Orientational disorder of [Mg(H2O)6] octa­hedra in the novel magnesium selenite hydrate Mg(SeO3)·7.5H2O

The crystal structure of magnesium selenite 7.5‐hydrate, Mg(SeO₃)·7.5H₂O (space group P6₃/mmc), is characterized by two crystallographically distinct [Mg(H₂O)₆]²⁺ octa­hedra, one of which is disordered over two different orientations. The selenite groups and water mol­ecules (with partially disordered H atoms) bridge the octa­hedra via hydrogen bonds. All the atoms are located on special positions, except for one water mol­ecule.     

Na10(glycine)2[H2W12O42]·28H2O

The title compound, decasodium diglycine di­hydro­geno­do­tetra­conta­do­deca­tung­state(10?) octa­cosa­hydrate, consists of a centrosymmetric paratungstate [H₂W₁₂O₄₂]^10? anion, ten Na⁺ cations, two zwitterionic glycine molecules and 28 water molecules of crystallization. Two glycine carboxylate O atoms coordinate three different Na⁺ cations, while the amino N atom forms hydrogen bonds with the paratungstate anion through both terminal and bridging O atoms.     

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.     

Ca2CuTe4O10Cl2, a new synthetic tellurium(IV) oxochloride

Single crystals of dicalcium copper tetra­tellurium deca­oxide dichloride, Ca₂CuTe₄O₁₀Cl₂, were synthesized via a transport reaction in sealed evacuated quartz glass tubes. The building units of the structure are irregular CaO₇ polyhedra, centrosymmetric CuO₄Cl₂ octa­hedra and two crystallographically distinct TeO₄E distorted bipyramids (E being the 5s² lone pair of Te^IV). The TeO₄E and CuO₄Cl₂ polyhedra together form planes that are connected by the Ca atoms. The CuO₄Cl₂ octa­hedra are isolated from each other by the other building units.     

Sr2Cu2TeO6Br2: honeycomb layers of copper(II) ions

Single crystals of distrontium(II) dicopper(II) tellurium(VI) hexa­oxide dibromide, Sr₂Cu₂TeO₆Br₂, were synthesized via solid state/gas phase reactions in sealed evacuated silica tubes. The building units are irregular SrO₄Br₃ polyhedra (a new type of coordination polyhedron around Sr^II), CuO₅ square pyramids and TeO₆ octa­hedra. The CuO₅ square pyramids and the TeO₆ octa­hedra together form layers in the bc plane bridged by Sr atoms. The Cu atoms are arranged to form puckered honeycomb layers. The Te atom lies on an inversion centre.     

(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.     

LiMn3(SeO3)2(HSeO3)6

The title compound, lithium trimanganese bis­[trioxo­selenate(IV)] hexa­kis[hydrogentrioxoselenate(IV)], is built up from a vertex‐sharing network of distorted Mn^IIIO₆ octa­hedra, SeO₃ and HSeO₃ pyramids and unusual Li(OH)₆ octa­hedra, resulting in a dense three‐dimensional structure. Mn, Li and one Se atom have site symmetries of , , and 3, respectively. An O—H⋯O hydrogen bond helps to establish the crystal packing.     

(Croconato‐κ2O,O′)bis­(1,10‐phenanthroline‐κ2N,N′)cobalt(II), and the nickel(II) and copper(II) analogues

The title complexes, [M(C₅O₅)(C₁₂H₈N₂)₂], with M = Co^II, Ni^II and Cu^II, all lie across twofold rotation axes, around which two 1,10‐phenanthroline ligands are arranged in a chiral propeller manner. The Co^II and Ni^II complexes are isostructural, with octa­hedral coordination geometry, while the local geometry of the Cu^II complex is severely distorted from octa­hedral.     

Comparative study of two chemically isostructural polymers: [Cu2(VO2)(HPO4)2(NO3)(bpy)2]·2H2O/H3PO4 (bpy is 2,2′‐bi­pyridine)

The title compounds, poly­[bis(2,2′‐bi­pyridine)­bis(μ₃‐hydrogen phosphato)­nitratodi‐μ₂‐oxo‐dicopper(II)­vanadium dihydrate], [Cu₂(VO₂)(HPO₄)₂(NO₃)(C₁₀H₈N₂)₂]·2H₂O, (I), and poly­[bis(2,2′‐bi­pyridine)­bis(μ₃‐hydrogen phosphato)­nitratodi‐μ₂‐oxo‐dicopper(II)­vanadium phospho­ric acid solvate], [Cu₂(VO₂)(HPO₄)₂(NO₃)(C₁₀H₈N₂)₂]·H₃PO₄, (II), were obtained by similar hydro­thermal methods but under different crystallization conditions. The trinuclear entity which serves as the basic unit in both structures presents two independent Cu^II ions immersed in similar square‐pyramidal N₂O₃ environments plus an octahedral VO₆ core and is organized into a one‐dimensional polymer, which is essentially identical in the two structures. The compounds are stabilized by different solvates, viz. two crystallization water mol­ecules in (I) and a phospho­ric acid mol­ecule in (II), which provide the main structural differences through the diversity of interchain interactions in which they serve as bridges.     

The titanium–thiolate complex [Li(C4H8O)4][Ti2(SC6H5)9]

In the title compound, tetrakis­(tetra­hydro­furan)­lithium(I) tri‐μ‐phenyl­thiol­ato‐bis­[tris­(phenyl­thiol­ato)­titanate(IV)], [Li(C₄H₈O)₄][Ti₂(C₆H₅S)₉], (I), the central structural motif of the [Ti₂(SC₆H₅)₉]^? anion features a face‐sharing bi‐octa­hedron. The charge is balanced with a [Li(C₄H₈O)₄]⁺ cation. The asymmetric unit contains Ti, Li and a heavily disordered tetra­hydro­furan mol­ecule on a threefold axis, and two terminal and a bridging thio­phenolate moiety and a slightly disordered tetra­hydro­furan mol­ecule on general positions.     

[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.     

Diaqua­bis[2′‐(4,5‐diaza­fluoren‐9‐yl­idene)picolinohydrazidato‐κ2N,O]zinc(II) tetra­hydrate: a metal–water chain complex containing cyclic water hexa­mers

In the title compound, [Zn(C₁₇H₁₀N₅O)₂(H₂O)₂]·4H₂O, cyclic water hexa­mers forming one‐dimensional metal–water chains are observed. The water clusters are trapped by the co‐operative association of coordination inter­actions and hydrogen bonds. The Zn^II ion resides on a centre of symmetry and is in an octa­hedral coordination environment comprising two O atoms and two N atoms from two 2′‐(4,5‐diaza­fluoren‐9‐yl­idene)picolinohydrazidate ligands and two water mol­ecules.     

The one‐electron oxidation product of a metallocenyl‐terminated cyanine

The 1‐(2,3,4,5,1′,2′,3′,4′‐octa­methyl­ferrocen‐1‐yl)‐3‐(ruth­eno­cen­yl)­allylium cation readily undergoes one‐electron oxidation to a dication in which an octa­methyl­ferrocenium moiety is bridged by a vinyl­ene group to a [(η⁶‐fulvene)(η⁵‐cyclo­penta­dienyl)­ruthenium]⁺ moiety. In the title compound, 1‐(2,3,4,5,1′,2′,3′,4′‐octa­methyl­ferrocen‐1‐yl)‐3‐(ruth­eno­cen­ylidene)prop‐1‐enium(2+) bis­(tetra­fluoro­borate), [Fe­Ru­(C₅H₅)(C₉H₁₃)(C₁₇H₁₉)]­(BF₄)₂, the C—C bond lengths in the bridge (average for two independent mol­ecules) are, starting from the ipso octa­methyl­ferrocenium carbon and ending at the exo carbon of the coordinated fulvene, 1.455 (6), 1.344 (3) and 1.449 (8) Å, indicating a localized electronic structure.     

Isolated pentaiodide anions in [K(18‐crown‐6)]I5

(1,4,7,10,13,16‐Hexaoxa­cyclo­octa­decane‐κ⁶O)­potassium penta­iodide, [K(C₁₂H₂₄O₆)]I₅, obtained by slow evaporation of an ethanol solution of KI, 18‐crown‐6 and I₂, contains [K(18‐crown‐6)]⁺ cations (C_i symmetry) and I₅⁻ anions (C₂ symmetry), which are arranged in alternating layers parallel to (001). In contrast to the well known tendency of I₅⁻ ions to form chains and nets, the I₅⁻ units in the title compound are isolated.     

Ag3.5Bi7.5S13, a new member (N = 8) of the homologous series [Bi2S3]2·[AgBiS2](N−1)/2

The silver bismuth trideca­sulfide Ag_3.5Bi_7.5S₁₃ crystallizes in the monoclinic space group C2/m. Its structure is built up of two alternating kinds of layered modules parallel to (001). In the module denoted A, octa­hedra around the metal positions (M = Ag/Bi, M2 and an S atom on 2/m, other atoms on m) alternate with paired monocapped trigonal prisms around Bi. The NaCl‐type module B is composed of parallel eight‐membered chains of edge‐sharing octa­hedra running dia­gonally across it. Ag_3.5Bi_7.5S₁₃ is the member with N = 8 of the pavonite homologous series ^NP of ternary compounds with the general formula [Bi₂S₃]₂·[AgBiS₂]_(N−1)/2.     

Partially oxidized ruthenium phosphine thiol­ates: [Ru(pySO2)0.33(pyS)1.67(dppe)] and [Ru(pySO2)0.355(pyS)1.645(dppp)]

The crystal structures of [1,3‐bis­(diphenyl­phosphino)ethane‐κ²P,P′](pyridine‐2‐sulfinato‐κ²N,S)(pyridine‐2‐thiol­ato‐κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.33(C₅H₄NS)_1.67(C₂₆H₂₄P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppe)] (x = 0.67), (I), and [1,3‐bis­(diphenyl­phosphino)propane‐κ²P,P′](pyridine‐2‐sulfinato‐κ²N,S)(pyridine‐2‐thiol­ato‐κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.355(C₅H₄NS)_1.645(C₂₇H₂₆P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppp)] (x = 0.645), (II), are composed of neutral distorted octa­hedral Ru^II complexes with chelating pyridine‐2‐thiol­ate, pyridine‐2‐sulfinate and biphosphine ligands. The S atoms are trans to each other, while pairs of P and N atoms are in cis positions. Partial double‐bond character is observed for C—S. The crystal packing consists of monolayers stabilized by C—H⋯O and C—H⋯S inter­actions, and is affected by the alkyl‐chain lengths.     

Bis(acesulfamato‐κO4)diaqua­bis­(3‐methyl­pyridine‐κN)nickel(II)

In the crystal structure of the title compound [systematic name: diaqua­bis(6‐methyl‐2,2‐dioxo‐1,2,3‐oxathia­zin‐4‐olato‐κO⁴)bis­(3‐methyl­pyridine‐κN)nickel(II)], [Ni(C₄H₄NO₄S)₂(C₆H₇N)₂(H₂O)₂], the Ni^II centre resides on a centre of symmetry and has a distorted octa­hedral geometry. The basal plane is formed by two carbonyl O atoms of two monodentate trans‐oriented acesulfamate ligands and two trans aqua ligands. The axial positions in the octa­hedron are occupied by two N atoms of two trans pyridine ligands. Mol­ecules are stacked in columns running along the a axis. There are π–π stacking inter­actions between the mol­ecules in each column, with a distance of 3.623 (2) Å between the centroids of the pyridine rings. There are also O—H⋯O inter­actions between the columns.     

Dicarbonyldi‐μ‐chloro‐cis,cis‐η4‐1,5‐cyclo­octa­dienedirhodium(I)

The title compound, dicarbonyl‐1κ²C‐di‐μ‐chloro‐1:2κ⁴Cl‐[cis,cis‐2(η⁴)‐1,5‐cyclo­octa­diene]­di­rhodium(I), [Rh₂Cl₂(C₈H₁₂)(CO)₂], consists of a di­chloro‐bridged dimer of rhodium, with a non‐bonded Rh?Rh distance of 3.284 (2) Å. One Rh atom is coordinated to two carbonyl ligands, while the other Rh atom is coordinated to the cyclo­octa­diene moiety.     

Iron(III) dihydrogenphosphate(I)

The structure of rhombohedral (R) iron(III) tris­[di­hydrogen­phosphate(I)] or iron(III) hypophosphite, Fe(H₂PO₂)₃, has been determined by single‐crystal X‐ray diffraction. The structure consists of [001] chains of Fe³⁺ cations in octa­hedral sites with symmetry bridged by bidentate hypophosphite anions.     

Two new [Ni(tren)2]2+ complexes: [Ni(tren)2]Cl2 and [Ni(tren)2]WS4

Both title compounds, bis­[tris(2‐amino­ethyl)­amine]­nickel(II) dichloride, [Ni(tren)₂]Cl₂, (I), and bis­[tris(2‐amino­ethyl)­amine]­nickel(II) tetra­thio­tungstate, [Ni(tren)₂]WS₄, (II), contain the [Ni(tren)₂]²⁺ cation [tren is tris(2‐amino­ethyl)­amine, C₆H₁₈N₄]. The tren mol­ecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni²⁺ is located on a centre of inversion surrounded by one crystallographically independent tren mol­ecule. In the [Ni(tren)₂]²⁺ cation of (II), the Ni atom is bound to two crystallographically independent tren mol­ecules. The Ni atoms in the [Ni(tren)₂]²⁺ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren mol­ecules. The counter‐ions are chloride anions in (I) and the tetrahedral [WS₄]^2? anion in (II). Hydro­gen bonding is observed in both compounds.