Synthesis and crystal structures of [Na{Ph2P(S)NP(S)Ph-2}(L)] (where L = triglyme or tetraglyme); two air stable complexes containing six-membered S-P-N-P-S-Na rings

The title complexes [Na{Ph2P(S)NP(S)Ph-2}(L)] (where L = triglyme 1, or tetraglyme 2) were prepared in an aqueous/methanolic mixture by reaction of the sodium salt of Ph2P(S)NHP(S)Ph-2 with the respective glyme ligand. Compound 1 crystallizes in the orthorhombic space group Pbca with a = 19.526(5), b = 16.102(4), c = 21.168(5) Angstrom, and Z = 8. The complex is monomeric with all four oxygen atoms of the glyme moiety coordinated to the Na+ cation. The S atoms of the Ph2P(S)NP(S)Ph-2 anion are bound in a symmetrical fashion to the sodium cation. Compound 2 crystallizes in the triclinic space group with a = 10.747 (3), b = 11.541(3), c = 14.932(4) Angstrom, alpha = 81.28(3), beta = 81.96(4), gamma = 74.41(3)degrees and Z = 2. This structure was also found to be monomeric, with the additional oxygen of tetraglyme giving a seven coordinate rather than six coordinate Na+ cation.