Crystal and Molecular Structure of Benzylidenimine Trisulfide

Abstract

The crystal and molecular structure of benzylidenimine trisulfide has been determined. Crystals are orthorhombic with a = 16.610(2), b = 9.984(6), c = 4.386(4), Z = 2 and space group P2,2,2. 773 unique reflections of positive measured intensity, recorded with a Syntex P i Automatic Diffractometer, were refined by full-matrix least-square methods to a conventional R value of 0.023. The molecule has a crystallographic two-fold axis and S-S bond lengths of 2.051(1) A. These are intermediate in length between the long inner and short outer S-S bonds of the chemically analogous tetrasulfide. The S-N and N-C bond lengths are 1.661(3) and 1.269(3), respectively. The crystal packing is determined by S-S van der Waals interaction between adjacent molecules along the c axis.

Cocrystallization of (μ-S2)2– and (μ-S)2– and Formation of an [η2-S3N(SiMe3)2] Ligand from Chalcogen Reduction by (N2)2– in a Bimetallic Yttrium Amide Complex

“…This is clearly a flexible metal fragment that can bind a variety of ligands. 21 The 1.704(2) Å S−N distance in 5 is also similar to those in these two organic complexes, 1.668(2) and 1.680(2) Å, in the former 14 and 1.661(3) Å in the latter. 20,21 Three examples were found in the crystallographic literature in which an S 3 unit is bound η 2 to one metal and η 1 to another atom: (C 5 H 5 ) 2 Ru 2 (CO)S 5 , 26 (C 5 H 4 t Bu) 3 Nb 3 S 12 , 27 and (C 5 H 5 )-Ti(C 5 H 5 S 5 ).…”

“…21 The 1.704(2) Å S−N distance in 5 is also similar to those in these two organic complexes, 1.668(2) and 1.680(2) Å, in the former 14 and 1.661(3) Å in the latter. 20,21 Three examples were found in the crystallographic literature in which an S 3 unit is bound η 2 to one metal and η 1 to another atom: (C 5 H 5 ) 2 Ru 2 (CO)S 5 , 26 (C 5 H 4 t Bu) 3 Nb 3 S 12 , 27 and (C 5 H 5 )-Ti(C 5 H 5 S 5 ). 28 The first two examples have an S 3 ligand bridging two metal centers in polymetallic complexes, and the third example has a TiS 3 C linkage formed by thermal rearrangement of (C 5 H 5 ) 2 TiS 5 .…”

“…The terminal sulfur, S1, has the shorter Y–S distance, 2.673(6) Å, in comparison with the 2.840(6) Å length for Y–S2. The 2.052(1) Å S1–S2 distance is only slightly shorter than the 2.0823(8) Å S2–S3 length, and both are in the range defined by [( t Bu 2 FSi)NBu t ]SSS[ t BuN(SiF t Bu 2 )] [2.102(1) Å] and (PhCHN)SSS(NCHPh) [2.051(1) Å] . The 1.704(2) Å S–N distance in 5 is also similar to those in these two organic complexes, 1.668(2) and 1.680(2) Å, in the former and 1.661(3) Å in the latter. , …”

“…Complex 5, to our knowledge, contains the first example of the [S 3 N(SiMe 3 ) 2 ] − ligand. The closest examples of S 3 NR 2 moieties of any kind in the crystallographic literature are organic compounds: a bis(fluorosilylamino)trisulfide, [( t Bu 2 FSi)NBu t ]SSS[ t BuN-(SiF t Bu 2 )], isolated in 1973 from sulfur and the lithium salt of the amine,20 and the benzylidenimine trisulfide, (PhCHN)-SSS(NCHPh), identified in 1991 from the reaction of sulfur with benzylamine in the presence of lead oxide 21.…”

Crystal and Molecular Structure of Benzylidenimine Disulfide

“…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.…”