Abstract
I) (N(C2Hs)4)(UO2(N 3)3) , M,=526.34, orthorhombic, P2~2121, a = 7.768 (4), b = 12.047 (3), c=18-016(6)/~, V=1686(2)A 3, Z=4, D x= 2.073 Mg m -3, 2(Mo Ka) = 0.71073 A, # = 9.15 mm -1, F(000) = 984, T = 294 K, R = 0.031 for 1184 independent reflections (I > 3tr(/)). A polymeric chain is formed between uranyl groups by sharing two of the three azide ligands, the third being coordinated only to one uranium. The uranyl group is thus pentacoordinated in its equatorial plane, leading to the classical pentagonal bipyramidal configuration. The tetraethylammonium ions are located between poly- meric chains. (II) (N(CH3)414((UO2)a(Na)80).H20, M,= 1476.9, monoclinic, P2Jn, a=21.893 (4), b = 22.586 (4), c= 9.070 (1)A, fl= 94.31 (1) °, V= 4472 (2) A 3, Z = 4, D x = 2.194 Mg m -a, 2(Mo Kct) = 0.71073 A, /t = 10.34 mm -1, F(000) = 2728, T= 294K, R =0.041 for 2063 independent reflections (1>3o(/)). The compound contains hexanuclear anions ((UO2)6(N3)I602 )8- and tetramethylammonium cations. The anion is formed by two triangular units (three UO 2 groups with a g3- bridging O 2- bonded to the three U atoms), linked by a symmetry centre. Six g2-N~- ligands are located on the edges of such triangles while two others are bonding two triangular units; the last eight azides included in the complex anion act as unshared ligands. Each uranium atom is then seven- coordinated in a nearly perfect pentagonal bipyramidal geometry.
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