Polysulfonylamine: XXIX. Synthese von Organothallium(III)-dimesylamiden sowie Röntgenstrukturanalysen von (Me 3SiCH 2) 2TIN(SO 2Me) 2 und (Me 3SiCH 2) 2TIN(SO 2Me) 2·H 2O

Abstract

The compounds R 2TlN(SO 2Me) 2 (R = Me 3SiCH 2 ( 2), R 2TICI with AgN(SO 2Me) 2. The reaction of PhTI(O 2CCF 3) 2 with Me 3SiN(SO 2Me) 2 afforded PhTl[N(SO 2Me) 2] 2 ( 5). Further, the (1/1) addition compounds of 2 with H 2O ( 2a), 3 with 18-crown-6, 4 with DMF, and 5 with pyridine were isolated and characterized. 2 crystallizes in the monoclinic space group P2 1/ n with a = 1026.4(4), b = 1118.0(3), c = 1798.3(7) pm, β = 102.67(3)°, U = 2.0133(12) nm 3, Z = 4. The thallium atoms are linked by two (NSO) bridges orginating from different (MeSO 2) 2N − ligands to form eight-membered [TlNSO] 2 rings (TlN 260.9(3) pm, TlO 281.3(3) pm, CTlC 175.9(2)°). The MeSO 2 groups exocyclic to the eight-membered rings act as (SO) bridges between nitrogen and thallium atoms of neighbouring rings (TlO 279.9(3) pm). Thus, layers consisting of centrosymmetric eight-membered [TlNSO] 2 rings and centrosymmetric twenty-membered [TlNSOTl-OSNSO] 2 rings are formed. The coordination polyhedron of the thallium atoms is a moderately distorted trigonal bipyramid with the two carbon atoms as apices. This structure is compared with the known crystal structure of the corresponding indium compound. The hydrate 2a crystallizes in the triclinic space group P 1 with a = 742.7(2), b = 1003.8(2), c =1446.5(3) pm, α = 92.33(2), β = 97.98(2), γ = 92.40(2)°, U = 1.0659(4) nm 3, Z = 2. Its structure consists of polymeric srands, in which [R 2Tl(OH 2)] units are connected by (NSO) 1 bridges (Tl-N 272.3(3), TlO 1 277.5(2), Tl-OH 2 251.2(2) pm, CTlC 172.3(1)°). Additionally, at each thallium atom a four-membered [TlNSO 2] chelate rings is formed through a weaker interaction with the oxygen atom O 2 geminal to the bridging oxygen O 1 (Tl⋯O 2 288.1(3) pm. The thallium atoms in 2a display irregular (C 2NO 3) hexacoordination.