Polysulfonylamine .75. Complexation of a dimeric diorganotin(IV)-amide hydroxide with neutral ligands: Synthesis of [Me(2)Sn(mu-OH){N(SO(2)Me)(2)}(L)](2) (L=HMPA, Ph(3)PO, Ph(3)AsO) and crystal structures of complexes with L=HMPA and Ph(3)PO

A new synthesis of the known dimeric hydroxide [Me(2)Sn(mu-OH)(NMs(2))](2) (1; Ms = MeSO(2)) in good yield involved treating Me(2)SnO with HNMs(2). The reaction of 1 with two equivalents of the appropriate uncharged ligands in refluxing MeCN afforded the novel complexes [Me(2)Sn(mu-OH)(NMs(2))(hmpa)](2) (2), [Me(2)Sn(mu-OH)(NMs(2))(OPPh(3))](2) . 2MeCN (3) and [Me(2)Sn(mu-OH)(NMs(2))(OAsPh(3))](2), . 2MeCN. The crystal structures of 2 (monoclinic, space group P2(1)/c) and 3 (triclinic, P (1) over bar) were determined by low-temperature X-ray diffraction and compared with the known structure of 1. The centrosymmetric molecules of 2 and 3 (MeCN in lattice cavities) display a four-membered [SnO(H)](2) ring and hepta-coordinated tin atoms in a distorted pentagonal-bipyramidal environment. The apical positions are occupied by the methyl groups (C-Sn-C 151.1 degrees for 2, 159.9 degrees for 3). The approximately co-planar equatorial positions are occupied by the OH oxygen atoms (Sn-O 206.1 and 213.2 pm for 2,208.5 and 212.1 pm for 3), the donor atom of the OPZ(3) ligand (Sn-O 222.5 pm for 2, 232.6 pm for 3), and the nitrogen and one oxygen atom of the Ms(2)N(-) chelating ligand (Sn-N/Sn-O 289.3/308.7 pm for 2, 267.3/297.9 pm for 3). The values of the endocyclic O-Sn-O' and Sn-O-Sn' angles are 70.0 and 110.0 degrees for 2, 71.2 and 108.8 degrees for 3. In both molecules, the OH groups are hydrogen bonded to an oxygen atom of the Ms(2)N(-) ligands.