Organogermanium(IV), -tin(IV), and -lead(IV) esters of tetramethylenedithiocarbamic acid. The crystal and molecular structure of (tetramethylenedithiocarbamato)triphenyltin(IV) and -lead(IV)

Article abstract of DOI:10.1021/om00131a001

Eight organo group 14 esters of tetramethylenedithiocarbamic acid, R_nE(S₂CNC₄H₅)_4-n, where E = Ge, n = 3, and R = C₂H₅, E = Sn, n = 2, and R = CH₃, C₂H₅, n-C₄H₉, n-C₈H₁₇, and C₆H₅, E = Sn, n = 3, and R = n-C₄H₉ and C₆H₅ (I), and E = Pb, n = 3, and R = C₆H₅ (II), have been synthesized from the ammonium salt of the carbamic acid and the group 14 chloride in methanol or chloroform and characterized by elemental analyses, physical properties, and infrared, Raman, mass, and, for the tin compounds, ^119mSn M?ssbauer spectroscopies. The crystal and molecular structures of two isomorphous examples (tetramethylenedithiocarbamato)triphenyltin(IV) (I) and -lead(IV) (II) were determined. I: mp 170-173°C, C₂₃H₂₃NS₂Sn, crystallizes in the space group Pcab with a = 23.784 (12) ?, b = 16.408 (5) ?, c = 11.346 (4) ?, V = 4427.8 (30) ?³, α = β = γ = 90.0°, Z = 8, ρ_calcd = 1.488 g cm^-3. II: mp 166-168°C, C₂₃H₂₃NPbS₂, is isomorphous with a = 11.360 (3) ?, b = 23.593 (10) ?, c = 16.558 (4) ?, V = 4437.9 (25) ?³, Z = 8, ρ_calcd = 1.750 g cm^-3. The structures were solved from 2669 and 1720 data points, respectively, measured by ambient temperatures with monochromatic Mo Kα radiation (λ = 0.71069 ?), and refined to final R values of 5.3 (I) and 8.3% (II). The monodentate ligands give distorted T_d symmetry at each metal center with bonded d(M-S) of 2.468 (3) and 2.56 (1) ? vs. nonbonded d(M?S) of 3.106 (3) and 3.26 (1) ?, respectively, for I and II.