Sperfrochimico Acru. Vol. 43A. No. 3. pp 395400. 1987. 0584&8539/X7 $3.

00 + 0 (Ml
Pnnted in Great Bntam Pergamon Journals Ltd.

Infrared and Raman spectra of CuClz. 2(H,D)z0 and

K2CuCI, - 2(H,D)20. Vibrational modes, assignment and coupling
of the water librations

H. TANAKA*, J. HENNING, H. D. LUTZ-F and G. KLICHE$

Laboratorium fiir Anorganische Chemie, Universitiit Siegen, Postfach 101240, D 5900 Siegen, F.R.G. and
*Max-Planck-Institut fiir Festkarperforschung, D 7000 Stuttgart, F.R.G.

Abstract-The i.r. and Raman spectra of CuCI, 2H20 and K,CuCl, 2H20 and of deuterated samples of
these compounds are presented in the range 50-1700 cm-’ at liquid helium, liquid nitrogen, and ambient
temperatures. The spectra obtained are discussed and compared with the literature data in terms of both
bonding structure of the water molecules and vibrational modes, assignment, intermolecular coupling, and
combination bands of the H,O, HDO, and D,O librations. The i.r. and Raman bands of the librational
modes of CuCI, 2H,O are very broad even at liquid helium temperature indicating orientational disorder of
the water molecules.

INTRODUCTION because of the very fast anion exchange which takes place in
the discs. For the low-temperature measurements the variable
So far there have been a number of i.r. and Raman temperature cells RIlCjVLT 2 and Oxford CF 100 were used.
The Raman measurements, including single crystal studies,
spectral studies on CuCl, .2H,O (CCD), [l-5] and
were performed on a Coderg T 800 triple monochromator
K,CuCl, 2H20 (PTD) [ 1,4-7] and, hence, the inter- Raman spectrometer with the usual right-angle geometry and
nal modes of the water molecules are well character- with 488.0 nm radiation from an Ar+ ion laser. The low-
ized. However, the lower frequency bands and their temperature spectra were recorded using a variable tempera-
assignments are still ambiguous. The most remarkable ture cell (Coderg model CRN2). The signal-to-noise ratio of
the very weak Raman bands in the libratory mode region was
spectral features of these compounds are (i) the large
improved by averaging over up to 60 scans with a Nicolet
frequency shifts due to intermolecular coupling, (ii) the model 535 signal averager.
very small intensity of the H,O librational modes in The i.r. spectra of KZCuC14’2(H,D),0 were recorded
both i.r. and Raman spectra of CuC12. 2Hz0, and (iii) using KC1 pellets obtained by pressing CUC~~.~(H,D)~O
samples with excess KCI [5].
the ostensible absence of normal HDO librations in
the spectra of partially deuterated compounds of RESULTS
K2CuCI,.2H20. In order to investigate these
phenomena in more detail the i.r. and Raman spectra Internal modes of the water molecules
of these hydrates have been re-examined and measure- The frequencies of the internal modes of the water
ments made at liquid helium temperature. molecules, i.e. H,O, HDO, and D,O, respectively, of
CuCl, 2H20 crystallizes in the orthorhombic space both compounds correspond fairly well to those
group Pbmn-D &, K,CuCl,.2H20 in the tetragonal reported in the literature [2, 51 and, hence, will there-
space group P4/mmm-D::, each with Z = 2. In both fore not be given in this paper. The spectra obtained at
hydrates, there are plane CuC12(H20), units con- liquid helium temperature do not reveal any additional
nected by hydrogen bonds via common Cl- ions to band splitting or phase transitions. The frequency
sheets and chains, respectively [5, 8,9]. Group theoret- shifts compared with those from the spectra recorded
ical treatments of the external and internal vibrational at ambient and liquid nitrogen temperature are small.
modes are given in [l] (CCD) and [4, 51 (PTD).
Librationai and translator): modes
EXPERIMEVTAL The librational modes of the water molecules of
CuCl, 2H20 give rise only to weak and broad bands
Polycrystalline samples and singlecrystals of CuCI, 2H20
and of deuterated specimens were obtained by crystallization
in the i.r. and Raman spectra, even at liquid helium
from solutions of CuCl, in appropriate H20;DZ0 mixtures. temperature (see Figs 1 and 2). However, some modes
The i.r. spectra were recorded on a Perkin--Elmer model additional to those reported in the literature [l, 3, 51
580 spectrophotometer and Bruker IFS 114 Fourier- were observed. The translatory modes are strong and
transform-interferometer using nujol mulls and NaCl discs in
sharp in the Raman spectra, even at ambient tempera-
the range of 400&800 cm- ’ and nujol mulls on polyethylene
films from 8m50 cm- ‘, Normal KBr discs cannot be used ture, but likewise broad as the librations in the i.r.
spectra. Assignments of the bands recorded including
the Raman single crystal data are given in Figs 1 and 2.
The i.r. spectra of K,CuCl, 2H20 reveal relatively
*Present address: Faculty of School Education, Hiroshima
University, Shinonome Hiroshima 734, Japan.
strong bands in the Hz0 (HDO, D,O) librational
+ Lattice vibration spectra XLIV. Part XLIII, H. D. LUTZ,J. mode region, which become very sharp at liquid
HENNING and H. HAELSELER. J. moles. Struct., in press. helium temperature (see Fig. 3). In the case of partially
396 H. TANAKA
et al.

; ,., :
” . . ..
. .

; 690 “L.,
:.,

302
\ 3O%D

248
304

60%D
1 I

b
‘2 ..
472
1’ ‘..

/./ 525 ‘:h.;: “,,

300 238 :
00% D ,,....i .’ .i >.
.....-\ v ‘.: ..

...““““...._,...__ ..:’
.:I ‘. ,z 532
‘.+
* i.: ‘<

4* 459

.
,’ :
.5 , I
,:: ,’ *

*_------.,,-.. ,‘+& i2,\ ,S.’

: 1 RX RX 461
il I’
*3
* 302

L J

1000 cm-’ 750 500 600 400 cm-’ 200

Fig. 1. Infrared spectra (nujol mulls) of CuCl, .2H,O at different degrees of deuteration in the Hz0
librational and translatory mode region at liquid helium, liquid nitrogen, and ambient temperature (dashed,
full, and dotted lines, respectively); R ‘, R*. and RX, librational modes of the H,O, HDO, and D20 molecules,
respectively; v, antisymmetric CuO stretching vibration, .*, bands due to paraffin. Translatory modes below
2OOcm-‘, 57, 81, 104, 130, 138, 146, and 186 em-’ at liquid nitrogen temperature (see also [3]).
 1.r. and Raman spectra of CuC12.2(H,D)z0 and K2CuC14.2(H,D)20 397

deuterated samples most bands split to three or more with respect to the intensity and halfwidth of the
components. Assignments of the bands observed are librational modes. This finding is unexpected because
given in Table 1. the structures of the CuClz(H,O)z units present and
the surroundings of the water molecules, i.e. type D
DISCUSSION
after [lo] (see below), are very similar in these
Intensity and halfwidth of the HZ0 librational bands hydrates. The reason for the very broad i.r. and Raman
bands of CuCl, ‘2HzO in the Hz0 librational and
The low-temperature i.r. and Raman spectra of
translatory region, even at liquid helium temperature,
CCD and PTD reveal different behaviour, especially
may be orientational disorder of the water molecules.
17
Thus, the oxygen atoms can be disordered in such a
manner as discussed for Ba(C103)z. Hz0 type halates
111
[ll], namely, that the real bonding structure of the
Hz0 molecules is not type D, but type J after [lo], i.e.
bonding to copper occurs via one of the two lone-pairs.
In the case of PTD, however, not only the mean, but
also the local structure is type D, i.e. a trigonal
arrangement of the Cu-OH, units. This different
behaviour is possibly caused by the adjacent K+ ions.
O%D
37
Bonding structure and nature of the HDG cibrations
246

The order and relative intensities of the Hz0

409
librational modes, viz. the wagging (y), twisting (t), and
rocking vibrations (r), depend strongly on site sym-
694
metry and bonding type of the water molecules
_...j
[ 1 l-141. In the case of a tetrahedral environment of
the Hz0 molecules the order of the frequencies is
24(
v, G v, < vy compared to v, + v, >vY for trigonal en-
vironment, as found from both theoretical calculations
[ 121 and experimental studies [ll, 131. Furthermore,
twisting librations possess very strong Raman bands in
the case of tetrahedral environment, but only weak
bands for a trigonal arrangement [1 1, 131. The wag-
ging librations are also normally more intense in the i.r.
spectra than the rocking ones [ 13, 141. These features
are observed in the spectra of PTD and, hence, confirm
the trigonal arrangement of the water molecules in this
5O%D compound.
62
The most interesting discovery in the spectra of
PTD, however, is the fact that the HDO librations
observable in partially deuterated samples are clearly
40
H and D out-of-plane vibrations, as already discussed
in [5] and predicted from theoreticalcalculations [ 121,
and not “normal” HDO twisting and wagging modes
a despite the non-distorted water molecules present of
site symmetry C,,. The frequencies of these H and D
out-of-plane vibrations are similar to those of the Hz0
and DzO wagging modes, respectively, and are not

Fig. 2. Raman spectra of CuCI, .2H,O at different degrees

of deuteration in the H,O librational and translatory mode
36 95%D region at liquid nitrogen (full line) and ambient temperature
234 (dotted and dashed line); spectrum with improved signal/no-
ise ratio due to multiple scan and signal averaging technique,
dashed line. Wavenumbers in parentheses obtained from
401
room temperature spectra. Abbreviations as for Fig. 1.
Species (unit cell group II,,,) of the Raman bands obtained
from single crystal studies at ambient temperature; A,, 111,
217, and409; B,,, 67,248,and 693;&,,, 237 and 392; B,,.. 39(‘?).
&
670, and 721(?)cm ‘; the very weak-bands at 392 (v&i), 676;
and 721 cm _ ’ (both H,O librations) were not observed in the
:m-’ 200 400 600 800 spectra of polycrystalline samples
398 H. TANAKA et al.

intermediate between these modes as for “normal” Intermolecular coupling of the Hz0 librations
HDO librations. Normal HDO twisting and wagging The internal modes of the water molecules of both
vibrations are obviously only possible in the case of CCD and PTD are strongly coupled, as already dis-
non-distorted Hz0 molecules in a tetrahedral environ- cussed in [2, S]. This behaviour is caused by a vi-
ment [13]. brational mteraction of adjacent Hz0 molecules,

O%D

I
1505
...” ..”
,..”

....”
,,..’
“\ ..:.
,...
.“’ ; ,...’.,...’
,/.”

775

._._ I u-4
1430

-441,
1600 1400 1200 1000 800 cm-’ 400

Fig. 3. Infrared spectra (KC1 pellets) of KZCuC14.2H20 at different degrees of deuteration in the HZ0
bending, Hz0 librational, and translatory mode region at liquid helium, liquid nitrogen, and ambient
temperature (full, dashed, and dotted lines, respectively).
 1.r. and Raman spectra of CuCl, .2(H,D)zO and K2CuC1, 2(H,D)zO 399

especially those connected by hydrogen bonds via band, especially pronounced at liquid helium tempera-
common Cl- ions in the order -OHz-Clz-Hz& ture (see Fig. 3), is remarkable for overtones in the
[S, 8, 91, and results in large splittings of the various spectra of solid hydrates. (iii) There is bad agreement
unit cell modes. In this work we found a similar strong with the results of neutron inelastic scattering studies
coupling of the Hz0 librational modes of PTD shown [15].
from a splitting of the corresponding bands in the i.r. Unequivocal assignment of the i.r. and Raman
spectra of partially deuterated samples at liquid helium bands of CuCI, .2H,O in the region of the Hz0 li-
temperature (see Fig. 3). The number of components brational and translatory modes is less clear and, hence,
expected equals the number of possible arrangements we disagree partially with the interpretation given in
in the dimeric hydrogen-bond section discussed above, [ 11. For instance, there are strong indications, e.g. the
e.g DzO/DzO, D,O/HDO, and D,0/H20 for the Cu-0 bond lengths in CCD and PTD, viz. 197 and 196
DzO librations with decreasing coupling in this order. pm [S, 891, that the antisymmetric CuO stretching
Most components of these splittings are observed, e.g. vibration, (the highest wavenumber translatory mode)
two of the three DzO librations and all three D out-of- must be ascribed to the i.r. band at 485 cm- ‘, which is
plane vibrations of the HDO molecules (see Table 1). shifted on deuteration to 472 and 461 cm-‘, respect-
No splitting is observed for isotopically homogenous ively (see Fig. I), and not to the broad band at about
samples because only one unit cell mode of the 390 cm - ’ as proposed in [ 11. The latter band, which is
wagging vibration is ir. active, see [S]. shifted to 300 cm I on deuteration, must be one of the
librational modes. Correct assignment of the i.r. bands
Assignments of’the bands in the H20 librational mode
which are shifted on deuteration as HZ0 librational
region
modes (v~~,~/v~~,~ = 1.3-1.4), Gz. at 771, 696, 390, and
Our assignments of the bands observed in the i.r. perhaps at 345 cm-’ (see Fig. l), and the correspond-
spectra of K,CuCl,. 2H20 (see Table 1) resemble ing Raman bands (see Fig. 2 and [ 11, to the various in-
closely those given in [5]. However, some features of the plane and out-of-plane librations is not possible. The
spectra are not fully clear namely; (i) the intensity of the Raman band at 254 cm-‘, which is likewise strongly
band at 725cm-‘, which is ascribed to the Hz0 affected on deuteration (see Fig. 2), however, is prob-
rocking libration, is unusually low compared to that of ably due to a Cu-OH, bending vibration (see [l]).
the wagging mode at 560 cm- ’ (see Fig. 3); and (ii) the Finally, it may be noted here that the Raman band at
band at 1048 cm-’ must be interpreted as overtones 63 cm-’ (see Fig. 2) has a positive temperature coef-
and combination bands of various unit cell group ficient (dv/dT > 0) in contradiction to the normal
modes of both the HZ0 wagging lilaation near behaviour of lattice modes.
560 cm-’ and the twisting mode at 560 cm ’ observed
in the Raman spectrum [7]. Because of the large CONCLUSION
isotopic shift of this band in the spectra of deuterated
samples, viz. vH,o/vH,,o,D,O = 1.36, the participation The i.r. and Raman spectra of CuCl, ‘2HzO and
of translatory vibrations supposed in [5] is thought KzCuCl, .2H,O reveal the following main spectral
unlikely. The small halfwidth and large intensity of this features in the librational mode region, (i) strong
intermolecular coupling of the bands and, hence,
splitting of these modes into three or more com-
Table 1. 1.r. bands (cm-‘) of KZCuC1,.2(H,D),0 in the ponents in partially deuterated samples of
H,O, HDO and D,O librational mode region at liquid K2CuC14. 2HzO at liquid helium temperature, (ii)
helium temperature. For the bands at ambient and liquid orientational disorder of the water molecules of
nitrogen temperature see Fig. 3. CuCl,.2HzO as shown by the very large halfwidths of
the bands, even at liquid helium temperature, and (iii)
HDO
H D Remarks that the vibrational modes of the HDO molecules are
H,O D,O
H and D out-of-plane vibrations rather than “normal”
Out-of-plane librations (HDO), H,O and D,O wagging HDO librations. In the case of the internal modes of
vibration
the water molecules, the literature data are confirmed.
561 545 391 416 Coupled
533 403 HDO/H,O
560 416 uncoupled Acknowledgements-The authors thank the Deutsche
563 384 411 HDO/D,O Forschungsgemeinxhaft and the Fonds der Chemischen
Industrie for financial support. One of the authors (H.T.) is
In-plane librations (HDO), H,O rocking vibration
indebted to the Japanese Ministry of Education, Science, and
725 see text
Culture for a research stay fellowship.
Combination bands and over-tones of librations
1048 1053 780 773 2xR;
819 ? REFERENCES

CuO stretching vibration [l] I. R. BEA~TIE, T. R. GILSON, and G. A. OZIN, J. &em.

460 447 coupled Sot. A 1969, 534.
451 H,O-Cu-HDO [2] R. A. FIFER and J. SCHIFFER, J. them. Phys. 54, 5097
(1971); ibid. SO, 21 (1969).
400 H. TANAKAet al.

[3] K. FUKUSHIMA,Bull. them. Sot. Japan 44,372 (1971). S. SRIKANTA,Acta Crystallogr. B%, 827 (1970).
[4] D. M. ADAMsand D. C. NEWTON,J. them. Sot. A 1971, [lo] R. CHIDAMBARAM, A. SEQUEIRA,and S. K. SIKKA,J.
3507. them. Phys. 41,3616 (1964).
[5] G. M. THOMAS,M. FALK and 0. KNOP, Can. J. Gem. [ 111 W. ECKERSand H. D. LUTZ, Spectrochimica Acta 41A,
52, 1029 (1974). 1321 (1985).
[6] D. M. ADAMSand P. E. LOCK, J. them. Sot. A 1971, [12] A. ERIK~~ON and J. LINDGREN,J. molec. Scruct. 48,417
2801. (1978).
[7] V. C. SAHNI and M. L. BANSAL,Phys. Stat. Sol. (b) 90, [13] H. D. LUTZand H. CHRISTIAN, J. molec. Struct. 101,199
41.5 (1978). (1983).
[S] S. W. PETERSON and H. A. LEVY,J. &em. Phys. 26,220 [ 143 V. P. TAYAL,B. K. SRIVASTAVA, D. P. KHANDELWAL and
(1957). H. D. BIST, Appl. Spectrosc. Rev. 16,43 (1980).
C91R. CHIDAMBARAM, Q. 0. NAVARRO, K. [lS] Z. AMILIU~, Report 1977, IAEA-R-1104-F, INIS
LINGGOATMODO, S.-G. LIG, L.-H SUH,A. SEQEIRAand Atomindex 9, Abstr. No. 38021 (1978).