Structural characterization of heterometallic platinum complexes with non-transition metals. Part IV. Heteropenta- and heterohexanuclear complexes

There are 18 heteropentanuclear Pt4M (×5), Pt3M2 (×3), Pt2M3 (×2), PtM4 (×5), Pt3HgRe, Pt2Ge2Hg, and Pt2Fe2Tl and 14 heterohexanuclear Pt4M2 (×5), Pt2M4 (×5), PtM5 (×2), Pt2Co2Na2, and PtOs3Sn2 (M=non-transition metal) complexes for which structural data are available and were classified and analyzed. These complexes crystallized in the following crystal classes: monoclinic (48.5%)>triclinic (31%)>orthorhombic (10%)>cubic, trigonal and tetragonal each (3.5%). The inner coordination spheres about Pt atoms are three- (Y shape), four- (square planar), five- (trigonal bipyramidal), six- (pseudo-octahedral), and seven-coordinated (4+3), whereas the former (three) and the last one (seven coordinated) are rarities. The square planar by far prevails [Pt(II) and pseudo-octahedral (Pt(IV)]. The M atoms are two- (Tl), three- (Hg), four- (tetrahedral) (Li, Ge, Sn, In, Sb, Zn, Cd, and Hg), six- (Na), and eight- (Tl) coordinated. The mean Pt-M bond distance elongated in the order 2.435 Å (M=Ge)<2.440 Å (In)<2.530 Å (Sb)<2.640 Å (Li)<2.680 Å (Pt)<2.708 Å (Sn)<2.763 Å (Hg). The most common bonding atom is μ3-S, and the mean M-μ3S bond distance elongated in the order 2.37 Å (Pt)<2.385 Å (Zn)<2.555 Å (Cd)<2.62 Å (Hg)