Structural studies of some o-substituted S-phenyl thiobenzoates. I. Crystal structure of S-phenyl o-chlorothiobenzoate and S-phenyl o-bromothiobenzoate

Abstract

Structural characteristics ofS-phenylo-chlorothiobenzoate (I) andS-phenylo-bromothiobenzoate (II) have been investigated by single crystal X-ray diffraction. It was shown that the crystals are isomorphous and crystallize in the monoclinic space groupP2₁ withZ=2. The unit cell parameters are:a=10.150(3),b=7.672(2),c=7.595(2) Å,β=91.28(1)° for C₁₃H₉ClOS (compoundI) anda=10.141(3),b=7.764(2),c=7.653(2) Å,β=90.14(3)° for C₁₃H₉BrOS (compoundII). The structures were solved by heavy-atom methods and refined by full-matrix least-squares, from room-temperature data collected with a Philips PW 1100 diifractometer, to conventionalR factors of 0.056 forI and 0.044 forII. The structures consist of independent molecules held together by intermolecular interactions. Molecular packing is influenced by the presence ofo-substituted Cl or Br atoms. The Cl atoms in structureI as well as the Br ones in structureII are directed to the centers of the pi-electronic system of theo-substituted phenyl rings belonging to the neighboring molecules. The six Cl⋯C and Br⋯C distances range from 3.651(10) to 3.869(9) Å and from 3.644(6) to 3.890(6) Å, respectively. The C1 (or Br) atom is additionally directed towards the two carbon atoms (C3 and C4) in anothero-substituted phenyl ring, the C1⋯lC and Br⋯C distances being 3.786(9) and 3.849(10) Å inI and 3.727(6) and 3.881(6) Å inII. The torsion angle C6-C7-S-C8 is-170.2(7)° inI and 168.6(4)° inII. The angles between the planar O-C7-S central fragment of the molecule, on the one hand, and theo-substituted phenyl ring, on the other, are 113.9(3)° in I and 110.9(2)° inII. The corresponding values for the angles between the O-C7-S fragment and the nonsubstituted phenyl ring are 115.8(3)° and 114.3(2)° in compoundsI andII, respectively.