Crystal Spectra of Metal Coordination Compounds. II.

Violet Form of CoPy2Cl2 and

CoCl2·6H2O
J. Ferguson

Citation: The Journal of Chemical Physics 32, 533 (1960); doi: 10.1063/1.1730730
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 32, NUMBER 2 FEBRUARY, 1960

Crystal Spectra of Metal Coordination Compounds. II. Violet Form of CoPy 2Cl 2 and
CoCI 2 '6H 20
J. FERGUSO~

Division of Chemical Physics, C.S.l.R.O. Chemical Research Laboratories, Melbourne, Australia

(Received August 7, 1959)

A microspectrophotometric study of the visible polarized crystal spectra of the violet form of cooalt di-
pyridine dichloride and cobalt chloride hexahydrate is reported. An analysis of the band structure of the
former is made in terms of non interacting, complex units, but in the latter, interaction between a cooalt
ion and the chloride ions on next nearest neighbor complexes, in addition to the ligands, is needed for a
successful analysis of the spectrum.

INTRODUCTION 4p state is not split and remains triply degenerate,

the previous paperl the absorption spectra of a
I )J
number of tetrahedral cobalt (II) complexes were
reported. The present paper is concerned with the
crystal spectra of two octahedrally coordinated cobalt
(II) compounds with known crystal structure, CoCI 2 •
6H 20 and the violet form of CoPyzCh.
The crystal absorption spectrum of cobalt chloride
hexahydrate has previously been reported by Gieles-
sen2 and Pappalardo. 3 Pappalardo's work was done with
unpolarized light and as will be shown the absorption
spectrum is so strongly anisotropic that measurements
with unpolarized light confuse the analysis of the
bands. Gielessen had noted the marked anisotropy of
the absorption, but he was not interested in an analysis
of the band structure. The present analysis was made
possible by the recent crystal structure determination
in which it was shown that the basic octahedral unit is
CoCh(H 20)4 and not Co(H 20) 6++. 4
Octahedral Co++ complexes are red in color and the
spectrum of the ion in water is well known. The spec-
trum of single crystals of CoS04 • 7H 20 has been studied
by Holmes and McClure," and it is nearly identical
with that of Co++ in water. The spectrum of Co (NOB) 2'
7H 20 was determined in the present work and it is also
the same as Co++ in water. The absorption band is
broad and asymmetrical, centered at about 500 mJ.l.
It is likely that the asymmetry is linked to a distortion
of the water octahedron as a result of the Jahn-Teller
effect.6 This asymmetry is developed to a marked ex-
tent in CoCh ·6H20 and can best be explained by
considering the 'interaction between a Co++ ion and
the next nearest neighbors as well as the six ligands.
The ground state of the cobalt (II) ion is split under
the effect of an octahedral field into three levels,
4Tlg(F) , 4Tzg (F) , and 4A zg (F), while the excited
J. Ferguson, J. Chern. Phys. 32, 528 (1960); hereafter called I.
I
2 J. Gielessen, Ann. Physik 22, 537 (1935).
3 R. Pappalardo, Phil. Mag. 4, 219 (1959).
• Mizuno, Ukei, and Sugawara, J. Phys. Soc. Japan 14, 383
(1959).
5 O. G. Holmes and D. S. McClure, J. Chern. Phys. 26, 1686
(1957).
6 H. A. Jahn and E. Teller, Proc. Roy. Soc. (London) A161,
220 (1937); H. A. Jahn, Proc. Roy. Soc. (London) AI64, 117
(1938).
4T1g (P). The 2G, 2H, ZP, and 2D states must also be
considered and a diagram published by Low 7 gives the
calculated energy levels of the various levels as a func-
tion of cubic field strength in Oh symmetry.
EXPERIMENTAL
The experimental arrangement was similar to that
described in I except that a special stageS was used to
record the spectra at low temperature. The prepara-
tion of the cobalt dipyridine dichloride is described in
the literature9 and the cobalt chloride hexahydrate was
analytical grade recrystallized from water.
CRYSTAL STRUCTURE OF CoCI,·6H 2 0
The crystal structure has recently been reported by
Mizuno, Ukei, and Sugawara. 4 It is monoclinic with the
unit cell dimensions a= 10.34, b= 7.06, c= 6.67 A,
and /3=122° 19'. Figure 1 shows projections of the
CoCIz(HzO)4 units (a) on the (010) face and (b) on
the (001) face of the crystal. The remaining two mole-
cules of water, which are in the lattice, are not included
in the projections. The cleavage plane is parallel to
the (001) and this is the well-developed face when the
crystals are grown from solution. The projection in
Fig. 1 (b) is then the relevant one for the spectral
measurements as the light was incident on the (001)
face. The b crystal axis is parallel to the needle axis and
the Co-Cl bonds lie in the ac plane at right angles to
the b axis. The crystals are strongly dichroic and appear
orange with the electric vector perpendicular to the b
axis and mauve with the vector parallel to the b axis.
These colors depend, of course, on the crystal thickness.
The complex unit belongs lO to the point group D4h
and the arrangement of the four water molecules is
square planar.
CRYSTAL STRUCTURE OF CoPy,C1 2
The structure of the stable violet form of cobalt
dipyridine dichloride has been determined by Dunitz. ll
W. Low, Phys. Rev. 109, 256 (1958).
7
Spectrochim. Acta (to be published).
8
9 A. Hantzsch. Z. Anorg. u. allgem. Chern. 159, 18 (1927).
10 Eyring, Walter, and Kimball, Quantum Cllcmistry (John
Wiley & Sons, Inc., New York, 1944), p. 387.
11 J. D. Dunitz, Acta Cryst. 10, 307 (19S7).

533

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 534 J.
Cl
o 0
c a
(0)
It is monoclinic with the unit cell dimensions a=34.42,
b= 17.38, c=3.66 A, and ,),=90°. The structure consists
of polymeric chains, running parallel to the c axis
(needle axis), each chlorine being shared by two co-
balt ions. Figure 2 shows the interatomic distances and
angles. The arrangement of the four chloride ions sur-
rounding each cobalt ion is rectangular planar so that
the octahedral unit CoPy2Cl4 has the point symmetry
D 2h , not D 4h • The y complex axis has been taken bisect-
ing the smaller Cl-Co-Cl angle (85.5°) and the z
axis coincident with the Co-N direction. The crystals
are poorly developed needles showing dichroism.
CRYSTAL SPECTRUM OF CoPy 2 Cl,
The absorption spectrum of a single crystal at room
temperature is shown in Fig. 3 for light incident on the
(100) face. The spectrum appears to be made up of
four bands, three of which overlap. Photographs of the
spectrum at low temperature, however, show the ap-
pearance of a narrow band at about 18 700 em-I.
CRYSTAL SPECTRUM OF CoCh·6H 20
The crystal spectrum shows a considerable amount of
structure even at room temperature. As well as two
broad bands there are other much narrower ones which
are further sharpened on cooling the crystal. Figure 4
shows the spectrum at room temperature and low tem-
perature in polarized light. The striking feature about
the absorption spectrum is the marked anisotropy of
some of the bands, particularly the broad band at about
22 000 em-I. If the spectrum is taken in unpolarized
light it is difficult to observe this band as it has an ap-
parent optical density of about 0.3 (50% transmission)
and is broad.
The spectra in Figure 4 were recorded on the Beck-
man DK2 spectrophotometer and the resolution is not
sufficient to resolve the structure of the weak narrow
bands. These were obtained from photographs taken
with the Hilger medium spectrograph and their posi-
tions are given in Table 1. They are indicated by
arrows in Fig. 4. The positions of these bands agree
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FERGUSON
•
FIG. 1. Crystal
structure of cobalt
b chloride hexahy-
drate, projections of
CoCI,(H20), units
(a) on the (010)
face and (b) on the
(001) face.
(b)
fairly well with those reported by Gielessen,2 but in-
clude one or hvo more than those given by Pappalardo. 3
There is an interesting intensity change and shift of
the group of narrow bands on cooling the crystal. Those
from 19800 cm-I to 20400 cm-I decrease in intensity
and the remaining ones increase in intensity. It is likely
that the former represent "hot" bands, transitions
arising from the vibrationally excited ground state.
DISCUSSION
Band Widths
Both sharp and broad bands often appear in the
spectra of transition metal complex ions. The reason
for this can easily be seen by considering the dependence
of the ground and excited states on the crystal field
strength. 12 When the upper state of an electronic transi-
tion has the same, or nearly the same, orbital electron
configuration as the ground state, then the bands
appear sharp.
Pappalard0 3 and Low have calculated the energy
levels of both doublet and quartet states of Co++
in an octahedral field. These calculations show that
three electronic states should be considered for the
spectral region covered by the present work. Two of
these are quartet states 4TIy (P) and 4A 2u (F) and the
other is a doublet state 2Tla(P). The appearance of
the narrow bands in the spectrum of CoCb ·6H20 can
be linked to the transition from the ground state to the
doublet state, because this has essentially the same
orbital configuration as the ground state. Spectra of
CoPy2Cb at low temperatures show the appearance of a
narrow band, but overlap by the more intense broad
bands in the same region obscures the detection of
others.
Transitions from the ground state to the two quartet
states 4Tla (P) and 4A 2g (F) should result in broad
bands, with the transition to the latter being broader
and weaker than the other. In order to identify the
bands it is necessary to consider the orientations of
the complexes in the crystals.
12 L. E. Orgel, J. Chern. Phys. 23, 1824 (1955).
 CRY S T ,\ L SPECT R A 0 F V] 0 LET CoP y , C 12 ;\ N D C 0 C 1, . () H 2 0 53:;

£1 C:Z
1

o
~
so ,. "
r
FIG. 2. Crystal structure
of cobalt dipyridine di- o,.
chloride, interatomic dis- z
en
tances and angles. O----f-tl-i---l:-.::t.-o N ~
01

31!OJ.V!l3d VOJ. "'OOl!!

LI 91 61 OZ IZ sz

o
...
Cobalt Dipyridine Dichloride
SO (i
r
,."
CoPy2Cb belongs to the point group D2h because there
is a slight rhombic distortion of the tetragonal sym- z '"'"
cn
::;
metry. This means that the triple orbital degeneracy -<
of the 4T1g state in octahedral symmetry is removed. 3l<n.lVl<Jdf'l3.J. MOl
0-)

The correlations between the irreducible representa-

tions of Oh, D4h , D2h , and C2h are given in Table II.
It is seen that the components of the ground state are
4B 1g , 4B2g and 4B3 in D Zh • Xeglecting the rhombic dis-
(J
tortion it is easy to see that from the positions of Cl-
and Py in the spectrochemical series13 the dx • and dyz
orbitals should be less stable than the dxy orbital. This
means that the ground state should be doubly degener-
ate, 4Eg , with the 4A 2g state possibly some few hundred
cm-1 above it. It seems likely that the rhombic distor-
tion in CoPy2Cb has its origin in the Jahn-Teller effect
so that the 4Ea level is split into 4B2a and 4B 3y •
A decision must be made as to which band represents
the transition to the upper state 4 A g ( 4 A 20 in 0,,). It is
"0
.,/ J. ""odie ai.. (o}
FIG. 4. Crystal spectrum of cobalt chloride hexahydrate at
room temperature and low temperature, in polarized light. The
arrows show the position of the bands recorded in Table I.
assumed that the band at about 16 000 cm-I, polarized
perpendicular to the needle axis, represents this transi-
tion. This is so because the spectra of CoPy4Cb and
CoPY4(NCSh14 show no pronounced splitting of the
absorption band, and the components are grouped close
together so that a simple tetragonal distortion is un-
likely to produce a splitting as large as 3000 cm-1 in
CoPy2Ch. Also, the 4A2o state should lie below the
4T1g (P) state for Dq less than about 1000 cm-1 and the
ligand field in CoPy2Cl 2 seems certainly less than this;
in fact it represents the lowest field of any octahedral
complex of cobalt (II) studied in the present work.
If we assume, therefore, that the band at 16 200 cm-1
is the transition to the upper 4A g state, it remains to
identify the other bands. For this it is necessary first
to consider the projections of the transition moments

TABLE I. Positions of the narrow bands in the spectrum of

CoCr.·6H20 at low temperature (±20 cm-1 ).
20
WAVENUMBER. x 10·$ (em·'). 19850cm-1 20 230 cm-1 (a pol.)
FIG. 3. Crystal spectrum of cobalt dipyridine dichloride in 20030 20 250 (b pol.)
polarized light. 20 120 (a po1.) 20 410
20 130 (b pol.) 20 580
20 850
13 R. Tsuchida, Bull. Chem. Soc. Japan 13, 395 (1938).

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 536 J. FERGFSOK

TABLE II. Correlation table for the resolution of Ok into D'h, TABL~ IV. Vibro!lic represen~ations in D2h (product of ground
Dv., and C!h. Only the g representations are given. electromc state, eXCited electromc state and perturbing vibration)
for CoPy2CI,.
Oh D'h D'h C2h
-------- .. ----~--- Symmetry repre-
sentation of per- Symmetry ropresentation of the product of
Ala Aln An Aa turbing vibration ground and excited electronic wave functions
A 2g Bla An An
E. A.+B'g B 2 .+B3g A.+A.
T,g A 2 .+Eg B1g+B'g+B' g B.+A.+B g Ag RIg B'g B~{y
Tz. B2g+E. B,.+B2g+B3g B.+A.+B.
{3lu B lu A" B,. B2u
{l,,, B 2u B7,,~ Au B lu
(lEU BEU B,. B lu Au
on the crystal axes, in particular the absorption in-
tensities.
Table III gives the absorption intensities which Cobalt Chloride Hexahydrate
would be observed with electric vector directions
parallel to each of the three crystal axes, for transitions It would appear from the success of the analysis of
of unit intensity along each of the three molecular axes, CoPy2 Cl 2 that the analysis of the spectrum of CoCh·
assuming no intercomplex interaction. Because the 6H20 should follow on closely similar lines. Such an
absorption spectrum was observed for light incident approach would treat the symmetry of the complex as
D4h and consider projections of the molecular axes on
on the (100) face of the crystal, the projectioHs on the
band c crystal axes are relevant. the crystal axes. The ground state should be 4A 2o from
The electronic transitions are forbidden for electric arguments about the relative field strengths of the CI-
dipole absorption and internal u vibrations are assumed and H 20, similar to those used for CoPy2C/z, and the
to be the mechanism whereby intensity is stolen from excited states which fall in the spectral region examined
more energetic allowed transitions. The possible u will be 4A 2o (F), 4Eg (P) and 4B Ig (P). The fundamental
fundamentals belong to the representations B Iu , B zu , vibrations which satisfy the symmetry requirements as
and Batt of D 2h , and these can now be combined with all perturbers are a2 .. , {32u, and ~u. However, combinations
the possible direct products of the ground and excited of these vibrations with the electronic states cannot
states as shown in Table IV. Only those vibronic explain the polarization of the bands in the spectrum.
combinations with symmetry BItt, B 2u , or Bau are allowed The fu(X, y) transition moment projects mainly on the
(A lu is inactive) and correspond to transition moments b crystal axis and none of the strong bands is b polarized.
along the z, x, and y molecular axes, respectively. In addition the strongly polarized band at 22 000 cm-1
The assignment of the 16 200 cm-l band to an upper is difficult to understand with this scheme. Because of
4A g state which is polarized perpendicular to the c the failure of this model, an attempt was made to
crystal axis (parallel to b) means that the ground state include the effect of interactions other than from the
must be 4Bag, since BSflX AgX ({3Iu, {3zu, {33u) = B 2u , B 1u , six ligands in the octahedron. The next nearest neigh-
Au; zero projection on the c axis, Table III. Either a bors of the Co++ ion are the four CI-- ions which lie
Bag or B 2g ground state is consistent with the interpre- toward the corners of the unit cell, each 4.SA from the
tation of the rhombic distortion as arising from the Co++ ion. \Vhen these together with the six ligands are
Jahn-Teller effect. considered, it is easily seen, Fig. 1, that the field around
The assignment of the other three bands follow from the Co++ is C2h • The correlations between D4h and C2h
Fig. 3 and Tables III and IV. The highest energy com- are given in Table I where the twofold axis of C2h is
ponent has nearly equal absorption intensity along taken to be identical with the twofold axis which bi-
the band c crystal axes and must be assigned to an sects the H20~Co~H20 band angle in D 4h •
upper 4Bsg state because BggXBag=Ag, and from Table The ground state is now 4Bg while the excited states
I this should result in three active components B lu , are 4A g(F), 4Bo(P) , 4A u(P), and 4B o(P). The z axis
B 2u , and B 3u • The other two bands have the same (Au representation) is coincident with the b crystal axis
polarization ratio, roughly 2/1 (c/b) and this is ex- and the x and y axes (B,,) lie in the ac plane. It is only
pected for both Big and Bza upper states.
TABL~ V. Vihro~ic rcpresent.ations in C2h (product of ground
ciectrolllc state, eXCIted electromc state, and perturbing vibration)
TABLE. III. Sg~ares
of the projections (absorption intensities) of for CoCb·6H20.
umt transitIOns moments on the crystal axes in CoPy2CI 2 •
Symmetry repre-
Crystal axis sentation of per- Symmetry representation of the product of
Complex axis and rep- turbing vibration ground and excited electronic wave functions
resentation in D2h a b c
Ao Bo
x (B 2 ,,) 0.57 0.43 0
Y (B 3 .) 0 0 1 Au B"
z (B lu ) 0.43 0.57 0 Bu Au

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 CRYSTAL SPECTRA OF VIOLET
the au and {3u vibration fundamentals which are capable
of removing the symmetry prohibition of the electronic
transition. The combinations of these with the direct
products of the ground state and possible excited states
are given in Table V. This shows that the absorption
bands should be unpolarized if the au and {3u vibra-
tions are equally efficient perturbers. The analysis of
the spectrum depends on the assumption that one
species is much more efficient than the other and this
can be related to the mechanics of the vibrations
and/or the nature of the excited state from which the
intensity is stolen.
Speculation about the mechanism of possible perturb-
ing vibrations is unwarranted at this stage, but the
question of the nature of the allowed electronic transi-
tions from which the intensity is stolen can be con-
sidered. Usually it is assumed that the perturbing
vibration mixes the dn configuration of the ion with a
dn-1p configuration. 15
There does not appear to be exact knowledge of where
the d- p transitions are located in complex ions, and
unless they are strongly lowered from the free ion
value they must surely lie at too high an energy to be
considered for intensity stealing. 16 The possibility then
enters that electron transfer states involving essentially
ligand to metal transitions are the states from which
the intensity for the d-d transitions is stolen. In
CoCI2 (H 20)4 the Co~CI electron transfer transition
should be the most important state from which the
intensity is stolen and the spectrum in Fig. 4 can be
analyzed on this assumption. The important vibrations
will be ones which are essentially Co-Cl stretching
modes, a2u in D4h and {3" in C2h . With the (3u vibration
as effecting the perturbation then the transitions have
the following polarizations: 4B g-,;4 Ag (F), b polarized;
4B q-,;4B g (P), a polarized; 4B y -,;4A g (P) , b polarized;
4B g-,;4B g (P), a polarized.
The strongly polarized band at 22 000 cm-1 is now
interpreted as 4B g-,;4B g (P) being a split component of
the octahedral band and the one at 18 500 cm-1 repre-
sents the accidently degenerate pair 4B y -,;4A g(P) and
4B g-,;4B,,(P), the other components of the octahedral
4T1g-,;4T1g transition. The weaker 4Bg-,;4Ag(F) transi-
14 Unpublished work.
10 A. D. Liehr and C. J. Ballhausen, Phys. Rev. 106, 1161
(1957).
16 Ballhausen and Liehr 15 assume the d - P transition is lowered
from about 120000 cm-1 to about 60 000 cm-1 in Cu++ to explain
strong absorption at about 2000 A.
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CoPy 2 Cl 2 AND CoCI 2 ·6H 2 0 537
tion is assumed to lie at about 18 000 cm-1 covered by
the stronger 4B g-,;4A g (P) band. The structure de-
veloped in the latter band at low temperatures is pos-
sibly a component of the quartet-doublet transition
which also accounts for the narrow bands in the region
19000-21 000 cm-I . This state, 2T1g (P) in Oh sym-
metry, will be split by the lower crystalline field and in
addition the bands will. be complicated because they
are narrow and vibrational structure will be observed. 17
The strong polarization of these bands is explained by
the effect of the C2h field in the same way as for the
quartet-quartet transitions.
CONCLUSIONS
The two octahedral cobalt(II) complexes studied
here seem to represent examples of the two possible
situations which can arise in the crystal spectra of
molecular coordination compounds. In the first, that
of cobalt dipyridine dichloride, the electric field at the
metal ion has the symmetry of the ligands and the effect
of next nearest neighbors can be neglected to a very good
approximation. In the second, that of cobalt chloride
hexahydrate, the electric field at the metal ion is of
lower symmetry than that of the ligands because of
illtercomplex interaction. The spectrum of this complex
is now unlike that of the first type and for the case of
Co++ a large splitting between the components of the
triply degenerate 4T1y (P) state occurs. This splitting
reveals the presence of a doublet state [2T1g (P) ]
which is normally concealed by the stronger 4T1g (P)
state in the other octahedral complexes.
In I intercomplex interactions were found to modify
the absorption spectra of some polar tetrahedral com-
plexes. The crystal spectrum of CoCb ·6H20 has shown
that intercomplex interaction can also be significant
in octahedral complexes even though there is a centre
of symmetry. This, of course, means that considerable
care must be taken in the interpretation of crystal
spectra when the crystal structure is not known.
The analysis of the spectrum of cobalt chloride
hexahydrate suggests that the mechanism of the d-d
transitions in metal complexes can involve electron
transfer states as the source of the intensity.
ACKNOWLEDGMENT
The author wishes to thank Dr. A. L. G.' Rees and
Dr. N. S. Ham for helpful discussions.
17 For example, R. Pappalardo, Phil. Mag. 2, 1397 (1957).