The reactions of triarylphosphines and triarylarsines with chloramines B and T: crystal and molecular structures of triphenylarsine oxide–benzenesulphonamide (1 : 1) hemi-acetone solvate and tri-m-tolylphosphine oxide–toluene-p-sulphonamide (1 : 1)

Abstract

Triphenylarsine and triphenylphosphine react with chloramine-B, sodium N-chlorobenzenesulphonamide, to yield products of composition C₂₄H₂₂NO₃SM [(3; M = As) and 4; M = P)] and constitution Ph₃MO·H₂NSO₂Ph. Crystals of (3)·0.5(C₃H₆O) are triclinic, space group P with a= 12.783(2), b= 13.016(2), c= 8.513(1)Å, α= 97.40(1), β= 106.80(1)°, γ= 111.28(1)° and Z= 2: the structure was refined from diffractometer data to an R value of 0.035. The structure consists of cyclic centrosymmetric aggregates in which two molecules of Ph₃AsO are linked to two molecules of PhSO₂NH₂via hydrogen bonds of type O ⋯ H-N (SO₂Ph)–H ⋯ O: the As–O distance is 1.655(1)Å and the two independent N ⋯ O distances are 2.848(3) and 2.882(3)Å; the acetone from solution is disordered about an inversion centre. Crystals of (4)·0.5(C₃H₆O) are triclinic, space group P, and are isomorphous with those of (3)·0.5(C₃H₆O), with a= 12.712(5), b 12.811(9), c= 8.481(3)Å, α= 98.51 (3), β= 105.31 (3), γ= 111.81(5)°, Tri-m-tolylphosphine reacts with chloramine-T, sodium N-chlorotoluene-p-sulphonamide, to yield a similar product (5) of constitution (3-CH₃C₆H₄)₃PO·H₂NSO₂C₆H,-p-CH₃. Crystals of (5) are triclinic with a= 11.353(4), b= 13.694(5), c= 9.546(1)Å, α= 76.16(2), β= 87.52(2), γ= 112.24(3)° and Z= 2: the structure of (5) was refined from diffractometer data to an R value of 0.045. It consists of the same hydrogen-bonded array as (3), with N ⋯ O distances of 2.882(2) and 2.931 (2)Å.