Tri(<Emphasis Type="Italic">meta</Emphasis>-tolyl)antimony chloro(benzenesulfonate): synthesis and structure

Tri(meta-tolyl)antimony chloro(benzenesulfonate) (I) has been synthesized by the reaction between tri(meta-tolyl)antimony bis(benzenesulfonate) and tri(meta-tolyl)antimony dichloride (toluene; 0.5 h, 100°C). According to X-ray diffraction data, the antimony atoms in two crystallographically independent molecules Ia and Ib have a distorted trigonal bipyramidal coordination to chlorine and oxygen atoms in axial positions: OSbCl, 177.8(4)° (Ia), 178.6(4)° (Ib); CSbC, 114.0(9)°?127.6(8)° (Ia), CSbC, 114.4(8)°?128.0(8)° (Ib); Sb?C, 2.01(2)?2.139(18) Å, Sb?Cl, 2.453(7) Å, Sb?O, 2.163(13) Å (Ia), Sb?C, 2.07(2)?2.14(2) Å, Sb?Cl, 2.442(7) Å; Sb?O, 2.187(14) Å (Ib).     

Synthesis and structure of antimony compounds (Ph<Subscript>3</Subscript>SbBr)<Subscript>2</Subscript>O · 2PhH and [(2-MeC<Subscript>6</Subscript>H<Subscript>4</Subscript>)<Subscript>3</Subscript>SbBr]<Subscript>2</Subscript>O · 0.5PhH

Hydrolysis of triphenylantimony dibromide or tri(o-tolyl)antimony dibromide in benzene yields the solvates (Ph₃SbBr)₂O · 2PhH (triclinic modification) (I) and [(2-MeC₆H₄)₃SbBr]₂O · 0.5PhH (II), in which the Sb atoms have a distorted trigonal-bipyramidal coordination. The aryl ligands are in the equatorial positions; the bridging oxygen atom and the terminal Br ligands occupy the axial positions. The bond lengths in I: Sb-C, 2.103(2)–2.125(2) Å, Sb-O, 1.976(1) and 1.979(1); and Sb-Br, 2.7128(2) and 2.7592(2) Å. The bond lengths in II (Å): Sb-C, 2.109(6)–2.145(3) Å; Sb-O, 1.954(4)–1.958(4) Å; and Sb-Br, 2.7355(8)–2.7624(7) Å. The angles SbOSb are equal to 138.83(6)° in I and 170.8(3)° and 161.6° in II.     

Synthesis and crystal structure of a supramolecular adduct of the aqua nitrato complex of gadolinium [Gd(NO<Subscript>3</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>7</Subscript>]<Superscript>2+</Superscript> with macrocyclic cavitand cucurbit[6]uril

A supramolecular adduct of gadolinium aqua nitrato complex and cucurbit[6]uril { [Gd(NO₃)(H₂O)₇](C₅H₅N)@(C₃₆H₃₆N₂₄O₁₂)}(NO₃)₂·10H₂O is obtained by slow diffusion of methanol into an aqueous solution containing gadolinium nitrate, pyridine, and cucurbit[6]uril. According to single crystal X-ray diffraction data, water molecules coordinated to metal atom make hydrogen bonds to polarized carbonyl groups of the macrocycle. The heptaaquanitratogadolinium(III) [Gd(NO₃)(H₂O)₇]²⁺ cation is structurally characterized for the first time. Crystal system is triclinic, space group \(P\overline 1 \), a = 12.3137(4) Å, b = 14.2334(5) Å, c = 19.5629(6) Å; α = 80.850(1)°, β = 86.879(1)°, γ = 68.855(1)°; V = 3157.15(18) ų, Z = 2. Oriented hydrogen-bonded chains of alternating cucurbit[6]uril molecules and gadolinium aqua cations form in the crystal structure.     

Crystalline modifications of tetra-(p-tolyl)antimony benzene sulfonate

Two structural isomers (I and II) have been obtained via the crystallization of tetra-(p-tolyl)antimony benzene sulfonate from toluene or water. The antimony atom in compound I has a distorted trigonal bipyramidal coordination to the carbon and oxygen atoms in axial positions (Sb-C, 2.097(11) (eq.), 2.103(10) (eq.), 2.111(10) (eq.), 2.139(10) (ax.) Å; Sb-O, 2.400(7) Å; OSbC, 176.9(3)°, C_eqSbC_eq, 115.3(4)°, 118.7(4)°, 119.1(4)°). A crystal of compound II is built of tetrahedral tetra-(p-tolyl)stibonium cations (Sb-C, 2.097(2), 2.097(2), 2.105(2), 2.106(3) Å; CSbC, 104.68(9)°-117.25(9)°) and benzene sulfonate anions (S-O, 1.439(2), 1.451(2), 1.454(2) Å; OSO, 112.82(15)°-113.70(16)°; OSC, 104.74(13)°-105.78(12)°).     

Synthesis and structure of tri(<Emphasis Type="Italic">o</Emphasis>-tolyl) antimony dioximates

Tri(o-tolyl) antimony dioximates were synthesized by the reaction of tri(o-tolyl) antimony with 5-nitrofurfural and thiophen-2-carbaldehyde oximes in ether in the presence of hydrogen peroxide or tert-butylhydroperoxide (1: 2: 1 mol). Antimony atoms in the reaction products have distorted trigonal-bipyramidal coordination with the intramolecular distances Sb···N shorter than the sum of the van der Waals radii of Sb and N by ~1 Å.     

Crystal and molecular structure of (±)-2-[(1<Emphasis Type="Italic">S</Emphasis>,3<Emphasis Type="Italic">S</Emphasis>)-3-acetyl-2,2-dimethylcyclobutyl]-N-(<Emphasis Type="Italic">p</Emphasis>-tolyl)acetamide

The structure of (±)-2-[(1S,3S)-3-acetyl-2,2-dimethylcyclobutyl]-N-(p-tolyl)acetamide has been determined by single crystal X-ray diffraction analysis. The crystal belongs to triclinic system, space group P-1, a = 8.8700(18) Å, b = 10.331(2) Å, c = 10.363(2) Å, α = 71.11(3)°, β = 65.06(3)°, γ = 72.18(3)°, V = 798.6(3) ų, Z = 2, formula unit C₁₇H₂₃NO₂. The title compound has a fragment of 2,2-dimethylcyclo-butane and its conformation represents semi-chair. The intermolecular hydrogen bonds N-H...O and C-H...O are revealed.     

Crystal Structure of <Emphasis Type="Italic">DL</Emphasis>-Valinium Tetrafluoroantimonate(III) Monohydrate

The crystal structure of an antimony(III) fluoride complex of the composition (C₅H₁₂NO₂)SbF₄·H₂O (I) involving a cation of α-amino isovaleric acid (DL-valine, Val) is determined. Crystals are monoclinic: a = 12.2024(2) Å, b = 6.1636(1) Å, c = 15.5167(3) Å, Z = 4, space group P2₁/c. The structure is formed of DL-valinium (C₅H₁₂NO₂)⁺ cations, complex [SbF₄]_n^n? anions having a polymeric chain structure, and crystallization water molecules. The [SbF₄]_n^n? complex anions consist of trigonal SbF4E bipyramids joined together by asymmetric bridging Sb–F(3)···Sb bonds. The structural units are organized into a threedimensional framework via N–H···F, N–H···O, and O–H···F hydrogen bonds.     

μ<Subscript>2</Subscript>-Oxobis[(aroxo)tris(<Emphasis Type="Italic">para</Emphasis>-tolyl)antimony]: Synthesis and Structure

µ₂-Oxobis[(2,4,6-tribromophenoxo)tris(para-tolyl)antimony] (I), µ₂-oxobis[(2,3,4,5,6-pentachlorophenoxo) tris(para-tolyl)antimony] (II), and µ₂-oxobis(2,4-dinitrophenoxo)tris(para-tolyl)antimony] (III) have been synthesized with high yields by the reaction of tris(para-tolyl)antimony with 2,4,6-tribromo-, 2,3,4,5,6-pentachloro-, and 2,4-dinitrophenol, respectively, in ether in the presence of tert-butylhydroperoxide. The Sb atoms in complexes I, II, and III have a distorted trigonal bipyramidal coordination with the aroxyl ligands and the bridging oxygen atom in axial positions. The central Sb–O–Sb moiety in molecules of complexes I–III has an angular structure.     

Synthesis and structure of tris(4-<Emphasis Type="Italic">N,N</Emphasis>-dimethylaminophenyl) antimony(V) dicarboxylates and diaroxides

Tris(4-N,N-dimethylaminophenyl)antimony dicarboxylates (4-Me₂NC₆H₄)₃Sb[OC(O)R]₂ (R = C₆H₄Me-2 (I), C₆H₄Me-4 (II), CH=CHPh (III)), (4-Me₂NC₆H₄)₃Sb[OC(O)C(O)O] (IV), and (4-Me₂NC₆H₄)₃Sb[OC(O)C₆Cl₄C(O)O] (V)) and tris(4-N,N-dimethylaminophenyl)antimony diaroxides (4-Me₂NC₆H₄)₃Sb(OAr)₂ (Ar = Ph (VI), C₆H₂Br₃-2,4,6 (VII), and C₆H₃Me₂-2,6 (VIII)) have been synthesized by the reaction of tris(4-N,N-dimethylaminophenyl)antimony in ether with carboxylic acids or phenols in the presence of hydrogen peroxide. According to X-ray diffraction analysis data, the Sb atoms in compounds I and VII have a distorted trigonal-bipyramidal coordination, and the axial OSbO angles are 175.4(1)° and 177.9(3)°, respectively. The Sb-O bond lengths are 2.133(3) and 2.142(2) Å in compound I and 2.089(5) Å in compound VII.     

The crystal structure of [Mg(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>][VO(edta)] · 3.5H<Subscript>2</Subscript>O

The crystal structure of complex [Mg(H₂O)₆][VO(edta)] · 3.5H₂O (I) was determined by X-ray diffraction study. The crystals are monoclinic, a = 6.779 Å, b = 13.373(6) Å, c = 25.054 Å, β = 96.55°, Z = 4, space group P2₁. The unit cell contains two independent [VO(edta)]^2? anions, two independent [Mg(H₂O)₆]²⁺ cations, and seven crystal-water molecules. The coordination polyhedron of each vanadium atom is formed by five donor atoms of the edta ligand (2N + 3O) (V(1)-N(1), 2.278 Å; V(1)-N(2), 2.149 Å; V(2)-N(3), 2.301 Å; V(2)-N(4), 2.165 Å; V-O(acet), 2.00 ± 0.02 Å) and the oxygen atom of the oxo group (V-O, 1.60 ± 0.01 Å). The edta ligands and the vanadium atom form three glycinate rings: two R-type rings and one G-type ring (one acetate branch remains free), as well as an E-type ring with an asymmetric gauche configuration. The [Mg(H₂O)₆] cations are slightly distorted octahedra (Mg-O, 2.013–2.132 Å, the OMgO angles are 86.6°–94.2°). The H₂O molecules form a bifurcate system of H-bonds. The crystals of compound I belong to OD-type structures with an incomplete ordering of layers.     

Synthesis and structure of tetraphenylantimony and triphenylantimony 4-oxybenzoates

Solvate Ph₃Sb[OC(O)C₆H₄(OH-4)]₂ · 1/2Et₂O (I) has been synthesized by the reaction between triphenylantimony and 4-oxybenzoic acid in the presence of hydrogen peroxide in diethyl ether. Tetraphenylantimony 4-oxybenzoate, which crystallizes from DMSO in the form of solvate Ph₄SbOC(O)C₆H₄(OH-4) · DMSO (II), has been synthesized from pentaphenylantimony and triphenylantimony bis(4-oxybenzoate) or 4-oxybenzoic acid. According to X-ray diffraction data, an antimony atom in molecules of compounds I and II has a trigonal bipyramidal coordination. Crystals of compound I contain two crystallographically independent types of molecules (A and B). The Sb-C and Sb-O distances, the equatorial CSbC and axial OSbO angles are, respectively, 2.083(9)–2.103(8)Å; 2.068(5), 2.128(5)Å; 117.6(3)°–124.2(3)° and 171.5(2)° (IA); 2.103(9)–2.135(8)Å; 2.086(5), 2.154(6)Å;110.2(3)°–138.0(4)° and 174.8(2)° (IB). In compound II, Sb-C is 2.117(2)–2.175(2) Å, Sb-O is 2.247(2) Å, and C_eqSbC_eq and OSbC_ax angles are 110.89(9)°–133.30(9)° and 177.05(7)°, respectively. The Sb…O=C intramolecular contacts are 3.151(7), 3.153(8) Å (IA), 2.985(8), 3.008(9) Å (IB), and 2.975(5) Å (II). Molecules IA and IB are conformation isomers, which differ from each other by the arrangement of carboxyl groups with respect to the equatorial plane.     

Two Mn(II) chloride complexes containing guest molecules

Two phenanthroline-manganese inclusion complexes with [MnCl(H₂O)(phen)₂]⁺ core have been synthesized and characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses. Uncoordinated 2-mercaptothiazole (tzdtH) and 2-mercaptobenzothiazole (bztzH) as guest molecules are included in the complexes with formulas [MnCl(H₂O)(phen)₂]Cl·tzdtH (1) and {[MnCl(H₂O)(phen)₂]Cl}₂·bztzH (2). X-ray structural analyses for complexes revealed that the complex 1 is triclinic, space group P1 with a=9.724(1) Å, b=11.858(1) Å, c=12.644(2) Å; β=89.056(2)°; Z=2, D _c=1.513 Mg m^?3, F(000)=638 and the complex 2 is triclinic, space group P1 with a=9.861(1) Å, b=11.476(1) Å; c=12.908(3) Å; β=84.991(2)°; Z=1, D _c=1.511 Mg m^?3, F(000)=600. Two complexes exhibit high stability up to 650°C. The molar specific heat capacities for the two complexes 1 and 2 can be estimated as being 96.175±0.332 and 72.505±0.364 J mol^?1 K^?1 at 298.15 K by RD496-III microcalorimeter, respectively.     

Tetraphenylantimony <Emphasis Type="Italic">N</Emphasis>-benzoylglycinate: synthesis and structure

Tetraphenylantimony N-benzoylglycinate (I) has been synthesized by the reaction between pentaphenylantimony and N-benzoylglycine in toluene. According to X-ray diffraction data, the antimony atom in a molecule of complex I has a trigonal bipyramidal coordination to the oxygen atom in axial position. The Sb?C_eq, Sb?C_ax, and Sb?O bond lengths are 2.116(6)?2.138(6), 2.183(6), and 2.200(4) Å, respectively. The intramolecular Sb?O=C distance between the carbonyl oxygen atom and the central antimony atom is 3.35(2) Å.     

Crystal Structure of Tetra- and Pentasodium Salts of Nitrilotris(methylenephosphonic Acid)

Tetra- and pentasodium salts of nitrilotris(methylenephosphonic acid) N(CH₂PO₃)₃H₆ (NTP) have been studied by single-crystal X-ray diffraction and spectroscopy. [Na₈(H₂O)₁₂{NH(CH₂PO₃)₃H}₂] · H₂O crystallizes in triclinic system, space group P1?, Z = 1, a = 7.1515(2) Å, b = 11.1590(3) Å, c = 12.0583(3) Å; α = 92.077(2)°, β = 106.145(2)°, γ = 5.628(2)°, CCDC No. 1432091. The crystal structure comprises two-dimensional layers lying along planes (011?), where dimeric molecules are linked by bridges each comprising four Na hydration octahedra. The [Na₅(H₂O)₁₁{NH(CH₂PO₃)₃}] · 2H₂O crystals are monoclinic, space group P2₁/n, Z = 4, a = 6.3024(2) Å, b = 21.5639(7) Å, c = 18.1608(6) Å; β = 91.261(3)°, CCDC No. 1497161. The crystal packing comprises alternating layers in planes [020] made of two-dimensional nets of Na hydration polyhedra, and columns of Na hydration octahedra lying in planes [040], with acid moieties in between.     

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).     

Synthesis and crystal structure of the silver nitrate complex with 4,4′-trimethylenedipiperidine [Ag(C<Subscript>13</Subscript>H<Subscript>26</Subscript>N<Subscript>2</Subscript>)]NO<Subscript>3</Subscript>

A new coordination compound [AgNO₃(C₁₃H₂₆N₂)] was synthesized and structurally characterized. The crystals are triclinic: space group P \(\bar 1\), a = 6.157(1) Å, b = 10.074(1) Å, c = 14.153(1) Å, α = 102.36(1)°, β = 92.16(1)°, γ = 107.33(1)°, V = 813.7(2) ų, ρ_calcd = 1.552 g/cm³, Z = 2. The structure contains centrosymmetric rings formed by two Ag⁺ ions and two bridging trimethylenedipiperidine ligands. The coordination of Ag⁺ ions is close to linear (Ag(1)-N(1), 2.192(5) Å; Ag(1)-N(2), 2.212(5) Å; angle N(1)Ag(1)N(2), 162.7(2)°). Anions NO ₃ ^? form weak bonds with silver ions (Ag(1)…O(1), 2.783(5) Å; Ag(1)-O(3), 2.893(5) Å) and combine rings into supramolecular bands running in the diagonal direction of the unit cell.     

Structural characterization of a mixed-ligand complex of copper(II) with 1,10-phenanthroline and the <Emphasis Type="Italic">m</Emphasis>-aminobenzoate ion

A new copper(II) complex of 1,10-phenanthroline (C1₂H₈N₂) and the meta-aminobenzoate ion (m-amb; C₇H₆NO ₂ ^? ), having the formula Cu(C₁₂H₈N₂)(C₇H₆NO₂)Cl?0.5H₂O, is prepared and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. The structure is built up from monomeric units in which the coordination environment around the metal ion is a square plane arising from a bidentate 1,10-phenanthroline molecule, a monodentate m-amb anion, and a chloride ion. A very long (Cu–N = 2.856(5) Å) bond to the nitrogen atom of an adjacent m-amb ion generates [101] polymeric chains in the crystal. The crystal structure is consolidated by N–H???O and O–H???O hydrogen bonds and C–H???O, C–H???Cl, and aromatic π–π stacking interactions. Crystal data: C₁₉H₁₅ClCuN₃O_2.5, M _r = 424.33, monoclinic, P2₁/n (No. 14), a = 9.8200(5) Å, b = 10.9291(7) Å, c = 16.3803(9) Å, β = 105.293(3)°, V = 1695.74(17) ų, Z = 4, R(F) = 0.043, wR(F ²) = 0.122.     

Crystal structure of copper(II) <Emphasis Type="Italic">trans</Emphasis>-bis-(4-phenyliminopentan-2-onate)

trans-Bis-(4-phenyliminopentan-2-onato)Cu(II) (5), which is a phenyl-substituted ketoimine, was synthesized, and an X-ray study was performed for this compound. Crystal data for CuN₂O₂C₂₂H₂₄: a = 11.4557(3) Å, b = 26.6845(9) Å, c = 14.2976(5) Å, β = 113.2270(10)°; space group P2₁/n, Z = 8, d _calc = 1.363 g/cm³, R = 0.033. The structure is molecular and built of isolated trans complexes. The central copper atom is surrounded by four atoms (2O+2N) with the average distances Cu-O 1.904(3) Å and Cu-N 1.962(3) Å. The polyhedron around the copper atom is a distorted tetrahedron; the average values of the O-Cu-O and N-Cu-N trans bond angles are 147(2)° and 150(2)°, respectively. The average value of the O-Cu-N angles is 94(1)°.     

Formation of the high-pressure modification of hydrated talc at 450°C and 4 GPa: <Emphasis Type="Italic">In situ</Emphasis> diffraction study

The formation of the high-pressure hydrous phase Mg₃Si₄O₁₀(OH)₂?xH₂O (10 Å phase) through the reaction “talc + water” at 450°C and 4 GPa was studied using diamond anvil cell. The powder diffraction measurements in situ, performed at the Siberian Center of Synchrotron and Terahertz Radiation (SSTRC), were applied to refine the lattice parameters, atomic coordinates and the occupancy of interlayer H₂O site in the structure of 10 Å phase at 450°C and 4 GPa. The lattice parameters are a = 5.234(1) Å, b = 9.053(2) Å, c = 10.87(1) Å, β = 99.2(1)°, and V = 508.5(6) ų (space group C2/m). The results of Rietveld refinement show the best fit for the trioctahedral mica structure with split position Ow of the interlayer H₂O molecule. The half occupancy of the Ow site corresponds to one H₂O molecule per formula unit.     

Erbium(III) and lutecium(III) complexes [Ln(H<Subscript>2</Subscript>O)<Subscript>8</Subscript>][Cr(NCS)<Subscript>6</Subscript>] · 5H<Subscript>2</Subscript>O: Synthesis and crystal structure

[Ln(H₂O)₈][Cr(NCS)₆] · 5H₂O aqua complexes, where Ln = Er (1), Lu (2), have been found in an aqueous solution instead of binary complex salts with an organic ligand in their cation, when crystal products of the reaction between Ln(NO₃)₃ · 6H₂O (Ln = Er, Lu), K₃[Cr(NCS)₆] · 4H₂O, and 8-oxyquinoline (C₉H₇NO) were studied by X-ray diffraction. Crystals of complexes 1 and 2 are isostructural and crystallize in triclinic system, space group P\(\bar 1\), Z = 2. For complex 1: a = 9.0677(4) Å, b = 9.3115(4) Å, c = 16.9595 Å, α = 81.526(2)°, β = 86.153(2)°, γ = 83.879(2)°, V = 1406.33(10) ų, ρ_calc = 1.894 g/cm³; for complex 2: a = 9.0438(3) Å, b = 9.2880(3) Å, c = 16.9181(3) Å, α = 81.7250(10)°, β = 86.1600(10)°, γ = 83.8850(10)°, V = 1396.38(7) ų, ρ_calc = 1.926 g/cm³.