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) A in (II) to 3.0973(18) A 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 11 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.

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

DAL COLLE, Maurizio;
2009

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) A in (II) to 3.0973(18) A 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 11 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.
2009
Julio Zukerman, Schpector; I, ; Elisangela, Vinhato; Paulo R., Olivato; Alessandro, Rodrigues; DAL COLLE, Maurizio; Carlos, R. Cerqueira J. r.; Hadi D., Arman; Edward R. T., Tiekink
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/1377954
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 3
  • ???jsp.display-item.citation.isi??? 3
social impact