Synthesis and structure of tri-<Emphasis Type="Italic">m</Emphasis>-tolylantimony bis(1-adamantanecarboxylate)

Tri(m-tolyl)antimony bis(1-adamantanecarboxylate) (3-MeC₆H₄)₃Sb[OC(O)C₁₀H₁₅]₂ has been synthesized with a yield of 90.0% by the reaction of tri(m-tolyl)antimony with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide in ether. According to X-ray diffraction analysis data, the antimony atom has a distorted trigonal-bipyramidal coordination with the axially positioned oxygen atoms of carboxyl groups. The axial OSbO angle is 173.1(2)°; the equatorial CSbC angles are 112.0(1)°, 112.0(1)°, and 136.0(3)°; the Sb-O distance is 2.109(3)Å; the Sb-C distances are 2.103(5), 2.103(5), and 2.121(7) Å; intramolecular Sb…O(=C) contacts are 3.069(5) Å.     

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.     

Synthesis and structure of tris(4-<Emphasis Type="Italic">N,N</Emphasis>-dimethylaminophenyl)antimony bis(4-methyl benzoate)

The tris(4-N,N-dimethylaminophenyl)antimony bis(4-methyl benzoate) (I) was synthesized by the reaction of tris(4-N,N-dimethylaminophenyl)antimony with 4-methylbenzoic acid in ether in the presence of hydrogen peroxide. According to the X-ray diffraction data, in this molecule the antimony atom is in distorted trigonal-bipyramidal coordination (the axial angle OSbO is 176.15(4)°). The CSbC angles in the equatorial plane are 105.27(6)°, 108.01(6)°, 146.71(6)° (the sum is 359.99°). The Sb-O and Sb-C bond lengths are 2.131(1), 2.137(1) Å and 2.099(2), 2.100(1), 2.107(1) Å, respectively. The intramolecular contacts Sb...O=C are 2.826(1) and 2.928(1) Å.     

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.     

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)°).     

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 of new antimony(III) and bismuth(III) aryl compounds: Crystal and molecular structure of tris(5-bromo-2-methoxyphenyl)antimony

Tris(5-bromo-2-methoxyphenyl)antimony (I) (yield, 85%) and tris(5-bromo-2-methoxyphenyl)bismuth (II) (yield, 81%) were obtained by reacting 5-bromo-2-methoxyphenyllithium with antimony(III) chloride and bismuth(III) chloride, respectively. According to X-ray diffraction data, the antimony atom in I is highly coordinated. The Sb-C bonds lengths are 2.160(1) Å, 2.163(1) Å, and 2.157(2) Å; the Sb…O distances are 2.985(1) Å, 3.051(1) Å, and 3.052(1) Å. The CSbC bond angles vary in the range of 92.19(6)°-94.52(6)°. Molecules of I are linked via Sb(A)…Br(B) intermolecular contacts (3.742(2) Å) to form polymer chains.     

Redetermination and Crystallographic Analysis of the Structure of Sb-Containing Laffittite AgHg(As,Sb)S<Subscript>3</Subscript> From Chauvai (Kyrgyzstan)

The crystal structure of laffittite mineral AgHg(As,Sb)S₃ from the Chauvai deposit (Kyrgyzstan), containing about 10% of Sb atoms in the As³⁺ position, is re-determined (Aa space group, a = 7.7560(3) Å, b = 11.3340(4) Å, c = 6.6650(3) Å, β = 115.233(4)°, V =529.99(4) ų, d = 6.078 g/cm³, Z = 4, R = 0.0229). Crystallographic analysis of the structure reveales the presence of quite regular face-centered cubic cation and anion sublattices, thus confirming the assignment of the structure to the structural type of PbS. A deviation from the octahedral coordination of cations characteristic of this type is mainly related to a mutual asymmetric displacement of the cation and anion matrices.     

Tri-m-tolylantimony dibenzoate: Synthesis and structure

Tri-m-tolylantimony dibenzoate (II) has been synthesized by the reaction between tri-m-tolylantimony (I) and benzoic acid in diethyl ether in the presence of tert-butylhydroperoxide with a yield of 95%. According to X-ray diffraction data, a molecule of compound I is shaped as a trigonal pyramid with a lone pair on the antimony atom (Sb-C, 2.146(3), 2.148(3), and 2.152(3) Å; CSbC, 96.49(11)°, 96.91(11)°, and 97.28(11)°). An antimony atom in compound II has a distorted trigonal bipyramidal coordination to the oxygen atoms in axial positions. The Sb-C and Sb-O distances are 2.107(3)–2.121(3) Å and 2.134(2), 2.140(2) Å, respectively. The OSbO and CSbC angles are 175.68(9)° and 108.02(14)°–140.36(15)°, respectively. The Sb…O intramolecular contacts are 2.869(4) and 2.925(4) Å.     

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.     

π-Complexes of Cu(I) with Alkynes. Synthesis and Crystal Structure of Cs[CuCl<Subscript>2</Subscript>(HOCH<Subscript>2</Subscript>C≡CCH<Subscript>2</Subscript>OH)] ⋅ H<Subscript>2</Subscript>O

Crystals of anionic π-complex Cs[CuCl₂(HOCH₂C≡CCH₂OH)] ? H₂O were synthesized by reaction of 2-butyne-1,4-diol with CuCl in a saturated aqueous solution of CsCl at 90°C and studied by X-ray diffraction analysis. The crystals are triclinic (space group \(P\bar 1\) ; a = 10.155(4) Å, b = 7.828(4) Å, c = 7.115(3) Å, α = 102.62(4)°, β = 100.77(3)°, γ = 106.71(4)°, V = 509(1) ų, Z = 2) and consist of stacks of individual anions [CuCl₂(HOCH₂C≡CCH₂OH)]^? and hydrated [Cs ? H₂O]⁺ cations between the stacks. The Cu(I) atom has trigonal surrounding of two Cl atoms and the C≡C bond of 2-butyne-1,4-diol molecule. The Cu-(C≡C) distance in the π-core is 1.905(8) Å; the C≡C bond is elongated to 1.223(11) Å. In addition to hydrogen bonds O-H?Cl, crystals of the complex also contain O(w)?H-O and O(w)?Cl bonds stabilizing their structure.     

Synthesis and structure of tetraphenylantimony 1-adamantanecarboxylate and triphenylantimony bis(1-adamantanecarboxylate)

Reaction of pentaphenylantimony with triphenylantimony bis(1-adamantylcarboxylate) yielded the solvate of tetraphenylantimony 1-adamantylcarboxylate with benzene. Triphenylantimony bis(1-adamantylcarboxylate) was prepared from triphenylantimony and 1-adamantylcarboxylic acid in the presence of hydrogen peroxide in ether. X-ray studies showed that in the first and in the second product antimony atom has the distorted trigonal bipyramide coordination (OSbO and CSbO trans-angles are 179.42° and 174.58°, respectively). Sb-O interatomic distances are 2.154 and 2.202 Å, respectively. The carbonyl group oxygen atom is coordinated with the central atom, Sb?O interatomic distances are 2.570 and 3.396 Å, respectively.     

Tris(2-methoxy-5-bromophenyl)antimony bis(2-nitrobenzoate): Synthesis and specific features of the structure

Tris(5-bromo-2-methoxyphenyl)antimony bis(2-nitrobenzoate) (I) is synthesized by the reaction of tris(5-bromo-2-methoxyphenyl)antimony with 2-nitrobenzoic acid in the presence of hydrogen peroxide (mole ratio 1: 2: 1). According to the X-ray diffraction data, the antimony atom has distorted trigonal bipyramidal coordination. The axial angle OSbO is 177.92(11)°, equatorial bonds CSbC are 109.23(16)°–128.31(16)°, and the Sb-O and Sb-C bond lengths are 2.095(3)–2.125(3) and 2.098(4)–2.113(4) Å, respectively. A specific feature of the structure of complex I is the presence of intramolecular contacts Sb...O(CH₃) (2.992–3.175 Å along with the interactions Sb...O=C (3.039–3.117 Å). The structural organization in crystal is due to weak hydrogen bonds N-O...H-C, C=O...H-C, C-Br...H-C.     

Tris(<Emphasis Type="Italic">para</Emphasis>-tolyl)- and tris(4-fluorophenyl)antimony diaroxides: syntheses and structures

Bis(4-bromophenoxy)tris(para-tolyl)antimony (I), bis(4-nitrophenoxy)tris(para-tolyl)antimony (II), bis(4-nitrophenoxy)tris(4-fluorophenyl)antimony (III), bis(2,3,4,5,6-pentafluorophenoxy)tris(4-fluorophenyl) antimony (IV), and bis(2,3,4,5,6-pentachlorophenoxy)tris(4-fluorophenyl)antimony (V) (CIF files CCDC 1470829 (I), 1474589 (II), 1062337 (III), 1470476 (IV), and 1472954 (V)) are synthesized in high yields by the reactions of tris(para-tolyl)- and tris(4-fluorophenyl)antimony with 4-bromo-, 4-nitro-, 2,3,4,5,6-pentafluoro-, and 2,3,4,5,6-pentachlorophenol, respectively, in diethyl ether in the presence of tert-butyl hydroperoxide. The Sb atoms in compounds I–V have a distorted trigonal bipyramidal coordination with the aroxy groups in the axial positions (angles OSbO 174.08(11)°–179.4(5)°). The average Sb–C bond lengths in compounds I–V are similar and independent of the nature of the para-substituent in the aryl rings. The Sb–O distances are close to the sum of covalent radii of Sb and O atoms. Hydrogen bonds H···F are involved in the formation of the crystal structures of compounds III–V.     

X-ray diffraction structural investigation of two hafnium(IV) complexes with dipivaloylmethane

Synthesis and single crystal X-ray diffraction study of hafnium(IV) dipivaloylmethanate Hf(dpm)₄ and chloro-tris-(dipivaloylmethanato)hafnium(IV) Hf(dpm)₃Cl have been carried out. Crystal data: a = 22.6606(5) Å, b = 11.3990(4) Å, c = 19.8513(7) Å, β = 106.458(1)°, Pc, Z = 4, d _calc = 1.231 g/cm³, R = 0.075 for C₄₄H₇₆HfO₈; a = 10.6376(13) Å, b = 10.6701(10) Å, c = 19.4400(22) Å, α = 74.970(3)°, β = 75.672(3)°, γ = 61.725(2)°, P-1, Z = 2, d _calc = 1.366 g/cm³, R = 0.031 for C₃₃H₅₇ClHfO₆. The structures are molecular and are built from discrete mononuclear complexes joined by van der Waals interactions. Disordering of carbon atoms preserving at low temperature is observed for the compound Hf(dpm)₄. It has been found out that the structure contains two crystallographically unique complexes of hafnium(IV) with central atoms coordinated with eight oxygen atoms of four dipivaloylmethane ligands, bond lengths Hf-O fall within 2.084–2.222 Å, the distances Hf...Hf between the molecules are 10.07–13.87 Å. In Hf(dpm)₃Cl the hafnium atom is seven-coordinated with six oxygen atoms of three β-diketonate ligands and one chlorine atom, the distances Hf-O fall within 2.087–2.179 Å, the lengths of the bond Hf-Cl for two crystallographically independent molecules Hf(1) and Hf(2) are 2.466 Å and 2.442 Å, respectively.     

Syntheses and structures of tris(<Emphasis Type="Italic">para</Emphasis>-tolyl)-, tris(3-fluorophenyl)-, and tris(4-fluorophenyl)antimony dioximates

Tris(para-tolyl)antimony bis(2-oxybenzaldoximate) (I), tris(para-tolyl)antimony bis(2-nitrobenzaldoximate) (II), tris(para-tolyl)antimony bis(2-bromobenzaldoximate) (III), tris(3-fluorophenyl)antimony bis(2-oxybenzaldoximate) (IV), tris(4-fluorophenyl)antimony bis(2-bromobenzaldoximate) (V), and tris(4-fluorophenyl)antimony bis(2-nitrobenzaldoximate) (VI) are synthesized by the reactions of tris(paratolyl)-, tris(3-fluorophenyl)-, and tris(4-fluorophenyl)antimony with 2-oxy-, 2-nitro-, and 2-bromobenzaldoxime in diethyl ether in the presence of tert-butyl hydroperoxide. The Sb atoms in complexes I–VI have a distorted trigonal bipyramidal coordination mode with the oximate ligands in the axial positions. CIF files CCDC nos. 1062231 (I), 1059962 (II), 1465384 (III), 1465109 (IV), 1471948 (V), and 1060387 (VI).     

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.     

Hydrolysis of coordinated aminoacetonitrile in a platinum(IV) complex. Crystal structure of [PtPy(NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>COO)Cl<Subscript>3</Subscript>]

Heating of a hydrochloric acid solution of trans-PtPy(NH₂CH₂CN)Cl₄ results in the hydrolysis of coordinated aminoacetonitrile to aminoacetic acid with the formation of a five-membered chelate ring attached to platinum through the nitrogen atom of the amino group and the oxygen atom of the carboxy group. X-ray diffraction analysis of [PtPy(NH₂CH₂COO)Cl₃] is carried out. The crystals are monoclinic: space group C2/c, a = 21.704(2), b = 8.7027(7), c = 15.576(1) Å, β = 126.606(1)^o, V = 2361.8(3) ų, Z = 8; R _hkl = 0.057, wR = 0.141. In the neutral complex, the Pt atom has a distorted octahedral coordination. The equatorial plane is formed by a Cl atom (Pt-Cl, 2.284(3) Å), the N atom of the Py molecule (Pt-N, 2.062(8) Å), and the N and O atoms of the bidentate-chelating ligand (Pt-N, 2.039(8); Pt-O, 2.026(7) Å); two Cl atoms are arranged in the apical positions (Pt-Cl, 2.301(3) and 2.312(3) Å). The five-membered chelate ring has a flattened gauche conformation with an NCCO torsion angle of 19(1)°.     

Crystal structures of [Zn(SALIMP)(CH<Subscript>3</Subscript>CO<Subscript>2</Subscript>)]<Subscript>2</Subscript> and [Cu(SALIMP)Cl] with 2-[[(2-pyridinylmethyl) imino]methyl]phenol (HSALIMP) as a ligand

Two complexes [Zn(SALIMP)(CH₃CO₂)]₂ (1) and [Cu(SALIMP)Cl] (2) are obtained by the reactions of zinc(II) and copper(II) salts with a tridentate Schiff base ligand 2-[[(2-pyridinylmethyl) imino]methyl]phenol (HSALIMP). Their structure is determined by single crystal X-ray diffraction. Data for complex 1: C₃₀H₂₈N₄O₆Zn₂, CCDC number: 668213, M _r = 671.3, monoclinic, C2/c, with a = 34.670(5) Å, b = 15.266(2) Å, c = 23.464(4) Å, β = 114.045(2)°, V = 11341(3) ų, Z = 16, F(000) = 5504, GOOF(F ²) = 0.894, the final R = 0.0520 and wR = 0.1272 for 10515 observed reflections with I > 2σ(I); complex 2: C₁₃H₁₂N₂OClCu, CCDC number: 668211, M _r = 311.24, triclinic, P-1, with a = 7.4050(8) Å, b = 10.2369(11) Å, c = 16.2873(17) Å, α = 87.728(2)°, β = 87.818(2)°, γ = 78.279(2)°, V = 1207.4(2) ų, Z = 4, F(000) = 632, GOOF(F ²) = 1.077, the final R = 0.0326 and wR = 0.0381 for 4209 observed reflections with I > 2σ(I).     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony dicarboxylates

Tris(5-bromo-2-methoxyphenyl)antimony bis(4-nitrophenylacetate) (I), tris(5-bromo-2-methoxyphenyl)antimony bis(2-methoxybenzoate) (II), and tris(5-bromo-2-methoxyphenyl)antimony bis(phenylpropiolate) (III) have been synthesized via the reaction between tris(5-bromo-2-methoxyphenyl) antimony and 4-nitrophenylacetic acid, 2-methoxybenzoic acid, and phenylpropiolic acid, respectively, in the presence of hydrogen peroxide (molar ratio: 1: 2: 1). According to X-ray diffraction data, the antimony atom in molecules of complexes I–III has a distorted trigonal bipyramidal coordination. The OSbO axial angles and the CSbC bond angles in the equatorial plane are 173.27(15)°, 172.96(11)°, 172.99(10)°, and 115.5(2)°–123.3(2)°, 108.81(16)°–129.32(17)°, and 110.66(17)°–127.91(17)°, respectively. The Sb-O bond lengths are 2.092(4) and 2.115(4)Å in I, 2.088(3) and 2.097(2) Å in II, and 2.096(3) and 2.120(3) Å in III. The Sb-C bonds range within 2.095(6)–2.123(6) Å in I, 2.107(4)–2.117(4) Å in II, and 2.097(4)–2.116(4) Å in III. Complexes I, II, and III are observed to have intramolecular Sb…OCH₃ contacts (3.169–3.226, 3.134–3.174, and 3.147–3.196 Å, respectively) in addition to Sb…O=C interactions (3.121, 3.139Å; 2.944, 3.038 A0; 3.111, 3.120 Å).