PENTACOORDINATED MOLECULES .63. DISTORTION COORDINATE FOR NONRIGID 5-COORDINATED GERMANIUM - SYNTHESIS AND MOLECULAR-STRUCTURE OF SPIROCYCLIC ANIONIC METHYLGERMANATES VARYING IN RING COMPOSITION (REPRINTED FROM INORG CHEM, VOL 25, PG 600, 1986)

Reaction of an organogermanium trichloride with a catechol or thiocate chol derivative in the presence of triethylamine, followed by a metath etical exchange, led to the isolation of the Et(4)N(+) salts of the fi ve-coordinated spirocyclic germanates [(C6H4O2)(2)GeMe][Et(4)N] (1), [ (MeC(6)H(3)S(2))(2)GeMe][Et(4)N] (2), [(C6Cl4O2)(2)GeMe][Et(4)N] (3), and [(C7H6S2)(2)GePh][Et(4)N] (4). X-ray analysis showed that the geom etry of 1 is close to a trigonal bipyramid, 2 is displaced about one-t hird toward the rectangular pyramid, and 3 is close to the rectangular pyramid. The low structural displacement for 1 is attributed to latti ce effects. The structures of 2 and 3 are discussed in terms of ligand effects, the insertion of ring sulfur atoms in 2, and the electron-wi thdrawing effect of chlorine ring atoms in 3, The structures of these and related anionic germanates follow the local C-2v constraint of the Berry pseudorotational coordinate with a trans basal angle, theta, fo r the ''limiting'' RP of 150.1 degrees, similar to that for other main -group elements in the five-coordinated state. 1 crystallizes in the t etragonal space group P4(1)2(1)2 with a = b = 9.834 (4) Angstrom, c = 22.275 (7) Angstrom, and Z = 4. 2 crystallizes in the orthorhombic spa ce group Pbca with a = 15.344 (2) Angstrom, b = 19.920 (5) Angstrom, c = 17.017 (5) Angstrom, and Z = 8. 3 crystallizes in the monoclinic sp ace group P2(1)/c with a = 10.011 (2) Angstrom, b = 16.793 (3) Angstro m, c = 16.386 (5) Angstrom, beta = 93.78 (2)degrees, and Z = 4. The fi nal conventional unweighted agreement factors were 0.045 (1), 0.065 (2 ), and 0.049 (3).