The first bipodal thiocarbamic acid ester,O,O′-diethylN,N′-(p-phenylenedicarbonyl)bis(thiocarbamate)

Abstract

The title compound, C(14)H(16)N(2)O(4)S(2), is the first reported X-ray crystallographic structure determination of a bipodal O-alkyl N-benzoylthiocarbamate. This compound crystallizes in a cis-S,O orientation (Z,Z' configuration), with the two S/O moieties anti relative to one another, as indicated by the twofold rotation axis located at the center of the benzene ring.

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

“…As expected, the molecular structure of 2, matches the previously reported determination [14]. However, this report pays scant attention to the crystal packing which is crucial in the present study comparing this structure to the monoclinic form.…”

“…Overall, the ligand adopts a slightly twisted conformation with the twist being about the C2-C3 bond, connecting the carbamate residue to the plane through the central benzene ring, the N1-C2-C3-C4 torsion angle is -23.5(2)°, and twists about the C1-N1 and C2-N1 bonds within the S1 = C1-N1-C2 = O1 residue, as seen in the values of the C2-N1-C1-S1 and C1-N1-C2-O1 torsion angles of 169.19 (14) and -20.5(3)°, respectively. Thus, allowing for the anti disposition of the doubly bonded S1 and O1 atoms, the overall conformation for the bipodal ligand in 3 matches that found for the monoclinic polymorph of the R = Et ester (2) with the exception of the C1-N1-C2-O1 torsion angle which is about 15° wider, probably to minimise repulsion between the oxygen atoms.…”

“…The molecular structures are shown in Figure 2 and selected geometric parameters collated in Table 2. The structure of 2 has been reported previously [14]. However, full details are included here to enable a comparison of the molecular and crystal structures obtained under identical conditions.…”

“…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].…”

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…”