Journal of Molecubr

Structure, 79 (1982)465-468 465

ElsevierScientificPublishingCompany,Amsterdam-PPrintedinTheNetherlands

INFRARED AND RAMAN STUDIES OF CYCLOHEXANE, CHLOROCYCLOHEXANE AND

BROMOCYCLOHEXANE

S. HOLLY, G. JALSOVSZKY and 0. EGYED

Central Research Institute for Chemistry of the Hungarian
Academy of Sciences, Budapest (Hungary)

ABSTRACT
On the basis of the ir vapour spectrum of cyclohexane, the
-1
assignment of a weak band at 947 cm to the u15 fundamental is
probable. We discovered the completely forbidden vll fundamental
/ of cyclohexane in the vapour spectrum at 1110.7 cm-', which
la2g
has been observed so far in liquid phase only. On the basis of
the liquid and solid phase ir and the liquid phase Raman spectra
of bromocyclohexane, the vibrational frequencies are given between
-1
1500 and 100 cm , along with their distribution among the equa-
-1
torial and axial conformers between 1500 and 400 cm . In addition
to C-Br and C-Cl stretching and bending of halocyclohexanes, the
breathing modes of the cyclohexane skeleton are also assigned.

INTRODUCTION
In our opinion, the extensively studied family of cyclohexane
and its derivatives still has some novelties in store for spectro-
scopists. This short paper deals with some intermediate results
of our investigations on cyclohexane, chlorocyclohexane and bromo-
cyclohexane.

EXPERIMENTAL
The ir spectra were recorded with a Nicolet 7199 FT-IR system.
The spectra of liquids and solids were taken wrth a resolution of
-1
ca. lcm , vapour phase spectra were taken with a resolution of
ca. 0.25 or 0.12 cm -1 , respectively. Raman spectra were measured
with a Cary 82 spectrophotometer using the 514.5 nm line of a
Spectra Physics Ar+ ion laser for excitation.
Samples of commercial origin were distilled repeatedly until
they were found gas chromatographically pure.

0022-2860/82/0000-0000/$02.75@ 1982 Elsevler ScientificPubllshing Company

466

RESULTS
Cdclohexane
The infrared and Raman spectra /including polarized Rarnan/ of
liquid cyclohexane and the high-resolution infrared spectrum of
cyclohexane vapour show that one of the three a2u fundamentals ex-
pecked to occur below 1500 cm -1 cannot be assigned satisfactorily.
According to Obremski, et al. /l/ the ir band at 1014 cm-l /liquid
-1
phase/, accordrng to Wiberg and Shrake /2/ the ir band at 1032 cm
/liquid phase/ is assigned to the third band of a2u species, where-
as Takahashi, et al. /3/ had assigned earlier these two bands to
a combination of the a vibration at 802 cm -1
with the eU vibra-
lg
tion at 248 cm -1 and to that of the e vibration at 778 cm -L /Cal-
4
culated value/ with the eu normal vibration at 248 cm -1 , respecti-
vely. According to 'their calculations the third a2u vlbratlon band
can be expected to occur at 923 cm -1 , but they were unable to ob-
serve this band because of the overlap with the strong perpendicu-
lar band at 902 cm -l /3/.
The fine structure of the bands observable in the infrared
vapour spectrum recorded In our laboratory suggests that the very
weak band with a centre of ca. 947 cm -' 1s a parallel band /Flg.l./,
and thus it may be assigned to the a 2u normal mode with a calculated
frequency of 923 cm -' /3/. Furthermore, the spacing of the Q-branches
-I
of the band with a centre of 1012 cm allows one to assign it to an
a2u normal mode as well. According to our assumption the band cen-
-1 arises
tered around 1039 cm from a combination.

WRVENUMBERS WAVENUMBERS
-1 -1
Fig. 1. The 947 cm band of Fig. 2. The 1110.7 cm band
cyclohexane vapour. of cyclohexane vapour.
 461

In the infrared vapour spectrum there 1s a very weak band at

1110.7 cm -1 /Fig.Z./, assigned by Wiberg and Shrake /2/ and by
Bernard /4/ to a totally forbidden a fundamental, ull, on the
2g
basis of the infrared liquid spectrum and Wiberg's and Shrake's
final normal coordinate computation. These authors found no coun-
terpart of this band in the vapour phase spectrum /in fact they
found three unassigned infrared liquid bands with no counterparts
-1
in the vapour phase spectrum, at 1159, 1110 and 787 cm /.
Our Raman studies confirm the observation of Miller and Golob
/5/ that the v3 fundamental of a species appears as a polarized
-1 lg -1
line at 1465 cm . However, even under a resolution of 0.25 cm , we
could not find the 785 cm -' band of eg species assumed by Ito /6/
and Obremski, et al. -1
/I/. It is noted that the 2924 cm band of
ambiguous polarization according to Wiberg and Shrake /2/ is polar-
ized /p= 0.3/ according to our measurements.

Chlorocvclohexane and bromocvclohexane

Kozlma and Sakashita /7/ investigated the energy difference
between the two stable isomers of chlorocyclohexane on the basis of
the integrated band intensities of vapour spectrum. Their paper
gives the infrared and Raman frequencies and relative intensities
belonging to the equatorial and axial conformations.
With chloro- and bromocyclohexane, the Raman spectrum of the
liquid and the ir spectra of the vapour, liquid and solid /at 113 K/
were studied. Band frequencies of bromocyclohexane obtained between
-1
1500 and 100 cm are given in Table l., together with the assign-
ment of bands to the equatorial and axial conformers and the depo-
larization values. It was derived
Raman and ir spectra from the
-1 can be assigned to
that the Raman shifts of 732/e/ and 687/a/ cm
-1
the C-Cl stretching, and those of 684/e/ and 657/a/ cm to the
C-Br stretching. The very strong and polarized Raman lines at 342
cm -' /chl orocyclohexane/ and at 260 cm -' /b romocyclohexane/, re-
spectively, can be assigned to C-X bending.
We assume that the "breathing" mode of cyclohexane skeleton
induces the strong, polarized bands at 810/a/ and 820/e/ cm-l in
the Raman spectrum of chlorocyclohexane and the medium, polarized
-1
bands at 802/a/ and 809/e/ cm in the spectrum of bromocyclo-
hexane. One can also observe the corresponding bands in the ir
spectra at 809/a,w/ and 819/e,s/ cm -' for the chloro and at
805/a,vw/ and 811/e,s/ cm-' for the bromo derivative. The band
contours of the vapour spectra of chlorocyclohexane and bromocyclo-
hexane seem to confirm our assumption.
468

TABLE 1
Vibrational spectra of bromocyclohexane

460 m 458 m 0.17 a 1142 vw 1141 vvw dp a

501 In 500 m 0.17 e 1190 vs 1189 s 0.17 e
510 sh 508 sh ? a 1255 vs 1252 m 0.29 e
590 v-vw - - - a 1270 sh 1270 sh :p e
658 s 657 m 0.11 a 1300 w 1297 vw e
687 vs 684 s 0.21 e 1336 m 1333 m 0.33 e
777 vw - - - a 1350 w 1345 vw dp a
790 vw - - - e 1420 sh 1422 sh ? ?
805 vw 802 m 0.20 a 1440 w 1442 m dp ?
an s 809 m 0.20 e 1450 vs - - e
852 m 845 m 0.17 e 1464 w 1460 sh P e
865 w 862 vvw p a

vs = very Strong, s = strong, m = medium, w = weak,

v-w = very weak, vvw = very very weak, sh = shoulder

ACKNOWLEDGEMENTS
We are indebted to Mrs Temesvdri E. Major for the samples.

REFERENCES
1 R.J. Obremski, C-W. Brown and E-R. Lipplncott, J.Chem.Phys.,
49 119681 185.
2 K.B. Wiberg and A. Shrake, Spectrochim. Acta, 27A /1971/ 1139.
3 H. Takahashi, T. Shimanouchi, K. Fukushima and T. Miyazawa,
J. Mol. Spectry, 13 119641 43.
4 L. Bernard, J. Chum. Phys., 63 /1966/ 772.
5 F.A. Miller and H.R. Golob, Spectrochlm. Acta 20 /1964/ 1517.
6 M. fto, Spectrochim. Acta 21 /1965/ 2063.
7 K. Kozima and K. Sakashita, Bull. Chem. Sot. Jap., 31 /1958/ 796.