Structural evaluation of three 2-phenylpyrazolo[4,3-c]quinolin-3-one monohydrates

Abstract A single crystal X-ray diffraction and theoretical study has been carried out on mono hydrates of three 2H-pyrazolo[4,3-c]quinolin-3(5H)-one derivatives, namely 6-methyl-2-phenylpyrazolo[4,3-c]quinolin-3-one, 3 , 6-methyl-2-(4-chlorophenyl)pyrazolo[4,3-c]quinolin-3-one, 4 , and 8-methyl-2-(4-nitrophenyl)pyrazolo[4,3-c]quinolin-3-one, 5 . The monohydrates were obtained on recrystallization from moist solvents. While there are three tautomeric forms possible for such pyrazolo[4,3-c]quinolin-3-one molecules, the sole form isolated in the solid [( X )⋅(H 2 O)] ( X  =  3 , 4 and 5 ) compounds was the quinoloid form – the one calculated to be the most stable at the M06-2X/6-311++G(d,p) level of theory. Excellent agreement was found between the calculated and X-ray determined structures. Molecule 5 in [( 5 )⋅(H 2 O)] is very near planar while both molecules 3 and 4 in their respective hydrates are much less so as a consequence of angles about 24° between the two aromatic rings. In each hydrate, the pyrazolo[4,3-c]quinolin-3-one molecule is bonded to three water molecules and each water molecule is likewise H-bonded to three pyrazolo[4,3-c]quinolin-3-one molecules. While the water molecules are H-bonded to 3 and 4 via the pyridinyl N and 2x the carbonyl O atoms, in [( 5 )⋅(H 2 O)] the H-bonds are to pyridinyl N, carbonyl O and a nitro O atoms. Calculations indicated that the found arrangement in [( 5 )⋅(H 2 O)] is more stable than one using the connections as found in [( 3 )⋅(H 2 O)] and [( 4 )⋅(H 2 O)]. While each of the hydrates possess strong N H⋯O and O H⋯O hydrogen bonds, and weaker C H⋯π and π⋯π interactions, the supramolecular arrays are very different.