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.     

X-ray structural study of fluorinated β-diketonate complexes of zirconium(IV)

Three novel complexes of zirconium(IV) are prepared and characterized by single crystal X-ray diffraction: zirconium(IV) pivaloyltrifluoroacetonate Zr(ptac)₄, zirconium(IV) trifluoroacetylacetonate Zr(tfac)₄, and zirconium(IV) hexafluoroacetylacetonate Zr(hfac)₄. Crystal data for C₃₂H₄₀F₁₂ZrO₈: a = 19.9842(6) Å, b = 11.8417(3) Å, c = 16.4831(5) Å; β = 95.2880(10)°, monoclinic, space group Cc, Z = 4, d _calc = 1.491 g/cm³, R = 0.061. Crystal data for C₂₀H₁₆F₁₂ZrO₈: a = 21.5063(15) Å, b = 7.9511(5) Å, c = 16.0510(10) Å; β = 113.736(4)°, monoclinic, space group C2/c, Z = 4, d _calc = 1.860 g/cm³, R = 0.047. Crystal data for C₂₀H₄F₂₄ZrO₈: a = 15.3533(13) Å, b = 20.2613(15) Å, c = 19.6984(17) Å; β = 95.828(2)°, monoclinic, space group P2₁/c, Z = 2, d _calc = 2.004 g/cm³, R = 0.078. All the structures are molecular and include isolated mononuclear Zr(β-dik)₄ complex molecules. Coordination environment of zirconium atom is made by eight oxygen atoms of four β-diketonates; the coordination polyhedron is an almost regular square antiprism. The Zr-O distances fall within 2.14–2.23 Å. Complexes in the structures are joined by van der Waals interactions. Using the structural data, the van der Waals energies of crystal lattices of the studied compounds are calculated by the atom-atom potential method.     

Crystal and molecular structures of two modifications of a chelate compound of Pb[(<Emphasis Type="Italic">iso</Emphasis>-C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>2</Subscript>PS<Subscript>2</Subscript>]<Subscript>2</Subscript>

A chelate compound Pb[(iso-C₄H₉)₂PS₂]² is synthesized. Using X-ray diffraction data, the crystal structures of two modifications of this compound are determined (X8 APEX diffractometer, MoK _α radiation, 14169 F _hkl , R = 0.0480 for the low temperature α-form and 6261 F _hkl , R = 0.0387 for the β-form studied at ambient temperature). The crystals are triclinic: a = 11.047(2) Å, b = 14.486(3) Å, c = 32.048(6) Å; α = 91.30(3)°, β = 99.73(3)°, γ = 101.61(3)°, V = 4942.9(17) ų, Z = 8, ρ_calc = 1.682 g/cm³ (α-modification) and a = 11.2124(5) Å, b = 14.6989(7) Å, c = 17.1644(6) Å; α = 109.393(1)°, β = 94.989(2)°, γ = 101.649(1)°, V = 2576.83(19) ų, Z = 4, ρ_calc = 1.613 g/cm³ (β-modification), space group \(P\bar 1\) for both polymorphs. The structures are molecular, coordination cores of PbS₄ are tetragonal pyramids with Pb atoms in the vertices and S atoms in the base. In both structures intermolecular Pb...S contacts yield supramolecular ensembles comprising by four molecules, where PbS₄₊₂ cores form planar aggregates of edge-sharing octahedra. The ensembles are joined by weak intermolecular S...S interactions resulting in the development of polymeric chains along the a axis.     

Structure of the 1:1 complex of dimethyl sulfoxide with hydroquinone: Supramolecular architecture based on D-H⋯A hydrogen bonds (D = O,C; A = O, π)

The hydroquinone-dimethyl sulfoxide-toluene system was investigated by thermal and X-ray diffraction analyses. The crystal structure of the 1:1 complex of hydroquinone with dimethyl sulfoxide was determined. Crystal data: C₈H₁₂O₃S, M = 188.24, triclinic system, space group P1¯, unit cell parameters: a = 7.4202(2) Å, b = 8.4046(3) Å, c = 8.7340(3) Å; α = 100.830(1)°, β = 99.794(1)°, γ = 114.129(1)°; V = 469.35(4) ų, Z = 2, d _calc = 1.332 g/cm³, R1 = 0.028, T = 100 K. The molecules are linked in a supramolecular assembly via D-H...A hydrogen bonds (D = O, C; A = O, π).     

Crystal and molecular structure of (hexafluoroacetylacetonato) (pivaloylacetonato)copper(II)

The crystal structure of (hexafluoroacetylacetonato)(pivaloylacetonato)copper(II) has been determined. Crystal data for CuO₄C₁₃H₁₄F₆: a = 8.288(2) Å, b = 8.682(2) Å, c = 12.307(2) Å; α = 90.75(3)°, β = 94.29(3)°, γ = 106.60(3)°; V = 845.7(3) ų, space group \(P\overline 1 \), Z = 2, d_calc = 1.617 g/cm³. The coordination polyhedron of the copper atom is formed by four oxygen atoms of two different β-diketonate ligands with Cu-O distances within 1.874–1.946 Å; the O-Cu-O bond angles are 94.8° and 90.6°. The complexes are united into centrosymmetrical “dimers” with Cu...Cu distances of 4.365 Å.     

Synthesis and structural investigation of hafnium(IV) complexes with acetylacetone and trifluoroacetylacetone

Two volatile hafnium(IV) complexes with acetylacetone and trifluoroacetylacetone (HL) have been prepared and their structures have been studied at ?30°C. Crystal data for C₂₀H₂₈HfO₈: a = 21.5493(4) Å, b = 8.36720(10) Å, c = 13.9905(3) Å; β = 116.5550(10)°, space group C2/c, Z = 4, d _calc = 1.692 g/cm³, R = 0.015. Crystal data for C₂₀H₁₆F₁₂HfO₈: a = 8.1039(12) Å, b = 11.4499(14) Å, c = 15.790(2) Å; α = 99.341(4)°, β = 103.175(4)°, γ = 108.185(4)°, space group P?1, Z = 2, d _calc = 2.003 g/cm³, R = 0.074. Both structures are molecular and comprise isolated complex molecules HfL₄. The hafnium atom is coordinated with eight oxygen atoms of four β-diketonate ligands, Hf-O distances varying from 2.153 Å to 2.191 Å. The molecules make van der Waals contacts in the structures.     

Synthesis of spiro[(6-phenyl-3,4-dihydro-2H-1,3-dioxine)-2<Emphasis Type="Italic">R</Emphasis>(<Emphasis Type="Italic">S</Emphasis>), 3′-(19′,28′-oxidooleanan)]-4-ones and X-ray diffraction analysis of their configuration

The structure of two stereoisomeric spiroadducts of allobetulone with 5-phenyl-2,3-dihydrofuran-2,3-dione was established by X-ray diffraction (XRD) analysis. The crystals of the 2R isomer are orthorhombic, P2₁2₁2₁, a = 10.825(5) Å, b = 12.849(6) Å, c = 23.358(9) Å; V = 3249(2) ų, Z = 4, d _calc = 1.200 g/cm³; the crystals of the 2S isomer hemihydrate are triclinic, P1, a = 11.505(7) Å, b = 12.192(8) Å, c = 13.123(8) Å; α = 103.35(5)°, β = 100.80(5)°, γ = 90.98(5)°; V = 1756(2) ų, Z = 2, d _calc = 1.127 g/cm³. The molecular structure of the spiroadducts is discussed.     

Synthesis and crystal structure of the π copper(I) cyanide complex with N,N′-diallyl thiocarbamide 2CuCN · (C<Subscript>3</Subscript>H<Subscript>5</Subscript>NH)<Subscript>2</Subscript>CS

Crystals of the π copper(I) cyanide complex with N,N′-diallyl thiocarbamide, 2CuCN · (C₃H₅NH)₂CS (I), are synthesized from an aqueous-methanol solution of potassium nitroprusside, diallyl thiocarbamide on a copper electrode using the method of alternating-current electrochemical synthesis. The crystals are monoclinic: space group P2₁/n, a = 6.9440(5) Å, b = 13.760(1)) Å, c = 12.733(1) Å, β = 97.280(9)°, V = 1206.8(2) ų, Z = 4, R = 0.0361, R _w = 0.0362 for 2836 independent reflections with F ≥ 4σ(F). A unique polymeric structure is built due to the Cu(I)-(C=C) π bond and the bridging function of the thioamide S atom of the ligand molecule and one of the two independent cyano groups.     

Crystal structures of two one-dimensional coordination polymers constructed from Mn<Superscript>2+</Superscript> ions,chelating hexafluoro-acetylacetonate anions,and flexible bipyridyl bridging ligands

The syntheses and crystal structures of two one-dimensional coordination polymers, [Mn(C₅HO₂F₆)₂(C₁₆H₂₀N₂)] _n (1) and [Mn(C₅HO₂F₆)₂(C₂₀H₂₀N₂)] _n (2), are described, where C₅HO₂F₆ ^? is the hexafluoro acetylacetonate anion, C₁₆H₂₀N₂ is 1,6-bis(4-pyridyl)-hexane, and C₂₀H₂₀N₂ is 1,4-bis[2-(3-pyridyl)ethyl]-benzene. In both phases, the metal ion lies on a crystallographic twofold axis and is coordinated by two chelating C₅HO₂F₆ ^? anions and two bridging bipyridyl ligands to generate a cis-MnN₂O₄ octahedron. The bridging ligands, which are completed by crystallographic inversion symmetry in both compounds, connect the metal nodes into zigzag [20 1 ] chains in 1 and contorted [001] chains in 2. Intrachain C–H???O interactions occur in 1 but not in 2, which may be correlated with the relative orientations of the ligands. Crystal data: 1, C₂₆H₂₂F₁₂MnN₂O₄, M _r = 709.40, monoclinic, C2/c (No. 15), a = 9.3475(2) Å, b = 16.6547(3) Å, c = 18.3649(4) Å, β = 91.1135(8)°, V = 2858.50(10) ų, Z = 4, R(F) = 0.030, w R(F ²) = 0.075. 2, C₃₀H₂₂F₁₂MnN₂O₄, M _r = 757.44, monoclinic, C2/c (No. 15), a = 19.9198(2) Å, b = 10.6459(2) Å, c = 16.8185(3) Å, β = 119.8344(8)°, V = 3093.91(9) Å3, Z = 4, R(F) = 0.032, w R(F ²) = 0.078.     

Synthesis,thermal analysis,IR spectrum,and crystal structure of rubidium hexanitratothorate

Rubidium hexanitratothorate was synthesized, and its crystal structure was determined by X-ray diffraction analysis: space group P2₁/n; a = 8.347(1) Å, b = 6.890(1) Å, c = 13.069(1) Å, β = 91.88(1)°, Z = 2; 1812 independent reflections, R = 0.0165.     

Supramolecular architecture of catechol and its 2:1 complex with dimethylsulfoxide

The crystal structures of catechol (o-dihydroxybenzene) and its 2:1 complex with dimethylsulfoxide are determined at T = 150 K. Crystal data: C₁₄H₁₈O₅S, M = 298.37, triclinic, space group P \(\bar 1\), unit cell parameters: a = 7.7285(13) Å, b = 9.9924(17) Å, c = 10.3188(18) Å, α = 89.963(4)°, β = 89.968(4)°, γ = 69.076(5)°, V = 744.3(2)ų, Z = 2, D _x = 1.331 g/cm³, R1 = 0.048; C₆H₆O₂, M = 110.11, monoclinic, space group P2₁/n, a = 9.8206(6)Å, b = 5.5903(3)Å, c = 10.4439(6)Å, β = 114.952(2)°; V = 519.85(5) ų, Z = 4, D _x = 1.407 g/cm³, R1 = 0.0289. In the 2:1 complex the molecules are joined in a supramolecular ensemble by D-H...A hydrogen bonds (D = O, C; A = O, π); in catechol they are bonded only by O-H...O. The state diagram of the catechol-dimethylsulfoxide system is examined by DTA.     

Molecular structure of 2-methoxy-4-pyrrolidinyl-6-trinitromethyl-1,3,5-triazine

An X-ray diffraction study of 2-methoxy-4-pyrrolidinyl-6-trinitromethyl-1,3,5-triazine was carried out. The crystals are triclinic; C₉H₁₁N₇O₇; M = 329.25; a = 8.536(1) Å, b = 9.378(2) Å, c = 9.7401(8) Å; α = 79.13(1)°, β = 73.974(8)°; γ = 72.76(1)°; V = 710.8(2) ų, d _c = 1.54 g/cm³, Z = 2, space group P1ˉ. The molecule on the whole is planar, except the pyrrolidine ring, which has a twist conformation. No significant π-π interactions and hydrogen bonds of C-H⋯N or C-H⋯O type were found in the crystal, and the molecule packing is stabilized only due to van der Waals interactions. Original Russian Text Copyright ? 2008 by V. V. Bakharev, A. A. Gidaspov, I. A. Litvinov, and E. V. Mironova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 187–189, January–February, 2008.     

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>, Ni<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript>) and the 3-amino 4-methyl benzoate ion

The syntheses and crystal structures of the layered coordination polymers M(C₈H₈NO₂)₂ [M = Mn (1), Co (2), Ni (3) and Zn (4)] are described. These isostructural compounds contain centrosymmetric trans-MN₂O₄ octahedra as parts of infinite sheets; the ligand bonds to three adjacent metal ions in μ³-N,O,O′ mode from both its carboxylate O atoms and its amine N atom. In each case, weak intra-sheet N–H?O and C–H?O hydrogen bonds may help to consolidate the structure. Crystal data: 1, C₁₆H₁₆MnN₂O₄, M _r = 355.25, monoclinic, P2₁/c (No. 14), a = 10.6534(2) Å, b = 4.3990(1) Å, c = 15.5733(5) Å, β = 95.1827(10)°, V = 726.85(3) ų, Z = 2, R(F) = 0.026, wR(F ²) = 0.067. 2, C₁₆H₁₆CoN₂O₄, M _r = 359.24, monoclinic, P2₁/c (No. 14), a = 10.6131(10) Å, b = 4.3374(4) Å, c = 15.3556(17) Å, β = 95.473(4)°, V = 703.65(12) ų, Z = 2, R(F) = 0.041, wR(F ²) = 0.091. 3, C₁₆H₁₆N₂NiO₄, M _r = 359.02, monoclinic, P2₁/c (No. 14), a = 10.6374(4) Å, b = 4.2964(2) Å, c = 15.2827(8) Å, β = 95.9744(14)°, V = 694.66(6) ų, Z = 2, R(F) = 0.028, wR(F ²) = 0.070. 4, C₁₆H₁₆N₂O₄Zn, M _r = 365.68, monoclinic, P2₁/c (No. 14), a = 10.6385(5) Å, b = 4.2967(3) Å, c = 15.2844(8) Å, β = 95.941(3)°, V = 694.89(7) ų, Z = 2, R(F) = 0.038, wR(F ²) = 0.107.     

Crystal structure of the [NiL](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>·H<Subscript>2</Subscript>O complex,where L is a chiral dioxatetraazamacrocyclic ligand based on the natural monoterpene (+)-3-carene

The crystal structure of the nickel(II) perchlorate complex with a chiral dioxatetraazamacrocyclic ligand (L) based on the natural monoterpene (+)-3-carene was determined by XRD (X8 APEX diffractometer, MoK _α, 2θ _max = 50°, 4278 F _hkl , R = 0.0290). Monoclinic crystals with a = 11.3550(2) Å, b = 9.4850(2) Å, c = 14.0209(3) Å; β = 104.645(1)°, V = 1461.02(5) ų, Z = 2, space group P2₁. According to XRD data, the complex has a composition [NiL](ClO₄)₂·H₂O. Its ionic structure is composed of [NiL]²⁺ complex cations, ClO ₄ ^? outer-spheric anions, and crystal water molecules. In the complex cation, the NiN₄ coordination unit is a tetrahedrally distorted square formed by coordination of the tetradentate cycle-forming ligand L.     

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 Iron(III) hydrogen diphosphate FeHP<Subscript>2</Subscript>O<Subscript>7</Subscript>

The crystal structure of the β modification of iron(III) hydrogen diphosphate FeHP₂O₇ has been refined by the Rietveld method using powder X-ray diffraction data. The compound crystallizes in the monoclinic system, space group P2₁/n, Z = 4, a = 7.9756(1) Å, b = 12.8260(2) Å, c = 4.8664(6) Å, β = 98.6404(8)°, V = 492.16(1) ų. The structure was refined in the isotropic approximation (pseudo-Voigt function), R _p = 0.024, R _wp = 0.033, R _Bragg = 0.091, R _F = 0.067, and compared with the structures of other compounds M^IIIHP₂O₇ (M^III is a trivalent metal).     

Synthesis and crystal structure of a new Schiff base ligand and its cobalt(II) complex

The crystal structures of cobalt(II) Schiff base complex (Co^IIL₂ · H₂O) and Schiff base ligand 3,5-dichlorosalicylidene-2-chlorophenylmethylamine (HL) have been determined by single-crystal X-ray analysis. The geometry around cobalt in Co^IIL₂ · H₂O is distorted tetrahedral. Co^IIL₂ · H₂O crystallizes in the monoclinic system, in space group C2/c, with crystallographic parameters: a = 12.9143(16) Å, b = 8.8326(16) Å, c = 25.115(3) Å, β = 92.791(10)°, V = 2861.4(7) ų, Z = 4, F(000) = 1420, and the final R indices (I > 2σ(I)) are R ₁ = 0.0440, wR ₂ = 0.1272. HL crystallizes in the monoclinic system, in space group P2₁/c, with crystallographic parameters: a = 11.9764(15), b = 8.2331(10), c = 14.2211(17) Å, β = 98.723(6)°, V = 1386.0(3) ų, Z = 4, F(000) = 640, and the final R indices (I > 2σ(I)) are R ₁ = 0.0397, wR ₂ = 0.1018.     

Two copper complexes with imidazole ligands: Syntheses,crystal structures and fluorescence

Two copper (imidazole) complexes, namely, [Cu(im)₆]Cl₂ · 4H₂O (1), and [Cu(im)₆]Cl₂ · 2H₂O (2) (im-imidazole) have been synthesized by hydrothermal method. Single-crystal X-ray analysis revealed that the complex 1 belongs to triclinic system, space group P \(\bar 1\) with a = 8.8097(18) Å, b = 9.0812(18) Å, c = 10.586(2) Å; α = 75.08(3)°, β = 83.14(2)°, γ = 61.84(3)°; R ₁ = 0.0562, wR ₂ = 0.1607. In compound 1, [Cu(im)₆]²⁺ cation and counter anions Cl^? alternatively array in an ABAB fashion via N-H...Cl hydrogen bonding. Compound 2 falls into monoclinic system, space group P2₁/n with a = 8.073(2) Å, b = 13.239(2) Å, c = 15.0810(10) Å; β = 97.940(10)°; R ₁ = 0.0434, wR ₂ = 0.1243. The equatorial ligands are involved into a complex hydrogen bond network that involves the chloride anions and uncoordinated water molecules. We report there synthesis, crystal structure, thermal stability, IR spectrum and fluorescent property.     

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 kinetics of thermal decomposition of the Zn(II) complex with vanillin

A complex [Zn(C₈H₇O₃)₂(H₂O)₂] (C₈H₈O₃ is vanillin) has been synthesized and characterized by IR, elemental analysis, and X-ray diffraction single-crystal analysis. The crystals are monoclinic, space group C2/c, a = 22.236(8) Å, b = 10.594(2) Å, c = 7.8190(16) Å, α = 89.90(3)°, β = 106.87(4)°, γ = 89.99(3)°, V = 1762.6(8) ų, Z = 4, F(000) = 832, S = 1.079, ρ _c = 1.521g cm^?3, R = 0.0221, R _w = 0.0604, μ = 1.433 mm^?1. The Zn²⁺ ion is six-coordinated with a distorted octahedron geometry. The complex forms a three-dimensional network through intermolecular hydrogen bonds. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal conditions by the TG and DTG methods. The kinetic equation can be expressed as dα/dt = Ae^?E/RT 2(1 ? α)[1 ? ln(1 ? α)]^1/2. The kinetic parameters (E, A), activation entropy ΔS ^≠, and activation free-energy ΔG ^≠ were also gained.