Intramolecular H⋯S interactions in metal di-(isopropyl)dithiocarbamate complexes

Abstract

Intramolecular C–H⋯S interactions create restricted rotation of groups within di(isopropyl)dithiocarbate complexes.

An Unusual Mercury(II) Diisopropyldithiocarbamate Coordination Polymer

“…There is one intramolecular C-H···S hydrogen bond of ~ 2.4 Å between S1 and H2, creating an electronic Cl N asymmetry about the two isopropyl groups within each ligand, in agreement with previous reports. [9][10][11] All ligand bond lengths are similar to those in other DIPDTC complexes. 9-11, 48, 51-55 The structure of polymeric 2 contains a bonding motif that is new for mercury dithiocarbamate complexes 1 .…”

“…Spectra obtained using a mixture of 1 and 2 (determined using solid-state 199 Hg NMR spectroscopy) contained a single set of signals that remained indistinguishable even at lower temperatures (238 K). In addition, DOSY-NMR at room temperature ( Figure S2) revealed a single set of signals with a single revealed kinetic insights on the restricted rotation of the isopropyl groups (due to intramolecular C-H·· S interactions and steric effects) 9,11 Examination of the variable-temperature experimental data yielded an energy barrier (ΔG ‡ ) to free rotation at coalescence (268 K) of 59 kJ mol -1 , which is in excellent agreement with our previously reported data for NaDIPDTC (56 kJ mol -1 ) 11 and PbDIPDTC (57 kJ mol -1 ) 9 , indicating an equivalent transition state during isopropyl bond rotation (despite the fact that experiments were performed in different solvents). The values for ΔH ‡ (37 kJ mol -1 ), ΔS (-75 J mol -1 K -1 ) and an activation energy of 40 kJ mol -1 are somewhat similar to those for NaDIPDTC and PbDIPDTC indicating comparable degrees of C-H···S and steric interactions.…”

“…Three signals appearing between δc 19.8 to 21.0 ppm are assigned to nonequivalent methyl groups arising from the presence of intra-and intermolecular C-H···S interactions in the solid state, a phenomenon that has been previously observed. 9,11 In the spectrum of 2, C2, In both cases, all peaks for carbon atoms bonded to nitrogen (C1, C8, C4, C5, C9, and C12) are partially split and broadened which we attribute to residual dipolar coupling between 14 N and 13 C. [58][59][60] In 1, the splitting is more pronounced and likely attributed to a longer longitudinal relaxation time constant (T1) for 14 N, or the higher visual crystallinity of 1 compared to 2. These observations in the solid state 13 C NMR acquired using individually isolated (on the basis of morphology) single crystals of 1 and 2 are supported by comparison to the crystallographic data.…”

Examination of the structures, energetics, and vibrational frequencies of small sulfur‐containing prototypical dimers, (H2S)2 and H2O/H2S

“…The properties of molecules and reactions involving H 2 S and other sulfur‐containing molecules have solicited few investigations since the 1970s. Despite the prevalence and importance of these attractive SH interactions, particularly in biochemical systems containing cysteine residues or other thiol‐containing biomolecules, the homogeneous and heterogeneous S analogues of (H 2 O) 2 depicted in Figure have received comparatively little attention. Investigations into the homogeneous (H 2 S) 2 and heterogeneous H 2 O/H 2 S dimers provide insight into interactions with sulfur‐containing molecules as well as accurate energetics and vibrational signatures to compare with the H 2 O dimer.…”

N-(Dibenzylcarbamothioyl)-3-methylbutanamide: Crystal structure, Hirshfeld surfaces and antimicrobial activity

“…The deformation density represents differences between the total electron density of a molecule and the electron density of "neutral spherical unperturbed atoms" superimposed in the same of the molecule [50,51]. The electrostatic deformation density map reveals the presence of a charge depletion region (in red) at the hydrogen atoms (hydrogen atoms H1/H14 of NH and CH2 groups) which is directed towards the charge concentration region (in blue) over oxygen atom, facilitating formation of the H···O contacts in the crystal.…”