Two new organotin-phosphoramidates, [(RNH)3PO]2Cl2Me2Sn, R = tBu (1), C6H5CH2 (2), have been synthesized and characterized by 119Sn, 31P{1H}, 1H, 13C{1H} NMR and IR spectroscopies, elemental and single crystal X-ray analysis. In the two structures, the N atom in the phosphoramide is almost planar and the resulting low Lewis base character results in the absence of HB interactions in the solid state. The Sn coordination geometry at 1 and 2 is octahedral with the phosphine moieties in a trans fashion in the axial positions; the chlorine atoms are also trans. In both cases the Sn atom is located in the inversion centre, making half of the molecule related by symmetry. The distances Sn-O, Sn-Cl and Sn-C are within expected values. The O-Sn-O angle is trans (180°), but the Sn-O-P angles are about 145°, this geometrical parameters had been observed in related structures [1]: [(Me2N)3PO]2X2Me2Sn, X = Br [2], Cl [3]; [(Me2N)3PO]2X2Et2Sn, X = I [4], Br [5]; {(C5H10N)2[(p-F-Ph)C(O)NH]PO}2Cl2Me2Sn [6], [(R)2(PhC(O)NH)PO]2Cl2Me2Sn, [7] R = tBuNH, C4H8N, C5H10N, and (Me)(Cy)N.

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