Infrared Spectra of Gaseous and Crystalline Cyanogen Halides

Abstract

The infrared spectra of gaseous ClCN and BrCN at room temperature are reported for the LiF, NaCl, KBr, and CsBr prism regions. Several upper stage bands as well as bands due to C13 appear in both spectra. Assignments are given, from which a number of the vibrational constants are evaluated and the Fermi resonant levels treated by a first-order perturbation method. The spectra of crystalline ClCN, BrCN, and ICN at −180°C is also recorded. Absorption bands, including several due to C13 and N15, are assigned and the spectra are discussed in terms of the available x-ray crystal data.

Raman spectra of molecular crystals at high pressures. Part VI—bromine cyanide

“…8 Sample dimensions, spectroscopic equipment and techniques and calibration procedures were essentially the same as those described in a previous paper, 1 and details will not be repeated here. 6,7 Wavenumber accuracy for the present work is estimated to be š1 cm 1 , and pressure accuracy is about 0Ð1 GPa for values up to 8 GPa and 0Ð2 GPa at higher values, where there is some evidence of gradients in the samples, as indicated by the widths of the ruby fluorescence lines. 3, where the points have been fitted to quadratic curves as a guide to the eye.…”

“…4 It indicates that the two stretching modes, 1 (C-N) and 2 (C-Br), each produce two components in the crystal, as a result of coupling of the two molecules in the unit cell, one being Raman-and the other infrared-active. 6,7 As far as we are aware, no previous spectroscopic studies of solid BrCN at high pressures have been reported. There are also three Raman-active optical translational modes.…”

High-Resolution Infrared Spectrum of BrCN in the ν2 and ν1/2ν2 Regions

“…The vibrational polyad 1 /2 2 has been investigated in the infrared with low resolution (8). This polyad, which is of medium intensity, forms a doublet, with centers at 571 and 691 cm Ϫ1 .…”

N-Cyano-N,N,N-trialkylammonium salts. Synthesis and reactions

“…The ether-extracted portion was distilled to give 1.10 g (82%) of ZV-methyl-ZVethylaniline. Diethylcyanamide was analyzed as follows: ir (thin film) 2213 cm-1 (strong, CN); nmr (CCI3) 1.25 (t, CH$, 6 H) and 3.20 (q, CH2, 4 H); mass spectrum m/e (rel abundance) 98 (M+, 34), 87 (6), 85 (42), 84 (6), 83 (6), 70 (11), 69 (12), 58 (25), 56 (6) , 55 (100), 53 (6), 49 (9), 48 (10), 47 (22), 44 (9), 43 (98), 42 (20), 41 (6).…”

“…The nmr spectrum (CC14) had signals at 0.91 (t, CH3, 3 ), 1.07-1.80 (br, CH2, 4 H), 2.85 (s, CH3, 3 ), 3.17 (t, CH2, 2 H), 6.43-6.63 (m, phenyl ring, 3 ), 6.91-7.23 (m, phenyl ring, 2 H). Di-n-butylcyanamide was characterized as follows: bp 70-71°( 0.5 mm); ir (thin film) 2205 cm-1 (strong, CN); nmr (CC14) 0.97 (t, CH3, 6 ), 1.20-1.90 (m, CH2, 8 H), 2.97 (t, CH2, 4 H); mass spectrum m/e (rel abundance) 154 (M+, 23), 139 (7) , 125 (9), 112 (10), 111 (44), 98 (9), 97 (7), 86 (8), 83 (7), 70 (11), 69 (100), 57 (44), 55 (19), 43 (13), 42 (10), 41 (41), 39 (8).…”