Synthesis, Crystal Packing Aspects and Pseudosymmetry in Coordination Compounds with a Phosphorylamide Ligand.

This work reports the synthesis and crystal structure of new closely related coordination compounds, [ML2]center dot nTHF, where M is Zn or Mn; L is a phosphorylmethylamide derivative of benzothiadiazole; n = 1 (M = Zn) and 1, 2 (M = Mn); and THF is tetrahydrofuran. The zinc compound, 1 center dot THF, crystallizes in a high-symmetry space group, I4(1)/a, that is relatively rare for compounds with organic ligands. The corresponding manganese congener, 2 center dot THF, with a similar crystal packing, features a pseudosymmetrical structure P2(1)/c of the doubled volume of the unit cell as compared to 1 center dot THF. The main difference between the structures lies in a different arrangement of solvate THF molecules, which likely modulates the crystal packing of the complexes. Another manganese solvatomorph, 2 center dot 2THF, reveals a fundamentally different crystal packing while exhibiting a similar geometry of the complex. We consider the problem of localization of solvate THF molecules and the types of their disorder by the example of compounds 1-2.