The crystal structures of N-benzamido-meso-tetraphenylporphyrin (NHCOC6H5-Htpp; 1), (N-benzimido-meso-tetraphenylporphyrinato)(methanol)zinc(II) [Zn(N-NCOC6H5-tPP)(MeOH); 2(MeOH)], and (acetato)(N-benzamido-meso-tetraphenylporphyrinato)cadmium(II) [Cd(N-NHCOC6H5-tpp)(OAc); 3] were established. The coordination sphere around Zn2+ ion in 2(MeOH) is a distorted trigonal bipyramid with N(2), N(5), and 0(2) lying in the equatorial plane, whereas, for Cd2+ 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 0(2). Cd in 3 acquires five-coordination with five strong bonds [Cd(l)N(1) = 2.319(5) Angstrom, Cd(l)-N(2) = 2.252(5) Angstrom, Cd(l)-N(3) = 2.332(5) Angstrom, Cd(l)-O(2) = 2.292(5) Angstrom, and Cd(l)0(3) = 2.317(5) Angstrom] and with one secondary intramolecular interaction [Cd(l)...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(l)-N(3)] strongly bonded to Zn2+ in 2(MeOH) and to Cd2+ in 3 is adopted as a reference plane 3N. For the Zn2+ complex, the pyrrole nitrogen bonded to the benzamido (BA) ligand lies in a plane with a dihedral angle of 33.8degrees with respect to the 3N plane, but for the Cd2+ complex, this dihedral angle is found to be 31.4degrees. In the former complex, Zn2+ and N(5) are located on the different side at -0.08 and 1.39 Angstrom from its 3N plane, and in the latter one, Cd2+ and N(5) are also located on the different side at 1.08 and -1.51 Angstrom from its 3N plane. VT NMR (H-1 and C-13) studies of 3 show that the acetate acts as a bidentate ligand and the OAc- exchange does not occur in CD2Cl2. Moreover, the NH proton [i.e., H(5)] of 3 in CD2Cl2 is observed as a sharp singlet at delta = -1.13 ppm with Deltanu(1/2) = 4 Hz at 20 degreesC indicating that the intermolecular proton exchange between water and NH proton is rapid.