Octahedral Tilting in MM′X4 Metal-Oxide Organic Layer Structures

Vougo-Zanda, M. ; Anokhina, E.V. ; Duhovic, S. ; Liu, L. ; Wang, X. ; Oloba-whenu, O.A. ; Albright, T.A. ; Jacobson, A.J. (2008-04-29)

Staff publication


Three metal-oxide organic frameworks have been synthesized and characterized: vanadium 1,4-benzenedicarboxylate, V2O2F0.6(OH)1.4(BDC)·0.4H2O (1); indium 1,4-benzenedicarboxylate, In2F2.2(OH)1.8(BDC)·1.6H2O (2); and aluminum 1,4-benzenedicarboxylate Al2F3(OH)(BDC) (3). The three-dimensional structures of 1, 2, and 3 have the same framework topology as the previously reported vanadium (III) 1,4-benzenedicarboxylate, VIII2(OH)2F2(BDC). The frameworks consist of inorganic layers constructed from corner sharing ML6 octahedra (M = V, In, Al and L = OH, F) linked by BDC ligands. The structures are related to a general class of perovskite-related layer structures with composition MM′X4. The layers show characteristic distortions that can be related to tilting of the ML6 octahedra. In particular the structure of 1 consists of O−V distances that strongly alternate along the b axis. The electronic consequences of this distortion then create a tilting of the 1,4-benzenedicarboxylate ligand about the a axis. Crystal data: 1, orthorhombic, space group Pmna, a = 7.101(2) Å, b = 3.8416(11) Å, c = 20.570(6) Å; 2, orthorhombic, space group Cmcm, a = 7.490(4) Å, b = 21.803(1) Å, c = 8.154(4) Å; 3, monoclinic, space group P21/m, a = 10.7569(8) Å, b = 6.7615(3) Å, c = 7.1291(3) Å, β = 76.02(1)°.