Synthesis and crystal structure of the new complex cobalt and nickel oxide Sr<Subscript>2.25</Subscript>Y<Subscript>0.75</Subscript>Co<Subscript>1.25</Subscript>Ni<Subscript>0.75</Subscript>O<Subscript>6.84</Subscript>

The complex cobalt and nickel oxide Sr_2.25Y_0.75Co_1.25Ni_0.75O_6.84 has been synthesized by the citrate method. The oxygen content of the oxide has been determined by iodometric titration. The crystal structure of the compound has been refined using X-ray powder diffraction data (a = 3.7951(2) Å, c = 19.700(1) Å, χ₂ = 1.15, R _F ² = 0.0586, R _p = 0.0365, R _wp = 0.0462). Sr_2.25Y_0.75Co_1.25Ni_0.75O_6.84 has the structure of the second member of the Ruddlesden-Popper series A _{n + 1}B_nO_{3n + 1}.     

Crystal and molecular structure of [Au(C<Subscript>14</Subscript>H<Subscript>24</Subscript>N<Subscript>4</Subscript>)][H<Subscript>3</Subscript>O](ClO<Subscript>4</Subscript>)<Subscript>4</Subscript>

The crystal and molecular structure of doubly protonated tetraazamacrocyclic complex of gold(III) [Au(C₁₄H₂₄N₄)][H₃O](ClO₄)₄ has been determined. The crystals are monoclinic: a = 11.158(2) Å, b = 8.243(1) Å, c = 14.756(2) Å; β = 98.65(1)°, V = 1341.8(3) ų, Z = 2, ρ(calc) = 1.134 g/cm³, space group P2₁/n. The structure is built of almost flat centrosymmetrical Au(C₁₄H₂₄N₄)]³⁺ and [H₃O]⁺ cations and [ClO₄]^? anions. The gold atom is coordinated with four nitrogen atoms of the ligand forming a flat square. The coordinated ligand is protonated at its γ-carbon atoms of the two six-membered chelate rings. The Au-N bond lengths are almost identical (the mean value is 1.994 Å). The six-membered rings of the complex contain C=N diimine bonds. The [H₃O]⁺ oxonium ion has H-bonds with the oxygen atoms of perchlorate ions.     

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.     

Phase equilibria in the system LaMnO<Subscript>3</Subscript>-SrMnO<Subscript>3</Subscript>-SrCrO<Subscript>4</Subscript>-LaCrO<Subscript>3</Subscript>

A continuous solid solution LaMn_1?y Cr _y O₃ with an orthorhombic structure is found to exist in the range of 0.0 ≤ y ≤ 1.0. An orthorhombic solid solution La_1?x Sr _x CrO₃ exists in the range of 0.0 ≤ x ≤ 0.1. The stability boundaries are determined for the perovskite phase La_1?x Sr _x Mn_1?y Cr _y O₃. An isobaric-isothermal section LaMnO₃-SrMnO₃-SrCrO₄-LaCrO₃ of the system La₂O₃-SrO-Mn₃O₄-Cr₂O₃ in air at 1100°C is designed.     

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).     

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.     

Three- and four-coordinated silver(I) ions in the coordination polymers [Ag(Me<Subscript>4</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript> and [Ag(2,3-Et<Subscript>2</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript>

The coordination polymers [AgPF₆(Me₄Pyz)₂] (I) and [AgPF₆(2,3-Et₂Pyz)₂] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) ų, ρ_calcd = 1.660 g/cm³, Z = 4. The structure of I is built of polymeric zigzag [Ag(C₈H₁₂N₂)] _∞ ⁺ chains and octahedral [PF₆] anions. The coordination polyhedron of the Ag⁺ ion is a flat triangle. Crystals of II are tetragonal, space group P \(\bar 4\)2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) ų, ρ_calcd = 1.627 g/cm³, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag⁺ cations linked by four bridging ligands of diethylpyrazine Et₂Pyz. The coordination polyhedron of the Ag⁺ ion is an irregular four-vertex polyhedron.     

Crystal Structure of [UO<Subscript>2</Subscript>SO<Subscript>4</Subscript>{(CH<Subscript>3</Subscript>)HNCONH(CH<Subscript>3</Subscript>)}<Subscript>2</Subscript>]

The single crystals of [UO₂SO₄{(CH₃)HNCONH(CH₃)}₂] (I) were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 6.847(1) Å, b = 14.259(3) Å, c = 14.297(3) Å, β = 93.451(4)°, space group P2₁/n, Z = 4. The main structural units of crystals I are ribbons whose composition coincides with the composition of the compound. The crystal chemical formula of the complex is AT³M ₂ ¹ (A = UO ₂ ²⁺ ).     

Synthesis and crystal structure of strontium borate Sr<Subscript>4</Subscript>B<Subscript>14</Subscript>O<Subscript>25</Subscript>

The new compound Sr₄B₁₄O₂₅ (4SrO · 7B₂O₃) corresponding to an oxide ratio of 4: 7 has been identified and synthesized in the SrO-B₂O₃ system. The crystal structure of the compound has been determined (space group Cmc2₁, a = 7.734(5) Å, b = 16.332(5) Å, c = 14.556(5) Å, Z = 4, 702 F(hkl), R = 0.078). The borate anions form a three-dimensional framework consisting of borate groups of two types: three-ring structures (2□, Δ) and BO₃ triangles. Layers formed by 14-membered rings composed of boron-oxygen tetrahedra and triangles packed within the layer according to the herringbone pattern can be distinguished in the framework. The strontium atoms are located on the mirror symmetry planes between these layers. The compound is metastable and decomposes, on long-term storage, into strontium di- and metaborate.     

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 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.     

Refinement of LiFe<Subscript>5</Subscript>O<Subscript>8</Subscript> crystal structure

The crystal structure and the formation conditions of crystals of the LiFe₅O₈ ordered phase obtained from the solution-melt of the Bi₂O₃-Fe₂O₃-B₂O₃-LiCl quadruple system are refined. The crystals are black, octahedral, of cubic symmetry (space group P4₃32). Unit cell parameters: a = 8.3339(1) Å, V = 578.82(1) ų, Z = 4, d _calc = 4.753 g/cm³. From 6046 of the collected array I _hkl 358 are independent (R _int = 0.0321). As a result of anisotropic refinement of structural parameters, R ₁ factor is found to be 0.0186 (wR ₂ = 0.0467). Lithium atoms are in octahedral environment, Li-O is 2.109(1) Å; iron atoms are of two types: in octahedra with Fe-O (by two) distances of 1.9586(9) Å, 2.0152(9) Å, and 2.0652(10) Å and tetrahedra with Fe-O (three) 1.8848(10) Å and 1.914(2) Å. The structure is of inverted spinel type.     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.     

Structural features of bismuth borates in the system <Emphasis Type="Italic">n</Emphasis>Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-<Emphasis Type="Italic">m</Emphasis>B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The crystal structures of general composition nBi₂O₃-mB₂O₃ were analyzed and systematized with the use of the structures of borate groups. Based on the CNs calculated by the bond valence method, the shapes of bismuth coordination polyhedra derived from an octahedron were suggested. A correlation was found between the number of BO₃ triangles and BO₄ tetrahedra in borate groups, the average CN of Bi atoms, and the degree of distortion of Bi polyhedra as a function of the m: n ratio, as well as between the polarity of BO₄ tetrahedra and noncentrosymmetry of the structures. The role of Bi³⁺ with the active E pair in the manifestation of specific features of the forms of bismuth polyhedra and the types of connection of boron polyhedra was elucidated.     

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.     

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.     

X-ray diffraction study of CsZn<Subscript>2</Subscript>Br<Subscript>5</Subscript>

CsZn₂Br₅ crystals are studied by X-ray diffraction. The compound crystallizes in the monoclinic system with the unit cell parameters a = 6.8880(12) Å, b = 10.4703(19) Å, c = 6.5197(9) Å, β = 108.25°, V = 446.55 ų, ρ_calcd = 4.960 g/cm³. Refractive indices are n _p = 1.640 and n _p = 1.754.     

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.     

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).     

Crystal structure of osmium selenobromide OsSe<Subscript>2</Subscript>Br<Subscript>12</Subscript>

The crystal structure of the compound OsSe₂Br₁₂ obtained by the reaction of OsBr₄ with SeBr₄ or Se in liquid bromine at 100°C was studied by X-ray powder diffraction. The structure of osmium selenobromide corresponds to a specific type: space group C2/m, a = 14.0464(2) Å, b = 11.05398(14) Å, c = 6.50340(9) Å, β = 112.2645(11)°, Z = 2; R _B = 0.03946, R _wp = 0.05403, χ² = 4.261 for 479 reflections and 53 refinement parameters. The X-ray diffraction analysis confirmed the earlier assumption concerning the cation-anion structure of the compound representing a packing of nearly regular [OsBr₆]^2? octahedra as anionic complexes and deficient [:SeBr₃]⁺ tetrahedra as cationic complexes in which the missing vertex is occupied by the lone electron pair of selenium.