Self-assembly of NH-pyrazoles via intermolecular N-H.N hydrogen bonds.
The crystal structures of two NH-pyrazole derivatives forming intermolecular N-H.N hydrogen bonds are reported: 5-methyl-4-(3-methylpyrazol-5-yl)pyrazol-3-ol, C(8)H(10)N(4)O (P1), and 3-methyl-5-dihydro-1H-naphtho[1,2-d]pyrazole hemihydrochloride, C(12)H(12)N(2).-C(12)H(13)N(2)(+).Cl(-) (P2). 26 other structures are surveyed in order to obtain a deeper insight into the ways NH-pyrazoles self-assemble by means of intermolecular N-H.N hydrogen bonds in molecular crystals. A limited number of compounds form chains or dimers via homonuclear N(+)-H.N positive-charge-assisted hydrogen bonds, typical of proton sponges, which can be remarkably short [e.g. N.N 2.714 (3), N-H 1.09 (3), H.N 1.63 (3) Å, N-H.N 169 (3) degrees in (P2)]. Most pyrazoles, however, pack via neutral N-H.N bonds which are formally assisted by resonance (resonance-assisted hydrogen bond, RAHB) through the.N=C-C=C-NH. iminoenamine fragment, contained in the ring, giving rise to dimers, trimers, tetramers and infinite chains of pyrazole molecules. Surprisingly, the resonance does not appear to shorten the N-H.N bond with respect to the accepted mean value N.N 2.97 (10) Å for non-resonant N-H.N bonds. It is shown that this is due to the internal pi-delocalization of the pyrazole ring, which can be hardly increased by the hydrogen-bond interaction, except in symmetrically 3,5-substituted pyrazoles which display N.N distances as short as 2.82 Å, identical C-C and C-N distances in the two halves of the pyrazole molecule, and typical phenomena of N-H.N dynamical proton disorder, detectable by (15)N-CP/MAS solid-state NMR.
Dipartimento di Chimica and Centro di Strutturistica Diffrattometrica, Università di Ferrara, I-44100 Ferrara, Italy. m38@dns.unife.it
V
Bertolasi
P
Gilli
V
Ferretti
G
Gilli
C
Fernàndez-Castaño