Abstract: | The title complex, trans‐bis(dimethylformamide‐κO)bis{N,N′‐N′′,N′′′‐tetra‐tert‐butyloxybis(phosphonic diamide‐κO)]}manganese(II) dichloride dihydrate, Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis‐chelate amido–pyrophosphate (pyrophosphoramide) complex containing an OP(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The MnII atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six‐membered chelates involving the fragments C(O)NHP(O), (X)NP(O) X = C(O), C(S), S(O)2 and P(O)] and OP(O)(N)2]2. This analysis shows that the six‐membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N—H...O and N—H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O—H...Cl hydrogen bonds. |