Chlorido(η⁴-cycloocta-1,5-diene)(N,N′-diethylthiourea-κS)rhodium(I)

Abstract

In the title rhodium(I) complex, [RhCl(C8H12)(C5H12N2S)], N,N′-diethyl­thio­urea acts as a monodenate S-donor ligand. The rhodium(I) coordination sphere is completed by the Cl atom and the COD [= 1,5-cyclo­octa­diene] ligand inter­acting through the π-electrons of the double bonds. If the midpoints of these two bonds are taken into account, the Rh atom exhibits a distorted square-planar coordination. The syn conformation of the N,N′-diethyl­thio­urea ligand with respect to the Cl atom is stabilized by an intra­molecular N—H⋯Cl hydrogen bond. A weak inter­molecular N—H⋯Cl inter­action links mol­ecules along the a axis.

Assessment of intermolecular N–H…F and N–H…Cl hydrogen bonding in stabilising hetero- and homodimers in solution

“…1 H NMR (400 MHz, CDCl 3 ): d 8.51 (d, J ¼ 8.9 Hz, 2H), 8.07 (s, 2H), 7.72 (d, J ¼ 9.0 Hz, 2H), 2.50 (t, J ¼ 7.5 Hz, 2H), 1.85 -1.72 (m, 2H), 1.49 -1.23 (m, 8H), 0.89 (t, J ¼ 6.9 Hz, 3H). 13 …”

“…1 H NMR (400 MHz, CDCl 3 ): d 10.06 (s, 1H), 8.45 (d, J ¼ 8.9 Hz, 1H), 7.60 (d, J ¼ 8.9 Hz, 1H), 7.51 (d, J ¼ 8.7 Hz, 1H), 6.94 (d, J ¼ 8.7 Hz, 1H), 4.52 (s, 2H), 3.24 (s, 2H), 2.30 (d, J ¼ 7.1 Hz, 4H), 1.86 (dt, J 1 ¼ 13.4 Hz, J 2 ¼ 6.7 Hz, 2H), 0.99 (d, J ¼ 6.6 Hz, 12H). 13 …”

“…Given the increasing importance of weak hydrogen bonds in crystal engineering (10), chemical biology and drug design (11), we became interested in exploiting if intermolecular NZH· · ·F and NZH· · ·Cl hydrogen bonds can enhance the stability of dimeric supramolecules in solution. To the best of our knowledge, no studies were reported to assess the contribution of these two intermolecular hydrogen bonds in stabilising supramolecular systems, even though they have been proposed in solution and observed in crystal structures (12,13). In this paper, we describe the evaluation of the stability of a series of new heterodimers in organic solvents which reveals that both NZH· · ·F and NZH· · ·Cl intermolecular hydrogen bonds exist in solution and stabilise the heterodimers to a measurable extent.…”