Probing the Electronic Properties and Interaction Landscapes in a Series of N -(Chlorophenyl)pyridinecarboxamides
Résumé
A 3 x 3 isomer grid of nine N-(chlorophenyl)pyridinecarboxamides (NxxCl) is reported with physicochemical studies and single crystal structures (Nx = pyridinoyl moiety; xCl = aminochlorobenzene ring; x = para-/meta-/ortho-). Reaction of the substituted p-/m-/opyridinecarbonyl chlorides (Nx) with p-/m-/o-aminochlorobenzenes (xCl) yields the nine compound NxxCl series. Several of the nine NxxCl crystal structures display structural similarities with their halogenated NxxX and methylated NxxM relatives (x = p-/m-/osubstitutions; X = F, Br; M = methyl). Indeed, five of the nine NxxCl crystal structures are isomorphous with their NxxBr analogues as the NpmCl/Br, NpoCl/Br, NmoCl/NmoBr, NopCl/Br and NooCl/Br pairs. In the NxxCl grid, the favoured hydrogen bonding mode is aggregation by N-H…Npyridine interactions, though amide…amide intermolecular interactions are noted in NpoCl and NmoCl. For the NoxCl triad, intramolecular N-H…Npyridine interactions influence molecular planarity, whereas NppClH2O (as a monohydrate) exhibits O-H…O, N-H…O1W and O1W-H…N interactions as the primary hydrogen bonding. Analysis of chlorinecontaining compounds on the CSD is noted for comparisons. The interaction environments are probed using Hirshfeld surface analysis and contact enrichment studies. The melting temperatures Tm depend on both the lattice energy and on molecular symmetry (Carnelley's rule). The melting points can be well predicted from a linear regression of the two variables. The relationships of the Tm values with the total energy, the electrostatic component and the strongest hydrogen bond components were analyzed.
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