Spectrochimica Acta Part A 61 (2005) 29662973

Molecular structure of 3-aminobenzoic acid complexes with alkali metals

R. Swisocka,
E. Regulska, M. Samsonowicz, T. Hrynaszkiewicz, W. Lewandowski
Department of Chemistry, Biaystok Technical University, Zamenhofa 29, 15-435 Biaystok, Poland
Received 5 August 2004; accepted 8 November 2004

Abstract
The vibration (FT-IR, FT-Raman), electronic (UVVis) and NMR (1 H and 13 C) spectra for 3-aminobenzoic acid and its alkali metal salts
were recorded. The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 3-aminobenzoic acid
was studied. The assignment of the vibration spectra was done. Characteristic shifts of band wavenumbers and changes in band intensities
along the metal series were observed. Good correlation between the wavenumbers of the vibrational bands in the IR and Raman spectra for
3-aminobenzoates and ionic potential, electronegativity, atomic mass and affinity of metal cations were found. The chemical shifts of protons
(1 H NMR) and carbons (13 C NMR) in the series of studied alkali metals were also observed. Optimized geometrical structures of studied
compounds were calculated by ab initio and density functional methods.
2004 Elsevier B.V. All rights reserved.
Keywords: 3-Aminobenzoates; FT-IR; FT-Raman; NMR; Geometrical structure

1. Introduction
The benzene derivatives are compounds of great interest
because of their chemical and biological properties. Benzoic
acid, its derivatives and their complexes are commonly used
food preservatives as well as antiseptic agents applied in various industrial branches: pharmaceutics, textile and cosmetics
[1,2].
Benzoic, salicylic and nicotinic acids are regarded as
model systems representing a wide group of aromatic ligands, which are incorporated into enzymes and other biologically important molecules. The effect of some metals on the
electronic system of benzoic, salicylic and nicotinic acids has
been investigated by the methods of molecular spectroscopy
[3,4]. In our earlier paper [5] the influence of different cations
on the electronic structure of the aromatic ring as well as the
carboxylic anion of the halogens substituted benzoic acids
was investigated. Systematic changes in both infrared and
Raman spectra were observed. The relationship between the
wavenumbers of spectral bands and the ionic potential and
atomic mass of halogens and cations was noticed.

Corresponding author. Tel.: +48 85 743 5107; fax: +48 85 743 5417.
E-mail address: w-lewando@wp.pl (W. Lewandowski).

1386-1425/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2004.11.010

In this paper the influence of lithium, sodium, potassium,

rubidium and cesium on the electronic system of the 3aminobenzoic acid was studied. There are only few papers in
the literature about spectroscopic study of 3-aminobenzoates:
of sodium [6], yttrium and lanthanides [710], silver [11]
and scandium (III) [12]. We have not found any references
concerning spectroscopic study of the series of alkali metals
from lithium to cesium 3-aminobenzoates so the vibration
(FT-IR, FT-Raman), electronic (UVVis) and NMR (1 H and
13 C) spectra were recorded for 3-aminobenzoic acid and its
alkali metal salts. Characteristic shifts of band wavenumbers
and changes in band intensities along the metal series were
observed. Optimized geometrical structures of studied compounds were calculated. The relationship between certain parameters of the metal (i.e. ionic potential, electronegativity
and atomic mass) and electronic charge distribution in the
whole molecule of the studied compounds was discussed.

2. Experimental
Lithium, sodium, potassium, rubidium and cesium 3aminobenzoates were prepared by dissolving the powder of
3-aminobenzoic acid in the water solution of the appropriate
metal hydroxide in a stoichiometric ratio. All reagents were


R. Swisocka
et al. / Spectrochimica Acta Part A 61 (2005) 29662973

Sigma analytical chemicals. The mixed solution was slowly

condensed at 70 C to about 30% of starting volume. The solution was then left at the room temperature for 4872 h until
the sample crystallized in the solid-state. Then, the remaining solvent was removed by drying under reduced pressure
at 110 C. Obtained complexes were anhydrous in the IR
spectra of solid state samples the lack of bands characteristic
for crystallizing water was observed. The elemental analysis
was done and obtained results confirmed the stoichiometry
(1:1). The precipitates were white for lithium, sodium and
potassium but the ones of rubidium and cesium were light
brown. They were well water-soluble.
The IR spectra were recorded with the EQUINOX
55, BRUKER FT-IR spectrometer within the range
4000400 cm1 . Samples in the solid state were measured
in KBr matrix. Pellets were obtained with a hydraulic press
under 739 MPa pressure. Raman spectra of solid samples in
capillary tubes were recorded in the range of 4000400 cm1
with a FT-Raman accessory of the Perkin Elmer System 2000.
The resolution of spectrometer was 1 cm1 . The electronic
spectra in the UV-visible range were recorded from aqueous
solutions with DR 4000/U HACH UVVis spectrometer using quartz cells of 1 cm lengths. The NMR spectra of D2 O
saturated solution were recorded with the NMR AC 200 F,
Bruker unit at room temperature. TMS was used as an internal
reference.
To calculate optimized geometrical structures, a few
quantum-mechanical methods were used: (i) ab initio
HartreeFock (HF), (ii) density functional (DFT) hybrid method B3PW91, which uses the Beckes threeparameter functional with nonlocal correlation provided
by PerdewWang 91 expression, (iii) the DFT hybrid
method B3LYP with nonlocal correlation provided by
LeeYoungParr expression. The 6-311++G** basis set was
used as the largest standard basis set available for all atoms.
All theoretical calculations were performed using the Gaussian 98W (v.5.4) package of programs [13] running on a PC
computer.

3. Results and discussion

The chemical composition of the compounds obtained
in this work was estimated by elemental analysis. The obtained results showed that the metal:ligand ratio was 1:1.
The exemplary obtained results of elemental analysis for
sodium 3-aminobenzoate are as follows: %C = 52.94 (calculated 52.83); %H = 3.87 (calculated 3.87); %N = 8.83 (calculated 8.80).
3.1. FT-IR and FT-Raman spectra
The vibration spectra of the synthesized 3-aminobenzoates were recorded and assigned. The assignment was
done on the basis of literature data [14,15] and our previous
semiempirical calculations [16]. The observed IR and Raman

2967

bands together with their relative intensities and band assignments of the studied metal salts with 3-aminobenzoic acid are
presented in Table 1. The bands are numbered along with the
notation used by Versanyi [14] and Rzaczynska [17].
The bands occurring in the spectra were divided into three
groups: (i) connected with carboxylic anion vibrations, (ii)
amino group vibrations, and (iii) those connected with aromating ring vibrations. In the first group characteristic wide
and intense bands responsible for the asymmetric stretching of the carboxylic anion [asym (COO ): 15631558 cm1
IR spectra, 15691556 cm1 Raman spectra] and symmetric one [sym (COO ): 14191388 cm1 IR spectra,
14261387 cm1 Raman spectra] were observed (Table 1).
The bands assigned to the symmetric in-plane deformations
of the carboxylic anion (sym : 622619 cm1 IR spectra)
and asymmetric one (asym : 886878 cm1 IR spectra) as
well as symmetric (sym : 774768 cm1 IR, 771769 cm1
Raman spectra) and asymmetric (asym : 549533 cm1
IR, 542535 cm1 Raman spectra) out-of-plane deformations of the carboxylic anion were presented as well in
Table 1.
The two strong IR bands observed in the 34293423
and 33493325 cm1 ranges were assigned to the stretching modes of NH2 group (asym and sym , respectively)
and in the 16281624 cm1 to the symmetric in-plane deformations (sym ) of the NH2 . The asymmetric in-plane
deformations of amine group (asym : 11301122 cm1 IR
spectra and 11291119 cm1 Raman spectra) were also observed. The medium band of (NH2 ) appeared in the range:
12691259 cm1 IR spectra and 12741260 cm1 and
Raman spectra (Table 1).
The bands connected to the aromatic ring vibrations
[(CC), (CH), (CN), (CH), (CH), (CC)] were observed
in the whole spectral range (4000400 cm1 ) and they are
also presented in Table 1.
The characteristic bands occurring in the IR spectra of
3-aminobenzoates, which do not exist in the spectra of free
acid, as well as the lack of some other bands, which are characteristic for free acid could be observed. According to the
literature data [1416], the appearance of the bands connected
with symmetric or asymmetric vibrations of carboxylic group
as well as the disappearance of the C O band (1629 cm1 )
proves that exchanged of hydrogen by the metal ion takes
place. The very broad band in the 33002000 cm1 which
are assigned to the stretching modes of OH group (OH ) arising from rather strong hydrogen bonding disappeared in the
IR spectra of alkali metal salts too. After the introduction
alkali metal atom instead of hydrogen atom decrease of halfwidth in majority of the bands was observed. In our opinion
it resulted from the reduction of hydrogen bonding action in
the molecule.
The changes of intensities and wavenumbers of the bands
of aromatic system, carboxylic anion and amine group in the
case of salts were discussed comparing to the free ligand. The
bands which indicate aromatic properties of benzene derivatives mainly occur within the range of 16401370 cm1


R. Swisocka
et al. / Spectrochimica Acta Part A 61 (2005) 29662973

2968

Table 1
Wavenumbers (cm1 ), intensities and assignments of selected bands occurring in the IR and Raman spectra of Li, Na, K, Rb and Cs 3-aminobenzoates in
comparison to 3-aminobenzoic acid
Hydrogen
IR

1563 vs
1563 s
1528 vs
1484 sh
1450 s
1388 vs
1354 sh

Lithium
R

1582 vw

1483 vw
1449 vw
1388 s

1220 m

1225 m

1139 w

1095 w
1072 m

1093 vw
1171 m

1003 w
918 m
894 m
846 w
789 s
758 vs

1005 vs
912 vw

798 s

Sodium

Potassium

Rubidium

Cesium

IR

IR

IR

IR

IR

3429 s
3340 s
3216 m

1628 sh
1614 s
1595 s
1563 vs
1490 m
1452 s
1419 vs
1315 s
1269 m
1215 w
1196 m
1165 w
1122 w
1104 vw
1071 w
1043 w
1021 w
996 m
910 m
886 w
802 s
769 vs
734 w
690 m
675 w
622 w
561 m
549 vw
523 w
430 w
910 m

3079 w
3067 w

3427 m
3335 m
3214 m

1628 sh
1618 sh
1594 s
1561 vs
1488 vw
1454 s
1413 vs
1316 m
1266 m
1222 vw
1196 w
1165 w
1130 w

1072 w
1041 w
1020 vw
997 w
927 w
895 w
881 w
806 m
769 s
734 w
683 m
677 m
621 w
554 w
535 w
514 w
432 w

3050 w

3426 m
3326 m
3221 m

1628 s

1594 s
1558 vs
1487 m
1449 m
1398 vs
1318 m
1262 m
1222 w
1199 w
1168 vw
1129 w
1110 w
1071 w
1040 w
1020 vw
997 w
923 w
893 vw
879 w
800 m
768 s
732 m
684 m
677 m
620 w
567 w
533 w
502 w
421 w

3070 w
3061 w

1605 m
1594 m
1556 m

1449 m
1406 s
1303 m
1263 m

1164 m
1129 m

1073 m

998 vs

800 s
771 m

678 s

536 s

3423 m
3325 m
3221 m

1626 s

1593 s
1558 vs
1484 m
1448 m
1398 vs
1315 m
1261 m
1224 w
1201 w
1167 w
1129 w
1109 w
1069 w
1040 w
1020 w
996 w
923 w

878 m
799 m
768 s
732 m
684 m
675 m
619 w
568 w
533 w
501 w
425 vw

3064 w
3055 vw

1604 m

1567 m

1402 m
1302 m
1261 m

1163 m
1126 w

1068 m

997 s

798 s

676 m

535 s

3425 s
3349 s
3212 m

1624 s

1591 s
1559 vs
1482 m
1448 m
1388 s
1310 s
1259 s
1224 vw
1200 w

1129 m
1103 m
1060 m
1040 w
1020 w
993 m
922 w
893 w
879 sh
797 m
774 s
733 m
691 m
672 m
619 m
569 w
536 w
508 w
425 vw

3065 vw

1605 w
1589 w
1557 w

1610 s
1591 s
1569 m

1451 s
1426 s
1310 s
1270 s

1167 s
1122 s

1071 s

996 vs

803 s
770 s

674 s

1607 w
1592 w
1565 w

1462 w
1424 w
1312 vw
1274 vw

1165 vw
1119 vw

1067 vw

997 vs

807 w
769 vw

675 w

542 vw

1447 w
1387 m
1311 w
1267 w

1069 w

998 m

799 m

672 m

536 m

Assignment
[14,17]
asym (NH2 )
sym (NH2 )
2
sym (NH2 )
8a
8b
asym (COO )
19b
19a
sym (COO )
(C N)
(NH2 )
13
9b
asym (NH2 )
18b
18a

12
7b
17b
asym (COO )
11
sym (COO )

4
sym (COO )
asym (COO )
6a
15

: stretching; : in plane; : out of plane deformations; s: strong; vs: very strong; m: medium; sh: shoulder; w: weak; vw: very weak.

[8a, 8b, 19a, 19b bands of stretching vibration (C C)],

11801040 cm1 [9b, 18a, 18b bands of in plane deformation
(C H)] and of 9001000 cm1 [band number 12 of out of
plane deformation (C H)]. The wavenumbers of aromatic
bands numbered as 8a, 8b, 9b, 18b increase in comparison to
free acid (also19b except of Rb and Cs), but in the case of
bands numbered as 18a (in Raman spectra) and 12 (IR and
R) the wavenumbers decrease. The intensity decreases in the
case of bands numbered as 7b, 13, 17b, 18a and 19b (IR).
Intensity of the other bands increases or does not change in
comparison to free acid.
3.1.1. Analysis of the wavenumbers of carboxylic anion
and amino group vibrations
The influence of the metal on vibrational structure of 3aminobenzoates expressed in the shift of selected bands along
the metal series was investigated. The observed changes in
the wavenumber of carboxylic anion bands in the series

Li Na K Rb Cs were small, but characteristic and

general tendency might be observed. The wavenumbers of
the symmetric stretching bands sym (COO ) in IR and Raman spectra decreased in the series Li Cs. The wavenumbers of the bands assigned to the symmetric sym (COO )
and asymmetric asym (COO ) in plane deformations and
the asymmetrical stretching asym (COO ) bands also decreased in IR spectra with the change of the metal from
lithium to rubidium. Cesium 3-aminobenzoate was an exception and the wavenumbers of the mentioned bands for
it were observed at slightly higher values than for rubidium one. The wavenumbers of out of plane deformation
asym (COO ) bands in IR and Raman spectra scattered.
The magnitudes of distance between wavenumbers due to
asymmetrical and symmetrical stretching vibration of COO
group [
= asym (COO ) sym (COO )] increases in the
series Li Na K = Rb Cs. These distances, in cm1 ,
are respectively as follows: 144, 148, 160, 160, and 171.


R. Swisocka
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2969

Table 2
The linear equations and correlation coefficients of examined correlation of chosen bands from spectra of 3-aminobenzoatesand some metal parameters
The bands in IR or Raman spectra

(COO )

s (COO ) (Raman)
as (COO )
s (COO )
(NH2 )
7b
8a (Raman)
8b
19b

The linear equations and correlation coefficients

Ionic potential

Electronegativity

Inverse of atomic mass

Atomic mass

Affinity

y = 4454.1x + 1364.9
R = 0.9691
y = 5488.9x + 1361.8
R = 0.9230
y = 1108.5x + 871.07
R = 0.9437
y = 468.85x + 616.17
R = 0.9825
y = 1466.8x + 1250.8
R = 0.9927
y = 1235.8x + 914.37
R = 0.9956
y = 840.59x + 1599
R = 0.9620
y = 448.76x + 1589.5
R = 0.8085
y = 1065x + 1477
R = 0.9111

y = 150x + 1273
R = 0.9828
y = 185.75x + 1247.8
R = 0.9406
y = 35.303x + 849.96
R = 0.9051
y = 15.214x + 606.99
R = 0.9601
y = 48.523x + 1221.3
R = 0.9889
y = 40.99x + 889.42
R = 0.9945
y = 27.031x + 1582.7
R = 0.9316
y = 14.549x + 1580.8
R = 0.7894
y = 34.417x + 1456.3
R = 0.8867

y = 188.54x + 1394.4
R = 0.8461
y = 218.72x + 1398.8
R = 0.7586
y = 56.06x + 877.99
R = 0.9844
y = 20.941x + 619.23
R = 0.9051
y = 64.796x + 1260.4
R = 0.9044
y = 55.921x + 922.4
R = 0.9293
y = 40.691x + 1604.3
R = 0.9605
y = 19.627x + 1592.5
R = 0.7293
y = 46.374x + 1484
R = 0.8183

y = 0.221x + 1415.9
R = 0.9042
y = 0.301x + 1426.3
R = 0.9515
y = 0.0427x + 883.05
R = 0.6836
y = 0.0226x + 621.5
R = 0.8921
y = 0.0707x + 1267.5
R = 0.8993
y = 0.0537x + 928.09
R = 0.8140
y = 0.0331x + 1608.1
R = 0.7128
y = 0.0289x + 1595.1
R = 0.9782
y = 0.0613x + 1489.7
R = 0.9863

y = 2.0865x + 1297.5
R = 0.9502
y = 2.5395x + 1280.3
R = 0.8938
y = 0.5414x + 853.17
R = 0.9647
y = 0.222x + 608.95
R = 0.9737
y = 0.694x + 1228.2
R = 0.9830
y = 0.5863x + 895.3
R = 0.9888
y = 0.4047x + 1585.7
R = 0.9694
y = 0.2154x + 1582.5
R = 0.8123
y = 0.5056x + 1460.6
R = 0.9053

This indicates an increase in the ionic character of bond in

the series Li Cs [12,18]. According to other authors [19]
these results may suggest bidentate coordination, in which
both oxygen atoms are coordinated to the metal, sustains the
resonance between equivalent C O bonds.
The wavenumbers of bands in IR spectra representing (NH2 ) vibrations decrease in the series
Li Na K Rb Cs. The wavenumbers of the
bands assigned to the asymmetric asym (NH2 ) and symmetric sym (NH2 ) in plane deformations change in the
studied series as follows: Li = Na = K > Rb > Cs and
Na < Li > K = Rb = Cs, respectively. The above-mentioned
bands of NH2 group vibrations in Raman spectra also
scatter. The asymmetrical asym and symmetrical sym
stretching vibrations of NH2 group decrease from lithium
to rubidium, but for cesium 3-aminobenzoate attain the
largest value. The participation of the NH2 group in the
hydrogen bond formation is not probable, since the equation: sym (NH2 ) = 345.5 + 0.876asym (NH2 ) is not fulfilled
[20].
The correlation between selected bands and some
metal parameters was studied. The wavenumbers of the
sym (COO ), asym (COO ) and sym (COO ) bands in IR
spectra and sym (COO ) bands in Raman spectra were correlated with four metal parameters: electronegativity, ionic
potential (defined as ratio of charge of the metal ion to its
ionic radius), atomic mass or inverse of atomic mass and
electronic affinity of the metal. The wavenumbers of those
bands correlate in the linear fashion with all tested factors at the statistically important level. For the symmetric
sym (COO ) in plane deformations the correlation coefficients are 0.9825, 0.9601, 0.9051 and 0.9737 for ionic potential, electronegativity, inverse of atomic mass and electronic
affinity, respectively. For correlation between the asymmetric

one asym (COO ) and the same metal parameters the correlation coefficients are 0.9437, 0.9051, 0.9844 and 0.9647,
respectively. For the symmetric stretching the correlation coefficients are 0.9691, 0.9828, 0.9042 and 0.9502 for ionic
potential, electronegativity, atomic mass and electronic affinity, respectively. Corresponding linear equations are gathered
in Table 2. The correlation coefficients for the symmetric
stretching sym (COO ) band in Raman spectra are 0.9230,
0.9406, 0.9515 and 0.8938 for ionic potential, electronegativity, atomic mass and electronic affinity, respectively. The
analysis of correlation coefficients shows that all of the examined metal parameters correlate very well with the changes
in wavenumbers of selected carboxylic anion vibrations. It is
difficult to choose the most important metal parameter of proposed ones in view of influence of the metal on the vibration
structure of carboxylic anion.
The correlation coefficients for the (NH2 ) band are
0.9927, 0.9889, 0.9044, and 0.9830 for ionic potential, electronegativity, inverse of atomic mass and electronic affinity
of the metal, respectively. The analysis of this data shows that
ionic potential is the most important metal parameter in view
of influence of the metal on the vibration structure of amino
group.

3.1.2. Analysis of the wavenumbers of the aromatic ring

vibrations
The wavenumbers of the aromatic ring bands change toward the series of metal ion. Some of them show decreasing
tendency along the metal series (7b, 8b, 19b) but those of
11, 18a and 19a bands decrease except that of sodium. The
wavenumbers of other aromatic bands do not change systematically. The wavenumbers of all bands in Raman spectra do
not show any tendency.

2970

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et al. / Spectrochimica Acta Part A 61 (2005) 29662973

The shift of the aromatic bands (regular and irregular) expresses the influence of the metal on the vibrational structure
of the aromatic ring. The wavenumbers of 7b, 8b and 19b
bands in IR spectra and 8a band in Raman spectra were correlated with the metal parameters as it was done in the case of
band wavenumber related to carboxylic anion vibrations. The
correlation coefficients for 7b band with ionic potential, electronegativity, inverses of atomic mass and electronic affinity
of the metal are 0.9956, 0.9945, 0.9293 and 0.9888, respectively. The correlation coefficients for 8a band in Raman spectra and the same metal parameters are 0.9620, 0.9316, 0.9605
and 0.9694, respectively. The correlation coefficients for 8b
band with ionic potential, electronegativity, atomic mass and
electronic affinity are 0.8085, 0.7894, 0.9782, 0.8123, and
for 19b band they are 0.9111, 0.8867, 0.9863 and 0.9053,
respectively. The wavenumbers of some other bands reflecting vibrations of the aromatic ring were analyzed as well to
estimate the influence of the metal on the uniform electronic
charge distribution around the aromatic ring. However, it is
difficult to say which of tested parameters is the most responsible for the influence of the metal on the vibration structure
of the aromatic ring. The linear equations of all of the examined correlations are gathered in Table 2.

Table 3
Chemical shifts in 1 H NMR spectra of 3-aminobenzoates in comparison to
3-aminobenzoic acid
Proton
numbera

Chemical shifts, (ppm)

3-Aminobenzoic acid

Li

Na

Rb

Cs

2a
4a
5a
6a

7.18
6.75
7.09
7.12

7.20
6.50
6.92
7.09

7.19
6.50
6.92
7.09

7.19
6.50
6.90
7.08

7.15
6.48
6.87
7.05

7.14
6.47
6.87
7.03

The atoms are numbered as Fig. 1.

Table 4
Chemical shifts in 13 C NMR spectra of 3-aminobenzoates in comparison to
3-aminobenzoic acid
Carbon Chemical shift, (ppm)
numbera 3-AminobenLi
zoic acid

Na

Rb

Cs

1
2
3
4
5
6
7

140.48
114.62
147.60
117.35
127.41
115.38
170.97

141.01
114.57
147.67
117.37
127.43
115.49
170.44

142.09
114.12
147.48
117.37
127.23
115.49
169.95

147.41
119.32
152.64
122.55
132.41
120.66
175.04

131.44
114.59
148.91
118.16
129.03
116.85
168.08
a

140.12
114.84
147.65
117.40
127.46
115.46
171.02

The atoms are numbered as Fig. 1.

3.2. UV spectra
All water solutions of studied compounds absorb strongly
at 209 nm (209 = 1.3 104 l mol1 cm1 for lithium and
sodium; 1.9 104 ; 2.6 104 and 2.1 104 l mol1 cm1
for potassium, rubidium and cesium 3-aminobenzoates,
respectively). Around 300 nm they absorb weakly, the
molar absorptivities are 299 = 0.9 103 l mol1 cm1 ;
302 = 0.8 103 l mol1 cm1 ;
299 = 1.5 103 l mol1
1
3
1
cm
and 290 = 4.0 10 l mol cm1 for lithium,
sodium, potassium and rubidium 3-aminobenzoates, respectively. Cesium 3-aminobenzoate absorbs considerably
stronger (300 = 1.4 104 ). The values of 3-aminobenzoates
absorption increase along the series Na Cs. The last
mentioned absorption band appear almost at the same

max for lithium, sodium, potassium and cesium, only for

rubidium one can observe the shift to lower wavelength. This
absorption band is due to * transition. Rubidium and
cesium 3-aminobenzoates solutions were colored, so they
absorb in the visible region: 417 = 3.1 103 l mol1 cm1
and 432 = 1.3 103 l mol1 cm1 , respectively. It might be
caused by charge transfer transition.
3.3. NMR spectra
1H

NMR and 13 C NMR spectra were recorded and the

obtained data are gathered in Tables 3 and 4, respectively.
The atom positions were numbered as in Fig. 1. The chemical

Fig. 1. Structures of (a) 3-aminobenzoic acid, (b) lithium 3-aminobenzoate and (c) sodium 3-aminobenzoate.


R. Swisocka
et al. / Spectrochimica Acta Part A 61 (2005) 29662973

shifts of protons (1 H NMR) and carbons (13 C NMR) in the

series of alkali metals express the influence of studied metal
on the electronic charge around those atoms.
Although, the differences in chemical shifts of protons
along metal series are small, one can observe decrease in
chemical shifts of all protons. The decrease of chemical shifts
is regular in the series Li Cs. The chemical shifts of all protons decreased with increasing atomic number of element. In
comparison to free 3-aminobenzoic acid all proton bands (except 2a in salts of Li, Na and K) are shifted diamagnetically.
This suggests that introduction of studied metals causes a
decrease in ring current intensity and according to the literature data a decrease in aromaticity [2123]. The chemical shifts of proton numbered 2a are the highest in the free
acid as well as in the salts. That means that the lowest electronic charge density is around (2a) proton, which is situated between carboxylic and amine groups. In comparison
to free 3-aminobenzoic acid proton in position 2a is shifted
paramagnetically in the case of lithium, sodium and potassium salts. The highest density is observed around proton in
position 4a.
13 C NMR spectra data are gathered in Table 4. The chemical shifts of carbon atoms in positions 7, 1 and 2 are higher
than chemical shifts of carbon atoms in free ligand (except
of potassium and rubidium for C2). The chemical shifts of
carbon atoms in positions 3, 4, 5 and 6 are lower (except of
cesium) than chemical shifts of carbon atoms in free ligand.
Only in the case of cesium salt the chemical shifts of all carbon atoms are significantly higher in comparison with free
ligand ones. The highest electronic charge density is observed
around ring carbons in position 2, 4 and 6, while the lowest
one around C7 and C3.
The differences between chemical shifts of carbon atoms
along metal series are small and irregular. Only the values
of chemical shifts of C7 and C2 atoms regularly decrease
in the series Li Rb. The changes of chemical shifts are
the highest for C7 and C1 atoms, for other atoms they are
very small. Only for cesium the changes of chemical shifts
for all carbon atoms are high and they amount from 3.38 to
15.97. In the case of cesium one can observe paramagnetic
effect. Although changes along metal series are irregular, the
effect of ring current decrease is the evidence for affecting the
electronic charge in the aromatic ring by metal ion connected
to the carboxylate anion.
3.4. The calculated geometrical structures
To calculate optimized geometrical structures a few
quantum chemical methods were applied: HF/6-311++G** ,
B3PW91/6-311++G** and B3LYP/6-311++G** . The distances between atoms and the bond angels were calculated and given exemplary for lithium 3-aminobenzoate in
Tables 5 and 6. The atoms are numbered as in Fig. 1. Geometric aromaticity indices [24], dipole moments and energies
for lithium 3-aminobenzoates were calculated, and are presented in Tables 7 and 8.

2971

Table 5
The bond lengths calculated for lithium 3-aminobenzoate using three
methods
Bond
lengtha

HF/6311++G**

B3PW91/6311++G**

B3LYP/6311++G**

C7 C1
C7 O9
C7 O10
O9 Li11
O10 Li11
C1 C2
C2 H2a
C2 C3
C3 N8
N8 H8a
N8 H8b
C3 C4
C4 H4a
C4 C5
C5 C5a
C5 C6
C6 H6a
C1 C6

1.499
1.248
1.247
1.846
1.845
1.386
1.074
1.389
1.340
0.996
0.996
1.391
1.077
1.384
1.076
1.384
1.072
1.387

1.494
1.272
1.271
1.858
1.856
1.392
1.085
1.394
1.009
1.009
1.401
1.087
1.390
1.086
1.340
1.083
1.400
1.397

1.498
1.275
1.274
1.854
1.853
1.395
1.084
1.399
1.400
1.010
1.010
1.403
1.086
1.392
1.085
1.392
1.082
1.398

The atoms are numbered as Fig. 1.

The changes of the bond lengths and bond angles, calculated by HartreeFock method, for 3-aminobenzoic acid as
well as lithium and sodium 3-aminobenzoates are presented
in Tables 9 and 10, respectively. The bond lengths C7 O9 are
higher in salts comparing to free 3-aminobenzoic acid, but
C7 O10 bonds are shorter in the metal benzoates. The latter

Table 6
The bond angels calculated for lithium 3-aminobenzoate using three methods
Bond
anglea

HF/6311++G**

B3PW91/6311++G**

B3LYP/6311++G**

O9
O9
C7
C7
C7
C1
C1
C1
C1
C4
C2
C6
C5

119.738
120.587
119.366
120.005
83.783
120.518
118.866
118.906
119.675
120.759
120.623
119.939
119.885

119.579
120.924
119.390
120.079
83.038
120.652
118.942
118.434
119.203
120.793
120.681
119.991
119.934

119.700
120.656
119.455
120.122
83.016
120.658
119.016
118.565
119.283
120.789
120.640
119.959
119.975

C7 C1
C7 O10
C1 C2
C1 C6
O10 Li11
C2 C3
C6 C5
C2 H2a
C6 H6a
C5 C6
C3 N8
C5 H5a
C4 H4a

The atoms are numbered as Fig. 1.

Table 7
Dipole moments and energy calculated for lithium 3-aminobenzoate using
three methods

Dipole moment (D)

Energy (hartreea )
a

HF/6311++G**

B3PW91/6311++G**

B3LYP/6311++G**

3.2080
480.4217

3.1236
483.1220

3.0014
483.3233

1 hartree = 2625.500 kJ/mol.


R. Swisocka
et al. / Spectrochimica Acta Part A 61 (2005) 29662973

2972

Table 8
Geometric aromaticity indices calculated for lithium 3-aminobenzoate using
three methods

Table 10
The bond angels calculated for 3-aminobenzoic acid and for lithium and
sodium 3-aminobenzoates using HF/6-311++G** method

Geometric
aromaticity
indices [24]

HF/6311++G**

B3PW91/6311++G**

B3LYP/6311++G**

Bond angle

3-Aminobenzoic acid

Lithium 3aminobenzoate

Sodium 3aminobenzoate

Aj
BAC
HOMA
GEO
EN
I6

0.999
0.970
0.998
0.002
0.000
99.155

0.998
0.937
0.981
0.006
0.013
98.464

0.998
0.951
0.976
0.004
0.019
98.652

O9
O9
C7
C7
C7
C1
C1
C1
C1
C4
C2
C6
C5
C3
C3

124.584
121.893
117.307
121.641
108.272
120.459
118.398
119.035
120.677
121.050
120.722
119.744
119.807
121.043
120.892

119.738
120.587
119.366
120.005
83.783
120.518
118.866
118.906
119.675
120.759
120.623
119.939
119.885
114.385
114.215

118.482
123.113
119.545
120.180
88.693
120.706
119.080
118.731
119.470
120.804
120.547
119.931
119.981
114.165
113.944

Aj : normalized function of variance of bond lengths in the perimeter of the

molecule; BAC: bond alternation coefficient; HOMA: abbreviation from
Harmonic Oscillator Model of Aromaticity (HOMA = 1-EN-GEO); GEO:
geometric contribution to the aromaticity; EN: energetic contribution to the
aromaticity; I6 : Bird indice, which describes the geometric contribution to
the aromaticity.

bond lengths vary in free acid molecule but in salts they are
almost equal. It indicates symmetric structure of carboxylic
ion. These bonds (C7 O9 and C7 O10) are slightly longer
in lithium than in sodium 3-aminobenzoate, but in the case of
O9 Me11 and O10 Me11 bonds it is inversely. The O9 H11
bond is shorter than suitable bond in benzoates. Analyzing the
bond lengths of aromatic ring one can observe that aromaticity of molecule increases in salts comparing with free acid
molecule. Geometric aromaticity indices (Table 11) confirm
this thesis.
The values of C C C bond angles in aromatic ring become equalized along the series H Li Na, indicating
increasing aromaticity in the series. On the contrary to our
previous results for alkali metal benzoates electronic system
of 3-aminobenzoates stabilizes along with the decrease in
electronegativity of the metal.
Table 9
The bond lengths calculated for 3-aminobenzoic acid and for lithium and
sodium 3-aminobenzoates using HF/6-311++G** method
Bond length

3-Aminobenzoic acid

Lithium 3aminobenzoate

Sodium 3aminobenzoate

C7 C1
C7 O9
C7 O10
O9 Me(H)11
O10 Me(H)11
C1 C2
C2 H2a
C2 C3
C3 N8
N8 H8a
N8 H8b
C3 C4
C4 H4a
C4 C5
C5 C5a
C5 C6
C6 H6a
C1 C6

1.492
1.186
1.328
0.946

1.386
1.074
1.391
1.375
0.990
0.989
1.395
1.077
1.381
1.076
1.385
1.072
1.388

1.499
1.248
1.247
1.846
1.845
1.386
1.074
1.389
1.340
0.996
0.996
1.391
1.077
1.384
1.076
1.384
1.072
1.387

1.509
1.244
1.243
2.201
2.199
1.386
1.074
1.390
1.402
0.996
0.996
1.390
1.077
1.385
1.076
1.384
1.072
1.388

The atoms are numbered as Fig. 1.

C7 C1
C7 O10
C1 C2
C1 C6
O10 Me(H)11
C2 C3
C6 C5
C2 H2a
C6 H6a
C5 C6
C3 N8
C5 H5a
C4 H4a
N8 H8a
N8 H8b

The atoms are numbered as Fig. 1.

The following model of interaction may explain this observation. In the case of alkali metal benzoates the negative
charge of carboxyl anion causes perturbation of electronic
charge distribution in the ring. In the case of 3-aminobenzoic
acid presence of electron donating amino group leads to
the increase in electron density in the ring, while carboxyl
group causes the draw of electrons back from the ring. This
brings about the shift of electronic charge and in consequence
the perturbation of electronic charge distribution in the ring.
Forming of carboxyl anion due to the connecting of alkali
metal suppresses the electron drawing effect of carboxyl
group and thus restores uniform charge distribution within
the aromatic ring. This effect increases with the decrease in
electronegativity of connected metal, what can be observed
in our results.
Comparing values of dipole moment for molecule of
3-aminobenzoic acid and its sodium and lithium salts
one can observe an increasing tendency: 2.39 D for
free acid 3.21 D for sodium salt 6.09 D for lithium
Table 11
Geometric aromaticity indices calculated for 3-aminobenzoic acid and for
lithium and sodium 3-aminobenzoates using HF/6-311++G** method
Geometric
aromaticity
indices

3-Aminobenzoic acid

Lithium 3aminobenzoate

Sodium 3aminobenzoate

Aj
BAC
HOMA
GEO
EN
I6

0.998
0.943
0.995
0.005
0.000
98.519

0.999
0.970
0.998
0.002
0.000
99.155

0.999
0.973
0.998
0.001
0.000
99.222

Aj : normalized function of variance of bond lengths in the perimeter of the

molecule; BAC: bond alternation coefficient; HOMA: abbreviation from
Harmonic Oscillator Model of Aromaticity (HOMA = 1-EN-GEO); GEO:
geometric contribution to the aromaticity; EN: energetic contribution to the
aromaticity; I6 : Bird indice, which describes the geometric contribution to
the aromaticity.


R. Swisocka
et al. / Spectrochimica Acta Part A 61 (2005) 29662973

salt. The energy (kcal/mol) shows decreasing tendency:

473.5 480.4 634.8. Obtained results show that
degree of ionic bonding increases from H to Na atom, because of an increase in symmetrization of carboxylate ion
and in aromaticity of molecule.

2973

Acknowledgement
Presented work was supported by Bialystok Technical

University (theme no. W/IIS/31/03).

References
4. Conclusion
Spectral characteristic of the alkali metal 3-aminobenzoates has been done. The intensities and wavenumbers of the majority of aromatic system bands in IR and
Raman spectra increased in the case of salts comparing
to the free ligand, although for some of them the intensity and wavenumbers decreased. The magnitudes of separation between wavenumbers of asymmetrical and symmetrical stretching vibrations of COO group
increase in the
series Li Na K = Rb Cs. It indicates on the increase
in degree of ionic bonding between metal ion and COO
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substituents: electron donating NH2 group and withdrawing
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cause the increase of stabilization in studied series.
The conclusion is: it cannot be claimed that in each situation perturbation of electronic structure occurs in the series
Li Cs. Sometimes we could observe the opposed effect. In
our work on 3-aminobenzoic acid salts, alkali metals restore
uniform distribution of electronic charge in molecule. This
conclusion is only assumption, which will be verified in our
next work.

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