Date of Award

1982

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Abstract

The single crystal X-ray structures of eight compounds have been determined representing the Inorganic, Organometallic, and Organic Natural Product classes of molecules. Of the natural product compounds, two varieties of terpenes are represented; monoterpenes and sesquiterpenes. The monoterpene, 3-trans,6-trans-dihydroxymenthene (C(,10)H(,18)O(,2)), crystallizes in space group C2 with lattice constants a = 17.837(4), b = 7.113(7), c = 8.096(2) (ANGSTROM), (beta) = 102.17(6)(DEGREES). The structure is described by a disordered hydrogen bonding network extending in three dimensions throughout the crystal. Irazunolide (C(,17)H(,18)O(,5)), based on the eudesmane structure, is a sesquiterpene lactone crystallizing in space group P2(,1)2(,1)2(,1) with lattice constants a = 7.793(1), b = 9.394(1), c = 21.439(3) (ANGSTROM). Lactone fusion occurs at C6, C7 in a trans manner. Melrosin-A (C(,12)H(,28)O(,10)), one of the first examples of a biogentically correct cis, cis-germacranolide is found in space group P2(,1)2(,1)2(,1) with lattice constants a = 11.993(7), b = 3.138(4), c = 15.965(13) (ANGSTROM). The structures of two hydride bridged organometallic compounds are reported. They are: {Et(,4)N} {((mu)(,1)-H)((mu)(,2)-PPh(,2)(CH(,2))(,4)PPh(,2)){Mo(,2)(CO)(,8)} (1) and {Ph(,4)P} {((mu)(,1)-H)((mu)(,2)-PPh(,2)(CH(,2))PPh(,2))Mo(,2)(CO)(,8)} (2). The compound (1) crystallizes in space group P(')1 with the following lattice constants a = 8.760(2), b = 13.940(4), c = 19.686(4) (ANGSTROM), (alpha) = 105.75(2)(DEGREES), (beta) = 93.59(2)(DEGREES), (gamma) = 97.38(2)(DEGREES). For (2) the space group is P2(,1)/(,c) with lattice constants a = 1.886(6), b = 18.545(9), c = 20.156(6) (ANGSTROM), (beta) = 91.03(4)(DEGREES). The compounds contain doubly bridged molecular anions with the geometry of the metal-carbonyl framework determined primarily by the length the alkyl bridge. Two complete inorganic structures both tetracyanonickelates are reported. The compound Cs(,2)Ni(CN)(,4) (.) H(,2)O is found in the hexagonal space P6(,1) or P6(,5), with lattice constants a = b = 9.556(1), c = 19.290 (ANGSTROM). The compound SrNi(CN)(,4) (.) 5H(,2)O crystallizes in the monoclinic space group C2/m with lattice constants a = 10.3582(5), b = 15.3218(8), c = 7.2597(14) (ANGSTROM), (beta) = 98.665(9)(DEGREES). A structure of partial resolution, Na(,2)Ni(CN)(,4) (.) 3H(,2)O is also reported, with refinement failing to proceed below 19%. The problem with this structure is probably one of twinning as redefinition of the origin provided no improvement of the model. All of the structures display a pseudohexagonal arrangement of Ni(CN(,4))('2-) columns, packing in the crystal much like rods. The structural dependence on cation size, state of hydration, and choice of metal is still not well understood.

Pages

238

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