ISOSTRUCTURAL TRIGONAL-BIPYRAMIDAL CU(11) AND NOMINALLY 1-PERCENT CU(11)-DOPED ZN(11) COMPLEXES WITH N-5 LIGATION

[Cu(C6H18N4)(C10H10N2)](ClO4)2, (1-benzylimidazole)[N,N-bis(2-aminoeth yl)- 1,2-ethane-diamine]copper(II) diperchlorate (1), M(r) = 566.88, m onoclinic, P2(1)/c, a = 10.549 (1), b = 9.2465 (9), c = 25.256 (2) ang strom, beta = 101.42 (1)-degrees, V = 2415 (1) angstrom3, Z = 4, D(m) = 1.54 (1), D(x) = 1.559 Mg m -3, lambda(Mo Ka) = 0.71073 angstrom, mu = 1.18 mm-1, F(000) = 1172. T = 296 (1) K, R = 0.048, wR = 0.069 for 3063 reflections. [Zn0.99Cu0.01(C6H18N4)(C10H10N2)](ClO4)2, 1% Cu(II)- doped [N,N-bis(2-amino-ethyl)-1,2-ethanediamine]zinc(II) diperchlorate (2), M(r) = 568.72, monoclinic, P2(1)/c, a = 10.708 (1), b = 9.229 (2 ), c = 25.205 (2) angstrom, beta = 101.867 (8)-degrees, V = 2438 (1) a ngstrom3, Z = 4, D(m) = 1.54 (1), D(x) = 1.549, lambda(Mo Kalpha) = 0. 71073 angstrom, mu = 1.30 mm-1, F(000) = 1176, T = 295 (1) K, R = 0.04 1, wR = 0.055 for 3282 reflections. The isostructural distorted trigon al-bipyramidal MN5 cations are separated by perchlorate anions. Equato rial M-N distances are similar in both cations [range 2.083 (3) to 2.1 05 (3) angstrom for (1); 2.073 (3) to 2.084 (3) angstrom for (2)]. In contrast, the axial M-N distances differ substantially [2.043 (3) and 1.971 (3) angstrom for (1); 2.255 (4) and 2.054 (3) angstrom for (2)]. Axial contraction in the copper complex (1) is consistent with a d(z) 2 ground state.