Reactions of [Zn{S2P(OR)2}2] with nitrogen bases and the single-crystal X-ray structures of [Zn{S2P(OPri)2}2]·H2NCH2CH2NH2 and [Zn{S2P(OPri)2}2]·NC5H5

Abstract

The adducts [Zn{S₂P(OR)₂}₂]·L [L = H₂NCH₂CH₂NH₂(en), MeHNCH₂CH₂NHMe (dmen), Me₂NCH₂CH₂NMe₂(tmen), 2,2′-bipyridyl,1,10-phenanthroline,2,9-dimethyl-1,10-phenanthroline, or pyridine; R = Et or Prⁱ] and the ionic compounds [Zn(en)₃][S₂P(OR)₂]₂ and [Zn(dmen)][S₂P(OR)₂]₂ have been isolated by treating [Zn{S₂P(OR)₂}₂] with L in the appropriate stoicheiometry. The crystal structures of [Zn{S₂P(OPrⁱ)₂}₂]·en (1) and [Zn{S₂P(OPrⁱ)₂}₂]·py (2) have been determined: (1), monoclinic, space group P2₁/c, with a= 13.402(8), b= 16.470(9), c= 12.294(7)Å, β= 99.0(1)°, and Z= 4; (2), monoclinic, space group P2₁/n with a= 21.28(1), b= 8.35(1), c= 16.27(1)Å, β= 99.5(1)°, and Z= 4. Diffractometer data were collected for both crystals [of which 1 340 (1) and 1 940 (2) were above background] and both structures were refined to R 0.073. In (1) the zinc atom is four-co-ordinate forming two Zn–N bonds [2.077(13) and 1.922(16)Å] to the bidentate ethylenediamine molecule and two Zn–S bonds [2.292(5) and 2.331(5)Å] to the monodentate dithiophosphate ligands. In (2) the zinc atom is five-co-ordinate being bonded to pyridine [Zn–N 2.015(12)Å], and to two bidentate dithiophosphate ligands. One ligand is bonded to the metal more symmetrically [Zn–S 2.502(4) and 2.358(4)Å] than the other [Zn–S 2.269(4) and 3.032(4)Å]. The ³¹P n.m.r. spectra of a number of these compounds have been examined. A correlation between the positions of the resonances and the mode of bonding of the [S₂P(OR)₂]^– groups to the metal has been established.