Triarylantimony Dicaroxylates Ar3Sb[OC(O)R]2 (Ar = Ph,p-Tol; R = 2-C4H3O, 3-C5H4N): Synthesis and Structure

Bis(2-furoinate)triphenyl- and tri-p-tolylantimony and bis(3-niacinate)triphenylanitmony were synthesized by reacting triarylantimony (Ar₃Sb; Ar = Ph, p-Tol) with 2-furancarboxylic and 3-pyridinecarboxylic acids in the presence of hydrogen peroxide. According to X-ray diffraction data, Sb atoms have trigonal bipyramidal coordination polyhedra. The Sb–O distances are 2.117(4), 2.137(4) Å; 2.136(2), 2.158(2) Å, and 2.112(1), 2.101(2) Å, the Sb···O distances are 2.866(4), 2.798(4) Å; 2.816(2), 2.774(2) Å, and 3.054(2), 3.168(2) Å, respectively.     

Synthesis and Structure of Triphenylantimony Bis(Acetophenoneoximate)

Triphenylantimony bis(acetophenoneoximate) was synthesized by the reaction of triphenylantimony with hydrogen peroxide in the presence of acetophenone oxime (taken in the molar ratio of 1 : 1 : 2) in ether. The structure of the obtained compound was determined by X-ray diffraction. The Sb atom has a distorted trigonal-bipyramidal coordination with the oxime groups in the axial positions. The Sb–C(Ph)_eq bond lengths are 2.110(1)–2.113(1) Å, and the Sb–O distances are 2.058(1) and 2.067(1) Å. The intramolecular Sb(1)···N(1, 2) contacts and O(1)SbO(2) axial angle are 2.990(1), 2.916(1) Å and 172.49(4)°, respectively.     

Synthesis and Structure of 2-tert-Butylphenoxytetraphenylantimony

2-tert-Butylphenoxytetraphenylantimony Ph₄SbOC₆H₄(Bu-t)-2 was prepared by the reaction of pentaphenylantimony with 2-tert-butylphenol in toluene at 20°. The structure of the obtained compound was determined by X-ray diffraction. The Sb atom in this compound has a distorted trigonal-bipyramidal coordination with the aroxy group in the axial position. The Sb–C(Ph)_eqand Sb–C(Ph)_axdistances are 2.111(7)–2.138(7) and 2.180(7) Å the Sb–O and O–C_Ardistances are 2.143(4) and 1.363(8) Å, respectively. The C(Ph)_axSbO_Araxial angle is 174.1(2)°, while the SbOC angle is 126.7(4)°.     

Synthesis and Structure of Tetraphenylantimony Oximates Ph4SbON=CRR′ (CRR′ = C6H9−C6H9-2 and R = Ph,R′ = C(O)Ph)

The reaction of pentaphenylantimony and the oxime HON=CRR taken in 1 : 1 molar ratio in toluene gave tetraphenylantimony oximates Ph₄SbON=CRR (CRR = C₆H₉–C₆H₉-2 (I) and R = Ph, R = C(O)Ph (II)). According to X-ray diffraction data, the Sb atoms in I and II have a distorted trigonal-bipyramidal coordination with oximate ligands in the axial positions. The C_axSbO angles are 177.6(1)° in I and 176.58(6)° in II. The Sb–C bond lengths lie in the ranges of 2.120(4)–2.203(4) Å for I and 2.122(2)–2.181(2) Å for II. The Sb–O bond lengths are 2.120(2) Å (I) and 2.166(1) Å (II). The lengths of the intramolecular Sb···N contacts are 2.806(3) and 2.918(2) Å in I and II, respectively.     

Reaction of Tetraphenylantimony Bromide with o-Tolylbismuth Bis(2,5-dimethylbenzenesulfonate). The Formation of Tetranuclear Anion [Bi4Br16]4–

The [Ph₄Sb]₄[Bi₄Br₁₆] complex was synthesized via reaction of tetraphenylantimony bromide with o-tolylbismuth bis(2,5-dimethylbenzenesulfonate) and studied using X-ray diffraction analysis. This compound has ionic structure and consists of tetraphenylstibonium cations and a four-charge tetranuclear anion [Bi₄Br₁₆]^4– formed by two pairs of edge-sharing iBr₆ octahedra. The Sb–C bond lengths are equal to 2.05(1)–2.10(1) Å, the Bi–Br distances lie within the 2.649(2)–3.246(2) Å range, and the Sb(1)···Br(7) distance is equal to 3.934(2) Å.     

Synthesis and Structure of μ-Peroxo-bis(4-bromophenoxotri-p-tolylantimony)

-Peroxo-bis(4-bromophenoxotri-p-tolylantimony) was synthesized by reacting 4-bromophenol with tri-p-tolylstibine in the presence of hydrogen peroxide. According to X-ray diffraction data, the Sb atoms have trigonal bipyramidal coordination. In the centrosymmetric molecule, the two Sb atoms are joined via bridging peroxo group disordered over two sites. The Sb–O(1,2') bond lengths are equal to 1.999(6) and 2.03(1) Å, the Sb···O(2,1') distances are equal to 2.605(9) and 2.626(5) Å, respectively. The lengths of the terminal Sb–O(3) bonds are 2.093(3) Å.     

μ-Oxo-Bis[(Bromo)Tri-m-Tolylantimony]: Synthesis and Structure

-Oxo-bis[(bromo)tri-m-tolylantimony] was synthesized by the reaction of tri-m-tolylstibine with hydrobromic acid in ether in the presence of hydrogen peroxide. The complex was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with the bromine and the bridging O atoms in the axial positions. The Sb(1)–C(Ph) distances vary from 2.085(9) to 2.111(8) Å. The Sb(1)–Br(1) and Sb(2)–Br(2) bond lengths are 2.739(2) and 2.735(2) Å, respectively; the Sb–O_br distances measure 1.949(1) Å.     

Synthesis and Structure of Tetra- and Triphenylantimony Organosulfonates

Tetraphenylantimony 2-naphthalenesulfonate (I), tetraphenylantimony phenylmethanesulfonate (II), and bis(tetraphenylantimony) sulfate (III) were synthesized via reaction of pentaphenylantimony with 2-naphthalenesulfonic acid, triphenylantimony bis(phenylmethanesulfonate), and triphenylantimony sulfate, respectively, in toluene. Triphenylantimony bis(phenylmethanesulfonate) (IV) was synthesized from triphenylstibine, phenylmethanesulfonic acid, and hydrogen peroxide (taken in the molar ratio of 1 : 2 : 1). Organoantimony betaine (V) was obtained by reacting triphenylstibine with phenylmethanesulfonyl chloride in the presence of hydrogen peroxide. The structures of the compounds synthesized were determined using X-ray diffraction analysis. The Sb atoms in I–IV have distorted trigonal bipyramidal coordination. The Sb–C and Sb–O distances are equal to 2.100(4)–2.140(3) and 2.644(2) Å in molecule I, 2.105(2)–2.131(2) and 2.699(1) Å in II, 2.096(6)–2.169(6) and 2.101(6), 2.271(3) Å in III, and 2.101(3)–2.102(5) and 2.111(2) Å in IV. In V, the Sb atoms have close tetrahedral (2.105–2.115 Å) and remote (2.65, 3.019 Å) octahedral environment (the oxygen atoms of sulfo group of their own and neighboring molecules). Two betaine molecules are joined through the O atoms of the sulfo groups of bidentate phenylmethanesulfonate ligands to form a centrosymmetrical dimer. The intermolecular C(1)–H(1)···O(1) hydrogen bonds (3.10 Å) are formed that strengthen the dimer.     

Synthesis and Structure of New Crystal Modification of Tetraphenylantimony 4-Methylbenzenesulfonate

Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony with arenesulfonyl chlorides in toluene taken in a molar ratio of 1 : 1 : 2 in air. The structure of tetraphenylantimony 4-methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb–C(Ph)_eq bond lengths vary in the 2.099(2)–2.123(2) Å range, and the Sb–C(41) and Sb–O(1) distances are 2.136(2) and 2.499(1) Å, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.     

μ-Oxo-Bis(Tetraphenylantimony): Synthesis,Structure, and Reactions

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords -oxo-bis(tetraphenylantimony) (I) in a 63% yield. The latter compound can be converted to bis(tetraphenylantimony) carbonate or phthalate by the action of carbon dioxide or phthalic anhydride, respectively. According to X-ray diffraction data, the antimony atoms in compound Ihave a distorted trigonal-bipyramidal coordination (Sb–O 2.0050(4) Å, the SbOSb angle 151.71(9)°). The molecule of bis(tetraphenylantimony) phthalate is composed of two equal fragments, and its Sb atoms also have trigonal-bipyramidal coordination (Sb–O 2.2421(8) Å; Sb–C 2.176(1), 2.115(1), 2.130(1), and 2.137(1) Å).     

Synthesis and Structure of Tetraphenylantimony Nitrite

Tetraphenylantimony nitrite was synthesized by reacting pentaphenylantimony with triphenylantimony dinitrite at a molar ratio of 1 : 1 in toluene, and its structure was determined using X-ray diffraction analysis. The Sb atom is coordinated to the oxygen atom of the axial nitrite group to form a trigonal bipyramid. The Sb–C(Ph)_eq distances vary within the 2.103–2.111(3) Å range, and the S–O(1) and Sb–C(41) bond lengths are equal to 2.386(3) and 2.156(3) Å, respectively. The Sb...N distance and the axial C(41)SbO(1) angle are equal to 3.133(4) Å and 174.7(1)°, respectively.     

Structural Features of Triorganylantimony Dicarboxylates R3Sb[OC(O)R′)]2

Triphenylantimony dibenzoate Ph₃Sb(O₂CPh)₂, triphenylantimony bis(methylbenzoates) Ph₃Sb(O₂CC₆H₄Me-n)₂ (n = 2, 4), and tri-p-tolylantimony bis(trichloacetate) p-Tol₃Sb(O₂CCCl₃)₂, whose Sb atoms have trigonal bipyramidal coordination, were studied using X-ray diffraction analysis. The Sb–O bond lengths are equal to 2.119(2) and 2.144(2); 2.115(2); 2.118(2) and 2.127(2); 2.133(2) Å, the Sb···O(=C) intramolecular contacts are equal to 2.797(2) and 2.698(2); 2.845(2); 2.814(2) and 3.030(2); 3.119(2) Å, respectively. The following correlation was found in the structures of triorganylantimony dicarboxylates: the shorter the Sb···O(=C) distances, the greater the equatorial angle on the side of the intramolecular contacts.     

Synthesis and Structure of Organoantimony Peroxides

Organoantimony peroxides (Ar₂SbO)₄(O₂)₂ (Ar = Ph, p-Tol) were synthesized by oxidation of triarylantimony with hydrogen peroxide in the presence of nitrosophenol or 4-chlorophenol in an ether solution. X-ray diffraction analysis of peroxides obtained revealed that four antimony atoms have octahedral coordination and are connected via bridging oxygen atoms and two peroxide groups. The C–Sb, Sb–O_br, Sb–OO, and O–O distances are equal to 2.106–2.127, 1.958–1.974, 2.202–2.246, 1.471, 1.470 Å (Ar = Ph) and 2.086–2.139, 1.932–1.983, 2.215–2.289, 1.445–1.466 Å (Ar = p-Tol).     

Synthesis and Structure of Triphenylantimony Dipropionate

Triphenylantimony dipropionate Ph₃Sb[OC(O)C₂H₅]₂was prepared by reacting triphenylantimony dibromide with sodium salt of propionic acid in toluene at 90°C. The structure of the compound was determined by X-ray diffraction. The coordination of the Sb atom in the compound is a trigonal bipyramid with the carboxylic groups in the axial positions. The Sb(1)–C(Ph)_eqdistances vary in the 2.099(7)–2.135(6) Å range; the Sb(1)–O(1,3) distances are 2.113(5) and 2.109(5) Å, respectively. The value of the O(1)Sb(1)O(3) axial angle is 175.0(2)°.     

Synthesis and Structure of μ-Oxobis[(nitrito)triphenylantimony]

Triphenylantimony dibromide was reacted with sodium nitrite in aqueous acetone to obtain -oxobis[(nitrito)triphenylantimony]. According to single-crystal X-ray diffraction data, the Sb atoms in the molecule have a trigonal bipyramidal coordination. The molecule is centrosymmetric, the two Sb atoms are linked with each other by a bridging oxygen atom [the SbOSb angle is 141.8(2)°, and the Sb···Sb distance is 3.7354(5) Å]. The Sb-Obr and Sb-Oterm bond lengths are 1.9768(1) and 2.257(3) Å, and the Sb···O and Sb···N distances are 3.020(4) and 3.070(6) Å, respectively.     

Die Kristallstruktur von Tetrachloräthylencarbonat—Antimon(V)-chlorid,C2Cl4O2CO·SbCl5

Zusammenfassung Die Kristallstruktur des Adduktes Tetrachloräthylencarbonat—Antimon(V)-chlorid, C₂Cl₄O₂CO·SbCl₅ wurde mit Hilfe der Schweratom-Methode aus dreidimensionalen Röntgendaten bestimmt und nach der Methode der kleinsten Quadrate bis zu einemR-Wert von 13,1% verfeinert (Raumgruppe P2₁/n — Nr. 14;a=10,13,b=12,15 undc=12,55 Å, =108°40). Die Elementarzelle enthält 4 Moleküle C₂Cl₄O₂CO· SbCl₅. Das Antimonatom ist oktaedrisch von 5 Chloratomen und dem Carbonylsauerstoffatom des Tetrachloräthylencarbonats umgeben (Sb–Cl 2,28–2,33 und Sb–O 2,40 Å).

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The crystal structure of tetrachloroethylene carbonate antimony(V) chloride, C₂Cl₄O₂CO·SbCl₅

The crystal structure of the adduct tetrachloroethylene carbonate antimony(V)-chloride, C₂Cl₄O₂CO·SbCl₅, has been determined by the heavy-atom method from three-dimensional X-ray data. The refinement of the parameters was carried out by least-squares resulting anR-value of 13.1% (space group P2₁/n — No. 14;a=10.13,b=12.15 andc=12.55 Å, =108°40). The unit cell contains 4 discrete molecules C₂Cl₄O₂CO·SbCl₅. The antimony atom is coordinated octahedrally by 5 chlorine atoms and the carbonyl oxygen atom of tetrachloroethylene carbonate (Sb–Cl 2.28–2.33 and Sb–O 2.40 Å).

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Mit 2 Abbildungen     

μ-Oxo-Bis[(arenesulfonato)triphenylantimony]: Synthesis and Structure

-Oxo-bis[(4-methylbenzenesulfonato)triphenylantimony] (I) and -oxo-bis[(2,5-dimethylbenzenesulfonato)triphenylantimony] (II) were synthesized by reacting triphenylstibine Ph₃Sb with tri-p-tolylbismuth bis(4-methylbenzenesulfonate) and tri-p-tolylbismuth bis(2,5-dimethylbenzenesulfonate), respectively, in toluene in the presence of air moisture. According yo X-ray diffraction data, the antimony atoms in the compounds synthesized have a distorted trigonal bipyramidal configuration. The SbOSb angles are equal to 138.5(2)° and 180°, respectively. A bent molecule I contains the Sb(1)···Sb(2) (3.690(1) Å) and Sb···S(1,2) (3.521(2), 3.559(2) Å) intramolecular contacts. In a linear molecule II, the Sb···S distances are equal to 3.438(1) Å.     

Solvothermal Synthesis, Crystal Structure, and Properties of the First Zinc Containing Thioantimonate(III) [Zn( tren)] 2Sb 4S 8·0.75 H 2O

Yellow crystals of the title compound were obtained under solvothermal conditions reacting elemental Zn, Sb, and S in a solution of tris(2-aminoethyl)amine (=tren) and water. The compound crystallises in the monoclinic space group P2₁/c with a=13.0247(7), b=22.308(2), c=12.1776(6) Å, and =105.352(6)°. In the structure of [Zn(tren)]₂Sb₄S₈·0.75 H₂O two [Zn(tren)]²⁺ cations are bound to the [Sb₄S₈]^4– anion via S atoms. The Zn²⁺ ions are in a trigonal bipyramidal environment of four N atoms of the tetradentate tren ligand and one S atom of the [Sb₄S₈]^4– anion. The anion is formed by SbS₃ and SbS₄ units which share common corners and edges. The interconnection mode yields three different non-planar Sb₂S₂ heterorings. The shortest intermolecular Sb–S distance amounts to about 3.7Å, and taking this long separation into account undulated chains running along [001] are formed with the water molecules residing in the pocket-like cavities. Upon heating the compound decomposes in one step starting at about 240°C. The final decomposition product was identified as ZnS and Sb₂S₃ by X-ray powder diffractometry. Additionally, spectroscopic data as well as synthetic procedures for [Zn(tren)]₂Sb₄S₈·0.75 H₂O are reported.     

Synthesis and Structure of Tetraphenylantimony γ-Alkylacetylacetonates

Tetraphenylantimony -ethylacetylacetonate and -allylacetylacetonate were synthesized by reacting pentaphenylantimony with -ethylacetylacetone or -allylacetylacetone in toluene. Their structures were determined by X-ray diffraction analysis. The coordination polyhedron of the antimony atom is a distorted octahedron. In the tetraphenylantimony -ethylacetylacetonate, the Sb–C bond lengths vary in the 2.156(2)–2.170(1) Å range, the SbOC(1)C(2)C(1")O" heterocycle is symmetric, and the Sb–O and O–C distances are 2.201(1) and 1.284(2) Å, respectively. In the tetraphenylantimony -allylacetylacetonate, the Sb–C bond lengths vary in the 2.159(1)–2.167(1) Å range and the Sb–O(1,2) distances are 2.234(1) and 2.191(1) Å.     

Tetra- and Triarylantimony Fluorobenzoates: Synthesis and Structures

The reactions of pentaarylantimony (Ar₅Sb, where Ar = Ph or p-Tol) with triarylantimony bis(pentafluorobenzoate) and triarylantimony bis(3,4,5-trifluorobenzoate) in toluene afforded tetraarylantimony pentafluoro- and 3,4,5-trifluorobenzoates in up to 90% yields. The starting triarylantimony bis(pentafluorobenzoates) and bis(3,4,5-trifluorobenzoates) were prepared in ether by oxidative addition involving triarylstibine, hydrogen peroxide, and pentafluorobenzoic or 3,4,5-trifluorobenzoic acid, respectively, in up to 98% yields. Tetra-p-tolylantimony pentafluorobenzoate and triphenylantimony bis(pentafluorobenzoate) were structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with axial carboxy groups. In these compounds, the Sb atoms and carbonyl O atoms are linked by intramolecular contacts, which are especially pronounced in the latter complex (the Sb···O(=C) distances are 3.377(3) and 2.943(2), 3.167(2) Å, respectively).