Transition metal complexes with ­thiosemicarbazide‐based ligands. XLIII.

In the title compound, [ZnCl(C₂H₇N₃S)₂]Cl, the Zn^II ion is five‐coordinated in a distorted trigonal–bipyramidal arrangement, with the hydrazine N atoms located in the apical positions. The structure is stabilized by N—H?Cl hydrogen bonds, which involve both the Cl atoms and all the hydrogen donors, except for one of the two thio­amide N atoms. A comparison of the geometry of thio­semicarbazide and S‐­methyl­iso­thio­semicarbazide complexes with Zn^II, Cu^II and Ni^II shows the pronounced influence of the hydrogen‐bond network on the coordination geometry of Zn^II compounds.     

Aqua(phthalocyaninato‐κ4N)magnesium(II) 3‐chloropyridine disolvate

The structure of the title compound, [Mg(C₃₂H₁₆N₈)(H₂O)]·2C₅H₄ClN, comprises MgPcH₂O [Pc is phthalocyaninate(2−)] and 3‐chloropyridine solvent molecules interacting via O—H...N hydrogen bonds and π–π interactions. The central Mg atom is (4+1)‐coordinated by four equatorial isoindole N atoms of the macrocycle and by the O atom of an axial water molecule. The MgPcH₂O molecule is not planar, the Mg atom being displaced by 0.496 (2) Å from the isoindole N₄ plane towards the water O atom. MgPcH₂O molecules related by a twofold screw axis interact via O—H...N_azamethine hydrogen bonds, forming a polymeric chain along the b axis, while those related by inversion centres form π–π interacting dimers.     

Aqua(dipicolinato‐κ3O2,N,O6)(1,10‐phenanthroline‐κ2N,N′)manganese(II) monohydrate

In the title compound [systematic name: aqua(1,10‐phenanthroline‐κ²N,N′)(pyridine‐2,6‐di­carboxyl­ato‐κ³O²,N,O⁶)manganese(II) monohydrate, [Mn(C₇H₃NO₄)(C₁₂H₈N₂)(H₂O)]·H₂O, the manganese(II) centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.248 (3) and 2.278 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.179 (3) Å, and Mn—O = 2.237 (2) and 2.266 (2) Å] and one water mol­ecule [Mn—O = 2.117 (3) Å], and it exhibits a strongly distorted octahedral geometry, with trans angles ranging from 144.12 (9) to 158.88 (11)°. Extensive intermolecular hydrogen‐bonding interactions involving coordinated and uncoordinated water mol­ecules and the carboxyl O atoms of the dipicolinate ligand, as well as a stacking interaction involving the phenanthroline rings, are observed in the crystal structure.     

[2,6‐Bis(1H‐benzimidazol‐2‐yl‐κN3)­pyridine‐κN](di­methyl­form­amide‐κO)­(thio­sulfato‐κ2O,S)­nickel(II) mono­hydrate

The structure of the title compound, [Ni(ths)(bbip)(dmf)]·­H₂O [ths is thio­sulfate, S₂O₃; bbip is 2,6‐bis(1H‐benz­imidazol‐2‐yl)­pyridine, C₂₁H₁₃N₅; and dmf is di­methyl­form­amide, C₃H₇NO], is monomeric, with the nickel ion octahe­drally surrounded by an N,N′,N′′‐tridentate bbip mol­ecule, an S,O‐bidentate ths mol­ecule and an O‐monodentate dmf mol­ecule. The H atoms of the hydration water mol­ecule and the amino groups of bbip are involved in hydrogen bonding and determine a spatial organization of broad layers parallel to (001), which are connected by weak interactions.     

{4‐[(Carbamimidoylhydrazono)methyl‐κ2N1,N4]‐5‐hydroxymethyl‐2‐methylpyridinium‐3‐olate‐κO}(methanol‐κO)copper(II) dinitrate

The title compound, [Cu(C₉H₁₃N₅O₂)(CH₄O)](NO₃)₂, consists of square‐planar cationic complex units where the Cu^II centre is coordinated by an N,N′,O‐tridentate pyridoxal–aminoguanidine Schiff base adduct and a methanol molecule. The tridentate ligand is a zwitterion exhibiting an almost planar conformation. The dihedral angles between the mean planes of the pyridoxal ring and the six‐ and five‐membered chelate rings are all less than 2.0°. The charge on the complex cation is neutralized by two nitrate counter‐ions. Extensive N—H...O and C—H...O hydrogen bonding connects these ionic species and leads to the formation of layers. The pyridoxal hydroxy groups are the only fragments that deviate significantly from the flat layer structure; these groups are involved in O—H...O hydrogen bonding, connecting the layers into a three‐dimensional crystal structure.     

Bis(5‐hydroxy‐2‐hydroxy­methyl‐4‐pyrone‐κ2O4,O5)bis(2‐hydroxy­methyl‐5‐oxido‐4‐pyrone‐κ2O4,O5)­calcium(II) tetrahydrate

In the title compound, [Ca(C₆H₅O₄)₂(C₆H₆O₄)₂]·4H₂O, which is a kojic acid–Ca²⁺ complex, the Ca atom is on a twofold axis and is octacoordinated by O atoms from four pyrone ligand mol­ecules. The hydroxyl and ketone O atoms of each ligand form a five‐membered chelate ring with the Ca atom. The crystal structure is stabilized by partial stacking and O—H?O hydrogen bonds.     

Aqua(oxydiacetato‐κ3O,O′,O′′)(pyridine‐3‐carboxamide‐κN1)copper(II) sesquihydrate

In the monomeric title compound, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)]·1.5H₂O, the Cu^II cation is bound in a square‐pyramidal coordination to a tridentate oxydiacetate (ODA) ligand, a monodentate pyridine‐3‐carboxamide (p3ca) ligand and one aqua ligand, where the two organic ligands form the basal plane and the water O atom occupies the unique apical site. The ODA ligand presents a slight out‐of‐plane puckering in its central ether O atom, while the p3ca ligand is essentially planar. The availability of efficient donors and acceptors for hydrogen bonding results in the formation of strongly linked hydrogen‐bonded bilayers parallel to (101), with an interplanar distance of 3.18 (1) Å and a stacking separation between the bilayers of 3.10 (1) Å, both of them governed by extended π–π interactions. The disordered nature of the solvent water molecules around inversion centres is discussed. The monoaqua compound is compared with the octahedral diaqua analogue, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)₂], reported recently [Perec & Baggio (2009). Acta Cryst. C 65 , m296–m298].     

Aqua[bis(pyrimidin‐2‐yl‐κN)amine](carbonato‐κ2O,O′)copper(II) dihydrate

The title mononuclear complex, [Cu(CO₃)(C₈H₇N₅)(H₂O)]·2H₂O, was obtained by fixation of CO₂ by a mixture of copper(II) tetra­fluoro­borate and the ligand bis­(pyrimidin‐2‐yl)­amine in ethanol/water. The Cu^II ion of the complex has a distorted square‐pyramidal environment, with a basal plane formed by two N atoms of the ligand and two chelating O atoms of the carbonate group, while the apical position is occupied by the O atom of the coordinating water mol­ecule. In the solid state, hydrogen‐bonding interactions are dominant, the most unusual being the Watson–Crick‐type coplanar ligand pairing through two N—H?N bonds. Lattice water mol­ecules also participate in hydrogen bonding.     

Bis(2‐chloro‐5‐methylpyridine‐κN)bis(nitrato‐κ2O,O′)copper(II)

In the molecule of the title compound, [Cu(NO₃)₂(C₆H₆ClN)₂], the Cu atom lies on an inversion centre and is six‐coordinated by two pyridine N atoms and four nitrate O atoms in trans positions. The nitrate acts as an unsymmetrical bidentate ligand. The coordination geometry is octahedral, with the Cu—N and the two Cu—O distances being 1.9939 (16), 2.0246 (16) and 2.4866 (19) Å, respectively. There are five types of C—H⋯O hydrogen bonds. Two of these generate two‐dimensional molecular networks in the direction of the a axis, and the others connect adjacent molecular networks.     

mer‐Di­aqua­bis(1H‐imidazole‐κN3)(orotato‐κ2N3,O4)­nickel(II)

The title mononuclear complex, [Ni(C₅H₂N₂O₄)(C₃H₄N₂)₂(H₂O)₂] or [Ni(HOr)(im)₂(H₂O)₂] (im is imidazole and H₃Or is orotic acid, or 2,6‐dioxo‐1,2,3,6‐tetra­hydro­pyrimidine‐4‐carboxylic acid), has been synthesized and the crystal structure determination is reported. The Ni^II ion in the complex has a distorted octahedral coordination geometry comprised of one deprotonated pyrimidine N atom and the adjacent carboxyl­ate O atom of the orotate ligand, two tertiary imidazole N atoms and two aqua ligands. An extensive three‐dimensional network of OW—H⋯O and N—H⋯O hydrogen bonds, and π–π and π–ring interactions are responsible for crystal stabilization.     

(Nitrato‐κO)bis(pyridine‐2‐carboxamide‐κ2N1,O)mercury(II) nitrate

In the title compound, [Hg(NO₃)(C₆H₆N₂O)₂]NO₃, the Hg^II atom is five‐coordinate. The distorted square‐pyramidal mercury(II) coordination environment is achieved by two N,O‐bidentate picolinamide ligands, with one O‐monodentate nitrate ion in the apical position. A seven‐coordinate extended coordination environment is completed by two additional weak Hg...O interactions, one from the coordinated nitrate ion and one from the other nitrate ion, to give seven‐coordination. The molecules are linked into a two‐dimensional network by N—H...O hydrogen bonds.     

cis‐Bis­[1,3‐bis(2‐fluoro­phenyl)­triazenido‐κ2N1,N3]­bis­(pyridine‐κN)cadmium(II)

In the title compound, [Cd(C₁₂H₈F₂N₃)₂(C₅H₅N)₂], the Cd atom lies on a crystallographic twofold axis in space group Iba2. The coordination geometry about the Cd^II ion corresponds to a rhombically distorted octahedron, with two deprotonated 1,3‐bis(2‐fluoro­phenyl)­triazenide ions, viz. FC₆H₄NNNC₆H₄F⁻, acting as bidentate ligands (four‐electron donors). Two neutral pyridine (py) mol­ecules complete the coordination sphere in positions cis with respect to one another. The triazenide ligand is not planar (r.m.s. deviation = 0.204 Å), the dihedral angle between the phenyl rings of the terminal 2‐fluoro­phenyl substituents being 24.6 (1)°. The triazenide and pyridine Cd—N distances are 2.3757 (18)/2.3800 (19) and 2.3461 (19) Å, respectively. Intermolecular C—H⋯F interactions generate sheets of mol­ecules in the (010) plane.     

Two isomorphous ZnII/CoII complexes with tri‐tert‐butoxysilanethiol and histamine,and (4‐hydroxymethyl‐1H‐imidazole‐κN)bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II)

The complexes [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], and [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], are isomorphous. The central Zn^II/Co^II ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH₂ groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The Zn^II atom in [(1H‐imidazol‐4‐yl‐κN³)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ²O,S)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₄H₆N₂O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins.     

Di‐μ‐acesulfamato‐κ3N,O:O;κ3O:N,O‐bis[(acesulfamato‐κ2N,O)bis(3‐methylpyridine)cadmium(II)]

In the structure of the title compound, [Cd₂(C₄H₄NO₄S)₂(C₆H₇N)₂], the dinuclear Cd^II complex is located on a twofold axis with two Cd²⁺ ions bridged by two oxide O atoms. Each Cd²⁺ ion is additionally coordinated in an equatorial plane by two N and three O atoms of the acesulfamate ligands and axially by two N atoms of the 3‐methylpyridine ligands, resulting in a distorted pentagonal bipyramidal coordination. We present here an example of a supramolecular assembly based on hydrogen bonds in a mixed‐ligand metal complex; intermolecular C—H...O hydrogen bonds give rise to R₄⁴(40) rings, which lead to one‐dimensional chains.     

Bis­[1,3‐bis(2‐methyl­tetrazol‐5‐yl‐κN4)­triazenido‐κN2]­nickel(II)

The title compound, [Ni(BMTT)₂], where BMTT is 1,3‐bis(2‐methyl­tetrazol‐5‐yl)­triazenide (C₄H₆N₁₁), presents a molecular complex with tridentate ligands. The tridentate mode of the ligand is realised through the central N atom of the triazene group and two N atoms of the two tetrazole rings. The [Ni(BMTT)₂] mol­ecule is the meridional isomer, with crystallographic symmetry in space group P4₂/n. The nickel centre has a distorted octahedral environment, with two axial Ni—N bonds of 2.041 (2) Å and four equatorial Ni—N bonds of 2.0739 (14) Å. The mol­ecules are linked together by van der Waals interactions only.     

Aqua(4,4′‐oxy­dibenzoato‐κO)­cadmium(II)

The Cd atom in the polymeric title compound, [Cd(C₁₄H₈O₅)(H₂O)]_n, is linked to four carboxyl O atoms and a water mol­ecule in a five‐coordinate coordination polyhedron that is midway between a square pyramid and a trigonal bipyramid. The Cd atom and the water molecules both lie on the same twofold axis and the central O atom of the 4,4′‐oxydibenzoate moiety lies on another twofold axis. Covalent Cd—O bonds lead to the formation of a layer architecture perpendicular to the twofold axis, the layers being held together by hydrogen bonds in the third direction.     

Diaquabis(4‐fluorobenzoato‐κO)bis(nicotinamide‐κN)cobalt(II)

The title compound, [Co(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂], is a three‐dimensional hydrogen‐bonded supramolecular complex. The Co^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₃²(6), R₂²(12) and R₂²(16) rings, which lead to two‐dimensional chains. An extensive three‐dimensional network of C—H...F, N—H...O and O—H...O hydrogen bonds and π–π interactions are responsible for crystal stabilization.     

Dibromo(pyridoxal semicarbazone‐κ3N1,O3,O3′)copper(II)

The title compound, di­bromo(3‐hydroxy‐5‐hydroxy­methyl‐2‐methyl‐4‐pyridine­carbox­aldehyde semicarbazone‐κ³N¹,O³,O^3′)copper(II), [CuBr₂(C₉H₁₂N₄O₃)], consists of discrete complex units with the tridentate pyridoxal semicarbazone ligand as a zwitterion in an almost planar configuration. The Cu^II ions are in a distorted square‐pyramidal coordination, with the equatorial Br atom at a distance of 2.4017 (6) Å and the apical Br atom at a distance of 2.6860 (6) Å.     

Triaqua(2,2′‐bipyridine‐κ2N,N′)(nitrato‐κO)manganese(II) nitrate

The crystal structure of the title compound, [Mn(NO₃)(C₁₀H₈N₂)(H₂O)₃]NO₃, contains a monomeric [Mn(NO₃)(bpy)(H₂O)₃]⁺ cation (bpy is 2,2′‐bi­pyridine) and a nitrate anion. The Mn^II ion is coordinated by one chelating bpy [Mn—N 2.241 (3) and 2.259 (3) Å], three water mol­ecules [Mn—O 2.120 (3)–2.188 (3) Å] and a nitrate ligand [Mn—O 2.228 (2) Å] in a distorted octahedral geometry. There are O?H—O hydrogen‐bonding interactions between the ligated water mol­ecules and the ligated and unligated nitrate anions, resulting in double columns of stacked cations and anions.     

A novel dinuclear bismuth(III) coordination compound: bis(μ‐pyridine‐2,6‐dicarboxylato)‐κ4O2,N,O6:O6′;κ4O2:O2′,N,O6‐bis[(azido‐κN)(1,10‐phenanthroline‐κ2N,N′)bismuth(III)] tetrahydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR, X‐ray photoelectron spectroscopy and single‐crystal X‐ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi^III centre is seven‐coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted pentagonal–bipyramidal (BiO₃N₄), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. Two types of π–π stacking interactions are found, with centroid‐to‐centroid distances of 3.461 (4) and 3.641 (4) Å.