The crystal structures of N-benzamido-meso-tetraphenylporphyrin (NHCOC(6)H(5)-Htpp; 1), (N-benzimido-meso-tetraphenylporphyrinato)(methanol)zinc(II) [Zn(N-NCOC(6)H(5)-tpp)(MeOH); 2(MeOH)], and (acetato)(N-benzamido-meso-tetraphenylporphyrinato)cadmium(II) [Cd(N-NHCOC(6)H(5)-tpp)(OAc); 3] were established. The coordination sphere around Zn(2+) ion in 2(MeOH) is a distorted trigonal bipyramid with N(2), N(5), and O(2) lying in the equatorial plane, whereas, for Cd(2+) ion in 3, it is a sitting-atop derivative with a distorted trigonal bipyramidal geometry in which the apical site is occupied by atoms N(2) and O(2). Cd in 3 acquires five-coordination with five strong bonds [Cd(1)-N(1) = 2.319(5) A, Cd(1)-N(2) = 2.252(5) A, Cd(1)-N(3) = 2.332(5) A, Cd(1)-O(2) = 2.292(5) A, and Cd(1)-O(3) = 2.317(5) A] and with one secondary intramolecular interaction [Cd(1)...N(4)]. The porphyrin ring in these two complexes is distorted to a large extent. The plane of the three pyrrole nitrogen atoms [i.e., N(1)-N(3)] strongly bonded to Zn(2+) in 2(MeOH) and to Cd(2+) in 3 is adopted as a reference plane 3N. For the Zn(2+) complex, the pyrrole nitrogen bonded to the benzamido (BA) ligand lies in a plane with a dihedral angle of 33.8 degrees with respect to the 3N plane, but for the Cd(2+) complex, this dihedral angle is found to be 31.4 degrees. In the former complex, Zn(2+) and N(5) are located on the different side at -0.08 and 1.39 A from its 3N plane, and in the latter one, Cd(2+) and N(5) are also located on the different side at 1.08 and -1.51 A from its 3N plane. VT NMR ((1)H and (13)C) studies of 3 show that the acetate acts as a bidentate ligand and the OAc(-) exchange does not occur in CD(2)Cl(2). Moreover, the NH proton [i.e., H(5)] of 3 in CD(2)Cl(2) is observed as a sharp singlet at delta = -1.13 ppm with Delta nu(1/2) = 4 Hz at 20 degrees C indicating that the intermolecular proton exchange between water and NH proton is rapid.

The crystal structures of the dimer form of copper(II) tetraphenylporphyrin N-oxide, [Cu(tpp-N-O)]2 (3-dimer), and zinc(II) tetraphenylporphyrin N-oxide, [Zn(tpp-N-O)]2 (4-dimer), were established. The geometry at the copper ion in 3-dimer is essentially square-pyramidal with one oxygen bridge [O(1A)] occupying the apical site, giving a much larger Cu-O bond distance compared to those at the basal plane. The respective Cu...Cu distance and Cu-O-Cu angle in the core of 3-dimer are 3.987(4) A and 148.1(3) degrees. The Zn(1) atom in 4-dimer has a distorted square-pyramidal [4 + 1] coordination geometry that gives a tau-value of 0.19. The respective Zn...Zn distance and Zn-O-Zn angle in the dimeric unit of 4-dimer are 4.025(3) A and 148.1(2) degrees. The 3-dimer displays axial X-band electron paramagnetic resonance spectral features (Es = 0) in the powder state at 4 K, giving g parallel = 2.51 (A(parallel,s) = (9.6 +/- 0.2) x 10-3 cm(-1)) and g(perpendicular) = 2.11 and in the same powder state at 293 K giving Ds = 0.0731 cm(-1) (as derived from DeltaMs = 1 lines) or 0.0743 cm(-1) (as derived from the DeltaMs = 2 lines). In addition, 3-dimer displays a DeltaMs = 2 transition at g = 4.17 indicating the presence of spin-exchange coupling. The anisotropic exchange interaction (Ds(ex)= 0.132 cm(-1)) gives the main contribution to Ds in 3-dimer. The theoretical fit of the susceptibility and effective magnetic moment data of 3-dimer in the temperature range of 5-300 K gives 2J = 68 cm(-1), g = 2.01, p = 0.06, and a temperature-independent paramagnetism of 10(-6) cm3 mol(-1). This magnetic susceptibility data indicates that the copper(II) ions in 3-dimer are coupled in a ferromagnetic manner with the ground-spin triplet stabilized by 68 cm(-1) with regard to the singlet.