To investigate the structural basis of triboluminescence, several known tetrahedrally coordinated Mn(II) complexes have been synthesized according to literature methods and their crystal structures have been determined by X-ray diffraction. Among them, (MePh3P)(2)[MnCl4] (2), a = 15.4804(4) Angstrom, cubic, space group P2(1)3, Z = 4; (Et4N)(2)- [MnBr4] (4), a = 13.362(1) Angstrom, c = 14.411(1) Angstrom, tetragonal, space group P42(1)m, Z = 4; MnBr2(OPPh3)(2) (7), a = 9.974(1) Angstrom, b = 10.191(3) Angstrom, c = 10.538(2) Angstrom, alpha = 65.32(1)degrees, beta = 63.49(1)degrees, gamma = 89.44(2)degrees, triclinic, space group P1, Z = 1; and MnBr2(OAsPh3)(2) (10), a = 17.816(3) Angstrom, b = 10.164(1) Angstrom, c = 18.807(3) Angstrom, orthorhombic, space group Pca2(1), Z = 4 were reported to be triboluminescent and (Me4N)(2)[MnCl4] (3), a = 9.016(3) Angstrom, b = 36.90(2) Angstrom, c = 15.495(3) Angstrom, beta = 90.72(3)degrees, monoclinic, space group P2(1)/n, Z = 12. and MnI2(OAsPh3)(2) (11), a = 10.094(4) Angstrom, b = 10.439(2) Angstrom, c = 34.852(2) Angstrom, alpha = 83.17(4)degrees, beta = 86.09(2)degrees, gamma = 75.16(3)degrees, triclinic, space group P1, Z = 4, were reported to be not triboluminescent. The result supports the correlation between space group acentricity and triboluminescence activity.