Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

Synthesis and Crystal Structure of Nitrosoruthenium Triammino Complex [RuNO(NH3)3Cl(H2O)]Cl2

This paper reports on a procedure for the synthesis of the compound [RuNO(NH₃)₃Cl(H₂O)]Cl₂. The complex was studied by IR spectroscopy and X-ray phase and X-ray diffraction analyses. Crystal data for RuCl₃N₄O₂H₁₁: a = 13.151(2), b = 6.852(1), c = 10.361(1) , V = 933.6(2) ², space group Pna2 ₁ , Z = 4, d _calc = 2.181 g/cm³, d _exp = 2.178 g/cm³. The structure consists of the [RuNO(NH₃)₃Cl(H₂O)]²⁺ complex cations and Cl^– anions. The compound crystallizes as small orange red isometric orthorhombic crystals well soluble in water and insoluble in concentrated hydrochloric acid and organic solvents and is stable when stored in air.     

Tetrahedral complexes of zinc(II) chloride with N- and O-containing organic ligands: Synthesis and crystal structures of [ZnCl2(C12H12N2O)] and [ZnCl2(H2O)2](Me4Pyz)2

New complex chlorides [ZnCl₂(ODA)] (I) (ODA=oxydianiline, C₁₂H₁₂N₂O) and [ZnCl₂(H₂O)₂](Me₄Pyz)₂ (II) (Me₄Pyz = 2,3,5,6-tetramethylpyrazine) were synthesized and crystallographically characterized. Crystals of I are monoclinic, space group C2/c, a = 22.682(2) ?, b = 12.646(1) ?, c = 9.951(1) ?, β = 93.23(2)°, V = 2849.7(5) ?³, ρ_calc = 1.569 g/cm³, Z = 8. Structure I contains cyclic fragments consisting of two tetrahedral complexes (ZnCl₂N₂) and two coordinated bridging oxydianiline ligands. Crystals of II are monoclinic, space group P2(1)/c, a = 8.972(2) ?, b = 13.862(3) ?, c = 17.528(4) ?, β = 101.72(3)°, V = 2134.5(7) ?³, ρ_calc = 1.384 g/cm³, Z = 4. In structure II, supramolecular pseudo-metallocycles are formed due to formation of hydrogen bonds O(w)-H…N between coordinated water molecules and noncoordinated nitrogen atoms of tetramethylpyrazine molecules.     

Mixed-ligand complex compounds [Pb(Phen)×{(iso-C4H9)2PS2}2] and [Pb(2,2′-Bipy){(iso-C4H9)2PS2}2] and formation of supramolecular assemblies in their crystal structures

Mixed-ligand complex compounds [Pb(Phen)(i-Bu₂PS₂)]₂ (I) and [Pb(2,2′-Bipy)(i-Bu₂PS₂)]₂ (II) were synthesized. Their structures were determined from X-ray diffraction data (X8 APEX diffractometer, MoK _α radiation, 6392 _Fhkl , R = 0.0233 for I and 3937 F _hkl , R = 0.0252 for II). Crystals I are triclinic: a = 10.2662(3) Å, b = 12.3037(2) Å, c = 14.8444(4) Å; α = 92.054(1)°, β = 103.473(1)°, γ = 105.561(1)°, V = 1746.89(8) ų, Z = 2, ρ_calc = 1.532 g/cm³, space group P . Crystals II are monoclinic: a = 9.3462(3) Å, b = 26.3310(12) Å, c = 28.5345(13) Å; β = 96.436(1)°, V = 6977.9(5) ų, Z = 8, ρ_calc = 1.489 g/cm³, space group P2₁/n. The structures are built from mononuclear molecules. In both structures, the intermolecular contacts between the Pb and S atoms of the neighboring mononuclear molecules form supramolecular assemblies involving two molecules. The environment of the Pb atoms in the assemblies is a pentagonal bipyramid, N₂S₄₊₁. The assemblies are joined into ribbons by π-π interactions of the Phen rings in I and C…C short contacts between the pyridine rings in II. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, E. A. Sankova, T. E. Kokina, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 123–131, January–February, 2008.     

Crystal and molecular structure of the [Y(Phen){( i -C4H9)2PS2}2NO3] mixed-ligand compound

The [Y(Phen){(i-C₄H₉)₂PS₂}₂NO₃] mixed-ligand compound (I) was synthesized. Its structure was determined by X-ray diffraction analysis (X8 APEX diffractometer, λMoK _α , 3788 F _hkl , R = 0.0677). Crystals I are orthorhombic: a = 10.6495(8) Å, b = 20.006(2) Å, c = 35.317(4) Å, V = 7524.4(13) ų, Z = 8, ρ_calc = 1.324 g/cm³, space group Pbca. The structure is built of mononuclear discrete molecules. The N₂O₂S₄ coordination polyhedron of the Y atom is a distorted dodecahedron. Original Russian Text Copyright ? 2008 by V. L. Varand, L. A. Glinskaya, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 182–186, January–February, 2008.     

Crystal and molecular structure of (NH4)2[UO2(NO3)4] and [(NH4)(18C6)]2[UO2(NO3)4]

Single crystals of diammonium tetranitratouranylate (NH₄)₂[UO₂(NO₃)₄] (I) and a new diammonium tetranitratouranylate complex with 18-crown-6 [(NH₄)(18C6)]₂[UO₂(NO₃)₄] (II) have been synthesized by the reaction of diaquadinitratouranyl tetrahydrate with ammonium nitrate in a nitric acid solution and the reaction of the same reagents with 18C6 in an ethanol solution, respectively. The X-ray diffraction analysis of compounds I and II has been performed. Crystals of compounds I and II are monoclinic, Z = 2, space group P2₁/n, a = 6.4075(5) ?, b = 7.7851(7) ?, c = 12.4461(12) ?, β = 101.239(1)°, V = 608. 94(9) ?³ for compound I and a = 10.542(9) ?, b = 8.590(8) ?, c = 22.5019(19) ?, β = 101.632(1)°, V = 2058.3(3) ?³ for compound II. The [UO₂(NO₃)₄]²⁻ complex anion in compounds I and II contains two monodentate and two bidentate cyclic nitrato groups, and the coordination number of uranyl is 6. The 18C6 molecule in the structure of compound II has the classic crown conformation and combined with the ammonium ion by three hydrogen bonds. Compounds I and II formed by electrostatic attraction forces between counterions are stabilized by (NH₄⁺)NH...O(NO₃⁻) interionic hydrogen bonds.     

X-ray powder diffraction features of manganites DyM 3I M 3II Mn4O12 (MI = Li, Na, K; MII = Mg, Ba)

Manganites DyM₃^IMg₃Mn₄O₁₂ and DyM₃^IBa₃Mn₄O₁₂ (M^I = Li, Na, K) were synthesized by the solid-state reaction of dysprosium and manganese(III) oxides and magnesium and corresponding alkali metal carbonates. The X-ray powder diffraction studies showed that the crystals are orthozhombic with the following unit cell parameters and densities: DyLi₃Mg₃Mn₄O₁₂—a = 10.88 ?, b = 10.73 ?, c = 19.63 ?, V ⁰ = 1656.2 ?³, Z = 8, ρ_calc = 5.36 g/cm³, ρ_pycn = 5.11 ± 0.05 g/cm³; DyNaMg₃Mn₄O₁₂—a = 10.55 ?, b = 10.72 ?, c = 18.28 ?, V ⁰ = 2067.4 ?³, Z = 8, ρ_calc = 4.60 g/cm³, ρ_pycn = 4.88 ± 0.09 g/cm³; DyK₃Mg₃Mn₄O₁₂—a = 10.56 ?, b = 10.72 ?, c = 20.89 ?, V ⁰ = 2206.0 ?³, Z = 8, ρ_calc = 4.60 g/cm³, ρ_pycn = 4.92 ± 0.06 g/cm³; DyLi₃Ba₃Mn₄O₁₂—a = 10.53 ?, b = 10.69 ?, c = 21.28 ?, V ⁰ = 2395.4 ?³, Z = 8, ρ_calc = 5.58 g/cm³, ρ_pycn = 5.98 ± 0.12 g/cm³; DyNa₃Ba₃Mn₄O₁₂—a = 10.53 ?, b = 10.74 ?, c = 23.00 ?, V ⁰ = 2602.3 ?³, Z = 8, ρ_calc = 5.39 g/cm³, ρ_pycn = 5.30 ± 0.07 g/cm³; DyK₃Ba₃Mn₄O₁₂—a = 10.52 ?, b = 10.75 ?, c = 25.69 ?, V ⁰ = 2905.2 ?³, Z = 8, ρ_calc = 5.04 g/cm³, ρ_pycn = 5.00 ± 0.18 g/cm³.     

Structure and properties of double complex salts [Co(NH3)6][Fe(CN)6] and [Co(NH3)6]2[Cu(C2O4)2]3

Double complex salts (DCSs) [Co(NH₃)₆][Fe(CN)₆] (I) and [Co(NH₃)₆]₂[Cu(C₂O₄)₂]₃ (II) and complex [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O (III) are synthesized and investigated by single crystal XRD, crystal optics, and elemental analysis. The crystalline phases of I, II, and III (R-3, P2₁/c, and Pnnm space groups respectively) have the following crystallographic characteristics: a = 10.9804(2) ?, b = 10.9804(2) ?, c = 10.8224(3) ?, V = 1130.03(4) ?³, Z = 3, d _x = 1.65 g/cm³ (I); a = 9.6370(2) ?, b = 10.2452(2) ?, c = 13.2108(3) ?, V = 1932.90(9) ?³, Z = 2, d _x= 1.97 g/cm³ (II), and a = 11.7658(3) ?, b = 11.7254(3) ?, c = 14.1913(4) ?, V = 1304.34(5) ?³, Z = 2, d _x = 1.68 g/cm³ (III). This paper investigates the products of DCS thermolysis in a hydrogen atmosphere: the intermetallic compound CoFe with the bcc parameter a = 2.852 ? for I and a heterogeneous mixture of Co and Cu in the decomposition of II. The coordinated CN⁻ and C₂O₄²⁻ groups then turn into NH₃, hydrocarbons, and CO₂. The dominant hydrocarbon is methane.     

Structure of [RuNO(NH3)3(H2O)Cl](NO3)2, product of interaction between hydroxonitrotriamminenitrosoruthenium(II) chloride and nitric acid

The structure of the product formed on boiling [RuNO(NH₃)₃(NO₂)(OH)]Cl·0.5H₂O in 3 M HNO₃ is determined by XRD. The crystals belong to monoclinic symmetry. Crystallographic data for H₁₁ClN₆O₈Ru are: a = 13.7924(4) ?, b = 6.9114(2) ?, c = 12.3577(4) ?, β = 111.863(1)°, V = 1093.27(6) ?³, Z = 4, d _calc = 2.185 g/cm³, space group Cc. The structure is built of complex [RuNO(NH₃)₃(H₂O)Cl]²⁺ cations and NO₃⁻ anions. The compound is studied by IR spectroscopy and X-ray phase analysis. Original Russian Text Copyright ? 2009 by V. A. Emel’yanov, E. V. Kabin, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 598–601, May–June, 2009.     

Synthesis and X-ray diffraction study of R[UO2(CH3COO)3] (R = H3O+ or NH(C2H5) 3+ )

Single crystals of (H₃O)[UO₂(CH₃COO)₃] (I) and (NH(C₂H₅)₃)[UO₂(CH₃COO)₃] (II) are synthesized, and their structures are studied by X-ray crystallography. Compound I crystallizes in the tetragonal crystal system with the unit cell parameters a = 13.70640(10) ?, c = 27.5258(5) ?, V = 5171.14(11) ?³, space group I4₁/a, Z = 16, R = 0.0238. The crystals of compound II are orthorhombic with the parameters a = 13.3685(3) ?, b = 10.6990(3) ?, c = 12.2616(3) ?, V = 1753.77(8) ?³, space group Pna2₁, Z = 4, R = 0.0228. The uranium-containing structural units of crystals I and II are [UO₂(CH₃COO)₃]⁻ island mononuclear groups belonging to the A B₃⁰¹(A = UO₂²⁺, B⁰¹ = CH₃COO⁻) crystal-chemical group of uranyl complexes. [UO₂(CH₃COO)₃]⁻ complexes are linked into a three-dimensional framework by electrostatic interactions with the outer-sphere cations and by hydrogen bonds involving the hydrogen atoms of hydroxonium (I) or triethylammonium (II) with the oxygen atoms of the acetato groups.     

Synthesis, Formation Mechanism, and Crystal Structure of the Nitrosoruthenium(II) Nitrochloride Complex Fac-K2[RuNO(NO2)2Cl3]

Procedures for synthesis of the first nitrochloride complex of nitrosoruthenium(II), fac-K₂[RuNO(NO₂)₂Cl₃], are described and the mechanism of its formation is suggested. The compound was investigated by IR spectroscopy and X-ray phase and X-ray diffraction analyses. Crystal data for Cl₃N₃O₅K₂Ru: a = 7.050(1), b = 7.524(2), c = 10.125(2) , = 90.44(3), = 103.17(3), = 90.51(3)°, V = 522.9 ³, space group , Z = 2, d _calc = 2.589 g/cm³. The structure consists of the complex anions fac-[RuNO(NO₂)₂Cl₃]^2– and K⁺ cations. The complex crystallizes as triclinic plates and red orange prisms; it is well soluble in water, not readily soluble in KCl solutions, and insoluble in ethanol and acetone; the complex is stable when stored in air.     

Reaction of trans-[RuNO(NH3)4(OH)]Cl2 with nitric acid and synthesis of ammine(nitrato)nitrosoruthenium complexes

The reaction of trans-[RuNO(NH₃)₄(OH)]Cl₂ with nitric acid has been studied. Reaction products have been identified by IR spectroscopy, NMR, mass spectrometry, powder and single-crystal X-ray diffraction, and chemical analysis. Synthesis methods have been developed for amminenitrosoruthenium complexes containing outer-sphere and coordinated nitrate ions: trans-[RuNO(NH₃)₄(H₂O)](NO₃)₃ (I), trans-[RuNO(NH₃)₄(NO₃)](NO₃)₂ (II), and fac-[RuNO(NH₃)₂(NO₃)₃] (III). Complex II has two polymorphs: monoclinic and tetragonal. The latter has been studied by X-ray crystallography.     

Copper(II) Complexes with N-(3-Hydroximino-2-methylbutan-2-yl)methylamine (HL): Synthesis and Properties. Crystal and Molecular Structures of [Cu(HL)Cl2] and [Cu(HL)(H2O)2SO4]n

Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl₂(I), Cu(HL)(SO₄) · 2H₂O (II), and Cu(HL)(NO₃)₂(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C₆H₁₄Cl₂CuN₂O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) ų, space group P2₁/c, _calcd = 1.679 g/cm³, Z = 4 for R ₁ = 0.0250; for II(C₆H₁₈CuN₂O₇S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) ų, space group P2₁/c, _calcd = 1.753 g/cm³, Z = 4 for R ₁ = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H₂O) + 2O(SO₄)). Complexes I–IIIare characterized by IR and EPR spectroscopy.     

Crystal and molecular structures of the Rh[(C2H5O)2PS2]3 and Co[(C6H5O)2PS2]3 chelate compounds

The crystal structures of the Rh[(EtO)₂PS₂]₃ (I) and Co[(PhO)₂PS₂]₃ (II) chelate compounds were determined from X-ray diffraction (XRD) data (CAD-4 diffractometer, MoK _β radiation, 1193 F _hkl , R = 0.0516 for I and 513 F _hkl , R = 0.0305 for II). Crystals I are monoclinic: a = 14.233(3) Å, b = 13.570(3) Å, c = 14.272(3) Å; β = 90.66(3)°, V = 2756.3(10) ų, Z = 4, ρ_calc = 1.587 g/cm³, space group C2/c. Crystals II are trigonal: a = 15.149(2) Å, c = 30.306(6) Å; V = 6023.2(16) ų, Z = 6, ρ_calc = 1.493 g/cm³, space group R3ˉ. Structures I and II consist of discrete mononuclear molecules. The coordination polyhedra of the M atoms (M = Rh, Co) are distorted octahedra formed by six sulfur atoms of three cyclic bidentate (RO)₂ PS₂⁻ ligands. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 2, pp. 330–334, March–April, 2008.     

Crystal and molecular structure of [RuNO(NO2)4OHCuPy n ] heterometallic complexes

Heterometallic complexes [RuNO(NO₂)₄OHCuPy₂(H₂O)] (I) and [RuNO(NO₂)₄OHCuPy₃] (II) are described structurally for the first time. In complex I, the ruthenium anion is coordinated to the copper atom by the bridging OH group and two bridging nitro groups; in complex II, by the bridging OH group and one bridging nitro group. Dimers are formed in the crystal lattice of complex II due to the interaction of the copper atom and the nitro group of the ruthenium anion in trans position to the bridging NO₂ group.     

Heteropoly Complexes Na0.5Cs2 ? x[H0.5 ? xM

Crystals of novel heterepoly complexes (HPC) Na_0.5Cs_{2 − x} [H_{0.5 − x} M _x ^II X^III(OH)₆Mo₆O₁₈] · 7−8H₂O (M^II = Fe, Mn; X^III = Cr, Al) are synthesized. Crystal structures of the complexes Na_0.5Cs_{2 − x} [H_{0.5 − x} Fe_xCr(OH)₆Mo₆O₁₈] · 7H₂O (I) (x = 0.19) and Na_0.5Cs_{2 − x} [H_{0.5 − x} Mn_xAl(OH)₆Mo₆O₁₈] · 8H₂O (II) (x = 0.22) are determined (space group Pbcn, Z = 8, a = 23.023(4) Å, b = 22.064(4) Å, c = 11.606(3) Å, V = 5895.66 ų for I and a = 22.972(9) Å, b = 22.002(8) Å, c = 11.543(5) Å, V = 5834.18 ų for II, respectively). The [X^III(OH)₆Mo₆O₁₈]³⁻ ligands were found to be coordinated in monodentate fashion to M atoms due to the participation of a terminal O atom of the cis-MoO₂ group in coordination with the Fe and Mn atoms, which was confirmed by IR data. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 663–676. Original Russian Text Copyright ? 2005 by Gavrilova, Molchanov.     

Crystal and molecular structures of Ni[(iso-C4H9)2PS2]2 and Pd[(iso-C4H9)2PS2]2 chelates

Crystal structures of chelate compounds Ni[(iso-C₄H₉)₂PS₂]₂ (I) and Pd[(iso-C₄H₉)₂PS₂]₂ (II) have been determined by X-ray diffraction: diffractometer X8-APEX, MoK _α∔ -radiation, 1048 F _hkl , R = 0.0544 for I and CAD-4 diffractometer, MoK _α∔ -radiation, 1283 F _hkl , R = 0.0347 for II. The crystals are rhombic: a = 12.921(5) Å, b = 17.094(5) Å, c = 22.971(5) Å; V = 5074(3) ų, Z = 8, calc = 1.250 g/cm³, space group Pbca for I and a = 13.312(3) Å, b = 16.130(7) Å, c = 23.171(5) Å; V = 4975(3) ų, Z = 8, ρ_calc = 1. 208 g/cm³, space group Pbca for II. The structures of I and II are formed by discrete mononuclear molecules. Coordination cores MS₄ (M = Ni, Pd) approach planar square configurations. Original Russian Text Copyright ? 2005 by L. A. Glinskaya, T. G. Leonova, T. E. Kokina, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp. 715–720, July–August, 2005.     

Crystal structure of cadmium iodide complexes with acetamide and propaneamide [Cd(CH3CONH2)6][Cd2I6] and [Cd(C2H5CONH2)6][Cd2I6]

The complexes of CdI₂ with acetamide (AA) and propaneamide (PrA) of the composition [Cd(AA)₆][Cd₂I₆] (I) and [Cd(PrA)₆][Cd₂I₆] (II) were synthesized and studied by X-ray diffraction. Isostructural crystals I and II are triclinic: a = 7.285(3) and 8.066(6), b = 11.266(4) and 11.649(3), c = 11.554(3) and 12.063(2) ?, α = 100.96(2)° and 102.74(2)°, β = 91.59(2)° and 91.73(4)°, γ = 100.76(3)° and 101.05(4)°, V = 912.5 and 1081.9 ?³, respectively; space group , Z = 1. Original Russian Text ? I.A. Zamilatskov, E.V. Savinkina, D.V. Al’bov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 6, pp. 407–410.     

Synthesis and Crystal Structure Investigation of Trinitrotriamminerhodium(III) [Rh(NO2)3(NH3)3]

Synthesis of the complex [Rh(NO₂)₃(NH₃)₃] is described. The compound crystallizes as monoclinic colorless plates. Crystal data: a = 7.176(10), b = 10.407(2), c = 10.989(2) , = 93.27°, V = 819.3(2) ³, space group , Z = 4, d _calc = 2.367 g/cm³. The structure is molecular and built of neutral complexes having cis-facial configuration. The unit cell of the crystal contains two independent complexes.     

A series of open-framework tin(II) phosphates: A[Sn4(PO4)3] (A=Na,K, NH4)

A new series of isostructural open-framework tin(II) phosphates with general formula A[Sn₄(PO₄)₃], where A=Na, K, NH₄, has been synthesized by hydrothermal methods. The crystal structures of NaSn₄(PO₄)₃ (I) and KSn₄(PO₄)₃ (II) have been solved by single crystal X-ray diffraction methods. Both phases crystallize in the trigonal space group R3c (#161) with Z=6 and cell parameters a=9.5508(13) Å, c=24.083(3) Å for I, and a=9.7124(11) Å, c=24.363(3) Å for II. The structure consists of a negatively charged [Sn₄(PO₄)₃]⁻ framework with channels running parallel to the a- and b-axes where the charge compensating A⁺ cations are located. An interesting feature is that half of the channels are empty due to the specific geometry of the SnO₃ units—the lone electron pair of the tin atoms “protrudes” in these channels thus preventing the insertion of A⁺. The new phases have also been characterized by infrared and thermogravimetric analyses.