AsianJournalofSpectroscopy,11,3&4,2007,169172

SpectroscopicandIntraMolecularStudiesofPharmaceuticallyImportantBenzoicAcidand
itsAminoSubstitutents
Y.P.Singha,R.A.SinghbandRatneshDasc

a
DepartmentofPhysics,Govt.WomensPolytechnicCollege,Sagar(MP),INDIA
470001.Email:Y_P_S_2k@Yahoo.com
b
DepartmentofPhysics,Dr.H.S.GourUniversity,Sagar(MP),INDIA,470001
c
DepartmentofChemistry,Dr.H.S.GourUniversity,Sagar(MP),INDIA,470001,
Email:ratnesh_das@breakthru.com

ABSTRACT

ThevibrationalabsorptionspectraofBenzoicAcidsMonomermoleculesanditsaminosubstitutents
have been studied using GF matrix and AM1 method. Assuming Cs point symmetry, vibrational
assignments for the observed frequencies have been proposed. The spectra exhibit distinct features
originating from low frequency vibrational modes caused by intramolecular motion. Normal modes
have been calculated and an assignment of the observed spectra has been proposed. Experimental
frequenciesarecomparedwiththoseobtainedbyG.F.MatrixandAM1method.
Keywords:BenzoicAcid,o,m,pAminoBenzoicAcid,FTIRSpectra,AM1,G.F.Matrix

INTRODUCTION
Carboxylic acids (RCOOH) are a common
and important functional group and provide the
point of success to the carboxylic acids derivatives
(acetylchlorides,esters,amidesetc.)andtherefore,
it has been extensively studied by spectroscopic
methods. Spectroscopist's interest has been
concerned with structure and vibrational
frequencies.

The aim of the present study is a IR

spectroscopic analysis of Benzoic Acid (BA), which
havefoundconsiderableattentionintheliterature1
8
.Wecomparedexperimentalresultswithcalculated
frequencies of BA using force matrix method and
AM1,PM3andG.F.Matrixmethod.Thesemethods
wereabletoaccountbreadthofspectrumaswellas
description of vibrational modes to encourage the
application of a similar procedure to a larger and
morecomplexgroup.

STRUCTURE AND GEOMETRY OF BENZOIC

ACID
Benzenederivativescontainingacarboxylic
or amino group possess C 1 symmetry. From aniline
and toluene, the geometry parameters were
transferred. Cartesian coordinates of the molecules
under investigation were calculated on the basis of
geometricalparametersasshowninTable1

EXPERIMENTAL
Benzoic acid was purchased from Sigma
ChemicalCo(USA).Benzoicacidformsawhitetooff
whitecrystallinepowderwithmeltingpointof159c.

I.R. Spectrum has been recorded in the

liquid phase in the range 4004000cm1 on Perkin
Elmer spectrometer Model 397. Preparation of KBr
Pallets: A small amount of finally grounded solid
sample was intimately mixed with about 100 times
or more than its weight of Potassium bromide
powder. The finally grounded mixture was than

pressed under very high pressure in a press (about

10/cm2) to form a small pallet (about 12 mm thick
and1cmindiameter).
The accuracy of the measurements was
estimatedtobewithin3cm1andtheresolutionwas
betterthan2cm1throughtheentirerangeforboth
thespectra.
COMPUTATIONALANDTHEORETICALDETAILS
Innoncomplexmolecules,theGFMatrix9is
givenby:
Gtt=3Ni=1(BtiBti)1/miwheret,t=
1,2,3,,3N6
Inwhichmiisthemassoftheatomtowhich
the subscript I refers and Bti , Bti are constants
determinedbygeometryofmolecule.
Internal coordinate St are related with
Cartesiandisplacementcoordinateias:
St=3Ni=1Btiiwheret=1,2,3..,3N6
OnsolvingG.F.matrixforanyatomisobtained
as:
Gtt=3N=1St.St
Where dot represents the scalar product of two
vectorsand=1/m,thereciprocalofthemassof
atom

The AM1 semi empirical approaches was

performed as implemented in MOPAC program 10
and the PRECISE keywords were used. We have
transformed the harmonic force fields, determined
initially in the Cartesian coordinates, were
transformed to the force fields in the internal local
coordinates.Theforcefieldsobtainedwereusedto
calculate the potential energy distribution (PED)11.
Contributionsgreaterthan10%aregiven.
RESULTSandDISCUSSIONS

2. Due to anharmonicity, the harmonic vibrational

frequencieswerefoundtobeloweredby1to3%in
GFMatrixmethodexceptAM1method.
Benzoic acid contains 15 atoms so that it has 39
normal modes. The calculated normal modes are
distributed among 27 a and 12 a species of Cs
symmetry group. The table 2 also shows that PED
contributions for 39 normal modes. These
assignments are partly based on the calculated
frequencies. As the table 2 is selfexplanatory, we
shalldiscusshereonlysomeimportantpoints.
OHStretch:ExperimentalOHstretchbandfrequency
1

forBAis3507cm whichwasshiftedby97cm
as reported by Antony et al13 and which is also
higher than those observed by others7,16.
TheoreticallycalculatedfrequenciesbyG.F.andAM1
1

are3579.2cm and3627.6cm ,respectively.

presented
in
table2,
CH3sstretch: As
experimentalCH3sstretchfrequencyforBAis2987
cm

. Antony et al13 observed this frequency for

benzoic acid at 2943 cm

. Calculated frequencies
1

thisbandsis1823cm forBA,whichishigherthan
thecalculatedfrequencies.Antonyetal13observed
1

this frequency for benzoic acid at 1752 cm .

TheoreticallycalculatedfrequenciesbyG.F.andAM1
1

are1716.5cm and1726.2cm respectively.

OHBend:Ourobservationsforthisbendis1328BA.
Antony et al13 observed this frequency for benzoic
1

acid at 1381 cm . Trout et al observed 1328

frequency for COO symmetric stretch, so our
assignment was totally reversed by this one.
Computationally calculated frequencies by G.F. and
1

Wehademployedaverylargebasissetfor
thecomputationalofthefrequencies.Firstinfrared
frequencies were calculated for the BA ( Cs
Symmetry) at the AM1 and G F Matrix level of
theory.Wecangetinformationfromcomputational
vibrational spectra only when we compare it with
experimentalspectrum.Ourresultsaregivenintable

byG.F.andAM1are3010.9cm and3172.0cm
respectively.
C=O stretch: experimental observed frequencies for

AM1 are 1311.5 cm and 1441.9 cm

respectively.
COstretch:ExperimentalfrequencyforBAis1228
1

cm respectively.Antonyetal13didnotobserved
this frequency for benzoic acid. Theoretically
calculated frequencies by G.F. and AM1 are 1243.8
cm

and1435.7cm

respectively.

OCO Deformation: We observed this bend

1

frequency at 668cm for BArespectively which is

comparative to others14,16 . Theoretically calculated
frequencies by G.F. and AM1 are 657.7 cm

and

646.3cm respectively.
Torsion: Experimental observed frequency for this
bendforBAis591cm

.Antonyetal15observed
1

this frequency for benzoic acid at 444 cm .

Computationally calculated frequencies by G.F. and
AM1are593.4cm

and571.9cm

respectively.

NH 2 GroupModes

The number of internal vibrations for a group is

given by 3m3, where m is the number of atoms in
the group. Thus NH 2 has 6 modes of vibrations.
Thesemodesareas:twostretchingvibrations(one
symmetricandoneasymmetric)bothbelongingtoa
species, two angle deformations (scissoring and
rocking),oneoutofplanewaggingofNH 2 andone

modeat1630cm and1055cm respectively.

A.K.Tiwari19 got inplane bending mode at 1621
cm

androckingmodeat952cm

.D.N.Singh20
1

observed wagging vibration at 592 cm and he

didntgot
torsion mode. A.K.Tiwari19 observed these
1

vibrations at 626 cm and 274 cm

respectively. In present study we get frequencies
forthemasshownintable3.
COOHGroupModes

Intheparentmoleculebenzeneifoneofthe
hydrogenatomisreplacedbyaCOOHgroup,nine
more normal modes would appear. They are as:
OHStretching,COStretching,C=OStretching,in
planerocking, inplane bending of CO, inplane
bending of C=O, inplanebending of OH, outof
plane wagging, and outofplane torsion.. J.
Antony et al13 studied vibrational spectra of
benzoicacidandgotC=OStretchingat1745cm

torsionvibrationofNH 2 .
There are three major differences between
the CH and NH stretching frequencies. First, the
forceconstantforNHstretchingisstronger,thereis
a larger dipole moment associated with the NH
bond,andfinally,theNHbondisusuallyinvolvedin
hydrogenbonding.Thestrongerforceconstantleads
to a higher frequency for absorption. The NH
stretchingfrequencyisusuallyobservedfrom3500
3200 cm1. The larger dipole moment leads to a
stronger absorption and the presence of hydrogen
bondinghasadefiniteinfluenceonthebandshape
andfrequencyposition.

He observed inplane bending and rocking

, CO stretching at 1050 cm
bending at 594 cm
1804 cm

mode at 554 cm

, C=O inplane bending at

1

, rocking

, torsion mode at 594 cm

and wagging mode at 441 cm

628 cm

mode at 628 cm

. Florio et aI
1

, CO

,COinplanebendingat

, OH stretch at 3785 cm
1

1
15

observed C=O Stretching at 1752 cm

stretchingat1347cm

, CO inplane

, OH stretch at 3785 cm
1

, rocking

, and wagging mode at 160

cm . In present study we get frequencies as

shownintable4.

The NH 2 stretching modes appear in the

1

region 3500 3100 cm and the asymmetric

component has slightly higher magnitude than the
symmetric component. D.N.Singh 19 observed
asymmetric modes at 3465 cm
mode at 3360 cm

and symmetric

. However, A.K.Tiwari

observed them at 3449 cm

respectively.

and 3367 cm

20

CONCLUSIONS
Theoretical
semiempirical
quantum
mechanical AM1 and GF matrix calculations of the
geometryandvibrationalfrequenciesoftheBenzoic
acid and its amino substitutents are presented in
thispaperandcomparedwithinfraredspectra.The
calculated geometries and frequencies agree well
with the experimental ones, but there are some

differences between frequencies mainly due to

intermolecular interactions, anharmonicity and
computationalbasisset.

8.

V.K.Rastogi,M.P.RajpootandS.N.Sharma;
Ind.J.Phy;58B,311(1984).
9.
E.B.Wilson ,J C Decius and P C Cross,
Molecular Vibrations, Mc GrawHill Book
Co.,(1955)
10. Win MOPAC Molecular Orbital Program,
FujitsuLimited,(1997)
11. G. Keresztury and G. Jalsovsky, J. Mol.
Structure,304,(1971)
12. J.M. Bakker, G. Meyer, M. Kabelac and
M.S. de Vries, Phy Chem Chem Phys, 6,
2810,(2004).
13. J.Antony,G.V.Helden,G.MeijerandB.
Achmidt,J.ofChemicalPhysics,122,
(2005).
14. G.M. Florio, E.L. Sibert and T.S. Zwier;
FaradayDiscuss,118,315,(2001).
15. G.M.Florio, T.S.Zweir and E.L.Sibert, J.
Chem.Phys;118,1735,(2003).
16. K.C.Light and T. Carrington; Adv. Chem.
Phys;114,263,(2000).
17. R.Glaser,J.Org.Chem;66,771,(2001).
18. M.J.Wojick,K.SzczepenekandM.Boczar,
Int.J.Mol.Sci;4,422,(2003).
19. D.N.Singh,Ph.D.Thesis,BanarasHindu
University,Banaras,India,(1980).
20. A.K.Tiwari,Ph.D.Thesis,Dr.H.S.Gaur
University,Sagar,India(2004).

ACKNOWLEDGEMENTS

The authors are grateful to Director,

DirectorateofTechnicalEducationMadhyaPradesh,
Bhopal and Head, Department of Physics, Dr.
H.S.Gour University, Sagar (MP), India and Central
Drug Research Institute, Lucknow, India for IR
spectra, Hypercube Inc for providing Hyperchem
Package7formolecularmodeling.
REFRENCES

1.
WWW.Chemicalland21.com,Nov.(2005).
2.
Foyes principle of medicinal Chemistry,
5th edition, Lippincott Williams and
Wilkins,NewYork,(2002)
3.
J.H.S.Green, W.kynaston and L.S.Lindsey,
SpectrochimActaA;17,486,(1961).
4.
J.H.S.Green, D.J.Harrison, Spectrochim
Acta;26A,1925,(1970).
5.
J.H.S.Green,SpectrochimActa;33A,575,
(1977).
6.
Y.KimandK.Machida,SpectrochimActa,
42A,8,881,(1986)
7.
A.Theoret, Spectrochim Acta A, 27, 11,
(1971).

Table1AssumedBondLengthandBondangleinBenzoicandAminoBenzoicAcids.

BondAngle(Degree)

Bond

Bondlength(A )
ByDFT
Experimen
Method18
tal

ByMOPAC
Calculation

BondAngle

ByDFTMethod
18

Experiment
al

ByMOPAC
Calculation

O 2 H 6 1.00

0.98

1.06

C 7 O 2 H 6

110.27

106.00

C 7 O 1 1.230

1.26

1.19

O1C 7 O 2

123.26

122.2

122.81

C 7 O 2 1.323

1.27

1.21

O 2 C 7 C1

114.50

118.0

118.10

C 7 C 1 1.486

1.48

1.10

C1C 7 O1

122.24

122.0

121.42

C 1 C 2 1.400

1.39

1.40

C 7 C1C 2

121.40

118.0

121.53

C 2 C 3

1.391

1.38

1.39

C 6 C1C 7

119.90

119.9

119.96

C 3 C 4 1.395

1.37

1.40

C 6 C1C 7

118.70

118.8

119.96

C 4 C 5 1.395

1.38

1.39

C1C 2 C 3

119.86

120.1

120.00

C 5 C 6 1.390

1.40

1.40

C2 C3C 4

120.02

119.9

119.98

C 6 C 1

1.400

1.39

1.39

C3C 4 C5

120.15

120.3

120.02

C 2 H 1

1.082

0.79

1.10

119.98

119.7

119.98

C 3 H 2

1.084

0.96

1.10

120.02

119.8

119.99

1.084

0.91

1.10

119.48

119

120.00

1.084

0.96

1.10

120.66

121

120.00

119.85

120

119.99

120.07

119

120.00

C 4 H 3
C 5 H 4
C 6 H 5
CN
NH

1.083

0.79

1.10

1.103

1.10

1.11

1.154

1.12

1.13

C 4 C5C6
C5C6C7
C1C 2 H1
H1C

C3

C 2 C 3 H 2
H2 C3C 4

119.91

118

119.50

C3C 4 H3

119.94

118

119.63

H3C 4 C5

120.09

119

120.01

C3C5H 4

119.93

120

119.96

121.12

121

121.23

118.86

118

118.63

119.98

119

119.99

148.95

150

147.95

103

95.6

H 4 C 5 C 6
C5C6H5
H 5 C 6 C1
CNH
HNH

Table2ExperimentalandCalculatedFrequenciesandPotentialDistributioninC 6 H 5 COOH

Assignment

ExperimentalFrequencies

(incm

GFMatrix
Frequencies
(incm

Frequencies(incm

PEDandMode

AM1

1
2

3507
3217

3579.2
3210.6

OHstr
CHstr

3627.3
3188.2

3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27

3130
3100
3087
2987
1823
1696
1585
1499
1456
1328
1228
1292
1280
1186
1179
1129
1074
1029
1000
808
668
600
548
420
317

3118.8
3111.5
3072.4
3010.9
1716.5
1648.1
1561.4
1518.7
1443.8
1311.5
1243.8
1312.3
1277.3
1171.4
1192.5
1134.6
1063.1
1011.1
1013.9
801.3
652.7
587.3
525.6
412.1
310.5

CHstr
CHstr
CHstr
CHstr
C=Ostr
CCringdeformation
CCstr
COHbnding
CCHbending
OHbending
COstr
CChbending
OHbend
CHib
COHbending
Ringid+COstr
RingCCHbending
Ringid+CCstr
CHod
CHod
OCOdeform
RingCCCbending
COHbending
CObending
C=Obending

3190.2
3102.2
3175.7
3172.0
1786.2
1921
1765.5
1638.6
1572.6
1441.9
1435.7
1378.9
1359.0
1314.7
1229.4
1198.3
1177.5
1168.0
1089.4
796.5
646.3
536.8
509.9
409.6
286.0

Assignment

ExperimentalFrequencies

(incm

GFMatrix
Frequencies
(incm

PEDandMode

Frequencies
(incm
AM1

28

980

971.6

CCwagging

1013.2

29

970

967.3

CCwagging

995.6

30

929.5

rocking

971.8

31

935

937.6

CCwagging

894.5

32

850

844.1

RingCCH

886.3

33

812

801.9

RingCCHbend

825.9

34

709

719.8

C=Oo.p.bend

723.6

35

664

657.1

RingCCHbend

610.2

36

613

609.3

torsion

611.9

37

591

593.4

torsion

571.92

38

190

199.4

wagging

150.6

39

57.6

twisting

44.0

Table3InternalVibrationsofNH 2 group

ModeofVibration

mAminoBenzoicAcid

oAminoBenzoicAcid
1

NHAsymmetric
Stretching
CNHSymmetric
Stretching
NH 2 InPlaneBending
NH 2 Rocking

Wagging
Torsion

pAminoBenzoicAcid(in

(incm )
3622(E),3601.6(GF)
3530.9(M)
3325(E),3342.9(GF)
3530.9(M)
1156(E),1162.3(GF)
1219.5(M)
536(E),527.1(GF)
558.1(M)

(incm )
3472(E),3490.1(GF)
3492.4(M)
3225(E),3207.6(GF)
3464.6(M)
1110(E),1123.5(GF)
1217.7(M)
541(E),531.3(GF)
537.2(M)

cm )
3509(E),3521.3(GF)
3512.2(M)
3462(E),3487.2(GF)
3490.0(M)
1132(E),1140.1(GF)
1143.9(M)
523(E),529.3(GF)
539.3(M)

459(E),441.8(GF)
440.5(M)
279(E),284.7(GF)
281.7(M)

432(E),441.8(GF)
497.4(M)
281(E),280.2(GF)
251.2(M)

412(E),408.3(GF)
380.2(M)
291(E),300.1(GF)
326.0(M)

E:Experimentalfrequencies
GF:TheoreticalfrequenciescalculatedbyGFMatrixmethod
M:TheoreticalfrequenciescalculatedbyMOPACmethod

Table4InternalVibrationsofCOOHgroup

ModeofVibration

OHStretching

COStretching

C=OStretching

BendingCO

BendingC=O

BendingOH

Rocking
a
Wagging

Torsion

BenzoicAcid(cm
3389(E)
3379.2(GF)
3427.3(M)
1823(E)
1818.1(GF)
1821.0(M)
1696(E)
1716.5(GF)
2076.2(M)
420(E)
412.1(GF)
409.6(M)
317(E)
310.5(GF)
200.0(M)
1328(E)
1343.8(GF)
1435.7(M)
664(E)
657.1(GF)
610.2(M)
288(E)
293.4(GF)
271.9(M)
709(E)
719.8(GF)
723.6(M)

oAminoBenzoicAcid(cm
3338(E)
3315.6(GF)
3427.8(M)
1856(E)
1846.3(GF)
1959.2(M)
1590(E)
1581.5(GF)
1549.9(M)
440(E)
421.5(GF)
414.5(M)
351(E)
362.4(GF)
259.5(M)
1360(E)
1358.9(GF)
1355.5(M)
601(E)
619.3(GF)
637.1(M)
293(E)
284.7(GF)
281.7(M)
758(E)
751.8(GF)
753.5(M)

E:Experimentalfrequencies
GF:TheoreticalfrequenciescalculatedbyGFMatrixmethod
M:TheoreticalfrequenciescalculatedbyMOPACmethod

mAminoBenzoicAcid(cm
3420(E)
3431.1(GF)
3427.5(M)
1845(E)
1863.2(GF)
2075.5(M)
1603(E)
1621.1(GF)
1551.2(M)
450(E)
431.3(GF)
437.2(M)
335(E)
338.2(GF)
334.3(M)
1310(E)
1321.6(GF)
1435.5(M)
650(E)
579.4(GF)
579.5(M)
293(E)
285.2(GF)
266.7(M)
789(E)
751.7(GF)
744.1(M)

pAminoBenzoicAcid(cm
3400(E)
3429.1(GF)
3431.7(M)
1793(E)
1728.2(GF)
1737.3(M)
1657(E)
1631.1(GF)
1600.7(M)
441(E)
411.2(GF)
416.4(M)
366(E)
371.1(GF)
377.5(M)
1337(E)
1332.3(GF)
1331.7(M)
692(E)
706.2(GF)
754.3(M)
291(E)
300.1(GF)
326.0(M)
768(E)
786.1(GF)
875.3(M)