Nakamoto 2006

Infrared and Raman Spectra of Inorganic and
Coordination Compounds
Kazuo Nakamoto
Marquette University, Milwaukee, WI, USA
1 INTRODUCTION spectral charts of selected compounds are shown in each

section.
The following definitions and abbreviations have been
Although this article is intended to review the applica-
adopted throughout this article. The word molecule may
tions of infrared (IR) and Raman spectroscopy in inorganic also represent an ion. The words frequency [n D c/l, where
and coordination chemistry, it was clearly not possible c is the velocity of light (3 ð 1010 cm s1 ) and l (cm) is the
to present all important topics and results in the lim- wavelength] and wavenumber (nQ D 1/l, cm1 ) are used
ited space available. To obtain a more broad and detailed interchangeably although they have different dimensions.
coverage of the field, the reader should consult the refer- Thus, an expression such as “a frequency shift of 3 cm1 ”
ence books1 – 6 listed at the end. References are also given is used. Other abbreviations and symbols employed are
for vibrational spectra of minerals7,8 and organometallic as follows: IR, infrared; R, Raman; RR, resonance raman;
compounds9 which are not included in this review. Exten- n, stretching; υ, in-plane bending or deformation; rw , wag-
sive collections of spectral charts10,11 of inorganic com- ging; rr , rocking; rt , twisting; p, out-of-plane bending.
pounds and sources of spectral data12 on inorganic and Subscripts a, s and d denote antisymmetric, symmetric and
organometallic compounds are available. Annual reports degenerate modes, respectively. M denotes a metal ion, and
on vibrational spectra of inorganic and organometallic X represents a halogen except for general formulas Xm Yn .
compounds13 are indispensable to keep up with the ever- Values in parentheses in the tables indicate calculated or
increasing new literature. Finally, review articles on specific estimated values. Point group notations are given in italic
groups of compounds14 – 24 are listed and group frequency type, e.g. C2v .
charts (Appendices 1–5) are given to compensate for any
unbalanced presentation.
In this article, molecules and ions are classified according 2 DIATOMIC MOLECULES
to their structural types, and the structure–spectra corre-
lations are discussed for each type. Most sections contain Diatomic molecules have only one vibration along the
illustrations of normal modes of vibration, IR/Raman selec- chemical bond, and its frequency (wavenumber, nQ , in cm1 )
tion rules, tables of observed frequencies, band assignments is given by
and short discussions. Vibrational spectra of coordination 1 K
compounds containing these molecules (ions) as ligands are nQ D 1
2pc m
also discussed. For compounds of unusual structures (ring,
cage, etc.), only the observed frequencies and band assign- where K is the force constant (mdyn Å1 or 102 N m1 ) and
ments are given for representative compounds. IR/Raman m is the reduced mass, defined by
1 1 1
D C 2
m m1 m2
Handbook of Vibrational Spectroscopy, Online © 2006 John Wiley & Sons, Ltd.
This article is © 2006 John Wiley & Sons, Ltd.
This article was published in the Handbook of Vibrational Spectroscopy in 2006 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027325.s4104
Infrared and Raman Spectra of Inorganic and Coordination Compounds 1873
Table 1. Vibrational frequencies of diatomic molecules (cm1 ). 2.1 Monoatomic ligands

Molecule n Molecule n Atoms such as H, N, O and halogen (X) coordinate
to a metal (M) as monoatomic ligands. Hydrido (M–H)
H2 4161.13 F35 Cl 773.88 complexes of relatively heavy metal atoms such as
35
HD 3632.06 ClBr 439.5
D2 2993.55 BrO 723.4
Cr, Mo, Rh and Ir exhibit n(M–H) and υ(M–H) in
HF 3961.64 BrF 669.9 the ranges 2250–1700 and 800–600 cm1 , respectively.1
H35 Cl 2886.01 BrCl 444.3 Hydrogen stretching frequencies involving nontransition
H37 Cl 2883.89 IF 610.2 elements are found in the group frequency chart given
D35 Cl 2091.05 ICl 381.5 in Appendix 1. Halogens are the most common ligands
D37 Cl 2088.05 IBr 266.8
in coordination chemistry. Terminal halogen stretching
H79 Br 2558.76 HO 3637.4
H81 Br 2558.40 DO 2681.1 vibrations [nt (M–X)] appear in the regions 750–500 cm1
HI 2229.60 CN 2080 for M–F, 400–200 cm1 for M–Cl, 300–200 cm1 for
12
CO 2143.16 ClO 713 M–Br and 200–100 cm1 for M–I. However, the nb (M–X)
13
CO 2096.09 NOC 2273 of the bridging halogeno complexes are much lower than
14
N2 2331 NO 1374–1358 those of terminal halogeno complexes. In general, the
14
NO 1876.11 O2 C 1876
15
NO 1843.04 O2 1580 ratio nb /nt is in the range 0.6–0.9.1 Appendix 2 shows a
F2 892.1 O2 1094 group frequency chart for halogen stretching frequencies
Cl2 557 O2 2 791/736 involving nontransition elements.
Br2 316.8 Cd2 2C 183 The n(MDO) vibrations of oxo complexes, ODM(IV)-
I2 213.3 Hg2 2C 160 (porphyrin), are at 1007, 1025, 754 and 852 cm1 for V,
Cr, Mn and Fe, respectively. Similarly, the n(MN) of
where m1 and m2 are the masses of the two nuclei (atomic nitrido complexes, NM(V)(porphyrin), are at 1017, 1049
weight units). For example, m D 0.9573 and nQ D 3962 cm1 and 875 cm1 , for the Cr, Mn and Fe, respectively.1 These
(observed value) for the HF molecule. Then K is calcu- and many other metal–ligand vibrations can be assigned
lated to be 8.87 mdyn Å1 . A more accurate value (Ke ) can definitively by using metal isotope techniques.14 As an
be obtained by using the wavenumber corrected for anhar- example, Figure 1 shows the RR spectra of the n(FeDO) of
monicity (!e ). In the case of HF, Ke D 9.65 mdyn Å1 since ODNA Fe(TPP) (NA Fe D Fe in natural abundance contain-
!e D 4139 cm1 . In homopolar XX molecules (D1h ), the ing 92% 56 Fe; TPP D tetraphenylporphyrin). The band at
vibration is not IR-active but is Raman-active, whereas it 852 cm1 can be assigned to the n(FeDO) since it is shifted
is both IR- and Raman-active in heteropolar XY molecules to 856 cm1 by 56 Fe/54 Fe substitution and to 818 cm1 by
16 18
(C1v ). O/ O substitution.
Table 1 lists observed frequencies of typical diatomic
molecules. Several trends in frequencies can be noted.
First, the effect of the reduced mass (m) is seen in the
2.2 Diatomic ligands
frequency order H2 > HD > D2 . In this case, m increases
Molecules such as CO, NO, O2 , N2 and H2 and anions such
in the same order while K is constant. Such a mass
as OH and CN coordinate to a metal atom to form a large
(isotope) effect is also seen for the pairs 12,13 CO, 14,15 NO,
H35,37 Cl and H79,81 Br, indicating that the isotope shift 818
becomes smaller as the relative mass difference between 852
822
856
isotope pairs (m/m) becomes smaller. Second, the effect
of force constant is seen in the series HF > HCl > HBr > NAFe NAFe
Intensity
16O 18O
2 54Fe 2 54Fe
HI. Here, the K value decreases as the chemical bond
becomes weaker in the same order whereas the reduced
mass does not vary appreciably. Similar trends are noted in
the series IF > ICl > IBr, N2 > CO > NO > O2 , NOC >
NO > NO and O2 C > O2 > O 2
2 > O2 . The last two
series are useful in determining the electronic structure of (a) ∼
ν/cm−1 (b) ∼
ν/cm−1
these diatomic ligands in coordination compounds. In the
Figure 1. The n(FeDO) bands of ODFe(TPP) (in O2 matri-
F2 > Cl2 > Br2 > I2 series, m increases and K decreases in ces at ¾15 K) observed in RR spectra (406.7-nm excitation).
the same order. Hence both mass effect and force constant (a) 16 ODNA Fe(TPP) and its 54 Fe analog; (b) 18 ODNA Fe(TPP) and
effect are operative. its 54 Fe analog.
DOI: 10.1002/9780470027325.s4104
1874 Spectra–Structure Correlations
100
Transmission (%)
80
60
H2O
40
H2O
20 ν(C N)
0
4000 3000 2000 1800 1600 1400 1200 1000 800 650
∼
ν/cm−1
100
Transmission (%)
80
60
40 ν(Co C) ν(Pt C)
20
0
600 500 400 300
∼
ν/cm−1
Figure 2. IR spectra of K3 [Co(CN)6 ] (solid line) and K2 [Pt(CN)4 ] 3H2 O (broken line).
number of coordination compounds. Upon coordination, the

X
n(X–X) or n(X–Y) vibrations of these diatomic ligands are Y X Y z
generally shifted to lower frequencies. In the low-frequency ν1
x y
Y Y
region, n(M–X) and υ(M–X–Y) or n(M–Y) and υ(M–Y–X) ν1
vibrations appear depending upon whether the coordination
occurs via the X or Y atom. In most cases, the bending
frequencies are lower than stretching frequencies. Figure 2 ν2a
shows the IR spectra of two cyano complexes. The bands at
2129, 564 and 416 cm1 of K3 [Co (CN)6 ] are due to n(CN), ν2
n(Co–C) and υ(CoCN), respectively. Similarly, those at − + − ν2b
2133, 505 and 411 cm1 of K2 [Pt(CN)4 ] Ð 3H2 O are due to
n(CN), n(Pt–C) and υ(PtCN), respectively. Review articles
are available on the vibrational spectra of metal carbonyls,15
ν3
cyano complexes3 and dioxygen complexes.16 ν3
Figure 3. Normal modes of vibration of linear and bent XY2

molecules. (C and denote vibrations going upward and down-
3 TRIATOMIC MOLECULES ward, respectively, in the direction perpendicular to the plane of
the paper).
Figure 3 shows the three normal modes of vibration of
the linear YXY molecule (D1h ). These vibrations also same selection rules hold for the bent X3 (C2v ), XXY
represent the normal modes of the linear X3 (D1h ), XXY (Cs ) and XYZ (Cs ) molecules. Table 3 lists the observed
(C1v ) and XYZ (C1v ) molecules with slight modifications. frequencies of bent triatomic molecules. It is interesting
Under D1h symmetry, n1 is Raman-active but not IR-active, that NO2 C (nitrosonium ion) is linear but NO2 (nitrite
whereas n2 and n3 are IR-active but not Raman-active ion) is bent, and that Br3 and I3 are linear but Cl3
(mutual exclusion rule). However, all the vibrations are is bent. Table 4 lists the vibrational frequencies of linear
both IR- and Raman-active under C1v symmetry. Table 2 and bent XY2 -type halides obtained in inert gas matrices
lists the observed frequencies of linear X3 , XXY, YXY and or in the gaseous state. In linear halides, the trend n3 > n1
XYZ molecules. holds, whereas the opposite trend is seen for bent halides
The three normal modes of vibration of the bent YXY with one exception (PbCl2 ). It should be noted that all
molecule (C2v ) are also shown in Figure 3. In this case, three vibrations are shifted to lower frequencies in the order
all three vibrations are both IR- and Raman-active. The MF2 > MCl2 > MBr2 > MI2 .
DOI: 10.1002/9780470027325.s4104
Table 2. Vibrational frequencies of linear triatomic molecules Table 4. Vibrational frequencies of triatomic metal halides
(cm1 ). (cm1 ).
Molecule na1 n2 n3 a Molecules Structure n1 n2 n3
N3 1344 645 2041 MgF2 Linear 550 249 842

Br3 164 53 191 MgCl2 Linear 327 93 601
I3 114 52 145 MgBr2 Linear 198 82 497
NNO 2223.8 588.7 1284.9 MgI2 Linear 148 56 445
OCO 1388, 1286b 667 2349 ZnF2 Linear 596 150 754
SCS 658 397 1533 ZnCl2 Linear 352 103/100 503
SeCSe 369.1 313.1 1301.9 ZnBr2 Linear 223 71 404
ONOC 1396 570 2360 ZnI2 Linear 163 67.6 337.5
OUO2C 880 140 950 HgF2 Linear 568 170 642
ClBrCl 278 ¾135 225 HgCl2 Linear (348) 107 405
FHF 583.1 1286.0 1331.2 HgBr2 Linear (219) 73 294
HCN 3311 712 2097 HgI2 Linear (158) 63 237
DCN 2630 564 1925 KrF2 Linear 449 233 596/580
ClCN 714, 784b 380 2219 XeF2 Linear 497 213.2 555
BrCN 574 342.5 2200 SnF2 Bent 592.7 197 570.9
ICN 485 304 2188 SnCl2 Bent 354 (120) 334
NCO 2155 630 1282, 1202b SnBr2 Bent 237 84 223
NCS 2053 486/471 748 PbF2 Bent 531.2 165 507.2
NCSe 2070 424/416 558 PbCl2 Bent 297 – 321
PbBr2 Bent 200 64 –
an
1 and n3 correspond to n(XX) and n(XY), respectively, in XXY type,
and to n(XY) and n(YZ), respectively, in XYZ type.
b Splitting due to Fermi resonance.
Table 5. Vibrational frequencies of pseudohalogeno complexes

(cm1 ).
Table 3. Vibrational frequencies of bent triatomic molecules
(cm1 ). M(XYZ)n n (XY) υ (XYZ) n (YZ)
Molecule n1 n2 n3
Co(NCS)4 2 2062 481 837
16
Au(SCN)4 700 458/413 2130
OH2 3657 1595 3756 Co(NCSe)4 2 2053 433/417 672
16
OHD 2727 1402 3707 Pd(SeCN)4 2 521 410/374 2114/2105
16
OD2 2671 1178 2788 Co(NCO)4 2 1325 620/617 2217/2179
18
OD2 2657 1169 2764 Mo(OCN)6 3 1296/1140 595 2205
SH2 2615 1183 2627 Ni(CNO)4 2 1122 479/470 2184
SD2 1892 934 2000 Mn(N3 )4 2 1330/1267 650/630 2058
SeH2 2345 1034 2358
SeD2 1687 741 1697 Normal mode descriptions such as n(XY) and n(YZ) are not applicable
O3 1134.9 716.0 1089.2 to the last four compounds since the bond orders of the X–Y and Y–Z
O3 1016 600.9 802.3 bonds are similar.
ONO 1325 752 1610
ONO 1327 806 1286
OSO 1147 517 1351 M–NCS isothiocyanato M–SCN thiocyanato
OClO 944.8 448.7 1107.6 complex complex
Cl3 253 – 340 M–NCSe isoselenocyanato M–SeCN selenocyanato
All the data were obtained in the gaseous or inert gas matrix state. complex complex
M–NCO isocyanato M–OCN cyanato complex
complex
3.1 Triatomic ligands M–ONC isofulminato M–CNO fulminato
complex complex
The linear pseudohalide anions such as NCS , NCSe , Table 5 lists the vibrational frequencies of these com-
NCO and ONC can coordinate to a metal through either plexes together with that of an azido (–N3 ) complex. Thus
one of the end atoms. As a result, the following linkage far, no examples of isofulminato complexes are known.
isomers are formed: Several empirical criteria have been proposed to distinguish
DOI: 10.1002/9780470027325.s4104
Transmission (%)
100 X
80 Y
Y
60
ρw(NO2) Y
40
δ(ONO)
20 ν (NO ) ν (NO ) ν1 (A1) ν2 (A1) ν3a ( E ) ν4a ( E )
as 2 s 2
0 νs (XY) δs (YXY) νd (XY) δd (YXY)
1600 1400 1200 1000 800 600 500 400 300
∼ −1 Figure 5. Normal modes of vibration of pyramidal XY3
ν/cm
molecules.
Figure 4. IR spectrum of Na3 [Co(NO2 )6 ].
Table 6. Vibrational frequencies of pyramidal XY3 molecules
1 (cm1 ).
these linkage isomers. In general, the n(CN) of the M–NCS
group (near and below 2050 cm1 ) is lower than that of Molecule n1 (A1 ) n2 (A1 ) n3 (E) n4 (E)
the M–SCN group (near 2100 cm1 ), and the n(CS) of the
former (860–780 cm1 ) is higher than that of the latter NH3 3335.9a 931.6a 3414 1627.5
(720–690 cm1 ).1 Coordination compounds of linear tri- 3337.5 968.1
atomic ligands such as CS2 17 and CO2 take a variety of ND3 2419 748.6a 2555 1191.0
structures.1 749.0
PH3 2327 990a 2421 1121
Examples of bent triatomic ligands are NO2 , NH2 , 992
H2 O and SO2 . The NO2 ion coordinates to a metal in AsH3 2122 906 2185 1005
a variety of ways. Among them, the linkage isomerism SbH3 1891 782 1894 831
between N-bonded nitro and O-bonded nitrito complexes OH3 C 3560 1095 3510 1600
is well known. For example, the red nitrito complex NF3 1035 649 910 500
NCl3 535 347 637 254
[Co NH3
5 (–ONO)]Cl2 is gradually converted to its yellow
PF3 893.2 486.5 858.4 345.6
nitro isomer. The two n(NO2 ) of nitrito complexes are PCl3 515.0 258.3 504.0 186.0
well separated (¾1440 and ¾1080 cm1 ) whereas they PBr3 390.0 159.9 384.4 112.8
are close in nitro complexes (¾1400 and ¾1330 cm1 ). PI3 303 111 325 79
Distinction between these isomers can be made on this SO3 2 967 620 933 469
basis. Upon coordination, the Co–NO2 group exhibits three SeO3 2 807 432 737 374
ClO3 933 608 977 477
new vibrations, rw (wagging), n(Co–N) and rr (rocking), in BrO3 805 418 805 358
the low-frequency region. These vibrations are seen at 623, IO3 796 348 745 306
449/372 and 276/249 cm1 , respectively, in the IR spectrum
a Splitting due to inversion doubling.
of Na3 [Co(–NO2 )6 ] shown in Figure 4. Vibrational spectra
of these linkage isomers have been reviewed.18
Transmission (%)
100
80
ν2
4 FOUR-ATOM MOLECULES 60 ν4
40 ν2
ν1 ν1 ν4
20 ν3
The normal modes of vibration of a pyramidal XY3 ν3
0
molecule (C3v ) are shown in Figure 5. All four vibrations 1600 1400 1200 1000 800 600 500 400 300
∼
ν/cm−1
are both IR- and Raman-active. Table 6 lists the vibrational
frequencies of typical compounds. In general, molecules Figure 6. IR spectra of K[ClO3 ] (solid line) and K[IO3 ] (dashed
such as NH3 and PH3 show the trends n3 > n1 and n4 > n2 , line).
whereas ions such as SO3 2 and IO3 show the opposite
trends. In some cases, the two stretching vibrations (n1 and and n4 are IR-active whereas n1 , n3 and n4 are Raman-
n3 ) are too close to be distinguished empirically. Figure 6 active. Table 7 lists the vibrational frequencies of planar
shows the IR spectra of KClO3 and KIO3 . Substitution of XY3 molecules, and Figure 8 shows the Raman spectrum
one of the Y atoms by a Z atom (e.g. XY2 Z) lowers the of KNO3 in aqueous solution. As expected, the totally sym-
symmetry from C3v to Cs . Then the degenerate vibrations metric (n1 ) vibration appears strongly. Although calcite and
(n3 and n4 ) split into two bands, and all six vibrations aragonite have the same chemical composition (CaCO3 ),
become both IR- and Raman-active. The same selection their IR spectra are different because the local (site) sym-
rule holds for the XYZW (C1 ) molecule. metries of the CO3 2 ion in these two crystals are different
The four normal modes of vibration of a planar XY3 (D3 and Cs , respectively ). As a result, n1 becomes IR-
molecule (D3h ) are shown in Figure 7. Vibrations n2 , n3 active and n3 and n4 split into two bands in aragonite.
DOI: 10.1002/9780470027325.s4104
As expected, these compounds exhibit six vibrations in both

Y + the IR and Raman spectra. If one of the Y atoms of a pla-
nar XY3 molecule is replaced by a Z atom (e.g. XY2 Z), the
X − symmetry is lowered to C2v . If two Y atoms are replaced
+ + by two different atoms (e.g. XYZW), the symmetry is fur-
Y Y
ν1(A′1) ν2(A′′2)
ther lowered to Cs . Then, all six vibrations become IR- and
νs (XY) π(XY3) Raman-active.
Other four-atom molecules such as H2 O2 take a nonpla-
nar structure (C2 ) in which the molecule is twisted around
the central O–O bond by ¾90° . Under C2 symmetry, all
six normal vibrations are IR- and Raman-active. In H2 O2 ,
these bands are observed at 3607 and 3608 [n(OH)], 1394
[n(OO)], 1266 and 864 [υ(HOO)] and 317 cm1 (p). On
ν3(E ′) ν4(E ′) the other hand, molecules such as N2 F2 and N2 O2 2 exist
νd (XY) δd (YXY) in two forms: trans-planar (C2h ) and cis-planar (C2v ). For
example, the trans-planar N2 O2 2 ion exhibits three bands
Figure 7. Normal modes of vibration of planar XY3 molecules.
(1031, 492 and 371 cm1 ) whereas the cis-planar N2 O2 2
ion shows five bands (1314, 1047, 830, 584 and 330 cm1 )
Table 7. Vibrational frequencies of planar XY3 molecules
(cm1 ). in the IR spectra.
Planar X–Y–Z–W (e.g. HNCS), X–Y–Z–Y (e.g.
Molecule n1 A01
n2 A002
n3 E0
n4 E0
HONO) and X–Y–Y–Y (e.g. HN3 ) molecules take Cs
symmetry, and all six vibrations are both IR- and Raman-
10
BF3 888 719.3 1505.8 481.1 active. For example, HN3 exhibits n(NH) at 3324, n(NN)
11
BCl3 472.7 – 950.7 253.7 at 2150 and 1273, υ(HNN) at 1168, υ(NNN) at 527 and p
11
BBr3 278 374 802 150
11
BI3 192 – 691.8 101.0
at 588 cm1 .
AlF3 – 286.2 909.4 276.9
AlCl3 393.5 – 618.8 150
AlBr3 228 107 450–500 93 4.1 Four-atomic ligands
AlI3 156 77 370–410 64
GaCl3 386.2 – 469.3 132
GaBr3 219/237 95 – 84 Pyramidal XY3 ligands such as NH3 , AsH3 , SbH3 and PF3
GaI3 147 63 275 50 coordinate to a metal via the X atom. Among them, NH3
Ca[CO3 ] (calcite)a – 879 1492–1429 706 (amine) complexes have been studied most extensively.
Ca[CO3 ] (aragonite)a 1080 866 1504, 1492 711, 706 Figure 9 shows the IR spectra of hexammine complexes
K[NO3 ]a – 828 1370 695
SO3 1065 497.5 1390 530.2 of Co(III), Cr(III) and Ni(II). In addition to the NH3 vibra-
SeO3 923 – 1219 305 tions, these amine complexes exhibit the M–NH3 rocking
[rr (NH3 )], M–N stretching [n(M–NH3 )] and υ(NMN) vibra-
a IR spectra. tions in the regions 850–650, 500–250 and 330–200 cm1 ,
ν1
respectively. The SO3 2 (sulfite) ion coordinates to a metal
1050 as a unidentate ligand through the sulfur or the oxygen
Intensity
KNO3 aq atom. Although the symmetry of the M–SO3 moiety is

C3v in the former, it may be lowered to Cs in the lat-
ter. Then, the doubly degenerate vibrations of the free ion
ν3 ν4 split into two bands in the O-bonded complex. Furthermore,
1800 1600 1400 1200 1000 800 600 400 200 0 coordination via the sulfur atom shifts n3 (SO3 ) to higher
∼
ν/cm−1 frequencies relative to the free ion, whereas the opposite
Figure 8. Raman spectrum of K[NO3 ] in aqueous solution
trend holds for coordination via the oxygen atom. Thus, the
(488.0-nm excitation). n3 of the S-bonded SO3 2 ligand in [Co(NH3 )5 (SO3 )]Cl is
at 1110 cm1 whereas that of the O-bonded SO3 2 ligand
Some XY3 molecules (ClF3 and BrF3 ) take the unusual in Tl2 [Cu(SO3 )2 ] is at 902 and 862 cm1 . Similar rules are
T-shaped structure of C2v symmetry. This geometry can be applicable to the SeO3 2 (selenite) coordination.
derived from a trigonal-bipyramidal structure in which two The planar CO3 2 (carbonate) ion (1) coordinates to
equatorial positions are occupied by two lone-pair electrons. a metal as a unidentate (2) or a bidentate (3) ligand.
DOI: 10.1002/9780470027325.s4104
100
Transmission (%)
80
Cr
Co
60
Ni
40
20 ν(NH3)
δd (NH3) ρr(NH3)
δs (NH3)
0
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 650
∼
ν/cm−1
Figure 9. IR spectra of [Co(NH3 )6 ]Cl3 (solid line), [Cr(NH3 )6 ]Cl3 (dot-dashed line) and [Ni(NH3 )6 ]Cl2 (dotted line).
In both cases, the doubly degenerate vibration of the Table 8. Vibrational frequencies of tetrahedral XY4 molecules
free ion (n3 ) splits into two bands. However, the split- (cm1 ).
ting is larger in the bidentate (1593 and 1265 cm1
Molecule n1 n2 n3 n4
in [Co(NH3 )4 CO3 ]Cl) than in the unidentate (1453 and
1373 cm1 in [Co(NH3 )5 CO3 ]Br) complex. Similar trends CH4 2917 1534 3019 1306
are noted for NO3 (nitrato) complexes. SiH4 2180 970 2183 910
GeH4 2106 931 2114 819
M M NH4 C 3040 1680 3145 1400
O O O O CF4 908.4 434.5 1283.0 631.2
C CCl4 460.0 212.2 792/765a 313.5
C C
CBr4 267 123 672 183
O O O O O
CI4 178 90 555 123
Free ion (D3h) Unidentate (Cs) Bidentate (C2v) SnCl4 369.1 95.2 408.2 126.1
(1) (2) (3) SnBr4 222.1 59.4 284.0 85.9
SnI4 147.7 42.4 210 63.0
CoCl4 2 269 – 311/291b 135
CoBr4 2 166 – 231/222b 96
CoI4 2 118 – 202/194b 56
5 FIVE-ATOM MOLECULES SiO4 4 819 340 956 527
PO4 3 938 420 1017 567
AsO4 3 837 349 878 463
Figure 10 illustrates the four normal modes of vibration SO4 2 983 450 1105 611
of a tetrahedral XY4 molecule. All four vibrations are CrO4 2 846 349 890 378
Raman-active, whereas only n3 and n4 are IR-active. MnO4 834 346 902 386
Table 8 lists the vibrational frequencies of typical XY4 a Fermi resonance between n and n C n
.
3 1 4
b Splitting due to lowering of symmetry in the
molecules. In general, n3 > n1 and n4 > n2 , although n2 > solid state.
n4 in XH4 molecules. Figure 11 shows the Raman spectrum
of K2 SO4 in which the totally symmetric (n1 ) mode appears 981 ν1
strongly. Molecules such as SF4 , SeF4 and TeF4 assume a
Intensity
K2SO4 aq
distorted tetrahedral structure (C2v ) which can be derived
from a trigonal-bipyramidal geometry with a lone pair of ν4 ν2
ν3
electrons occupying one of the equatorial positions. These
1800 1600 1400 1200 1000 800 600 400 200 0
~
ν/cm−1
Y
Figure 11. Raman spectrum of K2 [SO4 ] in aqueous solution
X (488.0-nm excitation).
Y
Y Y
molecules exhibit all nine normal vibrations in Raman
ν1(A1) ν2(E ) ν3(F2) ν4(F2) spectra.
νs (XY) δd (YXY) νd (XY) δd (YXY) If one of the Y atoms of an XY4 molecule is replaced
Figure 10. Normal modes of vibration of tetrahedral XY4 by a Z atom (e.g. XY3 Z), the symmetry is lowered to
molecules. C3v . If two Y atoms are replaced (e.g. XY2 Z2 ), the
DOI: 10.1002/9780470027325.s4104
Table 9. Correlation table for Td , C3v , C2v and C1 .
Point n1 n2 n3 n4
group
Td A1 (R) E(R) F2 (IR, R) F2 (IR, R)

C 3v A1 (IR, R) E(IR, R) A1 IR, R
C E(IR, R) A1 IR, R) C E(IR, R)
C 2v A1 (IR, R) A1 IR, R
C A2 R
A1 IR, R
C B1 IR, R
A1 IR, R
C B1 IR, R
C B2 (IR, R) C B2 (IR, R)
C1 A(IR, R) 2A(IR, R) 3A(IR, R) 3A(IR, R)
symmetry is lowered to C2v . In XY2 ZW and XYZWU Table 10. Vibrational frequencies of square-planar XY4 mole-
types, the symmetry is further lowered to Cs and C1 , cules (cm1 ).
respectively. Then, the selection rules are changed as
XY4 n1 (A1g ) n2 (B1g ) n3 (A2u ) n4 (B2g ) n6 (Eu ) n7 (Eu
shown in Table 9. The number of IR-active vibrations is ns (XY) υ(XY2 ) p na (XY) nd (XY) υd (XY2 )
six for XY3 Z (e.g. CCl3 F) and eight for XY2 Z2 (e.g.
SO2 Cl2 ). ClF4 505 288 425 417 680–500 –
Figure 12 shows the seven normal modes of vibration of BrF4 523 246 317 449 580–410 (194)
a square-planar XY4 molecule. Vibrations n3 , n6 and n7 are ICl4 288 128 – 261 266 –
IR-active, whereas n1 , n2 and n4 are Raman-active. Table 10 XeF4 554.3 218 291 524 586 (161)
AuCl4 347 171 – 324 350 179
lists the vibrational frequencies of typical square-planar AuBr4 212 102 – 196 252 ¾110
XY4 molecules. XeF4 is the only example of a neutral AuI4 148 75 – 110 192 113
molecule having a square-planar structure. This structure PdCl4 2 303 164 150 275 321 161
can be derived from the octahedral geometry where the PdBr4 2 188 102 114 172 243 104
two axial positions are occupied by two lone pairs of PtCl4 2 330 171 147 312 313 165
PtBr4 2 208 106 105 194 227 112
electrons. PtI4 2 155 83 105 142 180 127
n5 (B2u ) is inactive under D4h symmetry. n1 (A1g ) is polarized and

Y Y + + n2 (B1g ) and n4 (B2g ) are depolarized in Raman spectra.
X −
5.1 Five-atomic ligands
Y Y + +
When a tetrahedral ion such as SO4 2 coordinates to a metal
ν1(A1g ) ν2(B1g ) ν3(A2u ) (sulfato complex), the lowering of symmetry is different
νs (XY) δ(YXY) π for the unidentate and bidentate coordination as shown in
(4–7).
+ −
M
O O M O O O O
S S S
O O O O O O
− + Free ion Unidentate complex Bidentate complex
ν4(B2g ) ν5(B2u ) ν6(Eu ) (Td) (C3v) (C2v)
νa (XY) π νd (XY)
(4) (5) (6)
M O O M
S
O O
Bridged bidentate
complex (C2v)
ν7 (Eu ) (7)
δd (YXY)
Figure 12. Normal modes of vibration of square-planar XY4 Then, the selection rules are changed as shown
molecules. previously in Table 9. Figure 13 shows the IR spectra
DOI: 10.1002/9780470027325.s4104
λ /µm
8 9 10 11
ν1
D 3h C4v D 5h
Figure 14. Structures of XY5 molecules.

ν3
molecules such as PF5 and AsCl5 exhibit eight normal
Absorption
vibrations as shown in Figure 15. Among them, five

vibrations (2A002 and 3E0 ) are IR-active, and six vibra-
ν1 tions (2A01 , 3E0 and E00 ) are Raman-active under D3h
ν3 symmetry. In general, the four stretching vibrations fol-
ν3
low the trend n5 (equatorial) > n3 axial
> n1 equatorial
>
n2 (axial). For example, PF5 exhibits these vibrations at
ν1 1026, 944, 817 and 640 cm1 , respectively.
Tetragonal-pyramidal molecules such as SF5 and BrF5
ν3 ν3 exhibit nine normal vibrations as shown in Figure 16.
ν3 Under C4v symmetry, six (3A1 and 3E) vibrations are IR-
active and all nine (3A1 , 2B1 , B2 and 3E) vibrations are
1200 1100 1000 900
Raman-active. In this case, the four stretching frequencies
∼
ν/cm −1 show the trend n1 (axial) >n7 (equatorial) >n2 (equatorial)
>n4 (equatorial). For example, BrF5 shows these vibrations
Figure 13. IR spectra of [Co(NH3 )6 ]2 (SO4 )3 Ð 5H2 O (solid line), at 682, 644, 570 and 535 cm1 , respectively.
[Co(NH3 )5 SO4 ]Br (dot-dashed line) and (8) (dotted line).
The only known example of a planar pentagonal XY5
of [Co(NH3 )6 ]2 SO4 )3 Ð 5H2 O, [Co(NH3 )5 SO4 ]Br and molecule is the XeF5 ion. This D5h structure can be
(8). derived by replacing the two axial fluorine ligands of the
pentagonal-bipyramidal IF7 molecule with two lone-pair
electrons. Then, only three (A002 and 2E01 ) vibrations are
NH2
IR-active and only three (A01 and 2E02 ) are Raman-active
(NH3)4Co Co(NH3)4 (NO3)3
SO4 under D5h symmetry. In agreement with this prediction,
the XeF5 ion exhibits three Raman bands at 502, 423
(8) and 377 cm1 . The trigonal-bipyramidal and tetragonal-
pyramidal structures can be ruled out since they predict
In the first complex, n3 does not split, and n1 appears six and nine Raman-active vibrations, respectively.
very weakly. Thus, the symmetry of its SO4 2 ion is
approximately Td . In the second complex, n3 splits into two
bands and n1 appears with medium intensity, suggesting 7 SEVEN-ATOM MOLECULES
C3v symmetry of the SO4 2 ion. In the last complex, n3
splits into three bands whereas n1 is of medium intensity. An octahedral XY6 molecule (Oh ) exhibits the six normal
Therefore, its symmetry is regarded as C2v . Similar changes modes of vibration shown in Figure 17. Vibrations n1 (A1g ),
are seen for n4 and n2 . The modes of coordination of other n2 (Eg ) and n5 (F2g ) are Raman-active whereas only n3
tetrahedral ligands such as ClO4 (perchlorato complex) (F1u ) and n4 (F1u ) are IR-active. Since n6 is inactive, its
can also be determined on the same basis. frequency is estimated from the analysis of combination and
overtone bands. Table 11 lists the vibrational frequencies
of hexahalo molecules. In most cases, the order of the
6 SIX-ATOM MOLECULES stretching frequencies is n1 > n3 × n2 whereas that of
the bending frequencies is n4 > n5 > n6 . Within the same
As shown in Figure 14, an XY5 molecule may take a family of the periodic table, the stretching frequencies (n1
trigonal-bipyramidal (D3h ), a tetragonal-pyramidal (C4v ) or and n3 ) decrease as the mass of the central atom increases.
a planar pentagonal (D5h ) structure. Trigonal-bipyramidal Thus, AlF6 3 > GaF6 3 > InF6 3 > TlF6 3 . This trend in
DOI: 10.1002/9780470027325.s4104
Y′
Y
X
Y
Y
Y′
ν1 (A ′1) ν2 (A ′1) ν3 (A ′′2) ν4 (A ′′2)
νs (XY3) νs (XY′2) νa (XY′2) π (XY3)
ν5 (E ′) ν6 (E ′) ν7 (E ′) ν8 (E ′′)
νa (XY3) δ (XY3) δ (XY′2) ρr (XY′2)
Figure 15. Normal modes of vibration of trigonal-bipyramidal XY5 molecules.
Y′ Y
Y Y
Y X Y
X
Y
Y Y
ν1 (A1) ν2 (A1) ν3 (A1) Y
ν (XY′) νs (XY4) π (Y′XY4)
Y
ν1 (A1g) ν2 (Eg) ν3 (F1u)
ν (XY) ν (XY) ν (XY)
ν1 (B1) ν5 (B1) ν6 (B2)

νa (XY1) δa (XY4) δs (XY4)
ν4 (F1u) ν5 (F2g) ν6 (F2u)

δ (YXY) δ (YXY) δ (YXY)
ν7 (E ) ν8 (E ) ν9 (E )
νd (XY4) πd (XY4) δd (XY4)
Figure 17. Normal modes of vibration of octahedral XY6
molecules.
Figure 16. Normal modes of vibration of tetragonal-pyramidal
XY5 molecules. MCl6 2 > MBr6 2 > MI6 2 . The metal isotope shift in the
n3 vibration of gaseous UF6 by 235 U/238 U substitution is
n1 indicates the order of the M–F stretching force constants only 0.65 š 0.1 cm1 since the relative mass difference
since the central atom does not move in this mode. Across between the two isotopes (m/m) is very small.
the periodic table, the stretching frequencies increase as the If one of the Y atoms in octahedral XY6 molecules is
oxidation state of the central atom becomes higher. replaced by a Z atom, the resulting XY5 Z molecule takes
An example is given by AlF6 3 < SiF6 2 < PF6 < C4v symmetry. If two Y atoms are replaced, the XY4 Z2
SF6 . A similar effect is seen in the series VF6 3 < VF6 2 < molecule may take cis (C2v ) or trans (D4h ) geometry. If
VF6 . As seen in many other cases, the metal–halogen three Y atoms are replaced, the XY3 Z3 molecule may
stretching vibrations decrease in the order MF6 2 > be a cis–trans (meridional ) or a cis–cis (facial ) isomer
DOI: 10.1002/9780470027325.s4104
Table 11. Vibrational frequencies of octahedral XY6 molecules 8 X2 Yn MOLECULES

(cm1 ).
Molecule n1 n2 n3 n4 n5 n6 Figure 18 shows the three possible structures of the X2 Y4

(Y2 X–XY2 ) molecule in which the X–XY2 moiety is
AlF6 3 541 (400) 568 387 322 (228) planar. The molecular symmetry becomes D2h (t D 0° ,
GaF6 3 535 (398) 481 298 281 (198) planar), D2d (t D 90° , staggered) or D2 (0° < t < 90° ,
InF6 3 497 (395) 447 226 229 (162) intermediate) depending on the twisting angle (t) between
TlF6 3 478 387 412 202 209 (148) the two XY2 planes. An example of D2h structure is given
SiF6 2 663 477 741 483 408 –
GeF6 2 624 471 603 339/359 335 – by N2 O4 . It exhibits six vibrations (1712, 1380, 808, 672,
SnF6 2 592 477 559 300 252 – 482 and 266 cm1 ) in the Raman spectra and five vibrations
SnCl6 2 311 229 303 166 158 – (1748, 1262, 750, 420 and 381 cm1 ) in the IR spectra,
SnBr6 2 190 144 224 118 109 – as predicted by the D2h selection rules. The D2d and D2
SnI6 2 122 93 161 84 78 – structures can be distinguished by comparing the observed
VF6 676 538 646 300 330 –
VF6 2 584 – 578 273 – – number of vibrations with that predicted for each structure:
VF6 3 533 – 511 292 – – five IR and nine Raman for D2d and eight IR and 12 Raman
WF6 770 676 711 258 321 (127) for D2 . For example, B2 Cl4 in the gaseous and liquid states
WCl6 437 331 373 160 182 – takes the D2d structure since it exhibits five IR bands at
PtF6 656 (601) 705 273 (242) (211) 917, 730, 617, 291 and 180 cm1 .
PtF6 2 611 576 571 281 210 (143)
PtCl6 2 348 318 343 183 171 (80) If the X–XY2 moiety is not planar, the molecule may take
PtBr6 2 213 190 243 146 137 – the trans (C2h ), gauche (C2 ) or cis (C2v ) conformations,
UF6 666 530 619 184 200 – depending on the angle of the internal rotation around the
X–X bond. Figure 19 shows the structures of these three
n1 (Ag ) is polarized and n2 (Eg ) and n5 (F2g ) are depolarized in Raman
spectra. conformers. Most of the compounds of this type exist as
the trans- or gauche-isomer or a mixture of both since the
Table 12. Number of IR-active and Raman-active stretching cis-isomer is not stable. The trans- and gauche-isomers are
vibrations for octahedral XYn Z6n -type molecules. expected to show six and 12 IR bands, respectively. For
example, P2 Cl4 is trans in all physical states since it exhibits
Molecule Point group IR/Raman n (X–Y) n (X–Z)
six IR bands at 508, 501, 275, 202, 139 and 91 cm1 . On
XY6 Oh IR F1u
the other hand, P2 H4 is gauche in the gaseous state and
Raman A1g , Eg trans in the solid state. N2 F4 is a mixture of the trans- and
XY5 Z C 4v IR 2A1 , E A1 gauche-isomers in all states.
Raman 2A1 , B1 , E A1 Figure 20 illustrates the 18 normal vibrations of the
trans-XY4 Z2 D4h IR Eu A2u nonplanar bridging X2 Y6 molecule in which the two XY2
Raman A1g , B1g A1g
moieties are linked via two bridging Y0 atoms. Under D2h
cis-XY4 Z2 C 2v IR 2A1 , B1 , B2 A1 , B1
Raman 2A1 , B1 , B2 A1 , B1 symmetry, it exhibits eight IR (2B1u , 3B2u and 3B3u ) and
mer-XY3 Z3 a C 2v IR 2A1 , B2 2A1 , B1
Raman 2A1 , B2 2A1 , B1
fac-XY3 Z3 a C 3v IR A1 , E A1 , E τ τ
Raman A1 , E A1 , E
a mer, cis–trans; fac, cis–cis. D2h D2d (τ = 90°) D2 (τ ≠ 90°)
with C2v or C3v symmetry, respectively. Table 12 lists the Figure 18. Three conformations of X2 Y4 molecules (the X–XY2
number of IR- and Raman-active stretching vibrations of moiety is planar).
these XYn Z6n molecules. Using this table, it is possible
to distinguish geometric isomers such as the trans- and
cis-isomers and the mer- and fac-isomers. For example,
the trans-OsCl4 Br2 2 ion (D4h ) exhibits one n(Os–Cl)
at 307 cm1 (Eu ), whereas the cis-OsCl4 Br2 2 ion (C2v )
shows four n(Os–Cl) at 329 (A1 ), 307 (B1 ), 295 (A1 )
and 288 cm1 (B2 ) in the IR spectra. The IR and Raman cis (C 2ν) trans (C 2h) gauche (C 2)
spectra of octahedral mixed-halo complexes have been Figure 19. Three conformations of X2 Y4 molecules (the X–XY2
reviewed.19 moiety is nonplanar).
DOI: 10.1002/9780470027325.s4104
Y Y
Y′
X X −
Y′ +
ν1(Ag) ν2(Ag) ν3(Ag)
Y ν(XY) Y ν(XY′) δ(XY2)
− +
+
+ −
−
ν4(Ag) ν5(Au) ν6(B1g)
+ −
ring def. ρt (XY2) ν(XY′)
− +
+ −
ν7(B1g) ν8(B1u) ν9(B1u)

− +
ρw(XY2) ν(XY) ρr (XY2)
ν10(B1u) ν11(B2g) ν12(B2g)

ring def. ν(XY) ρr (XY2)
+ + − −
+
− + − − −
ν13(B2u) ν14(B2u)
+ + + ν15(B3g) +
ν(XY′) ρw(XY2)
δ(XY2)
ν16(B3u) ν17(B3u) ν18(B3g)

ν(XY) ν(XY′) δ(XY2)
Figure 20. Normal modes of vibration of bridged X2 Y6 molecules.
10 Raman (4Ag , 2B1g , 2B2g , and 2B3g ) bands. Molecules X2 Y6 molecules may also take an ethane-like structure
such as B2 H6 and Al2 Cl6 belong to this type. For example, in which two XY3 moieties are linked via the central X–X
B2 H6 exhibits the stretching vibrations of the terminal XY2 bond. Depending on the magnitude of internal rotation
group at 2526 (n1 ), 2613 (n8 ), 2597 (n11 ) and 2518 cm1 about the X–X bond, it may take the staggered (D3d ),
(n16 ), and those of the bridging X2 Y02 at 2096 (n2 ), 1756 eclipsed (D3h ) or gauche (D3 ) conformation. Figure 21
(n6 ), 1924 (n13 ) and 1615 cm1 (n17 ). In general, the ratios shows the 12 normal modes of vibration for the staggered
of the average terminal and bridging stretching frequencies (D3d ) conformation. The A1g (n1 , n2 , n3 ) and Eg (n10 , n11 ,
range from 0.74 to 0.61. The same selection rules hold for n12 ) vibrations are Raman-active, whereas the A2u (n5 , n6 )
the planar bridging M2 X6 2 ions (M D Pd and Pt, X D Cl, and Eu (n7 , n8 , n9 ) vibrations are IR-active and A1u (n4 )
Br and I), although the terminal and bridging vibrations vibration is inactive under D3d symmetry. The P2 O6 4 ion
are closer in frequency and strongly coupled in this exhibits six Raman bands at 1062, 670, 275, 1168, 508,
case. For example, the Pt2 Cl4 2 ion exhibits the terminal 383 cm1 and five IR bands at 942, 562, 1085, 494 and
stretchings at 350–330 cm1 and bridging stretchings at 200 cm1 in the order of the normal modes given above.
320–290 cm1 . The Raman band at 275 cm1 is the n (P–P) of the central
DOI: 10.1002/9780470027325.s4104
Y
X
Y Y
X
Y Y (a) C2v D4h
Y (b)
ν1(A1g ) ν2(A1g ) ν3(A1g ) ν4(A1u )
(c) D3h (d) D2h
ν5(A2u ) ν6(A2u) ν 7( E u) ν 8( E u)
(e) D4d
Figure 22. Structures of X2 Yn molecules.

ν9(Eu ) ν10(Eg ) ν11(Eg ) ν12(Eg ) 1745 (3ν1+ν2+182)
1427 (2ν1+ν2+182)
1109 (ν1+ν2+182)
Figure 21. Normal modes of vibration of ethane-type X2 Y6
1447 (4ν1+182)
1410 (2ν1+770)
1128 (3ν1+182)
816 (2ν1+182)
1088 (ν1+770)
500 (ν1+182)
molecules.
1573 3ν1+ν2
1257 2ν1+ν2
943 ν1+ν2
1903 6ν1
1587 5ν1
1272 4ν1
953 3ν1
636 2ν1
625 ν2
320 ν1
bond. Other examples of ethane-type molecules include
770
182
Intensity
Si2 H6 , Ge2 H6 , N2 H6 2C and S2 O6 2 . These molecules show

the central n(X–X) vibrations at 434, 229, 1027 and
293 cm1 , respectively. The D3h and D3d selection rules
are similar except that the Eu modes (IR-active) of D3d
become both IR- and Raman-active (E0 ) in D3h .
X2 Y7 molecules shown in Figure 22(a) belong to the C1 ,
Cs or C2v point group, depending on the relative orientation 2000 1500 1000 500 0
∼
ν/cm−1
of the two XY3 groups. Seventeen vibrations are IR-active
under C2v symmetry, but all 21 vibrations are IR-active Figure 23. RR spectrum of [(n-C4 H9 )4 N]2 Re2 F8
Ð 4H2 O (530.9-
under C1 or Cs symmetry. The na and ns of the XYX nm excitation).
bridge are observed at 915 and 730 cm1 , respectively,
for P2 O7 4 and at 785 and 700 cm1 , respectively, for in the Raman spectra (345 and 320 cm1 , respectively,
Cl2 O7 . for Mo2 Cl8 4 and Re2 F8 2 ) because displacements of
The symmetry of the X2 Y8 (Y3 X–Y–Y–XY3 ) molecule heavy metal atoms which are linked by strong multiple
may be low enough to allow all 24 normal vibrations in bonds produce large changes in polarizability. Furthermore,
both IR and Raman spectra. The na (XYYX), ns (XYYX), these compounds, under resonance conditions, exhibit a
n(Y–Y) and υ(XYYX) of the bridging group are at 988, series of overtones of n(M–M), n(M–X) (X D halogen)
784, 890 and 397/328 cm1 , respectively, for the P2 O8 4 and combination bands from which one can calculate
ion, and 1062, 834, 854 and 328/236 cm1 , respectively, for the frequency corrected for anharmonicity (!e ). Figure 23
the S2 O8 4 ion. In other X2 Y8 molecules such as Mo2 Cl8 4 shows the RR spectrum and vibrational assignments of the
and Re2 Cl8 2 , two XY4 units are linked via the X–X bond Re2 F8 2 ion. It is seen that the n(Re–Re) at 320 cm1 (n1 )
(multiple metal–metal bond) as shown in Figure 22(b) so is markedly enhanced, and a series of overtones (nn1 , up
that the overall symmetry becomes D4h (eclipsed form). to n D 6) and combination bands involving n2 [n(ReF) at
These metal–metal bonds exhibit strong n(M–M) vibrations 625 cm1 ] are observed.
DOI: 10.1002/9780470027325.s4104
X2 Y9 molecules such as shown in Figure 22(c) belong H

to the D3h point group, and exhibit four terminal and four B
bridging stretching vibrations. In Cr2 Cl9 3 , these vibrations O O
are at 375, 360, 342 and 320 cm1 for the terminal and at B B
280, 261, 234 and 222 cm1 for the bridging groups. Other H O H
examples include W2 Cl9 3 , Ir2 Cl9 3 and Pt2 Br9 .

The X2 Y10 molecule may take either one of the two (a) H3B3O3 (D3h ) (b) B6Cl62− (Oh )
structures shown in Figure 22(d) and (e). The Re2 Cl10 2

2−
ion takes the double-bridged D2h structure, and its IR O
spectrum shows four terminal (367–321 cm1 ) and two
O O
bridging (278–250 cm1 ) vibrations, although these modes
may be mixed to some extent. Other examples are Ti2 Cl10 2
and Nb2 Cl10 . The symmetry of the single-bridge Y5 X–XY5 O O
molecule may be D4d (staggered) or D4h (eclipsed). The (c) B5H9 (C4ν ) (d) C5O52− (D5h )
IR and Raman spectra of S2 F10 and Te2 F10 have been
assigned on the basis of D4d symmetry. These compounds
exhibit the n(X–X) of the central bond at 247 and 168 cm1 ,
respectively.
9 MOLECULES OF OTHER TYPES (f)

(e) C60 (Ih ) C70 (D5h )
There are many molecules which do not belong to any Figure 24. Structures of boron and carbon compounds.
structural types described in the preceding sections. These
include ring, cage and other unusual structures. In the fol- boron compounds. The group frequency charts for n(BH),
lowing, vibrational spectra of some of these molecules are n(BX) and n(BO) vibrations are given in Appendices 1, 2
discussed for each nontransition element. More complete and 3, respectively.
information can be found in the original references cited in
Nakamoto.1
9.2 Compounds of carbon
9.1 Compounds of boron The carbon oxide anions such as Cn On 2 (n D 3, 4 and 5)

take the planar ring structures. As an example, Figure 24(d)
Boron compounds take a variety of structures, some of shows the structure of the C5 O5 2 ion. Because of the
which are shown in Figure 24(a)–(c). H3 B3 O3 (boroxine) aromaticity of these rings, their IR spectra exhibit n(CDO)
forms a planar ring structure of D3h symmetry shown in (a) below 1600 cm1 which is much lower than for nor-
whereas the B6 skeleton of the B6 X6 2 ion (X D halogen) mal ketones (¾1700 cm1 ). The well-known C60 molecule
assumes an octahedral structure of Oh symmetry shown in (buckyball/soccerball) takes the form of a regular trun-
(b). In the latter, its 30 normal vibrations are grouped into cated icosahedron which consists of 20 hexagonal and
B–B skeletal and B–X terminal vibrations; one B–B (n7 ) 12 pentagonal faces [Figure 24(e)] and belongs to the high-
and two B–X (n8 , n9 ) vibrations are IR-active, and three est symmetry Ih point group. Although C60 possesses 174
B–B (n1 , n3 , n5 ) and three B–X (n2 , n4 , n6 ) vibrations are (3 ð 60 6) normal vibrations, it exhibits only four IR and
Raman-active. As shown in Figure 25, the B–B vibrations 10 Raman bands, as predicted from the selection rules for
are insensitive whereas the B–X vibrations are sensitive to the Ih point group. The C70 (rugbyball) molecule consists
halogen substitution. Boron hydrides (boranes) are known of 25 hexagonal and 12 pentagonal faces [Figure 24(f)],
for their unusual structures. For example, B5 H9 takes the and its symmetry (D5h ) is much lower than that of C60 .
structure shown in Figure 24(c) where the five boron atoms As a result, 31 vibrations are allowed in the IR and 53
form a square-pyramidal skeleton, with four hydrogen vibrations in the Raman spectra. However, the numbers of
atoms bridging four base boron atoms while five hydrogen observed bands are much smaller (11 IR and 18 Raman)
atoms are bonded terminally to each boron atom so that the than those predicted, because of band overlappings and
symmetry of the whole molecule is C4v . Review articles20,21 intensity variations. Figure 26 compares the IR spectra of
are available for the vibrational spectra of these and other C60 and C70 . The structures and physical properties of C60
DOI: 10.1002/9780470027325.s4104
0.200
C60
IIa
ν8 0.154
ν9
ν7
527
0.108
IIIa
577
0.062
1428
1183
0.016
D (IR)
IVa −0.030
Absorbance
(a)
0.200
C 70
0.154
× 30
1430
IVb
0.108
578
565
535
674
1414
0.062
1460
795
1134
642
458
0.016
IIIb ×8
ν2 −0.030
ν6 1600 1300 1000 700 400
ν4
ν1 (b) ~
ν/cm−1
ν5
Figure 26. IR spectra of C60 and C70 .
I(Ra)
ν3
× 3 IIb
2100 ν(SiSi)
δ(SiH)
1200 1000 800 600 400 200 ν(SiH)
∼
ν/cm−1 IR
Figure 25. (a) IR and (b) Raman (514.5-nm excitation) spec-
Raman intensity
tra of solid Cs2 [B6 Cl6 ] (II), Cs2 [B6 Br6 ] (III) and Cs2 [B6 I6 ]
IR absorption
(IV).
and its derivatives have been reviewed extensively.22 Group

frequency charts for the n(CH), n(CX) and n(CO) are given
in Appendices 1, 2 and 3, respectively.
Raman
2100 800 600 400 200 0

9.3 Compounds of silicon ∼
ν/cm−1
Silanes such as Si5 H10 (D5h ) and Si6 H12 (D3d ) take non- Figure 27. IR and Raman (632.8-nm excitation) spectra of
Si6 H12 .
planar ring structures consisting of five and six SiH2
units, respectively. Figure 27 shows the IR and Raman
spectra and band assignments for Si6 H12 . Silicates form (n2 , E), 800–1000 cm1 (n3 , F2 ) and 450–600 cm1 (n4 ,
a variety of structures, some of which are shown in F2 ). More information can be found elsewhere.23 Group
Figure 28. In general, the tetrahedral SiO4 unit exhibits frequency charts for n(SiH), n(SiX) and n(SiO) vibrations
four vibrations at 750–830 cm1 (n1 , A1 ), 300–400 cm1 are given in Appendices 1, 2 and 3, respectively.
DOI: 10.1002/9780470027325.s4104
L N4S4
Intensity
(Si3O9)6− (Si6O18)12−
N4Se4
L
L
(Si4O11)n6− 100 300 500 700

~
ν/cm−1
Figure 28. Structures of silicates.
Figure 30. Raman spectra of N4 S4 (crystal) and N4 Se4 (powder)
O O O CF3 (647.1-nm excitation). L denotes a laser line.
N N
N
O O CF3 CF3 O O−
P
(a) N2O5(C2ν) (b) N(CF3)3(C3) P 4−
O O
P P
− O− P P O
S P P O
N N S S P O O−
N N
SN (a) P64− (D6h) (b) P3O93− (D3h) (c) S6 (D3d)
S S N
N S
(c) N3S3− (D3h) (d) N4S4 (D2d) S H
SO O N
S
Figure 29. Structures of nitrogen compounds. O O
O O H H O• •
O O SO O O
9.4 Compounds of nitrogen N
(d) S8 (D4d) H
(puckered) (e) (SNH)4 (C4v) (f) S3N2O2 (C2v)
Figure 29(a)–(d) illustrate the structures of four nitrogen
compounds. The N2 O5 molecule (a) takes a planar structure Figure 31. Structures of phosphorus and sulfur compounds.
of C2v symmetry in the gaseous state. In the solid state,
however, it becomes an ionic crystal consisting of NO2 C
and NO3 ions (see Tables 2 and 7, respectively). The
9.5 Compounds of phosphorus
NC3 skeleton of N(CF3 )3 (b) is suggested to be flat, and
the overall symmetry is regarded as C3 . The N3 S3 ion
(c) takes the planar ring structure (D3h ) while the N4 S4 The P6 4 ion takes the planar ring structure (D6h ) shown in
molecule (d) forms a cage structure (D2d ). The latter is Figure 31(a), and exhibits three Raman bands at 356 (A1g ),
expected to show seven IR and 12 Raman bands under 507 (E2g ) and 202 cm1 (E2g ). The phosphorus oxide anion
D2d symmetry. Figure 30 shows the Raman spectra of N4 S4 P3 O9 3 [D3h , Figure 31(b)] exhibits nine IR and 14 Raman
and N4 Se4 (crystalline state) below 800 cm1 . In general, bands. The terminal PO2 group exhibits n(PO2 ), υ(PO2 ),
the n(NS), υ(NSN)/υ(SNS) and n(SS) bands appear at r(PO2 ), rw (PO2 ) and rt (PO2 ) bands at 1250–950, ¾600,
800–700, 600–700 and ¾200 cm1 , respectively, although ¾500, ¾400 and ¾300 cm1 , respectively. Vibrational
strong vibrational couplings occur among these modes. spectra of phosphorus compounds have been reviewed.24
Replacement of sulfur by selenium shifts these modes to Group frequency charts for phosphorus compounds are
lower frequencies. given in Figure 32 and the Appendices.
DOI: 10.1002/9780470027325.s4104
ν (P=O) ν (S = O), ν (S−O)

ν (P− O) ν (S − F)
ν (P− F) ν (S − Cl)
ν (P− Cl) ν (S − Br)
ν (P− Br) ν (S − S)
ν (P− P) δ (O − S − O)
ν (P =S) ν (P− S) δ (F− S − F)
δ (O−P− O) δ (Cl−S− Cl)
δ (F−P− F) δ (Br−S− Br)
δ (Cl−P− Cl)
1400 1200 1000 800 600 400 200 0
δ (Br−P− Br) ∼
ν/cm−1
1400 1200 1000 800 600 400 200 0
∼
ν/cm−1
Figure 34. Group frequency chart of sulfur compounds.
Figure 32. Group frequency chart of phosphorus compounds. 1000 cm1 . The n(NH) and υ(SNH) of the former are
observed at 3325 and ¾1300 cm1 , respectively. These and
other vibrations involving hydrogen motions can be iden-
9.6 Compounds of sulfur tified by H/D substitution. Below 1000 cm1 , the n(SN),
υ(NSN) and υ(SNS) bands appear in the regions 860–700,
The S4 2 ion takes a nonplanar C2 structure which is similar 470–250 and 330–200 cm1 , respectively, although they
to that of H2 O2 , whereas the S4 2C ion assumes a square- are coupled with each other. The S3 N2 O2 molecule takes
planar ring structure of D4h symmetry. The latter exhibits the zigzag chain structure of C2v symmetry shown in
one IR and three Raman bands. Molecules such as S6 and S8 Figure 31(f). Figure 34 shows a group frequency chart for
take the puckered ring structures shown in Figure 31(c) and sulfur compounds. The group frequency charts for n(SH),
(d). The (SNH)4 molecule forms an eight-membered crown- n(SX) and n(SO) are given in Appendices 1, 2 and 3,
shaped ring of C4v symmetry [Figure 31(e)]. Figure 33 respectively.
shows the Raman spectra of (SNH)4 and (SND)4 below
100 ACKNOWLEDGMENTS
80
Most of the figures in this article were taken from a book
60 by the author.1 These include the IR and Raman spectra in
Figures 23, 25, 26, 27, 30 and 33, which had been reported
40
by other workers and reproduced there with permission. The
20 author again expresses his sincere thanks to these workers.
Intensity (%)
Special thanks go to Professor Michael A. McKinney of

0 Marquette University who kindly drew some structural
(a) 1000 800 600 400 200
diagrams (Figures 14, 18 and 22) for this article.
100
80
ABBREVIATIONS AND ACRONYMS
60
R Raman
40
TPP Tetraphenylporphyrin
20
0 REFERENCES
(b) 1000 800 600 400 200
~
ν/cm −1
1. K. Nakamoto, ‘Infrared and Raman Spectra of Inorganic and
Figure 33. Raman spectra of (a) (SNH)4 and (b) (SND)4 (647.1- Coordination Compounds’, 5th edition, John Wiley, New
nm excitation). York (1997).
DOI: 10.1002/9780470027325.s4104
2. S.D. Ross, ‘Inorganic Infrared and Raman Spectra’, McGraw- 12. N.N. Greenwood, E.J.F. Ross and B.P. Straughan, ‘Index of
Hill, London (1972). Vibrational Spectra of Inorganic and Organometallic Com-
3. L.H. Jones, ‘Inorganic Vibrational Spectroscopy’, Marcel pounds’, Butterworth, London, Vols. 1–3 (1972–77).
Dekker, New York, Vol.1 (1971). 13. ‘Spectroscopic Properties of Inorganic and Organometallic
4. J.R. Ferraro, ‘Low-frequency Vibrations of Inorganic and Compounds’, Chemical Society, London and Royal Society
Coordination Compounds’, Plenum Press, New York (1971). of Chemistry, Cambridge, Vols. 1–32 (1967–1999).
5. G. Herzberg, ‘Molecular Spectra and Molecular Structure. 14. K. Nakamoto, Angew. Chem., Int. Ed. Engl., 11, 666 (1972).
I. Spectra of Diatomic Molecules’, Van Nostrand, Toronto 15. P.S. Braterman, ‘Metal Carbonyl Spectra’, Academic Press,
(1950). London (1975).
6. G. Herzberg, ‘Molecular Spectra and Molecular Structure. II. 16. K. Nakamoto, Coord. Chem. Rev., 100, 363 (1990).
Infrared and Raman Spectra of Polyatomic Molecules’, Van 17. I.S. Butler and A.E. Fenster, J. Organomet. Chem., 66, 161
Nostrand, Toronto (1945). (1974).
7. W.P. Griffith, ‘Advances in the Raman and Infrared Spec- 18. J.L. Burmeister, Coord. Chem. Rev., 3, 225 (1968).
troscopy of Minerals’, in “Spectroscopy of Inorganic-based
Materials”, eds R.J.H. Clark and R.E. Hester, John Wiley, 19. W. Preetz, G. Peters and D. Bublitz, Chem. Rev., 96, 977
New York, 119–186 (1987). (1996).
8. J.A. Gadsden, ‘Infrared Spectra of Minerals and Related 20. W.J. Lehmann and I. Shapiro, Spectrochim. Acta, 17, 396
Inorganic Compounds’, Butterworth, London (1975). (1961).
9. E. Maslowsky, Jr, “Vibrational Spectra of Organometallic 21. A. Meller, Organomet. Chem. Rev., 2, 1 (1967).
Compounds”, John Wiley, New York (1977). 22. H.W. Kroto, J.E. Fischer and P.E. Cox, ‘The Fullerenes’,
10. R.A. Nyquist, R.O. Kagel, C.L. Putzig and M.A. Leugers, Pergamon Press, London (1973).
‘The Handbook of Infrared and Raman Spectra of Inorganic 23. J. Etchepare, Spectrochim. Acta, Part A, 26, 2147–2154
Compounds and Organic Salts’, Academic Press, San Diego, (1970).
CA (1997). 24. L.C. Thomas, ‘The Interpretation of the Infrared Spec-
11. ‘IR Handbook of Inorganic Chemicals’, Bio-Rad Laborato- tra of Organophosphorus Compounds’, Heyden, London
ries, Philadelphia, PA (1997). (1974).
APPENDICES
Appendix 1 Group frequency chart for hydrogen stretching frequencies
FH
FH ClH
ClH
BrH BrH
IH
IH
OH
OH
SH
SH
SeH
SeH
NH
NH
PH
PH
AsH AsH
CH
CH SiH
SiH
GeH
GeH
Terminal BH Bridged BH
BH
AlH
AlH
4000 3500 3000 2500 2000 1500
∼
ν/cm−1
DOI: 10.1002/9780470027325.s4104
Appendix 2 Group frequency chart for halogen stretching frequencies

1500 1000 500 0
F
BX Cl
Br
I
Cl
AlX Br
I
F
Cl
CX Br
I
F
Cl
SiX Br
I
F Cl
GeX Br
I
F
NX Cl
Br
F
Cl
PX Br
I
F Cl
AsX Br
I
Cl
OX Br
I
F
SX Cl
Br
F
SeX Cl
Br
1500 1000 500 0

∼
ν/cm−1
Appendix 3 Group frequency chart for oxygen stretching and bending frequencies
2400 2000 1500 1000 500 0
BO
ν(BO) δ(OBO)
ν(CO) δ(OCO)
CO
ν(SiO) δ(OSiO)
SiO
ν(NO) δ(ONO)
NO
ν(PO) δ(OPO)
PO
ν(SO) δ(OSO)
SO
ν(SeO) δ(OSeO)
SeO
ν(ClO) δ(OClO)
ClO
ν(BrO) δ(OBrO)
BrO
ν(IO) δ(OIO)
IO
2400 2000 1500 1000 500 0
∼
ν/cm−1
DOI: 10.1002/9780470027325.s4104
Appendix 4 Characteristic frequencies of inorganic ions (broken lines indicate Raman-active

vibrations)
2000 1500 1000 500
ν1 ν3 ν2
[NCO]−
ν1 ν3 ν2
[N3]−
ν1 ν3 ν2
[NCS]−
ν1 ν3 ν2
[NO2]−
ν3 ν1 ν2
[UO2]2+
ν3 ν1 ν2
[ClO2]−
ν3 ν1 ν2 ν4
[CO3]2−
ν3 ν1 ν2 ν4
[NO3]−
ν3 ν1 ν2 ν4
[BO3]3−
ν1 ν3 ν2 ν4
[SO3]2−
ν3 ν1 ν2 ν4
[ClO3]−
ν3 ν1 ν2 ν4
[BrO3]−
ν3 ν1 ν2 ν4
[IO3]−
ν3 ν1 ν4 ν2
[SO4]2−
ν3 ν1 ν4 ν2
[ClO4]−
ν3 ν1 ν4 ν2
[PO4]3−
ν3 ν1 ν4
[MnO4]−
ν3 ν1 ν4 ν2
[CrO4]2−
ν3 ν1 ν4 ν2
[SeO4]2−
ν1 ν3 ν4 ν2
[MoO4]2−
ν3 ν1 ν4 ν2
[AsO4]3−
ν1 ν3 ν4 ν2
[WO4]2−
2000 1500 1000 500
∼
ν/cm−1
DOI: 10.1002/9780470027325.s4104
Appendix 5 Characteristic frequencies of metal complexes containing simple ligands (frequency ranges
include bidentate and bridged complexes for the ligands marked with an asterisk)
2000 1500 1000 500
ν(CN) ν(MC)δ(CMC)
M CN
ν(CS) δ(NCS)
ν(CN)
M NCS•
ν(CO) ν(MC)
M CO•
δd (NH3) δs (NH3) ρr (NH3) ν(MN)δ(NMN)
M NH3
δ(NH2) ρw(NH2), ρt (NH2) ρr(NH2) ν(MN)
M NH2 (for Hg2+ complex)
ν(NO2) δ(NO2) ρw(NO2) ν(MN)
M NO2•
ν(ONO) ν(ONO) δ(ONO)
M ONO
ν(CO) π δ(OCO) ν(MO)
ν(CO) ν(CO)
M OCO2•
ν(NO) ν(NO) ν(NO) π
M ONO2
δd (OSO) δd (OSO)
ν(SO)
M OSO3•
δ(HOH) ρw(OH2), ρr(OH2), ρt(OH2)
M OH2
2000 1500 1000 500

∼
ν/cm−1
DOI: 10.1002/9780470027325.s4104

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Infrared and Raman Spectra of Inorganic and

1 INTRODUCTION spectral charts of selected compounds are shown in each

Table 1. Vibrational frequencies of diatomic molecules (cm1 ). 2.1 Monoatomic ligands

number of coordination compounds. Upon coordination, the

Figure 3. Normal modes of vibration of linear and bent XY2

Molecule na1 n2 n3 a Molecules Structure n1 n2 n3

N3 1344 645 2041 MgF2 Linear 550 249 842

Table 5. Vibrational frequencies of pseudohalogeno complexes

As expected, these compounds exhibit six vibrations in both

KNO3 aq atom. Although the symmetry of the M–SO3 moiety is

Table 9. Correlation table for Td , C3v , C2v and C1 .

Td A1 (R) E(R) F2 (IR, R) F2 (IR, R)

n5 (B2u ) is inactive under D4h symmetry. n1 (A1g ) is polarized and

Figure 14. Structures of XY5 molecules.

vibrations as shown in Figure 15. Among them, five

Figure 15. Normal modes of vibration of trigonal-bipyramidal XY5 molecules.

ν1 (B1) ν5 (B1) ν6 (B2)

ν4 (F1u) ν5 (F2g) ν6 (F2u)

Table 11. Vibrational frequencies of octahedral XY6 molecules 8 X2 Yn MOLECULES

Molecule n1 n2 n3 n4 n5 n6 Figure 18 shows the three possible structures of the X2 Y4

ν7(B1g) ν8(B1u) ν9(B1u)

ν10(B1u) ν11(B2g) ν12(B2g)

ν16(B3u) ν17(B3u) ν18(B3g)

Figure 20. Normal modes of vibration of bridged X2 Y6 molecules.

(c) D3h (d) D2h

Figure 22. Structures of X2 Yn molecules.

Si2 H6 , Ge2 H6 , N2 H6 2C and S2 O6 2 . These molecules show

X2 Y9 molecules such as shown in Figure 22(c) belong H

examples include W2 Cl9 3 , Ir2 Cl9 3 and Pt2 Br9 .

structures shown in Figure 22(d) and (e). The Re2 Cl10 2

9 MOLECULES OF OTHER TYPES (f)

9.1 Compounds of boron The carbon oxide anions such as Cn On 2 (n D 3, 4 and 5)

and its derivatives have been reviewed extensively.22 Group

2100 800 600 400 200 0

(Si4O11)n6− 100 300 500 700

ν (P=O) ν (S = O), ν (S−O)

Special thanks go to Professor Michael A. McKinney of

Appendix 1 Group frequency chart for hydrogen stretching frequencies

Appendix 2 Group frequency chart for halogen stretching frequencies

1500 1000 500 0

Appendix 4 Characteristic frequencies of inorganic ions (broken lines indicate Raman-active

2000 1500 1000 500

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