Problems

85

fusing six-membered rings and 145.8 pm for the bond fusmg five- and ~ix-membcred
rings.
Buckminsterfullerene has a high electron affinity. Treatment .... ith up to si.1.. molc!>
of a n alkali metal such as potassium or rubidium gives products
(3.3)
which show metallic conducti vity. If only three moles of potassIUm or rubidium arc
allowed 10 react, the products consist of K )C60 and Rb J C 60 which bi=com.; superconducti ng at temperatures below 18 K and 30 K . rcspectively.'o These compounds
have a face-centered cubic cryolite structure wilh a closest -pack cd array of ('~o
anions with M+ ions in the tetrahedral and octahedral holes (see Ch<lptcr 4). Al
present it docs not appear that thesc supcrconduc t or~ will prove compeliti\e with the
cuprate high-temperature supercondu ctors (CIJ;Jpter 7) because of their much lower
crilicallemperalure and the fact that they arc qu ite susceptible to oxidatIon.
Buckminslerfu llerene, e ftO , appears to be the first of a large numbe r of alil1lroplc
fu llcrenes: C 70 is already fairly well known it probably ha~ the shape of a rugb}
ball - and other C. molecules with II = 76, 84, 90, 94 have been i~olaled. Even larger
molecules with n equal to 240 and even 540 ha ve been suggested. 31

Problems

3.1

Assign the molecules in Figs. 3.2, 3.4. and 3.7 to their appropnalc

PQIIII

groups.

3.2

Assign the molecules in Figs. 15. 3.6, and 3.8 to their appropriate POlOt groups.

3.3

Assign the foll owing molecules to their appropriate point groups.

a. cyclopropane

c. CO:

r.

d. B2H6

e. p.

g. BF)

h, PH )
1-1

k_

eel,

Cl lC-C

i. O,SCI

I
0-8
\

0-1-1
I.

o
I

, p-p

."/

...

I
" I

I I

H
3.4

Assign the foll owing to their appropriate point groups.

a. Iris(oxalato)chromium{lll)

b. tris(carbonato)coba ll(lll )

c. tris(glycinato}cobalt(ll l)

3.5

Croups with {~, O~. T 4 , C 1 , C" and C1 ~)'mmctrJcs were assigm:d in the lext hy ln~pectlOli.
Take the molecules given as illuslrations of these symmetrie~ (hg~ 3 10 and 3 II t and
run them th rough the flowchart (Fig. 116) 10 assign thClr proper point groups.

3.6

Although most molecules In point groups [~. O~. T J CI' C. and C 1 may be assIgned by
inspection, some appea r unusua l. Consider the cubiC symmetry of cubanc. C~H~

~n

ro

Fleming, R. M.; Ramirez.. A P.: Rossemslr;y. M J.: Murphy, 0 W . lI addun. R C. ZahurJJ... S

Makhija, A. V. Nature 1991. 152, 787.

~J Diederich. F.;

\I

Etl!. R.: Rubin, Y~ Whctten, R. L.; Beck. R. Alvarez.. M.. An:z.. S.. Scnsharma. 0 Wud!.

F.; Kheman, K.

c.;

Koch. A. Sci ..n.... 1991 , 252, 548;

Krolo, H PUr.' Arpl. Chl"m 1990.6-', .tI17

Jl~

86

3 S'I'mm.h'l' .nd G up Th , 'I'

what point group does it belong? Consider the pentagonal dodecahedron. (For a model,
see Appendix H.) To what poi nt group does it belong?

Ii

3.7

Find the symmctry elements, if any, in the objects shown in Fig. 3. l.

3.8

In the discussion of crystallography, translational symmetry was likened to movmg ducks

and blinking eyes. Extend this disc ussion to the action of a strobe light blinking r times
per second relatIve to the fo llowing.
a. ducks moving with a certain linear velocity
b. a spoked wheel spinning at a certain angular velocity

3.9

Why does SF 4 have

C~"

symmetry rather than Col.? (See Fig. 6.4).

3.10 Ftnd all of the symmet ry elements in an octahedron.

3.11 Tns(2.aminocthoxo)cobal t(lI l) (Fig. 3.12b) was assigned C l symmetry, but the methylene
groups of the ligand were not drawn out explicitly. Does consideration of these groups
change the symmetry? DISCUSS.
3.12 GallcheH 20 2 has C 1 symmetry. What are the symmetries of the eclipsed (cis) conformation and the anti (trans) conformation?

3. 13 On page 64 thc argument is made that a molecule with a center of symmetry. i. cannot have
a molecular dipole moment. Prove thl!> same rule using a molecule with a center of
~ymmelry and summlOg up the indi vidual bond moments.
3.14 Meso molecules such as R.S-l.2-dichlorol.2-difiuoroethane are usually cited as achlral
because they possess a mirror plane (when in the perfectly eclipsed conformer, a stipulation that is orten omitted). What is the symmetry of this conformer? In other conformations? Discuss why meso molecules show no optical actilltly.
3.15 WhIch of the following molecules will have dIpole moments?

s=c=S

Cl-F

F-O

3.1 6 What are the symmetnes of the no rmal modes of vibration of these molecules?

,N

F"I \
F

--,

--

---

F-O

Problam$

87

3.17 Unlike the water molecule, carbon dioxide has no dipole moment. How l~ it possible for
any of its vibrational modes to be infrared active?
3.18 Skctch thc normal vibrational modcs for CO~ .lIld Indicate which you e\jX'cl III he

infmred or R .. man active. or both.

3. 19 A h)-drogen bond consists ofa posllive hydrogen between two vcry negative nonmetalliC
atoms, One of thc strongest hydrogen bonds known. the HF 1 ion. will be discu~scd in
Chapter 8. Possible arra ngements of the atoms in rFHF]~ ion are a) linear or 1'>1 bent.
with either: i) equal. [F---H--Fr, or ii) unequal, [F-H---~F]~, bond lengths. The fun
damental vibrational absorption frequencies (in em-I) of the h)-drogen difluonde anion
and the deuterosubstituted anion are as listed below.52
HF;

OF;

1550em

1140 cm- I
860 em-I

1200cm~1

675cm- 1

II..

Activity

675cm~1

Raman

Suggest the structure of the hydrogen dinuoride ion. Explain your reasoillng

3.20 Proceeding through an analysis analogous to that described in thiS chapler for BeI J ,
derive the Irreducible representatio ns for the normal vibmtions of XeF~ (Fig. J.~4) and
determine which are IR active, which are Raman active, and which are neither
3.2 1 Dctermme the number of fundamental vibratIOns that would be expected for XeF .. if it
were tetrahed ral. How many ofthes.e would be infrurcd o r Raman acti\e? Comp>lre Ihe~e
rcs ults as well al> those obtamed from Problem 3 :W with thc c\pcnmental d:,t" gl\en nn
page 70. ami give as many rea!>On~ a~ pos~ible for elimlO;ltmg the tctmheural '1fI1I.lUre.

3.22 Determme the irreducible representat10n of each of the fundamental \ ibrations of

lrull~

[PICl!Br l ]2- (a square planar structure). WhIch are IR ucti\e'!

3.23 Use your answer to Problem 3.n and Footnote 28 to determme whelher the first over
lOne of an y of the fundamental vibratIons of "ans[PtCI!Br!)l- will be IR actIve.
3.24 How many absorptions would you expect \0 sec: in the infr'lred spectrum of the
CIF 3 molecule?

T.~haped

3.25 Infrared and Raman spc<:tm of crystalline banum rhodizonate have bl:en reported H
From an inspection of the data. the author concluded that the rhodizonate ion. C"O;, ,
(Fig. 16.35) probably has D6~ symmetry. Examine the data below Ifrequency in cm I)
and explain thiS conclusion,
152 (IRJ

275 (I R)

380( IR)

1071 (IRI

1278 (I R)

1305(lR)

450 (Raman)
1475 (1R)

548 (R;llnan)
1551 (Raman)

3.26 Bromine penla!1uoride reacts with lithium mtrate to produce BrON02

3LiNO J

+ BrF5 -

3LiF

+ BrONO l + 2FNO z + O 2

(3.-1)

Draw the slrucllrre of the planar BrON0 2 molecule "nd determmc the Irrt."uu(:ihlo:: repft."senlahons for its vibmtlOnal modes. Which mouel> are IR ..ctive .LIlU \\.hich ()nc~ ;Ire
Rama n aC h vt."? (Wilson. W. W.: Chnste. K. O. 111"'): Clrl'm 19K7 . J"_ t.~7.U

" Harns, D. c.; Bcnolucci, M. D. Sy"""erry Qnd Speelro5COI'y, Dover: New York, 1989; p 160.
H

Bailey. R. T. J. Chen!. Soc .. Chern. Commun. 1970. 322.

88

3 Sym m e "y ond Group Th eo ry

3.21 FIg. 3.25 shows removal of B from octahedral ABIo to gl~e square pyramidal AB) and
loss of a second B to gIve seesaw AB 4. Suppose that instead of the geometries shown.
thc AB) rcarr:lngcd to gi\(:.1 trigonal bipyramidal structu re and AB4 assumed a squarc
planar shape. What orbita l symmetries and degeneracIes ",ould occur for these two cases'l
3.Z8 Con~idl"r thc following All. molecules and determine Ihe symmctTlcs and degenerJ1cle~
of the ~. p. and Ii orbitals on A In each.

a.

AH~

h. AB4 (square planc)

(cube)

c. A B) (trigonal pyramid)

d. AB j (trigonal plane)

e. AS" IT-shapeJ

f. AB4 (rectangular plane)

3.21} For cach of thc follow111g molecule!>. determllle what alQmic orbitals on the central atom

arc :l!lowed by symmetry to be used in the construction of sIgma hybrid orbnals.

a. NH3 (trigonal pyramid)

b. BI', (trigonal plane)

c. SF" (octahcdron)

d. PF ~ (Higonal bipyrilmid)

3.30 A chemist isolated an unknown transitIon metal complex with a formula of AB 6 . Fi~e
potential structures were considered, belonging 10 pomt groups O~, DJ~' D6~' DJ~' and
V ,d Spectroscopic s t udic ~ led 10 the con c lu ~ ion that thc {J orbiwl~ originating on A in the
c,)mph:~ were completely nondegenenlte . Sketch .. ~truc tural formu la that is con~i~tenl
with e<lch of the five point group assignments and decide which structures can be climl'
nated on the basis of the ex.perimental results.
3.31 What atomic orbitals on carbon m the planar COi- anion could be used (on the basis
of symmetry) to construct in-plane and out-or-plane 1t bonds? First answer the question
hy thinking about the orientations of the orbitals relative to the geometry of the ion,
then answer it by usmg reducible represenlations and the appropnate character table
3.32 What is the symmetry of buckminsterfullerene?' Do you e.~pect It to be chiral? To ha\c
a dipole moment? To be soluble m benzene" Buckminsterfullerene was named after R
Buckminster Fuller, who became best known for his populanzation of the geodesic dome
Is a geodesIc dome the same as a segment of buckminsterfullerene? What is the symmetry
of the bis(4-t-bulylpyridine)osmyl deri vallve of buckminsterfullerene (Fig. 3.34)? Do you
e;\pe<:t it \0 be chiral? To have a lIipole moment? To be soluble in benzene?
3.33 How many

DC

NMR signals do you expect to see for C 60? How many for C,o?

3.34 Look up carbon-carbon bond lengths (single, double, and aromatic) in an organic chemIstry textbook and compare wnh the bond lengths III buckyball. What can you conclude
about the bonding in buckyball?
3.35 Depending upon the condillons, reactanl ratios, etc., the products of Eq. 3.2 consist of(l)
a toluene-soluble fraction that gives a single, sharp chromatographic peak for a material
that analyzes C 6 00 4 0s(NC,H.C.H 9h and yields the structure shown in Fig. 3.34. and
(2) a precipitate that analyzes as CfoOIO~Os(NC,H.C.H9hh. What is the significance of a
single bis(4+bulylpyridinc)osmyl derivative (I) of buckminsterfullerene? When {Zl IS
analyzed chromatographically. five peaks arc observed . Discuss.
3.36 It has been suggested that if the potassium (or rubidium) atoms in the M]C",o superconductors could somehow be placed inside the buckyballs, they would be protected,
(lnd then these superconductors would nol be susceptible to ox idation. CommenL

.. tn

,m~"'cnng

thIS question. you mil) find II u;,eful 10 bUIld

CI'o'm. Ed"". 1989. 66, 182

--

---

--

~I

model of buckyball See Villa!. 1 J J

Proble m$

89

Fig. 3.35 Scannmg

electron micrograph of a
cluster of quasicrystals of
AI 6 CuLi). [Counesy of
B. Dubost and P. Sainfort.
Pcchiney. France.]

3.37 What arc the symmetries of the follow ing?

a. a baseball

h. a baseball glove

e. a baseball bat

d. a VOlleyball

a hockey puck

f. a soccerball

t'.

g. a football

h. a seamless rubber ball

:\.38 Construct models of the tetrahedron, the octahedron (both with and without "propeller
blades" represen ting chelate rings), and the icosahedron (Appendi>; 1-1), Find and marl
as many symmetry dements as you can.

J.J9 Recently "quasicrystals" having the shape of a trmcontahedron havc becn discovered In
specially prcpared alloys of aluminum and other mClals. A trmcontahedron i:. a regul<H
polyhedron with 30 identical, d mmond-shaped faces (Fig. 3.35). Qua:.iCT}stals seemingly
defy the rules of symmetry that do not allow a periodic structure huving unit celb wilh
fh'e-fold symmetf}.ss What is the symmetry ora triacontahedron'l Can you mal..e a model
of il similar to the polyhedra gIven III Appendilt H?
3.40 Figures 3.36 and 3.37 illustrate IWO woodcuts by artisl Maurrts Escher. Wha! s)mmetr)

elements can you find? !"

3.41 Among the thirteen pOSSIble monoclinic space groups are P2 1, P2 1

111.

and P2 1

Com-

pare these space groups by listing the symmetry elements for each,
:l\ om ~ cannll t be located cry'tallographlc;l11y if there me he'I\} atom ..
present. In ~I stud y of l'hF;Sb1 F 11 , the hydrogen bonded cation wa~ found 1,\ have"
structure Ilf either:

3.42 Oft en hydrogcn

["'

F -- H ---F

/" J'

or

[\.---11 ---'- J'

I')

H
!i

II

(b)

Horgan. J Sdena' I990.147. 1020- 1022.

For II. comprebensl~e "olume companng symmetry 111 art, mUSIC, chemistry. and o ther human endca\'onsee Symmetry: Unifying Hltmlln UnJer5/{1'IJing: H3rgiuai, I. Ed .. Pergamon: I\e\\ Yorl. 19Hf,

Fig. 3.36 " Butterfly, Bat,

Bird, Bee," a woodcut
by Maurits Escher.
[ Reproduced with
permission; Copyright 1990
M. C. Escher c/o Cordon
Art-Baam- Holland.]

Fig . 3.37 "Depth," a

woodcut by Maurits
Escher. [ Reproduced with
permission; Copyright 1990
M. C. Escher c/o Cordon
Arl - Baam- H olland.]

Problems

91

The author~ stated that "[The structurel has space group PI. Owing to the ~trongly 'tatteri ng Sb atoms. the H atoms ... could not be definitely localized.
l"he H,F; Lon
is located on a s)"mmetry center of the space group and therefore ha~ [a or b~ Choo'<
one.] conrormatlO n:' ~' Discuss how the correct conformation. a or b. can be <.:ho~cn b)
symmetry arguments even if the hydrogen atoms cannot be located.

3.43 Fig. 3.38 is a stereoview of the uni t cell of Fe(CO)~(IIL_PPhlCHzCHIPPh21 y,hLch Cr}~
tallizes in thc monochnic space group P2. /c. Find the lo}mmetry clements of the unit
cell [Hint: Find three easily recognized atoms In the Fe(COI~('1L-PPh2CJ-ilCH1PPh~ )
molecule and connect corresponding atoms 10 the four molccules m the unil cell with lie
lines. Thmk about the relation of the interstion of these lie lines and the symmetr)
elements.]

Fig. 3.38 Stereovicw or the unit ce ll of

Fc(CO)il1l -]>hlPCH,CH~PPh11.

R. L.: Rhei ngolil. A. L.; Hamcrskl. J . J.; C:"t le. C. K.

1635- 1639. Reproduced with permi~~ i on .1

Or~f/lwmrtfllli(\

thorn Keller_
191'13 . J.

u~ual procedure for identifying chiral molecule, j, to look lOr a mirror pl.tne ttT
\11
However. a center of Inversion Ii a S:) also produce!> an achiral mllleeul~ (,,~~ R. \1.::dimelhyl-I.2-diphcnyldiphosphinc disulfid..:: Fig. 3.3). The pre~ence of nn Sol a \i, \.\ ill <lho
!'e~\J11 in lin achirnl molecule. b the (R.W-2J-lham1llohutane)(5.S'2J-diaminobUl;lndzinc(ll) iOIl (Fig. 3.39) chiral? What about Ihe hi,(S.S',2.'diaminllhut.rnC)7inc(111 Il'n"

3.4J The

Fig. 3.39 The

(R,R' -2.1-dl.lmin"hut,,"~, I,
f S. S' -2.3-d lam i nLlbul ant').linc( lI ) Ion.

3.45 Look at the drawings accompanying Problem 3.6. Is it possible to superimpose the cube
on the dodecahedron? Castleman and coworkersu have recently dctccted a cation with
mfe = 528. identified as Ti 8 Ct2' It is believed thaI the Il!anium atoms form a cube wuh
the addition of twelve carbon atoms to complete a pentagonal dodecahedron Dmw thc
proposed structure. What is its point group symmetry?

"Moolz.. D.: Barlm3RR. K. Allgeh. Chl'ffl. f,,1. Ed. e"g/. 1988.17. J91
'" Guo. B C, Kems. K P.. Casllem3R. A. w~ Jr Scil'llre 1\192. ]J.~. 1411 141~