The expansion of crystal engineering as an emerging research field has been accompanied by significant interest in the nature of intermolecular interactions and their subsequent use in the formation of solid-state structures. Supramolecular chemistry and crystal engineering based on the spontaneous self-assembly of metal ions and bridging organic building blocks are of great current interest. From perspective of the synthetic chemist, the challenge is to develop strategies that allow precise structural and stoichiometric control of the topology in the resultant systems. In this context the thiosemicarbazide based ligands has significant chelating properties and they may also stabilize different oxidation states of metal ions [1-3]. Coordination chemistry of manganese compounds is an area of considerable interest. These complexes are important not only for their redox active role in several biochemical processes, but also for the diversity of their magnetic properties. In this presentation, we report five new Mn(III) monomers with quadridentate Schiff-base N1,N4-di(R1-salicyliden)-S-R2-isothiosemicarbazide (H2R1R2L) of the general formula Mn(R1R2L)X·nS, where R1 = H, 5CH3, R2 = CH3, C2H5; X = NCS, N3, BPh4, ClO4, ReO4, S = solvent molecules H2O, CH3CN, C2H5OH , n = 0, 1, 2. The different surroundings and crystallizations of the anion (X) or solvent(S) around the metal Mn(III) ion not allowed us to find a unique formula for the complexes. The architectures of complexes depend greatly on the experimental conditions including the nature of anion, substitutient and solvent used in the crystallization process. During crystallization, solvent molecules and anions take part in molecular aggregation and change the overall crystal structure in the solid state. The crystal structure of a series of these compounds was determined. The obtained manganese Schiff bases complexes can be divided into 2 groups: 1. Five coordinated complexes with tetragonal pyramidal configuration: [Mn(R1R2L )NCS], [Mn(R1R2L )N3]·CH3CN; 2. Six coordinated with octahedral structure: [Mn(R1R2L)(H2O)2]ClO4, [Mn(R1R2L)(H2O)ReO4], [Mn(R1R2L)(C2H5OH)(H2O)]BPh4·C2H5OH. The formation of dimeric unities in the investigated selection has not been observed. Different disposition of anion (X)/solvent (S) (within the coordination sphere or outside it) leads to various supramolecular networks. [1] Garbalau N. V., Revenco M.D., Ablov A.V., Russ. J. Inorgan. Chem., 1972, 17,136. [2] Garbalau N. V., Revenco M.D., Russ. J. Inorgan. Chem., 1972, 17, 2176. [3] Revenco M. D., Palamarciuc O. V., Bourosh P. N., Lipkowski J., Gdaniec M., Simonov Y. A., Clérac R., Inorg. Chem. Acta, 2011, 368,157.