Studies of fine and hyperfine structures of paramagnetic resonance spectra in single crystals of Mn2+: tetramethylammoniumtetrachlorozincate are reported. As sufficient numbers of lines were not obtained at room temperature, measurements were done at liquid nitrogen temperature (77 K). The Mn2+ spin Hamiltonian parameters are evaluated employing a large number of resonant line positions observed for various orientations of the external magnetic field. The values of the zero field parameters that give good fit to the observed EPR spectra are obtained. The values of different parameters are: g = 1.9834 +/- 0.0002, A = (105 +/- 2) x 10(-4) cm(-1), B = (100 +/- 2) x 10(-4) cm(-1), D = (349 +/- 2) x 10(-4) cm(-1), E=(106 +/- 2) x 10(-4) cm(-1) and a = (21 +/- 1) x 10(-4) cm(-1). The percentage of covalency of the metal-ligand bond has also been determined. From the optical absorption study, the lattice distortion is suggested. The observed bands are assigned as transitions from the (6)A(1g)(S) ground state to various excited quartet levels of Mn2+ ion in a cubic crystalline field. The electron repulsion parameters (B and Q and crystal field parameters (D-q and alpha) providing a good fit to the observed optical spectra are evaluated and the values are: B = 737 cm(-1), C = 2322 cm(-1), D-q = 670 cm(-1) and alpha = 76 cm(-1). The considerable decrease in the values of B and C parameters from free ion values (B = 960 cm(-1), C = 3325 cm(-1)) has indicated that there exists a fair amount of covalent bonding between the central metal ion and the ligand. On the basis of deviations Delta g = g - 2.0023 it has been ascertained whether electrons are transferred to or from the central ion by the action of bonding. (C) 2007 Elsevier B.V. All rights reserved.