The molecular and crystal structures of complex [SnCl3(HBs)] (I) (Fig.), where H2Bs – salicylic aldehyde benzoylhydrazone, are determined by X-ray crystallography [1]. Tin(IV) adopts distorted octahedral coordination and the H2Bs is coordinated in a O(C=O)–N(N=CH)–O(Ph) tridentate-chelate mode. Equatorial Sn(1)–Cl(1) distance is shorter than axial Fig. Molecular structure I ones both for isolated molecule and for crystal structure (donation of electron density to the Cl(1) atom from the opposite N(2) atom). Theoretical results of periodic PW-DFT calculations for I obtained with VASP satisfactorily reproduced the experimental crystal structure. To mimic the isolated molecule of I, we used MP2/6-311G(d,p) method/basis set combination. In contrast to PW-DFT, all Sn–Cl and the Sn(1)–O(2) bond lengths in isolated molecule are in very good agreement with experimental ones. To obtain detailed information on the chemical bonding pattern in I, the topological analysis in terms of the Bader’s “Atoms in Molecules” (AIM) theory of experimental, PW-DFT and MP2/6-311G(d,p) calculated electron density distribution functions was carried out. In accordance with AIM, the crystal structure of I is formed by the C–H···Cl and C–H···O bonds, specific Cl···Cl and Cl···N interactions and weak C(π)···C(π) and H···H contacts. Analysis of AIM charges has revealed that amount of charge transferred from ligand to SnCl3 moiety is equal to ≈0.3 e that leads to significant redistribution of bond lengths. Comparison of geometry and characteristics of electron density distribution indicates the weakening of coordination Sn–O and Sn–N bonds in isolated molecule in comparison with crystal up to 10 kcal/mol. This effect was explained by the intermolecular H···Cl bonding. According to the Hirshfeld surface analysis, these interactions have the most pronounced contribution to the crystal packing energy. The significance of this communication lies in both the detailed inspection of the crystal packing effect on the coordination bonds of the tin(IV) atom and intermolecular interactions governing the supramolecular self-assembly of hydrogen-bonded chains by means of specific interactions and π···π stacking. The usage of the topological analysis for study of chemical bonding in complexes of tin(IV) allowed estimation of such important bond characteristics as the nature of Sn–Cl, Sn–O and Sn–N bonds and their energies. Both experimental and theoretical values are in qualitative agreement.