RESUMO
The face-sharing bioctahedral molybdenum(VI) oxide fluoride anion [Mo2O6F3]3- has been isolated in the new compound [Cu(3-apy)4]3(Mo2O6F3)2 (3-apy = 3-aminopyridine) and has been characterized by experimental and computational techniques. Single-crystal X-ray diffraction studies show that the structure of the [Mo2O6F3]3- anion resembles two distorted face-sharing octahedra, each with three short terminal metal-ligand bonds and three long metal-ligand-metal bridging interactions. Aspects of the electronic structure, as well as geometric comparisons of the bond lengths and angles in [Mo2O6F3]3- with those in the similarly distorted [MoO3F3]3- anion, suggest that the six terminal ligand positions of the confacial bioctahedra are occupied exclusively by oxide ligands and that the three bridging sites are occupied by fluorides. Crystal data for [Cu(3-apy)4]3(Mo2O6F3)2: trigonal space group R3 (No. 148) with hexagonal axes of a = 13.881(1) A and c = 31.783(3) A (Z = 3).
RESUMO
Out-of-center "primary" electronic distortions are inherent to the oxide fluoride anions of the early d0 transition metals. In the [NbOF5]2- anion, the Nb5+ moves from the center of the octahedron toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond. The combined results of single-crystal X-ray diffraction and electronic structure calculations indicate that the primary distortion of the [NbOF5]2- anion is affected by the coordination environment that is created by the three-dimensional extended structure. The formation of bonds between an M(L)4(2+) (M = Cd2+, Cu2+; L = 3-aminopyridine, 4-aminopyridine) cation and the oxide and/or trans-fluoride ligands of the [NbOF5]2- anion weakens the pi component of the Nb=O bond. At the same time, hydrogen bond interactions between the equatorial fluorides and the aminopyridine groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF5]2- anion. These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF5]2- anion are illustrated in the structures of three new niobium oxide fluoride phases, [4-apyH]2[Cu(4-apy)4(NbOF5)2] (4-apy = 4-aminopyridine), Cd(3-apy)4NbOF5 (3-apy = 3-aminopyridine), and Cu(3-apy)4NbOF5, that were synthesized and characterized using X-ray diffraction. Crystal data for [4-apyH]2[Cu(4-apy)4(NbOF5)2]: tetragonal, space group /4(1)/ acd (No. 142), with a = 20.8745(8) A, c = 17.2929(9) A, and Z= 8. Cd(3-apy)4NbOF5: tetragonal, space group P4(3) (No. 78), with a = 8.4034(4) A, c = 34.933(3) A, and Z = 4. Cu(3-apy)4NbOF5: monoclinic, space group P2(1)/n (No. 14), with a = 8.822(1) A, b = 16.385(3) A, c = 8.902(1) A, beta = 109.270(3) degrees, and Z = 2.
RESUMO
We describe a new chiral tubule-forming lipid in which the C-O-P phosphoryl linkage of the archetypal tubule-forming molecule, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine, "DC(8,9)PC", is replaced by a C-P linkage. Tubule formation with this phosphonate analogue proceeds under the same mild conditions as with DC(8,9)PC and produces similar yields, but synchrotron small-angle X-ray scattering, atomic force microscopy, and optical microscopy show the new tubules to have diameters 1.94 times as great, to be significantly shorter, and to be thinner-walled. A significant portion of the enantiomerically pure chiral phosphonate precipitate is in the form of stable open helices, and these helices are divided almost evenly between left- and right-handed members.