| dc.description.abstract | X-ray crystal structure studies using the multiple film equiinclination Weissenberg technique were completed on three classes of metal complexes. These include: (1) Copper(II) chloride complexes of substituted pyridine N-oxides, including the crystal and molecular structures of di-mu-(pyridine oxide)-bis(dichlorocopper(II)) and trans-dichlorodiaguobis(4-nitropyridine N-oxide)copper(II). Di-mu-(pyridine N-oxide) -bis (dichlorocopper (II)), [(C5H5NO)CuCl2]2, exists in the crystalline state as oxygen bridged dimers, with the N-oxide oxygen atom serving as the bridging atom. These dimers are, themselves, chlorine bridged together in the x direction forming infinite one dimensional chains. The crystal system is monoclinic, space group P2_1/b (c axis unique) with unit cell dimensions a= 5.884(5), b = 10.049 (5), c = 13.643(5) angstroms and Y = 104° 52(10)'. The coordination geometry about the copper ion is highly distorted square prismatic. The bond distances in the square prism are Cu-O, 1.979(11) and 2.036(11) angstroms and Cu-Cl, 2.206(5), 2.217(5) and 2.836(5) angstroms. The final conventional R factor for 1144 non-zero reflections was .084. Trans-dichlorodiaquobis(4-nitropyridine N-oxide) copper(II), (C5H4N2O3)2CuCl2 . 2H2O, crystallizes in the monoclinic space group P2_1/c (C 52 h) and has unit cell parameters a = 13.892(5), b = 5.556(2}, c = 11.341(5)11. and beta = 93° 50(10)'. The coordination geometry of the copper(II) ion is distorted octahedral with bond distances, Cu-Cl, 2.310(4)A; Cu-OH2, 1.99(2) angstroms and Cu-O_N-oxide, 2.69(2) angstroms. The molecules are held together in the crystal by an intricate system of hydrogen bonds and nitro group interactions. The final R for 764 observed reflections was .089. (2) Complexes containing dimethyl sulfoxide including the crystal and molecular structure of trans-dichlorobis (dimethyl sulfoxide)palladium(II). This complex crystallizes in space group P2_1/c of the monoclinic system and has unit cell parameters a = 6.48(1), b = 9.380(5), c = 9.562(4) angstroms and beta = 111° 49(10) '. The palladium atom has regular square planar geometry with the two chlorine atoms and the two dimethyl sulfoxide molecules bonded through the sulfur atom in the coordination sphere. Important bond lengths are Pd-Cl, 2.290(6), Pd-S, 2.291(5) and S-O, 1.46(2) angstroms. 1258 non-zero reflections was .118. The fin al R for \t 1\ (3) Eight coordinated rare earth complexes including the crystal and molecular structure of tris(acetylacetonato) (phenanthroline)europium(III). This complex crystallizes in space group P2_1/c and has unit cell dimensions a = 9.670(8), b = 21.339(5), c = 16.497(5) angstroms and beta = 116° 11(10)'. The coordination geometry of the complex is square antiprismatic with six Eu-o bonds of 2.39(4) angstroms and two Eu-N bonds of 2.67(6)A. The final R for 1776 observed data was .106. | |
