María J. Vidarte

Synthesis, crystal structure and spectroscopic properties of diarganothallium (III) derivatives of 2,6-diacetyl-pyridine-monothiosemicarbazone

Abstract Dimethyl(2,6-diacetyl-pyridine-monothiosemicarbazonato)thallium(III), [TlMe2(L)], and Diphenyl-(2,6-diacetyl-pyridine-monothiosemicarbazonato)thallium(III) chloroform solvate, [TlPh2(L)],CHCl3 were prepared by reacting the corresponding diorganothallium(III) hydroxide with 2,6-diacetyl-pyridinemonothiosemicarbazone (HL). [TlMe2(L)] crystallizes in the triclinic space group P l (no. 2) with a = 7.064(3), b = 9.149(2), c = 12.377(2) A , α = 79.378(11), β = 74.92(2), γ = 82.75(2)°, Z = 2, R 1 = 0.0305, Rw 2 = 0.0673 . [TlPh2(L)].CHCl3 crystallizes in the monoclinic space group C2/c with a = 23.559(3), b = 13.582(2), c = 16.808(3) A , β = 106.04(1)°, Z = 8, R 1 = 0.0620, Rw 2 = 0.1155 . Both complexes consist of molecules in which the deprotonated ligand is S,N(3),N(4),O-bonded to the thallium atom [TlMe2(L)], Tl  S = 2.872(2), Tl  N (3) = 2.590(6), Tl  N (4) = 2.686(2), Tl  O = 2.883(6) A ; [TlPh2(L).CHC]3, Tl  S = 2.791(6), Tl  N (4) = 2.579(14), Tl  O = 2.86(1) A ]. A weak bond Tl…O′ [TlMe2(L)], 3.050(2) A; [TlPh2(L)].CHCl3, 3.42(1) A] between neighbouring molecules give rise to weakly bonded dimers. The 1H, 13C and 205Tl NMR spectra of both compounds in DMSO indicate that the bonding scheme observed in solid state is only partially retained in solution, where at least two isomers are observed.

THE CRYSTAL STRUCTURE OF DICHLORODIPHENYLBIPYRIDINE LEAD(IV), [PbPh2Cl2(bipy)]

Figure 1. ORTEP plot showing the molecular structure of [PbPh2Cl2(bipy)] (50% probability ellipsoids). Selected bond distances (Ä) and angles (°): Pb-C( l l ) 2.189(4), Pb-C(21) 2.208(5), Pb-N(l) 2.507(4), Pb-N(2) 2.515(4), Pb-Cl(l) 2.6355(12), Pb-Cl(2) 2.6583(12), C(11)-Pb-C(21) 176.86(17), C( l l ) -Pb-N(l) 88.09(15), C(21)-Pb-N(l) 90.88(15), C(ll)-Pb-N(2) 87.38(14), C(21)-Pb-N(2) 89.49(15), N(l)-Pb-N(2) 65.71(12), C(l l ) -Pb-Cl( l ) 90.46(12), C(21)-Pb-Cl(l) 92.48(13), N(l)-Pb-Cl(l) 88.27(9), C(ll)-Pb-Cl(2) 90.85(13), C(21)-Pb-Cl(2) 89.05(13), N(2)Pb-Cl(2) 93.32(10), Cl(l)-Pb-Cl(2) 112.68(4).

Dichlorobis(3,5-dimethylpyrazole-N2)methylphenyltin(IV)

The title compound, [SnCl(2)(CH(3))(C(6)H(5))(C(5)H(8)N(2))(2)], was obtained by reaction of dichloromethylphenyltin(IV) and 3, 5-dimethylpyrazole (dmpz) in chloroform, and was recrystallized from acetone. The structure consists of octahedral all-trans [SnMePhCl(2)(dmpz)(2)] molecules, with the Sn atom coordinated to two C [Sn-C 2.127 (5) and 2.135 (4) A], two Cl [Sn-Cl 2.5753 (8) A] and two N atoms [Sn-N 2.357 (3) A]. The dmpz ligands, bound to the metal through their unprotonated N atoms, form weak intra- and intermolecular hydrogen bonds with the Cl ligands via their NH groups, giving rise to a polymeric chain along the c axis.

THE CRYSTAL STRUCTURE OF DICHLORODIPHENYLPHENANTHROLINELEAD(IV), [PbPh2Cl2(phen)]

Figure 1. ORTEP plot showing the molecular structure of [PbPhiC^phen)] (for clarity only one molecule is represented). Ranges of selected bond lengths (A) and angles (°) in the four independent molecules: Pb-C(l) 2.182(8)-2.200(8)? Pb-C(7) 2.184(8)-2.199(9), Pb-N(l) 2.512(8)2.552(8), Pb-N(2) 2.507(8)-2.568(7), Pb-Cl(l) 2.603(3)-2.658(2), Pb-Cl(2) 2.608(2)-2.641(2), C(l)-Pb-C(7) 169.7(3)-174.5(3), N(l)-Pb-N(2) 64.6(2)-66.3(3), CI(l)-Pb-Cl(2) 106.51(8)110.65(10).