Crystal and Molecular Structure of Benzylidenimine Disulfide

Abstract

. Can. J. Chem. 52,2985Chem. 52, (1974. The crystal and molecular structure of benzylidenimine disulfide has been determined. Crystals are n~onoclinic with space group P2,/c, Z = 4, a = 12.93(2), b = 5.554(9), c = 20.46(3) A. and B = 112.5(2)'. A full matrix least squares refinement on 2304 unique reflections of positive intensity measure collected on a Pi Automatic diffractometer produced a conventional R of 0.029. The molecular geometry is very similar to that in the corresponding tetraand trisulfides with a fairly short sulfur-sulfur bond length of 2.033(2) 8, and a fairly long sulfur-nitrogen bond length of 1.690(3) A. (7) to optimize the yield of the disulfide. The product was isolated as an this effect, data previously described (6, 7) and recrystallized froln beno n very similar compounds with differing zene to give white needles melting at 100 1 0 0 . 5 '~ numbers of sulfur atoms in the sulfur chain (lit. (7) 100-100.5 -C). h01 and 1111 Weissenberg photowould be highly desirable. A preceding paper (6) graphs with systematic absences of the type / = in + I discussed the structure of the odd membered on the 1701 layer and k = 211 + 1 along the 0kO axis established the space group as P2,Jc. Unit cell pararneters chain, benz~lidenimine trisulfide. This paper were determined at room temperature by least squares reports the crystal and molecular structure of adjustment to the 28 values of 38 well centered reflections the comparable compound with an even measured on a Syntex P i Diffractonieter. The crystal membered sulfur chain, benzylidenimine di-used for intensity measurements had dimensions of sulfide.0.6 mm x 0.6 mm x 0.35 mm. The maximum variation in transmission factor was less than 4.5Z. and no absoro- background. Thus, the peak intensity, N,, = N , -

Synthesis and characterisation of bis[(methylthio)carbonyl]polysulphanes

“…could lose alkyl chloride (route a), prior to their rearrangement The sulphenyl chloride (15) was not detected spectroscopically under any of the reaction conditions summarised in Scheme 1. Attempts to prepare it by chlorination of the disulphane (2) or (18) with sulphuryl chloride yielded methanesulphenyl chloride (19) together with the acid chloride (21) or (17), respectively. Thus, the C-SMe bond was cleaved rather than the central S-S bond.…”

“…Other products from this reaction included the carbamoyldisulphane (29), 1 -(methylthio)carbonyl-2-(N-methyl-N-phenylcarbamoyl)disulphane (27),' and O-methyl-N-methyl-N-phenylthiocarbamate (28)' When the isolated sulphenamide (25) was treated with hydrogen chloride, the sulphenyl chloride (15) was obtained which reacted directly in situ with the dithiocarbonate (11) to give the disulphane (2). On standing in CDCl, at 25 "C, compound (15), prepared as above, rearranged cleanly to the acid chloride (17) with tt-= 75 min; no methanesulphenyl chloride (19) was formed.…”

“…46-50 "C (0.06 mmHg); R = Et; b.p. 45-57 "C (0.05 mmHg)] gave, with 85% recovery, distillates containing (16), and the lower boiling alkoxythiocarbonyl chloride, RO(C=S)Cl, and methanesulphenyl chloride (19) present in equal amounts. These recombined completely within 1 day at -20 "C to yield pure compound (16).…”