| Full text | |
| Author(s): |
Zukerman-Schpector, Julio
[1]
;
Vinhato, Elisangela
[2]
;
Olivato, Paulo R.
[2]
;
Rodrigues, Alessandro
[2]
;
Dal Colle, Maurizio
[3]
;
Cerqueira, Jr., Carlos R.
[2]
;
Arman, Hadi D.
[4]
;
Tiekink, Edward R. T.
[1, 4]
Total Authors: 8
|
| Affiliation: | [1] Univ Fed Sao Carlos, Dept Quim, Lab Cristalog Estereodinam & Modelagem Mol, BR-13565905 Sao Carlos, SP - Brazil
[2] Univ Sao Paulo, Inst Quim, Conformat Anal & Elect Interact Lab, BR-05513970 Sao Paulo - Brazil
[3] Univ Ferrara, Dipartimento Chim, I-44100 Ferrara - Italy
[4] Univ Texas San Antonio, Dept Chem, San Antonio, TX 78249 - USA
Total Affiliations: 4
|
| Document type: | Journal article |
| Source: | Zeitschrift für Kristallographie; v. 224, n. 10, p. 484-492, 2009. |
| Web of Science Citations: | 3 |
| 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 center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom 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 center dot center dot center dot 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 center dot center dot center dot 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 center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051. (AU) | |