Synthesis, structure, and properties of di-mu-phenoxo-bridged dinuclear (CuNiII)-Ni-II and (CuCoII)-Co-II complexes and cyclic di-mu-phenoxo-mu-amido-bridged tetranuclear (Cu2Zn2II)-Zn-II and Cu-4(II) complexes derived from the 1,2-bis(2-oxidobenzamidato)benzenecuprate(II) dianionic ligand-complex

Dipotassium N,N'-1,2-phenylenebis(2-carbamoyl-kappa N-phenolato-kappa O]cup rate(II)), K-2[CuL], reacts with nickel(II), cobalt(II), and zinc(II) aceta tes, and 2,2'-bipyridine in a 1:1:2 molar ratio in methanol to yield the he tero-metal dinuclear complexes [CuLNi(bpy)(2)]. 3MeOH(1.3MeOH), [CuLCo(bpy) (2)]. 2DMF (2.2DMF), and [CuLZn(bpy)(2\)]. 1.5H(2)O (3), respectively. Crys tal data for 1: P (1) over bar (No: 2) with a = 15.969(2), b = 23.494(3), c = 12.705(2) Angstrom, alpha = 92.15(1), beta = 91.652(10), gamma = 101.521 (9)degrees, V = 4663(1) Angstrom(3), and Z = 4; 2, P2(1)/c (No. 14) with a = 12.604(3), b = 24.364(5), c = 13.823(2) Angstrom, beta = 94.49(1)degrees, V = 4231(1) Angstrom(3), and Z = 4. 1 and 2 have a similar discrete di-mu- phenoxo- bridged dinuclear structure, in which the Cu(II) ion assumes a squ are-planar geometry with the N2O2 donors atoms consisting of two amido nitr ogen and two phenoxo oxygen atoms of the tetradentate ligand, and the Ni(lI ) or Co(II) ion assumes an octahedral geometry with the two phenoxo oxygens of the tetradentate ligand and four nitrogen atoms from two bpy. The magne tic-susceptibility data were reproduced based on the isotropic spin Hamilto nian H = - 2JS(1).S-2 With J = - 118.0 cm(-1), (S-1, S-2) = (1/2, 1) for 1 and J = -11.0 cm(-1), (S-1, S-2) = (1/2, 3/2) for 2, respectively. When 3 w as recrystallized from DMF/2-propanol, [CuLZn(bpy)](2). 2DMF (3') was obtai ned. The 1: 1 :1 reaction of K-2[CuL'], copper(II) acetate monohydrate, and 2,2'-bipyridine in methanol yielded [CuL'Cu(bpy)](2). 2MeOH (4), (H4L' =1, 2-bis(hydroxybenzamido)-ethane). Crystal data for 3': Pbca (No. 61) with a = 19.143(2), b - 18.195(2), c = 16.832(3) Angstrom, and Z = 4; 4, P2(1)/n ( No. 14) with a = 13.407(1), b = 13.172(4), c = 13.764(2) Angstrom, beta = 9 4.11(1)degrees, V = 2424.4(8) Angstrom(3), and Z = 4; 3' and 4 have a simil ar cyclic di-mu-phenoxo-mu-amido-bridged tetranuclear structure, which can be described as two di-mu-phenoxo-bridged dinuclear units bridged together by the coordination of one amido oxygen atom from each dinuclear unit to th e zinc(II) or copper(II) ion of the other dinuclear unit, with Zn(1)-O(3)* = 2.004(3) and Cu(2)-O(4)* = 1.924(4) Angstrom bond distances, respectively . In the tetranuclear structure, the copper(ll) ion coordinated by the tetr adentate ligand assumes a square-planar geometry and the zinc(II) or the ot her copper(lI) ion assumes a square-pyramidal coordination geometry with tw o phenoxo-oxygen atoms, two nitrogen atoms of bpy, and one amido oxygen ato m. The magnetic susceptibility of 4 was reproduced by an equation derived f rom the H = - 2J(S-1.S-2 +S-3.S-4) - 2J'(S-2.S-3 +S-4.S-1) Spin Hamiltonian with J = - 14.6 cm(-1) and J' = -4.0 cm(-1).