Symmetrisation, isomerism and structural studies on novel phenylmercury(II) thiosemicarbazonates: correlation of the energy barrier to rotation of the amino group with the bonding parameters of the thioamide group

The reactions of phenylmercury(II) acetate with a series of alkyl, aryl and heterocyclic thiosemicarbazones in ethanol formed novel phenylmercury(II) derivatives of stoichiometry [HgPhL] [HL = RN3N2HC1(S)N1H2 = cyclopentanone 1, cyclohexanone 2, benzaldehyde 3, 2-hydroxybenzaldehyde 4, 4-methoxybenzaldehyde 5, pyrrole-2-carbaldehyde 6, thiophene-2-carbaldehyde 7 or furan-2-carbaldehyde 8 thiosemicarbazone], characterised with the help of analytical data, physical properties, IR, far-IR, multinuclear NMR (1H, 13C, 199Hg) spectroscopy and X-ray crystallography of complexes 1, 5 and 6. The 1H and 13C NMR data suggest that the N2H group is deprotonated during reaction with phenylmercury(II) acetate and co-ordination occurs via the N3,S atoms in a chelating mode. The 199Hg NMR data suggest symmetrisation phenomenon for complexes 3 and 5, 2[HgPhL] ⇌ HgPh2 + [HgL], which is supported also by 1H and 13C NMR data. The δ(Hg) values reveal that shielding of Hg with the change of organic group in the thiosemicarbazones decreases in the order: 2-hydroxybenzene ⋙ furan > benzene > 4-methoxybenzene thiophene ≈ cyclohexanone ≈ cyclopentanone > pyrrole and the Lewis basicity of the thiosemicarbazones varies in the opposite order. The 1H and 13C NMR data reveal that 7 and 8 show isomerism. There are two strong [Hg–C 2.063(7) 1, 2.069(10) 5, 2.049(11) 6; Hg–S 2.382(2) 1, 2.357(3) 5, 2.377(3) Å 6] and one weak bond [Hg–N3 2.489(6) 1, 2.611(7) 5, 2.492(9) Å 6], with CPh–Hg–S bond angles of 162.9(2), 174.2(3), 165.8(3)° respectively. The weak intermolecular interactions via Hg · · · N2 [3.001(6) Å] in 1 and via Hg · · · S in 5 [3.518(3) Å] and 6 [3.528(3) Å] form centrosymmetric dimers and Hg formally acquires four-co-ordination with two strong (Hg–C, Hg–S), one weak (Hg · · · N3) and one secondary (Hg · · · N2 or S) bonds. The preferred dimer formation via N2 nitrogen in 1, rather than via sulfur atoms (5 and 6) despite Hg · · · S affinity represents an unusual bonding mode. From the low-temperature 1H NMR studies of some selected complexes, the energy barrier (ΔGTc*, Tc is coalescence temperature) to rotation of the amino group about the C1–N1 bond was calculated and correlated with bonding parameters of the thioamide group in the solid state.