Abstract

Room-temperature single-crystal X-ray studies are recorded for 4-nitrophenoxide (4-np¯) salts, variously hydrated, of the Group 1 metals, M(4-np^-).χH₂O, for M = Li, Na (redetermination), K (already recorded), Rb and Cs. Li(4-np).3H₂O is monoclinic, space group Pc, a 11·359(3), b 7·518(3), c 10·855(4) Å, β 90·56(3)°, Z = 4; conventional R on |F| was 0·056 for N_o 2098 independent `observed" (I > 3σ(I)) reflections. Na(4-np).2H2O is orthorhombic, Ima2, a 6·888(6), b 19·699(8), c 6·436(8) Å, Z = 4, R 0·031 for N_o 664. Rb(4-np).H₂O is orthorhombic, Pbca, a 11·82(3), b 19·724(7), c 7·199(1) Å, Z = 8, R 0·036 for N_o 1465. Cs(4-np).3H₂O is monoclinic, P 2₁/c, a 13·337(2), b 12·770(5), c 6·311(2) Å, β 100·56(3)°, Z = 4, R 0·031 for N_o 2636. Whereas the lithium compound is essentially a discrete mononuclear neutral molecular complex [(4-np-O)Li(OH₂)₃] with four-coordinate lithium, the other compounds exhibit two- or three-dimensional sheet polymer structures with 4-nitrophenoxide moieties providing O-C₆H₄-NO₂ head-tail connecting motifs between successive metal atoms.