The sodium complex [{Ph2P(O)NH(2,6-Me2C 6H3)}Na{Ph2P(O)N(2,6-Me2C 6H3)}]2 (2) with the ligand N-(2,6-dimethylphenyl)diphenylphosphinic amide was synthesized involving the reaction of the neutral ligand [Ph2P(O)NH(2,6-Me2C 6H3)] (1) and sodium bis(trimethylsilyl)amide in toluene at 60 °C. The calcium complex [{Ph2P(O)NH(2,6-Me 2C6H3)CaI(THF)3}I] (3) was obtained by the reaction between the neutral ligand 1 and anhydrous calcium diiodide in THF at ambient temperature. The solid-state structures of the complexes were established by single-crystal X-ray diffraction analysis. In the solid-state structure of 2, the sodium ion is coordinated through the chelation of oxygen atom attached to the phosphorus atom. Two different P-N and P-O bond lengths are observed, which indicates that one ligand moiety is anionic, whereas the second one is neutral. In the solid-state structure of 3, the calcium atom adopts distorted octahedral arrangement through the ligation of two phosphinic amide ligands, three THF molecules, and one iodide ion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.