Base controlled polydiazeniumdiolation of 4-heptanone and a new water layer structure.

In a stoichiometry-controlled reaction, nitric oxide adds to the enolate of 4-heptanone at ca. -23 degrees C to give mono-, bis-, or tris-diazeniumdiolate (-N2O2(-)) products: potassium 4-heptanone-3,3,5-tris(diazeniumdiolate) (1), potassium butanoate 2,2-bis(diazeniumdiolate) (2), and potassium butanoate 2-diazeniumdiolate (3). The diazeniumdiolate products are stable crystalline solids under ambient conditions and as solids exothermally decompose at high temperatures. Single-crystal X-ray data measured for the dihydrate 3 reveal a new layer aggregation, L4(4)8(8), as octameric water aggregates in a stair conformation which interacts minimally with the cation of the salt.