Crystal structures of Ti(NH<Subscript>4</Subscript>)<Subscript>2</Subscript>P<Subscript>4</Subscript>O<Subscript>13</Subscript> and Sn(NH<Subscript>4</Subscript>)<Subscript>2</Subscript>P<Subscript>4</Subscript>O<Subscript>13</Subscript>

The characteristics of crystal structures of the titanium(IV) diammonium (Ti(NH₄)₂P₄O₁₃) and tin(IV) diammonium (Sn(NH₄)₂P₄O₁₃) tetraphosphates, which are isostructural with similar silicon(IV) and germanium(IV) salts, have been obtained by the Rietveld method using X-ray powder diffraction data. The compounds crystallize in the triclinic system, space group P \(\overline 1 \), Z = 2, a = 15.0291(7) Å, b = 7.9236(4) Å, c = 5.0754(3) Å, α = 99.168(3)°, β = 97.059(3)°, γ = 83.459(3)° for Ti(NH₄)₂P₄O₁₃ and a = 15.1454(7) Å, b = 8.0103(5) Å, c = 5.1053(3) Å, α = 99.898(6)°, β = 96.806(3)°, γ = 83.881(4)° for Sn(NH₄)₂P₄O₁₃. The structure is refined in the isotropic approximation using the pseudo-Voigt function: R _p = 0.077, R _Bragg = 0.045, R _F = 0.057 for Ti(NH₄)₂P₄O₁₃; R _p = 0.082, R _Bragg = 0.044, R _F = 0.046 for Sn(NH₄)₂P₄O₁₃. The hydrogen atoms of the ammonium cations are placed in the calculated positions. A comparative analysis of the structures of the compounds of the M^IV(NH₄)₂P₄O₁₃ (M^IV = Si, Ge, Ti, Sn) series has been carried out.     

Synthesis,crystal structure,and thermal properties of [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][AuCl<Subscript>4</Subscript>]<Subscript>2</Subscript>

The double complex salt [Pd(NH₃)₄][AuCl₄]₂ was synthesized and studied by X-ray diffraction: a = 7.5234(6) Å, b = 7.7909(5) Å, c = 8.0247(6) Å, α = 108.483(2)°, β = 106.497(2)°, γ = 99.972(3)°, V = 409.43(5) ų, space group P \(\overline 1 \), Z = 1, ρ_calod = 3.456 g/cm³, R = 0.0267. The compound was characterized by powder X-ray diffraction, thermal analysis, and IR and Raman spectroscopy. The metal products of thermolysis of the complex were studied by powder X-ray diffraction.     

Synthesis,structure, and properties of V<Subscript>2</Subscript>O<Subscript>3</Subscript>(XO<Subscript>4</Subscript>)<Subscript>2</Subscript> (X = S,Se)

Compounds described as V₂O₃(XO₄)₂, where X = S or Se, were prepared from vanadium(V) oxide mixtures with concentrated sulfuric and selenic acids. The physicochemical properties of the products were studied; for V₂O₃(SeO₄)₂, the crystal structure was determined by powder X-ray diffraction and neutron diffraction, and its key differences from the structure of V₂O₃(SO₄)₂ were identified. V₂O₃(SeO₄)₂ crystallizes in the monoclinic system with the unit cell parameters a = 15.3831(2)Å, b = 5.54096(5)Å, c = 9.71644(7)Å, β = 111.886(1)°, V = 768.51ų, space group C2/c (no. 15).     

Crystal structure and properties of [M(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>, (M = Ir,Rh, Ru)

The crystal structures of compounds from the series [M(NH₃)₅Cl](NO₃)₂, (M = Ir, Rh, Ru) were described. The compounds crystallized in the tetragonal crystal system, space group I4, Z = 2. Crystal data for [Ir(NH₃)₅Cl](NO₃)₂ (I): a = 7.6061(1) Å, b = 7.6061(1) Å, c = 10.4039(2) Å, V = 601.894(16) ų, ρ_calc = 2.410 g/cm³, R = 0.0087; [Rh(NH₃)₅Cl](NO₃)₂ (II): a = 7.5858(5) Å, b = 7.5858(5) Å, c = 10.41357(7) Å, V = 599.24(7) ų, ρ_calc = 1.926 g/cm³, R = 0.0255; [Ru(NH₃)₅Cl](NO₃)₂ (III): a = 7.5811(6) Å, b = 7.5811(6) Å, c = 10.5352(14) Å, V = 605.49(11) ų, ρ_calc = 1.896 g/cm³, R = 0.0266. The compounds were defined by IR spectroscopy and XRPA and thermal analyses.     

Synthesis,structure, and properties of the thermolysis products of [Os(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl][ReCl<Subscript>6</Subscript>]

The crystal structure of [Os(NH₃)₅Cl][ReCl₆] has been refined by X-ray powder analysis: a = 11.645(3) Å, b = 8.3788(2) Å, c = 15.277(4) Å, β = 91.029(6)°, V = 1490(1) ų, d _x = 3.163 g/cm³, space group P2₁/m, Z = 4. The thermolysis product of the salt in a hydrogen atmosphere is a solid substitution solution Os_0.5Re_0.5: a = 2.753(2) Å, c = 4.366(3) Å, space group P6₃/mmc; coherent scattering region (CSR) is ～230 Å.     

Thermolysis of [Pt(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][ReHlg<Subscript>6</Subscript>] (Hlg = Cl,Br). Structure refinement for [Pt(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][ReCl<Subscript>6</Subscript>]

Thermal decomposition of [Pt(NH₃)₄][ReHlg₆] binary complex salts (Hlg = Cl, Br) in a hydrogen atmosphere has been studied. Polycrystal X-ray diffractometry indicated that two-phase metallic systems are the final products of thermolysis. Structure refinement was performed for [Pt(NH₃)₄][ReCl₆] by the combined technique involving decomposition of the diffractogram into individual reflections, isolation of reflections most sensitive to the position of separate light atoms, and full-profile analysis. Crystal data for PtReN₄Cl₆H₁₂: a = 11.616(1) Å, b = 10.998(1) Å, c = 10.377(1) Å, V = 1148.1 ų, space group Cmca, Z = 4, d _x = 3.831 g/cm³. The indices are R_p = 5.48%, R_wp = 10.01%, R(F²) = 12.62%. The coordination polyhedron of Re is an almost regular octahedron: Re-Cl 2.34–2.36 Å, ∠ Cl-Re-Cl 86.9–90.3°; the coordination polyhedron of Pt is a square: Pt-N 2.04 Å, ∠N-Pt-N 90.4°.     

Orientational disorder in crystal structures of (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>ZrF<Subscript>7</Subscript> and (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

Crystal structures of (NH₄)₃ZrF₇ (I) and (NH₄)₃NbOF₆ (II) are refined by X-ray diffraction at room temperature. The compounds are isostructural and belong to the structural type of elpasolite: space group F23; a(I) = 9.4185(3) Å, a(II) = 9.3371(5) Å; V(I) = 835.50(5) ų, V(II) = 814.02(8) ų; Z = 4; R(I) = 0.0145, and R(II) = 0.0138. The refinement of the structures in the space group Fm3m yields abnormally short X-X distances in the pentagonal bipyramid MX₇ (X = F, O). The oxygen atom in II is identified by Nb-X distances and occupies one of the axial vertices of the bipyramid. The Nb atom in II is statistically distributed over the position 24f, while Zr in I resides in the symmetry center. The pentagonal bipyramid MX₇ has six independent orientations in I and twelve in II. One of three crystallographically independent ammonium groups of the structures is disordered over six or twelve equivalent orientations.     

Bismuth aluminoborate Bi<Subscript>0.96</Subscript>Al<Subscript>2.37</Subscript>(B<Subscript>4</Subscript>O<Subscript>10</Subscript>)O: Synthesis and crystal structure

The crystal structure of a new bismuth aluminoborate Bi_0.96Al_2.37(B₄O₁₀)O is studied by single-crystal X-ray diffraction. The Bi_0.96Al_2.37(B₄O₁₀)O single crystals are hexagonal (space group \(P\bar 6\) 2m). The unit cell parameters are as follows: a = b = 4.587(4) Å, c = 2.253(9) Å, α = β = 90°, γ = 120°, V = 168.60 ų, Z = 1.     

Palladium clusters Pd<Subscript>4</Subscript>(SR)<Subscript>4</Subscript>(OAc)<Subscript>4</Subscript> and Pd<Subscript>6</Subscript>(SR)<Subscript>12</Subscript> (R = Bu,Ph): Structure and properties

The structures of the Pd₄(SBu)₄(OAc)₄ (I) and Pd₆ (SBu)₁₂ (II) palladium clusters are determined by the X-ray diffraction method. For cluster I: a = 8.650(2), b = 12.314(2), c = 17.659(4) Å, α = 78.03(3)°, β = 86.71(2)°, γ = 78.13(3)°, V = 1800.8(7) ų, ρcalcd = 1.878 g/cm³, space group P \(\bar 1\), Z = 4, N = 3403, R = 0.0468; for structure II: a = 10.748(2), b = 12.840(3), c = 15.233(3) Å, α = 65.31(3)°, β = 70.10(3)°, γ = 72.91(3)°, V = 1767.4(6) ų, ρ calcd = 1.605 g/cm³, space group P \(\bar 1\), Z = 1, N = 3498, R = 0.0729. In cluster I, four Pd atoms form a planar cycle. The neighboring Pd atoms are bound by two acetate or two mercaptide bridges (Pd…Pd 2.95–3.23 Å, Pd…Pd angles 87.15°–92.85°). In cluster II, the Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.09–3.14 Å, the PdPdPd angles being 118.95°–120.80°. The Pd atoms are linked in pairs by two mercaptide bridges. The formation of clusters I and II in solution is proved by IR spectroscopy and calorimetry. Analogous clusters are formed in solution upon the reaction of palladium(II) diacetate with thiophenol.     

Crystal structures of <Emphasis Type="Italic">trans</Emphasis>-[Re<Subscript>6</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>2</Subscript>L<Subscript>4</Subscript>] complexes,L = pyridine or 4-methylpyridine

The structures of three novel octahedral rhenium cluster compounds [Re₆S₈(CN)₂(py)₄]·H₂O (1), [Re₆S₈(CN)₂(4-Mepy)₄] (2), [Re₆S₈(CN)₂(4-Mepy)₄]·4-Mepy (3) (py = pyridine, 4-Mepy = 4-methylpyridine) are determined by X-ray crystallography. Crystal data are: C2/m space group, a = 14.813(1) Å, b = 14.772(1) Å, c = 9.2122(6) Å, β = 119.085(2)°, V = 1761.7(2) ų, d _x = 3.318 g/cm³, R = 0.0585 (1); I4₁/amd space group, a = 16.0018(3) Å, c = 14.7186(5) Å, V = 3768.81(16) ų, d _x = 3.169 g/cm³, R = 0.0489 (2); P2₁/c space group, a = 9.0452(4) Å, b = 15.8065(7) Å, c = 15.2951(6) Å, β = 103.700(2)°, V = 2124.57(16) ų, d _x = 2.957 g/cm³, R = 0.0245 (3). Molecular cluster complexes interact via π-π stacking affording 3D frameworks in 1 and 2 and chains in 3.     

Synthesis,crystal structure,and properties of [Rh(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl][ReBr<Subscript>6</Subscript>]

A binary complex salt [Rh(NH₃)₅Cl][ReBr₆] has been synthesized and investigated by X-ray diffraction analysis. Crystal data: a = 8.541(5) Å, b = 12.015(6) Å, c = 16.496(9) Å; α = 73.695(10)°, β = 89.746(9)°, γ = 89.676(9)°, V = 1624.7 ų, space group \(P\overline 1 \), Z = 4, D _x = 3.635 g/cm³, R = 0.12. It is shown that the product of thermolysis of the salt in the atmosphere of hydrogen and helium is a solid solution Rh_0.5Re_0.5 with hcp cell parameters a = 2.731(5) Å and c = 4.368(7) Å.     

Crystal Structure of New One-Dimensional Triple Molybdate Na<Subscript>2</Subscript>K<Subscript>2</Subscript>Cu(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The title compound (disodium dipotassium copper(II) tris-[molybdate (VI)]) is prepared by form melt and characterized by single crystal X-ray diffraction and UV-vis spectroscopy. It crystallizes in the triclinic space group P-1 with a = 7.4946(8) Å, b = 9.3428(9) Å, c = 9.3619(9) Å, α = 92.591(7)°, β = 105.247(9)°, γ = 105.496(9)°, V = 604.7 ų, and Z = 2. Its structure is isotypic with that of Na₄Mn(MoO₄)₃. It is formed by Cu₂O₁₀ distorted bi-octahedral dimers linked by two bridging bidentate Mo₂O₄ tetrahedra and, additionally, two monodentate Mo₁O₄ tetrahedra to form Cu₂Mo₄O₂₀ units. These units are linked by the insertion of Mo₃O₄ tetrahedra to build infinite ribbons disposed along the c axis. All of these ribbons form a one-dimensional framework. Both K1 and K3 cations are located in the inversion center, and all the other atoms are at general positions. The structure model is supported by the bond valence sum (BVS) and charge distribution CHARDI methods. The Cu²⁺ cations adopt the [4+2] CuO₆ Jahn-Teller distortion giving rise to an intense d–d transition in the UV-vis absorption spectra.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Synthesis,crystal structure,and vibrational spectra of M<Subscript>4</Subscript>V<Subscript>2</Subscript>O<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript> (M = K,Rb, Cs)

Synthesis was performed and physicochemical properties were studied for the M₄V₂O₃(SO₄)₄ complexes, where M = K, Rb, or Cs. Their crystal structures were determined using the set of data from X-ray diffraction and neutron diffraction studies. All compounds crystallize in a triclinic lattice (space group \(P\bar 1\), Z = 2) with the parameters: a = 7.7688(2), 7.8487(1), 8.1234(1) Å; b = 10.4918(3), 10.8750(2), 11.1065(1) Å; c = 11.9783(4), 12.1336(2), and 11.8039(1) Å; α = 76.600(2)°, 77.910(1)°, 79.589(1)°; β = 75.133(2)°, 75.718(1)°, 87.939(1)°; γ = 71.285(2)°, 72.189(1)°, 75.567(1)°; V = 881.78(5), 945.42(3), 1014.34(2) ų for K, Rb, Cs, respectively. The structure of M₄V₂O₃(SO₄)₄ was found to be formed by discrete complex anions V₂O₃(SO₄) ₄ ^4? incorporating two oxygen-bridged vanadium atoms in a distorted octahedral oxygen environment. The sulfate groups are coordinated by the vanadium atoms in the chelating mode with a large scatter of S-O interatomic distances and OSO angles. Every VO₆ octahedron has a short terminal vanadium-oxygen bond with a length of about 1.6Å. The V₂O₃(SO₄) ₄ ^4? complex anions in potassium and rubidium compounds differ from that in Cs₄V₂O₃(SO₄)₄ in the type of symmetry and mutual spatial orientation. The vibrational spectra were presented and interpreted in line with the structural analysis data.     

X-ray diffraction study of the monoclinic modification of [Cu(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> in the range 100-410 K

The monoclinic modification of [Cu(NH₃)₄](ReO₄)₂ complex salt in the range 100-410 K is studied by single crystal X-ray diffraction. The crystallographic data for 300 K are as follows: a = 10.6123(3) Å, b = 7.5443(2) Å, c = 15.2261(4) Å, β = 108.406(1)°, V = 1156.67(5) ų, space group Р2₁/n, Z = 4, d_x = 3.623 g/cm³. The coordination environment of the Cu atom, being a distorted square formed by four nitrogen atoms with Cu–N of 1.997-2.018 Å, is completed by the contacts with two oxygen atoms Cu…O of 2.472 Å and 2.598 Å. The comparative crystal chemical analysis with the triclinic modification of [Cu(NH₃)₄](ReO₄)₂ known in the literature is performed.     

Synthesis,characterization and very strong luminescence of a new 3 D europium sulfate Eu<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript>

A new 3 D europium sulfate Eu₂(H₂O)₄(SO₄)₃ 1 is synthesized solvothermally and characterized by single crystal X-ray diffraction, IR spectrum, TG, powder XRD, and ultraviolet excitation and emission spectrum. This compound crystallizes in the triclinic system with the space group P-1, a = 6.7520(9) Å, b = 9.1077(12) Å, c = 10.5910(14) Å, α = 94.432(2)°, β = 107.1170(10)°, γ = 99.160(2)°, V = 609.17(14) ų, Z = 2. The open framework of the title compound is an eight-membered ring channel along the crystallographic a-axis, which is built up by EuO₈ polyhedra and SO₄ tetrahedra.     

X-Ray diffraction data for new ferrites ErMFe<Subscript>2</Subscript>O<Subscript>5</Subscript> (M = Li,Na, K)

New ferrites ErMFe₂O₅ (M = Li, Na, K) were synthesized from erbium and iron(III) oxides and lithium, sodium, and potassium carbonates by solid-state annealing. According to X-ray powder diffraction, these compounds crystallize in the orthorhombic system with the following unit cell parameters: ErLiFe₂O₅, a = 10.510 Å, b = 10.776 Å, c = 14.270 Å, V ⁰ = 1616.16 ų; Z = 16, V _subcell ⁰ = 101.01 ų, ρ_X = 6.01 g/cm³, ρ_pycn = 5.97 ± 0.05 g/cm³; ErNaFe₂O₅, a = 10.519 Å, b = 10.785 Å, c = 15.510 Å, V ⁰ = 1759.56 ų, Z = 16, V _subcell ⁰ = 109.90 ų, ρ_X = 5.77 g/cm³, ρ_pycn = 5.72 ± 0.08 g/cm³; ErKFe₂O₅, a = 10.050 Å, b = 11.320 Å, c = 15.480 Å, V ⁰ = 1937.33 ų, Z = 16, V _subcell ⁰ = 121.08 ų, ρ_X = 5.46 g/cm³, ρ_pycn = 5.41 ± 0.04 g/cm³.     

Crystal Structures of New Chalcogenide- Containing Yttrium Orthosilicates Y<Subscript>2</Subscript>SiO<Subscript>4</Subscript>Q (Q = S,Se)

Compounds Y₂SiO₄Q (Q = S, Se) are obtained by the interaction of oxides and elemental substances in cesium chloride flux. The structures of these compounds are determined by the single crystal XRD analysis. These compounds isostructural and crystallize in the space group Pbcm with the following parameters: Y₂SiO₄S (I) a = 6.0462(8) Å, b = 6.8976(9) Å, c = 10.6558(13) Å, V = 444.39(10) ų; Y₂SiO₄Se (II) a = 5.9935(7) Å, b = 6.9216(8) Å, c = 10.7688(12) Å, V = 446.74(9) ų. The measured fluxing points are 1650±15 °С for I and 1850±15 °С for II.     

Structure of a new chelate complex MO<Subscript>2</Subscript>O<Subscript>3</Subscript>(dpm)<Subscript>4</Subscript>

A new Mo₂O₃(dpm)₄ compound (I) is synthesized by the interaction of Mo(CO)₆ with 2,2,6,6-tetramethylheptanedione-3,5 (dpm). The structure of complex I determined by the XRD method is as follows: triclinic crystal system, space group P–1, a = 10.1780(7) Å, b = 10.1817(6) Å, c = 13.3255(9) Å, α = 110.562(2)°, β = 102.233(2)°, γ = 93.9041(19)°, V = 1248.17(14) ų. The compound is characterized by IR spectroscopy, mass-spectrometry and thermogravimetric analysis (TGA).     

Chromites YbMCr<Subscript>2</Subscript>O<Subscript>5</Subscript> (M = Li,Na, K,Cs): X-ray diffraction study

Ytterbium alkali-metal chromites YbMCr₂O₅ (M = Li, Na, K, Cs) were synthesized by a ceramic procedure from the corresponding oxides and carbonates. Their crystal systems and unit cell parameters were determined by the homology method: for YbLiCr₂O₅, a = 10.34 Å, b = 10.62 Å, c = 15.05 Å, Z = 16, V ^o = 1653.74 ų, ρ_X-ray = 5.85 g/cm³, ρ_pycn = 5.81 ± 0.03 g/cm³; for YbNaCr₂O₅, a = 10.30 Å, b = 10.56 Å, c = 16.46 Å, Z = 16, V ^o = 1790.32 ų, ρ_X-ray = 5.64 g/cm³, ρ_pycn = 5.59 ± 0.07 g/cm³; for YbKCr₂O₅, a = 10.33 Å, b = 10.63 Å, c = 19.93 Å, Z = 16, V ^o = 2188.47 ų, ρ_X-ray = 5.95 g/cm³, ρ_pycn = 5.91 ± 0.03 g/cm³; and for YbCsCr₂O₅, a = 10.34 Å, b = 10.63 Å, c = 18.43 Å, Z = 16, V ^o = 2025.72 ų, ρ_X-ray = 5.19 g/cm³, ρ_pycn = 5.16 ± 0.05 g/cm³.