Synthesis and characterization of two new open-framework zinc phosphites [M(C6N4H18)][Zn-3(HPO3)(4)] (M = Ni, Co) with multi-directional intersecting 12-membered ring channels

摘要

Two new open-framework zinc phosphites, [M(C6N4H18)][Zn-3(HPO3)(4)] (M = Ni, Co), have been prepared under hydrothermal conditions. Single-crystal X-ray diffraction analysis shows that [Ni(C6N4H18)][ZN(3)(HPO3)(4)] (1) and [Co(C6N4H18)][Zn-3(HPO3)(4)] (2) are isostructural and both crystallize in the monoclinic space group C2/c with a = 15.325(3) angstrom, b = 9.792(2) angstrom, c = 14.514(3) angstrom, beta = 109.83(3)degrees, V = 2048.8(7) angstrom(3), Z = 4, R-1 = 0.0408 (I > 2 sigma(I)), and wR(2) = 0. 1104 (all data) for 1, and a = 15.277(2) angstrom, b = 9.8831(13) angstrom, c = 14.534(2) angstrom, beta = 109.328(2)degrees, V = 2070.7(5) angstrom(3), Z = 4, R-1 = 0.0380 (I > 2 sigma(I)), and wR(2) = 0.1093 (all data) for 2. The structures of 1 and 2 are built up from strictly alternating ZnO4 tetrahedra and HPO3 pseudo-pyramids linked through oxygen vertices to form the three-dimensional (3-D) open-frameworks with multi-directional intersecting 12-membered ring (12-MR) channels. The M(TETA) (M = Ni, Co) complexes self-assembled under hydrothermal system connect with the inorganic host via M-O-P linkages and interact with inorganic framework through weak H-bonds. The two compounds show intense photoluminescence upon photoexcitation at 235 nm. (c) 2005 Elsevier Inc. All rights reserved.