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.     

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 new soluble iron–oxo complexes: [Fe2(μ‐O)(μ‐O2CCF3)2(O2CCF3)2(C10H8N2)2] and [Fe4(μ3‐O)2(μ‐O2CCF3)6(O2CCF3)2(C10H8N2)2]·CF3CO2H

Two new iron–oxo clusters, viz. di‐μ‐tri­fluoro­acetato‐μ‐oxo‐bis­[(2,2′‐bi­pyridine‐κ²N,N′)(tri­fluoro­acetato‐κO)­iron(III)], [Fe₂O(CF₃CO₂)₄(C₁₀H₈N₂)₂], and bis(2,2′‐bi­pyridine)­di‐μ₃‐oxo‐hexa‐μ‐tri­fluoro­acetato‐bis­(tri­fluoro­acetato)­tetrairon(III) tri­fluoro­acetic acid solvate, [Fe₄O₂(CF₃CO₂)₈(C₁₀H₈N₂)₂]·CF₃CO₂H, contain dinuclear and tetranuclear Fe^III cores, respectively. The Fe^III atoms are in distorted octahedral environments in both compounds and are linked by oxide and tri­fluoro­acetate ions. The tri­fluoro­acetate ions are either bridging (bidentate) or coordinated to the Fe^III atoms via one O atom only. The fluorinated peripheries enhance the solubility of these compounds. Formal charges for all the Fe centers were assigned by summing valences of the chemical bonds to the Fe^III atom.     

(C6H14N2)2[VO(HPO4)5B2O]·H2O·H3PO4, a novel borophosphate cluster containing a single vanadium centre and linked by hydrogen bonds into a three‐dimensional framework

The title novel vanadium borophosphate compound, bis(1,4‐diazo­nia­[2.2.2]­octane) μ₃‐oxo‐oxopenta‐μ‐phosphato‐diboronvanadium monohydrate phosphoric acid solvate, containing the cluster anion [VO(PO₃OH)₅B₂O]⁴⁻, has been synthesized under mild hydro­thermal conditions. Extensive O—H⃛O and N—H⃛O hydrogen bonding is observed between the molecular units.     

A neodymium(III)–ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)]·H2O

The title compound, di­ammonium aqua‐μ‐carbonato‐tri‐μ‐­oxalato‐dineodymium(III) hydrate, (NH₄)₂[Nd₂(CO₃)(C₂O₄)₃(H₂O)]·H₂O, involving the two ligands oxalate and carbonate, has been prepared hydro­thermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (,,). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three‐dimensional network. The carbonate group acts as a bis‐chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis‐chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.     

(Et4N)4[V4O12]·2H2O

The title compound, tetrakis(tetraethylammonium) cyclo‐tetra‐μ‐oxo‐tetrakis[dioxovanadium(V)] dihydrate, (C₈H₂₀N)₄[V₄O₁₂]·2H₂O, was obtained by reacting V₂O₅ with (C₂H₅)₄NOH. It consists of a discrete centrosymmetric molecular anion, [V₄O₁₂]^4?, where four tetrahedral VO₄ units share two vertices with each other to form a ring. A water mol­ecule is attached on each side of the ring through hydrogen bonds.     

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).     

(NH4)3[VO2(SO4)2(H2O)2]·1.5H2O

The title compound, tri­ammonium cis‐di­aqua‐cis‐dioxo‐trans‐disulfatovanadate 1.5‐hydrate, was obtained by oxidizing V^IV to V^V in a 2 M sulfuric acid solution of vanadyl­ sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner‐sharing to form a discrete [VO₂(SO₄)₂(OH₂)₂]^3? anion. The water mol­ecules occupy cis positions in the equatorial plane of the vanadium octahedron.     

V2O2F4(H2O)2·H2O: a new V4+ layer structure related to VOF3

V^IV oxyfluorides are of interest as frustrated magnets. The successful synthesis of two‐dimensionally connected vanadium(IV) oxyfluoride structures generally requires the use of ionic liquids as solvents. During solvothermal synthesis experiments aimed at producing two‐ and three‐dimensional vanadium(IV) selenites with triangular lattices, the title compound, diaquatetra‐μ‐fluorido‐dioxidodivanadium(IV) monohydrate, V₂O₂F₄(H₂O)₂·H₂O, was discovered and features a new infinite V⁴⁺‐containing two‐dimensional layer comprised of fluorine‐bridged corner‐ and edge‐sharing VOF₄(H₂O) octahedral building units. The synthesis was carried out under solvothermal conditions. The V⁴⁺ centre exhibits a typical off‐centring, with a short V=O bond and an elongated trans‐V—F bond. Hydrogen‐bonded water molecules occur between the layers. The structure is related to previously reported vanadium oxyfluoride structures, in particular, the same layer topology is seen in VOF₃.     

Two new non‐centrosymmetric lithium salts of glycine: bis(glycine) lithium chromate monohydrate and bis(glycine) lithium molybdate

In bis­(glycine) lithium chromate monohydrate {systematic name: poly[aquadi‐μ‐glycinato‐μ‐tetra­oxochromato(VI)‐dilithium(I)]}, [CrLi₂(C₂H₅NO₂)₂O₄(H₂O)]_n, (I) (space group P2₁2₁2₁), and bis­(glycine) lithium molybdate {systematic name: poly[di‐μ‐glycinato‐μ‐tetra­oxomolybdato(VI)‐dilithium(I)]}, [Li₂Mo(C₂H₅NO₂)₂O₄]_n, (II) (space group P2₁), all atoms are located on general positions. The crystal structure of (I) is characterized by infinite chains of corner‐sharing [LiO₄] tetra­hedra, which are connected by glycine mol­ecules to form layers. [CrO₄] tetra­hedra are attached to the [LiO₄] tetra­hedra. Compound (II) contains dimers of [LiO₄] tetra­hedra which are connected by [MoO₄] tetra­hedra to form chains, which are in turn connected by glycine mol­ecules to form double layers.     

Dimeric hexakis(4‐methyl­benzoato)­bis(1,10‐phenanthroline)didyspros­ium(III)

The title compound, [Dy₂(C₈H₇O₂)₆(C₁₂H₈N₂)₂], forms binuclear complexes, viz. di‐μ‐4‐methyl­benzoato‐κ⁴O:O′‐bis[bis(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)] tetra‐μ‐4‐methyl­benzoato‐κ⁸O:O′‐bis[(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)]. There are two independent binuclear com­plexes in the asymmetric unit, both of which are centrosymmetric. In one, the Dy^III ions are linked by two bridging 4‐­methyl­benzoate groups, while in the other, the Dy^III ions are linked by four bridging 4‐methyl­benzoate groups. The remaining 4‐methyl­benzoate groups and 1,10‐phenanthroline units coordinate to just one metal ion in bidentate modes.     

The cyclic vanadylacetate (C24H20P)[V4O8(C2H3O2)4(NO3)]

In the title complex, tetraphenylphosphonium μ₄‐nitrato‐κ⁴O‐cyclo‐tetrakis(μ‐acetato‐O:O′)tetra‐μ‐oxo‐tetrakis[oxovana‐dium(V)], the anion lies about a twofold axis and consists of the cyclic [V₄O₈] unit coordinated by four acetato ligands with interatomic V?V distances of 3.269 (1) and 3.273 (1) Å. The double‐bonded O atom [N=O 1.102 (6) and N—O 1.268 (4) Å] of the nitrato ligand links the four V atoms with V—O bond distances of 2.613 (2) and 2.813 (2) Å. The negative charge of the complex is balanced by tetraphenyl­phosphonium cations occupying the Na positions in the NaCl‐type ionic packing of the structure.     

A mixed‐valence manganese(III)–manganese(IV) di‐μ‐oxo complex, [(cyclam)MnO]2(ClO4)2(NO3)

The title dinuclear di‐μ‐oxo‐bis­[(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ⁴N)­manganese(III,IV)] diperchlorate nitrate complex, [Mn₂O₂(C₁₀H₂₄N₄)₂](ClO₄)₂(NO₃) or [(cyclam)Mn­O]₂(ClO₄)₂(NO₃), was self‐assembled by the reaction of Mn²⁺ with 1,4,8,11‐tetra­aza­cyclo­tetra­decane in aqueous media. The structure of this compound consists of a centrosymmetric binuclear [(cyclam)MnO]³⁺ unit, two perchlorate anions and one nitrate anion. While the low‐temperature electron paramagnetic resonance spectra show a typical 16‐line signal for a di‐μ‐oxo Mn^III/Mn^IV dimer, the magnetic susceptibility studies also confirm a characteristic antiferromagnetic coupling between the electronic spins of the Mn^IV and Mn^III ions.     

[Cu{C2(COO)2}(H2O)3]·H2O,the first copper complex of acetyl­ene­dicarboxyl­ic acid

In the title compound, catena‐poly­[[[tri­aqua­copper(II)]‐μ‐acetyl­enedi­carboxyl­ato‐κ²O:O′′] hydrate], {[Cu(C₄O₄)(H₂O)₃]·H₂O}_n, the Cu^II ion is coordinated by two monodentate carboxyl­ate groups in trans positions and three water mol­ecules, thus forming a fivefold coordination polyhedron that can be described as a distorted square pyramid. All atoms are located on general sites. The polyhedra are connected by bifunctional acetyl­ene­di­carboxyl­ate ligands, to form almost linear chains parallel to [001]. Hydro­gen bonds involving the non‐coordinated water mol­ecule connect these chains to form a three‐dimensional framework.     

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.     

{[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.     

Co0.50VOPO4·2H2O

The crystal structure of cobalt vanadophosphate dihydrate {systematic name: poly[diaqua‐μ‐oxido‐μ‐phosphato‐hemicobalt(II)vanadium(II)]}, Co_0.50VOPO₄·2H₂O, shows a three‐dimensional framework assembled from VO₅ square pyramids, PO₄ tetrahedra and Co[O₂(H₂O)₄] octahedra. The Co^II ions have local 4/m symmetry, with the equatorial water molecules in the mirror plane, while the V and apical O atom of the vanadyl group are located on the fourfold rotation axis and the P atoms reside on sites. The PO₄ tetrahedra connect the VO₅ polyhedra to form a planar P–V–O layer. The [Co(H₂O)₄]²⁺ cations link adjacent P–V–O layers via vanadyl O atoms to generate an unprecedented three‐dimensional open framework. Powder diffraction measurements reveal that the framework collapses on removal of the water molecules.     

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.     

Pseudo‐merohedrally twinned praseodymium hexa­cyano­ferrate(III) tetrahydrate

Crystals of the title compound, di­aqua­hexa‐μ‐cyano‐ferrate(III)­praseo­dym­ium(III) dihydrate, Pr[Fe(CN)₆]·4H₂O or [PrFe(CN)₆(H₂O)₂]·2H₂O, are twinned with three components. The Pr atom is coordinated by eight atoms, viz. six N and two symmetry‐related water O atoms. The Pr polyhedron (Pr has site symmetry m2m, Wyckoff position 4c) is linked to an FeC₆ octahedron (Fe located on a site with imposed 2/m symmetry, Wyckoff position 4b) through N atoms, forming an infinite array. The second (symmetry independent) water mol­ecule lies on a mirror plane, is not included in coordination and is weakly hydrogen bonded to N atoms.     

[Cd{C2(COO)2}(H2O)3]·H2O,the first cadmium salt of acetylenedicarboxylic acid

In catena‐poly­[[[tri­aqua­cadmium(II)]‐μ‐acetyl­enedi­carboxyl­ato‐κ⁴O,O′:O′′,O′′′] hydrate], {[Cd(C₄O₄)(H₂O)₃]·­H₂O}_n, the Cd^II atom is coordinated by two bidentate carboxyl­ate groups and three water mol­ecules, thus forming a sevenfold coordination polyhedron with all atoms located on general sites. These polyhedra are connected by the bifunctional acetyl­enedi­carboxyl­ate ligands, forming zigzag chains running parallel to [120]. Hydro­gen bonds, which involve the non‐coordinated water mol­ecule, connect these chains to form a three‐dimensional framework.