I. A. Litvinov

Synthesis and Structure of Tetra- and Triarylantimony Oximates

Tetraphenylantimony acetophenoneoximate (I) and tetra-n-tolylantimony 3-nitrobenzaloximate (II) were synthesized by reacting pentaarylantimony with oxime or triarylantimony dioximate in toluene. Tri-n-tolylantimony bis(acetophenoneoximate) (III) and triphenylantimony bis(cyclohexanoneoximate) (IV) were synthesized by reacting triarylantimony with oxime and hydrogen peroxide. The structures of compounds I–IV were determined using X-ray diffraction analysis. The antimony atoms in I–IV are coordinated to the axial oxime groups to form a distorted trigonal bipyramid. The Sb–C(Ph) and Sb–O bond lengths and Sb...N intramolecular contacts in structures I and II lie within 2.114–2.135, 2.137–2.154, and 2.857–2.871 Å, respectively; the respective values in structures III and IV are 2.097–2.112, 2.058–2.080, and 2.779–2.874 Å.

Reaction of Triphenylbismuth Bis(arenesulfonates) with Triphenylstibine

Tetraphenylantimony arenesulfonates and diphenylbismuth arenesulfonates were prepared by reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine in toluene at 25°C. The crystal and molecular structure of diphenylbismuth 2,4-dimethylbenzenesulfonate was studied by single crystal X-ray diffraction. The molecules of the compound in the crystal form chains of Ph2BiOSO2C6H3Me2-2,4 fragments linked with oxygen atoms of the sulfo group of the bridging arenesulfonate ligand.

Synthesis and Structure of μ-Oxobis[triphenyl(furfuraloximato)antimony(V)]

Reaction of triphenylstibine with furfuraloxime in the presence of hydrogen peroxide in water-ether solution forms μ-oxobis[triphenyl(furfuraloximato)antimony(V)] in 90% yield. This complex has a dimeric structure in which two antimony atoms are bound with the bridge oxygen atom and two bridge oxime groups coordinating the metal atom by the oxygen as well as by the nitrogen atoms to form bicyclo[2.2.1]heptane fragment. SbOSb angle is 125.5(3)°, the bonds between the antimony atom and the bridge oxygen atoms [1.957(6) and 1.946(5) Å] are shorter than with the oxygen atoms of oxime groups [2.146(6) and 2.148(6) Å].

Synthesis and structure of tetraphenylantimony N, N-diethyldithiocarbamate

Tetraphenylantimony chloride was reacted with sodium N,N-diethyldithiocarbamate in water to obtain tetraphenylantimony N,N-diethyldithiocarbamate in 98% yield. According to X-ray diffraction data, the configuration of the molecule of tetraphenylantimony diethyldithiocarbamate is distorted octahedron, and the Sb-S bond lengths are 2.705(2) and 2.771(2) Å.

Halo Derivatives of 2,4-Dinitrothiolene 1,1-Dioxides: Synthesis and Structure

Procedures were developed for preparing representatives of a new type of halonitrothiolene 1,1-dioxides: mono- and dihalo derivatives of 2,2,4-tri- and 2,4-dinitro-3-thiolene 1,1-dioxides. An X-ray diffraction study showed that 2,5-dinitro-2,3-dichloro-3-thiolene 1,1-dioxide molecules exist in the crystal as enantiomeric pairs; the five-membered rings have the envelope conformation, with deviation of the sulfur atom from the ring plane; the halogen atom and nitro group at the multiple bond are essentially coplanar with the ring.

Synthesis and structure of the toluene solvate of tris(tetraphenylstiboxy)amine hydronitrate

The reaction of μ-oxobis(nitratotriphenylantimony) with pentaphenylantimony in toluene in the presence of moisture and carbon dioxide gives the toluene solvate of tris(tetraphenylstiboxy)amine hydronitrate [(Ph4SbO)3N]·NO3-·H3O+·2C7H8. According to X-ray diffraction data, the three Ph4SbO groups are bound with the central nitrogen atom by simple bonds [the N-O interatomic distances are 1.31(1)Å]. The NO2 fragment is planar (the sum of the bond angles at N1 is 359.7°). The antimony atom has a slightly distorted trigonal-bipyramidal coordination.

3-Methoxycarbonyl-4-phenyl-2-pyrrolidone in reactions with benzalmalonate and its analogs

Abstract3-Methoxycarbonyl-4-phenyl-2-pyrrolidone reacts with benzalmalonate and related compounds as an N-nucleophile affording adducts as an easily resolvable diastereoisomeric mixture. Structure of the synthesized compounds is studied by IR and 1H, 13C NMR spectroscopy. Structural parameters and configurations of the stereoisomers of one among the series of synthesized compounds was determined by X-ray structural analysis. The pyrrolidone ring of these compounds is shown to be present in an envelope conformation. The supramolecular structures in crystal are formed mainly on account of intermolecular hydrogen bonds of C-H⋯O type and π⋯π interactions.

Synthesis and Structure of Tetraphenylantimony Nitrate

The reaction of pentaphenylantimony with triphenylantimony dinitrate in toluene gives tetraphenylantimony nitrate in 99% yield. The X-ray diffraction data show that the antimony atom in the molecule of tetraphenylantimony nitrate has a distorted trigonal-bipyramidal coordination with axial location of the oxygen atom of the nitrate group. The Sb-O, Sbax, and Sb-Ceq bond lengths in two independent molecules of tetraphenylantimony nitrate are 2.498(3), 2.548(2); 2.134(3), 2.138(3); and 2.101(3)-2.112 Å.

Tetraphenylantimony Phenylglyoxylate: Synthesis and Structure

Pentaphenylantimony reacts with phenylglyoxylic acid in toluene to give tetraphenylantimony phenylglyoxylate in 88% yield. X-ray data show that the antimony atom in tetraphenylantimony phenylglyoxylate has the trigonal bipyramidal coordination with the oxygen atom in the axial position. The SbÄC distances are 2.114(4), 2.119(4), 2.142(4), and 2.173(4) Å; SbÄO distance, 2.299(3) Å; and CaSbO angle, 178.7(1)°.

Synthesis and Structure of Dinitrosulfodienes of the Thiolene 1,1-Dioxide Series

A synthesis of previously unknown rigidly fixed heterocyclic structures, dinitrosulfodienes of the thiolene 1,1-dioxide series, was developed, and their structure was studied. The geometry and structural parameters of 3-methyl-4-nitro-2-[nitro(phenyl)methylene]-3-thiolene 1,1-dioxide were determined by X-ray diffraction.