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Alkylation of tris(2,6-dimethoxyphenyl)stibine Ar3Sb, where Ar = 2,6-(MeO)2C6H3, with iodoethane in chloroform resulted in [Ar3EtSb]I, which further reacted with lead(II) nitrate to form [Ar3EtSb]NO3·0.75Н2О. The comparative characterization of the complexes was carried out by X-ray diffraction analysis, IR spectroscopy, and simultaneous thermal analysis. Antimony atoms in stibonium cations have a distorted tetrahedral coordination [CSbC angles 106.80(12)°–115.22(12)° and 105.33(14)°–115.33(14)°]. In a boiling aqueous solution, [Ar3EtSb]I and [Ar3EtSb]NO3·0.75Н2О decompose to tris(2,6-dimethoxyphenyl)stibine. [ABSTRACT FROM AUTHOR]

Bis(tetraphenylantimony) malonate was synthesized by the reaction of tetraphenylantimony bromide with silver malonate (the molar ratio was 2:1) in toluene. According to the X-ray diffraction data, the tridentate carboxylate ligand is a chelate. The coordination number of the Sb(1) atom involved in a contact with the carbonyl oxygen atom increases to six (Sb(1)—O(1), 2.199(7) Å; Sb(1)—O(3), 2.362(7) Å). Another antimony atom remains five-coordinate (Sb(2)—O(4), 2.304(7) Å). The antimony atoms Sb(1) and Sb(2) have distorted octahedral and trigonal-bipyramidal coordination geometry, respectively. [ABSTRACT FROM AUTHOR]

The crystalline heteroleptic bismuth(III) complexes, [Bi{S2CN(iso-C4H9)2}2(NO3)] (I) and [Bi{S2CN(C3H7)2}2Cl] (II), are isolated in preparative yields. Both compounds form 1D polymer structures and are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1877115 (I) and 1876364 (II)) and (13C, 15N) CP-MAS NMR spectroscopy. The coordination mode of each of the dialkyldithiocarbamate ligands is S,S′-anisobidentately terminal. The inorganic anions performing the μ2-bridging function participate in the binding of the adjacent metallic atoms to form zigzag polymer chains. A new mode of bismuth(III) binding involving all oxygen atoms (O,O'-anisobidentate coordination to each adjacent bismuth atom) is found for the bridging nitrate groups in compound I. The bismuth atoms in the studied compounds are characterized by the eightfold [BiS4O4] (I) or sixfold [BiS4Cl2] (II) environment. The thermal behavior of the synthesized complexes is characterized by the data of simultaneous thermal analysis, using parallel recording of thermogravimetry and differential scanning calorimetry curves. In both cases, Bi2S3 is the only final product of the thermal transformations of compounds I and II. [ABSTRACT FROM AUTHOR]

Abstract: Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear gold(III)-bismuth(III) complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n (II) are carried out. Compounds I and II are characterized in comparison by IR spectroscopy and 13C CP-MAS NMR. According to the X-ray diffraction analysis data (CIF file CCDC no. 1407705), the cationic moiety of compound II exhibits an unusually complicated supramolecular structure including six isomeric noncentrosymmetric complex cations [Au{S2CN(C3H7)2}2]+ (hereinafter A-F) and two binuclear anions [Bi2Cl9]3- as conformers. The isomeric gold(III) cations perform various structural functions. Owing to pair secondary interactions Au···S, cations B, C, E, and F form centrosymmetric ([E···E], [F···F]) and noncentrosymmetric ([B···C]) binuclear aggregates [Au2{S2CN(C3H7)2}4]2+, whereas cations A and D are not involved in dimerization. The strongest secondary Au···S bonds are formed between the binuclear and mononuclear cations, resulting in the formation of supramolecular cation-cationic polymer chains of two types: (⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅)n and (D⋅⋅⋅[E⋅⋅⋅E]⋅⋅⋅D⋅⋅⋅[F⋅⋅⋅F]⋅⋅⋅])n. In both chains, the gold atoms of the binuclear cations are characterized by a distorted octahedral coordination [S6], whereas in the mononuclear cations the gold atoms retain the square environment [S4]. The cation-anionic interactions are provided by secondary bonds Cl⋅⋅⋅S involving the terminal chlorine atoms of isomeric [Bi2Cl9]3- and the sulfur atoms of the binuclear cations [Au2{S2CN(C3H7)2}4]2+. The character of the thermal behavior of compounds I and II is studied by simultaneous thermal analysis with the identification of intermediate and final products of the thermal transformations. The thermolysis of compound I at 193-320°C is accompanied by the formation of Bi2S3 with an impurity of reduced metallic bismuth particles. The final products of the thermal transformations of compound II are reduced elemental gold and Bi2O3, and the thermal transformation intermediates are BiCl3 and Bi2S3. [ABSTRACT FROM AUTHOR]

Novel organic compounds of antimony(V), tris(2,6-dimethoxyphenyl)antimony diisocyanate and oxide, have been prepared and studied by X-ray diffraction analysis. Antimony atoms in the diisocyanate molecule and in two symmetrically independent molecules of the oxide exhibit trigonal-bipyramidal and tetrahedral coordination, respectively. [ABSTRACT FROM AUTHOR]

Interaction of tri- p-tolylbismuth with bromine in carbon tetrachloride has yielded tri- p-tolylbismuth dibromide. According to X-ray diffraction studies, bismuth atoms in both symmetrically independent dibromide molecules were in distorted trigonal bipyramid surrounding with equatorial aryl substituents. [ABSTRACT FROM AUTHOR]

The article presents a study of the physicochemical properties of dithiocarbamate complexes that are promising precursors of semiconductor film and nanosized sulfides. The characterization by high-resolution solid-state carbon-13 (C) and nitrogen-15 (N) nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction analysis of crystalline bismuth (III) N,N-dipropyl-dithiocarbamate (PDtc) is outlined. The use of direct methods of X-ray diffraction analysis to establish structure is tackled.

Hydrolysis of triarylbismuth bis(arenesulfonates) in acetone gives bismuth derivatives of the general formula [Ar3Bi(OSO2Ar’)]2O (Ar = Ph,p-Tol; Ar’ = Ph, C6H4Me-4, C6H3Me2-2,4, C6H3Me2-3,4). The structure of µ-oxobis[(3,4-dimethylbenzenesulfonato)triphenylbismuth] was established by means of X-ray diffraction. The molecule has a linear centrosymmetric structure with the bridging oxygen atom in the inversion center. The bismuth atom has a distorted trigonal bipyramidal coordination with the bridging oxygen atom and the arenesulfonate group in axial positions. The Bi-C and Bi-Oterm distances are 2.200(2), 2.204(3), and 2.442(2) Å, and the Bi-Obr distances are 2.067(1) Å. [ABSTRACT FROM AUTHOR]

The reactions of tetraphenylantimony chloride and bromide with carbamide were used to obtain tetraphenylantimony cyanamide in yields of 52 and 48%, respectively. According to X-ray diffraction data, the antimony atom has a distorted trigonal bipyramidal coordination with axial cyanamide and aryl groups [axial CSbN angle 177.76(7)°, Sb-C 2.107(2)-2.167.2, Sb-N 2.3383(18) Å]. [ABSTRACT FROM AUTHOR]

The reaction of triphenylbismuth, hydrogen peroxide, and phenol (molar ratio 1 : 1 : 2) in ether was used to synthesize triphenylbismuth diaroxides Ph3Bi(OAr)2 [Ar = C6H3(NO2)2-2,4, C6H2(NO2)3-2,4,6, C6H3Cl2-2,6, C6H2Cl3-2,4,6, C6H3Br2-2,4, C6H2Br3-2,4,6, C6H2Br2-2,4,Me-6, C6H2Br2-2,6, NO2-4]. At an equimolar reagent ratio, bridged bismuth compounds (Ph3BiOAr)2O are formed. The crystal structure of bis-(2,4-dinitrophenoxy)triphenylbismuth Ph3Bi[OC6H3(NO2)2-2,4]2 was studied by X-ray diffraction to show that the bismuth atom has a distorted trigonal bipyramidal coordination and the 2,4-dinitrophenoxyl ligands are axial. The CBiC and OBiO angles are 109.6(5)°, 122.3(5)°, 128.1(5)°, and 175.6(3)°. The Bi-O1,6 and Bi-C bond lengths are 2.256(10), 2.242(9) and 2.18(1), 2.18(1), 2.19(1) Å, respectively. [ABSTRACT FROM AUTHOR]