Christopher Glidewell

Effect of the counter-ion on the structures of tetraphenylantimony(V)–stibonium compounds: crystal and molecular structures of tetraphenylantimony(V) bromide, perchlorate, and tetraphenylborate

Crystals of Ph4SbBr are monoclinic, a= 16.293(3), b= 10.616(3), c= 12.507(2)A, β= 105.60(1)°, space group P21/n. The structure consists of trigonal bipyramidal molecules in which the apical Sb–Br bond is very long [2.965(1)A]: the apical and mean equatorial Sb–C distances are 2.151(9) and 2.102(9)A, respectively. The perchlorate [tetragonal, a= 12.670(2), c= 6.711(2)A, space group /] crystallises with isolated ions of almost perfect tetrahedral local symmetry; in the cation, the Sb–C distance is 2.095(2)A. The structures of a range of tetraphenylantimony(V) derivatives Ph4SbX are discussed in terms of the basicity/nucleophilicity of X. Crystals of Ph4SbBPh4 are tetragonal, a= 16.272(3), c= 13.703(3)A, with an I lattice: structure solution was attempted, without success, in all possible space groups. The SbPh4+ and BPh4– ions are scrambled.

The Structure of Triphenylmethanol, Ph3COH

C19H160 , Mr = 260.3, trigonal, R3, a = 19.307 (3), c = 26.735 (4) A, V= 8631 (2) A 3, Z= 24, Dx = 1.20 g cm -3, a(Mo Ka) = 0.71073/~, /.~ = 0.7 cm -1, F(000) = 3312, T = 294 K, R = 0.083, wR = 0.068 for 1022 observed reflections. The structure contains hydrogen-bonded pyramidal tetramers (which have approximate 32 symmetry) with one molecule lying on a crystallographic threefold axis and another in a general position. The analysis was complicated by disorder in the crystal lattice where 71% of the tetramers occupy one orientation and 29% another; these moieties have their phenyl rings in the same volume elements in the lattice. The O...O separations in the hydrogen-bond systems are 2.884 (10) and 2.896 (11)/~ in the major tetramer and 2.80 (3) and 2.90 (3) A in the minor tetramer. Introduction. We have been interested for some time in the structures of the series Ph3MOH (M = C, Si, Ge, Sn, Pb). Although full structural data are avail- able (see below) for the Si, Ge, Sn and Pb derivatives, no structural data are available for the Ph3COH

Phenyl(p-tolylsulfonylamino)(p-tolylsulfonylimino)-λ4-sulfane, a reaction product of diphenyl disulfide and chloramine-T

C 20 H 20 N 2 O 4 S 3 cristallise dans P1 avec a=10,140, b=12,465, c=9,665 A, α=101,88, β=114,57, γ=81,8 o , Z=2; affinement jusqua R=0,035. Les longueurs S(VI)-N et S(VI)-N(H) sont de 1,611 et 1,630 A respectivement, celles de S(IV)-N et S(IV)-N(H) sont respectivement de 1,593 et 1,678 A, et il y a deux contacts S...O intramoleculaires courts de 2,866 et 2,932 A, indiquant une structure ylidique, hautement polaire