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.     

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°.     

Crystal structure of bis(semicarbazido)copper(II) nitrate [Cu(NH<Subscript>2</Subscript>NHC(O)NH<Subscript>2</Subscript>)<Subscript>2</Subscript>](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The crystal structure of bis(semicarbazido)copper(II) nitrate [Cu(NH₂NHC(O)NH₂)₂](NO₃)₂ has been studied by X-ray diffraction. Monoclinic crystals, a = 6.835(2) Å, b = 7.733(2) Å, c = 10.320(3) Å, β = 105.701(3)°, V = 525.1(2) ų, space group P2₁/c, Z = 2, d _msd = 2.136 g/cm³, μ(MoK _α) = 2.143 mm⁻¹. The structure was solved with the program for automatic analysis of Patterson’s function and refined by full-matrix least squares in an anisotropic approximation for all non-hydrogen atoms using 753 independent reflections; R ₁ = 0.0203. The square environment of the Cu atom is formed from the amino nitrogen atoms of the hydrazine fragments and the C=O oxygen atoms of the two semicarbazide bidentate molecules (Cu-N 1.928 Å, Cu-O 1.999 Å). The axial positions are occupied by the O atoms of the NO ₃ ⁻ outer-spheric anions (Cu-O 2.505 Å). In the structure, the complex cations and the NO ₃ ⁻ anions are linked into a framework by N-H...O type hydrogen bonds. Original Russian Text Copyright ? 2007 by G. V. Romanenko, Z. A. Savelieva, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 2, pp. 370–373, March–April, 2007.     

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 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 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 and crystal structure of [Cr(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl][PdBr<Subscript>4</Subscript>]

A new binary complex salt — chloropentaamminechromium(III) tetrabromopalladate(II) [Cr(NH₃)₅Cl][PdBr₄] — has been synthesized. The compound was characterized by elemental, X-ray diffraction, and X-ray phase analysis. The salt is isostructural with the previously investigated compounds [M(NH₃)₅Cl][PtCl₄] (M = Ir, Rh, Ru, Co, Cr) and [CM(NH₃)₅Cl][PdBr₄] (M = Ir, Rh, Co). Crystallographic data: space group Pnma, a = 17.068(2) Å, b = 8.315(12) Å, c = 9.653(14) Å; V = 1370.0(3) ų, Z = 4, d _calc = 2.903 g/cm³.     

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.     

Uranyl cyanoacetate [UO<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(NCCH<Subscript>2</Subscript>COO)<Subscript>2</Subscript>]: Synthesis,crystal structure,and absorption spectra

The U(VI) complex with cyanoacetic acid, [UO₂(H₂O)₂(NCCH₂COO)₂] (I), was synthesized from an aqueous solution, and its X-ray diffraction analysis was carried out. The crystals are orthorhombic: space group Pca2 ₁, a = 25.9605(7) Å, b = 6.7634(2) Å, c = 6.3398(2) Å, V = 1113.15(6) ų at 100 K, and Z = 4. The coordination polyhedron of the uranium atom is a distorted pentagonal bipyramid. The cations UO ₂ ²⁺ are bound into infinite zigzag chains by the bridging carboxyl groups of one of the anions of cyanoacetic acid. The carboxyl oxygen atom of the second anion, which is not involved in coordination, and the nitrogen atoms of the cyano groups form hydrogen bonds with the coordination water molecules. The layer structure of the compound is formed through the hydrogen bonds. The absorption spectra in the visible and infrared ranges of the crystalline compound are measured and analyzed.     

Synthesis and crystal structure of (NH<Subscript>4</Subscript>)(CN<Subscript>3</Subscript>H<Subscript>6</Subscript>)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of (NH₄)(CN₃H₆)[UO₂(SeO₃)₂] (I) are synthesized and studied by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with the unit cell parameters: a = 7.0051(2) Å, b = 9.4234(3) Å, c = 9.5408(3) Å, α = 88.727(1)°, β = 70.565(1)°, γ= 77.034(1)°, space group P ₁, Z = 2, R = 0.0224. The main structural units of crystals I are the [UO₂(SeO₃)₂]^2? chains of the crystal-chemical group AB²B₁₁ (A = UO ₂ ²⁺ , B₂= SeO₃ ^2?, B₁₁= SeO₃ ^2?) of the uranyl complexes. The uranium-containing complexes are joined into a three-dimensional framework by the ammonium and guanidinium ions and a system of hydrogen bonds.     

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.     

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.     

Study of the monocarbonate complex of pentavalent neptunium (NH<Subscript>4</Subscript>)[NpO<Subscript>2</Subscript>(CO<Subscript>3</Subscript>)]

The single crystals of the Np(V) complex (NH₄)[NpO₂(CO₃)] (I) were synthesized and studied by X-ray diffraction. At 100 K, the crystals are hexagonal, space group P6₃ μmc, a = 5.0734(1) Å, c = 10.9191(2) Å, V= 243.399(11) ų, Z = 2, ρ(calcd) = 4.735 g/cm³. The absorption spectra of a crystal of I in the visible and infrared ranges were measured.     

Structural investigation of [Au(en)<Subscript>2</Subscript>]Cl(ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> and [Au(en)<Subscript>2</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>3</Subscript> complexes

Novel complex salts [Au(en)₂]Cl(ReO₄)₂ (I) and [Au(en)₂](ReO₄)₃ (II), en = ethylenediamine, are obtained. Their crystal structures are determined by single crystal X-ray diffraction. Complex I crystallizes in the triclinic crystal system: a = 6.2172(7) Å, b = 7.1644(8) Å, c = 8.8829(8) Å, α = 96.605(4)°, β = 110.000(4)°, γ = 97.802(4)°, P-1 space group, Z = 1, d _x = 3.905 g/cm³; complex II crystallizes in the monoclinic crystal system: a = 15.244(2) Å, b = 7.6809(8) Å, c = 9.3476(12) Å, β = 127.004(3)°, C2 space group, Z = 4, d _x = 4.057 g/cm³.     

Organometallic coordination polymers based on silver carboxylates: [AgCF<Subscript>3</Subscript>CO<Subscript>2</Subscript>(2,3-Et<Subscript>2</Subscript>Pyz)] and [AgCF<Subscript>3</Subscript>CO<Subscript>2</Subscript>(Bpeta)]

Coordination polymers [AgCF₃CO₂(2,3-Et₂Pyz)](I)(2,3-Et₂Pyz-C₈H₁₂N₂) and [AgCF₃CO₂(Bpeta)] (II) (Bpeta is 4′4-bipyridylethane, C₁₂H₁₂N₂) are synthesized. Their structures are determined. The crystals of compound I are monoclinic, space group P2(1)/n, a = 7.185(1), b = 14.754(1), c = 12.317(1)Å, β = 97.09(1)°, V = 1295.7(2) ų, ρ_calcd = 1.831 g/cm³, Z = 4. Structure I consists of infinite chains of doubled polymeric chains joined by silver carboxylate dimers [[Ag₂(CF₃CO₂)₂(Et₂Pyz)₂]_∞. The coordination polyhedron of Ag⁺ is a distorted tetrahedron. The crystals of compound II are orthorhombic, space group Pbca, a = 13.555(3), b = 13.991(3), c = 16.449(3) Å, V = 3119.5(11) ų, ρ_calcd = 1.725 g/cm³, Z = 8. Doubled polymeric chains with the Ag…Ag bond (3.16 Å) are also formed in structure II. Supramolecular layers are formed in the structure due to the weak π-π-stacking interaction between the aromatic groups of chains. The CF₃CO ₂ ^? anion is weakly bound to Ag⁺ (Ag-O_avg 2.790 Å).     

Synthesis,structure, and properties of M<Subscript>3</Subscript>VO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> (M = Rb,Cs)

Vanadium(V) complexes of general composition M₃VO₂(SO₄)₂ (M = Rb, Cs) were synthesized by a solid-state route. The individuality of the synthesized compounds was proved by X-ray and neutron diffraction, vibrational spectroscopy, and microscopic analysis. The X-ray diffraction patterns of M₃VO₂(SO₄)₂ were indexed to fit the monoclinic system (space group P2/c, Z = 4) with the following unit cell parameters: a = 11.6487(2) Å, b = 8.4469(2) Å, c = 12.1110(2) Å, β = 109.483(1)°, V = 1123.43 ų (Rb); a = 12.0546(3) Å b = 8.7706(2) Å, c = 12.6496(3) Å, β = 109.843(2)°, V = 1257.99 ų (Cs). In the crystal structure of M₃VO₂(SO₄)₂, [VO₂(SO₄)₂]^3? complex anions can be discerned in which the vanadium atom is surrounded by five oxygen atoms: two oxygen atoms form short terminal V–O bonds, and three oxygen atoms are from the two sulfato groups, one of which acts as a monodentate ligand and the other acts as a bidentate chelating ligand.     

Crystal structure of a new ternary molybdate in the Rb<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-Eu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>-Hf(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> system

A ternary salt system Rb₂MoO₄-Eu₂(MoO₄)₃-Hf(MoO₄)₂ was studied in the subsolidus area by X-ray phase analysis. A novel ternary molybdate, Rb_4.98Eu_0.86Hf_1.11(MoO₄)₆, formed in the system. The Rb_4.98Eu_0.86Hf_1.11(MoO₄)₆ rubidium-europium-hafnium molybdate crystals were grown by solution-melt crystallization under the spontaneous nucleation conditions. The structure and composition of this compound were refined by single crystal X-ray diffraction (X8 APEX automated diffractometer, MoK _α radiation, 1753 F(hkl), R = 0.0183). The crystals are trigonal, a = b = 10.7264(1) Å, c = 38.6130(8) Å, V = 3847.44(9) ų, Z = 6, space group R \(\bar 3\) c. The three-dimensional mixed framework of the structure comprises Mo tetrahedra and two types of octahedra, (Eu,Hf)O₆ and HfO₆. The large cavities of the framework include two types of the rubidium atom. The distribution of the Eu³⁺ and Hf⁴⁺ cations over two crystallographic positions was refined.     

Organic-inorganic hybrid perovskite (C<Subscript>6</Subscript>H<Subscript>5</Subscript>(CH<Subscript>2</Subscript>)<Subscript>2</Subscript>NH<Subscript>3</Subscript>)<Subscript>2</Subscript>CdCl<Subscript>4</Subscript>: Synthesis,structural and thermal properties

The present research work reports the study on crystal structure, vibrational spectroscopy and thermal analysis of organic-inorganic hybrid compound (C₆H₅(CH₂)₂NH₃)₂CdCl₄. Single crystals of bis(phenethylammonium)tetrachlorocadmate (C₆H₅(CH₂)₂NH₃)₂CdCl₄ (PEA–Cd) were obtained by diffusion at room temperature. This compound crystallizes in the orthorhombic space group C2cb with unit cell parameters a = 7.4444(2) Å, b = 38.8965(3) Å, c = 7.3737(2) Å and Z = 4. Single crystal structure has been solved and refined to R = 0.036 and wR = 0.092. The structure consists of an extended [CdCl₄]^2– network and two [C₆H₅(CH₂)₂NH₃]⁺ cations to form a two-dimensional perovskite system. The infrared (IR) spectrum of the title compound was recorded at room temperature. Differential scanning calorimetry (DSC) was used to investigate the phase transition; this compound exhibits a reversible single solid-solid phase transition.     

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.     

Supramolecular 2D structure of [Co(2-Me-Pyz)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The complex [Co(2-Me-Pyz)₂(H₂O)₄](NO₃)₂ is synthesized and its structure is determined. The crystals are monoclinic: space group P2₁/n, a = 10.685(2) Å, b = 6.837(1), c = 12.515(3) Å, β = 91.84(3)°, V = 913.8(3) ų, ρ_calcd = 1.042 g/cm ³, Z = 2. The Co²⁺ ion (in the inversion center) is coordinated at the vertices of the distorted octahedron by two nitrogen atoms of methylpyrazine and four oxygen atoms of the water molecules (Co(1)–N(1) 2.180(3), average Co(1)–O(w) 2.079(3) Å, angles at the Co atom 87.9(1)–92.1(1)°). Supramolecular pseudometallocycles are formed in the structure through the O(w)–H…N(1) hydrogen bonds between the coordinated H₂O molecules and the terminal nitrogen atoms of the 2-methylpyrazine molecules. Their interaction results in the formation of supramolecular layers joined by the NO₃ groups into a three-dimensional framework.