared and investigated for their structural, thermal and spectroscopic properties. The reaction of cadmium(II) thiocyanate with pyrimidine leads to the formation of four compounds, which from a structural point of view are closely related. In the most pyrimidine-rich 1 : 2 compound [Cd(NCS)(2)(pyrimidine)(2)](n) (1A) (1 : 2 = ratio between metal salt and the co-ligand pyrimidine) the Cd cations are linked by the pyrimidine ligands into layers and are additionally coordinated by two terminal N-bonded anions.

catena-Poly[[bis-[[bis-(3-amino-prop-yl)amine-κN,N',N''](thio-cyanato-κN)cadmium]-μ(4)-sulfato-κO,O:O',O'] methanol hemisolvate].

The asymmetric unit of the title compound, {[Cd(2)(NCS)(2)(SO(4))(C(6)H(17)N(3))(2)]·0.5CH(3)OH}(n), consists of two Cd(2+) cations, two thio-cyanate and one sulfate anion, two bis-(3-amino-prop-yl)amine co-ligands and one methanol molecule with half-occupancy. Each Cd(2+) cation is coordinated by four N atoms of one terminal N-bonded thio-cyanate anion and one bis-(3-amino-prop-yl)amine co-ligand, and by two O atoms of two symmetry-related sulfate anions, defining a slightly distorted octa-hedral coordination polyhedron.

Bis(3-methyl-pyridine-κN)bis-(thio-cyanato-κN)zinc.

The asymmetric unit of the title compound, [Zn(NCS)(2)(C(6)H(7)N)(2)], consists of one Zn(2+) cation and two thio-cyanate anions, all situated on special positions with site symmetry .m., and one 3-methyl-pyridine ligand.

Poly[bis-(μ(2)-pyrimidine-κN:N')bis-(seleno-cyanato-κN)zinc].

The asymmetric unit of the title compound, [Zn(NCSe)(2)(C(4)H(4)N(2))(2)](n), consists of one Zn(2+) cation located on a special position with site symmetry 2/m, one seleno-cyanate anion on a mirror plane and one pyrimidine ligand on a twofold rotation axis. The zinc cation is coordinated by six N atoms of four pyrimidine ligands and two N-bonded seleno-cyanate anions in mutually trans orientations within a slightly distorted octa-hedral coordination environment. The Zn atoms are μ-1,3-bridged via the pyrimidine ligands into a polymeric layer extending parallel to (100).

Bis(pyridazine-κN)bis-(seleno-cyanato-κN)zinc.

The asymmetric unit of the title compound, [Zn(NCSe)(2)(C(4)H(4)N(2))(2)], consists of one Zn(II) cation, located on a twofold rotation axis, one seleno-cyanate anion and one pyridazine ligand in general positions. The Zn(II) atom is coordinated by two N-atoms of two pyridazine ligands and two terminal N-bonded seleno-cyanate anions within a slightly distorted tetra-hedral coordination environment. In the crystal, discrete complex mol-ecules are arranged in layers parallel to the ac plane, with Zn(II)⋯Zn(II) distances of 8.

catena-Poly[[bis-(pyridine-κN)cadmium]-di-μ(2)-thio-cyanato-κN:S;κS:N].

The asymmetric unit of the title compound, [Cd(NCS)(2)(C(5)H(5)N)(2)](n), consists of two crystallographically independent Cd(II) cations, four thio-cyanato anions and four pyridine ligands. The Cd(II) atoms are each coordinated by four N atoms from two pyridine ligands and two thio-cyanato anions, each in a mutually cis orientation, and by two S atoms from two adjacent thio-cyanato anions within a slightly distorted octa-hedral coordination environment. The Cd(II) atoms are μ-1,3-bridged via the thio-cyanato anions into polymeric chains parallel to [001].

A rational route to SCM materials based on a 1-D cobalt selenocyanato coordination polymer.

Thermal annealing of a discrete complex with terminal SeCN anions and monodentate coligands enforces the formation of a 1D cobalt selenocyanato coordination polymer that shows slow relaxation of the magnetization. Therefore, this approach offers a rational route to 1D materials that might show single chain magnetic behaviour.

Solid-state transformation of [Co(NCS)2(pyridine)4] into [Co(NCS)2(pyridine)2]n: from Curie-Weiss paramagnetism to single chain magnetic behaviour.

Reaction of Co(NCS)(2) with pyridine (pyr) in aqueous solution at room temperature leads to the formation of the pyridine-rich 1:4 compound of composition [Co(NCS)(2)(pyridine)(4)] (1) reported recently. On heating, the pyridine-rich 1:4 compound transforms into its corresponding pyridine-deficient 1:2 compound of composition [Co(NCS)(2)(pyridine)(2)](n) (2), which decomposes on further heating. In the crystal structure of compound 2 the metal cations are coordinated by four N-atoms of two pyridine ligands and two N-bonded thiocyanato anions, each in mutually trans orientation, and by two S-atoms of two adjacent thiocyanato anions in a slightly distorted octahedral geometry.

catena-Poly[[μ(3)-hydroxido-tetra-μ(2)-pyrid-azine-1:2κN:N';1:3κN:N';2:3κN:N'-tetrakis(selenocyanato)-1κN,2κN,3κN-trizinc(II)]-μ-cyanido-1:2'κC:N].

In the crystal structure of the title compound, [Zn(3)(NCSe)(4)(OH)(CN)(C(4)H(4)N(2))(4)](n) one of the two crystallograph-ically independent zinc(II) cations is coordinated by two terminal N-bonded seleno-cyanato anions and two N atoms of two symmetry-related pyridazine ligands in a trigonal-bipyramidal geometry, while the other zinc(II) cation is coordinated by one terminal N-bonded seleno-cyanato anion, one μ-1,2-cyanido anion and three N atoms of three crystallographically independent pyridazine ligands in a slightly distorted octa-hedral coordination geometry. The zinc(II) atoms are further connected via a μ(3)-hydroxido anion into trinuclear building blocks. The formula unit consists of three zinc cations, four seleno-cyanato anions, one μ(3)-hydroxido anion, four pyridazine mol-ecules as well as one cyanido anion.

Poly[diaqua-tetra-μ-seleno-cyanato-cadmium(II)dipotassium(I)].

In the title compound, [CdK(2)(NCSe)(4)(H(2)O)(2)](n), the cadmium(II) cation is situated on a twofold rotation axis and is coordinated in a slightly distorted tetra-hedral geometry by two symmetry-related μ-1,1,1,3 and two-symmetry related μ-1,1,3,3 bridging seleno-cyanate anions, all of which are Se bonded. These bridging seleno-cyanate anions are further coordinated to two symmetry-related potassium ions. Each of the potassium ions is coordinated by one terminally bonded water mol-ecule and six seleno-cyanate anions, two of which are crystallographically independent.

Poly[(μ-4,4'-bipyridine)(μ-naphthalene-1,4-dicarboxyl-ato)manganese(II)].

In the crystal structure of the title compound, [Mn(C(12)H(6)O(4))(C(10)H(8)N(2))](n), the Mn atoms are each coordinated by four O atoms of naphthalene-1,4-dicarboxyl-ate anions and two N atoms of two symmetry-related 4,4'-bipyridine ligands within a strongly distorted octa-hedra. Two of the O atoms originate from one naphthalene-1,4-dicarboxyl-ate anion, whereas the remaining two O atoms derive from two symmetry-equivalent naphthalene-1,4-dicarboxyl-ate anions. Two Mn atoms are connected via the anions into dimers, which are further linked by the anions and the N-donor ligands into a three-dimensional coordination network.

Poly[(μ-4,4'-bipyridine)(μ-naph-tha-lene-1,4-dicarboxyl-ato)iron(II)].

The asymmetric unit of the title compound, [Fe(C(12)H(6)O(4))(C(10)H(8)N(2))], consists of two independent Fe(II) atoms, two naphthalene-1,4-dicarboxyl-ate anions and two 4,4'-bipyridine ligands. The Fe(II) atoms are each coordinated by four O atoms of the naphthalene-1,4-dicarboxyl-ate anions and two N atoms of the 4,4'-bipyridine ligands within a distorted octa-hedron. Two Fe(II) atoms are bridged via the carboxyl-ate groups of two symmetry-related anions into dimers, which are further connected into chains.

Poly[(μ(6)-naphthalene-1,4-dicarboxyl-ato-κO:O:O:O:O:O)iron(II)].

In the title compound, [Fe(C(12)H(6)O(4))](n), the Fe(II) atom is coordinated by six O atoms from six symmetrically equivalent naphthalene-1,4-dicarboxyl-ate ligands in a strongly distorted octa-hedral geometry. These octa-hedra are connected via common edges into chains that elongate along the a axis, with Fe⋯Fe distances of 2.9712 (4) and 2.