Crystal structures of EuLnCuS<Subscript>3</Subscript> (Ln = Nd and Sm)

The compound sulfides EuLnCuS₃ (Ln = Nd and Sm) were obtained for the first time. Their crystal structures were determined from X-ray powder diffraction data. The crystals of both compounds are orthorhombic (space group Pnma). The compound EuNdCuS₃ is isostructural with BaLaCuS₃; the unit cell parameters are a = 11.0438(2) Å, b = 4.0660(1) Å, c = 11.4149(4) Å. The compound EuSmCuS₃ is isostructural with Eu₂CuS₃; the unit cell parameters are a = 10.4202(2) Å, b = 3.9701(1) Å, c = 12.8022(2) Å.     

Crystal structure and properties of AHoCuS<Subscript>3</Subscript> (A = Sr or Eu)

The structures of complex sulfides AHoCuS₃ (A = Sr or Eu) have been determined by X-ray powder diffraction. The crystals of the compounds belong to the orthorhombic crystal system; they are isostructural (space group, Pnma; structure type Eu₂CuS₃). The unit cell parameters for SrHoCuS₃ and EuHoCuS₃ are a = 10.1487(1) Å, b = 3.9332(1) Å, c = 12.9524(2) Å and a = 10.1484(2) Å, b = 3.9195(1) Å, c = 12.8499(2) Å, respectively. The temperatures and enthalpies of phase transformations of complex sulfides AHoCuS₃ (A = Sr or Eu) have been determined.     

Refined Crystal Structures of SrLnCuS<Subscript>3</Subscript> (Ln = Er,Yb)

According to powder X-ray diffraction data, the crystal structures of compounds SrLnCuS₃ (Ln = Er, Yb) have been refined by minimizing the derivative difference in the anisotropic approximation for all atoms. Crystals are orthorhombic, space group Cmcm, structure type KZrCuS₃: a = 3.93128(3) Å, b = 12.9709(1) Å, c = 10.1161(1) Å, V = 515.843(9) ų, ρ_calc = 5.337 g/cm³, Z = 4, R_DDM = 3.73%, R_F = 2.06% (SrErCuS₃); a = 3.91448(4) Å, b = 12.9554(1) Å, c = 10.0332(1) Å, V = 508.842(8) Å3, ρ_calc = 5.487 g/cm³, Z = 4, R_DDM = 3.56%, R_F = 1.48% (SrYbCuS₃). The structure of SrLnCuS₃ is described by [LnCuS₃] twodimensional layers formed by distorted CuS₄ tetrahedra and LnS₆ octahedra with Sr²⁺ ions residing between the layers. The compounds are transparent for IR radiation in the range 3200–1800 cm^–1.     

Crystal structure of EuLaCuS<Subscript>3</Subscript>

The crystal structure of the EuLaCuS₃complex sulfide synthesized for the first time has been solved by X-ray powder diffraction. Crystals are orthorhombic, space group Pnma, Ba₂MnS₃-type structure, a = 8.1297(3) Å, b = 4.0625(1) Å, c = 15.9810(4) Å, V = 527.80(3) ų, Z = 4, and ρ_calc = 5.669 g/cm³. The La and Eu atoms are randomly disordered over two crystallographic positions with a coordination number of 7, and the Eu(La)-S bond lengths range from 2.892(6) to 3.078(6) Å. The CuS₄ tetrahedra with Cu-S interatomic distances of 2.358(5)–2.40(1) Å form chains running along the b axis.     

Crystal structure of EuLnAgS<Subscript>3</Subscript> (Ln = Gd and Ho) compounds

The crystal structures of the first prepared EuLnAgS₃ (Ln = Gd and Ho) compounds, which have two polymorphs, were determined by X-ray powder diffraction. α-EuLnAgS₃ phases are isostructural to BaErAgS₃ (monoclinic crystal system, space group C2/m): a = 17.3168(10) Å, b = 3.9683(2) Å, c = 8.3174(4) Å, β = 103.94° (EuGdCuS₃); a = 17.1729(12) Å, b = 3.9367(3) Å, c = 8.2905(6) Å, β = 103.9° (EuHoCuS₃). β-EuLnAgS₃ phases belong to the AgBiS₂ structure type (cubic crystal system, space group Fm-3m): a = 5.739(2) Å (EuGdCuS₃) and a = 5.678 Å (EuHoCuS₃). In the α-EuLnAgS₃ crystal structure, LnS₆ octahedra and AgS₅ trigonal bipyramids share edges to form a three-dimensional (3D) structure with channels accommodating Eu²⁺ ions. A decrease in Ln³⁺ ionic radius gives rise to the crystal-chemical contraction of the 3D structure.     

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.     

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.     

Structure and some properties of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>{CH<Subscript>3</Subscript>CON(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

A new complex [UO₂CrO₄{CH₃CON(CH₃)₂}₂] (I) was studied by thermal analysis, IR spectroscopy, and X-ray crystallography. The crystals are monoclinic: a = 13.8108(11) Å, b = 8.6804(7) Å, c = 13.0989(10) Å, β = 104.777(1)°, V = 1518.4(2) ų, space group P2₁/c, Z = 4, R = 2.39%. The structure of I contains infinite chains of the [UO₂CrO₄{CH₃CON(CH₃)₂}₂] composition running along [001]; the complex belongs to the AT¹¹M¹ ₂ crystal-chemical group (A = UO ₂ ²⁺ , T¹¹ = CrO ₄ ^2? , M¹ = CH₃CON(CH₃)₂) of uranyl complexes. The chains are linked into a three-dimensional framework due to hydrogen bonds between oxygen atoms of chromate ions and hydrogen atoms of methyl groups of the dimethylacetamide.     

Structure of A Coordination Polymer [Cu(En)<Subscript>2</Subscript>CrO<Subscript>4</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

The crystal structure of [Cu(En)₂CrO₄]_n (En is ethylenediamine) is determined: a = 14.7359(4) Å, b = 9.8083(3) Å, c = 14.2664(4) Å, V = 2061.98(10) ų, space group Cmce, Z = 8, d_x = 1.931 g/cm³. It is demonstrated that the studied phase is isostructural with [Сu(Еn)₂SO₄]_n. A pseudotetragonal copper atom coordination (Cu–N 2.0204 Å and 2.0244 Å, ∠N–Cu–N 84.73°) is completed to distorted octahedral by two oxygen atoms of chromate anions (Cu–O 2.433 Å and 2.380 Å).     

A novel metal chalcogenide: HgCd<Subscript>4</Subscript>S<Subscript>5</Subscript>

A novel metal chalcogenide HgCd₄S₅ (1) was synthesized from solid-state reactions and structurally characterized. Compound 1 crystallizes in the space group C222₁ of the orthorhombic system with four formula units in a cell: a = 12.5661(5) Å, b = 7.2551(5) Å, c = 10.7520(7) Å, V = 980.2(1) ų, Cd₄HgS₅, M _r = 810.49, D _c = 5.492 g/cm³, S = 1.010, μ(MoK _α) = 25.128 mm^?1, F(000) = 1408, R = 0.0611 and wR = 0.1495. Compound 1 is characterized by a 3-D cadmium sulfide framework structure with the infinite mercury sulfide chains located in the cavities.     

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.     

New polymorph of CaHPO<Subscript>4</Subscript> (monetite): synthesis and crystal structure

A novel form of anhydrous dicalcium phosphate CaHPO₄ (monetite) is synthesized hydrothermally and characterized by single crystal X-ray diffraction. It crystallizes in the orthorhombic space group Ccm2₁ with a = 6.242(1) Å, b = 6.994(2) Å, c = 7.003(3) Å, V = 305.73(16) ų and it has four independent unit formulas in the unit cell (Z = 4). A three-dimensional crystal structure can be described by {HPO₄}_n infinite zigzag chains linked by Ca–O bonds. The comparison to the crystal structures of other polymorphs is given.     

Crystal structure of KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> and KPb<Subscript>2</Subscript>Br<Subscript>5</Subscript>

The KPb₂Cl₅ and KPb₂Br₅ crystals are monoclinic (P2₁/c) with a microtwinned structure. X-ray analysis of chloride resulted in the parameters a = 8.854(2) Å, b = 7.927(2) Å, c = 12.485(3) Å; β = 90.05(3)°, d_calc = 4.78(1) g/cm³ (STOE STADI4, MoK_α, 2θ_max = 80°), R₁ = 0.0702 for 4094 F ≥ 4 σ(F) reflections. For bromide, a = 9.256(2) Å, b = 8.365(2) Å, c = 13.025(3) Å; β = 90.00(3)°, d_calc = 5.62(1) g/cm³ (Bruker P4, MoK_α, 2θ_max = 70°), R₁ = 0.0692 for 3076 F ≥ 4 (F) reflections.     

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.     

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.     

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.     

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.     

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.     

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).