Prevalence of the thioamide {⋯H–N–CS}2 synthon—solid-state (X-ray crystallography), solution (NMR) and gas-phase (theoretical) structures of O-methyl-N-aryl-thiocarbamides

Abstract

Structural investigations, i.e. solid-state (X-ray), solution ( 1 H NMR) and gas-phase (theoretical), on molecules with the general formula MeOC(LS)N(H)C 6 H 4 -4-Y: Y 5 H (1), NO 2 (2), C(LO)Me (3), Cl (4) have shown a general preference for the adoption of an E-conformation about the central C-N bond. Such a conformation allows for the formation of a dimeric hydrogen-bonded { … H-N-CLS} 2 synthon as the building block. In the cases of 1-3, additional C-H … O interactions give rise to the formation of tapes of varying topology. A theoretical analysis shows that the preference for the E-conformation is about the same as the crystal packing stabilisation energy and consistent with this, the compound with Y 5 C(LO)OMe, (5), adopts a Z-conformation in the solid-state that facilitates the formation of N-H … O, C-H … O and C-H … S interactions, leading to a layer structure. Global crystal packing considerations are shown to be imperative in dictating the conformational form of molecules 1-5.

N-(4-Bromophenyl)methoxycarbothioamide

“…Compound 1 was prepared in an excellent yield (93%) by standard methods [5] and it was characterised by spectroscopy (see Supplementary Materials for original spectra). The NMR data showed the expected resonances and integration ( 1 H).…”

“…Obviously, this principle will not hold if the substituent(s) concerned participate in significant, directional intermolecular interactions. There are several closely related crystal structures that are available for molecules of the general formula MeOC(=S)N(H)PhX-4, i.e., X = H [14], Me [15], and Cl [5]. Of these, the X = H compound adopts a distinctive molecular packing [15].…”

“…Crystals of these species are often forthcoming enabling the evaluation of systematic variations of the R, R′, and R″ substituents upon the molecular packing and solid-state luminescence [3,4]. Indeed, the uncoordinated molecules are also of interest, as they, too exhibit varied supramolecular association depending on aryl-bound substituents [5,6], especially in circumstances when the nitrogen-bound groups carry pyridyl functionality [7]. The title compound, O-methyl (4-bromophenyl)carbamothioate (1) is a known compound, being first reported in 1935 [8][9][10] and a method for its synthesis has been patented [11].…”

Crystal structure of the co-crystal O-isopropyl phenylcarbamothioate – 4,4′-bipyridine (2/1), C15H17N2OS

“…molecules of the general formula ROC(=S)N(H)R′ for R, R′ = alkyl/aryl [6], find interest in crystal engineering endeavours in terms of their ability to form thioamide-N-H· · · S(thione) hydrogen bonds and the influence of this upon molecular conformation [5][6][7] as well as their propensity to form co-crystals [8]. As a continuation of the latter studies, the title 2:1 co-crystal was isolated.…”

G 2 /M cell cycle arrest on HT-29 cancer cells and toxicity assessment of triphenylphosphanegold(I) carbonimidothioates, Ph 3 PAu[SC(OR) = NPh], R = Me, Et, and iPr, during zebrafish development

“…were prepared in high yields as described previously [22] and following well established protocols [23], i.e., via the reaction of Ph3PAuCl with the respective ROC(=S)N(H)Ph ligand [24] in the presence of base, and exhibited the same spectroscopic ( 1 H, 13 C{ 1 H} and 31 P{ 1 H}…”