Synthesis, characterization, and quantum chemical calculation studies on 3-(3-nitrophenylsulfonyl)aniline

Article abstract of DOI:10.1016/j.molstruc.2011.05.006

A novel partially reduced polynitro aromatic compound, 3-(3- nitrophenylsulfonyl)aniline (III), was found during the catalytic transfer hydrogenation of 3,3′-sulfonylbis(nitrobenzene) (I) to 3,3′-sulfonyldianiline (II). III was identified and characterized by elemental analysis, IR, ¹H NMR, and X-ray single crystal diffraction. The optimized geometries of III calculated by DFT-B3LYP/6-31G and HF/6-31G closely resemble the crystal structure. The frontier orbital gap and the electrostatic potential isosurface map of III were calculated and compared with those of I. HF/6-31G method is better than DFT-B3LYP/6-31G method to predict the vibrational frequencies by the comparisons between the calculated results and the experimental data. The present study of III, in general, may lead to the better understanding of the mechanisms and intermediates of the reduction of polynitro aromatic compounds, especially the nitro groups at the different aromatic rings, and may also help in designing and synthesizing new partial reduction products for technological applications.

Full text of DOI:10.1016/j.molstruc.2011.05.006

Journal of Molecular Structure 997 (2011) 110–116
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, characterization, and quantum chemical calculation studies
on 3-(3-nitrophenylsulfonyl)aniline
b,
Yi Li a,b, Haibao Zhang a, Yuanyuan Liu a, Fangshi Li a, , Xiaoning Liu
⇑
⇑
a Department of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, PR China
b College of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 7 April 2011
Received in revised form 5 May 2011
Accepted 5 May 2011
Available online 10 May 2011
A novel partially reduced polynitro aromatic compound, 3-(3-nitrophenylsulfonyl)aniline (III), was found
during the catalytic transfer hydrogenation of 3,30-sulfonylbis(nitrobenzene) (I) to 3,30-sulfonyldianiline
(II). III was identified and characterized by elemental analysis, IR, 1H NMR, and X-ray single crystal dif-
fraction. The optimized geometries of III calculated by DFT-B3LYP/6-31Gꢀ and HF/6-31Gꢀ closely resem-
ble the crystal structure. The frontier orbital gap and the electrostatic potential isosurface map of III were
calculated and compared with those of I. HF/6-31Gꢀ method is better than DFT-B3LYP/6-31Gꢀ method to
predict the vibrational frequencies by the comparisons between the calculated results and the experi-
mental data. The present study of III, in general, may lead to the better understanding of the mechanisms
and intermediates of the reduction of polynitro aromatic compounds, especially the nitro groups at the
different aromatic rings, and may also help in designing and synthesizing new partial reduction products
for technological applications.
Keywords:
3-(3-Nitrophenylsulfonyl)aniline
Synthesis
Characterization
Crystal structure
Quantum chemical calculation
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
mechanisms and intermediates of the reduction of polynitro aro-
matic compounds, especially the nitro groups at the different aro-
Aromatic amines are important organic raw materials and
widely used in chemical, pharmaceutical, agricultural chemicals,
photographic chemicals, additives, surfactants and polymer pro-
duction. Aromatic amines are generally made by the reduction of
aromatic nitro compounds. The main reduction methods include
catalytic hydrogenation, reduction with CO/H2O, reduction with
metal, reduction with sulfide, reduction with metal hydride, elec-
tro-chemical reduction, and photo-chemical reduction [1]. In these
methods, catalytic hydrogenation is environmentally friendly and
has a high yield and good selectivity, showing promising prospect
of application.
Catalytic transfer hydrogenation (CTH) is a special variation of
catalytic hydrogenation, in which hydrogen gas is replaced with
a hydrogen donor such as hydrazine hydrate [2]. CTH has potential
advantages including a small investment in equipment, mild reac-
tion conditions, operational simplicity, and partially reduced prod-
uct. It is particularly suitable for small batch, short-line production
of aromatic amines.
matic rings. It is urgent to identify CTH intermediates, because of
the requirement of the mechanism of the CTH reaction and the po-
tential usage of the partial reduction products.
Recently, we focus our attention on synthesis and characteriza-
tion various aromatic amines [5–10] and study their special
properties [11,12]. During our study on the CTH of 3,30-sulfonyl-
bis(nitrobenzene) (I) to 3,30-sulfonyldianiline (II), we found a par-
tially reduced intermediate (III) (Fig. 1). To the best of our
knowledge, neither the synthesis nor the theoretical studies on III
has been available till now.
In the present work, we wish to report the synthesis and char-
acterization of the novel compound III as well as the theoretical
studies on it by using DFT-B3LYP/6-31Gꢀ and HF/6-31Gꢀ methods.
2. Experimental
2.1. Materials and instruments
The reaction of nitro compounds to amines is usually through
the following process: –RNO2 ? –RNO ? RNHOH ? RNH2 [3].
Most of the research on the mechanisms and intermediates was
about the nitrobenzenes [4]. Little has been published on the
Starting material 3,30-sulfonylbis(nitrobenzene) (I) was com-
mercially available. All chemicals were reagent grade and were
used without further purification. The ferrihydrite catalyst was
prepared according to the method described in the literature [13].
Melting points were measured on an X-4 microscope electro-
thermal apparatus (Taike, China) and were uncorrected. Fourier’s
transformation infrared (FTIR) spectra were recorded in KBr pellets
⇑
Corresponding authors.
E-mail addresses: fangshi.li@njut.edu.cn (F. Li), xiaoningliu@163.com (X. Liu).
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.05.006

Y. Li et al. / Journal of Molecular Structure 997 (2011) 110–116
111
Fig. 1. Scheme of the catalytic transfer hydrogenation of 3,30-sulfonylbis(nitrobenzene) (I) to 3,30-sulfonyldianiline (II).
using an AVARTE360 FTIR spectrometer (Thermo Nicolet). 1H NMR
spectra were recorded on a Bruker AV-300 spectrometer at
300 MHz. The elemental analysis was performed with a Vario El
III elemental analyzer. The TLC was performed on the commercial
GF254 plates. The ‘‘spots’’ were located by a ZF-1 UV analyzer
(Shengke, Shanghai). The X-ray crystallographic analysis was per-
formed on a Nonius CAD4 single-crystal diffractometer equipped
with a graphite-monochromated Mo K
by using an /2h scan mode at 293 K.
a radiation (k = 0.71073 Å)
x
2.2. Synthesis
The reduction reaction was performed by heating a solution of I
(24.35 mmol) and ferrihydrite catalyst (4.50 mmol) in anhydrous
ethanol (150 mL) under reflux (78 °C) followed by slowly dropping
in hydrazine hydrate (146.7 mmol) in 0.5 h. The mixture was re-
fluxed for a specified time.
The reaction course was monitored by TLC using the solvent
system of ethyl acetate–petroleum ether–triethylamine (7:7:2).
The reaction liquid was sampled with a capillary and dissolved in
ethyl acetate.
Fig. 2. TLC monitoring the reaction solution.
2.3. Crystal structure determination
Table 1
White color crystals of III suitable for X-ray analysis were
grown from methanol. A crystal was put on a glass fiber. The dif-
fraction data were collected on a Nonius CAD4 single-crystal dif-
Crystal and structural refinement data of III.
Chemical formula
CCDC number
Temperature (K)
Wavelength (Å)
Space group
a (Å)
C24H20N4O8S2
292524
293(2)
0.71073
P21/c (No. 14)
12.231(2)
21.700(4)
10.453(2)
90.00
114.00(3)
90.00
2534.5(9), 4
1.459
fractometer equipped with a graphite-monochromated Mo K
a
radiation (k = 0.71073 Å) by using a x/2h scan mode at 293 K. The
crystal structure was solved by the direct method and refined by
the full-matrix leastsquares procedure on F2 using SHELXL-97 pro-
gram [14]. Positions of hydrogen atoms were located by geometri-
cal calculation (x, y, z and Uiso fixed to 1.2 times Uiso of the atom
they are bound to).
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3), Z
Density (calc) (g cmꢁ3
)
2.4. Computational methods
Abs. coeff. (mmꢁ1
)
0.267
The DFT calculations at 6-31Gꢀ basis set and the Hatree–Fock
calculations at 6-31Gꢀ basis set were performed with the Gaussian
03 software package [15–17].
F(0 0 0)
h ranges (data collection)
Index ranges
1152
1.82–25.28
ꢁ14 6 h 6 13
ꢁ26 6 k 6 0
0 6 l 6 12
4870
Reflections collected
Rint
3. Results and discussion
0.110
Independent reflections
Refinement method on F2
Goodness-of-fit on F2
4601
3.1. TLC results
Full-matrix least-squares
1.000
Final R indices [I > 2
r
(I)]
0.0796
0.1979
0.249/ꢁ0.223
The reaction course of I to II was monitored with TLC by
measuring the reaction solution as a function of time (Fig. 2).
At the beginning of the reaction (0 min), only the raw material
R indices (all data)
Residual (e Åꢁ3
)

112
Y. Li et al. / Journal of Molecular Structure 997 (2011) 110–116
Table 3
(I, Rf = 0.82) was detected. At 20 min, the product (II, Rf = 0.27)
and an unknown intermediate (III, Rf = 0.57) appeared. At 40
min, I was almost run out. At 60 min, only II was left.
A selection of bond lengths (Å) of III with esds in parentheses.
Parameters
X-ray
HF/6-31Gꢀ
B3LYP/6-31Gꢀ
S1AO4
S1AO3
S1AC7
1.429(4)
1.462(4)
1.762(5)
1.784(5)
1.197(5)
1.251(5)
1.470(6)
1.391(6)
1.341(7)
1.430(3)
1.441(4)
1.754(5)
1.776(5)
1.228(6)
1.227(6)
1.447(6)
1.364(7)
1.4353
1.4351
1.7752
1.7789
1.1933
1.1924
1.4587
1.3907
1.3854
1.4351
1.4353
1.7752
1.7789
1.1933
1.1924
1.4587
1.3907
1.4712
1.4711
1.8001
1.8112
1.2299
1.2292
1.4751
1.3906
1.3965
1.4711
1.4712
1.8001
1.8112
1.2299
1.2292
1.4751
1.3906
3.2. Identification of III
S1AC6
The intermediate III was separated and identified as 3-(3-nitro-
phenylsulfonyl)aniline, a new compound confirmed by IR, 1H NMR,
and elemental analysis. m.p. 147–148 °C; Elemental analysis: Anal.
Calcd for C12H10N2O4S: C 51.79, H 3.62, N 10.07; found C 51.66, H
3.63, N 10.04; 1H NMR (DMSO-d6) d: 5.73 (s, 2H, NH), 6.81–7.10
(m, 2H, ArAH), 7.16–7.95 (t, 3H, ArAH), 8.30–8.54 (m, 3H, ArAH);
N1AO2
N1AO1
N1AC4
N2AC11
C1AC2
S2AO8
S2AO7
S2AC19
S2AC18
O5AN3
O6AN3
N3AC16
N4AC23
IR (KBr, cmꢁ1
) m: 3482.8, 3391 (NAH), 3100 (Ar@CAH), 1629
(NAH), 1602, 1486, 1451 (Ar C@C), 1533, 1357 (Ar NAO), 1319
(ArANO2), 1162 (S@O).
3.3. Description of the crystal structure
Crystal data, experimental details, structure determination and
refinement of the compound III are reported in Table 1, and final
coordinates in Table 2. Bond distances are given in Table 3, and a
selection of bond and torsion angles in Table 4 and Table 5. The dis-
placement ellipsoid plot with the numbering scheme is shown in
Fig. 3 and a perspective view of the crystal packing in the unit cell
is shown in Fig. 4.
Crystal structure shows that the molecule III has the conforma-
tion with the two phenyl rings approximately perpendicular to the
C(6)ASAC(7) plane as shown by the values of the wl and w2
Table 4
A selection of bond angles (°) of III with esds in parentheses.
Parameters
X-ray
HF/6-31Gꢀ
B3LYP/6-31Gꢀ
O4AS1AO3
O4AS1AC7
O3AS1AC7
O4AS1AC6
O3AS1AC6
120.7(3)
108.4(3)
108.5(3)
108.4(2)
106.4(2)
103.1(2)
125.1(6)
120.0(5)
114.7(5)
119.9(5)
117.2(5)
119.7(5)
120.1(4)
118.6(4)
120.0(5)
118.3(4)
119.0(6)
122.3(6)
118.6(2)
108.4(2)
109.0(3)
106.5(2)
108.5(2)
105.1(2)
120.3(6)
119.5(6)
120.2(6)
119.1(6)
118.4(5)
118.5(4)
119.6(4)
118.6(4)
119.7(5)
123.6(6)
118.3(6)
121.1653
107.9946
107.9573
106.7587
106.9509
104.8925
124.9407
117.4808
117.5781
119.7359
118.9641
118.7277
119.2376
119.6327
119.2003
118.5564
120.7481
120.6465
121.1653
107.9573
107.9946
106.9509
106.7587
104.8925
124.9407
117.5781
117.4808
118.9641
118.7277
119.2376
119.6327
118.5564
119.2003
120.6465
120.7481
121.9887
107.9661
107.9192
106.5018
106.7143
104.438
124.9489
117.4859
117.5648
119.4184
118.9262
118.6928
119.0752
119.419
119.0945
118.3209
120.8679
120.6319
121.9887
107.9192
107.9661
106.7143
106.5018
104.438
124.9489
117.5648
117.4859
118.9262
118.6928
119.0752
119.419
parameters used to define the dihedral angles by
a linear
C7AS1AC6
O2AN1AO1
O2AN1AC4
O1AN1AC4
C2AC1AC6
C3AC4AN1
C5AC4AN1
C5AC6AS1
Table 2
Atomic coordinates of non-hydrogen atoms and their thermal parameters for III.
Atom
x
y
z
U (eq)
S1
S2
0.27645(13)
0.18293(14)
0.45331(8)
0.73346(7)
0.5288(2)
0.3717(2)
0.5159(3)
0.6334(3)
0.5773(2)
0.5170(2)
0.51334(18)
0.4371(2)
0.4701(2)
0.5163(2)
0.78818(16)
0.72650(18)
0.3979(3)
0.3906(2)
0.4343(3)
0.4825(2)
0.4911(2)
0.4470(2)
0.3955(3)
0.3397(3)
0.2952(3)
0.3062(3)
0.3627(3)
0.4070(2)
0.6696(2)
0.6198(3)
0.5695(3)
0.5698(3)
0.6191(2)
0.6682(2)
0.7266(2)
0.7680(3)
0.7620(3)
0.7172(3)
0.6760(3)
0.6817(2)
0.65667(15)
0.04528(16)
0.1680(5)
0.4310(5)
0.1751(6)
0.0641(4)
0.0591(4)
0.0691(15)
0.099(2)
0.0749(16)
0.146(3)
N1
N2
N3
N4
O1
O2
O3
O4
O5
O6
O7
O8
C1
C2
C3
C4
C5
ꢁ0.0233(5)
0.5499(5)
0.3572(5)
ꢁ0.2307(5)
0.0373(4)
ꢁ0.0997(4)
0.3283(3)
0.2499(3)
0.4077(4)
0.3208(4)
0.2364(3)
0.1806(3)
0.0680(5)
ꢁ0.0309(5)
ꢁ0.0614(5)
0.0125(4)
0.1150(4)
0.1424(4)
0.3686(4)
0.3798(5)
0.4509(6)
0.5053(6)
0.4950(5)
0.4238(4)
0.3048(4)
0.3675(5)
0.3831(5)
0.3399(4)
0.2785(4)
0.2598(4)
0.0361(4)
ꢁ0.0059(6)
ꢁ0.1203(7)
ꢁ0.1945(6)
ꢁ0.1529(5)
ꢁ0.0346(5)
C1AC6AS1
C8AC7AS1
C12AC7AS1
C10AC11AN2
C12AC11AN2
O8AS2AO7
O8AS2AC19
O7AS2AC19
O8AS2AC18
O7AS2AC18
C19AS2AC18
O6AN3AO5
O6AN3AC16
O5AN3AC16
C15AC16AN3
C17AC16AN3
C17AC18AS2
C13AC18AS2
C24AC19AS2
C20AC19AS2
N4AC23AC24
N4AC23AC22
ꢁ0.1538(6)
0.1983(5)
0.0552(4)
0.6505(4)
0.7735(4)
0.1559(5)
0.2686(5)
0.0175(4)
0.1802(4)
0.4875(6)
0.3693(6)
0.2627(6)
0.2803(6)
0.3988(5)
0.5011(5)
0.6348(5)
0.7012(6)
0.6751(7)
0.5866(7)
0.5228(6)
0.5452(5)
ꢁ0.0820(5)
ꢁ0.0962(6)
ꢁ0.0134(6)
0.0873(5)
0.1084(5)
0.0204(5)
ꢁ0.0823(5)
ꢁ0.1924(7)
ꢁ0.2892(7)
ꢁ0.2771(6)
ꢁ0.1644(6)
ꢁ0.0674(6)
0.1074(17)
0.0913(15)
0.0721(12)
0.0845(14)
0.1067(18)
0.1078(18)
0.0778(13)
0.0767(12)
0.0660(17)
0.0760(19)
0.0648(16)
0.0534(14)
0.0526(14)
0.0492(13)
0.0542(14)
0.079(2)
C6
C7
C8
C9
118.3209
119.0945
120.6319
120.8679
0.089(2)
0.085(2)
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
0.0669(17)
0.0515(14)
0.0461(13)
0.0602(15)
0.0619(16)
0.0529(14)
0.0505(13)
0.0439(12)
0.0474(13)
0.0716(18)
0.089(2)
Table 5
A selection of torsion angles (°) of III with esds in parentheses.
C7AS1AC6AC5
C7AS1AC6AC1
C6AS1AC7AC8
C6AS1AC7AC12
(T1 + T2 + 180)/2
(T3 + T4 + 180)/2
T1
T2
T3
T4
w1
w2
ꢁ107.1(5)
73.5(5)
ꢁ100.0(5)
77.2(5)
73.2
0.0767(19)
0.0742(19)
0.0672(17)
78.6

Y. Li et al. / Journal of Molecular Structure 997 (2011) 110–116
113
Fig. 3. X-ray structure of III (ellipsoids are shown at the 50% probability level) and the computed structure.
Fig. 4. A packing diagram of III. Hydrogen bonds are shown as dashed lines.
combination of torsion angles (Table 5). In such a way the molecule
is seen to adopt a typical arrangement intermediate between ‘but-
terfly’ and ‘propeller’ conformations (Fig. 3).
The d(CANH2) value in III [1.391(6) Å] is shorter than the com-
monly accepted value for
1.44–1.45 [18].
a
single C(sp2)AN(sp3) bond of
In the crystal, there are two crystallographically independent
molecules, A and B. Each NH2 in A or B donates two hydrogen
bonds, one to NO2 oxygen located on B or A to form an intramolec-
ular hydrogen bond (N2AH2ꢂ ꢂ ꢂO5 or N4AH4ꢂ ꢂ ꢂO2), and the other
to SO2 oxygen located on different molecules to form an intermo-
lecular hydrogen bond (NAHꢂ ꢂ ꢂO@S@O) (Figs. 3 and 4, Table 6).
In the resonant chain indicated by the shading (Fig. 5, above),
the resonance generates partial charges to strengthen the hydro-
gen bonds (Fig. 5, below). It has been reported that more efficient
hydrogen bonds can be established whenever the donor and accep-
The SAC distance at the side of aniline ring [on average
1.758(5) Å; (S1AC7 = 1.762(5) Å, S2AC19 = 1.754(5) Å] is shorter
than the accepted value of 1.763 [18,22] for the C(aromatic)ASO2
bond and shorter than the other SAC distance at the side of
nitrophenyl ring [on average 1.780(5) Å; (S1AC6 = 1.784(5) Å,
S2AC18 = 1.776(5) Å].
3.4. Quantum chemical calculations
Over the past couple of decades, many methods have been
developed for the purpose of crystal structure prediction. Compu-
tational methods can be used not only to predict how a molecule
will crystallize (i.e. unit cell, space group and all atomic positions),
even prior to the synthesis of the given molecule, leading to crys-
tallize with desired structural and physical properties, but also can
help to assess the undiscovered polymorphism, for a molecule with
a known crystal structure [23]. Recently, quantum-chemical calcu-
lation methods have become available to provide a powerful ap-
proach for crystal structure prediction [24–26].
tor groups are connected by a p-conjugated system (RAHB = reso-
nance assisted hydrogen bond) [18,19]. In spite of the resonance,
the NAHꢂ ꢂ ꢂO@S@O hydrogen bond in III appears to be intrinsically
rather weak. The Nꢂ ꢂ ꢂO distance on the shortest hydrogen bond of
III is 3.043(7) Å (Table 6), while the average value on intermolecu-
lar NAHꢂ ꢂ ꢂO hydrogen bonds is reported [20] to be 2.892(3) Å. The
m-aminophenylsulfonyl group in III mimics m-nitroanilines, be-
cause the average Nꢂ ꢂ ꢂO distance for 29 such compounds amounts
to 3.06(9) Å [21].
The formation of NAHꢂ ꢂ ꢂO@S@O hydrogen bonds can be
drawn from the values of the IR frequencies of the NH2 group (Ta-
3.4.1. Molecular geometry of III
ble 7). The values of the NH2 group for compound III (
and are slightly smaller than the values of
s = 3390 cmꢁ1
a = 3550–3500 and
s = 3450–3400 cmꢁ1 in the absence of inter-
actions [21].
m
a = 3482
DFT-B3LYP/6-31Gꢀ and HF/6-31Gꢀ calculations were performed
on III, respectively. The optimized structures were characterized to
the relative energy minimum of the potential surface by frequency
calculation. The optimized structure by HF/6-31Gꢀ is shown in
m
)
m
m

114
Y. Li et al. / Journal of Molecular Structure 997 (2011) 110–116
Table 6
Table 7
Hydrogen bonds (Å and °) of III.
Comparison of experimental IR spectrum of III with theoretical spectra (
m
cmꢁ1).
D–Hꢂ ꢂ ꢂA
d(D–H)
d(Hꢂ ꢂ ꢂA)
d(Dꢂ ꢂ ꢂA)
<(DHA)
Exp.
HF/6-31Gꢀ
B3LYP/6-31Gꢀ
Description
N2AH2Aꢂ ꢂ ꢂO7#1
N2AH2Bꢂ ꢂ ꢂO3#2
N2AH2Bꢂ ꢂ ꢂO5
0.86
0.86
0.86
0.93
0.86
0.93
0.93
0.93
0.93
0.9300
2.28
2.48
2.71
2.70
2.49
2.52
2.57
2.49
2.54
2.4900
3.043(7)
3.194(7)
3.433(7)
3.551(6)
3.297(8)
2.894(6)
2.922(8)
2.857(6)
2.915(8)
3.411(7)
149.00
141.00
142.00
152.00
156.00
105.00
103.00
104.00
105.00
169.00
3482
3390
3100
2925
1629
1602
1533
1486
1451
1356
1319
1162
1126
1083
991
3451
3383
m
m
m
(NAH)
(NAH)
(Ar @CAH)
C12AH12Aꢂ ꢂ ꢂO6
N4AH4Bꢂ ꢂ ꢂO2
1637
1618
1625
1534
m
(Ar C@C)
C5AH5Aꢂ ꢂ ꢂO3
C8AH8Aꢂ ꢂ ꢂO4
d (ArANO2)
C17AH17Aꢂ ꢂ ꢂO8
C20AH20Aꢂ ꢂ ꢂO7
C24AH24Aꢂ ꢂ ꢂO1
1466
1449
1352
m
m
m
(Ar C@C)
(ArANO2)
(S@O)
1352
1317
1155
1123
1076
Symmetry transformations used to generate equivalent atoms: #1 1 ꢁ x, ꢁ1/2 + y,
1/2 ꢁ z; #2 1 ꢁ x, 1 ꢁ y, 1 ꢁ z.
1160
1138
1081
991
d (Ar @CAH)
899
875
783
761
890
855
776
760
907
875
791
765
d (Ar @CAH)
d (Ar @CAH)
733
698
663
612
584
524
730
691
671
622
586
516
662
578
521
Fig. 5. The system of resonant chain (above) and the partial charges generated
(below).
Fig. 3. Some optimized geometric parameters are listed in Tables 3
and 4. Comparisons of the experimental bond lengths with the cal-
culated values show that for B3LYP method, the biggest bond dif-
ference is 0.0548 Å for C(1)–C(2) bond, and that for HF method is
0.0591 Å for N(1)AO(1) bond (Table 3), which suggest that both
methods can predict well the bond length of the system studied
here. On the contrary, in view of the bond angles difference be-
tween the experimental and calculated values, both methods give
biggest difference for O(6)AN(3)AO(5) bond angle (B3LYP 4.5889°
and HF 4.5807°, Table 4). Because of the hydrogen bonds (Figs. 3
and 4, Tables 3 and 4), the theoretical value of the angle related
to the nitro group is some different from the crystal data. In spite
of these differences, both the methods give satisfactory precision,
which shows that both the optimized geometries calculated by
B3LYP/6-31Gꢀ and HF/6-31Gꢀ methods can well reproduce the
crystal structure of III.
3.4.2. Electronic properties
The frontier orbitals, HOMO and LUMO, determine the way a
molecule interacts with other species. The frontier orbital gap
helps to characterize the chemical reactivity and kinetic stability
of the molecule. Small frontier orbital gap makes a molecule more
polarisable and is generally associated with a high-chemical reac-
tivity and low-kinetic stability [27]. The frontier orbital gap of III
(0.364 a.u.) is lower than that of I (0.417 a.u.), indicating that
replacing a nitro group with an amino group causes a higher chem-
ical activity.
The 3D plots of the atomic frontier orbitals are shown in Fig. 6.
It can be seen that the HOMO of III is distributed uniformly almost
over the aniline ring and shows considerable antibonding charac-
ter. The LUMO of III is found to be spread over the nitrophenyl ring.
The nodes of HOMO and LUMO are placed almost symmetrically.
The electrostatic potential isosurface map simultaneously dis-
plays molecular shape, size and electrostatic potential values. This
mapping is very useful in the investigation of the molecular
Fig. 6. The frontier molecular orbitals and the electrostatic potential isosurfaces of
III.
structure with its physiochemical property relationships [17].
The electrostatic potential isosurface map of III (Fig. 6) shows
clearly that the two major negative potential regions characterized
by yellowish red color around the nitro group and the sulfonyl
group, and the amino group exert a positive potential, whereas
the two benzene rings seem to have a potential halfway between
the two extremes, red and dark blue color. This mapping can be
used to explain the intra-charge transfer path.
3.4.3. Vibrational frequency of III
The experimental and the simulated infrared spectra are shown
in Fig. 7, where the calculated intensity is plotted against the

Y. Li et al. / Journal of Molecular Structure 997 (2011) 110–116
115
Fig. 7. FTIR spectra of I, III, and the predicted spectra of III by B3LYP/6-31Gꢀ and HF/6-31Gꢀ.
harmonic vibrational frequencies. Some primary calculated har-
monic frequencies calculated at B3LYP/6-31Gꢀ and HF/6-31Gꢀ lev-
els of theory are listed in Table 7 and compared with the
experimental data. The descriptions concerning the assignment
have also been indicated in the Table 7.
to 3,30-diaminodiphenyl sulfone (II). III was identified and charac-
terized by elemental analysis, IR, 1H NMR, and X-ray single crystal
diffraction. The optimized geometries of III calculated by DFT-
B3LYP/6-31Gꢀ and HF/6-31Gꢀ closely resemble the crystal struc-
ture. The frontier orbital gap and the electrostatic potential isosur-
face map of III were calculated and compared with those of I. The
comparisons between the calculated results and the experimental
data indicate HF/6-31Gꢀ method is better than B3LYP/6-31Gꢀ
method to predict the vibrational frequencies for III. The present
study of III, in general, may lead to the better understanding of
the mechanisms and intermediates of the reduction of polynitro
aromatic compounds, especially the nitro groups at the different
aromatic rings, and may also help in designing and synthesizing
new partial reduction products for technological applications.
Seen from Fig. 7 and Table 7, by using the HF/6-31Gꢀ method,
predicted vibrational frequencies are in good agreement with
experimental values except that some experimental vibrational
bands, such as ArANO2, cannot be predicted. On the other hand,
by using the B3LYP/6-31Gꢀ method, the experimental vibrational
bands of Ar C@C and ArANH2 cannot be predicted. Above
comparison shows that HF/6-31Gꢀ method is superior to B3LYP/
6-31Gꢀ method to predict the vibrational frequencies for the sys-
tem studied here.
4. Conclusions
Supplementary material
3-(3-nitrophenylsulfonyl)aniline (III) was first found during the
catalytic transfer hydrogenation of 3,30-dinitrodiphenyl sulfone (I)
CCDC-292524 contains the supplementary crystallographic
data for this article. These data can be obtained free of charge at

116
Y. Li et al. / Journal of Molecular Structure 997 (2011) 110–116
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