Journal of Molecular Structure 792793 (2006) 227238

www.elsevier.com/locate/molstruc

Molecular structure of 4-aminobenzoic acid salts with alkali metals

R. Swisocka, M. Samsonowicz, E. Regulska, W. Lewandowski *
Department of Chemistry, Biaystok Technical University, Zamenhofa 29, 15-435 Biaystok, Poland
Received 16 September 2005; accepted 31 October 2005
Available online 15 May 2006

Abstract
The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 4-aminobenzoic acid was studied. The
vibrational (FT-IR, FT-Raman) and NMR (1H and 13C) spectra for 4-aminobenzoic acid and its alkali metal salts were recorded. The assignment
of vibrational spectra was done. Characteristic shifts of bands and the changes in intensities of bands along the metal series were observed. The
changes of chemical shifts of protons (1H NMR) and carbons (13C NMR) in the series of studied alkali metals 4-aminobenzoates were observed
too. Optimized geometrical structures of studied compounds were calculated by HF, B3PW91, B3LYP methods using 6-311CCG** basis set.
Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman
spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.
q 2006 Published by Elsevier B.V.
Keywords: 4-Aminobenzoates; FT-IR; FT-Raman; NMR; Calculated geometrical structure

1. Introduction
The influence of amino group position toward the
carboxylic group of 2-, 3- and 4-aminobenzoic acids was
investigated previously [1]. The effect of some metals on the
electronic system of various derivatives of benzoic acid was
investigated and also reported in our earlier papers [26]. In
this paper, the effect of lithium, sodium, potassium, rubidium
and cesium on the electronic system of the 4-aminobenzoic
acid was studied.
The benzene derivatives are compounds of great interest
because of their chemical and biological properties, particularly the amino derivatives. 4-Aminobenzoic acid in the
0.1 mM range is a precursor of folic acid but at concentrations
a 100 times higher it can inhibit different bacteria [7]. The
antibacterial activity and its effect on bacterial DNA synthesis
were investigated by Richards and Xing [8]. 4-Aminobenzoic
acid is involved in the biosynthesis of folic acid, which is a
constituent of the Vitamin B complex and it is found in animal
and plant tissues. As a member of Vitamin B complex it is
reported to be an effective sunscreen agent and can be used to
soften or regress fibrotic tissue [9]. In medicine 4-aminobenzoic acid is mostly used as a protective drug against
* Corresponding author. Tel.: C48 85 746 9790; fax: C48 85 746 9782.
E-mail address: w-lewando@wp.pl (W. Lewandowski).

0022-2860/$ - see front matter q 2006 Published by Elsevier B.V.

doi:10.1016/j.molstruc.2005.10.060

UV-irradiation and in diagnostic tests for the state of the

gastrointestinal tract. Recently, such properties of 4-aminobenzoic acid as the capacity of inducing endogenous interferon
and its antioxidant, anticoagulant, fubrinolytic and immunomodulating activities were described [10], which open new
possibilities for its application in medicine. The potassium
4-aminobenzoate is used therapeutically in fibrotic skin
disorders [11].
In our knowledge, there are some papers in the literature
about spectroscopic study of 4-aminobenzoates. The Mg(II)
complexes of 2- and 4-aminobenzoic acids have been
investigated by thermal and spectroscopic methods and
compared to the orientation of the amino group with respect
to the carboxylate group [12]. These complexes are octahydrates and they have been formulated as consisting of the
octahedral [Mg(H2O)6]2C cation. The aminobenzoates are
outside the coordination sphere of the bivalent metal and
function as anions. The carboxylate group can function like a
bidentate ligand binding to a single metal or alternatively as
a bridging bidentate ligand coordinating to two metals or as a
monodentate ligand [13]. Carboxylate ligands that possess
additional donor sites, for example, amino group, can take part
in the formation of metal complexes with novel network
structure. The reported [12] crystal structure of the complex
[Mg(H2O)6](4-ab)2!2H2O has been explained in terms of
secondary H-bonding interactions between the coordinated
water molecules of [Mg(H2O)6]2C and the 4-aminobenzoate
(ab) both at the NH2 and COO sites. The amino (NH2)

228

Table 1
Wavenumbers (cmK1), intensities and assignments of selected bands occurring in the IR and Raman spectra of Li, Na, K, Rb and Cs 4-aminobenzoates in comparison to 4-aminobenzoic acid
Li 4-aminobenzoate
Calculated
wavenumber

Calculated intensity
IR
20.53
34.24
1.88
4.80
19.11
14.70

IR

IR

3389s
3201s

3390vw

3388m
3205m

K 4-ab
R

IR

Rb 4-ab
R

IR

4-Aminobenzoic acid

Cs 4-ab
R

IR

Assignment [19]

IR

3461m
3364s

nasNH2
nsNH2
2
20b
20a

3090
2550
1686vs
1626s
1601vs

nOH

Raman
63.58
279.12
155.35
16.10
107.20
88.87

3069w
3067m
3051m

1604vs

3402m
3204m
3073m

3043m

1620
1602
1586
1510
1509
1423

310.07
5.48
73.75
374.81
0.62
12.06

173.81
27.94
1.37
11.41
51.27
1.07

1612s
1562vw

1409
1342
1286
1284

789.82
1.44
0.11
92.49

214.92
0.02
0.50
21.26

1418vs
1330m

1169
1132
1114
1050
1005
966
958

49.66
12.73
10.22
5.30
1.16
0.01
1.68

2.64
20.42
1.58
0.69
0.11
0.01
0.08

1178s
1144w
1128w
1093m
1011w
971vw
958vw

1178w
1146m

867
845
819
812
787
701
667
645

22.24
14.13
3.73
0.04
66.72
11.38
1.29
156.58

60.54
0.07
5.41
0.02
0.58
0.27
6.28
1.14

863m
849s
824s
810s
786vs
698s
638m
625s

868m
854w
817w

594
542
532

108.70
0.08
162.85

0.81
0.35
10.89

549m
503m

493

246.49

10.47

475m

1601vs

3401m
3200m
3067m

3037w

1618s
1567vw

1597vs

3388m
3206m
3058m

3057m

1613s
1561w

1599vs

3067w
3032w

1609s
1553vw

1603vs

1530s
1446s
1422s

1511vw
1434w

1314vs

1351s
1296vs

1313w

1342w
1286m

1130m
1079w

962w

1132w

nCZO
bsNH2
8a
dNH2
8b
nasCOO
19a
19b
bOH
nsCOO
14
9b
nCN
nCOH
9a
9a
7a
bNH2
18a
17a

849m
830vw

920m
773s
845m

769w
847m

gOH
1
17b

685vw
640w

822w

700m
638w

828w

700vw
640w

618m

616w

501m
552m

504vw

10a
11
4
6b
bsCOO
nCZO
LiOs
basCOO
16b
gNH2
uNH2

1611s
1552vw

1602vs

1573s
1552vs
1490m

1262s

1516w

1434s
1397w
1274w

1086vw
1011w

1541vs
1491m

1407vs
1321m
1262s
1179s
1130m
1083m
1018w

1521w

1435m
1387w
1269w
1182w
1144m
1083vw

961vw

771w
702w
640w

510w

880m
849m
824m
812m
785s
693m
637w
622s

860s
854vw
810w
777vw
694vw
639w

1550vs
1498m

1402vs

1265s
1175m

1515w

1412s
1383w
1266w
1177m
1137m

1549vs
1490m

1384vs
1298m
1262s
1172s

1134m
1987m
1012w

1128m
1079m
1004w

965vw

853m
819m
808m
782s
693m
638w
619s

854s
830w
813w
783vw
685vw
639w

862m
848m

790s
697m
637m
617s

534w
501w

537vw

529m
502m

530w

522m
504m

485m

486vw

491m

496vw

1512w

1401m
1370w
1274w
1168w
1131m
1084vw

852m
833w

792vw
640w

523vw

1548vs

1379vs
1285m
1263s
1172s
1130m
1084m
1003w
976m

859m

793s
697m
637m
616s

518m
503m

1514w

1392m
1380m
1278w
1175w
1136w
1089vw
1008vw

502vw

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

3561
3461
3088
3087
3050
3049

Na 4-ab

n, stretching; b, in plane; g, out of plane deformations; r, rocking; t, twisting; d, scissoring; u, wagging; s, strong; vs, very strong; m, medium; sh, shoulder; w, weak.

442
430
377
335

30.54
0.17
13.16
12.39

0.24
0.04
0.00
0.16

419m

422vw

428vw

414w

519vw

LiOas
16a
rNH2
tNH2

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

229

functionality forms H-donor bonds (NH/O) with the O atom

of a coordinated water molecule. The spectroscopic characteristic of Cu(II) ternary complexes of 4-aminobenzoic acid and
phenanthrolines of the type [Cu(4-ab)2(phen)] has been
presented by Zoroddu et al. [14]. Wang et al. [15] reported
about syntheses and crystal structure of series of hydrogenbonded Ag(I) complexes from 4-aminobenzoic acid. This work
demonstrates that multifunctional organic ligands containing
nitrogen atom and carboxylic group are preferred building
blocks for preparing various switchable supramolecular
complexes through adjusting and controlling the pH value of
reaction system, where NH3 is a suitable base for controlling
carboxylic proton and plays an important role in the selfassembly process of these ligands with Ag(I). Moreover,
coordination covalent bonds, hydrogen bonds, pp stacking
interaction, and their combination are important tools for
construction of supramolecular architectures. Preparation and
crystal structure of the silver(I) complex involving two
different organic species: p-toluenesulfonate and p-aminobenzoic acid were reported by Smith et al. [16]. The
complexation of trivalent lanthanide cations with benzoic
acid derivatives in aqueous solution has been extensively
studied [17]. The thermodynamic parameters of formation of
complexes of lanthanides by 4-aminobenzoic acid were
determined by potentiometric and calorimetric titration
methods. Theoretical calculations of the charge distributions
on the carbon atoms of benzoate ligands were also performed.
We have not found any references on 4-aminobenzoates
spectroscopic study of the series of alkali metals from lithium
to cesium so in this paper the influence of lithium, sodium,
potassium, rubidium and cesium on the electronic system of the
4-aminobenzoic acid was investigated. The vibrational (FT-IR,
FT-Raman), and NMR (1H and 13C) spectra were recorded for
4-aminobenzoic acid and its alkali metal salts. It was
interesting to see characteristic shifts of band wavenumbers,
changes in band intensities and changes of chemical shifts of
1
H and 13C NMR in the series of alkali metal 4-aminobenzoates. 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 were discussed.
The theoretical IR and Raman spectra were obtained. The
calculated parameters were compared to experimental characteristic of studied compounds.
2. Experimental
Lithium, sodium, potassium, rubidium and cesium 4-aminobenzoates were prepared by dissolving the powder of
4-aminobenzoic acid in the water solution of the appropriate
metal hydroxide in a stoichiometric ratio (4-aminobenzoic acid
was obtained from Fluka Chemical Co., lithium hydroxide
from Sigma Chemical Co. and other hydroxides were from
Aldrich Chemical Co.). The mixed solution was slowly
condensed at 70 8C to about 30% of starting volume. Then
the solution was left at the room temperature for 4872 h until

230

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

Fig. 1. Experimental (a) and calculated (scaled) (b) IR spectrum of lithium 4-aminobenzoate.

the sample crystallized in the solid-state. The remaining

solvent was removed by drying under reduced pressure at
110 8C. Obtained complexes were anhydrousin the IR
spectra of solid state samples the lack of bands characterized
for crystallizing water was observed. The chemical composition of obtained compounds in this work was estimated by
elemental analysis.
The IR spectra were recorded with the EQUINOX 55,
BRUKER FT-IR spectrometer within the range 4000
400 cmK1. 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 cmK1 with a FTRaman accessory of the PerkinElmer System 2000. The
resolution of spectrometer was 1 cmK1.
The NMR spectra of D2O 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) HartreeFock
(HF), (ii) density functional (DFT) hybrid method B3PW91,
which uses the Beckes three-parameter functional with
nonlocal correlation provided by PerdewWang 91 expression,
(iii) the DFT hybrid method B3LYP with nonlocal correlation
provided by LeeYoungParr expression. The 6-311CCG**
basis set was used as the standard basis set available for all
atoms. All theoretical calculation were performed using the
GAUSSIAN 98W (v.5.4) package of programs [18] running on a
PC computer.

3. Results and discussion

The elemental analysis was done and obtained results were
confirmed the stoichiometry (1:1). The results of elemental
analysis for lithium 4-aminobenzoate (exemplary) are as

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

follows: %CZ58.72 (calculated 58.76); %HZ4.30 (calculated

4.94); %NZ9.75 (calculated 9.79).
3.1. FT-IR and FT-Raman spectra
The vibrational spectra of the synthesized 4-aminobenzoates were recorded and assigned. The observed IR and
Raman bands together with their relative intensities and band
assignments of studied metal salts with 4-aminobenzoic acid
are presented in Table 1. The bands are numbered along with
the notation used by Versanyi [19]. The calculating
wavenumbers and intensities of IR and Raman spectra of
lithium 4-aminobenzoate (exemplary) obtained by B3PW91
method and 6-311CCG** basis set are also shown in Table 1.
Theoretical wavenumbers were calculated according to the
formulae: nscaledZ0.996$ ncalculatedC25.7 [20]. The observed
and calculated (scaled) IR spectra for lithium 4-aminobenzoate
(exemplary) are shown at Fig. 1.
The characteristic bands occurring in the IR spectra of
4-aminobenzoates, which do not exist in the spectra of free
acid: symmetric (13791418 cmK1) or asymmetric (1541
1552 cmK1) stretching vibrations of carboxylic group (exemplary) were observed. As well as the lack of some bands, which
are characteristic for free acid (the CaO band, 1686 cmK1,
exemplary) was noted. The very broad band in the 3090
2550 cmK1, which were assigned to the stretching modes of
OH group n(OH) arising from hydrogen bonding disappeared
in the IR spectra of alkali metal salts too.
The changes of wavenumbers of the bands of aromatic
system in the case of salts were discussed comparing to the free
acid. The wavenumbers of aromatic bands numbered as 1 in IR
and Raman spectra, 8a (R), 17b (IR) 19a (R), 16b (except of
cesium salt in Raman spectra and sodium salt in IR spectra)
increase in comparison to free acid, while the wavenumbers of
19a, 10a and 4 bands in IR spectra and 4 band in Raman spectra
decrease. The intensity decreases in the case of bands
numbered as 19a (IR), 14 (IR), 17b (R) and 1 (IR). Intensity
of 19a (R), 8a(R), 1(R) and 10a (IR) bands increase in
comparison to free acid.
The wavenumbers of bands responsible for the amine group
in the IR and Raman spectra of salts also change in comparison
to 4-aminobenzoic acid. The wavenumbers of bands assigned

Fig. 2. The correlation of wavenumbers of bs(COO) vibrations and ionic

potential of alkali metal.

231

to the asymmetric and symmetric stretching vibrations of the

amine group in IR spectra and n(CN) in IR and Raman spectra
decrease comparing to the free acid. The intensities of ns(NH2)
decrease too, except of lithium aminobenzoate. The wavenumbers and also intensities of bands represented b(NH2)
vibrations in IR spectra increase except of rubidium salt. These
changes in wavenumbers of amine group bands occurring
under the influence of metal action on 4-aminobenzoic acid
may be caused by hydrogen bond breaking. Ligand set
containing nitrogen atoms and carboxylic groups is inclined
to form molecular complexes with head-to-head carboxylic
acid hydrogen bonds [15]. The bases such as NaOH or KOH
may cause breaking hydrogen bonding in these molecular
complexes.
The influence of the metal on vibration structure of
4-aminobenzoates expressed in the shift of selected bands
along the metal series was investigated. The wavenumbers of
the aromatic ring bands change toward the series of metal ion.
Some of them show decreasing tendency along the metal
series: 1, 4, 9b (except of cesium salt) in Raman spectra and 14
and 18a (except of lithium) in IR spectra but those of 11 and 8a
bands (IR) decrease from lithium to potassium salt but increase
from potassium to cesium salt. The other aromatic bands did
not change systematically. The wavenumbers of the symmetric
stretching bands of carboxylic anion ns(COOK) in IR and
Raman spectra were decreased in the series Li/Cs. The
wavenumbers of the bands assigned to the symmetric bs
(COOK) and asymmetric bas(COOK) in plane deformations
also decreased in IR spectra with the change of the metal from
lithium to cesium. The differences between wavenumbers of
bas(COOK) and bs(COOK) vibrations increase along the
series: Li!Na!K!Rb!Cs aminobenzoates. These values
in IR spectra are, respectively, as follows: 76, 88, 90, 95 and
98 cmK1. The wavenumbers of the asymmetrical stretching
bands of carboxylic anion group nas(COOK) in IR spectra
scatter but the magnitudes of separation between wavenumbers
due to asymmetrical and symmetrical stretching vibration of
COOK group nasKns increase in the series LiZNa!K!Rb!
Cs aminobenzoates. These values in IR spectra are, respectively, as follows: 134, 134, 148, 165 and 169 cmK1. It indicates
the higher degree of ionic bond [21]. The wavenumbers of
bands representing wagging vibrations (uNH2) increase from
lithium to potassium, but those of other NH2 vibration bands
scatter.
The correlation between chosen bands and some metal
parameters were also studied. The wavenumbers of the
bs(COOK), bas(COOK) and ns(COOK) bands in IR spectra
and nas(COOK) bands in Raman spectra were correlated with
some metal parameters: electronegativity, ionic potential
(defined as ratio of charge of metal ion and ionic radius),
atomic mass or inverse of atomic mass and affinity. The
wavenumbers of those bands correlate in the linear fashion
with all tested factors at the statistically important level. For the
symmetric bs(COOK) in plane deformations in IR spectra the
correlation coefficients are 0.991, 0.975, 0.915 and 0.985 for
ionic potential, electronegativity, inverse of atomic mass and
affinity, respectively. The best correlation (for ionic potential)

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

232

Table 2
Chemical shifts in 1H and 13C NMR spectra of alkali metal 4-aminobenzoates in comparison to 4-aminobenzoic acid
Atom positiona
H2a
H3a
H5a
H6a
C1
C2
C3
C4
C5
C6
C7
a

Experimental chemical shifts, d (ppm)

H

Li

Na

Rb

Cs

7.63
6.56
6.56
7.63
117.02
131.35
112.70
153.21
112.70
131.35
167.65

7.65
6.45
6.45
7.65
125.95
130.87
112.26
150.24
112.26
130.87
171.62

7.61
6.43
6.43
7.61
127.26
130.53
112.19
149.63
112.19
130.53
171.02

7.58
6.42
6.42
7.58
128.66
130.41
112.20
149.20
112.20
130.41
170.43

7.56
6.40
6.40
7.56
129.41
130.28
112.16
148.93
112.16
130.28
169.98

7.56
6.43
6.43
7.56
127.23
130.50
112.30
149.76
112.30
130.50
169.84

The atoms are numbered as in Fig. 3.

is presented at Fig. 2. For the asymmetric bas(COOK) in plane

deformations in IR spectra the correlation coefficients are
0.974, 0.940, 0.957 and 0.987 for ionic potential, electronegativity, inverse of atomic mass and affinity, respectively.
All results indicate good correlation in the linear fashion with
all tested factors at the statistically important level, but the
largest value of correlation coefficient is obtained for affinity.
For the symmetric stretching in IR spectra the correlation
coefficients are 0.923, 0.891, K0.965 and 0.917 for ionic
potential, electronegativity, atomic mass and affinity, respectively. Atomic mass is the most important parameter of metal,
which influences the vibration of carboxylic anion. The
correlation coefficients for the symmetric stretching in
Raman spectra are 0.926, 0.940, K0.937 and 0.888 for ionic
potential, electronegativity, atomic mass and affinity, respectively. The analysis of correlation coefficients shows that all of
examined metal parameters relate good to change in
wavenumbers of chosen 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.
Larger values of correlation coefficients were obtained for
u(NH2) band in IR spectra of series from lithium to potassium
4-amninobenzoates: K0.982, K0.937, 0.990, and K0.999 for
ionic potential, electronegativity, atomic mass and affinity,
respectively. These data show that affinity is the most
important metal parameter in view of influence of the metal
on the vibration structure of amino group.

Fig. 3. Structures of 4-aminobenzoic acid (a) and lithium 4-aminobenzoate (b).

The wavenumbers of 14 and 18a aromatic bands in IR

spectra and 1, 4, 11 and 9b band in Raman spectra are
correlated with the same metal parameters as in the case of the
bands related to carboxylic anion vibrations. The correlation
coefficients for 14 band are 0.971, 0.964, K0.944 and 0.940 for
ionic potential, electronegativity, atomic mass and affinity,
respectively. For 18a band they amount to 0.640, 0.661,
K0.833, and 0.572, respectively. The correlation coefficients
for 1 band in Raman spectra are 0.994, 0.978, 0.950 and
K0.997 for ionic potential, electronegativity, inverses of
atomic mass and affinity, respectively. For 4 band they are
0.981, 0.975, 0.938 and 0.979, respectively. The correlation
coefficients for 11 band are K0.948, K0.911, 0.984 and
K0.933 for ionic potential, electronegativity, atomic mass and
affinity, respectively. From above mentioned results it is
difficult to say, which of the tested parameters are mostly
responsible for the influence of metal on the vibration structure
of the aromatic ring.
3.2. NMR spectra
1

H and 13C NMR spectra of lithium, sodium, potassium,

rubidium and cesium 4-aminobenzoates were recorded and
obtained data in comparison to those of 4-aminobenzoic acid

Fig. 4. Correlation of chemical shifts on C7 atom and atomic radius of alkali

metal.

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

Table 3
Differences of chemical shifts in 1H and
Atom position

1
2
3
4
5
6
7

233

13

C NMR spectra of alkali metal 4-aminobenzoates in comparison to 4-aminobenzoic acid, Dd (ppm)

Li

Na

Rb

Cs

Dd (H)

Dd (C)

Dd (H)

Dd (C)

Dd (H)

Dd (C)

Dd (H)

Dd (C)

Dd (H)

Dd (C)

8.93
K0.48
K0.44
K2.97
K0.44
K0.48
3.97

K0.02
K0.13

K0.13
K0.02

10.24
K0.82
K0.51
K3.58
K0.51
K0.82
3.37

K0.05
K0.14

K0.14
K0.05

11.64
K0.94
K0.5
K4.01
K0.5
K0.94
2.78

K0.07
K0.16

K0.16
K0.07

12.39
K1.07
K0.54
K4.28
K0.54
K1.07
2.33

K0.07
K0.13

K0.13
K0.07

10.21
K0.85
K0.4
K3.45
K0.4
K0.85
2.19

0.02
K0.11

K0.11
0.02

Table 4
Theoretical obtained chemical shifts of 4-aminobenzoic acid in 1H and 13C NMR spectra, d (ppm)
Atom position

C1
C2
C3
C4
C5
C6
C7
H2a
H3a
H5a
H6a
H8a
H8b

4-Aminobenzoic acid

Li-4-aminobenzoate

Na-4-aminobenzoate

K-4-aminobenzoate

RHF/6-31G*

DFT-B3LYP/
6-311CG*

RHF/6-31G*

DFT-B3LYP/
6-311CG*

RHF/6-31G*

DFT-B3LYP/
6-311CG*

RHF/6-31G*

DFT-B3LYP/
6-311CG*

123.81
151.61
119.29
167.72
117.93
149.79
171.63
8.94
6.97
6.88
8.65
3.41
3.41

106.30
134.11
101.78
150.21
100.41
132.27
154.10
8.22
6.26
6.16
7.94
2.70
2.70

129.88
150.44
118.43
165.84
118.43
150.44
190.12
8.91
6.89
6.89
8.91
3.22
3.22

112.36
132.91
100.90
148.34
100.90
132.91
172.59
8.20
6.17
6.17
8.20
2.51
2.51

133.30
149.99
118.59
164.12
118.52
149.99
185.50
8.89
6.86
6.86
8.89
3.08
3.08

115.78
132.47
101.07
146.63
101.00
132.47
167.93
8.17
6.14
6.14
8.17
2.37
2.37

135.63
149.41
118.55
163.16
118.55
149.41
184.20
8.88
6.84
6.84
8.88
3.02
3.02

118.11
131.88
101.01
145.65
101.01
131.88
166.68
8.17
6.13
6.13
8.17
2.30
2.30

are gathered in Table 2. The atom positions were numbered as

in Fig. 3. The chemical shifts of protons (1H NMR) and carbons
(13C NMR) in the series of alkali metals express the influence
of studied metal on the electronic charge density around those
atoms.
The chemical shifts of protons numbered 2a and 6a, and 3a
and 5a are the same in pairs. The value of chemical shift of the
first pair is higher than d of the second one. It means that
electronic charge density is higher around positions 3a and 5a
comparing to positions 2a and 6a, therefore an increase in the
screening of these protons proceed [22]. The differences in
chemical shifts of protons along alkali metal 4-aminobenzoates
series are small, although in the case of H2a and H6a they are
clear. The dependences of chemical shifts (H2a, H6a) upon
atomic mass, inverse of atomic mass, electronegativity,
affinity, atomic and ionic radius, ionization and ionic potential
of alkali metal were investigated to estimate, which parameter
mainly influences on the electronic charge distribution. The
statistical analysis shows the best correlations for atomic and
ionic radius (RZK0.982), affinity (RZ0.994) and ionic
potential (RZ0.994) of alkali metal.
The same effect is observed in the case of carbon atom
chemical shifts. The chemical shifts of C2 and C6 carbon
atoms are higher than of C3 and C5. The differences between
chemical shifts of carbon atoms along metal series are small.
Only the values for C1 atom clearly increase in comparison to

4-aminobenzoic acid and increased in the series from lithium to

rubidium 4-aminobenzoates but one obtained for cesium is
smaller then d for rubidium salt. The values of chemical shifts
for other carbon atoms insignificantly decrease in the series
from lithium to rubidium, but the value for cesium salt was
higher then this for rubidium. The chemical shifts for C7 atom
decrease in the whole series from lithium to cesium

Fig. 5. Correlation of theoretical [RHF, DFT (GIAO)] predicted and

experimental obtained proton (NH omitted) and carbon chemical shifts of
4-aminobenzoic acid and Li, Na and K 4-aminobenzoates.

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

234

Table 5
)a between atoms, bonds angles and geometric aromaticity indices calculated for 4-aminobenzoates using three methods
The values of distances (A
Methods

HF/6-311CCG**

Metals

Li

Distance
1-2
2-3
3-4
4-5
5-6
1-6
1-7
7-9
7-10
10-11
9-11
4-8
8-8a
8-8b
2-2a
3-3a
5-5a
6-6a
Angles
1-2-3
2-3-4
3-4-5
4-5-6
5-6-1
2-1-6
1-7-9
1-7-10
7-9-11
7-10-11
9-11-10
2-1-7
6-1-7
1-2-2a
2-3-3a
3-4-8
4-8-8a
4-8-8b
8a-8-8b
4-5-5a

Na

Energy
Hartreeb
a
b

Li

Na

B3LYP/6-311CCG**
K

Li

Na

1.390
1.380
1.395
1.395
1.380
1.390
1.485
1.251
1.251
1.841
1.841
1.389
0.995
0.995
1.074
1.076
1.076
1.074

1.389
1.381
1.393
1.391
1.381
1.389
1.497
1.246
1.246
2.195
2.195
1.393
0.995
0.995
1.074
1.077
1.077
1.074

1.389
1.382
1.393
1.393
1.382
1.389
1.503
1.244
1.244
2.538
2.538
1.396
0.996
0.996
1.074
1.077
1.077
1.074

1.397
1.384
1.403
1.403
1.384
1.397
1.483
1.274
1.274
1.852
1.852
1.386
1.008
1.008
1.084
1.087
1.087
1.084

1.396
1.386
1.402
1.402
1.386
1.396
1.495
1.269
1.269
2.205
2.205
1.391
1.008
1.008
1.084
1.087
1.087
1.084

1.396
1.386
1.402
1.402
1.386
1.396
1.500
1.267
1.267
2.501
2.501
1.393
1.009
1.009
1.085
1.087
1.087
1.085

1.400
1.387
1.405
1.405
1.386
1.400
1.486
1.277
1.277
1.849
1.849
1.391
1.009
1.009
1.083
1.086
1.086
1.083

1.399
1.388
1.404
1.404
1.388
1.399
1.498
1.272
1.272
2.202
2.202
1.396
1.009
1.009
1.083
1.086
1.086
1.083

1.399
1.389
1.403
1.404
1.389
1.399
1.504
1.270
1.270
2.510
2.510
1.399
1.009
1.009
1.083
1.086
1.086
1.083

120.940
120.255
118.962
120.251
120.944
118.647
119.874
119.869
83.784
83.767
72.191
120.677
120.676
118.873
120.071
120.498
115.459
115.465
112.225
119.675

121.093
120.284
118.866
120.284
121.091
118.381
118.591
118.619
88.695
88.724
59.791
120.810
120.808
118.718
120.040
120.566
114.940
114.911
111.727
119.656

121.169
120.293
118.828
120.292
121.169
118.249
118.110
118.108
92.487
92.487
51.243
120.873
120.873
118.622
120.049
120.566
114.650
114.650
111.430
119.657

120.882
120.457
118.650
120.459
120.886
118.636
119.661
119.659
82.972
82.960
73.660
120.664
120.685
118.583
120.073
120.623
116.366
116.363
113.031
119.484

121.034
120.467
118.576
120.468
121.034
118.420
118.388
118.391
87.988
87.987
60.803
120.790
120.790
118.283
120.061
120.688
115.742
115.745
112.495
119.467

121.092
120.460
118.563
120.462
121.091
118.333
118.062
118.066
91.515
91.508
53.104
120.830
120.836
118.188
120.086
120.690
115.443
115.446
112.209
119.452

120.886
120.453
118.687
120.455
120.886
118.636
119.799
119.798
82.977
82.960
73.660
120.679
120.685
118.583
120.073
120.623
116.423
116.418
113.031
119.484

121.024
120.463
118.623
120.464
121.024
118.401
118.511
118.512
88.007
88.005
61.011
120.799
120.800
118.405
120.062
120.659
115.736
115.737
112.361
119.474

121.094
120.458
118.597
120.459
121.093
118.299
118.153
118.156
91.659
91.656
52.993
120.849
120.851
118.306
120.080
120.673
115.513
115.116
112.168
119.460

0.997
0.933
0.994
0.006
0
96.090

0.998
0.936
0.995
0.005
0
96.201

0.993
0.887
0.972
0.016
0.011
93.332

0.995
0.908
0.977
0.011
0.011
94.459

0.995
0.908
0.977
0.011
0.011
94.459

0.993
0.888
0.963
0.016
0.022
93.410

0.995
0.995
0.968
0.012
0.021
94.375

0.996
0.914
0.969
0.009
0.022
94.894

5.129

7.020

1.715

4.672

6.234

1.622

4.514

6.225

Geometric aromaticity indices

Aj
0.996
BAC
0.912
HOMA
0.990
GEO
0.010
EN

94.783
I6
Dipole moment
D

B3PW91/6311CCG**

2.103
K480.4

K634.8

K1072.1

K483.1

K637.8

K1075.5

K483.3

K638.1

K1075.7

Z10K10 m.
1A
1 hartreeZ2625.500 kJ/mol.

4-aminobenzoates, so the correlation between chemical shifts

of C7 atom and atomic mass, inverse of atomic mass,
electronegativity, affinity, atomic and ionic radius, ionization
and ionic potential of alkali metal was investigated. The
best correlations were obtained for atomic and ionic radius

(RZK0.996; K0.995), affinity (RZ0.982) and ionic potential

(RZ0.982) of alkali metal. The first mentioned correlation is
presented at Fig. 4.
Differences of chemical shifts in 1H and 13C NMR spectra of
alkali metal 4-aminobenzoates in comparison to

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

4-aminobenzoic acid are shown in Table 3. In the case of

studied compounds all values of protons are diamagnetically
shifted in comparison to 4-aminobenzoic acid (except of H2
and H6 for lithium salt). It indicates a decrease in intensity of
the ring current and an increase in the screening of these
protons in 4-aminobenzoates [3]. The chemical shifts of C2,
C3, C4, C5 and C6 atoms are shifted diamagnetically, but the
values for C1 and C7 are shifted to higher values comparing to
free acid. The largest changes of chemical shifts were observed
at C1 atom, it means a decrease in electronic charge density
around this nucleus and a decrease in the screening effect.
Theoretical 1H and 13C NMR spectra of lithium, sodium and
potassium salts were also obtained. Geometrical structures of
studied compounds were optimized by HF method. The GIAO
method was used for prediction of RHF (restricted Hartree
Fock) and DFT nuclear shieldings. Cheesemen recommended
these methods for studied compounds [23]. Theoretical
obtained chemical shifts of lithium, sodium and potassium
4-aminobenzoates in comparison with 4-aminobenzoic acid are
gathered in Table 4. The linear correlation between proton and
carbon RHF and DFT GIAO NMR shieldings of studied
compounds and experimental data is shown at Fig. 5. This data
show a good correlation between predicted and observed
proton and carbon chemical shifts. The correlation coefficients
amount to 0.998 and 0.997, respectively.
3.3. Calculated geometrical structure
To calculate optimized geometrical structures a few
quantum chemical methods were used: HF/6-311CCG**,
B3PW91/6-311CCG**, B3LYP/6-311CCG**. The
distances between atoms and the angels between bonds were
calculated. The atoms of molecule are numbered as Fig. 3.
Geometric aromaticity indices [24], dipole moments and
energies for 4-aminobenzoates were calculated too. The
obtained by three methods results for lithium, sodium and
potassium 4-aminobenzoates are presented in Table 5.
The studied results show that the bond distances of 7 carbon
atom and 9, 10 oxygen atoms vary in free 4-aminobenzoic acid
molecule, in which they are 1.357 and 1.211 (B3PW91),
respectively, but in the salts they are equal. It indicates about
symmetric structure of carboxylic ion. The same one we can
say about bonds of 9 and 10 oxygen atoms and atom of alkali
metal Me11. The lengths of C7O9 and C7O10 bonds slightly
decrease in the series from lithium to potassium 4-aminobenzoate, but in the case of O9Me11 and O10Me11 bonds
they, inversely, increase. The good correlation was observed
between lengths of these bonds and wavenumbers of the
bs(COOK) and bas(COOK) bands in IR spectra. Corresponding
correlation coefficients are presented at Figs. 6 and 7. The O9
Me11 bond lengths in alkali salts are near twice bigger than
suitable bonds in free acid (0.945-HF; 0.966-B391; 0.968B3LYP). The bond distances between 1 and 7 carbon atoms
distinctly increase from 4-aminobenzoic acid (1.477-HF;
1.471-B3PW91; 1.474-B3LYP) through lithium and sodium
to potassium 4-aminobenzoates. Comparing the bond lengths
of aromatic ring of studied 4-aminobenzoates and free acid

235

Fig. 6. Correlation between wavenumbers of bs(COOK) and bas(COOK) bands

in IR spectra and lengths of O9-Me11 bond.

(corresponding values of bond distances for 4-aminobenzoic

acid were previously described [1]) one can observe that the
values of them decrease in the series HOLiONaOK
4-aminobenzoates, it means an increase of delocalization and
increase of aromaticity of studied molecules. The differences
between the bonds decrease in the same order. The smallest
one, for potassium salt, amounts to 0.0110.016 according to
chosen method of calculation. The largest one, for 4-aminobenzoic acid, amounts to 0.0200.024. It indicates that
aromaticity of molecules increases along above series. The
energy shows decreasing tendency along the same series
4-aminobenzoic acidOLiONaOK 4-aminobenzoates.
This thesis is confirmed by aromaticity indices [24]: Aj
normalized function of variance of bond lengths; BACbond
alternation coefficient; HOMAabbreviation from Harmonic
Oscillator Model of Aromaticity (HOMAZ1-EN-GEO; GEOgeometric contribution to the aromaticity; ENenergetic

Fig. 7. Correlation between wavenumbers of bs(COOK) and bas(COOK) bands

in IR spectra and lengths of C7O9 bond.

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

236

Table 6
Atomic charges (e) of 4-aminobenzoates calculated by three methods
Atom position

HF/6-311CCG**

B3PW91/6311CCG**

B3LYP/6-311CCG**

Li

Na

Li

Na

Li

Na

C1
C2
C3
C4
C5
C6
C7
H2a
H3a
H5a
H6a
H8a
H8b
N8
Me11
O9
O10

1.743
K1.292
0.912
K1.249
0.912
K1.292
K0.232
0.238
0.213
0.213
0.238
0.257
0.257
K0.375
0.395
K0.468
K0.469

1.682
K1.151
0.810
K1.226
0.809
K1.153
K0.269
0.245
0.207
0.207
0.245
0.253
0.253
K0.377
0.667
K0.601
K0.601

1.491
K1.134
0.784
K1.207
0.784
K1.134
K0.362
0.235
0.208
0.208
0.235
0.252
0.252
K0.377
1.023
K0.628
K0.628

2.419
K1.465
0.988
K1.446
0.989
K1.466
K0.660
0.215
0.212
0.212
0.215
0.257
0.257
K0.284
0.187
K0.314
K0.314

2.521
K1.390
0.957
K1.486
0.957
K1.389
K0.798
0.219
0.208
0.208
0.219
0.250
0.250
K0.278
0.452
K0.449
K0.449

1.651
K1.384
0.923
K1.480
0.925
K1.384
K0.365
0.205
0.208
0.208
0.205
0.248
0.248
K0.279
1.034
K0.428
K0.428

2.012
K1.151
0.753
K1.102
0.752
K1.151
K0.511
0.187
0.165
0.165
0.187
0.243
0.243
K0.292
0.175
K0.337
K0.337

2.130
K1.078
0.729
K1.141
0.730
K1.079
K0.666
0.192
0.162
0.162
0.192
0.236
0.236
K0.286
0.413
K0.465
K0.465

1.283
K1.069
0.690
K1.114
0.690
K1.069
K0.313
0.179
0.161
0.161
0.179
0.237
0.237
K0.298
1.050
K0.503
K0.503

eZ1.6021892!10K19 C.

Fig. 8. Correlation between the differences in total charge on the carbon atoms and their isotropic shielding as result of 4-aminobenzoates formation.

Fig. 9. Correlation between the differences in atomic charge on the carbon atoms and their isotropic shielding as result of 4-aminobenzoates formation.

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

237

corresponding nuclear shielding as result of 4-aminobenzoates

formation (Fig. 8). A linear correlation between differences in
atomic charge on the each carbon atom of aromatic ring and its
nuclear shielding is also presented (Fig. 9). Comparing
differences in charge on carbon atoms and differences in
theoretically obtained nuclear shieldings the highest values
were observed on C1 carbon atom, which is situated near to
carboxylic group. However, the highest values of correlation
coefficient were obtained for C5 and C4 atoms.
A linear correlation between differences of atomic charge
on C7 atom as result of replacing H11 atom by alkali metal and
differences of chemical shifts of C7 atom in experimentally
obtained 13C NMR spectra was observed too. This dependence
is presented in Fig.10.
4. Conclusions
Fig. 10. Correlation between differences in atomic charge on the C7 carbon
atom and differences in experimental chemical shifts (C7) as result of 4aminobenzoates formation.

contribution to the aromaticity) and I6Birds indice, which

are presented in Table 5. Geometric aromaticity indices for free
4-aminobenzoic acid [1] (calculated exemplary by B3PW91
method: 0.989; 0.860; 0.962; 0.025; 0.014; 91.776; respectively) are visibly smaller then those for alkali salts.
The values of angles between CCC bonds in aromatic ring
become equalized along contrary series: potassium/
sodium/lithium salt. These results suggest that the perturbation of aromatic system of investigated molecules increases
from lithium to potassium salts. Taking into consideration data
obtained for free 4-aminobenzoic acid [1] these values of angles,
according to HF method, become equalized along the series:
benzoates of K/Na/Li/4-aminobenzoic acid. The smallest value of differences of angles is observed for free acid (2.21)
and the largest one for potassium salt (2.92). According to B3
PW 91 and B3LYP methods the series is K/Na/H/Li.
Comparing values of dipole moment for molecules of
lithium, sodium and potassium salts of 4-aminobenzoic acid
increasing tendency along the series: lithium/sodium/
potassium 4-aminobenzoates is observed. Such a value for free
acid is located between values for lithium and sodium
4-aminobenzoates.
The calculated Mulliken atomic charges on the atoms in
lithium, sodium and potassium 4-aminobenzoates molecules
calculated by HF/6-311CCG**, B3PW91/6311CCG** and
B3PLYP/6311CCG** methods are presented in Table 6. The
charges on 9 and 10 oxygen atoms in 4-aminobenzoic acid
calculated by B3PW91 method are K0.174 and K0.300,
respectively. They are different but those for alkali salts are
equal. The values of negative charge of them increase in series
H!Li!Na!K. They change similarly according to HF
method. The positive charge on C1 atom in 4-aminobenzoates
is larger then such in free acid. The charge on C7 atom in
4-aminobenzoic acid is positive, but it is negative in salts.
It is interesting to note a linear correlation between the
differences in total charges on the carbon atoms and

Spectral characteristic and calculated geometrical structure

of the alkali metal 4-aminobenzoates were investigated.
The conclusions are not clear, because the changes in
wavenumber and intensity of bands in IR and Raman spectra
are not clear in comparison to free acid. The wavenumbers of
some bands of aromatic ring in IR and Raman spectra of
4-aminobenzoates increase in comparison to 4-aminobenzoic
acid, which indicates about decrease in the perturbation of the
aromatic system (increase in aromaticity) of studied molecules.
However, the wavenumbers of the other bands decrease. The
wavenumbers of nNH2 bands in IR and nCN in IR and Raman
spectra decrease but those of bNH2 increase. Similarly
intensity of some bands decrease in the IR and Raman spectra
of salts in comparison to free acid. It could suggest that
destabilization of the electronic charge distribution of the salts
molecules increases (aromaticity decreases). Intensity of the
other bands increases or does not change in comparison to
4-aminobenzoic acid. In NMR spectra, the changes in chemical
shifts were observed too. The chemical shifts of proton NMR
for 4-aminobenzoates are changed diamagnetically in comparison to free acid. It also indicates about decreasing of
aromaticity of studied systems. The chemical shifts of carbon
atoms also decrease except of C1 and C7 atoms.
The results of previous research [2527] unambiguously
show, that 3d and 4f transition metals stabilize the aromatic
systems of many simple derivatives of benzoic acid, while
alkali and toxic heavy metals with low ionic potential, such as
Hg(I), Hg(II), Pb (II), Ag(I), perturb these structures.
Conclusions, which might be drawn from the present work,
as well as from the preceding one (regarding 1st group metal
3-aminobenzoates [5]) are ambiguous, because the ligands
studied presently are of more complex structure. Presence of
acidic (COOH group) and basic (NH2 group) centers in the
molecules of aminobenzoic acids causes a number of important
intra- and intermolecular interactions, and the formation of
supramolecular structures [15]. Breakage of the mentioned
interactions and bonds during the formation of salts and/or
complexes is accompanied by a number of additional energetic
and steric effects, which influence on the process of the
complex formation [15].

238

R. Swisocka et al. / Journal of Molecular Structure 792793 (2006) 227238

Characteristic shifts of band in IR and Raman spectra along

the metal series were also observed. A lot of bands decrease
from lithium to cesium. The changes of chemical shifts of
protons and carbons NMR spectra also occurred. The chemical
shifts of all protons and carbons (except of C1) decrease in the
series Li/Na/K/Rb/Cs. Good correlation between the
wavenumbers of the vibration bands in the IR and Raman
spectra and chemical shifts of NMR spectra for 4-aminobenzoates and ionic potential, electronegativity, atomic mass
and affinity of metals were found.
The geometrical structures were also investigated. Obtained
results show that introduction of alkali metal instead of
hydrogen in the carboxylic group causes equalization of bond
order in the carboxylic anion, what in effect increases ring
aromaticity.
The calculated parameters were compared to experimental
characteristic of studied compounds and they indicate good
linear correlation.
Acknowledgements
Presented work was supported by Bialystok Technical
University (theme no. S/IIS/24/04).
References
[1] M. Samsonowicz, T. Hrynaszkiewicz, R. Swisocka, E. Regulska,
W. Lewandowski, J. Mol. Struct. 744747 (2005) 345.
[2] W. Lewandowski, B. Dasiewicz, P. Koczon, J. Skierski, K. DobroszTeperek, R. Swisocka, L. Fuks, W. Priebe, A.P. Mazurek, J. Mol. Struct.
604 (2002) 189.
[3] P. Koczon, T. Hrynaszkiewicz, R. Swisocka, M. Samsonowicz,
W. Lewandowski, Vib. Spectrosc. 33 (2003) 215.
[4] W. Lewandowski, L. Fuks, M. Kalinowska, P. Koczon, Spectrochim.
Acta A 59 (2003) 3411.
[5] R. Swisocka, E. Regulska, M. Samsonowicz, T. Hrynaszkiewicz, W.
Lewandowski, Spectrochim. Acta A 61 (2005) 2966.

[6] E. Regulska, M. Samsonowicz, R. Swisocka, W. Lewandowski, J. Mol.

Struct. 744747 (2005) 353.
[7] C.M. Peres, R. Russ, H. Lenke, S.N. Agathos, FEMS Microbiol. Ecol. 37
(2001) 151.
[8] R.M.E. Richards, D.K.L. Xing, Int. J. Pharm. 116 (1995) 217.
[9] Z. Hu, J. Liu, L. Shen, D. Xu, Y. Xu, J. Chem. Crystallogr. 32 (2002) 525.
[10] S.I. Akberova, Biol. Bull. 29 (2002) 390.
[11] M. Masaki, Fragrance J. 26 (1998) 65.
[12] B.R. Srinivasan, S.C. Sawant, Thermochim. Acta 402 (2003) 45.
[13] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, fifth ed., Wiley, New York, USA, 1997.
[14] M.A. Zoroddu, R. Dallocchio, S. Mosca, Polyhedron 15 (1996) 277.
[15] R. Wang, M. Hong, J. Luo, L. Han, Z. Lin, R. Cao, Inorg. Chim. Acta 357
(2004) 103.
[16] G. Smith, D.E. Lynch, C.H.L. Kennard, Inorg. Chem. 35 (1996) 2711.
[17] S.J. Yun, S.K. Kang, S.S. Yun, Thermochim. Acta 331 (1999) 13.
[18] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R.
Cheeseman, V.G. Zakrzewski, J.A. Montgomery, R.E. Stratmann, J.C.
Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M. C.Strain,
O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C.
Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala,
Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B.
Foresman, J. Cioslowski, J.V. Ortiz, B.B. Stefanov, G. Liu, A. Liashenko,
P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith,
M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M.
Challacombe, P.M.W. Gill, B.G. Johnson, W. Chen, M.W. Wong, J.L.
Andres, M. Head-Gordon, E.S. Replogle and J.A. Pople, GAUSSIAN 98
(Revision A.1), Gaussian, Inc., Pittsburgh, PA, 1998.
[19] G. Versanyi, Assignments for Vibrational Spectra of 700 Benzene
Derivatives, Akademiai Kiado, Budapest, Hungary, 1973.
[20] P. Koczon, J. Cz. Dobrowolski, W. Lewandowski, A.P. Mazurek, J. Mol.
Struct. 655 (2003) 89.
[21] R. Kurpiel-Gorgol, Pol. J. Chem. 60 (1986) 749.
[22] Metody spektroskopowe i ich zastosowanie do identyfikacji zwiazkow
organicznych, in: W. Zielinski, A. Rajca (Eds.), WNT, Warszawa, 2000.
[23] E. Frish, R.D. Denington II, A. Keith, A.B. Nielsen, A.J. Holder, Gauss
View Reference Manual, Gaussian Inc., Wallingford, 2003.
[24] T.M. Krygowski, M. Cyranski, Tetrahedron 52 (1996) 1713.
[25] P. Koczon, H. Baranska, K. Bajdor, W. Lewandowski, Microchim. Acta
14 (1997) 165.
[26] W. Lewandowski, H. Baranska, Vib. Spectrosc. 2 (1991) 211.
[27] W. Lewandowski, H. Baranska, P. Moscibroda, J. Raman Spectrosc. 24
(1993) 819.