Jan., 1955 SPECTR.4 O F CiS-t?

YZnSI S O M E R S O F C O B a L T COGRDINATED COMPOUNDS 55

INFRARED ABSORPTION SPECTRA OF CIS-TRANS ISOMERS OF

COORDINATION COMPOUNDS OF COBALT(II1)
BY PAULE. MERRITT~ E. WIBERLES
AND STEPHEN
Contribution from the Walker Laboratory of Rensselaer Polytechnic Institute, Troy, N . Y .
Received July 66, 1964

The infrared absorption spectra of several cis-trans pairs of coordination compounds of cobalt show specific differences
between the cis and trans isomers. I n the case of the ethylenediamine-containing complexes a shift occurred in the 6.2-6.4
region of the spectrum with the trans isomer having a maximum peak a t a wave length of 0.04-0.08 p shorter than the cis
Isomer. I n the case of the cis and trans isomers of the cobalt complexes containing the tetraammine group a shift occurred
in the absorption band in the 12 p region with the cis isomer showing an absorption maximum at a wave length about 0.1-
0.2 p shorter than the trans isomer. All the compounds had an absorption maximum in the 6.1-6.5p region. This band
has been assigned to the (N-H) bending frequency in agreement with the assignment of Richards and Thompson.

Introduction
A fundamental idea in inorganic chemistry is that
coordination compounds, although numerous and
of different types, have only a small number of
stereochemical configurations. Recently an ex-
tremely interesting and important method for the
study of the absorption spectra of compounds in
the solid state was introduced by Stimson and
O’Donnelle and by Scheidt.8 The introduction of
this method has given great impetus to structural
studies of inorganic complex coordination com-
pounds. Although many infrared spectra of inor-
ganic compounds have been r e p ~ r t e d ,very
~ , ~ littIe
infrared work has been done to study the structure
of these coordination compounds.
A completely satisfactory method has not been
developed for distinguishing between cis and trans
isomers of metal coordination compounds of the
types Ma2b2, Mazbc, M(AA)zb2 and M(AA)2bc,
where a,b,c are monodentate groups, AA is a biden-
tate group and M is a metal. Previous workers
have applied physical methods to aid in the deter-
mination of structural configurations. Holtsclaw
and Sheetzs did a polarographic study of a series of
cobalt complexes. Basolo’ has studied the ultra-
violet region for differences in the absorption spec-
tra of cis and trans isomers of certain coordination
compounds in solution. Curran, et aZ.,8 have con-
ducted infrared absorption studies which have been
concerned with the effect of the charge of the me-
tallic ion on the nitrogen to metal coordinate bond
of complex compounds. Seng has studied the
absorption spectra of inorganic complexes of gly-
cine, and discussed their possible configurations.
This study was concerned with the application
of infrared absorption to aid in the differentiation
between cis and trans isomers of a group of cobalt-
containing complexes.
(1) Department of Chemistry, St. Lawrence University, Canton,
New York.
(2) M. M . Stimson and M. J. O’Donnell, J . A m . Chem. Soc., 74,
1805 (1952).
(3) U.Scheidt. Z.Nalurforeck., 76, 270 (1952).
(4) J. M. Hunt, M. P. Wisherd and L. C . Bonham, Anal. Chem., 92,
1478 (1950).
(5) F.A. Miller and C . H. Wilkins, ibid., 24, 1253 (1962).
(6) H. F. Holtzclaw, Jr., and D. P. Sheetz, J. Am. Chem. Soc., 75,
3053 (1953).
(7) F. Basolo, ibid., 72,4393 (1950).
(8) C. Curran, D. N. Sen, 8. Mizushima, and J. V. Quagliano,
Paper 62, Pittsburgh Conference on Anal. Chem. and App. Spec.,
March, 1954.
(9) D. N. Sen, “Infrared Studies of Some Coardination Com-
pounds,” Ph.D. Thesis. University of Notre Dame, 1953.
Experimental
Determination of Infrared Spectra.-Infrared absorption
spectra were obtained with a Perkin-Elmer Model 21 double
beam recording instrument and a Perkin-Elmer Model 12B.
A rock-salt prism was used in both instruments except in
the case of the Model 12B where a lithium fluoride prism
was used for the 2 t o 4 p region in order to obtain better dis-
persion. The compounds were studied using the selid po-
tassium bromide technique. About 1.5 mg. of compound
was intimately ground with about 98.5 mg. of dry potas-
sjum bromide that had been screened to 200 mesh particle
size. The mixture was placed in a die constructed in this
Laboratory and a rectangular sample was pressed. This
sample was placed in a suitable holder and then placed in
the infrared beam.
Preparation of Compounds
1 and 2 .-cis and trans-dichlorobis-( ethy1enediammine)-
cobalt (111) chloride were pre ared according to the method
of Bailar.l0 Anal. Calcd. E r (Co(en)&l2)Cl: Go, 20.7;
C1,37.3. Found: Go, 20.4; C1,37.3.
3 and 4.-cis- and trans-dinitrobis-( ethylenediamine)
cobalt (111) nitrate were prepared according to the method
of Holtzclaw, Sheete and McCarty.ll Anal. Calcd. for
( C O ( ~ ~ ) ~ ( N O ~ ) ~Co, ~ : N, 29.1. Found: Go,
) N O17.7;
17.9; N , 29.0.
5.-Tris-(ethylenediamine)-cobalt( 111) chloride was re-
pared by the method of Work.12 Anal. Calcd. for
(en)3)Clr: Go, 17.1; C1, 30.6. .Fopnd: Go, 17.2; C1, 30.7.
ho-
6.-Carbonatobis-( ethylenediamine)-cobalt( 111) chloride
was prepared by the method of Werner and Rapiport.13
And. Calcd. for (Co(en)&O3)Cl.HzO; Go, 21.5; C1,
12.9. Found: Go, 21.5; Cl, 13.1.
7.-cis-Chloroisothiocyan tobis-( ethylenediamine)-cobalt-
(111) thiocyanate was prepared by the method of Werner
and Schmidt as given by J a ~ 0 b s e n . l ~Anal. Calcd. for
(Co(en)z(NCS)Cl)SCN: Go, 17.8; N, 25.4. Found:
Go, 17.5; N, 25.2.
-
%-cis - Chloroisothiocyanatobis (ethylenediamine) - co-
balt(II1) chloride was obtained as a by-product of the prepa-
ration of cis-chloroisothiocyanatobis-(ethylenediamine)-co-
balt( 111) thiocyanate. It was recrystallized from hot
water and air dried. Anal. Calcd. for (Co(en)z(NCS)
C1)Cl: Go, 19.22; N, 22.9. Found.: Go, 19.0; N,22.8.
9 .-trans - Chloroisothiocyanatobis -(ethylenediamine)-co-
balt(II1) perchlorate was prepared by the method of Wer-
ner.l6 Anal. Calcd. for (Co(en)s(NCS)Cl)C1O4: Go,
15.9; N, 18.8. Found: Go, 16.2; N, 18.6.
10.-cis - - -
Uromoaquobis (ethylenediamine) cobalt( 111)
bromide was prepared by the method of Werner and
Schmidt.l6 Anal. Calcd. for (Co(en)2(HrO) Br)Brr: Go,
13.6; N, 12.9. Found: Co, 13.7; N, 13.0.
(10) J. C. Bailar, Jr., “Inorganic Syntheses,“ Vol. 11. John Wiley
and Sons, Inc., New York, N. Y., 1946,p. 222.
(11) H . Holtzolaw, D.P. Sheetz and B. McCarty, i b i d . , Vol. IV,
1963,p. 176.
(12) J. B. Work, ibid., Vol. 11, p. 221.
(13) A. Werner and J. Rapiport, A n n . , 388, 72 (1912).
(14) C. A. Jacobsen, “Encyclopedia of Chemical Reactions,”
Vol. 111. Reinhold Publ. Corp., New York, N. Y., 1949,p. 153.
(15) I b i d . , p . 154.
(16) A. Werner and R. Schmidt, Ann.. 386, 136 (1412).
56 PAULE. MERRITTAND STEPHENE. WIBERLEY VOl. 59
11.-trans - Hydroxoaquobis - (ethylenediamine) - cobalt (C-N) stretching frequency centers about the sub-
(111) bromide was prepared b the method of Werner and stitution of halogen atoms upon the nitrogen and
Lange.17 Anal. Calcd. for &o(en),(HzO)(OH))Br2: Co,
15.77; N, 15.0. Found: Co, 15.5; N, 14.8. further deuteration experiments of N-monosubsti-
12 and 13.--cds- and trans-dinitrotetraaminecobalt (111) tuted amides. Lenormant21 found that the 6.4 1
bromide were prepared by the method of Biltz and Bilts.18 band in these deuterated amides was shifted to
Anal. Calcd. for ( C O ( N H ~ ) ~ ( N O ~ ) ~Co,
N O ~21.1;
: N, lower frequencies by a factor of 1.05. This indi-
35.0. Found: co,21.3; N,34.9.
14 and 15.-cis- and trans-dinitrotetraamminecobalt( 111) cated, on the basis of the work of Richards and
chloride were prepared by the method of Bilte and Biltz.18 Thompson, that the assignment was better attrib-
Anal. Calcd. for ( C O ( N H ~ ) ~ ( N O ~ ) ~Co,
) C I :23.2; C1, uted to (C-N) stretching frequency. Also, Lenor-
13.8. Found: C0,23.0; C1, 13.6.
16 and 17.--n’s- and trans-dichlorotetraamminecobalt- mant observed that the 6.4 p band was totally ab-
(111) chloride; the cis salt was prepared by taking two sent in the spectrum of N-bromoethanamide. In
grams of carbonatotetraamminecobalt( 111) nitrate and dis- regard to this, Richards and Thompson noted that
solving in concentrated hydrochloric acid. The purple pre- the substitution of an electrophilic group on the
cipitate was filtered, washed with water and air-dried. amido-nitrogen sometimes decreases the frequency
Anal. Calcd. for (Co(NH3)&12)Cl: Co, 25.3; C1, 45.6.
Found: Co, 25.5; C1, 45.4%. One gram of the cis com- of this band. A band did appear at -6.0 p. Fur-
pound was added to a small amount of water and heated ther substantiation for the assignment of this band
over an open flame. The mixture changed to a green color came from Randall, et u Z . , ~ who~ observed that this
on heating. The mixture was filtered hot and the solid band was absent from the spectra of lactams.
obtained contained some of the purple compound which
could not be removed. Anal. Calcd. for (CO(NH~)~CIZ)- Based on the evidence presented by Lenormant,
C1: Co,25.3; C1,45.6. Found: Co,25.5; C1,45.4. and further evidence from their study of N,N-di-
18.-Carbonatotetraamminecobalt(III) nitrate was pre- substituted ethanamides, Letaw and GroppZ4
pared by the method described by Wa1t0n.l~ A n d . Calcd. have assigned this band to the ( G N ) stretching
for (CO(NH~),CO,)NO~J/ZHZO: Co, 22.8; N, 27.1. Found:
Co, 22.8; N, 27.1. frequency.
19.-Hexaamminecobalt(II1) chloride was prepared by From the observation of the spectra of the com-
the method of Bjerrum and McReyno1ds.W Anal. Calcd. pounds used in this study, evidence can be obtained
for (Co( NH3)O)Cl3: Co, 22.0; C1, 39.8. Found: Co, 21.8; to support the assignment of Richards and Thomp-
C1, 39.6.
son. As was previously pointed out, a strong band
Discussion and Results appeared in each spectrum in this region. These
data appear in Table I. In this table compounds
A strong absorption band appeared in the 6.1- that contain both the (C-N) and (N-H) groups
6.5 p region in the spectrum of each of the nineteen are listed as well as some that contain only the (N-
compounds studied. The assignment of the group H) group. Since this band appeared in all com-
frequency with which this band is identified is quite pounds, the assignment of Richards and Thompson
controversial. LenormantZ1 and Randall, et u Z . , ~ ~ is more reasonable.
have argued that this band is characteristic of the
amido (C-N) stretching frequency. Richards and TABLE I
Thompson2a and others have assigned it to the WAVE LENGTHOF .\BSORPTION BANDMAXIMUM1N SIX
(N-H) bending frequency. The latter base their ASD 12 p REGION
argument on the fact that primary amines absorb 6P
. 12 P
broadly in this region, with this band being cer- Reglon Region
Wave Wave
tainly due to this deformation. I n acetamide, the Formula
length,
P
length,
P
frequency and the structure of this band are un-
changed with respect to the primary amines. The 1 cis-[Co(en)~Cl~]Cl 6.48
absence of this band from the spectra of N,N-disub- 2 trans-[Co(en)zCI~]C1 6.30
stituted amides and the fact that one would expect 3 cis-[Co(en)2(N02)2]N03 6.32
to find (N-H) bending in this region of the spectra 4 trans-[Co(en)2(N02)2]NOs 6.24
of N-monosubstituted amides, is the basis for the 5 cis-[Co(en)3]Cla 6.44
assignment af this band. Richards and Thomp- 6 d~-[Co(en)~CO~]C1~H~0 6.34
son also studied the Raman spectra of CH3NHz 7 cis[Co(en)2(NCS)Cl]SCN 6.41
and CH3ND2,and found that with the introduction 8 ci~-[Co(en)~(NCS)Cl]Cl 6.40
of deuterium in place of the hydrogen, the (N-H) 9 trans- [Co(en)*(NCS)Cl] Cl04 6.34
bending band was shifted to a lower frequency by 10 cis- [Co(en)z(H~O)Br]Br2 6.36
a factor of 1.33-1.36. The (C-N) stretching band 11 trans-[Co(en)~(HzO)(OH)]Br~ 6 30
was shifted by a factor of 1.05. 12 cis-[Co(NHa)r( NOz)r]NOa 6.26 12.22
The evidence for the assignment of this band to 13 t~an~-[Co(NHa)q(NOs)i]NOa 6.22 12.27
14 c~s-[CO(NH~)((NO~)*JC~ 6.20-6.30 (b) 12.20
(17) A. Werner and K. Lango, A n n , 886, 97 (1912). 15 ~~U~S-[CO(NI-I~)~(NOZ)~]C~ 6.24 12.30
(18) H. Biltz and W. Biltz, “Laboratory Methods of Inorganio
Chemistry,” 2nd Ed., John Wiley and Sons, Inc.. New York, N. Y.,
16 c~s-[CO(NH~)~C~~]C~ 6.28 11.88
1928, p . 179-181. 17 tra~~-[C~(NHa)iClz]Cl 6.24 12.06
(19) H.F. Walton, “Inorganic Preparations,” Prentice-Hell, Inc., 18 [Co(NHa)rCOs]NOa“/2H10 6.28 12.06
New York, N . Y.,1948. 19 [CO(NHI)BICI~ 6.46
(20) J. Bjerrum and J. P. McReynolds, “Inorganic Syntheses,”
Val. 11, John Wiley and Sons, Inc., New York, N . Y.,p. 216.
(21) H. Lenormant. Ann. chim., 5 , 459 (1950). Examination of the spectra of the groups of com-
(22) H.M. Randall, R . G . Fowler, N . Fuson, and J. R. Dangl, pounds (1-11) containing ethylenediamine as the
“Infrared Determination of Organic Structures,” D. Van Nostrand inert constituent in the complex shows there is a
C o . , Inc., New York, N . Y., 1949.
(23) R. E . Richards and H. W. Thompson, J . Chem. Soe., 1248 (24) H. Lrtaw end A €1. Gropp, J Chem. P h y s . . 91, 1621
( 1047). (1953).
Jan., 1955 OF GAS MOLECULES
IKTERACTION WITH CAPILLARY
SURFACES 57

shift in the absorption band in the (N-H) bending

region between the cis and trans isomer of any one
compound. The absorption maxima of all com-
pounds of the cis series appeared a t approximately BO
the same wave length. The compounds of the
trans series show absorption maxima 0.04 to 0.08
p lower. For each pair of isomers as illustrated by
a typical example shown in Fig. 1, the trans isomer
has a maximum that appears a t a lower wave length
and a t a higher frequency than the cis isomer. This
fact can be used to differentiate between the cis 0
arid trans isomer of a given cobalt ethylenediamine- 2
containing complex. 0
-.
Although this band appeared a t approximately cn
the same wave length in the spectrum of both the 60
cis and trans isomer that contained four ammonia r"
molecules as the inert constituent of the complex, cn
a shift did occur in the broad band that appeared 2
in the 12 p region. I n the three cases studied the cl,
maximum of this absorption band of the trans series a
k
was a t a longer wave length and a lower frequency
t,han the cis isomer. The compounds of the trans
series have an absorption maximum which is 0.1- 8
0.2 p higher than the compounds of the cis series. -TRANS
This shift can be used to differentiate between the
cis and trans isomers of complex inorganic com-
poiuids containing cobalt and the tetrammine
group. U
Although the spectra of the cis and trans isomers 40
of individual compounds show definite differences,
the only regions showing consistent variation be-
tween the cis and trans isomer having similar groups
within the complex were the 6 and 12 p regions. 6.0 r.0
Acknowledgment.-The authors are indebted to MICRONS.
. -"--
Dr*
W,n t , John -.. Y-., fnvBehr-Manning
p r.v l i d > N _ v _ t"_--
h p 1 1 s ~nf t"__"
-I-y _ -_
hCorporationJ
e Mnrld 41
y"-
Fig. 1.TTypical shift of abFo!:ptiop ,m?ximuy. in . 6
region using czs- ana trans-alnitronis-(etnyleneaiam1ne]-
Perkin-Elmer Infrared Spectrophotometer. cobalt(II1) nitrate as example.

THE INTERACTIOX OF GAS MOLECULES WITH CAPILLARY ,4KD CRYSTAL

LATTICE SURFACES
BY w.A. sTEELE3*4AND G. D. HALSEY,
,JR,
Departnrent of Cheinistry, University of Washington, Seattle, Washington
Received J u l y 27, 1964

A theory of the interaction of gas inolecules with a structureless plane has been modified to treat capillary spaces. The
effect on the apparent area and energy of interaction is calculated. The interaction of a molecule with the surface of a simple
cubic lattice of atoms has been computed and compared with the crude model, Experimental data on the interaction of
helium, neon, argon, hydrogen, oxygen, nitrogen and methane with porous glass and saran charcoal are presented and
disrussed.

1. Introduction where E is the energy of interaction of the gas mole-

The apparent volume V of a vessel containing a
large surface area solid is given by the expression
V - V,,, = $"""/esp (-€/AT)- 1)dJ' (1.1)
(1) Presented a t the 120th national meeting of the American
Chemical Society, New Yotk, September 12-17, 1954. Partially sup-
ported by Contract AF19(604)-247 with the Air Force Cambridge
Research Center.
(2) Presented in partial fulfillment of the requirements for the
1'h.D. degree by W. A. S.
(3) National Science Foundation Pre-doctoral Fellow, 1953-1954.
(4) Pennsylvania State University. State College, Pa.
cule with the solid, in the volume element dV. We
have solved this problem previously5 for the case
of an isolated plane well composed of a structure-
less material with a hard-sphere repulsion for the
gas atom. This analysis led to a value for the dis-
tance of closest approach, the energy of intemction
a t this distance and the surface area of the solid.
We shall ndw consider some refined models: the
problem of capillary spaces in a structureless solid,
and that of the plane surface of a crystal of defi-
(6) W. A. Steele and G. D . Halsey, Jr., J . Chenz. P h y a . , 22, 979
(1954).