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The title complex, trans-bis­(dimethyl­formamide-κO)bis{­N,N′-N′′,N′′′-tetra-tert-butyl[­oxybis(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 O[P(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 O[P(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.


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Double nitrile...π interactions are relevant for the crystal packing of charge-diffuse conjugated tetracyanopropenide anions when combined with common heteroaromatic tris-chelate octahedral complexes, [Fe(phen)3]2−.

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The Cu atoms in the title complexes are five-coordinated in distorted trigonal bipyramidal environments by four N atoms of two 5,5′-dimethyl-2,2′-bi­pyridine ligands and one N atom of a dicyanamide anion, which is coordinated in a monodentate manner in the equatorial plane. The structures are stabilized by C—H...N and C—H...X hydrogen bonds (X = F and O) and π–π inter­actions between pyridine rings.
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