Molecular and Supramolecular Structures ofN-Phenyl Formamide and its Hydrated Clusters

Abstract

The amide, N-phenyl formamide (formanilide), and its water clusters have been studied in a jet expansion using laser-induced fluorescence excitation and mass-selected, resonant two-photon ionization (R2PI) techniques. The isomer with a trans configuration of the amide group (defined in Figure ) is identified through analysis of the partially resolved contour of its S1 ← S0 band origin. Ion-dip “hole-burn” spectra of the nonplanar cis isomer contain either symmetric or antisymmetric components of low-frequency progressions, providing evidence of a double-minimum ground state potential. Excited-state vibrations at 76 and 152 cm-1, which are strongly Franck−Condon active, show evidence of Duschinski mixing of the ground-state modes including Cring−N torsion. Water clusters have been observed for trans-formanilide only: two distinct 1:1 hydrates, two 1:2 hydrates, and a complex with at least four bound water molecules. (The cis isomer is also expected to form extremely stable complexes with water, but none have been detected experimentally in the present study.) The observed clusters are assigned using spectroscopic data, including band contours, to structural alternatives computed ab initio at the HF/6-31G* level. The 1:1 hydrates are assigned to a cluster in which water binds at the NH site and one in which water binds at the HCO site. In the 1:2 clusters, the addition of a further water molecule to each of the 1:1 clusters results in cyclic hydrogen-bonded structures, with the water dimer bridging between proton donor and proton acceptor sites of the host. The interactions are HCO···HOH and OCH···OH2 in one case and NH···OH2 and πring···HOH in the other. At the MP2/6-31G*//HF/6-31G* level, these structures are ca. 10 kJ mol-1 more stable than the nearest competitor, in part because of cooperative effects. The R2PI spectrum of the NH bound 1:2 cluster “C” is very similar to that of the indole(H2O)2 complex assigned by Zwier and co-workers. Its origin is red-shifted 482 cm-1 from trans-formanilide, and the electronic transition excites long intermingled vibrational progressions with frequencies of 29, 38, and 51 cm-1.

Free-Jet Rotational Spectrum and ab Initio Calculations of Formanilide

“…As a consequence the energy difference between the synoid and the anti rotamers (⌬E conf ) can be estimated to be about 8.4 kJ/mol, the anti species being the more stable. Ab initio calculations at the MP2/6-31G* level, performed by Dickinson et al (11), led to almost identical stabilities of the two isomers, a result not in agreement with the experimental evidence. They also found, recording R2PI holeburning spectra, that the ground state of the synoid conformer was split into two sublevels, due to a small barrier to planarity between two equivalent synoid forms with the formyl group above or below the benzene plane.…”

“…The anti and syn species (see Fig. 1) of FA have indeed been observed either in a chloroform solution (with about the same abundance) (10), or in the gas phase, with the abundance of the syn isomer estimated to be 6.5% (8,11). We thought that the rotational spectrum would have given a precise answer on the structure, conformation, and potential energy surface of the internal rotations in the proximity of the peptidic group of FA.…”

“…Its small negative value, which is almost the same for the NH and ND species, is compatible with out-of-plane low-energy motions, such as the C 1 ON and NOC formyl torsions, as observed in Refs. (8,11).…”

Synthesis, FT-IR, FT-Raman and quantum chemical investigations of N-(3-methylphenyl)-2,2-dichloroacetamide

“…The dipole moment measurements, X-ray and neutron diffraction studies demonstrated that the trans conformer of Nphenylacetamide is the predominant and most stable [14,15,39,[41][42]. The influence of the ring substituent on N-H stretching frequency of N-phenylacetamide and its derivatives may be the resultant steric effect, direct field effects, hydrogen bonding and bond polarisation effects [43].…”

“…Spectroscopic and crystal structural studies give valuable informations on bond properties. The -CO-NH-group adopts a planar 'peptide-like' conformation, as in the case of formamide [10], methyl hydrazinocarboxylate [11], N-methylformamide [12], o-methyl acetanilide [13] and formanilide [14,15].…”