Bis(tetraphenylantimony) succinate,malate, and tartrate: Syntheses and structures

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 C_axSbO_ax 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 C_eqSbC_eq 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) Å (I); 2.111(6)–2.163(5), 2.243(4) Å (II); 2.072(13)–2.169(11), 2.252(7), 2.284(7) Å (IIIa); and 2.047(11)–2.190(11), 2.224(7), 2.256(7) Å (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) Å (IIIb). For structures I, II, and III, the CIF files are CCDC 929151, 941542, and 941543, respectively.     

Synthesis and structure of bis(monohaloacetates) of tris(5-bromo-2-methoxyphenyl)antimony

Tris(5-bromo-2-methoxyphenyl)antimony bis(monohaloacetates) [(5-Br)(2-MeO)C₆H₃]₃Sb[OC(O)CH₂X]₂, X = Cl (I), Br (II), I (III) have been synthesized by the reaction of tris(5-bromo-2-methoxyphenyl)antimony with chloro-, bromo-, and iodoacetic acids in the presence of hydrogen peroxide. According to X-ray analysis the antimony atom in I–III has a distorted trigonal-bipyramidal coordination.     

Tri- and tetraphenylantimony propiolates: Syntheses and structures

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) Å (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) Å (III).     

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.     

Synthesis and structure of tri-m-tolylbismuth dicarboxylates

Tri-m-tolylbismuth bis(2-methoxybenzoate) (I) (84%), tri-m-tolylbismuth dibenzoate (II) (91%), and tri-m-tolylbismuth bis(trichloroacetate) (III) (92%) have been synthesized via the reaction between tri-m-tolylbismuth, carboxylic acid, and hydrogen peroxide. According to X-ray diffraction data, a bismuth atom in compounds I–III have a distorted trigonal bipyramidal coordination (disregarding the additional coordination of carbonyl oxygen atoms) to m-tolyl ligands in equatorial positions. The Bi-C bonds in compounds I, II, and III range within 2.193(3)–2.228(5) Å, and the Bi-O and Bi…O(=C) distances are 2.267(3), 2.282(3) Å and 2.791(6), 2.895(6) Å in I; 2.293(2), 2.296(3) Å and 2.815, 2.905(5) Å in II; and 2.278(4), 2.300(4) Å and 3.008(9), 3.115(9) Å in III. The equatorial CBiC angles on the side of Bi…O(=C) contacts are considerably enlarged, thus decreasing the other two angles (150.6°, 104.7°, and 104.7° in I, 140.2°, 107.4°, and 112.3° in II, and 138.0°, 110.1°, and 111.0° in III).     

Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C<Subscript>6</Subscript>H<Subscript>3</Subscript>(Br-5)(MeO-2)]<Subscript>3</Subscript>Bi[OC(O)CHal<Subscript>3</Subscript>]<Subscript>2</Subscript> (Hal = F,Cl): synthesis and structure

Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C₆H₃(Br-5)(MeO-2)]₃Bi[OC(O)CHal₃]₂, Hal = F (II) and Cl (III), have been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)bismuth (I) and trifluoroacetic acid and thrichloroacetic acid, respectively, in the presence of hydrogen peroxide in ether. According to X-ray diffraction data, a crystal of complex I contains two types of crystallographically independent molecules (a and b) both with a trigonal pyramid configuration. The bismuth atoms in complexes II and III have a distorted trigonal bipyramidal coordination with carboxylate substituents in axial positions. Axial OBiO angles are 166.3(3)° (II) and 171.6(2)° (III); equatorial CBiC angles are 118.0(3)°–123.1(3)° (II) and 113.6(3)°–127.4(3)° (III). Bi–C bond lengths are 2.189(7)–2.200(8) Å (II) and 2.190(8)–2.219(7) Å (III), and Bi–О distances are 2.280(6), 2.459(16) Å (II) and 2.264(5), 2.266(5) Å (III). Intramolecular contacts between the central atom and the oxygen atoms of carbonyl groups (Bi···O 3.028(9), 3.162(9) Å (II); 3.117(9), 3.202(9) Å (III)) are observed at maximum equatorial angles. The oxygen atoms of methoxy groups are coordinated to the bismuth atom. The Bi···O distances in complexes II and III (3.028(16), 3.157(16), 3.162(16) and 3.17(16), 3.143(16), 3.202(16) Å, respectively) are slightly longer than in complex I (3.007(9)–3.136(4) Å).     

Synthesis and structure of palladium complexes [Ph3PhCH2P]+[PdCl3(DMSO)]− · DMSO, [Ph4P]+[PdCl3(DMSO)]−, and [Ph4Sb(DMSO)]+[PdCl3(DMSO)]−

[Ph₃PhCH₂P]⁺[PdCl₃(DMSO)]^? · DMSO (I), [Ph₄P]⁺[PdCl₃(DMSO)]^? (II), and [Ph₄Sb(DMSO)]⁺[PdCl₃(DMSO)]^? (III) complexes have been synthesized via the reaction of palladium chloride with equimolar amounts of triphenylbenzylphosphonium chloride, tetraphenylphosphonium chloride, and tetraphenylstibonium chloride, respectively. According to X-ray diffraction data, the cations of complexes I (CPC = 104.90(8)°–111.61(9)°) and II (CPC = 105.12(10)°–111.46(10)°) have slightly distorted tetrahedral structures with P-C bond lengths of 1.786(2)–1.809(2) and 1.791(2)–1.799(2) Å, respectively. The antimony atom in the [Ph₄Sb(DMSO)]⁺ cation has a trigonal bipyramidal surrounding with the dimethyl sulfoxide (DMSO) oxygen atom in an axial position (Sb...O 2.567(2) Å). The palladium atoms in the square mononuclear anions of complexes I, II, and III are tetracoordinate, and Pd-Cl distances are 2.3101(5)–2.3104(5) Å, 2.2950(7)–2.2038(7) Å, and 2.2986(9)–2.3073(9) Å, respectively. The DMSO ligands are coordinated to the palladium atom through the sulfur atom (Pd-S, 2.2318(5) (I), 2.2383(6) (II), and 2.2410(9) Å (III)).     

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.     

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.     

Synthesis and structure of tris(4-N,N-dimethylaminophenyl)antimony(V) difluoride, dichloride, and dibenzoate

tris(4-N,N-Dimethylaminophenyl)antimony dichloride (I) was prepared by the reaction of tris(4-N,N-dimethylaminophenyl)antimony with copper dichloride. tris(4-N,N-Dimethylaminophenyl)antimony difluoride benzene disolvate II was synthesized from dichloride I and sodium fluoride in aqueous acetone with the subsequent crystallization from benzene. tris(4-N,N-Dimethylaminophenyl)antimony dibenzoate III was obtained from tris(4-N,N-dimethylaminophenyl)antimony and benzoic acid in the presence of hydrogen peroxide in ether or from silver benzoate and the corresponding dichloride in acetone. According to X-ray studies Sb atoms in two crystallographically independent molecules of dichloride, difluoride benzene solvate, and dibenzoate have the distorted trigonal bipyramide coordination [ClSbCl, FSbF, and OSbO trans angles are 178.12(2)°, 178.57(3)°, 177.30°, and 176.49° respectively). Sb-Cl, Sb-F, and Sb-O interatomic distances are 2.4719(7)-2.505(7); 2.106(4); 2.438(2); 2.1212(13) Å respectively. The oxygen atoms of carbonyl groups of the molecule III (C _2v molecular symmetry) are coordinated to the central atom [Sb-O distance 2.987(1) Å].     

Synthesis and molecular and crystal structures of binuclear complexes of Sm(III), Eu(III), Gd(III), Tb(III), and Dy(III) nitrates with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione

Binuclear complexes of Sm(III), Eu(III), Gd(III), Tb(III), and Dy(III) nitrates with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione (C₁₁H₂₀N₄O₂, SC)—[Sm(NO₃)₃(SC)(H₂O)]₂(I), [Eu(NO₃)₃(SC)(H₂O)]₂ (II), [Gd(NO₃)₂(SC)(H₂O)₃)]₂(NO₃)₂ (III), [Tb(NO₃)₃(SC)(H₂O)]₂ (IV), [Dy(NO₃)₃(SC)(H₂O)]₂ (V), are synthesized, and their X-ray diffraction analyses are carried out. The crystals of complexes I–V are monoclinic: space group P2₁/n for III and P2₁/c for I, II, IV, and V. In centrosymmetric coordination complexes II, III, IV, and V, the Ln atoms are coordinated by two O(1) and O(2) atoms of two molecules of the SC ligands bound by a symmetry procedure (1 ? x, ?y, 1 ? z), three bidentate nitrate anions, and a water molecule. The coordination numbers of the metal atoms are equal to 9, and the coordination polyhedra are considerably distorted three-capped trigonal prisms, whose bases include the O(1), O(2), O(12) and O(3), O(7), O(9) atoms. The dihedral angle between the bases of the prism is 18°, and that between the mean planes of the side faces is 55°–71° for I, 17° and 55°–71° for II, 16° and 55°–70° for IV, and 16° and 55°–70° for V. The Sm...Sm distance in complex I is 9.44 Å, Eu...Eu in II is 9.42 Å, Tb...Tb in IV is 9.36Å, and Dy...Dy in V is 9.36Å. The gadolinium atom in complex III is coordinated by two oxygen atoms of two ligand molecules bound by a symmetry procedure (?x, ?y + 1, ?z + 1), two bidentate nitrate anions, and three water molecules. One of the nitro groups in compound III is localized in the external coordination sphere of the metal. The coordination number of gadolinium is 9, and the coordination polyhedron is a significantly distorted three-capped trigonal prism, whose base includes the O(1), O(2), O(7) and O(4), O(5), O(9) atoms. The dihedral angle between the bases of the prism is 22.8°, and that between the mean planes of the side faces is 53°–72°. The Gd...Gd distance in complex III is 9.17 Å.     

Copper(I) halide complexes with N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L2+). Synthesis and crystal structures of the complexes [L0.5CuCl2], [L0.5CuCl0.72Br1.28], and [L0.5CuBr2]

The Eschweiler-Clarke reaction of ethylenediamine with formaldehyde and formic acid yielded N,N,N′,N′-tetramethylethylenediamine, which was alkylated with allyl chloride or allyl bromide to give the corresponding N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L²⁺) dihalides. In methanolic solutions of copper(II) halide and an appropriate ligand, ac electrochemical synthesis with copper wire electrodes afforded single crystals of Cu(I) complexes with L²⁺: [L_0.5CuCl₂] (I), [L_0.5CuCl_0.72Br_1.28] (II), and [L_0.5CuBr₂] (III). The crystal structures of complexes I–III were determined by X-ray diffraction study. The isostructural crystals of I and II are monoclinic, space group P2₁/n, Z = 4. For I: a = 7.632(4) Å, b = 11.318(5) Å, c = 10.635(5) Å, β = 98.551(7)°, V = 908.4(7) ų. For II: a = 7.7415(7) Å, b = 11.4652(9) Å, c = 10.7267(10) Å, β = 98.351(4)°, V = 942.0(2) ų. The organic cation L²⁺ acts as a bridge linking a pair of separate cuprous halide fragments Cu₂X₄. Although being isostoichiometric with I and II, complex III has a different structure. The crystals of III are monoclinic, space group P2₁/c, a = 6.519(2) Å, b = 9.060(3) Å, c = 16.284(6) Å, β = 97.219(4)°, V = 954.2(6) ų, Z = 4. In structure III, the inorganic fragment forms infinite polymer chains (CuBr ₂ ^? ) _n . The organic and inorganic parts are held together only by electrostatic interactions. Structures I–III are stabilized by hydrogen bonds (C)H…X (2.6–2.9 Å).     

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.     

New fluorochromatouranylates of alkali metals: Synthesis and structure

Four new fluorochromatouranylates, namely, K[UO₂(CrO₄)F] · 1.5H₂O (I), Rb[UO₂(CrO₄)F] · 1.5H₂O (II), Rb[UO₂(CrO₄)F] · 0.5H₂O (III), and Cs[UO₂(CrO₄)F] · 0.5H₂O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P2₁/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO₂(CrO₄)F] _n ^n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT³M² crystallochemical group, to which the studied compounds I–III also belong, is discussed.     

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)°).     

Stability and structure in solution of potassium and barium complexes with N,N’-diaryldiaza-18-crown-6: Crystal structure of N,N’-Bis(4-dimethylaminophenyl)diaza-18-crown-6 and its complex with barium perchlorate

It has been shown that N,N’-diaryldiaza-18-crown-6 ethers with p-dimethylamino-and p-methoxy groups in the benzene ring (aryl is 4-Mc₂NC₆H₄) (I) and 4-MeOC₆H₄ (II) form complexes with potassium and barium salts. The influence of these salts on the UV and ¹H NMR spectra of crown ethers I and II has been studied. The stability constants (logβ) of the complexes increase in the series II · Ba(ClO₄)₂ (2.0), I · Ba(ClO₄)₂ (2.3), II · KBr (2.8), I · KBr (3.0). N,N’-bis(4-dimethylphenylamine)diaza-18-crown-6 (L, I) and its complex with barium perchlorate Ba(ClO₄)₂ · L (III) are characterized by X-ray crystallography. The crystals of I are monoclinic: a = 13.778(2) Å, b = 5.9731(9) Å, c = 17.542(3) Å, β = 106.65(1)°, V = 1383.1(4) ų, Z = 2, space group P2₁/n, R = 0.0374 for 990 reflections with I > 2σ(I). The crystals of III are monoclinic: a = 17.275(4) Å, b = 8.017(2) Å, c = 26.935(4) Å, β = 100.47(2)°, V = 3669(1) ų, Z = 4, space group C2/c, R = 0.0320 for 1897 reflections with I > 2σ(I). The molecules of I and III are centrosymmetric. In III, the Ba atom is in the center of substituted diaza-18-crown-6 (DA18C6). The Ba atom is coordinated by all six donor atoms of diaza-18-crown-6 (av. Ba-O, 2.779(3) Å; Ba-N, 3.004(4) Å) and four oxygen atoms of two asymmetrically bound perchlorate groups (Ba-O, 2.832(4) and 3.031(4) Å) arranged below and above the plane of substituted diaza-18-crown-6. The conformations of the macrocycle in free and coordinated L are different.     

Oxidative addition reactions of tri(2-methylphenyl)antimony

Bis[??-oxo-tri(2-methylphenyl)antimony] (I) was synthesized via oxidation of tri(2-methylphenyl)antimony by hydrogen peroxide in ether. In the presence of 2-hydroxy-5-bromobenzaldoxime or furfural oxime, the reaction between these reactants (in a 1: 1: 1 molar ratio, respectively) yields (??-oxo)bis[2-hydroxy-5-bromobenzaldoximato-tri(2-methylphenyl)antimony] (II) or (??-oxo)bis[furfural-oximatotri(2-methylphenyl)antimony] (III). The structures of compounds I?CIII was determined by X-ray diffraction. In the centrosymmetric dimeric complex I, the Sb atom has a distorted trigonal-bipyramidal coordination with oxygen atoms in equatorial and axial positions. In II and III, the axial positions are occupied by the bridge oxygen atom and the oxygen atom of the oxime ligand. Bond length values are as follows: Sb-C 2.137(3)?C2.183(3), 2.116(7)?C2.131(7), and 2.105(5)?C2.126(6)?; Sb-O 1.934(2), 2.077(2), 1.973(4)?C2.151(4), and 1.9706(3)?C2.112(6) ? for I, II, and III, respectively. Intramolecular contacts Sb...N (2.953(8), 3.002(9), and 2.951(8) II and III.     

Synthesis and structure of Bis(tetraphenylantimony) 1,2-diphenylethanedione dioximate toluene solvate Ph4SbONC(Ph)C(Ph)ONSbPh4 · 2PhCH3 and tetraphenylantimony 2-hydroxy-1,2-diphenylethanone oximate Ph4SbONC(Ph)CH(Ph)OH

Bis(tetraphenylantimony) 1,2-diphenylethanedione dioximate toluene solvate Ph₄SbONC(Ph)C(Ph)NOSbPh₄ · 2 PhCH₃ (I) and tetraphenylantimony 2-hydroxy-1,2-diphenyl(ethanone oximate Ph₄SbONC(Ph)CH(Ph)OH (II) have been synthesized by the reaction of pentaphenylantimony with 1,2-diphenylethane dioxime and 2-hydroxy-1,2-diphenylethanone oxime in toluene. A molecule of compound I is centrosymmetric with an inversion center at the midpoint of the C-C bond in the ethane moiety. A crystal of compound II contains two types of crystallographically independent molecules A and B. Antimony atoms in compounds I and II have a distorted tetragonal bipyramidal surrounding: equatorial CSbC and axial CSbO angles are 114.95(10)°–126.82(11)° and 173.24(9)° (I), 117.2(2)°–122.9(2)° and 178.15(18)° (IIA), and 112.3(2)°–127.7(2)° and 175.09(18)° (IIB), respectively. The Sb-C and Sb-O bond lengths are 2.106(3)–2.182(3) and 2.1344(17) ÅI), 2.118(5)–2.4199(5) and 2.153(4)Å(IIA), and 2.106(5)–2.200(5) and 2.120(4) Å (IIB), respectively. A molecule of compounds I, IIA, and IIB has been found to contain Sb...N intramolecular contacts (2.838(3), 2.867(5), and 2.889(5)Å, respectively). Molecules of compounds IIA and IIB contain O-H...N hydrogen bonds (H...N, 1.91(9) and 2.06(8) Å, respectively).     

Crystal structures of nitrato-{4-bromo-2-[(2-hydroxyethylimion)methyl]phenolo}-(3,5-Dibromopyridine)copper and nitrato-{2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper

The crystal structures of nitrato-{4-bromo-2-[2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (I) and nitrato-{2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (II) are determined. The crystals of compound I are orthorhombic: a = 14.157(3) Å, b = 15.420(3) Å, c = 17.494(4) Å, space group Pbca, Z = 8, R = 0.067. The crystals of compound II are monoclinic: a = 10.675 Å, b = 13.973 Å, c = 14.007 Å, β = 111.92°, space group P2₁/n, Z = 4, R = 0.0464. In the structures of compounds I and II, the copper atom coordinates, correspondingly, singly deprotonated 4-bromo-2-[(2-hydroxyethylimino)methyl]phenol and 2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenol molecules, and 3,5-dibromopyridine, and the nitrate ion. The coordination polyhedron of the copper ion in complexes I and II is a slightly distorted tetragonal pyramid. The bases of the pyramids are formed by the imine and pyridine nitrogen atoms and the phenolic and alcoholic oxygen atoms, and the axial vertices are occupied by the oxygen atoms of the monodentate nitrato groups. In the complexes under study, the six-membered metallocycles have asymmetric gauche conformation. In crystal, complexes I are united, due to the slip plane a, through bifurcate hydrogen bonds into infinite chains along the direction [100]. Complexes II in crystal form two-dimensional networks by means of hydrogen bonds.     

Structures of triphenylbismuth dicarboxylates

Tripheylbismuth bis(trichloroacetate) (I), triphenylbismuth bis(chloroacetate) (II), and triphenylbismuth bis(bromoacetate) (III) were synthesized by the reaction of triphenylbismuth with carboxylic acid. The Bi atoms of the synthesized compounds have a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. The Bi-C bond lengths lie within intervals 2.194(2)–2.201(2), 2.193(8)–2.223(7), 2.191(4)–2.220(3) Å, the distances Bi-O and Bi···O(=C) are equal 2.308(2), 2.315(2), and 2.896(2), 2.931(2); 2.289(6), 2.302(6), and 2.891(6), 2.910(6); 2.295(3), 2.312(3), and 2.893(3), 2.920(3) Å in I, II, and III, respectively. Molecules of triphenylbismuth dicarboxylates show linear dependence between the maximum equatorial angle CBiC (on the side of a contact) and intramolecular distance Bi···O(=C).