THE JOURNAL OF CHEMICAL PHYSICS VOLUME 49, NUMBER 4 15 AUGUST 1968

Vibrational Spectra of IF 7 and ReF 7*

HOWARD H. CLAASSEN, EARL L. GASNER, AND HENRY SELIOt
Chemistry Division and Chemical Engineering Division, Argonne National Laboratory, Argonne, Illinois
(Received 29 February 1968)

Raman spectra of IF7 and ReF7 have been observed for the first time in the vapor state. Infrared spectra
of the vapors have also been re-examined. Earlier difficulties regarding possible coincidences in the IF7
spectra have been removed. The data suggest that both molecules belong to symmetry group D.,., although
there are some significant as yet unexplained differences between them.

INTRODUCTION studies by Bauer,9 who suggested approximate DSh

symmetry, but with the five fluorine atoms in the
The recent interest in noble-gas compounds has
equatorial belt not quite coplanar; the average I-F
focused renewed attention on some of the properties of
bond distance was 1.825 A. More recent data by
the closely related halogen fluorides. One of the most
Thompson and BarteIllO are consistent with D6h sym-
interesting problems in xenon chemistry, as yet un-
metry. Although the results reported are preliminary,
solved is the molecular structure of XeF6.1 The simple
they do show that the axial I-F distance is shorter than
electr;n pair repulsion model by Gillespie,2 which
the equatorial, in agreement with predictions of the
assumes that nonbonding electron pairs are spacially
Gillespie model. ll Single-crystal data12 have also been
equivalent to bonding electron pairs, predicts a penta-
reported for IF7, but there has been some cont~oversy
gonal bipyramidal structure. Preliminary elec~ron
regarding the interpretation of the data, whIch are
diffraction studies indicate that, although XeF6 devIates
apparently insufficient to discriminate between the D6h
significantly from octahedral symmetr~, the de!orm~
and Ca. models. 1a In any case, results are not necessarily
tion is far too small to fit the seven-coordmated Glllesple
relevant to the structure of isolated molecules of IF7;
structure. a,4 A reexamination of the compound IF7,
because, on the one hand, distortions in the solid state
analogous to XeF 6 by virtue of its seven bonding
are very common, and secondly, the samples were un-
electron pairs, is warranted.
doubtedly contaminated by the oxyfluoride. Nuclear
A recent calculationS based on fluorine repulsions
magnetic resonance studiesl4 on liquid IF7 and ReF7
suggested a lower symmetry than DSh for heptafiuorides,
were inconclusive, because they indicated that the
but a more detailed molecular orbital treatment for
molecules undergo rapid intramolecular exchange on the
eight different models for IF7 gave the lowest energy for
NMR time scale causing magnetic equivalence of the
a DSh model. 6 The molecular structure of IF7 was first
seven fluorine nuclei.
studied by Lord et al. in an investigation of its infrared
The early infrared study7 failed to observe one of the
and Raman spectra.7 It was concluded that IF7 has a
infrared-active fundamentals, as pointed out by
pentagonal bipyramidal structure of symmetr;: Doh.
Barlett,8 but no complete study of the vibrational
This conclusion appears to be correct, although It was
spectra has been published since that of Lord et al.7
based upon results obtained On samples somewhat
A more recent unpublished study]5 on the infrared and
contaminated with IOFs and other impurities. The
Raman spectra has again cast some doubts on the
oxyfluoride was first prepared and identified by Bartlett,
correctness of the D5h symmetry. The difficulties hinged
who also pointed out the desirability of repeating most
mainly on the two apparent coincidences between infra-
of the earlier work on IF7.8 A number of other techniques
red and Raman spectra and also on the question of the
have been applied to IF7 in attempts to elucidate its
state of polarization of one of the Raman-active
molecular structure. These include electron-diffraction
fundamentals. According to the selection rules for D6h
symmetry, coincidences between Raman and ~nfrared
* Work performed under the auspices of the U.S. Atomic Energy fundamentals are forbidden. One weakness of thIS study
Commission. .
t Present address: Department of Inorganic and AnalytIcal was that Raman studies were done on liquid IF 7, so the
Chemistry, Hebrew University, Jerusalem, Israel. . . question about coincidences was not solved conclusively.
1 Symposium on the Structure of Xenon Hexafluonde, Amencan
Physical Society Meeting, Chicago, Illinois, 27 March 1967. The availablity of a laser-excited Raman apparatus
2 R. J. Gillespie, Noble Gas c.ompounds, H. H. Hyman, Ed. h 33 182 (1960)
(University of Chicago Press, Chicago, Ill., 1963), p. 333. 9R. E. LaVilla and S. H. Bauer, J. Chem. P ys. , .
3 L. S. Bartell, R. M. Gavin, Jr., H. B. Thompson, and C. L. 10H. B. Thompson, Jr. and L. S. Bartell, Trans. Am. Crystal
Ph 3 2547 (1965) Assoc. 2, 190 (1966).
Chernick, J. Chern. ys. 4 , . . 11 R J Gillespie, Can. J. Chem. 38, 818 (1960).
12 R: rio Burbank and F. N. Bensey, Jr., J. Chern. Phys. 27, 981
K. Hedberg,
]. Chem. Phys.44,S. H. (1966). R. R. Ryan, and B. Wemstock,
Peterson,
1726
6 T. A. Claxton and G. C. Benson, Can. J. Chem. 44, 157 (1966). (1957).
8 R. L. Oakland and G. H. Duffey, J. Chern. Phys.46, 19 (1967). 13 J Donohue, Acta Cryst. 18, 1018 (1965).

7~. C: Lord, M. A. Lynch, Jr., W. C. Sch urnb,and E . J. 14

ChN. Bartlett, Beaton, L. W. Reeves, and E. J. Wells, Can.
42 2531S. (1964).
SI~N~if~!t~i/~~mi. ~eL~v~h~k~}r~~ ~~~: Soc. 1963, 342. J. 10 L~S: Ar'ighi, Ph.D. thesis, University of Wis<;onsin, 1965.
1803

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 1804 CLAASSEN, GASNER, AND SELIG

IF7
VAPOR
1
>-
l-
635
ii)
Z
ILl
I-
~
(!)
FIG. 1. Raman spectrum of IF? vapor
~ at 2 atm pressure and ""25C. Incident
Q: A
ILl light polarized: A-perpendicular, B-
~u 0 parallel to plane containing the slit and
I laser beam, and C-spectral slitwidth.
(f)

~0 200
FREQUENCY, em-)
400 600

afforded us the possibility of studying both infrared and
Raman spectra of molecules in the gaseous state.
Only two other heptafluorides are known, ReF7I6 and
OsF7P The latter compound is stable only at low
temperatures, so it will probably be impossible to study
its properties in the vapor state. The vibrational spectra
of ReF7 have been reported earlier.lB Although they
were shown to be consistent with Doh symmetry, a
number of questions remained unsolved; and hence a
comparison with IF7 is of interest. We have reinvesti-
gated the vibrational spectra of these molecules,
concentrating efforts on the Raman spectra of IF7 and
ReF 7in the gaseous state as well as on some refinements
and extension of the infrared data.
EXPERIMENTAL PROCEDURE
The ReF7 was prepared and purified by methods
described earlier.19 The IF7 was obtained by treating KI
with a large excess of fluorine at 250. The KI was
previously dried at 250 overnight under vacuum to
avoid formation of the oxyfluoride. Residual impurities
were removed by flashing off several vapor-pressure
heads at room temperature. The IOFo impurity was
thus reduced to well below one percent as shown by the
absence in our infrared spectrum of the sharp and
intense Q branch of IOFo at 927 cm-l .
Infrared spectra were observed over the range
200-4000 cm-1 with a Beckman IR-12 and a 10-cm
long cell, and down to 140 cm-1 with a Perkin-Elmer
301 and a 15-cm cell. Window materials were Agel
or polyethylene and cells were constructed of nickel. The
pressures of vapors in the cells were controlled by
16 J. G. MaIm, H. Selig, and S. Fried, J.
1510 (1960).
17 O. Glemser, H. W. Roesky, K. H. Hellberg, and H. V.
Werther, Chern. Ber. 99, 2652 (1966).
18 H. H. Claassen and H. Selig, J. Chern. Phys. 43, 103 (1965).
19 J. G. MaIm and H. Selig, J. Inorg. Nucl. Chern. 20, 189
(1961) .
Am. Chern. Soc. 82,
regulating the temperature of a side arm. Background
spectra were scanned with the sample condensed in the
side arm by a liquid-nitrogen bath.
Raman spectra were obtained by means of a Spex
Model 1400 double monochromator, a photomultiplier
cooled to about -50 and an ac lock-in amplifier. The
exciting light of 6328 A from a Spectra-Physics Model
125 laser was chopped mechanically at 400 cycles. The
cells were cylindrical fused silica cells 20 mm in diameter
and 20 mm long. They were thoroughly baked out and
preseasoned with samples which were discarded, then
filled with enough sample for one to two atmospheres
and sealed off. In use the cells were placed with one
window in contact with a mirror inside a box which
could be electrically heated to vaporize (in the case of
ReF7) the sample. The laser beam entered through the
top window and was reflected from the mirror to pass a
second time through the cells.
RESULTS
Figures 1 and 2 show the Raman spectra of IF7 and
ReF7, and Fig. 3 ~hows the infrared spectrum of IF7.
For the infrared spectrum of ReF7in the range 250-1500
cm-l , we refer to our earlier publication,I8 and now
report another absorption maximum at 217 cm-I of
moderately weak intensity.
The Raman spectrum of IF7 vapor is very similar to
that reported by Lord et al.7 for the liquid, except that
we find no evidence for the two frequencies that they
list between 150 and 200 cm-I. Frequency shifts from
liquid to vapor are quite small. The Raman spectrum of
ReF7 vapor is also very similar to that reported earlier
for the liquid. 18 Two new frequencies are found for the
vapor, but they are so weak that their reality must be
considered doubtful.
The infrared spectrum of IF7 is significantly different
from that reported by Lord et al.? but Bartlett and

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 VIBRATIONAL SPECTRA OF IF7 AND ReF 7 1805

ReF7
VAPOR

t
>- 736
t:
(/) ..
z
W

FIG. 2. Raman spectrum of ReF7 vapor ~

at 1 atm pressure and ",75C. Incident I!)
light polarized: A-perpendicular, B- ~
~w
paraIIeI to plane containing the slit and
laser beam, and C-spectral slitwidth. A
(/)

o 200
FREQUENCY, em-I

Levchuk8 have already pointed out that the earlier found in each spectrum and two of the Raman bands
workers used an impure sample. One point requiring are highly polarized, just as expected for Ds/I. symmetry,
comment is the absence of the 746-cm-1 band, the third but inconsistent with the D7/1. model. The question of
strongest band in our spectra, in the earlier work. 7 We coincidences has been used by others to argue against
can only surmise that impurity bands in the earlier Doh symmetry/5 but with gas data the difficulty
work obscured this spectral region, and date that we essentially disappears. The 365- and 352-cm-1 bands are
found the intensity ratio of the bands at 746 and 670 clearly not coincident, and the 676- and 670-cm-1 bands
cm-I to be constant. This ratio was carefully checked are probably not, so everything fits the Doh model.
many times using various sample preparation procedures There are three striking differences between the
and various fractionation techniques, and it was constant results for the two molecules. The first is that two bond-
within experimental accuracy. stretching, infrared-active fundamentals are found for
IF7, whereas only one is observed for ReF7. The second
DISCUSSION OF MOLECULAR STRUCTURE is that two intense and highly polarized Raman bands
Table I lists the observed bands for the two com- are observed for IF7 and only one for ReF7 Finally, the
pounds that probably represent fundamental vibrations infrared fundamentals of ReF7 have half-intensity
based on their high intensities and location in the widths roughly twice as great as those of IF7
spectrum. The first two differences could be explained by
Table II, except for the last two rows, is reproduced assuming that ReF7 had D7h symmetry. For this, as
from Ref. 7. It shows the vibrational selection rules for Table II shows, only three infrared and three Raman
various possible molecular symmetries of XY7 molecules. fundamentals would be expected. Curiously, it happens
It is evident that all the C symmetry groups can be that the fourth infrared band at 217 em-I could be
excluded for IF7 and ReF7 on the basis of numbers of interpreted as a difference band, 217~703-489, and
coincidences expected. In IF7 five fundamentals are two of the Raman bands could be interpreted as sum
bands, 597~2X299 and 645~299+353. The D7h model
can hardly be taken seriously, because the repUlsions
TABLE 1. Fundamental frequencies observed (cm-I ).
between fluorine atoms would not allow all seven to be
IF7 ReF 7 crowded into one plane. The near-coincidence between
Raman and infrared frequencies, 352 and 353 cm-t,
Raman Infrared Raman Infrared must be considered as accidental for either model.
Siegel and Northrop20 have found from x-ray diffraction
746 736p
676p 703 powder patterns that ReF6 and ReF7 are both cubic at
670 645 room temperature with identical unit cell sizes of 6.26 A.
635 p 597 Since the ReFs molecule has Oh symmetry, the similar
510dp 489dp
425 353 x-ray structure may be used to argue that the ReF7
365 352 molecule must also be nearly spherical (Doh) rather than
352 299
310 217 flat (D7h ). We believe, therefore, that the equilibrium
257
20 S. Siegel and D. A. Northrop, Inorg. Chern. 5, 2187 (1966).

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 1806 CLAASSEN, GASNER, AND SELIG

FIG. 3. Infrared spectrum of IF7 gas,

lO-cm path, "'25C. Sample pressures
were: A (background), B (5 torr), C
(30 torr), D (205 torr), and E (620 ton).
E

1302
1600 1500 1400 1300 1200 1100 1000 900
CM-I

configuration of ReF7 molecules is D5h , but that the
widths of the infrared bands representing angle-bending
motions suggest large intramolecular motions. Whereas
IF7 has sharp bands corresponding to rigid molecules,
ReF7 may be undergoing intramolecular fluorine ex-
change between axial and equatorial positions. Thus,
the latter is more like XeF6, a molecule apparently so
nonrigid that no absorption maxima at all can be found
in the angle-bending region. The spectra of ReF7 will be
interpreted in terms of D6h symmetry with the assump-
tion that two infrared fundamentals are coincident at
703 cm-I .
The striking differences, alluded to earlier, in the two
Raman spectra in the region above 600 cm-I merits
some discussion. The D5h symmetry allows two totally
symmetric fundamentals which should appear as in-
tense, polarized, sharp Raman bands, just as found for
IF7. How can the ReF7 spectrum appear so different?
Probably the answer lies in the molecular potential
function. The symmetry coordinates one would naturally
use for the totally symmetric species are an axial bond
stretching and an equatorial bond-stretching coordinate.
The normal coordinates, then, are linear combinations of
these in certain phase relationships, as determined by the
interatomic potential function.
One possibility is for both normal modes to contain
both symmetry coordinates in roughly equal amplitude,
but one being a vibration in-phase and the other just
out-of-phase. The in-phase mode preserves the near
spherical shape of the molecule and would be very
intense, very sharp, and highly polarized. The out-of-
phase mode is similar to the eg mode for octahedral
hexafluorides, in which a pair of opposite atoms moves
outward while the other four atoms move inward. This
mode results in a depolarized Raman band much less
sharp than the totally symmetric Raman band. The
out-of-phase mode for the heptafluoride, although it
must be polarized, by analogy will be only slightly
polarized and may be broad. The ReF7 molecule may fit
this possibility. The IF7 molecules, on the other hand,
may be a case where the two symmetric normal modes
approximate the two symmetry coordinates. Thus, the
problem of the striking difference in the two Raman
spectra can be explained on the basis of the same
symmetry but a distinct difference in the interatomic
potential function. This explanation may eventually be
verified when accurate normal coordinate calculation
can be done.
ASSIGNMENT OF VIBRATIONAL MODES
Table III lists all the observed bands for IF7 and a
tentative assignment to the species of the D6h group.

TABLE II. Some possible structures of XY7 molecules and corresponding selection rules.

Raman spectrum Coincidences

Symmetry Total Infrared
group frequencies Total Polarized spectrum Total Polarized

Da 10 3 1 3 0 0
C7v 10 7 2 4 4 2
CSv 12 9 " 6 6 3
Doh 11 5 2 5 0 0
Coh 11 11 4 8 8 4
C3v 12 11 5 11 11 5
C. 12 12 6 12 12 6
C 18 18 7 16 16 7
IF7(obs) 5 2 5 0 0
ReF7(obs) S 4 0

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 VIBRATIONAL SPECTRA OF IF7 AND ReF 7 1807

Khanna2J has done a normal coordinate calculation for TABLE IV. Infrared and Raman spectra of ReF7
vapor and tentative assignments.
1FT and our assignment is based, in part, on his results.
Although there are two mistakes in his G matrices and
Raman Infrared Assignment
his choice of which potential constants to set equal to
zero is quite arbitrary, the results are good enough to 736 "1
offer significant guidance in the assignments. aI'
A very unusual feature of this assignment is that 645
Jls(e/') definitely represents a bond-bending motion and 703 1''"3
a/'
is given the high value of 510 cm-t, while JIg (e2') should 299
be primarily a bond-stretching motion and is given the 703 '"
low value of 352 em-I. This unusual assignment was 353 '"6" et'
217 "7
required in order to explain all the intense infrared bands 597 I's el"
above 1100 cm-I as allowed binary combinations. 489 "9 e.'
Coincidentally, Khanna was led to 511 cm-I for the el" 352 1'10
fundamental by his calculations. Having made this 850 1'2+"7=862,1'6+"9=842
945 ".+",=944,1'1+1'7=953
choice for Jls, the other Raman-active fundamentals 1082 "1+"6=1089
follow as shown in the table. For the infrared-active 1180 1"+"9=1192
species, the 670- and 746-cm-1 bands may be assigned as 1286 "3+"S = 1300, 1'6+I'S= 1300
1350 "2+"a= 1348,1'.+1'.= 1348
shown, because the former is shaped more typically like 1438 1'1+1',=1439, vt+I'.=1439
a parallel band. The three bending modes are assigned in
the order of Khanna's calculated values. The lower part
of Table III shows the assignment of the infrared com-
bination bands. This is quite satisfactory. The 520- and windows, or, if due to IF7, may involve the inactive
837-cm-1 bands show up only at the highest sample frequency Jill (e2")'
pressure, and may be due to complex formation on the Table IV shows the tentative assignments for ReF7
This is similar to the one given earlier,1s except that the
new infrared frequency at 217 cm-1 is added, and the
TABLE III. Infrared and Raman spectra of IF 7 vapor
and tentative assignments. two Raman frequencies for Jls and Jig have been inter-
changed to make the assignment more similar to that of
Raman Infrared Assignment IF7
-.---.-'~-
An adequate normal coordinate treatment would be
676 VI
very desirable to establish or correct the assignments
a/ and to verify the explanation given above about the
635
670
v.Va symmetric Raman modes. At the present time, not
0",/1 enough is known about which potential constants to set
365 "4 equal to zero to do this significantly more reliably than
746
425
"5
"6 el' Khanna has done.
257 V7 A method to simplify potential functions that was
510 Vs et" pointed out many years ago by Heath and Linnett22 has
352 V9
e.' recently been shown to be very accurate for hexa-
310 VI0 fiuorides. 23 We consider application of this method to
520 ? (See text) heptafiuorides to be premature and feel that more
552 I'7+vto=567
837 ? (See text) testing on the simpler tri-, tetra-, and pentafiuorides is
886 "2+1'7=892 required before it can be applied with confidence to the
934 "1+"7=933, "6+"s=935
1058 1'2+"6 = 1060, ".+"10 = 1058
heptafiuorides.
1104 "6+"9= 1098, 1'1+"6= 1101
1177 Vs+I's=1180 ACKNOWLEDGMENT
1259 I'6+l's=1256
1302 112+1Ia=1305 We wish to thank Mrs. Leslie Keedy for the loan of
1349 "1+1Ia=1346
1387
one of the high-purity IF7 samples used in this work.
".+".=1381
1418 "1+".=1422
U D. C. Heath and J. W. Linnett, Trans. Faraday Soc. 44, 873,
878, 884 (1948).
:Ill H. Kim, P. A. Souder, and H. H. Claassen, J. Mol. Spectry.
21 R. K. Khanna, J. Mol. Spectry. 8, 134 (1962). 26, 46 (1968).

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