RbCrIII(C2O4)2·2H2O,Cs2Mg(C2O4)2·4H2O and Rb2CuII(C2O4)2·2H2O: three new complex oxalate hydrates

Rubidium chromium(III) dioxalate dihydrate [di­aqua­bis(μ‐oxalato)­chromium(III)­rubidium(I)], [RbCr(C₂O₄)₂(H₂O)₂], (I), and dicaesium magnesium dioxalate tetrahydrate [tetra­aqua­bis(μ‐oxalato)­magnesium(II)­dicaesium(I)], [Cs₂Mg(C₂­O₄)₂(H₂O)₄], (II), have layered structures which are new among double‐metal oxalates. In (I), the Rb and Cr atoms lie on sites with imposed 2/m symmetry and the unique water molecule lies on a mirror plane; in (II), the Mg atom lies on a twofold axis. The two non‐equivalent Cr and Mg atoms both show octahedral coordination, with a mean Cr—O distance of 1.966 Å and a mean Mg—O distance of 2.066 Å. Dirubid­ium copper(II) dioxalate dihydrate [di­aqua­bis(μ‐oxalato)­copper(II)­dirubidium(I)], [Rb₂Cu(C₂O₄)₂(H₂O)₂], (III), is also layered and is isotypic with the previously described K₂‐ and (NH₄)₂Cu^II(C₂O₄)₂·2H₂O compounds. The two non‐equivalent Cu atoms lie on inversion centres and are both (4+2)‐coordinated. Hydro­gen bonds are medium‐strong to weak in the three compounds. The oxalate groups are slightly non‐planar only in the Cs–Mg compound, (II), and are more distinctly non‐planar in the K–Cu compound, (III).     

Di­aqua­bis­(di­methyl sulfoxide)­bis(3,5‐di­nitro­benzoato)­zinc(II) and the synthesis of the Cu,Ni and Co analogs

In order to model processes of chemisorption in organic salts formed between di­nitro­benzoic acids (DNBH) and secondary amines (R₂NH), a series of compounds of composition [M^II(3,5‐DNB)₂(DMSO)₂(H₂O)₂] (where M^II is Zn, Cu, Ni or Co, 3,5‐DNB is the 3,5‐di­nitro­benzoate ion, and DMSO is di­methyl sulfoxide) have been prepared. In di­aqua­bis­(di­methyl sulf­oxide)­bis(3,5‐DNB)­zinc(II), [Zn(C₇H₃N₂O₆)₂(C₂H₆OS)₂(H₂O)₂], the 3,5‐DNB ions and mol­ecules of DMSO are monodentate ligands that are coordinated to the Zn atom through their O atoms. These ligands, together with two mol­ecules of water, form a slightly distorted octahedral coordination environment for the Zn atom, which lies on a center of symmetry.     

Two 2,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le–metal complexes (M = Cu and Ni)

The reaction of the diazine ligand 3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole (pod, C₁₂H₈N₄O), with Cu(CF₃SO₃)₂ or Ni(ClO₄)₂ afforded the title complexes di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole‐N²,N³]copper(II) bis­(tri­fluoro­methane­sul­fon­ate), [Cu(pod)₂(H₂O)₂](CF₃SO₃)₂, and di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le‐N²,N³]­nickel(II) diperchlorate, [Ni(pod)₂(H₂O)₂](ClO₄)₂. Both complexes present a crystallographically centrosymmetric mononuclear cation structure which consists of a six‐coordinated Cu^II or Ni^II ion with two pod mol­ecules acting as bidentate ligands and two axially coordinated water mol­ecules.     

Three different bonding modes of cyano groups in the coordination polymer [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O (en is 1,2‐diaminoethane)

Partial reduction of the Cu^II ions in the aqueous system Cu^II–en–[Ni(CN)₄]^2? (1/1/1) (en is 1,2‐di­amino­ethane) yields a novel heterobimetallic mixed‐valence compound, poly­[[aqua­bis(1,2‐di­amino­ethane)copper(II)] [hexa‐μ‐cyano‐tetra­cyano­bis(1,2‐di­amino­ethane)­tricopper(I,II)­dinickel(II)] dihydrate], [Cu(C₂H₈N₂)₂(H₂O)][Ni₂Cu₃(CN)₁₀(C₂H₈N₂)₂]·2H₂O or [Cu(en)₂(H₂O)][Cu(en)₂Ni₂Cu₂(CN)₁₀]·2H₂O. The structure is formed by a negatively charged two‐dimensional array of the cyano complex [Cu(en)₂Ni₂Cu₂(CN)₁₀]_n^2n?, [Cu(en)₂(H₂O)]²⁺ complex cations and water mol­ecules of crystallization. These last are involved in a complicated hydrogen‐bonding system. The cyano groups act as terminal, μ₂‐bridging or μ₃‐bridging ligands.     

A host–guest complex of di­aqua­bis­[1‐hydroxy‐2(1H)‐pyridine­thionato‐O,S]­magnesium(II) and 2,2′‐di­thio­bis­(pyridine N‐oxide)

The title compound, [Mg(C₅H₄NOS)₂(H₂O)₂]·C₁₀H₈N₂O₂S₂, is a two‐component host–guest material. The 2,2′‐di­thio­bis(pyridine N‐oxide) molecule has crystallographic twofold symmetry. The metal complex lies on an inversion centre and associates via C—H?S interactions into chains which thread the 2,2′‐di­thio­bis­(pyridine N‐oxide) lattice in perpendicular directions. Hydro­gen bonds exist between the water mol­ecules of the di­aqua­magnesium units and the N—O groups of the host lattice.     

Clemizoledichlorocobalt(II)

The structure of di­chloro­[1‐(p‐chloro­benzyl)‐2‐(1‐pyrrol­idinyl­methyl‐N)‐1,3‐benz­imidazole‐N³]­cobalt(II), [Co­Cl₂(C₁₉­H₂₀ClN₃)], contains a mol­ecule of clemizole bound in a bidentate manner to cobalt through its imidazole and pyrrolidinyl N atoms, with significantly different Co—N distances of 1.976 (5) and 2.126 (5) Å, respectively. The geometry around cobalt is distorted tetrahedral, with significantly different Co—Cl distances of 2.217 (2) and 2.233 (2) Å, and the pyrrolidinyl ring is disordered.     

A three‐dimensional inorganic/organic hybrid material, [Ni2(4,4′‐bipy)3(H2O)2V4O12]·2.5H2O

The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni₂­(V₂O₆)₂­(C₁₀H₈N₂)₃­(H₂O)₂]·­2.5H₂O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V₂O₆], [Ni­(4,4′‐bipy)₄O₂] and [Ni­(H₂O)₂­(4,4′‐bipy)₂O₂] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.     

Cobalt(II) and nickel(II) complexes of isoquinoline‐1‐carboxylate

trans‐Di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­cobalt(II) dihydrate, [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, and trans‐di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­nickel(II) dihydrate, [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, contain the same isoquinoline ligand, with both metal atoms residing on a centre of symmetry and having the same distorted octahedral coordination. In the former complex, the Co—O(water) bond length in the axial direction is 2.167 (2) Å, which is longer than the Co—O(carboxylate) and Co—N bond lengths in the equatorial plane [2.055 (2) and 2.096 (2) Å, respectively]. In the latter complex, the corresponding bond lengths for Ni—O(water), Ni—O(carboxylate) and Ni—N are 2.127 (2), 2.036 (2) and 2.039 (3) Å, respectively. Both crystals are stabilized by similar stacking interactions of the ligand, and also by hydrogen bonds between the hydrate and coordinated water molecules.     

Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

Cobalt(II) and nickel(II) complexes of quinoline‐2‐carboxyl­ate

The title complexes, trans‐di­aqua­bis­(quinoline‐2‐carboxyl­ato‐κ²N,O)­cobalt(II)–water–methanol (1/2/2), [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2CH₄O·2H₂O, and trans‐di­aqua­bis­(quinoline‐2‐car­box­yl­ato‐κ²N,O)­nickel(II)–water–methanol (1/2/2), [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2CH₄O·2H₂O, are isomorphous and contain Co^II and Ni^II ions at centers of inversion. Both complexes have the same distorted octahedral coordination geometry, and each metal ion is coordinated by two quinoline N atoms, two carboxyl­ate O atoms and two water O atoms. The quinoline‐2‐carboxyl­ate ligands lie in trans positions with respect to one another, forming the equatorial plane, with the two water ligands occupying the axial positions. The complex mol­ecules are linked together by hydrogen bonding involving a series of ring patterns which include the uncoordinated water and methanol mol­ecules.     

Diaquabis(1,3‐propanediamine‐κ2N,N′)nickel(II) bis(sulfanilate)

The title compound, [Ni(C₃H₁₀N₂)₂(H₂O)₂](C₆H₆NO₃S)₂, contains alternating layers of sulfanilate anions and di­aqua­bis(1,3‐propane­di­amine)­nickel(II) cations. The Ni atom lies on an inversion centre and is hexacoordinated by the 1,3‐propane­di­amine ligands, which function as N,N′‐bidentate ligands, and the water mol­ecules, which are in a trans arrangement. The sulfanilate anions are arranged in layers, with the sulfonate and amine groups directed towards opposite sides of the layer. The structure is stabilized by a network of hydrogen bonding between the O and N atoms of the sulfanilate anions, the water mol­ecules, and the N atoms of the 1,3‐propane­di­amine ligands.     

Three monoalkoxy‐substituted nido‐platinaboranes: [(PPh3)2PtB10H11‐8‐(OCH3)], [(PPh3)2PtB10H11‐8‐{OCH(CH3)2}] and [(PPh3)2PtB10H10‐9‐{OCH(CH3)2}]

Each of the title compounds, 8‐methoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane hemisolvate, [Pt(CH₁₄B₁₀O)(C₁₈H₁₅P)₂]·0.5CH₂Cl₂, (I), 8‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (II), and 9‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (III), has an 11‐vertex nido polyhedral skeleton, with the 7‐platinum centre ligating to two exo‐polyhedral PPh₃ groups and an alkoxy‐substituted polyhedral borane ligand. Compounds (II) and (III) are isomers. The Pt—B distances are in the range 2.214 (7)–2.303 (7) Å for (I), 2.178 (16)–2.326 (16) Å for (II) and 2.205 (6)–2.327 (6) Å for (III).     

1:2 Complexes of chloranilic acid with pyrazole and imidazole,and the aceto­nitrile solvate of a 1:1 complex with imidazole

2,5‐Di­chloro‐3,6‐di­hydroxy‐1,4‐benzo­quinone (chloranilic acid) forms X—H?Y (X, Y = N or O) and C—H?Cl hydrogen bonds with pyrazole and imidazole to afford bis­(pyrazolium) di­chloro­anilate and bis­(imidazolium) di­chloro­anilate, (I) and (II), both 2C₃H₅N₂⁺·C₆Cl₂O₄^2?, and imidazolium chloro­anilate aceto­nitrile solvate, C₃H₅N₂⁺·­C₆HCl₂O₄^?·C₂H₃N, (III). Their crystal structures demonstrate three novel supramolecular architectures based on supramolecular synthons to build a ladder, (I), a two‐dimensional network, (II), and a flat ribbon, (III).     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

The effects of substitution on tetrakis­(substituted imidazole)­copper(II) tri­fluoro­methane­sulfonates

The organic ligands 4‐methyl‐1H‐imidazole and 2‐ethyl‐4‐methyl‐1H‐imidazole react with Cu(CF₃SO₃)₂·6H₂O to give tetrakis(5‐methyl‐1H‐imidazole‐κN³)­cop­per(II) bis­(tri­fluoro­methane­sulfonate), [Cu(C₄H₆N₂)₄](CF₃SO₃)₂, and aqua­tetrakis(2‐ethyl‐5‐methyl‐1H‐imidazole‐κN³)copper(II) bis(tri­ fluoro­methane­sulfonate), [Cu(C₆H₁₀N₂)₄(H₂O)](CF₃SO₃)₂. In the former, the Cu atom has an elongated octahedral coordination environment, with four imidazole rings in equatorial positions and two tri­fluoro­methane­sulfonate ions in axial positions. This conformation is similar to those in the analogous complexes tetrakis­(imidazole)­cop­per(II) tri­fluoro­methane­sulfonate and tetrakis(2‐methyl‐1H‐imidazole)­cop­per(II) tri­fluoro­methane­sulfonate. In the second of the title compounds, the ethyl groups block the central Cu atom, and a square‐pyramidal coordination environment is formed around the Cu atom, with the substituted imidazole rings in the basal positions and a water mol­ecule in the axial position.     

[Fe(C12H8N3O2)Cl2(ROH)], with R = Me and Et

The title octahedral complexes, [bis(pyridine‐2‐carbonyl)­amin­ate]­di­chloro­(methanol)­iron(III), [Fe(C₁₂H₈N₃O₂)­Cl₂‐(CH₄O)], and [bis­(pyri­dine‐2‐carbonyl)­amin­ate]­di­chloro‐(ethanol)­iron(III), [Fe­(C₁₂H₈N₃O₂)Cl₂(C₂H₆O)], both crystallize in space group and have similar structures. Mono­anionic bpca^? [bis(pyridine‐2‐carbonyl)­amin­ate] acts as a planar tridentate ligand in both cases. Coordination bond distances are in the range typical of high‐spin Fe^III complexes. Carbon–oxygen distances are typical of a C=O double bond suggesting the negative charge of the bpca^? ligand is localized on the central N atom.     

The nitrate dihydrate of an aqua­dicopper(II) complex cation with guanidino­acetic acid and a novel trianionic disubstituted guanidine as ligands at 120 K

The structure of the title compound, aqua­[μ‐(N¹‐carboxylato­methyl­guanidino)­oxidoacetato](μ‐guanidino­acetic acid)­di­copper(II) nitrate dihydrate, [Cu₂(C₅H₆N₃O₅)(C₃H₇N₃O₂)(H₂O)]NO₃·2H₂O, contains two enantiomers of the di­copper(II) complex cation that comprise water, neutral zwitterionic guanidino­acetic acid and the trianion of (N¹‐carboxy­methyl­guanidino)­hydroxy­acetic acid as ligands. Extensive hydrogen bonding creates three‐dimensional connectivity but is largely confined to layers that each contain both cation enantiomers. These layers are related to one another by crystallographic symmetry and are therefore identical in composition and connectivity.     

Di­chloro­(norborna­diene)­platinum(II): a comparison with di­chloro­(cyclo­octa­diene)­platinum(II)

The crystal structure of the title compound, (bi­cyclo­[2.2.1]­hepta‐2,5‐diene)­di­chloro­platinum(II), [PtCl₂(C₇H₈)], has been determined from single‐crystal X‐ray analysis. The coordination sphere about the Pt atom is pseudo‐square planar, with shorter Pt—C distances than in the corresponding di­chloro­(cyclo­octa­diene)­platinum(II) complex.     

Three novel non‐centrosymmetric compounds of glycine: glycine lithium sulfate,glycine nickel dichloride dihydrate and glycine zinc sulfate trihydrate

The crystal structures of three compounds of glycine and inorganic materials are presented and discussed. The ortho­rhombic structure of glycinesulfatodilithium(I), [Li₂(SO₄)(C₂H₅NO₂)]_n, consists of corrugated sheets of [LiO₄] and [SO₄] tetrahedra. The glycine mol­ecules are located between these sheets. The main features of the monoclinic structure of di­aqua­di­chloro­glycinenickel(II), [NiCl₂(C₂H₅NO₂)(H₂O)₂]_n, are helical chains of [NiO₄Cl₂] octahedra connected by glycine mol­ecules. The orthorhombic structure of tri­aqua­glycinesulfatozinc(II), [Zn(SO₄)(C₂H₅NO₂)(H₂O)₃]_n, is made up of [O₃SOZnO₅] clusters. These clusters are linked by glycine mol­ecules into zigzag chains. All three compounds are examples of non‐centrosymmetric glycine compounds.     

The first X‐ray structure of a hexa­ammine­cobalt(III) salt with two different complex chloro­cadmium anions: synthesis,characterization and crystal structure of [Co(NH3)6]4[CdCl6][CdCl4(SCN)(H2O)]2Cl2·2H2O

In the title complex salt, tetra­kis[hexa­ammine­cobalt(III)] hexa­chloro­cadmate(II) bis­[aqua­tetra­chloro­thio­cyanato­cad­mate(II)] dichloride dihydrate, the discrete ions, i.e. [Co(NH₃)₆]³⁺, Cl⁻, [CdCl₆]⁴⁻ (located on an inversion centre) and [CdCl₄(SCN)(H₂O)]³⁻, together with cocrystallized water mol­ecules, are assembled by means of a network of hydrogen‐bonding inter­actions. This is the first X‐ray structure determination of a hexa­amminecobalt(III) salt with two different complex chloro­cadmium anions.