STRUCTURAL SYSTEMATICS OF 2 4-NITROPHENOXIDE COMPLEXES OF CLOSED-SHELL METAL-IONS - I - 2-NITROPHENOXIDES OF GROUP-1/

Room-temperature, single-crystal X-ray studies are recorded for the va riously hydrated Group 1 metal derivatives of 2-nitrophenol (2-npH = C 6H5NO3) A provisional determination is reported for Li(2-nD).1/2H(2)O, set as monoclinic, P2(1)/c, a 3.535(3), b 15.06(1), c 24.42(2) Angstr om, beta 91.7(1)degrees, Z = 8, conventional R on \F\ currently 0.18 f or N-o 875 'observed' (I > 3 sigma(I)) reflections. Na(2-np).H2O is mo noclinic, G2/c, a 34.23(2), b 3.624(4), c 35.48(2) Angstrom, beta 91.2 4(4)degrees, Z = 24, R 0.060 for N-o 1371. Rb(2-np).1/2H(2)O is monocl inic, C2/c (isomorphous with the previously determined potassium analo gue), a 25.269(9), b 5.381(5), c 12.010(3) Angstrom, beta 105.35(3)deg rees, Z = 8, R 0.046 for N-o 1380. Cs(2-np).1/2H(2)O is monoclinic, P2 (1)/n, a 7.648(3), b 26.19(1), c 8.713(6) Angstrom, beta 111.75(2)degr ees, Z = 8, R 0.061 for N-o 2347. All compounds except the lithium der ivative are two-dimensional polymeric sheets in which the aromatic rin gs project to either side of a core of metal atoms coordinated by a we b of 2-nitrophenoxide oxygen atoms in various bridging functionalities . The lithium compound is a novel 'stair' polymer with two crystallogr aphically independent lithium atoms at successive independent Li-O cro ssbars, the oxygen atoms of which are phenoxide-O of each of the two i ndependent ligands. The lithium atoms are alternately four- and five-c oordinate, the fourth coordination site of the first being occupied by the water molecule oxygen atom, while the fourth and fifth sites of t he second are occupied by the cis-2-nitro oxygen atoms of the two liga nds.