Search

In a crystal of tris(2-methoxy-5-chlorophenyl)antimony benzene solvate (5-Cl-2-MeO-C6H3)3Sb (I) ⋅ 1/2С6Н6 synthesized from SbCl3 and 2-methoxy-5-chlorophenyllithium with recrystallization from benzene, the antimony atoms are in a trigonal environment of ligands with the oxygen atoms of MeO groups coordinated to the metal atom (intramolecular Sb∙∙∙OМе distances are 3.053(1), 3.054(1), and 3.011(1) A, CN = 3 + 3). The effect of tert-butyl hydroperoxide on a mixture of tris(2-methoxy-5-chlorophenyl)antimony and bromoacetic, 3-fluorophenylacetic, and 2,3-difluorobenzoic acids in ether leads to the formation of trigonal bipyramidal triarylantimony dicarboxylates (5-Cl-2-MeO-C6H3)3Sb[OC(O)R]2, where R = CH2Br (II), CH2C6H4F-3 (III), C6H3F2-2,3 (IV) with carboxylate ligands in apical positions. In crystals of compounds II–IV, the metal atom is additionally coordinated to the oxygen atoms of О=С and МеО groups.

The synthesis methods, some reactions, and specific features of the structures of aryl compounds of pentavalent antimony and examples of their possible use are systematized and described on the basis of an analysis of the works published since 2009 to the present time. Some earlier works are also reviewed due to this special significance. When discussing the synthesis methods, the main attention is given to the most efficient approaches to the syntheses of the aryl compounds, for example, the reactions of ligand redistribution, substitution, and oxidative addition. The formation of heterocyclic antimony compounds is considered. The data on the biological and catalytic activities of selected antimony derivatives are presented. The bibliography consists of 318 references.

Complexes Ph3(C2H4O2)Sb⋅⋅⋅DMSO (I), (3-FC6H4)3(C2H4O2)Sb⋅⋅⋅DMSO (II), and (4‑MeC6H4)3-(C6H4O2)Sb⋅⋅⋅DMSO (III) are synthesized by the reactions of triarylantimony with ethylene glycol or pyrocatechol in the presence of an oxidant and dimethyl sulfoxide (DMSO). According to the X-ray diffraction analysis data, the Sb atoms in the complexes have the coordination of a distorted octahedron with the chelate cycle (C2H4O2 or C6H4O2) and two aryl groups in the equatorial plane, and the third aryl group and DMSO molecule occupy the axial positions. The СSbO axial angles are 173.59(5)° (I); 175.96(8)°, 175.93(8)° (II); and 174.07(8)° (III). The Sb⋅⋅⋅О=SMe2 distances (2.346(2)−2.407(2) A) considerably exceed the sum of covalent radii of the atoms.

The reactions of tris(3-fluorophenyl)antimony (3-FС6H4)3Sb with 3,5-dinitrobenzoic, bromoacetic, chloroacetic, and cinnamic acids in the presence of tert-butyl hydroperoxide afford tris(3-fluorophenyl)antimony bis(3,5-dinitrobenzoate (I), tris(3-fluorophenyl)antimony bis(bromoacetate (II), tris(3-fluorophenyl)antimony bis(chloroacetate) (III), and tris(3-fluorophenyl)antimony dicinnamate (IV). According to the X-ray diffraction data, the coordination mode of the Sb atoms in all compounds is a trigonal bipyramid (CIF files CCDC nos. 1576022 (I), 1576023 (II), 1575287 (III), and 1576967 (IV). The axial angles OSbO are 174.70(6)°, 175.92(15)°, 176.62(6)°, and 175.81(11)°. The Sb−O and Sb−С bond lengths are 2.117(2), 2.137(2), and 2.105(3)−2.119(2) A in I; 2.110(4), 2.129(4), and 2.096(5)−2.112(5) A in II; 2.118(2), 2.136(2), and 2.120(2)−2.128(2) A in III; and 2.142(3) and 2.115(3)−2.119(4) A in IV. The Sb⋅⋅⋅O intramolecular distances with the carbonyl oxygen atom (2.895(3), 2.968(4) A (I); 2.814(6), 2.930(6) A (II); 2.809(3), 2.933(4) A (III); and 2.601(4) A (IV)) are shorter than the sum of the van der Waals radii of Sb and O by ∼1.0 A.

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.

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).

Tetra-para-tolylantimony derivatives (4-MeC6H4)4SbX, X = OC(O)C6H4(NO2-2) (I), OC(O)C≡CPh (II), ON=CHC6H4(NMe2-4) (III)) have been synthesized by the reaction between penta-para-tolylantimony and 2-nitrobenzoic and phenylpropiolic acids and 4-dimethylaminobenzaldoxime in benzene. Using X-ray diffraction, it has been established that the Sb atoms in molecules of complexes I–III are in distorted trigonal bipyramidal coordination to X groups in axial positions. The Sb–O bond lengths are 2.2797(16) (I), 2.2925(17) (II), and 2.1357(17) A (III). The CSbO axial angles are 178.28(7)° (I), 178.57(9)° (II), 176.09(8)° (III).

The reactions of pentaphenylantimony with oximes or triphenylantimony dioximates in toluene afford tetraphenylantimony oximates Ph4SbON=CHR (R = C6H4Br-2 (I), C6H4NO2-2 (II), and C4H3S-2 (III)). Triphenylantimony dioximates are synthesized by oxidative addition from triphenylantimony and oxime in diethyl ether in the presence of tert-butyl hydroperoxide. According to the X-ray diffraction data (CIF files CCDC no. 1055414 (I), 1055634 (II), and 1061727 (III)), the coordination mode of the antimony atoms in the molecules of compounds I–III is a distorted trigonal bipyramid with the oxygen atom of the oximate ligand in the axial position. The structural organization of the crystals is caused by weak hydrogen bonds.

Triphenylantimony dioximates Ph3Sb(ON=CHR)2 (R = C6H4NO2-2 (I), C6H4NO2-3 (II), C6H4Br-2 (III), C6H4Br-3 (IV), and C4H2ONO2-5 (V)) have been synthesized by the reaction between triphenylantimony and oximes in diethyl ether in the presence of tert-butylhydroperoxide (1: 2: 1 mol/mol/mol). The antimony atoms in I–V have a distorted trigonal bipyramidal coordination. The axial ОSbO angles are 174.8(3)°, 174.4(3)° (I a, I b), 175.02(19)° (II), 175.62(9)° (III), 176.34(5)° (IV), and 172.0(4)° (V). The Sb–O and Sb–C bond lengths are 2.046(7)–2.088(6) and 2.075(9)–2.185(8) A in I a, I b, 2.079(5), 2.090(7), and 2.090(7)–2.115(7) A in II, 2.0712(19), 2.0744(19), and 2.096(3)–2.109(3) A in III, 2.065(4), 2.083(3), and 2.089(5)–2.140(5) A in IV, and 2.088(7) and 2.110(10)–2.116(14) A in V. The Sb···N intramolecular distances (2.779(10)–2.900(9) A) are ~1 A shorter than the antimony and nitrogen van der Waals radii in sum.

The solvates of tris(4-fluorophenyl)antimony diaryloxides with benzene, (4-FC6H4)3Sb(OAr)2 • 1/2PhH (Ar = C6H4Cl-4 (I), C6H4Br-4 (II), and C6H3Br2-2,4 (III)), were prepared by the reaction of tris(4-fluorophenyl)antimony with 4-chlorophenol, 4-bromophenol, and 2,4-dibromophenol in diethyl ether in the presence of tert-butyl hydroperoxide followed by recrystallization from a benzene–heptane mixture (2: 1). The antimony atoms in I, II, and III form a distorted trigonal-bipyramidal coordination with oxygen atoms in axial positions (CIF files CCDC nos. 1047500 (I), 1048172 (II), 1048212 (III)). The OSbO angles are 177.23(8)° (I), 177.34(12)° (II), and 179.47(16)° (III). The Sb–O and Sb–C bond lengths are 2.0519(16), 2.0508(18), and 2.105(2)–2.121(2) A (I); 2.045(3), 2.055(3), and 2.105(4)–2.126(4) A (II); and 2.066(3), 2.058(3), and 2.100(6)–2.107(5) A (III). The structural organization in crystals I–III is formed by weak intermolecular C−H•••F hydrogen bonds (H•••F 2.52 A (I), 2.52 A (II), and 2.61 and 2.51A (III)).

Tetra(para-tolyl)antimony aroxides, [(4-MeC6H4)4SbOC6H3Cl2-2,6] • 1/2TolH (IА, IВ), (4-MeC6H4)4SbOC6H3(NO2)2-2,4 (II), and (4-MeC6H4)4SbOC6H2(NO2)3-2,4,6 (III), are synthesized by the reactions of penta-para-tolylantimony with 2,6-dichlorophenol, 2,4-dinitrophenol, and 2,4,6-trinitrophenol, respectively, in toluene. The structures of the synthesized compounds are determined by X-ray diffraction analysis (CIF files CCDC 1050584 (I), 1433797 (II), and 999305 (III)). The Sb atoms in compounds IА, IВ, and II have a distorted trigonal bipyramidal coordination with the aroxy groups in the axial positions (axial angles CSbO are 178.01(6)°, 177.74(7)°, and 174.42(11)° and Sb–O angles are 2.244(1), 2.230(2), and 2.507(3) A). In crystal III, the CSbC angles in the tetrahedral cation [(4-MeC6H4)4Sb]+ are 103.6(2)°–116.22(2)°. A weak interaction is observed between the cation and picrate anion [OC6H2(NO2)3-2,4,6]–(Sb···O distance is 3.472(3) A).

The reaction of pentaphenylantimony with 2,4,6-trichlorophenol or bis(2,4,6-trichlorophenoxy)- triphenylantimony in toluene afforded (2,4,6-trichlorophenoxy)tetraphenylantimony. The reaction of triphenylantimony with tert-butyl hydroperoxide and 2,4,6-trichlorophenol led to the formation of bis(2,4,6-trichlorophenoxy) triphenylantimony; further reaction of the latter with triphenylantimony dichloride provided (2,4,6-trichlorophenoxy)triphenylantimony chloride. According to the XRD data, the antimony atoms in the prepared compounds had distorted trigonal-bipyramidal coordination with electronegative ligands in axial positions.

Reaction of sodium hexachloroosmate(IV) dihydrate with (2-oxopropyl)- and (2-carboxyethyl)-triphenylphosphonium chlorides in dimethyl sulfoxide afforded complexes [Ph3PR]2[OsCl6]·4DMSO, where R = CH2C(O)Me and CH2CH2C(O)OH. The complexes were characterized by X-ray diffraction method; phosphorus atoms in cations [Ph3RP]+ possessed slightly distorted tetrahedral coordination.

A dimeric oxide has been synthesized by the oxidation of tris(5-bromo-2-methoxiphenyl)antimony with tert-butylhydroperoxide (molar ratios: 1: 1, 1: 2, 1: 4) in a tetrahydrofurane solution and crystallized as the solvate [(5-Br-2-MeOC6H3)3SbO]2 · C4H8O (I). According to X-ray diffraction data, the antimony atoms in a binuclear centrosymmetric molecule of solvate I have a distorted trigonal bipyramidal coordination by the bridging oxygen atoms in axial and equatorial positions. Short MeO…Sb contacts (3.077(3)–3.257(4) A) have been identified.

A reaction of palladium dibromide with HBr and (cyclopropyl)(triphenyl)phosphonium bromide in water followed by recrystallization from acetonitrile or DMF afforded the complexes [Ph3(cyclo-C3H5)P]2+ [PdBr4]2− (I) and [Ph3(cyclo-C3H5)P]]2+ [Pd2Br6]2− (II). Recrystallization of complexes I and II from DMSO gave [Ph3(cyclo-C3H5)P]+[PdBr3(DMSO)]− (III). According to X-ray diffraction data, the P-C bond lengths in the tetrahedral (cyclopropyl)(triphenyl)phosphonium cations of complexes I–III are 1.773(5)–1.802(5) (I), 1.778(5)–1.802(5) (II), 1.767(5)–1.797(5) A III); the angles CPC are 107.4(2)°–111.1(2)° (I), 107.2(2)°–111.2(2)° (II), and 108.4(2)°–110.5(2)° (III), and (CIF file CCDC no. 999905 (I), 1035313 (II), 999907 (III)). In the square anions [PdBr4]2−, the Pd-Br bond length is 2.4333(5)–2.4459(5) A. In the planar centrosymmetric dinuclear anions [Pd2Br6]2−, the bond lengths Pd-Brbrid and Pd-Brterm are 2.4559(7), 2.4600(7) and 2.3952(7), 2.4045(8)A; the angles PdBrPd and BrtermPdBrterm are 92.57(2)° and 91.98(3)°, respectively. In the square anions [PdBr3(DMSO)]−, the DMSO molecule is coordinated by the Pd atom through the sulfur atom (Pd-Br, 2.3986(7)–2.4288(6) A; Pd-S, 2.2633(13) A).

Tetraphenylantimony phenylpropiolate (I) has been synthesized by the reaction between pentaphenylantimony and phenylpropiolic acid or triphenylantimony bis(phenylpropiolate) in toluene. Triphenylantimony bis(phenylpropiolate) (II) has been synthesized from triphenylantimony and phenylpropiolic acid in ether in the presence of tert-butylhydroperoxide. According to X-ray diffraction data, the antimony atoms in complexes I and II are in a trigonal bipyramidal coordination, and the axial CSbO and OSbO angles are 178.63(7)° and 177.68(7)°. The Sb-C and Sb-O bond lengths and the equatorial CSbC angles are 2.120(3)–2.166(3) and 2.267(2) A, and 113.44°, 114.80°, and 128.12° (I) and 2.104(2)–2.109(3) and 2.136(2) A and 108.38°, 108.38°, and 143.23° (II), respectively. Sb⋯O=(C) intramolecular contacts are 3.357(3) A (I) and 2.919(5) A (II).

Tri( meta-tolyl)antimony bis(benzenesulfonate) m-Tol 3Sb(OSO 2C 6H 5) 2 (1) has been synthesized by interaction of tri( meta-tolyl)antimony with benzenesulfonic acid in the presence of tert-butyl hydroperoxide (mole ratio 1:2:1) in ether solution. Antimony atoms in 1 have trigonal-bipyramidal coordination with arenesulfonate substituents in axial positions (OSbO 171.05(11)°, CSbC 116.21(19)°, 117.38(18)°, 126.40(15)°). The Sb-C and Sb-O distances equal 2.091(4), 2.098(4), 2.115(4) and 2.105(2), 2.116(3) Å. Intermolecular contact (Sb•••O 3.421(3) Å) occurs between the central atom and the oxygen atom of sulfonate group.

Gold complexes [p-Tol4Sb]+[p-TolAuCl3] (1) and [p-Tol4Sb]+[AuCl4] (2) have been synthesized by interaction of tetra-para-tolylstibonium chloride and aurichlorohydric acid tetrahydrate in acetone. In 1 the tetra-para-tolylstibonium cations are tetrahedral (Sb-C 2.091(7)-2.097(6) Å, СSbС 106.1(3)-112.7(3)), the [p-TolAuCl3] anions have squareplanar structure (Au-Cl 2.286(2)-2.389(2) Å, Au-C 2.028(7) Å, ClAuCl 89.92(9), 92.42(9),176.68(8), CAuCl 88.27(18), 89.57(18), 175.59(19)). In crystal 2 the geometrical characteristics of cations (Sb-C 2.076(7)-2.097(9), СSbС 106.5(3)-111.5(4)) and [AuCl4] squareplanar anions (Au-Cl 2.248(3)-2.278(3) Å, ClAuCl 89.17(9)-90.74(13), 177.24(16),177.61(13)) are similar to those in 1. Взаимодействием хлорида тетрапаратолилстибония с тетрагидратом золотохлористоводородной кислоты в ацетоне синтезированы комплексы золота [p-Tol4Sb]+[p-TolAuCl3] (1) и [p-Tol4Sb]+[AuCl4] (2). В 1 катионы тетра-паратолилстибония тетраэдрические (Sb-C 2.091(7)-.097(6) Å, СSbС 106.1(3)-112.7(3)), анионы [p-TolAuCl3] имеют плоскоквадратное строение (Au-Cl 2.286(2)-2.389(2) Å, Au-C 2.028(7) Å, ClAuCl 89.92(9), 92.42(9), 176.68(8), CAuCl 88.27(18), 89.57(18),175.59(19)). В кристалле 2 геометрические характеристики катионов (Sb-C 2.076(7)-2.097(9), СSbС 106.5(3)-111.5(4)) и плоскоквадратных анионов [AuCl4] (Au-Cl 2.248(3)-2.278(3) Å, ClAuCl 89.17(9)-90.74(13), 177.24(16), 177.61(13)) близки к найденным в I. V.V. Sharutin, vvsharutin@rambler.ru O.K. Sharutina, sharutinao@mail.ru V.S. Senchurin, senvl@rambler.ru South Ural State University, Chelyabinsk, Russian Federation. Шарутин Владимир Викторович – доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru Шарутина Ольга Константиновна – доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru Сенчурин Владислав Станиславович – кандидат химических наук, доцент, кафедра органической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: senvl@rambler.ru

Interaction of pentaphenylantimony with 2,6-dibromo,4-methylphenol or with bis(2,6- dibromo,4-methylphenoxy)triphenylantimony (1) leads to formation of 2,6-dibromo,4- methylphenoxytetraphenylantimony (2). In molecules of compounds 1 and 2 the antimony atoms have distorted trigonal-bipyramidal coordination with the oxygen atoms in axial positions (OSbO 179.20(15) (1), OSbC 179.7(9) (2)). The bond lengths Sb–C and Sb–O equal 2.090(5), 2.101(5), 2.110(5) and 2.088(4), 2.088(4) Å (1), 2.11(2), 2.11(2), 2.11(2), 2.17(3) and 2.234(18), 2.234(18) Å (2), respectively. Взаимодействием пентафенилсурьмы с 2,6-дибром,4-метилфенолом или с бис(2,6-дибром,4-метилфенокси)трифенилсурьмой (1) получена 2,6-дибром,4-метилфенокси-тетрафенилсурьма (2). В молекулах 1 и 2 атомы сурьмы имеют искаженную тригонально-бипирамидальную координацию с атомами кислорода в аксиальных положениях (OSbO 179.20(15) (1), OSbC 179.7(9) (2)). Длины связей SbC и SbO составляют 2.090(5), 2.101(5), 2.110(5) и 2.088(4), 2.088(4) Å (1), 2.11(2), 2.11(2), 2.11(2), 2.17(3) и 2.234(18), 2.234(18) Å (2) соответственно. V.V. Sharutin, vvsharutin@rambler.ru O.K. Sharutina, sharutinao@mail.ru V.S. Senchurin, senvl@rambler.ru South Ural State University, Chelyabinsk, Russian Federation Шарутин Владимир Викторович – доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru. Шарутина Ольга Константиновна – доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru. Сенчурин Владислав Станиславович – кандидат химических наук, кафедра органической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: senvl@rambler.ru

Tri(p-tolyl)antimony dichloride was prepared by oxidation of tri(p-tolyl)stibine with chlorine or copper(II) chloride. As found by X-ray diffraction analysis, the antimony atom in tri(p-tolyl)antimony dichloride has the configuration of trigonal bipyramid with axially located chlorine atoms. The Sb-Cl and Sb-C distances are 2.476(2) and 2.104(7) A, and the CSbC and ClSbCl angles are 120 and 180°, respectively.

Bis(μ3-2-oxybenzaldoximato-O,O′,N)-(μ2-oxo)-bis(5-bromo-2-methoxyphenyl)antimony, which crystallizes from toluene in the form of a solvate, has been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)antimony and 2-oxybenzaldoxime in the presence of hydrogen peroxide. According to X-ray diffraction data, the structurally equivalent antimony atoms in a binuclear complex molecule are linked via two tridentate bridging ligands and an oxygen atom and have a distorted octahedral coordination to the C2O3N surrounding The trans-angles of the octahedron are CSbO (168.7(1)°), CSbN (164.1(1)°), and OSbO (159.3(1)°), and the bond lengths are Sb-C (2.127(4), 2.159(3) A) and Sb-N (2.238(3) A). A molecule contains the three types of Sb-O distances with a bridging oxygen atom (1.950(1) A), the oxygen atoms of oxy groups (2.002(2) A), and the oxygen atoms of oxime groups (2.091(2) A). Sb⋯OCH3 intramolecular contacts (3.097, 3.290 A) also exist.

Phenylbismuth bis(2,5-dimethylbenzenesulfonate) (I), a coordination polymer in which a bismuth atom has a distorted square pyramidal coordination to an axial carbon atom (Bi-C, 2.247(5) A) and basal oxygen atoms (Bi-O, 2.390(9)–2.403(10) A), has been synthesized by the reaction between triphenylbismuth and 2,5-dimethylbenzenesulfonic acid (1: 2 mol/mol) in toluene and structurally characterized. Pentaphenylbismuth and pentaphenylantimony phenylate compound I to triphenylbismuth.

The reactions of pentaphenylantimony with succinic, malic, and tartaric acids (mole ratio 2: 1) in toluene afford bis(tetraphenylantimony) succinate (I), malate (II), and tartrate (III) in yields of 98, 92, and 94%, respectively. According to the X_ray diffraction analysis results, molecules I and II are centrosymmetric. In compound II, the hydroxy group in the acid residue is disordered over two positions. Crystal III includes two types of crystallographically independent molecules (a and b). The antimony atoms in compounds I, II, IIIa, and IIIb have distorted trigonal bipyramidal coordination modes. The axial angles CaxSbOax are 166.80(8)° (I); 174.8(2)° (II); 176.4(4)°, 177.4(3)° (IIIa); and 173.3(4)°, 172.7(4)° (IIIb). The equatorial angles CeqSbCeq vary in the ranges 99.3(1)°–154.5(1)° (I); 115.2(2)°–123.3(2)° (II); 115.7(4)°–123.3(4)° 115.2(5)°–125.6(5)° (IIIa); and 107.9(4)°-129.1(4)°, 113.7(4)°-124.8(5)° (IIIb). The Sb-C and Sb-O bonds are 2.138(3)-2.176(3), 2.319(2) A (I); 2.111(6)–2.163(5), 2.243(4) A (II); 2.072(13)–2.169(11), 2.252(7), 2.284(7) A (IIIa); and 2.047(11)–2.190(11), 2.224(7), 2.256(7) A (IIIb). The intramolecular distances Sb…O=C are 2.528(3) (I); 3.267(7) (II); 3.381(7), 3.436(7) (IIIa); and 3.351(7), 3.162(7) A (IIIb). For structures I, II, and III, the CIF files are CCDC 929151, 941542, and 941543, respectively.

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)A; 2.068(5), 2.128(5)A; 117.6(3)°–124.2(3)° and 171.5(2)° (IA); 2.103(9)–2.135(8)A; 2.086(5), 2.154(6)A;110.2(3)°–138.0(4)° and 174.8(2)° (IB). In compound II, Sb-C is 2.117(2)–2.175(2) A, Sb-O is 2.247(2) A, and CeqSbCeq and OSbCax 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) A (IA), 2.985(8), 3.008(9) A (IB), and 2.975(5) A (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.

The reaction of triphenylantimony with propiolic acid in the presence of hydrogen peroxide (molar ratios 1 : 2 : 1 and 1 : 1 : 1) in diethyl ether affords triphenylantimony dipropiolate Ph3Sb[OC(O)C≡CH]2 (I) and μ2-oxobis[(propiolato)triphenylantimony] [Ph3SbOC(O)C≡CH]2O (II). Tetraphenylantimony propiolate Ph4SbOC(O)C≡CH (III) is synthesized from pentaphenylantimony and propiolic or acetylenedicarboxylic acid in toluene. According to the X-ray diffraction data, the crystals of compounds I and III include two types of crystallographically independent molecules (a and b). The antimony atoms in molecules Ia, Ib, II, IIIa, and IIIb have the trigonal-bipyramidal coordination mode with different degrees of distortion. The OSbO and OSbC axial angles are 176.8(2)° (Ia, Ib), 170.17(15)°, 178.78(14)° (II), and 173.2(5)°, 174.4(5)° (IIIa, IIIb). The CSbC equatorial angles lie in the ranges 108.2(3)°–143.1(3)° (I), 109.0(2)°–131.0(2)° (II), and 113.1(4)°–125.4(4)° (III). The SbOSb angle in II is 141.55(19)°. The Sb-C bond lengths are 2.103(8)–2.141(5) (I), 2.105(5)–2.119(5) (II), and 2.076(12)–2.166(13) A (III). The Sb-O distances increase in a series of I, II, and III: 2.139(6)–2.156(7) (Ia, Ib); 2.206(4), 2.218(3) (II); and 2.338(10), 2.340(10) A (III).

Bis(tetraphenylantimony) tetrachlorophthalate (I) has been synthesized by the reaction between pentaphenylantimony and tetrachlorophthalic acid in toluene. According to X-ray diffraction data, an antimony atom in a molecule of compound I has a distorted trigonal bipyramidal coordination. The axial CSb(1,2)O angles are 170.14(6)° and 1175.31(6)°, and the equatorial CSb(1,2)C angles are 117.78(7)°–119.83(7)° and 117.95(7)°–120.05(7)°, respectively. The Sb(1,2)-O and Sb(1,2)-C bond length are 2.474(1), 2.310(1)A and 2.098(2)–2.147(2), 2.100(2)–2.164(2) A, respectively.

V.V. Sharutin, vvsharutin@rambler.ru O.K. Sharutina, sharutinao@mail.ru South Ural State University, Chelyabinsk, Russian Federation Шарутин Владимир Викторович – доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru. Шарутина Ольга Константиновна – доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru. Interaction of triphenylantimony with 4-bromophenol in the presence of tertbutylhydroperoxide in ether has led to the synthesis of bis(4-bromophenoxy)triphenylantimony, whose structure has been established by X-ray diffraction analysis. The antimony atom has distorted trigonal-bipyramidal coordination with aroxy groups in axial positions. The bond lengths equal: 2.094(4), 2.108(5), 2.109(5) Å for Sb–C; 2.062(4) and 2.066(3) Å for Sb-O. The axial angle OSbO equals 172.41(1)°. Взаимодействием трифенилсурьмы с 4-бромфенолом в присутствии трет- бутилгидропероксида в эфире синтезирована бис(4-бромфенокси)трифенилсурьма, строение которой установлено методом РСА. Атом Sb имеет искаженную тригонально-бипирамидальную координацию с ароксигруппами в аксиальных положениях. Длины связей Sb-C 2.094(4), 2.108(5), 2.109(5); Sb-O 2.062(4) и 2.066(3) Å. Аксиальный угол OSbO составляет 172.41(1)°.

V.V. Sharutin1, vvsharutin@rambler.ru O.K. Sharutina1, sharutinao@mail.ru V.S. Senchurin1, senvl@rambler.ru A.N. Neudachina1, neudachina.a@yandex.ru P.V. Andreev2, andreev@phys.unn.ru 1 South Ural State University, Chelyabinsk, Russian Federation 2 Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russian Federation Шарутин Владимир Викторович – доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru. Шарутина Ольга Константиновна – доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru. Сенчурин Владислав Станиславович – кандидат химических наук, доцент, кафедра органической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: senvl@rambler.ru Неудачина Анастасия Николаевна – студент, кафедра органической химии, Южно- Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: neudachina.a@yandex.ru Андреев Павел Валерьевич - аспирант, младший научный сотрудник НИЛ кафедры кристаллографии и экспериментальной физики. Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Н. Новгород, пр. Гагарина, 23А. E-mail: andreev@phys.unn.ru Interaction of silver iodide with triphenylstibine in dimethyl sulfoxide has led to the neutral complex iodotris(triphenylstibine)silver (1), whose structure has been established by Xray diffraction analysis. The silver atom has distorted tetrahedral coordination. The angles SbAgSb and SbAgI equal 106.501(13)°, 109.644(13)°, 111.099(13)° и 103.063(13)°, 111.594(14)°, 114.337(14)°, the bond lengths Ag–Sb and Ag–I equal 2.7291(4), 2.7326(4), 2.8087(4) и 2.7600(4) Å. Взаимодействием иодида серебра с трифенилстибином в диметилсульфоксиде синтезирован нейтральный комплекс иодотрис(трифенилстибин)серебро (1), строение которого установлено методом РСА. Атом Ag имеет искаженную тетрагональную координацию. Углы SbAgSb и SbAgI составляют 106,501(13)°, 109,644(13)°, 111,099(13)° и 103,063(13)°, 111,594(14)°, 114,337(14)°, длины связей Ag-Sb и Ag-I равны 2,7291(4); 2,7326(4); 2,8087(4) и 2,7600(4) Å.

P.V. Andreev1, andreev@phys.unn.ru V.V. Sharutin2, vvsharutin@rambler.ru O.K. Sharutina2, sharutinao@mail.ru 1 Nizhny Novgorod State University, Nizhny Novgorod, Russian Federation, 2 South Ural State University, Chelyabinsk, Russian Federation Андреев Павел Валерьевич  аспирант, младший научный сотрудник НИЛ кафедры кристаллографии и экспериментальной физики. Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Н. Новгород, пр. Гагарина, 23А. E-mail: andreev@phys.unn.ru. Шарутин Владимир Викторович – доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru. Шарутина Ольга Константиновна – доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru. Penta-p-tolylantimony interaction with 2,6-dibromo(4-tert-butyl)phenol has led to synthesis of the complex tetra-p-tolylantimony 2,6-dibromo(4-tert-butyl)phenoxide, whose structure has been established by X-ray diffraction. The antimony atom in the molecule (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4 has distorted trigonal-bipyramidal coordination with the aroxy group in axial position. The bond Sb-O is 2.229(2) Å, the axial angle CSbO is 176.82(10)°. Взаимодействием пента-пара-толилсурьмы с 2,6-дибром(4-трет-бутил)фенолом в толуоле синтезирован 2,6-дибром(4-трет-бутил)феноксид тетра-пара-толилсурьмы, строение которого установлено методом РСА. Атом Sb в молекуле (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4 имеет искаженную тригонально-бипирамидальную координацию с ароксигруппой в аксиальном положении. Связь Sb-O равна 2.229(2) Å, аксиальный угол CSbO составляет 176.82(10)°.