Polymorphism in bipodalO,O′-dimethylN,N′-(m-phenylenedicarbonyl)bis(thiocarbamate)

Abstract

The title compound, C12H12N2O4S2, crystallizes in white and yellow polymeric forms as a result of interesting anti-anti and syn-anti conformational isomerism of the thiocarbonyl and carbonyl moieties relative to one another. This work is the first reported X-ray crystallographic structure determination of isomers of this class of bipodal ligand. The white form, anti-anti, (I), crystallizes with the benzene ring lying about a twofold rotation axis, resulting in both of the thiocarbonyl and carbonyl moieties being anti relative to each other. The yellow modification crystallizes as syn-anti, (II), with one thiocarbonyl moiety syn and the other anti relative to the respective carbonyl groups. The individual molecules of both (I) and (II) are extensively linked through intermolecular hydrogen bonds. Intermolecular hydrogen bonding in (II) includes a network of bifurcated N-H...O and N-H...S hydrogen bonds, while molecules of (I) include bifurcated C-H...O hydrogen bonds.

On the selective methylation of benzoyl and furoylthiocarbamates as polydentate systems

“…These values indicate that both carbonyl and thiocarbonyl groups are on the same side of the molecule showing a Z,Z' conformation, which is in agreement with previously reported results for these types of compounds. 15,16,22 Table 3 (O1) distance is 2.881(4) Å, similar to the reported values found for other related derivatives. 23 The existence of the intramolecular and intermolecular hydrogen bonds, may…”

Bipodal benzoylthiocarbamic acid esters: crystal and molecular structures of R = Et (a polymorph), and of a binuclear Cu(I) complex, R = iPr

“…The new structures reported herein complement a relatively small number of literature precedents of benzoylthiocarbamide acid esters [11][12][13][14][15][16]. The compounds for which crystal structures have been determined are listed in Table 5.…”

“…5: Literature precedents for crystal structures of benzoylthiocarbamate esters and derived anions. Me [15]. In one of these, a syn arrangement of thione-S and ketone-O atoms is found for both residues, Figure 7A, but in the other polymorph, with crystallographically imposed 2-fold symmetry, the thione-S and ketone-O atoms are anti, Figure 7B.…”

“…Crystal structure determinations for benzoylthiocarbamic acid esters are comparatively rare according to a search of the Cambridge Structural Database [10]. As discussed in more detail below, there are some mono-functional molecules [11][12][13], three bipodal derivatives of which one [14,15], the tetragonal polymorph of [1,4- [14] is re-investigated in the present report, as well a sole example of a metal complex [16].…”

Crystal structure of 3,5-diaza-methyl-2-methyl-6-oxo-6-phenyl-4- thioxohexanoate, at 200 K, C12H14N2O3S

“…bis(thiocarbamate) -have been reported in the literature [1]. The structures of two compounds featuring the title compound's scaffold as moiety of apartially cyclic structureare also apparent in theliterature [2].…”