Barium vanadium(III) hydrogen ­phosphate,Ba3V2(HPO4)6

Hydro­thermally prepared Ba₃V₂(HPO₄)₆ contains a three‐dimensional network of V^IIIO₆ octahedra [d_av(V—O) = 2.014 (2) Å] and HPO₄ [d_av(P—O) = 1.537 (3) Å] tetrahedra, sharing vertices. 12‐coordinate Ba²⁺ cations [d_av(Ba—O) = 2.944 (4) Å] complete the structure.     

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)°].     

Caesium vanadium selenite,Cs(VO2)3(SeO3)2

Caesium vanadium(V) selenite contains infinite sheets of distorted vertex‐sharing VO₆ octahedra, capped by selenite groups [d_av(V—O) = 1.927 (4) Å and d_av(Se—O) = 1.709 (3) Å]. Interlayer caesium cations complete the structure [d_av(Cs—O) = 3.365 (4) Å].     

Lanthanum selenite,La2(SeO3)3

Hydro­thermally prepared La₂(SeO₃)₃ contains a three‐dimensional network of LaO₁₀ polyhedra [d_av(La—O) = 2.622 (3) Å] and SeO₃ pyramids [d_av(Se—O) = 1.691 (3) Å]. One of the SeO₃ pyramids is in a general position and the other has crystallographic m symmetry. There are pseudo‐channels in the [010] direction which are probably associated with the Se^IV lone pairs.     

[H3N(CH2)2NH3]0.5[BePO4], a ­beryllophosphate analogue of ­aluminosilicate zeolite gismondine

Hydro­thermally prepared ethyl­enedi­ammonium beryl­lo­phosphate, (C₂H₁₀N₂)_0.5[BePO₄], is an analogue of aluminosilicate zeolite gismondine. A three‐dimensional network of vertex‐sharing BeO₄ and PO₄ tetrahedra [d_av(Be—O) = 1.618 (3) Å, d_av(P—O) = 1.5246 (14) Å and θ_av(Be—O—P) = 139.8°] encapsulates the disordered ethyl­enedi­ammonium cations in an eight‐ring channel system.     

Hexagonal ammonium zinc ­phosphate, (NH4)ZnPO4, at 10 K

The title compound, (NH₄)ZnPO₄–HEX, is built up from a three‐dimensional network of ZnO₄ and PO₄ tetrahedra [d_av(Zn—O) = 1.9400 (7) Å and d_av(P—O) = 1.5396 (7) Å], fused together via Zn—O—P links [θ_av = 133.47 (4)°]. An undisordered linear Zn—O—P bond occurs (all three atoms lie on a threefold axis). Extra‐framework NH₄⁺ cations, which interact with the [ZnPO₄]^? framework by hydrogen bonds, complete the crystal structure.     

Structure Cristalline de l'Arseniate Double de Potassium et de Zirconium: KZr2(AsO4)3

Crystal Structure of KZr₂(AsO₄)₃ KZr₂(AsO₄)₃ crystals have been prepared by the flux method. The compound crystallizes in the rhombohedral system with the parameters: a = 9.028(1), c = 24.399(3) Å. The density is d = 3.694 g/cm³ and Z = 6. The space group is R3 c. The structure has been solved by isotypism with that of NaZr₂(PO₄)₃ to R = 0.041, for 353 independent reflections. It consists in 3-dimensional chains of AsO₄ tetrahedra and ZrO₆ octahedra. K⁺ ions are the center of the antiprism with K—O distances equal to 2.813 Å. The Zr–O and As–O distances have the same values of those usually observed (Zr–O = 2,05 Å and As–O = 1.66 Å).     

Dimorphic cerium(III) oxoarsenate(III) Ce[AsO3]

Colourless, water- and air-stable single crystals of cerium(III) oxoarsenate(III) Ce[AsO₃] were prepared by the reaction of cerium metal (Ce) and arsenic sesquioxide (As₂O₃) in the presence of cesium chloride (CsCl) as fluxing agent at 750 °C in an evacuated silica ampoule. Ce[AsO₃] crystallizes monoclinically (a = 902.89(8), b = 782.54(7), c = 829.68(7) pm, β = 103.393(3)°, Z = 8) in the space group P2₁/c and is isotypic with α-Pb[SeO₃]. There are two crystallographically different Ce³⁺ positions. (Ce1)³⁺ is coordinated by nine oxygen atoms (d(Ce–O) = 244–286 pm) and (Ce2)³⁺ by only eight (d(Ce–O) = 239–273 pm). Both crystallographically different As³⁺ cations form discrete ψ¹ tetrahedra [AsO₃]³⁻ (d(As–O) = 174–179 pm), which are attached to the Ce³⁺ cations via edges and corners. The second monoclinic modification of Ce[AsO₃] with the lattice parameters a = 439.32(4), b = 529.21(5), c = 617.34(6) pm and β = 105.369(3)° with Z = 2 was obtained by high-pressure synthesis (11 GPa, 1200 °C) and has both a higher density (6.31 vs. 6.13 g · cm⁻³) and a higher calculated Madelung part of the lattice energy (15,155 vs. 15,132 kJ · mol⁻¹). It adopts the space group P2₁/m, crystallizing isotypically with La[AsO₃], β-Pb[SeO₃], Pb[SO₃] (scotlandite) or K[ClO₃] and exhibits nine-fold coordinated Ce³⁺ cations exclusively (d(Ce–O) = 254–287 pm) along with tripodal [AsO₃]³⁻ anions (d(As–O) = 175–176 pm). Raman spectroscopy on both phases of Ce[AsO₃] shows stretching vibrations between 769 and 731 cm⁻¹ as well as asymmetric vibrations in the range of 659–617 cm⁻¹. The symmetric bending mode vibrations emerge in an interval from 340 to 410 cm⁻¹ and the asymmetric bending modes range between 230 and 290 cm⁻¹.     

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.     

Selenoarsenate aus wäßriger Lösung. Die Kristallstruktur von Na3AsO3Se · 12 H2O und Na3AsSe4 · 9H2O

Selenoarsenates from Aqueous Solutions. Crystal Structures of Na₃AsO₃Se · 12 H₂O and Na₃AsSe₄ · 9 H₂O Selenoarsenates are obtained from aqueous solutions as colourless hydrated salts by reactions either of As₂O₃ with NaOH and selenium or of Na₂Se with As₂Se₃ and selenium under strictly anaerobic conditions. Besides of tetrahedral anions AsO₃Se³⁻ and AsSe₄³⁻, extensive hydrogen bridge systems with rather strong O H …︁s Se bonds determine the structures. Na₃AsO₃Se · 12 H₂O is orthorhombic (P2₁2₁2₁) with a = 9.220(3), b = 13.018(3), c = 14.048(4) Å, Z = 4. Cubic Na₃AsSe₄ ·s 9H₂O (P2₁3) with a = 12.149(3) Å is isotypic to Schlippe's salt, Na₃SbS₄ · 9 H₂O. The full X-ray structure analyses from four-circle diffractometer data show the selenium atoms of the AsO₃Se³⁻ and AsSe₄³⁻ anions to be H-acceptors in six Se …︁ H O hydrogen bridges with d(Se …︁ O) = 3.357–3.693 Å and d(Se …︁ H) = 2.47–2.89 Å. The As Se bond in AsO₃Se³⁻ (2.283 Å) is shorter than in AsSe₄³⁻ (2.319 Å).     

X‐ray crystal of diprotonated tetra‐(2‐pyridyl)pyrazine (H2TPPZ), aqua Fe3+‐phen crystal and new lanthanide complexes of TPPZ and their biochemical studies

New complexes derived from M³⁺ salts with polyazine as monometallic such as [Fe (TPPZ)Cl₃].½H₂O (1) , [Cr (TPPZ)₂Cl₂]Cl.2EtOH (2) , [La (TPPZ)(NO₃)₂(H₂O)₂]NO₃.H₂O (3) in addition to [Fe (Phen)₃]3Cl.7H₂O (4) were isolated. Three bimetallic, [H₂TPPZ][(AuCl₄)₂]. H₂O (5) , [Ce₂(TPPZ)EtOH (NO₃)₃]3NO₃ (6) and [Nd₂TPPZCl₂(H₂O)₄]4Cl.CHCl₃. 4H₂O (7) and mixed ligand complexes, [Fe (TPPZ)(Phen)₂]Cl₃ (8) , [Fe (TPPZ) (Phen)₂][TPPZCl₃] (9) , [La₂(TPPZ)(Phen)₂(EtOH)₂]6Cl.CHCl₃.EtOH.H₂O (10) and [Nd₂(TPPZ)(Phen)Cl₄]2Cl.3H₂O (11) were synthesized and characterized. Crystal data of (4) is tetragonal, I4₁/a, a = b 35.951 (3) Å, c = 11.9055 (8) Å, α = 80.201 (2)° β = 78.846 (2)°, γ = 89.687 (2)° V = 741.06 (5)ų, Z = 1 while triclinic, P1, a = 7.3913 (3) Å, b = 9.7344 (4) Å, c = 10.6577 (4) Å, α = β = γ = 90°, V = 741.06 (5)ų and Z = 170 for (5) . Analyses, spectral and cyclic voltammetry studies indicate the bonding and the redox properties. Anticancer studies promised to be effective in lanthanides and some complexes were screened against antibacterial or antifungal.     

Crystal growth and structure of three new neodymium containing silicates: Na0.50Nd4.50(SiO4)3O,Na0.63Nd4.37(SiO4)3O0.74F0.26 and Na4.74Nd4.26(O0.52F0.48)[SiO4]4

Single crystals of Na_0.50Nd_4.50(SiO₄)₃O, Na_0.63Nd_4.37(SiO₄)₃O_0.74F_0.26, and Na_4.74Nd_4.26(O_0.52F_0.48)[SiO₄]₄ were synthesized via flux growth using a NaF/KF eutectic flux and the crystal structure was determined by single crystal X-ray diffraction. Na_0.50Nd_4.50(SiO₄)₃O and Na_0.63Nd_4.37(SiO₄)₃O_0.74F_0.26 adopt the apatite structure and crystallize in the hexagonal space group P6₃/m, while Na_4.74Nd_4.26(O_0.52F_0.48)[SiO₄]₄ crystallizes in the tetragonal space group I-4 and exhibits rare-earth mixing on the sodium site. The unit cells of the crystals are a = 9.5400(3) Å and c = 7.0331(5) Å for Na_0.50Nd_4.50(SiO₄)₃O, a = 9.5533(3) Å and c = 7.0510(4) Å for Na_0.63Nd_4.37(SiO₄)₃O_0.74F_0.26, and a = 12.1255(3) Å and c = 5.4656(2) Å for Na_4.74Nd_4.26(O_0.52F_0.48)[SiO₄]₄. These three compounds exhibit three-dimensional crystal structures that are discussed in detail in this paper.     

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.     

Three new acid M+ arsenates and phosphates with multiply protonated As/PO4 groups

The crystal structures of caesium dihydrogen arsenate(V) bis[trihydrogen arsenate(V)], Cs(H₂AsO₄)(H₃AsO₄)₂, ammonium dihydrogen arsenate(V) trihydrogen arsenate(V), NH₄(H₂AsO₄)(H₃AsO₄), and dilithium bis(dihydrogen phosphate), Li₂(H₂PO₄)₂, were solved from single‐crystal X‐ray diffraction data. NH₄(H₂AsO₄)(H₃AsO₄), which was hydrothermally synthesized (T = 493 K), is homeotypic with Rb(H₂AsO₄)(H₃AsO₄), while Cs(H₂AsO₄)(H₃AsO₄)₂ crystallizes in a novel structure type and Li₂(H₂PO₄)₂ represents a new polymorph of this composition. The Cs and Li compounds grew at room temperature from highly acidic aqueous solutions. Li₂(H₂PO₄)₂ forms a three‐dimensional (3D) framework of PO₄ tetrahedra sharing corners with Li₂O₆ dimers built of edge‐sharing LiO₄ groups, which is reinforced by hydrogen bonds. The two arsenate compounds are characterized by a 3D network of AsO₄ groups that are connected solely via multiple strong hydrogen bonds. A statistical evaluation of the As—O bond lengths in singly, doubly and triply protonated AsO₄ groups gave average values of 1.70 (2) Å for 199 As—OH bonds, 1.728 (19) Å for As—OH bonds in HAsO₄ groups, 1.714 (12) Å for As—OH bonds in H₂AsO₄ groups and 1.694 (16) Å for As—OH bonds in H₃AsO₄ groups, and a grand mean value of 1.667 (18) Å for As—O bonds to nonprotonated O atoms.     

Syntheses and structures of two new M6Li8(N3)a6 cluster-unit based compounds: Cs4Re6S8(N3)6·H2O and Na2Mo6Br8(N3)6·2H2O

The two new cluster compounds, Cs₄Re₆S₈(N₃)₆·H₂O (1) and Na₂Mo₆Br₈(N₃)₆·2H₂O (2), have been prepared via solution chemistry route, starting from the Cs₄Re₆S₈Br₆CsBr and Mo₆Br₁₂ precursors synthesized by solid state chemistry techniques, and structurally characterized (crystal data: Cs₄Re₆S₈(N₃)₆·H₂O (1): Orthorhombic, space group Pnam, a=10.0651(1) Å, b=15.8856(2) Å, c=20.1714(3) Å, V=3225.2(7) Å³, Z=4, d_calc=4.48 g cm⁻³, μ=27.43 mm⁻¹; Na₂Mo₆Br₈(N₃)₆·2H₂O (2): Orthorhombic, space group Ibam, a=11.5643(3) Å, b=14.3959(5) Å, c=17.0340(7) Å, V=2835.8(2) ų, Z=4, d_calc=3.63 g cm⁻³, μ=13.91 mm⁻¹). Their structures revealed that in both cases, the M₆Lⁱ₈ cluster core remains unchanged in the starting and final compounds whereas the bromine apical ligands (Br^a) are substituted by N₃ azide groups leading to M₆Lⁱ₈(N₃)^a₆ cluster unit. The new Cs₄Re₆S₈(N₃)₆·H₂O is the first example of a compound containing an octahedral rhenium cluster coordinated to azide groups.     

Mg7(AsO4)2(HAsO4)4: a new magnesium arsenate with a very strong hydrogen bond

A new compound, heptamagnesium bis­(arsenate) tetrakis(hydrogenarsenate), Mg₇(AsO₄)₂(HAsO₄)₄, was synthesized by a hydro­thermal method. The structure is based on a three‐dimensional framework of edge‐ and corner‐sharing MgO₆, MgO₄(OH)₂, MgO₅, AsO₃(OH) and AsO₄ polyhedra. Average Mg—O and As—O bond lengths are in the ranges 2.056–2.154 and 1.680–1.688 Å, respectively. Each of the two non‐equivalent OH groups is bonded to both an Mg and an As atom. One OH group is involved in a very short hydrogen bond [O⋯O = 2.468 (3) Å]. The formula unit is centrosymmetric, with all atoms in general positions except for one Mg atom, which has site symmetry . The compound is isotypic with Mn₇(AsO₄)₂(HAsO₄)₄ and M₇(PO₄)₂(HPO₄)₄, where M is Fe, Co or Mn.     

Poly[tetrasodium(I)‐tetra‐μ2‐bis(butane‐1,4‐diyldioxy)borato‐μ2‐1,4‐butane­diol]

In the title compound, [Na₄(C₈H₁₆BO₄)₄(C₄H₁₀O₂)]_n, there are two coordination types for the four independent Na⁺ cations: two Na⁺ cations bond to six diolate O atoms [Na—O = 2.305 (2)–2.609 (2) Å], while the other two are five‐coordinate via one 1,4‐butane­diol [2.289 (2) and 2.349 (3) Å] and four diolate O atoms [2.295 (2)–2.408 (2) Å]. Corresponding to this, there are three‐ and four‐coordinate diolate O atoms, the latter bridging Na atoms. The 1,4‐butane­diol mol­ecules lie on inversion centres. The boron stereochemistry shows minor local perturbations from its usual tetrahedral state [B—O = 1.457 (4)–1.503 (4) Å]. The resulting polymer packs as sheets parallel to the (10) plane crosslinked by the butane­diol mol­ecules. The structure was solved using data from a multiple crystal.     

The dinuclear scandium(III) cyclooctatetraenyl chloride complex di‐μ‐chlorido‐bis[(η8‐cyclooctatetraene)(tetrahydrofuran‐κO)scandium(III)]

Only a few cyclooctatetraene dianion (COT) π‐complexes of lanthanides have been crystallographically characterized. This first single‐crystal X‐ray diffraction characterization of a scandium(III) COT chloride complex, namely di‐μ‐chlorido‐bis[(η⁸‐cyclooctatetraene)(tetrahydrofuran‐κO )scandium(III)], [Sc₂(C₈H₈)₂Cl₂(C₄H₈O)₂] or [Sc(COT)Cl(THF)]₂ (THF is tetrahydrofuran), (1), reveals a dimeric molecular structure with symmetric chloride bridges [average Sc—Cl = 2.5972 (7) Å] and a η⁸‐bound COT ligand. The COT ring is planar, with an average C—C bond length of 1.399 (3) Å. The Sc—C bond lengths range from 2.417 (2) to 2.438 (2) Å [average 2.427 (2) Å]. Direct comparison of (1) with the known lanthanide (Ln) analogues (La, Ce, Pr, Nd, and Sm) illustrates the effect of metal‐ion (M ) size on molecular structure. Overall, the M —Cl, M —O, and M —C bond lengths in (1) are the shortest in the series. In addition, only one THF molecule completes the coordination environment of the small Sc^III ion, in contrast to the previously reported dinuclear Ln–COT–Cl complexes, which all have two bound THF molecules per metal atom.     

A new route to prepare the mixed oxo-ethylidyne-capped trinuclear tungsten(IV) cluster and the crystal structure of H2Na3[W3O(CCH3)-(O2CCH3)6(H2O)3][H2W12O40]·13.5H2O

The synthesis and the structural characterization of the title compound H₂Na₃[W₃O(CCH₃)-(O₂CCH₃)₆(H₂O)₃][H₂W₁₂O₄₀]·13.5H₂O are described. It is known that the mixed oxo-ethylidynecapped tritungsten cluster can be obtained by Zn dust reduction of Na₂WO₄·2H₂O in acetic anhydride. The title compound has been characterized by X-ray diffraction, UV/VIS and ¹H NMR spectra. The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV) and W(VI) respectively. The crystal is rhombohedral with the space group R32, a = 17.058 (3)Å, c = 49.665 (9)Å, γ=120°, V=12516(9)ų, Z=6, final R = 0.037 for 2071 reflections with I ≥3σ (I). Both the cluster cation and anion have a C₃ symmetry. The important interatomic distances in angstroms for the cluster cation are: W—W, 2.730(2); W—μ₃?O, 2.00; W—O (carboxy1), 2.12; W—O_t 2.18 (2).     

X-ray diffraction and vibrational data for a series of triphosphates type MIINa3P3O10.12H2O (MII = Cu,Ni and Mg) and their anhydrous forms MIINa3P3O10

Chemical preparation methods, X-ray diffraction and vibrational data are reported for six triphosphates type M^IINa₃P₃O₁₀.12H₂O (M^II = Cu, Ni and Mg) and their anhydrous forms M^IINa₃P₃O₁₀. These condensed phosphates are respectively, CuNa₃P₃O₁₀.12H₂O, MgNa₃P₃O₁₀.12H₂O, NiNa₃P₃O₁₀.12H₂O, CuNa₃P₃O₁₀, NiNa₃P₃O₁₀ and MgNa₃P₃O₁₀. The hydrate triphosphates were prepared by the method of ion-exchange resin, where as their anhydrous forms were prepared by total thermal dehydration of M^IINa₃P₃O₁₀.12H₂O (M^II = Cu, Ni and Mg).CuNa₃P₃O₁₀.12H₂O, MgNa₃P₃O₁₀.12H₂O and NiNa₃P₃O₁₀.12H₂O are isotypic, and crystallize in the monoclinic system, space group is P2₁/n, Z = 4, the unit-cell parameters are: CuNa3P3O10.12H2O, a = 15.052(8) Å, b = 9.234(3) Å,c = 14.767(8) Å and β = 90.03(5)°. MgNa3P3O10.12H2O: a = 15.049(1) (1) Å, b = 9.245(4) Å, c = 14 0.722(3) (2) Å and β = 90.00(5)°.NiNa₃P₃O₁₀.12H₂O: a = 15.010(1) Å, b = 9.208(4) Å, c = 14.710(2) Å and β = 90.00(5)°.The anhydrous forms CuNa₃P₃O₁₀, MgNa₃P₃O₁₀ and NiNa₃P₃O₁₀ crystallize in the monoclinic system, space group is P2₁/n, Z = 4, the unit-cell parameters are: CuNa₃P₃O₁₀, a = 12.464(0) Å, b = 8.437(7) Å, c = 12.083(1) Å and β = 109.77(8) °; MgNa₃P₃O₁₀: a = 11.931(4) (1) Å, b = 12.912(2) Å, c = 10.057(0) Å and β = 113.83(2)° and NiNa₃P₃O₁₀: a = 12.686(8)Å, b = 9.271(2) (4) Å, c = 11.440(3) Å and β = 102,95(5)°.