Redetermination of (D-penicillaminato)lead(II)

Abstract

In the title coordination polymer, [Pb(C5H9NO2S)]n {systematic name: catena-poly[(μ-2-amino-3-methyl-3-sulfido­butano­ato)lead(II)]}, the d-penicillaminate ligand coordin­ates to the metal ion in an N,S,O-tridentate mode. The S atom acts as a bridge to two neighbouring PbII ions, thereby forming a double thiol­ate chain. Moreover, the coordinating carboxyl­ate O atom forms bridges to the PbII ions in the adjacent chain. The overall coordination sphere of the PbII ion can be described as a highly distorted penta­gonal bipyramid with a void in the equatorial plane between the long Pb—S bonds probably occupied by the stereochemically active inert electron pair. The amino H atoms form N—H⋯S and N—H⋯O hydrogen bonds, resulting in a cluster of four complex units, giving rise to an R 4 4(16) ring lying in the ab plane. The crystal structure of the title compound has been reported previously [Freeman et al. (1974 ▶). Chem. Soc. Chem. Commun. pp. 366–367] but the atomic coordinates have not been deposited in the Cambridge Structural Database (refcode DPENPB). Additional details of the hydrogen bonding are presented here.

Lead(II) Complex Formation with Glutathione

“…There are also longer interactions in the coordination sphere with two additional Pb-S distances to the thiolate sulfur at 3.091 and 3.464 Å giving rise to double bridges in an infinite chain structure with Pb···Pb distances of 4.363 Å, and with one bridging Pb-O distance at 2.720 Å between the chains (with Pb···Pb distances of 4.66 Å). 64 Least squares curve-fitting of the k 3 -weighted EXAFS oscillation of PbPen over the k -range 2.6 – 9.5 Å -1 was performed with models derived from its crystal structure. A satisfactory fit was obtained with two Pb(N/O) and one Pb-S paths at 2.42 ± 0.04 and 2.68 ± 0.04 Å, respectively, which are slightly (~0.03 Å) shorter than the corresponding distances in the crystal structure.…”

“…61, 62 The crystal structure of the polymeric d -penicillaminato lead(II) complex PbPen, 63, 64 which has both short (2.714 Å) and long Pb-S bonds (3.091 Å and 3.464 Å), Pb-(O/N) bonds (2.444 Å, 2.451 Å and 2.720 Å) as well as thiolate bridged Pb···Pb interactions (4.363 and 4.663 Å), was used in the ATOMS program. Least-squares curve-fittings of the χ( k ) model function to the k 3 -weighted experimental EXAFS data for solutions A – E and samples A* – E* were performed to refine the structural parameters R, σ 2 , and in some cases also the coordination number N for each type of interaction.…”

Lead(II) Binding to the Chelating Agent d-Penicillamine in Aqueous Solution

“…The precipitate was filtered, washed with water, dried under vacuum, and identified by CHN elemental analyses and unit-cell dimensions. 32 , 33 …”

“…The same 1:1 compound crystallizes over a wide pH range from ∼2 to ∼11, even at high ligand:metal ratios. 32 , 33 The stability of this compound is probably due to the weak interactions between neighboring complexes in the PbPen crystal. 32 No attempt has been made previously to structurally characterize the Pb(II) complexes with penicillamine in solution.…”

The Chelating Behaviour of 3‐(4‐X‐Phenyl)‐2‐sulfanylpropenoic Acids with the PbII Ion – Relevance of the Lone Electron Pair in the Supramolecular Structures of the 2:1 Complexes

“…[7] In [Pb(PEN)] (PEN = d-penicillaminato), the ligand is N,O,S tridentate in the solid state. [8] In turn, the meso-2,3-dimercaptosuccinato ligand (m-DMSA 4-) binds Pb II ions through one O atom and two S atoms in aqueous solution. [9] Nevertheless, this variety of coordination modes is probably consistent with the behaviour of Pb II ions as a borderline acid according to the hard and soft acids and bases (HSAB) principle of Pearson.…”