The novel compounds PbCl2.(SCH2CH2NH3) (1), Pb(SCH2CH2NH2)(2).2PbCl(SCH2CH2NH2) (2), and Pb(SCH2CH2NH2)(2) (3) were synthesized by reaction of PbO or PbCl2 with [HSCH2CH2NH3]Cl and NaOH, and were characterized by elemental analysis, IR-, and UV/vis-spectroscopy. Single-crystal X-ray diffraction revealed different coordination modes for the two Pb atoms in 2. The Pb atom in the Pb(SCH2CH2NH2)(2) unit forms two covalent Pb-S and two intramolecular dative Pb...N bonds, leading to a pseudo trigonal bipyramidal configuration with a stereochemically active lone pair. The Pb atom in the PbCl(SCH2CH2NH2) unit, the first moiety structurally characterized of the PbCl(SR) type (R = organic group), forms covalent Pb-Cl and Pb-S bonds, an intramolecular dative Pb...N bond, and two intermolecular Pb...S contacts, giving a pseudo octahedral configuration with a stereochemically active lone pair as well. Despite the Pb(SCH2CH2NH2)(2) moiety exhibiting C-2 symmetry in 2, and C-1 symmetry in 3, its structural parameters are rather similar in the two compounds. The influence of the Pb...N bond on molecular structure and thermodynamic stability were estimated by means of quantum chemical ab initio methods. Although an analysis of the wave function in terms of natural bond orbitals (NBO) revealed that n(N) and n(p)(S) compete for the empty p-orbital of the Pb-II atom, the sigma-type n(N)-6p(Pb) interaction is stronger than the pi-type n(p)(S)-6p(Pb) interaction and hence determines the conformation of the compounds.