DIFFERENT COORDINATION BEHAVIOR OF 1,2-DIAMINOETHANE (EN) AND TETRACYANONICKELATE(II) UPON ACCOMMODATION OF POLAR GUEST MOLECULES IN THEIR METAL-COMPLEX HOSTS - CRYSTAL-STRUCTURES OF [M(EN)2NI(CN)4].2PHNH2 (M=NI, CU, ZN OR CD) AND [(CD(EN))2(EN)(NI(CN)4)2].4PHOH

The single-crystal structures have been determined for aniline and phenol clathrates. Aniline clathrates [M(en)2Ni(CN)4].2PhNH2 (M = Ni, Cu. Zn or Cd; en = 1,2-diaminoethane) are isomorphous, having monoclinic space group P2(1)/c (Z = 2). The unit cell parameters a, b, c and beta, and R index for the reflections used are: M = Ni, 9.452(3), 10.125(3), 13.440(3) angstrom and 107.27(2)-degrees, 0.0443 for 1806; for M = Cu, 9.547(4), 10.621 (5), 12.746(3) angstrom and 107.89(2)-degrees, 0.0635 for 1861; for M = Zn, 9.550(3), 10.407(2), 13.026(2) angstrom and 107.50(l)-degrees, 0.0513 for 1758; and for M = Cd, 9.924(2), 10.545(3), 12.51 0(l) angstrom and 107.63(1)-degrees, 0.0456 for 1829. The guest PhNH2 molecules are accommodated among [-M(en)2-NC-Ni(CN)2-CN-]n chains extending along the b axis. The bis(en)-chelated M atoms are linked with trans-di-mu-cyano-dicyanonickelate(II) moieties alternately, and adopt an elongated octahedral configuration along the chain. The phenol clathrate [{Cd(en)}2(en){Ni(CN)4}2].4PhOH belongs to the triclinic system, space group P1BAR, with a = 11.868(l), b = 13.030(l), c = 7.7113(6) angstrom, alpha = 105.956(7). beta = 94.951 (8), gamma = 91.584(9)-degrees, Z = 1 and R = 0.041 0 for 4095 reflections. Three kinds of crystallographically independent PhOH molecules are enclathrated in the three-dimensional host framework in which the en-chelated Cd atoms are linked with infinite [>Ni< (CN-Cd-NC-)2]n chains and Cd-NC-Ni(CN)2-CN-Cd and Cd-en-Cd bridges. Interhost, interguest and host-guest hydrogen-bond formation stabilize the whole crystal structures, which are compared with those of [M(en)2Ni(CN)4] complexes and the [Cd(en)Ni(CN)4].2C6H6 clathrate.