A combinatorial topological analysis and modeling of the self-assembly of crystal structures of LiCaSn-hP9 (space group P3m1, V = 230.36 angstrom(3)), Li2CaSn- cF16 (space group Fm-3m, V = 333.56 angstrom(3)), and Li20Ca28Sn44-oS92 (space group Cmcm, V = 2517.09 angstrom(3)) are performed using computer methods (ToposPro software package). The cyclic precursor clusters K3-0@LiCaSn involved in the self-assembly of the crystal structure of LiCaSn-hP9, as well as tetrahedral ones K4 for the crystal structure of Li2CaSn-cF16 and cyclic K3, tetrahedral K4, and pentagonal pyramids K6 for the crystal structure of Li20Ca28Sn44-oS92, are established. The self-assembly of the crystal structure of Li20Ca28Sn44-oS92, are established. The self-assembly of the crystal structure of Li20Ca28Sn44-oS92 involves S-3(1)(A) primary chains from the bound clusters K6 and K3, and S-3(1)(B) primary chains from the bound clusters K4 and K3. In the 2D layer, an chain with m symmetry is bound to the S-3(1)(B) chains on both sides. The framework S-3(3) structure is formed by binding 2D layers in the direction [100], whereas the distance between the equivalent 2D layers determines the value of vector a = 4.666 angstrom. The S1/3 primary chain of the intermetallic compound Li2CaSn-cF16 is formed as a result of the binding of tetrahedral metal clusters Li2CaSn with the binding index P = 8. The formation of the S3/2 layer occurs by binding parallel chains with the index P = 10. The distance between the axes of the primary chains from neighboring layers in the direction of axes X and Y corresponds to the value of the parameters of the cubic cell a = b = 6.935 angstrom. The S1/3 primary chain of the intermetallic compound LiCaSn-hP9 is formed as a result of the binding of the cyclic LiCaSn metal clusters with the binding index P = 4 and 5. The S2/3 layer is formed by binding parallel chains with the binding index P = 10. The distance between the axes of the primary chains corresponds to the value of the parameter of the hexagonal cell a = 4.94 angstrom.
