An analysis of structural, spectroscopic signatures, reactivity and anti-bacterial study of synthetized 4-chloro-3-sulfamoylbenzoic acid

Article abstract of DOI:10.1016/j.molstruc.2019.127176

In the current study, 4-chloro-3-sulfamoylbenzoic acid (CSBA) has been synthetized from 4-chloro-3-sulfamoylbenzoate. The explicit structure of the titled compound was authenticated by single crystal X-ray diffraction, vibrational and electronic spectroscopic signatures. The unambiguous structure in solid state was confirmed by single crystal X-ray diffraction technique and Hirshfeld surface analysis. The X-ray analysis reflect that the titled compound was crystallized in monoclinic crystal system with P2₁/c space group a = 4.9576(3) ?, b = 6.0315(3) ?, c = 29.8923(16) ?, β = 92.628(3)°, volume = 892.89(8) ?³ and Z = 4. In the solid phase structure, the molecules were interconnected by O–H?O and N–H?O hydrogen bonds and C–H?O intermolecular interactions forming a two dimensional sheet. These contacts were further envisaged by 3D-hirshfeld surface studies (d_norm) and 2D-fingerprint plots; which suggested that the O?H(39.9percent) contact contributed the highest to the surface. The molecular, vibrational and electronic properties of titled compound investigated by using quantum chemical calculations at DFT/B3LYP/6-311 + G(d,p) level of theory. An analysis each fundamental vibrational mode was performed with the help of potential energy distribution (PED) using VEDA4 program. In addition, frontier orbital analysis, global reactivity parameters, natural bond order (NBO) analysis, non-linear optical (NLO) calculation and molecular electrostatic potential (MEP) analysis were performed by same method in same phase. Bond dissociation energies have been calculated for all single acyclic bonds in order to study autoxidation mechanism and degradation properties of the present investigated molecule. The titled compound displayed moderate anti-bacterial activity against gram-positive and gram-negative bacteria.

Full text of DOI:10.1016/j.molstruc.2019.127176

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An analysis of structural, spectroscopic signatures, reactivity and anti-bacterial study
of synthetized 4-chloro-3-sulfamoylbenzoic acid
Ch Kavitha, K. Narendra, A. Ratnakar, Nuthalapati Poojith, C. Sampath, Subrata
Banik, P.A. Suchetan, Krishna Murthy Potla, Nuthalapati Venkatasubba Naidu
PII:
S0022-2860(19)31285-2
DOI:
https://doi.org/10.1016/j.molstruc.2019.127176
MOLSTR 127176
Reference:
To appear in: Journal of Molecular Structure
Received Date: 24 June 2019
Revised Date: 19 September 2019
Accepted Date: 1 October 2019
Please cite this article as: C. Kavitha, K. Narendra, A. Ratnakar, N. Poojith, C. Sampath, S. Banik, P.A.
Suchetan, K.M. Potla, N.V. Naidu, An analysis of structural, spectroscopic signatures, reactivity and anti-
bacterial study of synthetized 4-chloro-3-sulfamoylbenzoic acid, Journal of Molecular Structure (2019),
doi: https://doi.org/10.1016/j.molstruc.2019.127176.
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An analysis of structural, spectroscopic signatures, reactivity and anti-bacterial study of
synthetized 4-chloro-3-sulfamoylbenzoic acid
Ch. Kavithaa, K. Narendrab, A. Ratnakara, Nuthalapati Poojithc, C. Sampathd, Subrata Banike,
P.A. Suchetanf, Krishna Murthy Potlag*, Nuthalapati Venkatasubba Naiduh
aDepartment of Chemistry, Velagapudi Ramakrishna Siddhartha Engineering College,
Vijayawada-520007, A.P., India.
bDepartment of Physics, Velagapudi Ramakrishna Siddhartha Engineering College, Vijayawada
-520007, A.P., India.
cSri Ramachandra Institute of Higher Education and Research, Ramachandra Nagar, Porur,
Chennai-600 116.
dDepartment of Chemistry, B.M.S. College of Engineering, Bull Temple Road, Bengaluru-560
019, India
eSchool of Chemistry, University of Hyderabad, Hyderabad, 500046, India
fDepartment of Studies and Research in Chemistry, University College of Science, Tumkur
University, Tumkur-572 103, Karnataka, India.
gDepartment of Chemistry, Bapatla Engineering College, Acharya Nagarjuna University Post
Graduate Research Centre, Bapatla-522 102, A.P., India.
hDepartment of Chemistry, Sri Venkateswara University, Tirupati-517 502.
*Corresponding author: Dr. Krishna Murthy Potla (krishnamurthypotla@gmail.com)
Abstract
In the current study, 4-chloro-3-sulfamoylbenzoic acid (CSBA) has been synthetized from 4-
chloro-3-sulfamoylbenzoate. The explicit structure of the titled compound was authenticated by
single crystal X-ray diffraction, vibrational and electronic spectroscopic signatures. The
unambiguous structure in solid state was confirmed by single crystal X-ray diffraction technique
and Hirshfeld surface analysis. The X-ray analysis reflect that the titled compound was
crystallized in monoclinic crystal system with P21/c space group a = 4.9576(3) Å, b = 6.0315(3)
Å, c = 29.8923(16) Å, β = 92.628(3)°, volume = 892.89(8) Å3 and Z = 4. In the solid phase
structure, the molecules were interconnected by O-H…O and N-H…O hydrogen bonds and C-
H…O intermolecular interactions forming a two dimensional sheet. These contacts were further

envisaged by 3D-hirshfeld surface studies (dnorm) and 2D-fingerprint plots; which suggested that
the O---H(39.9%) contact contributed the highest to the surface. The molecular, vibrational and
electronic properties of titled compound investigated by using quantum chemical calculations at
DFT/B3LYP/6-311+G(d,p) level of theory. An analysis each fundamental vibrational mode was
performed with the help of potential energy distribution (PED) using VEDA4 program. In
addition, frontier orbital analysis, global reactivity parameters, natural bond order (NBO)
analysis, non-linear optical (NLO) calculation and molecular electrostatic potential (MEP)
analysis were performed by same method in same phase. Bond dissociation energies have been
calculated for all single acyclic bonds in order to study autoxidation mechanism and degradation
properties of the present investigated molecule. The titled compound displayed moderate anti-
bacterial activity against gram-positive and gram-negative bacteria.
Key words: sulfamoylbenzoic acid; BDE; Fukui reactive index; SCXRD studies; anti-bacterial
studies
1. Introduction
Sulfa-drugs (sulfonamides) are promising chemotherapeutic agents containing SO2-NH group as
a key functional group. The findings of sulfonamides is an important milestone event in the
human chemotherapeutic account. Sulfonamides and their derivatives have attracted intense
interest due to their useful biological and pharmacological properties, such as Alzheimer’s [1],
HIV [2], cancer [3, 4], rheumatoid arthritis [5], anti-inflammatory [6], carbonic anhydrase
inhibitor [7], insecticidal [8], anti-protozoal [9], anti-fungal [10] and anti-bacterial [11]. Besides
pharmaceutical applications, sulfonamides are also used as reagents in analytical chemistry for
concentration, separation, selective qualitative and quantitative determination of the 3d transition
metal cations [12-14].
Sulfonamide compounds have been studied extensively and numerous experimental and
computational reports. Gowda et al., [15] reported Infrared and NMR spectra of 4-
chlorobenzenesulfonamide
(I),
4-bromobenzenesulfonamide
(II),
4-
and
4-
fluorobenzenesulfonamide (III), and they have also analyzed X-ray crystallographic structure of
these aryl sulfonamides [16]. Karabacak et al., [17] analyzed theoretical investigation on the
molecular structure, infrared, Raman and NMR spectra of para-halogen benzene sulfonamides,
4-X-C6H4SO2NH2 (X=Cl, Br or F).

K. Govindarasu et al., [18] reported Synthesis, structural, spectroscopic studies, NBO analysis,
NLO and HOMO-LUMO of N-phenyl benzene sulfonamide by experimental and theoretical
approaches. S. Murugavel et al., [19, 20] analyzed synthesis, crystal structure analysis, spectral
investigations, DFT computations, biological activities and molecular docking studies of
sulfonamide derivative compounds. Vega-Hissi et al., carried out detailed theoretical studies on
sulphanilamide and its derivatives within the Hartree-Fock and density functional approaches
[21].
By keeping in view of the importance and applications of sulfonamide moieties, we have
accomplished synthesis, Hirshfeld surface analysis and experimental spectroscopic
characterization of the 4-chloro-3-sulfamoylbenzoic acid (CSBA) molecule with computational
study by DFT. To the best of our knowledge, there were no reports on crystal structure analysis,
Hirshfeld surface analysis and computational studies. The synthetized compound was
distinctively characterized by SCXRD, FT-IR and FT-Raman spectroscopic techniques. Spectral
data were also computed within DFT method in order to validate the used level of theory.
Computational studies within DFT method have demonstrated to be an effective tool for the
analysis of physical and chemical properties of various organic compounds [22-25] and in this
study, we used it to analyze both the global reactivity parameters and local quantum-molecular
descriptors of the molecule. Furthermore, Fukui functions, bond dissociation energy calculations
and anti-bacterial activity studies were performed for the synthetized molecule. In this
contribution, we herein disclose an analysis of structural, spectroscopic signatures, reactivity and
anti-bacterial study of synthetized 4-chloro-3-sulfamoylbenzoic acid.
2. Experimental methods
2.1. General
All chemical and solvents used for the synthesis were procured from commercial source. Fourier
transformed Infrared (FT-IR) spectrum (Fig. 1.) was recorded in Perkin Elmer Spectrum 1 FT-IR
spectrometer scan range from 450-4000 cm-1 with resolution 1.0 cm-1 by KBr pellets method.
Fourier transformed Raman spectrum (Fig. 2.) was recorded in Bruker 27: Standalone FT-Raman
spectrometer by using Nd:YAG laser source (wavelength: 1064 nm) with 2.0 cm-1 resolution in
the range 50-4000 cm-1. 1H-NMR spectrum was recorded in Bruker 400MHz spectrometer using
DMSO-d6 as a solvent and tetramethylsilane (TMS) as an internal standard.
2.2. Synthesis of 4-chloro-3-sulfamoylbenzoic acid

To a 50 mL round-bottomed flask, methyl-4-chloro-3-sulfamoylbenzoate (800 mg, 3.20 mmol)
was dissolved in tetrahydrofuran (8 mL) and the reaction mixture was cooled to 0ºC. To this
reaction mixture, an aqueous solution of 10 % lithium hydroxide (223 mg, 9.6 mmol) was added
and stirred for 2 h at room temperature. After completion of the reaction, the reaction mixture
was evaporated under reduced pressure and the aqueous layer was acidified with 6N
hydrochloric acid. Then the precipitate was filtered and dried under vacuum to afford a white
solid (610 mg, yield: 81.3 %) 4-chloro-3-sulfamoylbenzoic acid (Scheme -1). Recrystallization
has been carried out in ethyl acetate: dry ethyl ether (3:1) solution by slow evaporation crystal
growth technique at ambient temperature.
1H-NMR (400 MHz, DMSO-d6) δ: 13.60 (s, 1H, COOH), 8.51 (d, J = 2.0 Hz, 1H, Ph-H), 8.10
(dd, J = 8.2, 2.1 Hz, 1H, Ph-H), 7.82 (s, 2H, SO2NH2), 7.79 (d, J = 8.3 Hz, 1H, Ph-H).
2.3.X-ray crystallography studies
A colourless and needle shaped single crystal of the titled compound, with dimensions of 0.24
mm × 0.22 mm × 0.19 mm was selected and mounted on a Bruker APEX-II CCD diffractometer
with monochromated MoKα radiation (λ = 0.71073 Ǻ) at 296(2) K. The data was processed with
SAINT and corrected for absorption using SADABS [26]. The structure was solved by direct
method using the program SHELXL [27] and was refined by full-matrix least squares technique
on F2 using anisotropic displacement parameters for all non-hydrogen atoms. The carbon-bound
H atoms were placed in calculated positions (Carom-H= 0.93 Å and Cmethylene-H= 0.97 Å) and
were included in the refinement in the riding-model approximation, with Uiso (H) set to 1.2Ueq
(C). The oxygen and nitrogen bound H atoms were located from difference-Fourier maps and
refined as riding: O-H = 0.82 Å and N-H = 0.86 Å.
2.4. Computational tools
The quantum chemical calculations for 4-chloro-3-sulfamoylbenzoic acid were performed using
density functional theory with three parameter hybrid functional B3LYP with 6-311+(d,p) basis
set, and in calculating nonlinear optical properties we use CAM-B3LYP/6-311+(d). All the
calculations are performed using Gaussian09 software [28] and the examination of inputs/results
were performed through GaussView [29]. Initial geometry of the investigated compound was
extracted from single crystal X-ray coordinates. The computed wave numbers were scaled with
0.9613 to attain a good correlation with experimental wave numbers [30]. In addition, frontier

orbital analysis, global reactivity descriptors, NBO analysis, NLO calculations, BDE
calculations, MEP analysis and atomic charge analysis were performed by same method.
2.5. Hirshfeld surface analysis
3D-Hirshfeld surfaces [31-33] associated 2D-finger print analysis [34-36] was carried out for
CSBA compound by using powerful graphical tool CrystalExplorer3.1 software [37], which
accept CIF as the input file.
3. Results and discussion
3.1. Crystal structure and Hirshfeld surface analysis
The ORTEP diagram for the CSBA compound was given in Fig. 3, the interactions and packing
of molecules in the crystal lattice was shown in Fig. 4(a) and Fig. 4(b). The crystallographic data
and refinement parameters were summarized in Table 1. Geometric parameters for hydrogen
bonds and other intermolecular contacts (Å, °) operating in the crystal structures were listed in
Table 2.
The crystal structure of the titled compound can be explained in terms of the supramolecular
aggregation of the molecules first via strong hydrogen bonds followed by moderate or weaker
intermolecular interactions. The molecules are first interconnected via strong O-H…O hydrogen
bonds, namely O5-H18…O3, to form a R2 (8) dimeric motif. These inversion-related dimers are
2
extended into a one dimensional ribbon, wherein, the equivalent molecules are connected by two
anti-parallel C(6) chains of N4-H19…O7 hydrogen bonds. The adjacent ribbons are further
interlinked via another N-H…O hydrogen bond, namely N4-H20…O7. The C(6) chains of N4-
H20…O7 hydrogen bonds connect the 2-fold related molecules in the adjacent ribbons resulting
in a complex zig-zag two dimensional architecture. A complex three dimensional grid like
architecture is ensued via C15-H16…O5 interactions that interlink the molecules forming C(6)
chains. Thus, the two N-H…O hydrogen bonds and the C-H…O interactions have structure
directing characteristics- the former two extending a zero dimensional architecture to a two
dimensional structure, while, the later extending the two dimensional structure into a three
dimensional one.
The Hirshfeld surfaces for CSBA compound illustrated in Fig. 5(a), showing surfaces that have
been mapped over a dnorm (1) shape index (2) curvedness (3) and fragment patch (4) range of -
0.7311 to 1.0450 Å, -1.00 to 1.00 Å, -4.00 to 0.400 Å and 0.00 to 12.00 Å, respectively. In Fig.
5(b), the bright red spots are the hydrogen bonding centers O5-H18…O3, N4-H19…O7 and N4-

H20…O7 labeled as A, B and C, respectively. The other region which was pale red in colour
showed weak C15-H16…O5 intermolecular interaction marked as D on dnorm surface.
The relative contribution of the various interactions on the Hirshfeld surface was accounted for
the CSBA compound by fingerprint analysis. The fingerprint analysis reflection shown that the
O---H contacts can account for about 39.9 % of the total Hirshfeld surface area and these
interactions appeared as two distinct spikes of almost equal length (see in Fig.5(c)). The upper
spikes corresponds to donor spikes (hydrogen atom of acid group interact with oxygen atom of
acid group and hydrogen atom of sulfonamide group interact with oxygen atom of sulfonamide
group), while lower spikes corresponds to acceptor spikes (oxygen atom of acid group interact
with hydrogen atom of acid group, oxygen atom of sulfonamide group interact with hydrogen
atom of sulfonamide group and oxygen atom of acid group interact with hydrogen atom of
benzene ring); the remaining contribution were mostly due to H---H (16.9%), Cl---O (7.4%), Cl-
--C (4.7%) and C---C (3.5%) interactions, with only minor contribution from other O---O(1.7
%), Cl---N(1.7 %) and N---H (0.9 %) interactions.
3.2.Optimization of geometry
The optimization of CSBA compound (Fig. 3) performed at DFT/B3LYP/6-311G+(d,p) level of
theory. The optimized structures for CSBA compound possess C1point group with ground state
energy -1484.5762 a.u. Selected geometrical parameters bond length (Å), bond angle (º) and
torsion angle (º) of CSBA compound were outlined in Table 3. The C-C bond lengths
(DFT/XRD) of aromatic ring in the titled compound were in the range 1.3875-1.3998/1.378-
1.396 Å and for the benzene ring the C-C bond length was 1.3993 Å [38]. The bond length of
sulfonamide group were S2-O7 = 1.45235/1.4374 Å, S2-O6 = 1.45598/1.4258 Å, S2-N4 =
1.66847/1.5884 Å, S2-C12 = 1.82275/ 1.78 Å are close to the reported values S2-O7 = 1.457/1.435
Å, S2-O6 = 1.456/1.423 Å, S2-N4 = 1.706/1.636 Å, S2-C12 = 1.794/1.756 Å [39]. For the
carboxylic group (DFT/XRD) C8-O3 = 1.20772/1.252 Å, C8-O5 = 1.35213/1.273 Å, O5-H18
=
0.96872/0.8185 Å. Murthy et al. [40] reported (DFT/XRD) C8-O3 = 1.201/1.208 Å, C8-O5 =
1.359/1.304 Å, O5-H18 = 0.96749/0.886 Å. The C17-Cl1 bond length (DFT/XRD) is
1.75083/1.720 Å which was in good agreement with reported values [41]. At C17, the bond angle
(DFT/XRD) C12-C17-C15 was 120.3/120.1º and this enhancement of bond angle from 120º was
due to the presence of electronegative atom Cl1. At C8 position the bond angles were, C9-C8-O5
112.8/117.6º, O3-C8-O5 122.8/123.2º, C9-C8-O3 124.3/119.1º and the asymmetry in these angles

unveil the interaction between carbonyl groups and hydroxyl groups and thereby, supporting the
existence of intermolecular hydrogen between two acid groups of CSBA compound. The
sulfonyl bound benzene (C10-C12-C17) ring also appears to be a little distorted because of the SO2
group substituted at C12 position seen from the bond angle C10-C12-C17 (119.4º by DFT/XRD)
value which was lesser than typical hexagonal angle of 120º.
3.3.Vibrational analysis
The calculated (scaled) wave numbers, experimental IR, Raman bands and assignments were
given in Table 4. The carboxylic group was characterized by the OH stretch, C=O stretch and
OH out-of-plane deformation and by the C-O stretch and OH in-plane deformation. Wherein, the
OH stretching mode showed a band at 3623 cm-1 theoretically with IR intensity 125.1003,
Raman activity 157.5832 and a PED of 100 %. For the titled compound, carboxyl group C=O
stretching vibrational mode displayed a band at 1721 cm-1 (IR), 1720 cm-1 (Raman), 1722 cm-1
(DFT) with IR intensity 423.2576, Raman activity 138.0385 and a PED of 84 % which was
expected in the region 1750-1600 cm-1 [42,43]. The C=O in-plane deformations were expected in
the region 625±70 cm-1 [42]. The bands at 676, 641 cm-1 in the IR spectrum, 675 cm-1 in the
Raman spectrum and 674, 646 cm-1 (DFT) were assigned as C=O in-plane deformation modes.
The O-H in-plane deformation, coupled to the C=O stretching mode was expected in the region
1390±55 cm-1 [44], and the band at 1313 cm-1 in the IR spectrum, 1310 cm-1 in the Raman
spectrum and 1315 cm-1 (DFT) was assigned to the stretching vibration of the O5-H18 group.
The vibration modes associated with NH2 group were expected in the regions, 3300-3540 cm-1
(stretching), 1580-1640 cm-1, 1100-1300 cm-1 and 585-710 cm-1 (deformation modes)
respectively [42]. The NH2 group asymmetric stretching mode assigned to 3401 cm-1 (IR), 3403
cm-1 (Raman), 3495 cm-1 (DFT) with 44.9905 IR intensity, 28.6368 Raman activity and a PED
of 50 % (mode no 2) and symmetric stretching mode assigned at 3281 cm-1 (IR), 3279 cm-1
(Raman), 3383 cm-1 (DFT) with 32.8958 IR intensity, 91.3757 Raman activity and a PED of 50
% (mode no 3). The difference in calculated and experimental N-H vibrational values were 94
(IR spectrum), 102 (Raman spectrum) owing to N-H---O interactions in solid state. For the
CSBA compound, NH2 group deformation modes were assigned for 1042, 587 cm-1 (IR), 1518,
1043, 585 cm-1 (Raman), 1520, 1041, 587 cm-1 (DFT), which were in concordance with reported
values.

For the CSBA compound, the bands at 1284 cm-1 (IR), 1285 cm-1 (Raman), 1286cm-1 (DFT) and
1090, 1072 cm-1 (Raman), 1090, 1071 cm-1 (DFT) were assigned as asymmetric and symmetric
stretching vibrational mode of SO2 group, which was expected in the region 1330-1295 cm-1 and
1150-1125 cm-1, respectively [42]. The deformation modes of SO2 group were expected in the
regions, scissoring 560±40 cm-1, wagging 500±55 cm-1 and twisting 440±50 cm-1 [42]. These
modes were observed at 514, 458, 430, 389 cm-1 (experimentally) and calculated at 513, 460,
432, 393 cm-1 respectively.
The stretching vibrational modes of SN group assigns to 785 cm-1 in the Raman spectrum and at
782 cm-1 theoretically and with a PED of 56 % as expected [42]. The mode calculated at 825 cm-
1
with 74.4512 IR intensity, 18.1962 Raman activity and a PED of 15 % was assigned for CS
stretching vibrational mode of CSBA compound as expected [42]. In the present case, the band
at 548 cm-1 in the IR spectrum, 551 cm-1 in the Raman spectrum and 550 cm-1 (DFT) with IR
intensity 45.1653, Raman activity 2.1073 and a PED of 17 % was assigned for C-Cl stretching
mode which was expected in the region 710-505 cm-1 [42].
In the poly substituted aromatic rings, the C-H stretching modes showed absorbance between
3000-3100 cm-1 [45, 46] and DFT calculation gives these modes at 3096, 3086, 3073 cm-1 and
experimentally modes were observed at 3093, 3072 cm-1 in the IR spectrum, 3084 cm-1 in the
Raman spectrum. The aromatic ring stretching modes were calculated in the range 1562-1119
cm-1 and experimentally modes were observed in the range 1563-116 cm-1 as expected [42].
Previous literature [40], the ring breathing mode of 1,2,4 substituted phenyl ring is assigned at
1003 cm-1 (DFT) with PED 27 % with moderate Raman activity and low IR activity. The in-
plane and out-of-plane CH deformation bands were expected in the range 1000-1300 cm-1 and
750-1000cm-1, respectively [42] and for the CSBA compound, these modes were observed at
1352, 1145, 1115 cm-1 (IR), 1351, 1116 cm-1 (Raman), 1354, 1230, 1155, 1119 cm-1 (DFT) (in-
plane deformation), 832, 745 (IR), 833, 747 cm-1 (Raman), 956, 831, 749 cm-1 (DFT) (out-of-
plane deformation).
3.4.Natural bond orbital (NBO) analysis
The natural bond orbital (NBO) analysis were performed using NBO 3.1 program [47] as
executed in the Gaussian09 program at the DFT/B3LYP/6-311+G(d,p) method, which propose a
suitable basis for examining the hyper conjugative interactions. The NBO method transforms
delocalized molecular orbitals (MO) into a set of orbitals that are localized over the bonds as

bonding orbitals (σ, π), anti-bonding orbitals (σ*, π*), and effective lone pairs and higher energy
Rydberg orbitals on atoms [48]. From a second order perturbation theory, the stabilization
energy due to electron delocalization over the NBOs or hyperconjugation effect is obtained as
ꢇ
ꢂ ꢄ(ꢅ,ꢆ)
ꢃ
ꢀ(ꢁ)
=
(1)
ꢈ ꢉꢈ
ꢃ
ꢊ
Here, ꢋ and ꢋꢅ are the energies of jth and ith NBO, called as the donor and acceptor orbitals,
ꢆ
respectively for a hyperconjugation. ꢌ(ꢍ, ꢎ) and ꢏꢆ are the elements of off-diagonal Fock-matrix
between jth and ith NBOs, and electron population on jth orbital, respectively [48-50]. The large
E(2) values show the intensive interaction between electron-donors and electron-acceptors, and
the extent of conjugation of the entire system.
Second order interactions obtained by natural bond orbital analysis were tabulated in Table 5 and
Table 6. We report only those interactions that has stabilization energies (E(2)) more than 10
kcal/mol. The π electrons delocalization between these bonds are evident from the E(2) values of
electron donation from bonding π(C9-C13) orbitals to anti-bonding π*(O3-C8), π*(C10-C12)
and π*(C15-C17) orbitals, 21.28, 25.78 and 20.33 kcal/mol, respectively. There is electron
delocalization between the π and π* orbitals of these four bonds, and the higher values of
stabilization energies indicate that. We find large hyper-conjugation stabilization (E(2) = 47.46
kcal/mol) due to donation of lone pair of O5 (LP(2)) to the π*(O3-C8) orbital. This is expected
due to resonance effect within the acid group. Such large value of E(2) comes from strong overlap
between the lone pair of O5 atom and π*(O3-C8) through the off-diagonal Fock-matrix elements
(as large as 0.115), and large electron density of the lone pair NBO (1.81825) of oxygen. We do
not find any significant hyperconjugation that involves NBOs with atomic orbitals from Cl,
except donation from a lone pair of Cl (LP(2)) to π*(C15-C17). Corresponding E(2) is 10.86
kcal/mol, and it comes from small energy difference and a moderate Fock-matrix element value.
There are moderate stabilization energies due to electron delocalization within the SO2NH2 as
can be seen from the Table 5 and 6. However, this group does not have any significant
participation with the phenyl ring due to large energies of NBOs that involve the atomic orbital
of sulphur. Thus, a π electron rich -COOH group is capable of donating electrons to the benzene
ring and highly electronegative -Cl group can push electron towards it. The para-positioning of
these two ‘push-pull’ groups make the molecule a potential candidate for optical material.
3.5.NLO properties

The NLO materials have key applications in the field photonic devices, optoelectronics,
frequency mixing, dynamic image processing and second harmonic wave generation [51-53]. In
continuation of our earlier studies [54-69], in the present study, total dipole moment (ꢀ),
anisotropy of the polarizability (∆α), average linear polarizibility (<α>), and second-order
hyperpolarizibilitiy (γ) calculations were performed at DFT/CAM-B3LYP/6-311G+(d) level of
theory in the case static and results were listed in Tables 7 and 8. A study was done with the
asymmetric unit and the unit cell, the results with the unit cell are better than the asymmetric unit
as can be seen in Table 8. In this case we will work with the results of Table 8 divided by 4,
which is the number of asymmetric units of the unit cell. The total dipole moment and average
linear polarizability of the titled compound were 4.48 Debye and 18.95x10-24 esu. For the CSBA
compound, the average second-order hyperpolarizibilitiy (<γ>) was calculated and found to be
15.01х10-36 esu. Thus we have found that the total dipole moment of the CSBA molecule is
approximately 3.27 times greater than that of Urea and the second hyperpolarizability is 3.62
times greater than that of Urea [70]. Due to a load shift for group SO2, as can be seen in Fig. 6 of
the Potential Map, we can say that the z direction has a larger contribution, see αzz and γzzzz
.
3.6.Local reactivity calculations (Molecular electrostatic potential and Fukui functions)
Identification of molecular reactive sites (electrophilic and nucleophilic attack) as well as
hydrogen-bonding interactions [71,72] of the CSBA compound has been done by molecular
electrostatic potential quantum molecular descriptor is related to the electronic density and
visualized by rainbow color scheme (red-white-blue). Molecular electrostatic potential for the
CSBA compound depicted in Fig. 6 was calculated at B3LYP/6-311+G(d, p) level of theory.
Minimal MEP values (V(r) < -6.530 a.u.) and were in near vicinities of deprotonated oxygen
atoms, designating these locations possibly sensitive towards electrophilic attacks. MEP has the
maximal values (V(r) >6.530 a.u.) precisely at protonated atoms of oxygen and nitrogen
designating these locations as probably sensitive nucleophilic electrophilic attacks. The obtained
MEP results would help in understanding intermolecular hydrogen bond O5-H18…O3, C15-
H16…O5, N4-H19…O7 and N4-H20…O7 which was obtained from SCXRD analysis.
The chemical reactivities of atoms in the molecule were calculated using local reactivity
descriptor, Fukui functions (FF) [73], derived from conceptual density functional theory [73]. It
was defined by the change of electron density at a given point ρ(r) when an electron was
added/subtracted to a molecule. Thus, it was used as a tool to identify the nucleophilic,

electrophilic and radical attack center in a molecule. Equating the electron charge on an atom in
the molecule (q) to the electron density of the atom, three different types of FFs were defined to
identify which atom should be more responsive towards the nucleophilic, electrophilic and
radical reactions [74, 75].
ꢑ
(
)
ꢐ = [ꢏ ꢒ + 1 − ꢏ(ꢒ)]; for a nucleophilic attack,
(2)
(3)
(4)
ꢉ
( )
ꢐ = [ꢏ ꢒ − ꢏ(ꢒ − 1)]; for a electrophilic attack,
ꢓ
[ (
)
(
)ꢔ
ꢐ = ꢏ ꢒ + 1 − ꢏ ꢒ − 1 /2; for a radical attack
Different types of wave function analysis were available to obtain the charge (q). We use
Hirshfeld population analysis to calculate the FF. The Fukui reactive indices were given in Table
9. Understandably, the Chlorine atom has the highest value of all the three indexes, since both
HOMO and LUMO has contribution from p-orbitals of Chlorine atom. Similar argument holds
for the higher values of f+, f-, and f0 of O3 oxygen. Among the carbon atoms, the carbon to which
Chlorine atom was attached and the carboxylic carbon (C8) were found to be effective sites for
nucleophilic attack. The f+ values for these two centers were 0.087 and 0.080 respectively. The
C9 to which the carboxylic group was attached and emerged to be the most electrophilic carbon
center (f- value is 0.095). The C17 carbon has the highest f0 value among the entire carbon
centers, as expected because of high electronegative Chlorine attached to it.
3.7.Frontier Molecular Orbitals Analysis
The computation of the molecular orbitals, particularly the highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO) is an important tool to analyze the
molecular properties and reactivities. The difference between the energies of these two orbitals,
the HOMO-LUMO gap, i.e. the band gap (∆E) is directly related to the chemical stability of a
molecule, its chemical properties, spectroscopic properties and other NLO properties. From
Koopmans’ theory, the ionization potential of a molecule is equal to the negative of HOMO
energy (EHOMO), and its electron affinity is equal to negative of LUMO energy (ELUMO).
ꢕ = −ꢀꢖꢗꢘꢗ and ꢙ = −ꢀꢚꢛꢘꢗ.
(5)
Relations with the ꢀꢖꢗꢘꢗ and ꢀꢚꢛꢘꢗ and ∆E have been established to calculate chemical
properties like electronegativity(χ), global hardness(η), chemical softness(ν), chemical
potential(ꢀ), electrophilic index (ω) using conceptual density functional theory [75]. Unlike the

local reactivity indexes (f+, f- and f0) that gives the account of possible reactive site of a molecule,
these quantities enable us to understand the inertness and reactivity of a molecules as whole
towards chemical reactions, and this known as global reactivity parameters. These quantities are
calculated though the following equations [75].
ꢝ
ꢜ = ꢝꢁ ꢕ + ꢙ = ꢁ ꢀꢖꢗꢘꢗ + ꢀꢚꢛꢘꢗ
(6)
(7)
(8)
(
)
(
)
ꢞ = ꢝꢁ ꢀꢚꢛꢘꢗ − ꢀꢖꢗꢘꢗ
(
)
ꢟ = − ꢜ = − ꢝꢁ ꢀꢖꢗꢘꢗ + ꢀꢚꢛꢘꢗ
(
)
ꢠ = 1/ η
(9)
ω = μ2/2η
(10)
The pictorial representation of frontier orbitals for the titled molecule is shown in Fig. 7. HOMO
(MO 60, -7.9556 eV) was localized over whole molecule other than acid group and LUMO (MO
61, -2.5730 eV) was spread over whole molecule other than amine group and this reflect that
there was a charge transfer from amine group to acid group and energy gap between frontier
orbitals is 5.3826 eV. The global reactivity parameters for present titled molecule are: ionization
potential I = 7.9556 eV, electron affinity A = 2.5730 eV, electronegativity χ = 5.2643 eV, global
hardness η = 2.6913 eV, chemical potential µ = 5.2643 eV, Chemical softness ν = 0.3715 eV and
electrophilicity index ω = 5.1486 eV [76, 77].
Again, within the MO theory, the energy of electronic transition in the UV range is estimated by the
HOMO-LUMO energy gap, or the band gap. The oscillator strength is related to the dipole transition
matrix elements between HOMO and LUMO. The relation between the oscillator strength and
transition energy and NLO properties have been established in the literature [78]. When a crystal is
exposed to an oscillating electric field through radiation, the field perturbed the electronic distribution.
The perturbed electronic state can be expressed as a linear sum of all unperturbed complete set of
states. Consequently, the tensor for the frequency dependent NLO properties can be expressed in
terms of dipole transition matrix elements between the unperturbed ground state the excited states. We
note that this principle is used to calculate the NLO properties in so-called sum-over-state (SOS)
method [79]. The detail equation relating the NLO properties and oscillator strength is given in
reference 79.
The sketch of computed UV-Visible spectrum represented in Fig. S1 and Fig. S2. The
calculation is done in vacuum using optimized geometry from DFT/B3LYP/6311+G(d,p). The

electronic absorption spectra of title compound show an electronic absorption band with maxima
at λmax = 252 nm, which is good in agreement with theoretical value (λmax at 245 nm) and this
excitation corresponds to transition from highest occupied molecular orbitals (HOMO) and
lowest molecular orbitals (LUMO). The absorption wavelength λ (nm), excitation energies E
(eV) and oscillator strengths (f) for the CSBA molecule computed by same method and results
are listed in Table S1.
3.8.Mulliken atomic charge analysis
The Mulliken atomic charge calculations [80] of the CSBA compound performed at
DFT/B3LYP method by using 6-311+G(d,p) basic set. From the analysis, it indicates that
hydrogen atoms showed positive atomic charges in the range 0.162 to 0.208 a.u., but H18
(0.289), H19 (0.283) and H20 (0.298) atom possess more positive atomic charge value
proportional to other hydrogen atoms and were acidic in nature. Due to the presence of more
negative atomic charges values on nitrogen atom N4 (-0.485 a.u.) and oxygen atoms O3 (-0.300
a.u.), O5 (-0.219) and O7 (-0.078) net positive atomic charge value on hydrogen atom H18
(0.289), H19 (0.283) and H20 (0.298) may support the formation of hydrogen bond interactions in
the solid state.
3.9. Sensitivity towards autoxidation
Predicting shelf life of organic molecules is of importance for practical applications. In these
regards it is very important to estimate to what extent organic molecule of interest is sensitive
towards the autoxidation mechanism. The dissociation energies for the hydrogen abstraction (H-
BDE) of the benzene moiety have been correlated with sensitivity towards autoxidation and the
relevant interval of H-BDE values indicating sensitivity towards autoxidation has been
determined [81-84]. The importance of H-BDE parameter for biochemical processes has been
also established. Namely, it has been demonstrated that the breaking of C-H bonds is very
important for the phase I drug metabolism [85]. Another important aspect of applicability of H-
BDE parameter is environmental protection and the area of forced degradation. One of the most
important mechanisms for degradation of organic pollutants, and especially of pharmaceutical
molecules, is oxidation [86]. Therefore, considering the importance of this parameter, we have
used it in order to additionally investigate local reactivity of CSBA molecule. H-BDE values of
CSBA have been presented in Fig. 8.

It has been established so far that the relevant interval of H-BDE values that indicate sensitivity
towards autoxidation is between 70 and 90 kcal/mol [83,84]. Results obtained in this study for
H-BDE parameter indicate that CSBA molecule has no H-BDE values that would indicate its
sensitivity towards autoxidation mechanism. Namely, all H-BDE values are higher than the
upper threshold of 90 kcal/mol. This means that CSBA molecule might be highly stable in the
presence of oxygen and therefore could have long shelf life. It also means that its degradation
could be difficult under natural conditions, meaning that forced degradation via photo catalysts
might be employed for its removal. In the same time the BDE value of carbon-sulphur bond
calculated as 43.72 kcal/mol reveals that degradation could initiated by detaching of carbon-
sulphur bond.
3.10. Thermal Analysis
The thermal analysis of CSBA compound was done by thermo gravimetric analysis (TGA) and
differential thermal analysis (DTA) in nitrogen environment with heating rate 5oC/min up to
1200oC. The spectrum was recorded on EXSTAR TG/DTA 6300 instrument. From the analysis
of TGA curve (Fig.9), the primary weight loss of 0.33% over the temperature range of 30oC to
201oC is due to elimination of moisture and other volatile materials. The CSBA decompose
occur in three stages, the first from 201°C to 300°C with mass loss of 10.25%, after a major mass
loss of 71.91% is observed from 300°C to 400°C and finally 16.49% of mass is lost in the third
between 400-600°C. The residual mass of the compound was 0.5%. From the TGA curve, the
primary endothermic peak was observed at 255oC reflect the melting point of single crystal and
another endothermic peak at 318oC is accountable to the weight loss in TGA curve. The
sharpness of the peak reflects the good degree of crystallinity of the compound. From the thermal
we concluded that the crystal stable up to 201oC without any decomposition. Hence from the
TGA/DTA analysis, it may notice that the present investigated compound is stable and can be
used for NLO material upto 201oC.
3.11. Anti-bacterial activity
The synthesized CSBA compound were screened for in vitro anti-bacterial activity against gram-
positive bacteria (S. aureus and B. cereus) and gram-negative bacteria (E. coli and P.
aeruginosa) by disc diffusion method using DMSO as a solvent [87]. Zone of inhibition (ZI) in
mm for the tested compound was measured after 24-48 h incubation at 37°C for bacteria.
Ciprofloxacin was used as a standard drug under similar conditions and compared with the tested

compounds. Control test with solvents were performed for every assay but showed no inhibition
of microbial growth. The results revealed that the tested compound exhibited moderate anti-
bacterial activity against gram-negative and gram-positive bacterial strains and this could be
owing to the presence of sulfonamide moiety and electron-withdrawing chloro groups on the
benzoic acid (Table 10).
4. Conclusion
In conclusion, the compound 4-chloro-3-sulfamoylbenzoic acid (CSBA) was synthetized. The
explicit structure of CSBA was characterized by SCXRD, FT-IR, FT-Raman and quantum
chemical calculations. The calculated geometrical measures were in confirmation with the
SCXRD measures and the computed wave numbers were in accord with the experimentally
measured wave numbers. The MEP depiction reflected that the negative region confirmed over
deprotonated atoms which were possible sites for electrophilic attack and the positive region
confirmed over protonated atoms as possible sites for nucleophilic attack. HOMO was localized
over whole molecule other than acid group and LUMO was spread over the whole molecule
other than the amine group and this reflects that there was a charge transfer process from amine
group to acid group. For the titled compound, the second-order hyperpolarizibilitiy (γ) was
calculated and found to be 15.01х10-36 esu, which is 3.62 times that of the standard NLO material
urea. The absence of H-BDE values lesser than 70-85 kcal/mol, which showed that the CSBA
compound cannot be treated as sensitive towards autoxidation mechanism. The tested compound
showed moderate anti-bacterial activity against gram-negative and gram-positive bacterial
strains.
Acknowledgements
The authors are grateful to University Grant Commission-Network Resource Center (UGC-
NRC), School of Chemistry, University of Hyderabad for providing computational support. We
are also thankful to SAIF, Gauhati University and IIT, Chennai for the analysis support.
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Figure caption(s)
Scheme -1. Synthesis of 4-chloro-3-sulfamoylbenzoic acid.
Figure 1. Fourier transformed Infrared spectrum of 4-chloro-3-sulfamoylbenzoic acid.
Figure 2. Fourier transformed Raman spectrum of 4-chloro-3-sulfamoylbenzoic acid.
Figure 3. The ORTEP diagram of the 4-chloro-3-sulfamoylbenzoic acid with thermal ellipsoids
drawn at 50% probability with optimized geometry.
Fig. 4(a). Formation of a dimer via O-H…O hydrogen bonds; b. A view of the complex two
dimensional architecture formed by two N-H…O hydrogen bonds; c. Another view of the 2D
architecture displaying zig-zag nature.
Fig. 4(b). A partial view of the three dimensional grid like architecture formed by C-H…O
intermolecular interactions.
Fig. 5. Hishfeld surface analysis of 4-chloro-3-sulfamoylbenzoic acid.
Fig. 6. MEP plot of 4-chloro-3-sulfamoylbenzoic acid.
Fig. 7. HOMO-LUMO plots of 4-chloro-3-sulfamoylbenzoic acid.
Fig. 8. BDE for all single acyclic bonds of 4-chloro-3-sulfamoylbenzoic acid.
Fig. 9. DTA/TGA graph of 4-chloro-3-sulfamoylbenzoic acid.
Table caption(s)
Table 1. Crystallographic data and structure refinement parameters of 4-chloro-3-
sulfamoylbenzoic acid.
Table 2. Geometric parameters for hydrogen bonds and other intermolecular contacts (Å,°)
operating in the crystal structures of 4-chloro-3-sulfamoylbenzoic acid.
Table 3. Geometrical parameters of the 4-chloro-3-sulfamoylbenzoic acid.

Table 4. Calculated scaled wave numbers, observed IR and Raman bands and assignment of 4-
chloro-3-sulfamoylbenzoic acid.
Table 5. Second-order perturbation theory analysis of Fock matrix in NBO basis corresponding
to the intramolecular bonds of the CSBA compound.
Table 6. NBO results showing the formation of Lewis and non-Lewis orbitals.
Table 7. The electric dipole moment (ꢀ), linear polarizability (α) and second order hyper
polarizability (γ) of the asymmetric unit of title compound by CAM-B3LYP/6-311G+(d) in the
case static.
Table 8. The linear polarizability (α) and second order hyper polarizability (γ) of the cell unit of
title compound by CAM-B3LYP/6-311G+(d) in the case static.
Table 9. The Fukui reactive index (FRI) for nucleophilic (f+), electrophilic (f-) and radical (f0)
reactivities of different atom.
Table 10. Anti-bacterial activity of the CSBA compound against bacterial pathogens.
Supplementary Information
Figure S1. The sketch of computed UV-Visible spectrum of 4-chloro-3-sulfamoylbenzoic acid.
Figure S2. The sketch of experimental UV-Visible spectrum of 4-chloro-3-sulfamoylbenzoic
acid.
Table S1. The absorption wavelength λ (nm), excitation energies E (eV) and oscillator strengths
(f) for the CSBA compound computed at DFT/B3LYP/6311++G(d,p) method.

Table 1.
Crystal data and structure refinement for 4-chloro-3-sulfamoylbenzoic acid.
CCDC number
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
1920201
C7H6O4SClN
235.64
296.15
monoclinic
P21/c
a/Å
4.9576(3)
b/Å
6.0315(3)
c/Å
29.8923(16)
α/°
90
β/°
92.628(3)
γ/°
90
892.89(8)
Volume/Å3
Z
4
ρcalcg/cm3
1.753
0.647
ꢀ/mm-1
F(000)
480.0
Crystal size/mm3
Radiation
0.24 × 0.22 × 0.19
MoKα (λ = 0.71073)
6.892 to 60.062
-6 ≤ h ≤ 6, -8 ≤ k ≤ 8, -41 ≤ l ≤ 41
10070
2584 [Rint = 0.0257, Rsigma = 0.0221]
2584/3/140
1.241
2Θ range for data collection/°
Index ranges
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indexes [I>=2σ (I)]
Final R indexes [all data]
Largest diff. peak/hole / e Å-3
R1 = 0.0419, wR2 = 0.1037
R1 = 0.0443, wR2 = 0.1052
0.37/-0.49

Table 2.
Geometric parameters for hydrogen bonds and other intermolecular contacts (Å, °) operating in
the crystal structures of 4-chloro-3-sulfamoylbenzoic acid.
D-H…A ꢁ ꢁ ꢁ
D-H H…Aꢁ D…A
D-H…A
167
150
163
169
O5-H18...O3i
N4-H19...O7ii
N4-H20...O7iii
C15-H16...O5iv
0.82 1.83
0.85 2.28
0.84 2.21
0.93 2.60
2.6331
3.0467
3.0219
3.5155
i: -1-x,1-y,-z; ii: -1+x,y,z; iii: 1-x,1/2+y,1/2-z; iv: 1+x,1+y,z

Table 3.
Geometrical parameters of the 4-chloro-3-sulfamoylbenzoic acid.
Bond length (Å) DFT/XRD
C8-O3
C8-C9
C10-C12
C15-C17
C13-C9
S2-O6
1.20772/1.252
1.48971/1.484
1.39308/1.394
1.39370/1.386
1.39718/1.389
1.45598/1.4258
1.45235/1.4374
C8-O5
1.35213/1.273
1.39614/1.388
1.39985/1.396
1.38752/1.378
1.82275/1.7800
1.66847/1.5884
1.75083/1.7200
C9-C10
C12-C17
C13-C15
C12-S2
S2-N4
S2-O7
C17-Cl1
Bond angle (º) DFT/XRD
O6-S2-O7
O6-S2-N4
122.4/119.2
C12-S2-N4
O7-S2-N4
107.6/107.4
106.7/107.2
107.8/108.5
119.4/119.4
120.3/120.1
118.1/119.6
122.1/120.4
105.7/108.0
105.7/105.8
122.8/123.2
119.7/119.8
117.5/116.8
122.1/122.9
C12-S2-O6
O3-C8-O5
C10-C9-C13
C15-C17-Cl1
C12-C17-Cl1
C12-S2-O7
C10-C12-C17
C12-C17-C15
C13-C9-C8
C10-C9-C8
Torsion angle (º) DFT/XRD
O6-S2-C12-C10
O6-S2-C12-C17
N4-S2-C12-C10
O3-C8-C9-C13
O3-C8-C9-C10
-8.2/12.7
O7-S2-C12-C17
O7-S2-C12-C10
N4-S2-C12-C17
O5-C8-C9-C13
O5-C8-C9-C10
-53.3/-42.4
124.2/141.8
61.4/73.1
-179.7/-177.
0.3/0.3
174.0/-171.6
-120.9/-102.4
0.1/2.2
-179.7/-179.7

Table 4.
Calculated scaled wave numbers, observed IR and Raman bands and assignment of 4-chloro-3-
sulfamoylbenzoic acid.
B3LYP/6-311G++(d, p)
ν(IR)(cm-1) ν(Raman)(cm-1)
Assignment
ν (cm-1) IR intensity Raman activity
3623
3495
3383
3096
3086
3073
1722
1562
1535
1520
1354
1315
1286
125.1003
44.9905
32.8958
13.5854
0.906
157.5832
28.6368
91.3757
39.0879
143.906
39.8359
138.0385
121.6563
11.8495
3.6388
-
-
OH(100)
NH(50)
NH(50)
νCH(99)
νCH(51)
νCH(51)
νC=O(84)
νC=C(18)
νC=C(23)
δNH2(83)
3401
3281
3093
-
3072
1721
-
1532
-
1352
1313
1284
3403
3279
-
3084
-
1720
1563
1531
1518
0.4339
423.2576
67.4577
7.3653
44.5197
47.8115
163.3855
153.7678
2.28
22.5635
7.4928
1351
1310
1285
νOH(32)
νSO2(42)
δCH(10)
νOH(44)
δCH(15)
νC=C(15)
νSO2(27)
νSO2(17),
νC=C(11)
δCH(10)
δNH(83)
1155
238.7422
59.0964
1145
-
1119
1090
1071
4.6545
122.5881
92.3408
4.3601
18.3156
4.749
1115
1116
1090
1072
-
-
1066
1041
1003
965
108.3526
4.7781
80.2009
0.0047
2.8884
5.2138
20.3098
0.0774
0.2571
-
1042
-
-
1043
-
ring breathing (27)
δCH(45)
-
-
831
12.2233
832
833
δCH(48)
νCS(15)
νSN(16)
825
74.4512
18.1962
-
-
782
749
674
20.2025
62.9529
45.7856
10.8642
0.11
11.3182
-
785
747
675
νSN(56)
δCH(13)
745
676
δC=O(17)
δC=O(23)
νCCl (12)
δNH(19)
νCCl (17)
δC=O(18)
δSO2(15)
δSO2(23)
δSO2(17)
646
587
550
21.5916
375.3294
45.1653
1.4169
2.265
641
587
548
585
551
2.1073
513
460
432
6.3932
33.6788
10.6856
2.7591
0.9877
1.7013
-
-
-
514
458
430

393
11.9518
3.0486
-
389
δSO2(15)
aν-stretching; δ-in-plane deformation and out-of-plane deformation; τ-torsion; potential energy
distribution is given in brackets (%) in the assignment column.