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Licensed Unlicensed Requires Authentication Published by De Gruyter (O) October 12, 2009

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

  • Julio Zukerman-Schpector , Elisangela Vinhato , Paulo R. Olivato , Alessandro Rodrigues , Maurizio Dal Colle , Carlos R. Cerqueira Jr. , Hadi D. Arman and Edward R. T. Tiekink

Abstract

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)–(III) an intramolecular S … Ocarbonyl interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) Å in (I) to 2.924(2) Å in (II) to 3.0973(18) Å in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C–H … O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C–H … O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S … O interactions persist. The presence of intermolecular C–H … O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C–H … O interaction in the energetically-favoured conformation. (I): C12H13NO3S, triclinic space group P-1 with a = 5.392(3) Å, b = 10.731(6) Å, c = 11.075(6) Å, α = 113.424(4)°, β = 94.167(9)°, γ = 98.444(6)°, V = 575.5(6) Å3, Z = 2, R1 = 0.052; (II): C12H13NO4S, monoclinic P21/n, a = 7.3506(15) Å, b = 6.7814(14) Å, c = 23.479(5) Å, β = 92.94(3)°, V = 1168.8(4) Å3, Z = 4, R1 = 0.046; (III): C12H13NO5S, monoclinic P21/c, a = 5.5491(11) Å, b = 24.146(3) Å, c = 11.124(3) Å, β = 114.590(10)°, V = 1355.3(5) Å3, Z = 4, R1 = 0.051.


* Correspondence address: Universidade Federal de Sao Carlos, Departamento de Química, Laboratorio de Cristalogr, Cx. P. 676, 13565-905 Sao Carlos, SP, Brasilien,

Published Online: 2009-10-12
Published in Print: 2009-10

© by Oldenbourg Wissenschaftsverlag, München, Germany

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