Potassium bis(ethylenediamine)­copper(II) ferricyanide

The title compound, potassium bis(ethylenediamine‐N,N′)copper(II) hexacyanoferrate(III), K[Cu(C₂H₈N₂)₂]‐[Fe(CN)₆], contains [Cu(en)₂]²⁺ and [Fe(CN)₆]^3? complex ions, where en is ethylenediamine. The Fe^III and K⁺ ions lie on twofold axes and the Cu^II atom lies on an inversion center. The [Cu(en)₂]²⁺ ion has square‐planar coordination with a mean Cu—N distance of 1.992 (2) Å and the [Fe(CN)₆]^3? ion has distorted octahedral coordination with a mean Fe—C distance of 1.947 (2) Å.     

Self‐assembly of a one‐dimensional iron(II) coordination polymer with p‐phenylenebis(picolinaldimine)

catena‐Poly[[[dichloridoiron(II)]‐μ‐N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine] methanol disolvate], [FeCl₂(C₁₈H₁₄N₄)]·2CH₃OH, forms a one‐dimensional coordination polymer. The polymeric chains run parallel to the c axis. O—H...Cl—Fe and C—H...O hydrogen‐bonding interactions with methanol solvent molecules stabilize the open supramolecular framework. Each Fe^II atom adopts an octahedral geometry coordinated by four N atoms from two N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine ligands and completed by two cis Cl atoms. The compound has C₂ (and C_i) molecular symmetry, which is coincident with the crystallographic twofold symmetry at (0, y, ). The one‐dimensional structure is propagated via the crystallographic inversion center located at the benzene ring centroid (0, , 0).     

Synthesis and characterization of (cryptand‐222)potassium (2‐methylimidazolato)(meso‐tetraphenylporphinato)ferrate(II)–2‐methylimidazole–tetrahydrofuran (1/1/2)

Metalloporphyrin complexes containing an additional imidazole ligand can provide information about the effect of deprotonation or hydrogen bonding on the axial histidine unit in heme proteins. The title high‐spin five‐coordinate imidazolate‐ligated iron(II) porphyrinate, [K(C₁₈H₃₆N₂O₆)][Fe(C₄H₅N₂)(C₄₄H₂₈N₄)]·C₄H₆N₂·2C₄H₈O, has been synthesized and investigated. The solvated salt crystallizes with one 2‐methylimidazole molecule, two tetrahydrofuran solvent molecules and a potassium cation chelated inside a cryptand‐222 (4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) molecule. The imidazolate ligand is ordered. The average Fe—Np (Np is a porphyrin N atom) bond length is 2.113 (11) Å and the axial Fe—N_Im (N_Im is an imidazolate N atom) is 2.0739 (13) Å. The out‐of‐plane displacement of the Fe^II atom from the 24‐atom mean plane is 0.6098 (5) Å, indicating an apparent doming of the porphyrin core.     

Di­chloro­(methanol‐κO)[(methoxy)tris(1‐methyl‐1H‐imidazol‐2‐yl)­methane‐κ2N3]­iron(II) (ca 153 K)

In the quasi‐trigonal–bipyramidal environment of the five‐coordinate Fe^II atom in the title compound, [FeCl₂(C₁₄H₁₈N₆O)(CH₄O)], the methanol and one of the N‐atom donors of the potentially tridentate ligand are disposed axially: Fe—N(axial) is 2.149 (2) Å, Fe—N(equatorial) is 2.108 (2) Å and N—Fe—O is 174.14 (7)°.     

Tris(1,10‐phenanthroline‐κ2N,N′)iron(II) bis(2,4,5‐tricarboxybenzoate) monohydrate and tris(2,2′‐bipyridine‐κ2N,N′)iron(II) 2,5‐dicarboxybenzene‐1,4‐dicarboxylate–benzene‐1,2,4,5‐tetracarboxylic acid–water (1/1/2)

The title compounds, tris(1,10‐phenanthroline‐κ²N,N′)iron(II) bis(2,4,5‐tricarboxybenzoate) monohydrate, [Fe(C₁₂H₈N₂)₃](C₁₀H₅O₈)₂·H₂O, (I), and tris(2,2′‐bipyridine‐κ²N,N′)iron(II) 2,5‐dicarboxybenzene‐1,4‐dicarboxylate–benzene‐1,2,4,5‐tetracarboxylic acid–water (1/1/2), [Fe(C₁₀H₈N₂)₃](C₁₀H₄O₈)·C₁₀H₆O₈·2H₂O, (II), were obtained during an attempt to synthesize a mixed‐ligand complex of Fe^II with an N‐containing ligand and benzene‐1,2,4,5‐tetracarboxylic acid via a solvothermal reaction. In both mononuclear complexes, each Fe^II metal ion is six‐coordinated in a distorted octahedral manner by six N atoms from three chelating 1,10‐phenanthroline or 2,2′‐bipyridine ligands. In compound (I), the Fe^II atom lies on a twofold axis in the space group C2/c, whereas (II) crystallizes in the space group P2₁/n. In both compounds, the uncoordinated carboxylate anions and water molecules are linked by typical O—H...O hydrogen bonds, generating extensive three‐dimensional hydrogen‐bond networks which surround the cations.     

The infinite double‐stranded chain polymer catena‐poly­[[bis­(dicyan­amido)­zinc(II)]‐di‐μ‐1,2‐bis(1,2,4‐triazol‐1‐yl)­ethane‐κ4N4:N4′]

The coordination geometry of the Zn^II atom in the title complex, [Zn(C₂N₃)₂(C₆H₈N₆)₂]_n or [Zn(dca)₂(bte)₂]_n, where bte is μ‐1,2‐bis(1,2,4‐triazol‐1‐yl)­ethane and dca is dicyan­amide, is distorted compressed octahedral, in which the Zn^II atom lies on an inversion center and coordinates four N atoms from the triazole rings of four symmetry‐related bte ligands and two N atoms from two symmetry‐related monodentate dca ligands. The structure is polymeric, with 18‐membered spiro‐fused rings extending in the b direction and each 18‐membered ring involving two inversion‐related bte mol­ecules.     

A novel two‐dimensional nickel(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene and azide ligands

The coordination geometry of the Ni^II atom in the title complex, poly[diazidobis[μ‐1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene‐κ²N⁴:N^4′]nickel(II)], [Ni(N₃)₂(C₁₂H₁₂N₆)₂]_n, is a distorted octahedron, in which the Ni^II atom lies on an inversion centre and is coordinated by four N atoms from the triazole rings of two symmetry‐related pairs of 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene (bbtz) ligands and two N atoms from two symmetry‐related monodentate azide ligands. The Ni^II atoms are bridged by four bbtz ligands to form a two‐dimensional (4,4)‐network.     

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[[[(benzene‐1,3,5‐tricarboxylic acid)(1,10‐phenanthroline)cadmium(II)]‐μ‐oxalato] 1H‐benzotriazole solvate monohydrate]

In the title compound, [Cd(C₂O₄)(C₁₂H₈N₂)(C₉H₆O₆)]·C₆H₅N₃·H₂O, the Cd^II atom has a distorted pentagonal–bipyramidal geometry, defined by two N atoms and five O atoms from bidentate 1,10‐phenanthroline ligands, oxalate ligands and benzene‐1,3,5‐tricarboxylic acid ligands. The oxalate ligands in the asymmetric unit possess inversion symmetry. The triazole molecule is not coordinated to the Cd atom. The structure of the title compound features a one‐dimensional chain running along the crystallographic a axis, and a three‐dimensional supramolecular network is formed via aromatic π–π interactions and hydrogen‐bonding interactions.     

μ‐Oxo‐bis{[(6‐hydroxy­methyl‐2‐pyridyl­methyl)­bis(2‐pyridyl­methyl)­amine‐κ5N,N′,N′′,N′′′,O]­iron(III)} tetrakis­(perchlorate)

The novel μ‐oxo‐diiron complex [Fe₂O(BPHPA)₂](ClO₄)₄ [BPHPA is (6‐hydroxy­methyl‐2‐pyridyl­methyl)­bis(2‐pyridyl­methyl)­amine, C₁₉H₂₀N₄O], contains a binuclear centrosymmetric [Fe₂O(BPHPA)₂]⁴⁺ cation (the bridging O atom lies on an inversion centre) and four perchlorate anions. Each iron ion is coordinated by four N atoms [Fe—N = 2.117 (5)–2.196 (5) Å] and one O atom [Fe—O = 2.052 (5) Å] from a BPHPA ligand, and by one bridging oxo atom [Fe—O = 1.7896 (9) Å], forming a distorted octahedron. There are hydrogen bonds between the hydroxy group and perchlorate O atoms [O—H·O = 2.654 (7) Å].     

Tris{bis­[hydro­tris(1‐pyrazolyl)­borato‐κ3N2,N2′,N2′′]iron(III)} hexaiso­thio­cyanato­iron(III)

The title compound, [Fe(C₉H₁₀BN₆)₂]₃[Fe(NCS)₆] or [Fe^III(Tp)₂]₃[Fe^III(NCS)₆] [Tp is hydro­tris(1‐pyrazolyl)­borate], crystallizes in space group ; the asymmetric unit comprises one‐half of an [Fe(Tp)₂]⁺ cation, with its Fe atom on a crystallographic inversion centre, and one‐sixth of an [Fe(NCS)₆]³⁻ anion, on a site of symmetry. The anions and cations are stacked into a three‐dimensional supramolecular aggregate via two distinct types of weak C—H⋯π interactions.     

A novel two‐dimensional cobalt(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene

In the crystal structure of the title complex, poly­[[di­azidocobalt(II)]‐di‐μ‐1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene‐κ⁴N⁴:N^4′], [Co(N₃)₂(bbtz)₂]_n, where bbtz is 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene (C₁₂H₁₂N₆), the Co^II atom, which lies on an inversion centre, is six‐coordinated by four N atoms from four bbtz ligands and by two N atoms from two azide ligands, in a distorted octahedral coordination environment. The Co^II atoms are bridged by four bbtz ligands to form a two‐dimensional [4,4]‐network.     

Bis[bis­(2‐pyridylcarbon­yl)­aminato]­iron(III) perchlorate acetonitrile disolvate

The title compound, [Fe(C₁₂H₈N₃O₂)₂]ClO₄·2C₂H₃N, contains Fe^III in a distorted octa­hedral coordination environment, with the Fe—N(pyridine) bonds significantly longer than the Fe—N(amine) bonds. The crystal packing involves a bifurcated C—H⋯(O,O) contact that is also found in all other [M(C₁₂H₈N₃O₂)₂] complexes reported previously.     

Bis{μ‐2‐[3‐(cyclo­hexyl­ammonio)­propyl­imino­methyl]­phenolato}bis­[di­chloro­copper(II)]

The title compound, [Cu₂(C₁₆H₂₄N₂O)₂Cl₄], is a dinuclear copper(II) complex with inversion symmetry. Each Cu^II atom is five‐coordinated by two O and one N atom from two Schiff base ligands, and by two Cl atoms, giving an approximately trigonal–bipyramidal coordination environment.     

catena‐Poly[[diaquadiisothiocyanatoiron(II)]‐μ‐4,4′‐bi‐1,2,4‐triazole]: a one‐dimensional coordination polymer

In the title complex, [Fe(NCS)₂(C₄H₂N₆)₂(H₂O)₂]_n, the Fe^II atom is on an inversion centre and the 4,4′‐bi‐1,2,4‐triazole (btr) group is bisected by a twofold axis through the central N—N bond. The coordination geometry of the Fe^II atom is elongated distorted FeN₄O₂ octahedral, where the cation is coordinated by two N atoms from the triazole rings of two btr groups, two N atoms from NCS⁻ ligands and two water molecules. Btr is a bidentate ligand, coordinating one Fe^II atom through a peripheral N atom of each triazole ring, leading to a one‐dimensional polymeric (chain) structure extending along [101]. The chains are further connected through a network of O—H...N and C—H...S hydrogen bonds.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

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.     

Bis­[tris(2,2′‐bi­pyridine‐κ2N,N′)­ruthenium(II)] hexa­cyano­ferrate(III) chloride octahydrate

In the title compound, [Ru^II(C₁₀H₈N₂)₃]₂[Fe^III(CN)₆]Cl·8H₂O, the [Ru(bpy)₃]²⁺ (bpy is 2,2′‐bi­pyridine) cations and water mol­ecules afford intriguing microporous honeycomb layers, while the [Fe(CN)₆]³⁻ anions and the remainder of the water mol­ecules form anionic sheets based on extensive hydrogen‐bonding networks. The cationic and anionic layers alternate along the c axis. The Fe atom in [Fe(CN)₆]³⁻ lies on an inversion centre and the axial cyano ligands are hydrogen bonded to the water mol­ecules encapsulated within the micropores [N⋯O = 2.788 (5) Å], giving an unusual interpenetration between the cationic and anionic layers. On the other hand, the in‐plane cyano ligands are relatively weakly hydrogen bonded to the water mol­ecules [N⋯O = 2.855 (7) and 2.881 (8) Å] within the anionic sheets.     

Tris[2‐(1,3‐thiazol‐2‐yl‐κN)‐1H‐benzimidazole‐κN3]zinc(II) dinitrate ethanol hemisolvate monohydrate at 100 K

The Zn^II center in the dicationic complex of the title compound, [Zn(C₁₀H₇N₃S)₃](NO₃)₂·0.5C₂H₅OH·H₂O, is in a distorted octahedral environment with imperfect noncrystallographic C₃ symmetry. Each 2‐(1,3‐thiazol‐2‐yl)‐1H‐benzimidazole ligand coordinates in a bidentate manner, with the Zn—N(imidazole) bond lengths approximately 0.14 Å shorter than the Zn—N(thiazole) bond lengths. Charge‐assisted hydrogen bonds connect cations, anions and water molecules. A lattice void is occupied by an ethanol solvent molecule disordered about a crystallographic inversion center and π‐stacking is observed between one type of symmetry‐related benzene rings.     

catena‐Poly­[[di­aqua­di­chloro­iron(II)]‐μ‐1,4‐dioxane‐κ2O:O′]

The crystal structure of the title compound, [FeCl₂(C₄H₈O₂)(H₂O)₂]_n, contains six‐coordinate Fe^II atoms in approximately octahedral environments. The Fe^II atoms have symmetry, i.e. all pairs of identical ligands are trans. The structure consists of polymeric chains made up of dioxane mol­ecules, in the chair conformation with symmetry, linking the Fe^II centers. The chains are crosslinked by O—H?Cl hydrogen bonds.