Abstract: | Polysulfonylamines. CII. New Coordination Compounds Derived from Triorganyltin(IV) Dimesylamides and Uncharged Ligands: Mononuclear and Polynuclear Complexes with Molecular or Ionic Crystal Structures The purpose of this report is to draw attention to the remarkable versatility of the dimesylamides R3SnA [A– = (MeSO2)2N–; R = Me ( 1 a ) or Ph ( 1 b )] as precursors for pentacoordinate triorganyltin(IV) complexes belonging to four distinct structural types. Representative complexes were prepared by treating 1 a or 1 b in the appropriate molar ratios with unidentate thiourea or urea-type ligands or with the bidentate ligand [Ph2P(O)CH2]2 (DPPOE). The following compounds were characterized by X-ray analysis: [Me3Sn(A)(thiourea)] ( 2 a ; monoclinic, space group P21/n), [Ph3Sn(A)(tetramethylthiourea)] ( 2 b ; monoclinic, P21, two independent formula units), [Me3Sn(1-methylurea)2]+ · A– ( 3 a ; monoclinic, P21/c), [Ph3Sn(1,1-dimethylurea)2]+ · A– ( 3 c ; triclinic, P1), [{Ph3Sn(A)}2(μ-dppoe)] ( 4 ; triclinic, P1), [Ph3Sn(μ-dppoe)]nn+ · n A– · n MeCN ( 5 ; monoclinic, P21/c). The lattices of 2 a , 2 b and 4 contain discrete uncharged formula units which are mononuclear for 2 a and 2 b or dinuclear for 4 , whereas 3 a , 3 c and 5 have ionic structures featuring mononuclear cations for 3 a and 3 c or an infinite linear-polymeric cation for 5 . In all the structures, the tin atoms adopt trigonal-bipyramidal geometries, the apical positions being occupied in 2 a and 2 b by the S atom of the thiourea and one O atom of A–, in 3 a and 3 c by the O atoms of two urea-type ligands, in 4 by an O atom of the bridging DPPOE molecule and one O atom of A–, and in 5 by two phosphoryl O atoms from different bridging DPPOE ligands. In the structures of 2 a , 3 a and 3 c , the (thio)urea NH functions are connected to A– via intermolecular or interionic N–H … O and N–H … N hydrogen bonds. Crystals of [{Me3Sn(bipyH+ … A–)}2(μ-bipy)]2+ · 2 A– ( 6 ; monoclinic, C2/c) formed adventitiously in a reaction mixture containing 1 a and 4,4′-bipyridine. The rod-like supramolecular cation of 6 (length ca. 4 nm) is built up from two Me3Sn+ units bridged through bipy and unidentally coordinated by a monoprotonated bipy (= bipyH+), resulting in a trigonal-bipyramidal geometry around tin (N atoms apical); each of the terminal bipyH+ ligands forms an +N–H … N– hydrogen bond with one A–. |