title: Molecular Structures of Isomeric Ortho, Meta, and Para Bromo-Substituted α-Methylsulfonyl-α-diethoxyphosphoryl Acetophenones by X-ray and DFT Molecular Orbital Calculations.
abstract: The X-ray single crystal analysis of isomeric ortho, meta, and para bromo-substituted α-methylsulfonyl-α-diethoxyphosphoryl acetophenones showed that this class of compound adopts synclinal (gauche) conformations for both [-P(O)(OEt)2] and [-S(O)2Me] groups, with respect to the carbonyl functional group. The phosphonate, sulfonyl, and carbonyl functional groups are joined through an intramolecular network of attractive interactions, as detected by molecular orbital calculations at the M06-2X/6-31G(d,p) level. These interactions are responsible for the more stable conformations in the gas phase, which also persist in the solid-state structures. The main structural distinction in the title compounds relates to the torsion angle of the aryl group (with respect to the carbonyl group), which gives rise to different interactions in the crystal packing, due to the different positions of the Br atom.
authors.affiliation: †Institute for Environmental, Chemical and Pharmaceutical Sciences, Federal University of São Paulo, UNIFESP, Diadema 09972-270, SP Brazil.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Rodrigues
authors.affiliation: ‡Institute of Chemistry, University of São Paulo, USP, CP 26077, 05513-970 São Paulo, SP Brazil.
authors.forename: Paulo R
authors.initials: PR
authors.lastname: Olivato
authors.affiliation: §Department of Chemistry, Federal University of São Carlos, CP 676, 13565-905 São Carlos, SP Brazil.
authors.forename: Julio
authors.initials: J
authors.lastname: Zukerman-Schpector
authors.affiliation: §Department of Chemistry, Federal University of São Carlos, CP 676, 13565-905 São Carlos, SP Brazil.
authors.forename: Stella H
authors.initials: SH
authors.lastname: Maganhi
authors.affiliation: †Institute for Environmental, Chemical and Pharmaceutical Sciences, Federal University of São Paulo, UNIFESP, Diadema 09972-270, SP Brazil.
authors.forename: Adriana K C A
authors.initials: AK
authors.lastname: Reis
authors.affiliation: ∥Department of Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia.
authors.forename: Edward R T
authors.initials: ER
authors.lastname: Tiekink
mesh_terms: D000098:Acetophenones / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D011789:Quantum Theory; D014965:X-Rays
chemical_list: D000098:Acetophenones; D005740:Gases