Two novel types of metal complexes derived from tripod amines and acetylacetone

Condensations of tris(2-aminoethyl)amine (tren) with acetylacetone (acac) give two different types of complexes, depending upon the coexisting metal ions; one contains two tridentate ligands which have β-ketoimine moieties at all primary amino groups of tren, and the other has a pentadentate ligand having a β-ketoimine moiety at one of the three amino groups of tren. The Sr2+, Ca2+, Mg2+, and Mn2+ ion give the former type complexes and Cu+, Co3+, and Zn2+ give the latter. The crystal structures of all the complexes have been characterized by X-ray analyses. Crystal data for the Sr2+ complexes: SrC90H106N8O6B2, a = 12.32(1), b = 17.65(2), c = 10.98(1)A, α = 99.04(9), β = 104.53(9), γ = 104.47(9)°, V = 2176(4) A3, triclinic, P 1 , Z= 1 . For the Ca2+ complex: CaC90H106N8O6B2, a = 12.882(2), b = 15.904(4), c = 11.314(4) A , α = 102.37(2), β = 94.70(2), γ = 110.16(1)°, V = 2094(1) A 3 , triclinic, P 1 , Z = 1 . For the Mg2+ complex: MgC90H106N8O6B2, a = 12.839(4), b = 15.773(6), c = 11.199(3) A , α = 101.50(3), β = 95.35(3), γ = I10.24(2)°, V = 2052(1) A3, triclinic, P 1 , Z = 1 . For the Mn2+ complex: MnC90H106N8O6B2, a = 12.858(3), b = 15.818(6), c = 11.210(3) A , α = 101.80(2), β = 95.06(2), γ = 110.20(2)°, V = 2063(l) A3, triclinic, P 1 , Z = 1 . For the Cu2+ complex: CuC35H43N4OB, a = 11.060(5), b = 15.874(4), c = 17.886(4) A, β = 91.89(3)°, V = 3138(I) A3, monoclinic, P2 1 n , Z = 4 . For the Zn2+ complex: ZnC35H43N4OB, a = 11.084(4), b = 15.955(3), c = 17.838(2) A , β = 92.11(2)°, V = 3152(1) A 3 , monoclinic, P2 1 n , Z = 4 . For the C03+ complex: CoC35H43N4OBCl, a =1 7.996(2), b = 10.150(5), c = 19.741(2) A , β = 113.460(7)°, V = 3307(1) A 3 , monoclinic, P2 1 c , Z = 4. The selectivity of the products is discussed in terms of the ionic size and the affinity between the metal ion and the donor atoms. The reaction of acac with tris(3-aminopropyl)amine in the presence of the Ca2+ ion was also performed, the first type of the structure was found. The structure is also confirmed by X-ray analysis. Crystal data: CaC96H124N8O6B2, a = 12.364(4), b = 16.502(6), c = 12.008(5) A , α = 103.62(3), β = 91.14(3), γ = 110.09(2)°, V = 2222(1) A 3 , triclinic, P 1 , Z= 1 .