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).     

Na2Co(H2PO4)4·4H2O

In the title compound, disodium cobalt tetrakis­(dihydrogen­phosphate) tetrahydrate, the Co^II ion lies on an inversion centre and is octahedrally surrounded by two water molecules and four H₂PO₄ groups to give a cobalt complex anion of the form [Co(H₂PO₄)₄(OH₂)]^2?. The three‐dimensional framework results from hydrogen bonding between the anions. The relationship with the structures of Co(H₂PO₄)₂·2H₂O and K₂CoP₄O₁₂·5H₂O is discussed.     

K2[Mo2O4(C2O4)2(H2O)2]·3H2O

The crystal and molecular structure of dipotassium di‐μ‐oxo‐bis[aqua(oxalato‐O¹,O²)oxomolybdenum(III)] trihydrate, K₂­[Mo₂O₄(C₂O₄)₂(H₂O)₂]·3H₂O, has been determined from X‐ray diffraction data. In the dimeric anion, which has approximate twofold symmetry, each Mo atom is in a distorted octahedral coordination, being bonded to one terminal oxo‐O atom, two bridging O atoms, two O atoms from the oxalato ligand and one from the water mol­ecule. Bond lengths trans to the multiple‐bonded terminal oxo ligand are larger than those in the cis position, confirming the trans influence as a generally valid rule.     

Two saccharinate complexes: [Mn(phen)2(sac)(H2O)]+·sac– and [Co(bipy)2(sac)(H2O)]+·sac–

The title saccharinate complexes, aqua[1,2‐benzisothiazol‐3(2H)‐onato 1,1‐dioxide‐N]bis(1,10‐phenanthroline‐N,N′)man­ganese(II) 1,2‐benz­isothia­zol‐3(2H)‐onate 1,1‐dioxide,[Mn(C₇H₄NO₃S)(C₁₂H₈N₂)₂(H₂O)](C₇H₄NO₃S), and aqua[1,2‐benz­iso­thiazol‐3(2H)‐onato 1,1‐dioxide‐N]­bis­(2,2′‐bi­pyri­dine‐N,N′)­cobalt(II) 1,2‐benz­iso­thia­zol‐3(2H)‐onate 1,1‐di­oxide, [Co­(C₇H₄NO₃S)­(C₁₀H₈N₂)₂­(H₂O)]­(C₇H₄NO₃S), have been prepared and their crystal structures determined at 150 K. The structure of the manganese complex consists of repeated alternating [Mn(phen)₂(sac)(H₂O)]⁺ cations and non‐coordinated saccharinate anions. The water molecule, bound to manganese as part of a slightly distorted octahedral arrangement, is hydrogen bonded to an O atom of the SO₂ group in the saccharinate counter‐ion. In contrast, the cobalt complex has one pseudo‐octahedral [Co(bipy)₂(sac)(H₂O)]⁺ cation, with the cobalt‐bound water molecule hydrogen bonded to the N atom of the accompanying free saccharinate anion.     

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).     

A layered fluorinated gallium phosphate organically templated by propane‐1,3‐diaminium,an analog of the aluminophosphate MIL‐12: Ga2(PO4)F5·C3H12N2

Crystals of the oxyfluorinated gallium phosphate MIL‐12 (digallium phosphate penta­fluoride propane‐1,3‐diaminium), (C₃H₁₂N₂)[Ga₂(PO₄)F₅], were synthesized hydro­thermally at 453 K under autogenous pressure using propane‐1,3‐diamine as the structure‐directing agent. The title compound is isomorphous with the aluminium phosphate having the MIL‐12 structural type. The structure is built up from a two‐dimensional anionic network inter­calated by the diamine species. The inorganic layer is composed of corner‐linked GaO₂F₄ octa­hedra and PO₄ tetra­hedra. The diprotonated diamine group is located on a mirror plane, between the inorganic sheets, and inter­acts preferentially via hydrogen bonding through the ammonium groups and the terminal F and bridging O atoms of the inorganic layer. One of the Ga atoms lies on an inversion centre and the other lies on a mirror plane, as does the P atom, two of the phosphate O atoms and one of the F atoms.     

[Yb(H2O)8][Cd3Cl9(H2O)]·6H2O

The title compound, namely octa­aqua­ytterbium(III) aqua­nona­chloro­tricadmate(II) hexa­hydrate, [Yb(H₂O)₈][Cd₃Cl₉(H₂O)]·6H₂O, was prepared by evaporation at 278 K from an aqueous solution of the ternary system YbCl₃–CdCl₂–H₂O and was characterized by elemental chemical analysis and by X‐ray powder and single‐crystal diffraction studies. The crystal structure can be viewed as being built from layers of double chains of CdCl₆ and CdCl₅(H₂O) octahedra separated by antiprismatic [Yb(H₂O)₈]³⁺ cations. The stabilization of the structure is ensured by O—H⋯O and O—H⋯Cl hydrogen bonds. A comparison with the structures of SrCd₂Cl₆·8H₂O and CeCd₄Cl₁₁·13H₂O is presented.     

{[Ca5(C8H4O4)5(H2O)9]·8H2O}n: the first crystallographically characterized non‐transition metal salt of isophthalic acid

The reaction of CaCO₃ with isophthalic acid in water yields nona­aqua­penta‐μ‐isophthalato‐pentacalcium octahydrate, {[Ca₅(C₈H₄O₄)₅(H₂O)₉]·8H₂O}_n, a complex polymeric one‐dimensional column structure bearing metal–carboxyl­ate bonds and Ca‐bound terminal and bridging water mol­ecules, in addition to hydrogen‐bonded water mol­ecules of crystallization. The asymmetric unit comprises half of the formula unit, with one Ca²⁺ ion located on a twofold axis, and contains 16 unique strong O—H⋯O hydrogen bonds, some of which link the columns together.     

NaIn(CrO4)2·2H2O,the first indium(III) member of the kröhnkite family

Sodium indium(III) chromate(VI) dihydrate, NaIn(CrO₄)₂·2H₂O, synthesized from an aqueous solution at room temperature, is the first indium(III) member of the large family of compounds with kröhnkite [Na₂Cu^II(S^VIO₄)₂·2H₂O]‐type chains. The crystal structure is based on infinite octa­hedral–tetra­hedral [In(CrO₄)₂(H₂O)₂]⁻ chains along [010], linked via charge‐balancing Na⁺ cations. The slightly distorted InO₄(H₂O)₂ octa­hedra are characterized by a mean In—O distance of 2.125 Å. The CrO₄ tetra­hedra are strongly distorted (mean Cr—O = 1.641 Å). The Na atom shows an octa­hedral coordination, unprecedented among compounds with kröhnkite‐type chains. The NaO₆ octa­hedra share opposite edges with the InO₄(H₂O)₂ octa­hedra to form infinite [001] chains. The hydrogen bonds are of medium strength. NaIn(CrO₄)₂·2H₂O belongs to the structural type F2 in the classification of Fleck, Kolitsch & Hertweck [Z. Kristallogr. (2002), 217 , 435–443], and is isotypic with KAl(CrO₄)₂·2H₂O and MFe(CrO₄)₂·2H₂O (M = K, Tl or NH₄). All atoms are in special positions except one O atom.     

A hydrated ethyl­ene­di­ammonium salt of a new polymeric polyoxoanion: (H2en)4[Co(H2O)2(OH)2(VO)6(HPO4)4(PO4)4]·3H2O

The title compound, tetrakis­(ethyl­enedi­ammonium) tetra‐μ‐hydrogenphosphato‐di‐μ‐hydro­xo‐ tetra‐μ‐phosphato‐bis­(aqua­cobalt)­hexakis­(oxovanadium) trihydrate, was synthesized hydro­thermally at moderate temperature. The structure consists of diprotonated ethyl­enedi­ammonium cations and layers of the polyanions. The polyanion contains four PO₄ tetrahedra and three VO₅ square pyramids that are linked through corner‐sharing by alternating P—O—V, which gives rise to a chain. The chains, connected by CoO₄(H₂O)₂ octahedra, form layers, resulting in a two‐dimensional layered structure. The Co—O distances are in the range 1.984 (3)–2.038 (4) Å, the P—O distances 1.508 (3)–1.575 (3) Å and the V—O distances 1.585 (3)–2.010 (3) Å.     

Octa­hedral–tetra­hedral framework structures of InAsO4·H2O and PbIn(AsO4)(AsO3OH)

Indium arsenate(V) monohydrate, InAsO₄·H₂O, (I), crystallizes in the structure type of MnMoO₄·H₂O. The structure is built of In₂O₈(H₂O)₂ dimers (mean In—O = 2.150 Å) corner‐linked to slightly distorted AsO₄ tetra­hedra (mean As—O = 1.686 Å). The linkage results in a three‐dimensional framework, with small voids into which the apical water ligand of the InO₅(H₂O) octa­hedron points. The hydrogen bonds in (I) are of medium strength. Lead(II) indium arsenate(V) hydrogen arsenate(V), PbIn(AsO₄)(AsO₃OH), (II), represents the first reported lead indium arsenate. It is characterized by a framework structure of InO₆ octa­hedra corner‐linked to AsO₄ and AsO₃OH tetra­hedra. The resulting voids are occupied by Pb₂O₁₀(OH)₂ dimers built of two edge‐sharing highly distorted PbO₆(OH) polyhedra (mean Pb—O = 2.623 Å). The compound is isotypic with PbFe^III(AsO₄)(AsO₃OH). The average In—O bond length in (II) is 2.157 Å. In both arsenates, all atoms are in general positions.     

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.     

CsGa(H1.5AsO4)2(H2AsO4) and isotypic CsCr(H1.5AsO4)2(H2AsO4): decorated kröhnkite‐like chains in two unusual hydrogen arsenates

Hydro­thermally synthesized caesium gallium(III) hydrogen arsenate(V), CsGa(H_1.5AsO₄)₂(H₂AsO₄), (I), and isotypic caesium chromium(III) hydrogen arsenate(V), CsCr(H_1.5AsO₄)₂(H₂AsO₄), (II), represent a new structure type and stoichiometry among M^I–M^III hydrogen arsenates. The crystal structure, determined from single‐crystal X‐ray diffraction data, is based on an infinite octa­hedral–tetra­hedral chain and can be described as a decorated kröhnkite‐like chain. The chains extend parallel to [100] and are separated by ten‐coordinated Cs atoms. The hydrogen‐bonding scheme comprises one very short symmetry‐restricted hydrogen bond, with O⋯O distances of 2.519 (4) and 2.508 (4) Å in (I) and (II), respectively, and two further medium–strong hydrogen bonds, all of which reinforce the connections between adjacent chains. The average Ga—O and Cr—O bond lengths are 1.973 (15) and 1.980 (13) Å, respectively, and the average As—O bond lengths in the two protonated arsenate groups lie within a very narrow range [1.690 (18)–1.69 (3) Å]. The Cs atom is located on a centre of inversion, while the M^III and As2 atoms lie on twofold axes. Relationships to CaBa₂(HPO₄)₂(H₂PO₄)₂ and other compounds containing decorated kröhnkite‐type or kröhnkite‐like chains are discussed.     

Ca[Ag2(SCN)4]·2H2O

Calcium tetra­thio­cyanato­diargentate(I) dihydrate, Ca[Ag₂(SCN)₄]·2H₂O, contains eight‐membered Ag₄S₄ rings bonded together through shared atoms to form layers parallel to (100). The thio­cyanate groups link the layers to Ca–O chains running parallel to the c axis. The Ca atom is located on a twofold rotation axis parallel to b and is surrounded by four water molecules of crystallization and four thio­cyanate N atoms in a distorted square antiprism.     

A novel gallium arsenate organically templated by propane‐1,3‐diyldi­ammonium with a ULM‐3‐type open framework: [Ga3(AsO4)3(OH)F](C3H12N2)·H2O

Crystals of the title oxy­fluorinated gallium arsenate, viz. tris­(arsenato)­fluoro­hydro­xotrigallium ­propane‐1,3‐diyldiammonium monohydrate, were synthesized hydro­thermally at 453 K under autogenous pressure, using 1,3‐di­amino­propane as the structure‐directing agent. The solid crystallizes in the ortho­rhombic system and its structure was determined from single‐crystal X‐ray diffraction analysis. The structure is similar to that of gallium or aluminium phosphates with the ULM‐3 structural type and is built up from a three‐dimensional anionic framework composed of corner‐linked hexameric Ga₃(AsO₄)₃(OH)F units. The Ga atoms have an octahedral [GaO₄(OH)F] or trigonal‐bipyramidal [GaO₄(OH) and GaO₄F] coordination. These units are connected to one another and to the tetrahedral AsO₄ groups via OH or F bridges. The three‐dimensional framework contains ten‐ring channels along [010], crosslinked by eight‐ring channels along [110] and [10]. The diprotonated organic species and water mol­ecules reside within the ten‐ring channels. The cation is linked to the framework via an N—H⋯F hydrogen bond. A strong N—H⋯O hydrogen bond links the cation and the water mol­ecule.     

A monoclinic polymorph of uranyl dinitrate trihydrate, [UO2(NO3)2(H2O)2]·H2O

Di­aqua­dinitratouranyl(VI) monohydrate is monoclinic (space group P2₁/c), in contrast to its triclinic polymorph. The main building block of the structure is the finite non‐centrosymmetric [UO₂(NO₃)₂(H₂O)₂] cluster, which is a uranyl hexag­onal bipyramid that shares two non‐opposite equatorial edges with the nitrate triangles, such that the two water mol­ecules are at neighbouring equatorial vertices. There is an interstitial water site in the structure, which is located between adjacent [UO₂(NO₃)₂(H₂O)₂] clusters.     

Synthetic mansfieldite,AlAsO4·2H2O

Hydro­thermally prepared mansfieldite, AlAsO₄·2H₂O (aluminium arsenate dihydrate), contains a vertex‐sharing three‐dimensional network of cis‐AlO₄(H₂O)₂ octahedra and AsO₄ tetrahedra [d_av(Al—O) = 1.907 (2) Å, d_av(As—O) = 1.685 (2) Å and θ_av(Al—O—As) = 134.5 (1)°].     

NEt4OH·4H2O containing infinite hydro­xide–water ribbons

In tetraethyl­ammonium hydro­xide tetrahydrate, C₈H₂₀N⁺·­OH^?·­4H₂O, the array of mirror symmetric NEt₄⁺ cations gives rise to a system of parallel channels which are filled with hydrogen‐bonded anionic ribbons. The central part of each ribbon is constituted by a [OH^?(HOH)_4/2] spiro‐chain, with each hydro­xide ion accepting four strong linear hydrogen bonds [d(O?O) between 2.692 (1) and 2.727 (1) Å] but donating none. Additional (two‐coordinate) H₂O mol­ecules bridge between the (four‐coordinate) H₂O mol­ecules of the spiro‐chain [d(O?O) between 2.831 (1) and 2.835 (1) Å].     

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.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.