DISSIMILARITIES IN THOXYBENZOATO-O)-BIS(1,3-DIAMINOPROPANE-N,N')M(II)(M = CU, NI) COMPLEXES

The structures of trans-di thoxybenzoato-O)bis(1,3-diaminopropane-N,N' )Cu(II) (1) and the corresponding nickel(II) analogue (2) were determi ned by single-crystal X-ray diffraction methods. The compounds crystal lise in the monoclinic system, space group P2(1)/a (No. 14). 1: C22H32 CuN4O6, M-r = 514.25, a = 10.318(2), b = 9.620(2), c = 12.7296(14) Ang strom, beta = 103.910(14)degrees, V = 1226.5(4) Angstrom(3), Z = 2; 2: C22H32NiN4O6, M-r = 509.22, a = 10.100(2), b = 9.7220(11), c = 12.741 (5) Angstrom, beta = 99.86(3)degrees, V = 1232.5(5) Angstrom(3), Z=2. The compounds display crystal chemical isotypism. They are composed of discrete complex units connected by hydrogen bonds mediated by amino and carboxylate groups. Each complex unit consists of a central metal ion located at a centre of symmetry, six-membered chelate rings formed by 1,3-diaminopropane and axially coordinated para-methoxybenzoate an ions. The most notable difference between the nickel(II) and copper(II ) complex units is found in the axial M-O bond lengths, which are 2.14 4(2) and 2.497(4) Angstrom, respectively. The EHMO calculations assist ed by ESR and magnetic susceptibility measurements give the values of 7 and 1% for the d-s mixing to explain the axial elongation in 1 and 2 , respectively. Another difference is seen in the different skewness o f the chelate rings. Although the hydrogen bonding network is similar in both compounds, there are clear differences in the N-H stretchings in the IR spectra. Differences in the relative thermal motions of the non coordinated oxygen atoms of the carboxylate groups are probably de pendent primarily on the central metal atom and secondarily on hydroge n bonding. (C) 1997 Elsevier Science S.A.