Experimental and theoretical investigations of 4-chloro-N-(2-methoxyphenyl) benzamidoxime

Article abstract of DOI:10.1016/j.saa.2013.03.035

4-Chloro-N-(2-methoxyphenyl) benzamidoxime (CMB) has been synthesized and characterized by X-ray diffraction, ¹H NMR, ¹³C NMR, FT-IR and FT-Raman spectra. The X-ray study showed that CMB has a Z configuration, due to the strong intra

Full text of DOI:10.1016/j.saa.2013.03.035

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
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Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Experimental and theoretical investigations of
4-chloro-N-(2-methoxyphenyl)benzamidoxime
b
c
Yesim S. Kara a, , Seda G. Sagdinc , Nevzat Karadayı
⇑
a Department of Chemistry, Science and Art Faculty, Kocaeli University, Umuttepe Campus, 41380 Kocaeli, Turkey
b Department of Physics, Science and Art Faculty, Kocaeli University, Umuttepe Campus, 41380 Kocaeli, Turkey
c Yeßsilyurt Iron-Steel Higher Vocational School, Ondokuz Mayıs University, 55139 Samsun, Turkey
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
ꢀ
The crystal structure analysis of 4-
chloro-N-(2-
methoxyphenyl)benzamidoxime by
using X-ray crystallography.
In the crystal structure, the CMB
configuration is Z since AOH group is
in the same direction ANH group.
The calculated NMR chemical shifts
and vibrational frequencies are in
good accordance with experimental
values.
ꢀ
ꢀ
a r t i c l e i n f o
a b s t r a c t
Article history:
4-Chloro-N-(2-methoxyphenyl) benzamidoxime (CMB) has been synthesized and characterized by X-ray
diffraction, 1H NMR, 13C NMR, FT-IR and FT-Raman spectra. The X-ray study showed that CMB has a Z
configuration, due to the strong intramolecular NAHꢁ ꢁ ꢁO hydrogen bond and centrosymmetric dimer
form due to intermolecular OAHꢁ ꢁ ꢁN0 and OAHꢁ ꢁ ꢁO0 hydrogen bonds. The 2-methoxyphenyl and 4-chlo-
rophenyl rings are twisted from the mean plane of the hydroxyamidine group by 33.09 (1) and 44.89 (1)°,
respectively. The optimized molecular structure and vibrational frequencies have been calculated with
DFT (B3LYP) method by using a 6-311G(d,p) basis set. The 1H and 13C NMR chemical shifts were calcu-
lated by the gauge-including atomic orbital (GIAO) method with the B3LYP/6-311G (d,p) level. A compar-
ison between experimental and calculated theoretical results indicate that the density functional B3LYP
method provided satisfactory results for predicting IR, Raman, 1H NMR and 13C NMR spectra properties.
Ó 2013 Elsevier B.V. All rights reserved.
Received 28 November 2012
Received in revised form 27 February 2013
Accepted 3 March 2013
Available online 17 March 2013
Keywords:
4-Chloro-N-(2-
methoxyphenyl)benzamidoxime
X-ray
1H NMR
13C NMR
FT-IR
FT-Raman
Introduction
derivatives have been shown to possess several biological activities
such as, anti-tumor, analgesic and psychotropic, anti-malarial, try-
Amidoximes are important compounds bearing both a hydrox-
yimino and an amino group of the same carbon which makes them
useful precursors for the synthesis of a variety of heterocyclic com-
pounds such as oxadiazoles [1,2]. Additionally, amidoxime
panocidal and leishmanicidal, hypoglycemic and natriuretic activ-
ities [3–7]. Furthermore, amidoximes derivatives have been found
to be antileishmaniasl and antipneumocystic agents [8,9]. Aro-
matic amidoximes have been shown to be quickly converted into
amidines in vivo, so a number of amidoxime derivatives have been
used as prodrugs for amidines [10]. In addition, they have wide-
spread usage as bidentate ligands in the field of coordination
chemistry [11–13].
⇑
Corresponding author. Tel./fax: +90 262 3032057.
E-mail address: yesimkara@kocaeli.edu.tr (Y.S. Kara).
1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.03.035

352
Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
4-Chloro-N-(2-methoxyphenyl)benzamidoxime, C14H13ClN2O2,
was passed through a solution of 4-chlorobenzaldehyde oxime
(2 g, 13 mmol) in dry chloroform (30 mL) in an ice-salt bath. The
reaction mixture was left in a refrigerator for 16 h. The solvent
was removed under reduced pressure. The solution of 4-chloro-
N-hydroxybenzenecarboximidoyl chloride in benzene (15 mL)
was added slowly to 2-methoxyaniline (3.20 g, 26 mmol) in ben-
zene (20 mL) while stirring into the flask. After the reaction was
completed, the precipitate was filtered, and the solution was evap-
orated under reduced pressure. The residual solid was subjected to
flash column chromatography (eluent: ethyl acetate/petroleum
ether, 1:4) to 4-chloro-N-(2-methoxyphenyl) benzamidoxime.
(Fig. 1) is a new N-substituted amidoxime, and molecular confor-
mation of this compound has been stabilized by an intramolecular
NAHꢁ ꢁ ꢁO hydrogen bond and its synthesis has not yet been re-
ported in the literature, so we have experimentally synthesized
and investigated its crystal structure, FT-IR, FT-Raman, 1H NMR
and 13C NMR spectra in this study.
Many important chemical and physical properties of chemical
systems can be predicted from the initial principles obtained
through various computational techniques [14]. In recent years,
the ab initio and the density functional theory (DFT) have become
powerful tools in the investigation of molecular structures, vibra-
tional spectra and chemical shifts [15]. Therefore, in this study,
we have calculated the geometric parameters, vibrational frequen-
cies, GIAO 1H, and 13C chemical shifts of the title compound in the
ground state using B3LYP (Becke-3–Lee–Yang–Parr) methods with
a 6-311G (d,p) basis set. The calculated vibrational frequencies, 1H
and 13C NMR chemical shifts of CMB were compared with experi-
mental values.
(1.50 g, 42%), mp 152–153 °C. IR (KBr), m
(cmꢂ1): 3377 (NH), 3217
(OH), 1640 (C@N). 1H NMR (DMSO), d(ppm): 10.78 (s, OH, 1H),
7.44 (s, NH, 1H), 6.28–7.39 (m, aromatic, 8H), 3.78 (s, OCH3, 3H).
13C NMR (DMSO), d(ppm): 150.02 (C@N), 149.29–111.67 (aromatic
C), 56.14 (OCH3). The detailed descriptions of the FT-IR and NMR
spectra of the synthesized compound are given in the following
sections.
X-ray diffraction data of 4-chloro-N-(2-
methoxyphenyl)benzamidoxime (CMB)
Experiment
The colorless single crystals of the CMB compound appeared
through the gradual evaporation of the solvent from an ethanol
solution of the CMB compound at room temperature. Intensity
data for C14H13ClN2O2 were collected using a Stoe-IPDS-2 diffrac-
Materials and measurements
All of the chemicals and reagents used in the synthesis were
purchased from Fluka and Merck Chemical companies and were
used without any further purification. Melting point was deter-
mined on an Electrothermal melting point apparatus (IA-9200)
and uncorrected. The FT-IR spectrum of CMB was recorded with
a Shimadzu 8201 spectrometer using the KBr pellet technique in
the region of 4000–400 cmꢂ1, which was calibrated using polysty-
rene. FT-Raman spectrum have been recorded using a Nd:YAG la-
ser (1064 nm) for excitation in the region 3500–0 cmꢂ1 on a
Bruker-FRA-106/5 FT-Raman spectrometer with a scanning speed
of 200 cmꢂ1 minꢂ1 and spectral width of 4.0 cmꢂ1. NMR spectra
were recorded with a Bruker DPX-400 (400 MHz) NMR spectrom-
eter using DMSO-d6 as the solvent for 1H NMR and 13C NMR.
TMS has employed as an internal standard.
tometer (Mo K
a radiation, k = 0.71073(Å) at 296 K [17]. X-ray
diffraction analysis has revealed that the title compound
crystallized in a monoclinic system with a space group of P21/c.
The unit cell dimensions are a = 11.3499(11) Å, b = 8.9828(6) Å,
c = 13.5460(12) Å and V = 1376.1(2) Å3. The structure was solved
by direct methods using SHELXS-97 [18] and refined by a full-ma-
trix least-squares procedure using SHELXL-97 [18]. Molecular
graphics were prepared using ORTEP3 for Windows [19] and soft-
ware used to prepare the materials for publication: WinGX [20]. H1
and H4 of C14H13ClN2O2 were located in a difference Fourier map
and refined independently with isotropic displacement parameters
[O1AH1 = 0.89(4) Å and N2AH4 = 0.74(3) Å]. The other hydrogen
compounds were positioned geometrically and refined using a rid-
ing model, fixing the aromatic CAH distance at 0.93 Å and methyl
CAH distance 0.96 Å [Uiso(H) = 1.2Ueq(C, N) and Uiso(H) = 1.2Ueq(-
methyl C)]. The final difference Fourier maps showed no peaks of
chemical significance. The details of the crystal data, data collec-
tion, structure solution, and refinement for the structure of C14H13-
ClN2O2 are given in Table 1. Selected bond distances and bond
angles are given in Tables 2 and 3.
Synthesis
4-Chloro-N-(2-methoxyphenyl) benzamidoxime (CMB) was
synthesized according to the literature [16]. Chlorine gas (0.88 g)
Computational details
The crystal structure of the CMB monomer in the ground state
was used as an initial molecular geometry. The geometry optimiza-
tion of the molecule was carried out by using DFT/ B3LYP [21,22]
method with a 6-311G (d,p) basis set. The calculations were per-
formed by the GAUSSIAN-09W software package [23] and Gauss-
View 5.0 [24] molecular visualization program. The molecular
structure and vibrational frequencies of CMB as a dimer were stud-
ied by using a B3YLP/6-311G (d,p) basis set. The frequencies from
the B3LYP/6-311G (d,p) calculations have been scaled by a factor of
0.9682 [25].
Shielding tensors of this compound were evaluated by using the
GIAO (Gauge-Including Atomic Orbitals) formalism [26,27] imple-
mented in the Gaussian package, with the B3LYP functional, in con-
junction with the basis set given above. In order to express the
chemical shifts in ppm, the geometry of the tetramethylsilane
(TMS) molecule was optimized and its NMR spectrum was
Fig. 1. The molecular structure of C14H13ClN2O2, showing the atom- numbering
scheme. Displacement ellipsoids for non-H atoms are shown at 50% probability
level.

Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
353
Table 1
Table 3
Crystal data and structure refinement for compound C14H13ClN2O2.
Experimental and optimized geometrical parameters of CMB [bond length (Å), bond
angles (°), dihedral angles (°)].
Emprical formula
Formula weight
Temperature (K)
Wavelenght(Å)
Crystal system
Space group
a (Å)
C14H13ClN2O2
354.83
296 (2)
0.71073
Monoclinic
P21/c
11.3499(11)
8.9828(6)
13.5460(12)
90.000
94.865(7)
90.000
Parameters
Exp(a)
B3LYP(b)
B3LYP(c)
6-311G(d,p)
6-311G(d,p)
Bond lengths (Å)
C1AC2
C2AC3
C3AC4
C4AC5
C5AC6
C6AC1
C1AC7
C8AC9
1.390
1.388
1.382
1.381
1.381
1.382
1.388
1.491
1.405
1.379
1.392
1.374
1.391
1.379
1.406
1.376
1.262
1.377
1.350
1.399
1.745
0.961
1.012
2.160
2.540
–
1.399
1.391
1.390
1.391
1.390
1.400
1.483
1.416
1.390
1.398
1.387
1.396
1.394
1.403
1.376
1.295
1.399
1.369
1.421
1.760
0.983
1.013
2.121
2.549
2.586
3.223
1.860
1.860
2.778
2.228
2.586
2.121
2.549
1.380
1.362
1.364
1.386
1.381
1.477
1.403
1.369
1.382
1.368
1.383
1.381
1.401
1.358
1.285
1.419
1.367
1.422
1.733
0.886
0.743
2.126
2.511
2.608
3.216
1.896
1.896
2.739
2.739
2.608
2.127
2.511
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
1376.1(2)
4
1.336
0.277
C9AC10
Z
Density (calculated) (g cmꢂ3
)
C10AC11
C11AC12
C12AC13
C13AC8
C8AN2
N2AC7
C7AN1
N1AO1
C9AO2
O2AC14
C4ACl1
Absorption coefficient (mmꢂ1
F (000)
)
576
Crystal size (mm)
h Range for data collection (°)
h, k, l range
0.63 ꢃ 0.52 ꢃ 0.45 mm
2.72–26.50
ꢂ14 6 h 6 14
ꢂ11 6 k 6 11
ꢂ16 6 l 6 16
2846
2846 [R(int) = 0.0435]
2846/0/181
Integration
0.9081 and 0.8527
Full-matrix least-squares on F2
R1 = 0.0557, wR2 = 0.1427
R1 = 0.0882, wR2 = 0.1589
1.031
Reflections collected
Independent reflections
Data/restraints/parameters
Absorption correction
Tmax/Tmin
O1AH1
N2AH4
N2AH4ꢁ ꢁ ꢁO1
Refinement method
Final R indices [I > 2r(I)]
N2ꢁ ꢁ ꢁO1
O1AH1ꢁ ꢁ ꢁO10
O1ꢁ ꢁ ꢁO10
O1AH1ꢁ ꢁ ꢁN10
O10AH10ꢁ ꢁ ꢁN1
O1ꢁ ꢁ ꢁN10
O10AN1
R indices (all data)
Goodness of fit on F2
–
–
–
–
–
–
–
–
Largest diff.peak and hole(e Åꢂ3
CCDC deposition number
)
0.479 and ꢂ0.439
910511
O10AH10ꢁ ꢁ ꢁO1
N20AH40ꢁ ꢁ ꢁO10
N20ꢁ ꢁ ꢁO10
Table 2
Hydrogen bonding geometry(Å, °).
O1AH1ꢁ ꢁ ꢁN10 0.89(4) 1.90(4) 2.739(3) 158(3) ꢂx + 2, ꢂy + 1,
Bond angles (°)
O1AN1AC7
O2AC9AC8
O2AC9AC10
N1AC7AC1
C8AN2AC7
N1AC7AN2
C1AC6AC5
C1AC2AC3
C1AC7AN2
C8AC9AC10
C8AC13AC12
C9AC10AC11
C9AC8AC13
N2AC7AC1
N2AC8AC9
N2AC8AC13
Cl1AC4AC5
Cl1AC4AC3
C14AO2AC9
C6AC1AC2
C2AC3AC4
C3AC4AC5
C7AC1AC2
C7AC1AC6
C4AC5AC6
C2AC1AC7
C13AC8AC9
C13AC8AN2
C10AC11AC12
C8AC13AC12
N1AO1AH1
N2AH4ꢁ ꢁ ꢁO1
N10AO10AH10
N20AH40ꢁ ꢁ ꢁO10
O1AH1ꢁ ꢁ ꢁO10
O10AH1ꢁ ꢁ ꢁO1
110.74
114.53
125.28
115.58
131.57
121.84
120.34
120.75
115.58
120.19
120.30
120.04
118.95
122.42
115.96
125.05
119.34
119.26
117.67
118.66
119.24
121.40
120.20
121.14
119.58
120.20
118.95
125.05
120.34
120.30
98.39
112.20
115.18
124.73
116.49
126.58
123.38
120.66
120.65
119.84
120.08
120.90
120.22
118.90
119.84
116.89
124.19
119.44
119.43
119.91
119.17
119.20
121.12
120.36
120.42
119.20
120.36
118.90
124.19
120.01
120.90
102.06
102.01
–
112.36
114.68
124.98
116.52
129.50
121.36
120.73
120.79
121.80
120.33
120.72
120.11
118.67
121.80
116.47
124.84
119.40
119.43
118.57
118.96
119.14
121.16
120.74
120.74
119.21
120.24
118.67
124.84
119.91
120.72
101.71
103.07
101.71
103.07
122.47
122.47
ꢂz + 1
O1AH1ꢁ ꢁ ꢁO10 0.89(4) 2.61(4) 3.216(4) 126(3) ꢂx + 2, ꢂy + 1,
ꢂz + 1
N2AH4ꢁ ꢁ ꢁO10 0.74(3) 2.12(3) 2.511(3) 113(3)
calculated by using the same method and basis set as in the case of
the calculations on CMB. The calculated isotropic shielding con-
stants were then transformed to chemical shifts relative to TMS
by di = rTMS–ri.
Results and discussion
The geometrical structure of CMB
The crystal structure analysis of the CMB compound confirmed
the compound as 4-chloro-N-(2-methoxyphenyl) benzamidoxime
(Fig. 1). As seen Fig. 1, the amidoxime group is present in its neutral
form, N2AC7@N1AO1AH1, and the bond lengths and angles are
within normal ranges [28]. The mean planes of the 2-methoxy-
phenyl and the 4-chorophenyl rings are tilted with respect to each
other by 61.42 (9)° and, the amidoxime group forms dihedral an-
gles with the 2-methoxyphenyl and the 4-chlorophenyl rings of
33.09(1)° and 44.89(1)°, respectively. This value is less than that
reported for the bulky substituted N-aryl compound [29] due to
the lesser influence of steric crowding in the title compound.
The geometry of the solid-state structure is subject to intermo-
lecular forces, such as Van der Waals interactions and crystal pack-
ing forces. The biggest differences of bond amidoxime derivatives
show geometric isomerism because of the double bond between
the N and C atoms. The resulting structure of amidoximes showed
112.91
98.41
112.88
126.52
126.53
–
–
–
(continued on next page)

354
Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
as donor and acceptor of proton with interatomic distance of
Table 3 (continued)
2.739(3) and 3.216(4) Å for O1ꢁ ꢁ ꢁN10 and O1ꢁ ꢁ ꢁO10, respectively.
The molecule C14H13ClN2O2 contains two ring systems. For the
C1AC6 and C8AC13 rings we calculated, following the method of
Parameters
Exp(a)
B3LYP(b)
B3LYP(c)
6-311G(d,p)
6-311G(d,p)
O1AH1ꢁ ꢁ ꢁN10
O10AH10ꢁ ꢁ ꢁN1
158.13
158.12
–
–
154.02
154.02
Cremer and Pople [31],
2 = 171.19(9)° and a puckering amplitude Q = 0.0192(3) and a
phase angles h2 = 104.08(9)° and 2 = 115.98(9)°, and a puckering
a phase angles h2 = 70.33(8)° and
u
Dihedral angles (°)
C1AC7AN1AO1
C8AC9AC10AC11
C8AC13AC12AC11
C8AC9AO2AC14
C9AC10AC11AC12
C9AC8AC13AC12
C9AC8AN2AC7
N2AC7AC1AC6
N2AC8AC9AC10
N2AC8AC13AC12
Cl1AC4AC5AC6
Cl1AC4AC3AC2
C14AO2AC9AC10
C6AC1AC2AC3
C7AC1AC2AC3
C2AC3AC4AC5
C2AC1AC6AC5
C3AC4AC5AC6
C7AC1AC6AC5
C4AC5AC6AC1
C6AC1AC7AN1
C2AC1AC7AN1
C6AC1AC7AN2
C2AC1AC7AN2
C8AN2AC7AC1
N2AC7AN1AO1
N2AC7AC1AC2
C13AC8AC9AO2
C13AC8AC9AC10
C13AC8AN2AC7
C10AC11AC12AC13
C10AC9AO2AC14
C7AN1AO1AH1
N1AC7AN2AH4
N10AC70AN20AH40
N1AO1AH1ꢁ ꢁ ꢁN10
O1AH1ꢁ ꢁ ꢁN10AO10
H1ꢁ ꢁ ꢁN10AO10AH10
N10AO10AH10ꢁ ꢁ ꢁN1
O10AH10ꢁ ꢁ ꢁN1AO1
H10ꢁ ꢁ ꢁN1AO1AH1
u
ꢂ179.04
0.89
ꢂ179.61
0.21
ꢂ179.40
ꢂ0.19
ꢂ1.21
ꢂ177.43
0.98
amplitude Q = 0.0163(3), respectively.
We have investigated theoretically using quantum chemical
methods of the title compound in order to explain the features of
the molecular structure, FT-IR, FT-Raman and NMR spectra of
CMB. Therefore, firstly, we have optimized CMB as monomer and
dimer forms. The optimized geometries in both forms obtained
using the B3LYP/6-311G (d,p) method are shown in Fig. 4.
The geometry of the monomer structure was determined at the
B3LYP level of theory employing a 6-311G (d,p) basis set. The cal-
culated geometric parameters using the DFT/B3LYP method with a
6-311G (d,p) level for the CMB monomer were compared with the
X-ray geometrical parameters in Table 3. Comparing the theoreti-
cal values with the experimental ones indicates that most of the
optimized bond lengths are slightly larger than the experimental
values, as the theoretical calculations are performed for an isolated
molecule in the gaseous phase and the experimental results are for
a molecule in a solid state.
In the crystal structure, the C7@N1 bond length in the CMB
(1.285 Å) is almost equal in value to the standard value typical of
oximes [32] and amidoximes (ꢄ1.272–1.287 Å) [30]. This bond
length has been calculated as 1.262 Å for B3LYP methods for
CMB. The C7@N1 bond length is typical of X ¼ C2sp ꢂ Ns2p bonds
[32], whereas the C(8)AN(2) bond is slightly longer [1.401 Å],
which is characteristic of monosubtituted benzamidoximes. These
1.86
1.50
178.91
ꢂ0.78
ꢂ1.72
169.03
ꢂ42.91
178.21
ꢂ179.37
ꢂ177.24
176.97
ꢂ0.33
0.49
178.98
ꢂ0.97
ꢂ2.23
166.37
ꢂ33.24
ꢂ179.86
179.10
ꢂ179.67
179.91
ꢂ0.10
0.20
1.96
ꢂ170.84
36.16
ꢂ179.77
ꢂ179.66
179.71
ꢂ179.70
1.84
0.16
ꢂ179.96
ꢂ2.51
ꢂ0.77
2.24
177.70
ꢂ0.06
0.05
ꢂ177.25
0.15
0.15
0.30
ꢂ0.14
177.25
0.14
179.68
ꢂ0.56
132.48
ꢂ47.06
ꢂ42.91
137.56
ꢂ25.87
ꢂ3.59
137.54
ꢂ178.93
0.35
ꢂ13.25
ꢂ0.60
ꢂ0.33
175.68
ꢂ7.93
7.87
ꢂ177.45
ꢂ0.30
140.72
ꢂ36.75
ꢂ33.24
149.30
ꢂ40.87
ꢂ6.16
149.61
ꢂ177.76
1.37
ꢂ137.40
39.96
36.16
ꢂ146.48
ꢂ37.87
ꢂ5.82
146.49
178.04
ꢂ1.26
10.76
ꢂ14.94
results can be attributed to competition between electronic (n–
p
0.13
ꢂ0.27
ꢂ0.10
174.71
ꢂ13.33
1.84
interactions) and steric effects. These calculated bond lengths with
B3LYP method show the same tendency as experimental values.
Secondly, the molecular geometric parameters of the CMB di-
mer were also investigated by using the B3LYP/6-311G (d,p) level
(Fig. 4). The molecular structure of CMB dimer forms via two short
OAHꢁ ꢁ ꢁN (with the participation of the OAH of N-hydroxyl group
and the N atom of the other N-hydroxyl group) and two OAHꢁ ꢁ ꢁO
hydrogen bonds (with the OAH of N-hydroxyl group and the O
atom of the other N-hydroxyl group). The experimental selected
geometrical parameters of the CMB dimer are given in Table 2.
Comparative results obtained from the X-ray crystallographic and
computational studies of bond distances, angles and torsion angles
of the CMB dimer are presented in Table 3. The calculated geomet-
rical parameters of the CMB dimer have slightly larger bond
lengths of monomer form. Moreover, the largest discrepancies of
bond angles were observed for the angles that corresponded to
the nitrogen atoms in the amide and oxime groups.
175.81
ꢂ12.07
12.08
14.65
–
–
–
–
–
5.72
ꢂ14.85
ꢂ5.78
5.52
2.58
ꢂ14.57
14.79
ꢂ5.54
5.72
5.78
ꢂ2.58
a
X-ray structure of CMB.
Monomer form of CMB.
Dimer form of CMB.
b
c
that, oxime groups can have either a Z or an E configuration. The
amidoxime configuration is Z since the AOH group is in the same
direction as the ANH group. X-ray data shows that in the crystal
of CMB, a Z configuration can also be exhibited (Fig. 1) by stabiliza-
tion due to an intramolecular NAHꢁ ꢁ ꢁO hydrogen bond formed
through the ANH group of amide and the oxygen atom of oxime
(Table 2). It is presumed that this intramolecular hydrogen bond
contributes significantly to stabilization of a Z configuration of
N-unsubstituted and N-monosubstituted amidoximes [30].
As illustrated in Fig. 2 the hydrogen bond is of crucial impor-
tance to the self-assembly. Molecules are paired by two hydrogen
bonds involving the N-hydroxyl group rather than the amidoxime
moieties. Analysis of the crystal packing (Fig. 3) reveals that the
molecules are linked by intramolecular N2AH4ꢁ ꢁ ꢁO1 and intermo-
lecular O1AH1ꢁ ꢁ ꢁN10 and weak O1AH1ꢁ ꢁ ꢁO10 hydrogen bonds (Ta-
ble 2), forming a chain running along the b axis. O1AH1ꢁ ꢁ ꢁN10,
O10AH01ꢁ ꢁ ꢁN1, O1AH1ꢁ ꢁ ꢁO10 and O10AH10ꢁ ꢁ ꢁO1 hydrogen bonds
link pairs of molecules, forming centrosymmetric dimers. The
intermolecular interactions O1AH1ꢁ ꢁ ꢁN10 (ꢂx + 2, ꢂy + 1, ꢂz + 1)
and O1AH1ꢁ ꢁ ꢁO10 (ꢂx + 2, ꢂy + 1, ꢂz + 1) show that atom O1 act
Buzykin et al. [30] have shown O1ꢁ ꢁ ꢁN10 bond length as 2.789 Å
for N-phenyl-4-nitrobenzamidoxime in the crystal structure.
Although the experimental O1ꢁ ꢁ ꢁN10 bond length of CMB is found
as 2.739 Å (Table 2), this value is calculated as 2.778 Å by using
the B3LYP/6-311G (d,p) method. In addition, O1ꢁ ꢁ ꢁO10 bond length
of CMB is found as 3.216 Å (Table 2), this value is calculated as
3.223 Å a by using the B3LYP/6-311G (d,p) method.
The
N2AC7AN1AO1 = ꢂ3.59 Å, 4-chlorophenyl and 2-methoxyphenyl
rings were flat (C2AC1AC6AC5, C4AC5AC6AC1,
amidoxime
group
has
a
Z
configuration
C13AC8AC9AC10, C10AC11AC12AC13) because of having
approximately 0 Å dihedral angle. The dihedral angle between 4-
chlorophenyl ring and oxime group was ꢂ179.04 Å
(C1AC7AN1AO1). Similarly, the twist angle C9AC8AN2AC7 is
169.03 Å for between 2-methoxyphenyl ring and amide group. As
a result, the phenyl rings, amide and oxime group were not

Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
355
Fig. 2. A pair of molecules linked through intermolecular OAHꢁ ꢁ ꢁN bonds [Symmetry code: (i) ꢂx + 2, ꢂy + 1, ꢂz + 1]. Hydrogen bonds are shown as dashed lines.
the B3LYP/6-311-G (d,p) level are shown in Fig. 5. The HOMO is lar-
gely located on the oxime group (@NOH), 4-chlorophenyl and ami-
no group (ANH) moieties. The LUMO is localized on the oxime
group (@NOH), 2-methoxyphenyl and amino group (ANH)
moieties.
The energy levels of the HOMO (EHOMO) and LUMO (ELUMO) orbi-
tals computed at the B3LYP/6-311G (d,p) level for the title com-
pound is represented in Fig. 5, as stated above. An electronic
system with a larger EHOMO–ELUMO energy gap should be less reac-
tive than one with a smaller gap [33]. According to the MO calcu-
lations for this compound, the energy gap between EHOMO and
ELUMO is 4.322 eV; this large energy gap indicates that the title
compound should be quite stable.
Mulliken atomic charge population [34] has an important role
in the application of quantum chemical calculations to the molec-
ular system. This is because atomic charges affect the dipole mo-
ment, polarizability, electronic structure and other properties of
molecular systems. The selected atomic charges of the CMB mono-
mer obtained by Mulliken population analysis with B3LYP meth-
ods with a 6-311G (d,p) basis set are listed in Table 4. From the
listed atomic charge values, O1, O2, N1, N2 and C4 atoms exhibit
large negative charges, as do behaved electron donors. It is found
that the most positively charged atom is C7 as a behaved electron
acceptor.
Fig. 3. The crystal structure of (CMB). Hydrogen bonds are indicated by dashed
lines.
coplanar. As can be seen (Table 3) there was a good agreement
between experimental and calculated dihedral angles.
The analysis of 1H and 13C NMR spectra
Electronic properties of the studied molecules
The experimental and calculated NMR (1H and 13C) chemical
shifts for CMB are shown in Table 5 as values relative to TMS.
Experimental 1H and 13C NMR spectra are presented in Fig. 6
and Fig. 7, respectively. The correlation between the experimental
and calculated data was satisfactory (Table 5, R2 = 0.9906 for 1H
NMR spectrum, R2 = 0.9824 for 13C NMR spectrum). The 1H
The frontier molecular orbitals, HOMO (highest occupied
molecular orbital) and LUMO (lowest unoccupied molecular orbi-
tal) determine the way a molecule interacts with other species
and helps to characterize the chemical reactivity and the kinetic
stability of the molecule [33]. The HOMO and LUMO obtained by

356
Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
Fig. 4. The optimized structure obtained using B3LYP/6-311G(d,p) level of CMB molecule in the (a) monomer and (b) dimer form.
NMR spectrum of CMB in DMSO-d6 a signal at 10.78 ppm (corre-
sponding to the oxime AOH) appears, indicating the acidic nature
of this proton. This result is consistent with current literature
[35]. Cibian et al. [35] report a signal of OH at 10.66(s) ppm for
4-bromo-N-phenylbenzamidoxime. In this study, the signal of
the amide group (NH) was observed at 7.44(s) ppm. The aromatic
protons were observed in the NMR spectrum at 7.39–6.28 (m)
ppm. The protons on the methoxy group attached to C14 are
responsible for the singlet at 3.78 (s)ppm in the 1H NMR spec-
trum. In the 13C NMR spectrum, the chemical shift value of the
iminic carbon (C@N) was observed at 150.02 ppm. This value is
in agreement with the value reported earlier at 154 ppm for
N-(1-adamantyl)pyridine-2-carboxamideoxime by Arikan et al.
[36]. The signal at 149.29–111.67 and 56.14 ppm in the 13C
NMR spectrum corresponded to the aromatic carbons and carbon
of the methoxy group, respectively.

Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
357
Fig. 5. Calculated HOMO and LUMO energies using B3LYP/6311-G(d,p) level.
Table 5
Theoretical and experimental 13C and 1H isotropic chemical shifts (with respect to
TMS, all values in ppm) for the title compounds (CMB).
Table 4
The Mulliken atomic charges obtained by B3LYP meth-
ods with 6-311G(d,p) basis set for CMB molecule.
Atom
Exper.
GIAO
C(9)
C(7)
C(4)
C(1)
C(8)
C(6)
C(3)
C(2)
150.02
149.29
134.34
131.94
129.87
129.85
129.57
129.55
129.01
122.67
120.94
120.14
111.67
56.14
153.79
152.23
148.66
136.23
134.44
134.14
132.75
132.36
132.08
123.96
123.39
121.23
110.33
54.33
Atoms
O1
N1
C1
O2
N2
C2
ꢂ0.341
ꢂ0.209
ꢂ0.162
ꢂ0.376
ꢂ0.469
ꢂ0.030
0.022
C(5)
C3
C(11)
C(12)
C(13)
C(10)
C(14)
C4
C5
ꢂ0.234
0.025
C6
C7
ꢂ0.029
0.357
C8
0.122
Correlation coefficient (CC) R2
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(10)
H(11)
H(12)
H(13)
H(14A)
0.9824
10.79
7.75
7.36
7.27
7.16
7.13
6.74
6.52
6.50
6.07
4.09
3.64
3.59
0.9906
C9
0.181
C10
C11
C12
C13
C14
Cl
ꢂ0.124
ꢂ0.096
ꢂ0.103
ꢂ0.072
ꢂ0.130
ꢂ0.072
10.78
7.44
7.39
7.32
6.99
6.93
6.88
6.63
6.31
6.28
3.78
3.78
3.78
The analysis of the vibrational spectra
H(14B)
H(14C)
The experimental FT-IR and FT-Raman spectra along with the
theoretical spectra of CMB are represented in Figs. 8 and 9. The ob-
served and calculated frequencies using B3LYP/6-311G (d,p)
Correlation coefficient (CC) R2
In ppm based on the TMS reference, computed at the B3LYP/6-311(d,p) level.

358
Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
Fig. 6. Experimental 1H NMR spectrum of CMB.
Fig. 7. Experimental 13C NMR spectrum of CMB.
method together with their relative intensities, probable assign-
ments are summarized in Table 6.
with the OH stretching vibration occurred near 3250 cmꢂ1 in the
- and near 3115 cmꢂ1 in the b-oximes. In the crystal structure
a
In the high frequency region of the IR spectrum, the absorption
bands (due to OH, NH, CH and CH3 stretching vibrations) can be ex-
pected to appear. In oximes, the position of the band associated
of the benzamide oxime compound, it is connected via intermolec-
ular O1AH1ꢁ ꢁ ꢁN10, O10AH10ꢁ ꢁ ꢁN1, O1AH1ꢁ ꢁ ꢁO10 and O10AH10ꢁ ꢁ ꢁO1
hydrogen bonds to form
a two dimensional supramolecular

Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
359
Fig. 8. (a) Experimental and (b) simulated FT-IR spectra of CMB.
structure. The band on the lower frequency side is the result of
intermolecular associations [37]. In the IR spectrum of CMB, it is
observed at 3217 cmꢂ1 and calculated at 3339 cmꢂ1. Therefore,
the CMB used in our study is the dimer form in the solid state.
In amines, the NAH stretching vibrations occur in the region of
3500–3300 cmꢂ1. The strong and sharp band at 3377 cmꢂ1 in the
FT-IR spectrum is assigned to the NH stretching band. The NH
stretching of CMB has been calculated using the B3LYP/6-311G
(d,p) method at 3456 cmꢂ1. In this study, the lower ANH stretching
frequency is due to the presence of NAHꢁ ꢁ ꢁO inter molecular
hydrogen bonding between CMB molecules. The NH and OH
stretching bands found in the calculated Raman spectrum were
not observed in the experimental spectrum of CMB.
The bands observed in the 3150–2975 cmꢂ1 region assigned to
the CH stretching vibrations in the CMB dimer are in very close
proximity to the reported [38] range of 3100–3000 cmꢂ1. In this
region, the bands are not appreciably affected by the nature of
substituents [39]. In Raman spectrum, the band observed at
ꢄ3070 cmꢂ1, can be attributed without ambiguity to a symmetric
CH stretching mode.
A combination of m(C7@N1), d(NOH) and m(C7AN2) is observed
very strong band in IR at 1640 cmꢂ1 having a medium Raman
counterpart at 1636 cmꢂ1. The theoretically computed value of
these frequencies at (1640 cmꢂ1 for IR and 1611 cmꢂ1 for Raman)
matches with the experimental value. The identification of CAN
vibrations is a very difficult task, since the mixing of several bands

360
Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
Fig. 9. (a) Experimental and (b) simulated FT-Raman spectra of CMB.
is possible in the region. In CMB, the CAN stretching bands are
found to be present at 1398 and 1215 cmꢂ1. The benzene ring
modes predominantly involve CC bonds. The CAC stretching fre-
quencies are generally predicted in the 1650–650 cmꢂ1. Several
ring modes are affected by a substituent in the aromatic ring with
heavy substituents. Therefore, the bands tend to shift to somewhat
lower wavenumbers and the greater the number of substituents on
the ring, the broader the absorption regions [39]. The CC stretching
of CMB molecule is found in the FT-IR spectrum at 1566, 1383 and
The a
- and b-oxime frequencies in the 1300 and 900 cmꢂ1 re-
gion, are attributed to OAH deformation and NO stretching modes
[37,40]. The bands at 1327 and 1332 cmꢂ1 in the infrared and
Raman spectra are attiributed OAH in plane deformation bands.
The NO stretching modes are observed in the Raman spectrum
at 959 cmꢂ1 and in the IR spectrum at 955 cmꢂ1
.
Below 1000 cmꢂ1 several in-plane and out-of-plane deforma-
tion modes have been observed in the CMB spectra. The CH out-
of-plane bending modes of benzene derivatives are observed in
the region 1000–600 cmꢂ1. The aromatic CH out-of-plane bending
vibrations of CMB in IR spectrum are assigned to medium to strong
1327 cmꢂ1 and in Raman spectrum at 1568, 1332 and 1332 cmꢂ1
respectively.
,

Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
361
Table 6
The observed FT-IR, FT-Raman and calculated [B3LYP/6-311G(d,p) levels] frequencies along with their relative intensities and possible assignments of 4-chloro-N-(2-
methoxyphenyl)benzamidoximes [harmonic frequencies (cmꢂ1), infrared (IR) intensities (km molꢂ1), Raman scattering activities (Å amuꢂ1)].
Obs. IR.
Obs. R.
Aa
Ba
IR inten.
Rel
Raman act
Rel Abs
Assignments
Abs
16.37
–
100
–
0.38
–
–
0.9
3377(vs)
3217(s)
3147(s)
3570
3570
3449
3399
3211
3211
3207
3206
3206
3205
3205
3193
3187
3136
3065
3006
1694
1664
1641
1639
1637
1635
1605
1592
1565
1540
1534
1521
1507
1496
1492
1485
1479
1454
1445
1427
1408
1407
1361
3456
3456
3339
3290
3109
3109
3105
3104
3104
3103
3103
3091
3086
3036
2968
2910
1640
1611
1589
1587
1585
1583
1554
1541
1515
1491
1485
1473
1459
1448
1444
1437
1431
1407
1399
1382
1363
1362
1317
128
–
782
–
3
2
–
7
–
1
–
–
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
as(N2H4),
s(N2H),
s(N20H40)
as(O1H1),
as(O10H10)
s(O10H10)
m
as(N20H40)
242
–
50
–
m
m
m
432
116
172
343
–
89
24
36
71
–
s(O1H1),
s(CH)ring1
s(CH)ring1
s(CH)ring2
0
0
0
3124(s)
as(CH)ring2
s(CH)ring2
as(CH)ring1
s(CH)ring1
,
m
as(CH)ring2
0
3070(mw)
3019(w)
–
49
206
8
10
43
1
, ms(CH)ring2
,
m
3047(ms)
3015(ms)
2999(ms)
2974(ms)
2941(m)
2914(w)
2847(w)
1640(vs)
0.13
4.48
0.13
5.63
4.35
9.21
16.37
66.24
–
m
as(CH)ring1
0
35
1
,
s(CH)ring1
0
0
171
341
177
151
297
–
35
71
37
31
61
–
as(CH)ring1
as(CH)ring2
,
,
m
as(CH)ring1
44
34
72
128
518
–
mas(CH)ring2
2947(w)
as(CH3),
as(CH3),
m
m
as(CH3)0
as(CH3)0
s(CH3),
m
s(CH3)0
(C70@N10),d(N20O10H40),
(C70@N10),d(N20O10H40),
m
m
(C70AN20),
(C70AN20),
m
m
(C7@N1), d(N2O1H4),
(C7@N1), d(N2O1H4),
m
m
(C7AN2)
(C7AN2)
1636(m)
1601(vs)
7
1
–
–
483
–
100
–
as(C9O2)ring1
,
m
as(CC)ring1
,
,
.ring1 mas(C90O20)
0
0
0
1597(s)
1566(vw)
178
56
26
3
–
705
–
216
62
84
37
16
–
14
–
17
108
–
22.76
7.16
3.32
0.38
–
(CC)
,
ring1 ring1 d(CCH)ring1 ring1
,
1568(w)
262
351
30
49
–
54
73
6
10
–
(CC)ring2, d(C8N2H)
(CC)ring1 (CC)ring2
d(CCH)ring2 (CCl),
0
0
,
m
,
m
(CC)ring1
(C7@N1)
,m(CC)ring2
,
m
m
d(OH), d(NH), d(OH), d(NH)
1504(vs)
90.15
–
d(OH), d(NH), d(OH)0, d(NH)0
1508(m)
360
26
–
75
5
–
d(OH),
d(OH),
m
m
(CC)0,d(NH)0,m(CCl)0,d(OH)0,
(CC)0,d(NH)0,m(CCl)0,d(OH)0,
m
m
(CC), d(NH),
(CC), d(NH),
m
m
(CCl)
(CCl)
27.62
7.93
10.74
4.73
2.05
–
1.79
–
2.17
13.81
–
1479(w)
1462(s)
d(OH), d(CH3),d(CCH)rings
25
6
5
1
d(CH3), d(CH3)0
d(CH3), d(CH)ring1, d(CH3)0, d(CH)ring1
d(CH3), d(CH3)0
0
1446(vw)
1414(mw)
32
73
–
7
15
–
d(N2H)0, d(CH3)0, d(OH)0, d(N2H), d(CH3), d(OH)
d(N2H)0, d(CH3)0, d(OH)0, d(N2H), d(CH3), d(OH)
d(N2H)0, d(CH3)0, d(OH)0, d(N2H), d(CH3), d(OH),
1404(mw)
118
–
24
–
m
m
(C70@N10),
(C70@N10),
m
m
(C7@N1),
(C7@N1),
1398(s)
1383(w)
d(N2H)0, d(CH3)0, d(OH)0, d(N2H), d(CH3), d(OH),
0
0
76
264
0
16
55
0
d(CH)ring2, d(C1C7), d(CH)ring2 , d(C1C7)
m
m
m
(C7C1),
(C7C1),
(CAOH),
m
m
m
(C7AN2),
(C7AN2),
(CC)ring1
m
m
(C7C1)0,
(C7C1)0,
(CAOH)0,
(CAOH)0,
m
m
m
(C7AN2)0
227
–
29.03
–
(C7AN2)0
1332(mw)
1300(vw)
281
58
,m
(CC)0ring1
(CC)0ring1
1327(mw)
1361
1318
55
7.03
–
–
m
(CAOH),
m
(CC)ring1
,m
m
0
1312(vw)
1296(mw)
1328
1324
1314
1276
1242
1203
1200
1187
1173
1155
1133
1125
1099
1075
1056
1029
1007
1000
985
1286
1282
1272
1235
1203
1165
1162
1149
1136
1117
1097
1089
1064
1041
1022
996
66
2
4
349
136
38
11
0
8.44
0.26
0.51
44.63
17.39
4.86
20
–
4
–
d(CH)ring1,ring1
d(CH)ring2, d(CH)ring2
0
5
1
m
m
m
c
(CC)ring2, d(CACl),
m
,
(CC)ring2
,
m
(CACl)0
m
0
(C90O20), d(CH3)0
0
1250(vs)
1215(mw)
1175(m)
1161(vw)
1246(vw)
1219(w)
1180(w)
1164(w)
28
18
20
22
31
6
6
4
4
5
6
1
(C9AO2),d(CH)ring1 ring1
(N2AC8)0,
(CH3),
(CH3)0
,d(CH3),
0
m(N2AC8), d(CH)ring1,ring1
c
1.41
d(CH)ring1
d(CH)ring1, d(CH)ring1
(CH3),
(CH3)0
0
1150(vw)
1130(s)
1
0.13
14.32
3.58
2.05
19.44
3.58
c
c
1133(w)
112
28
16
152
28
116
52
0
532
16
77
84
–
50
9
10
2
x
x
x
(CC)rings
(CC)rings
(CH)rings
,
,
x
x
(CH)rings
(CH)rings
1090(s)
1091(ms)
1053(mw)
1029(vw)
19
203
55
43
12
11
–
4
0
42
11
9
2
2
d(CC)ring2
,
,
m
(CACl),
m
(CACl)0
ring2
0
1028(s)
1014(m)
d(CC)ring1,ring1
0
14.83
6.65
d(CC)ring1 ring1
,
m
m
(C14AO2)
(CACl),
(CACl)0
0
d(CC)ring2
m
ring2
959(w)
975
968
954
941
903
900
m
m
x
s(N1AO1)
as(N1AO1)
(CH)ring2 rin2
955(s)
68.03
2.05
9.85
10.74
–
–
0
2
–
0.4
–
,
943(s)
916(mw)
972
933
930
d(CH)ring2
–
–
d(N2C7N1), d(N20C70N10), (CCC)rings
8
2
d(N2C7N1), d(N20C70N10), (CCC)rings
0
921
850
849
840
809
797
792
753
892
823
822
813
783
772
767
729
3
0.38
9.59
9.85
0.51
7.42
20.97
1.79
18.29
0.38
–
2
–
9
16
–
40
3
–
0.4
–
2
3
–
8
0.6
5
c
c
c
c
(CH)ring1,ring1
905(mw)
837(s)
75
77
4
58
164
14
143
3
(CH)rings
(CH)rings
(CH)ring2,
ring2
832(vw)
777(mw)
729(mw)
0
793(m)
748(vs)
721(w)
712(m)
Skeletal
(OH),
Skeletal
x
x
(OH)0
0
x
x
(CH)ring1,ring1
(CC)ring2,
ring2
0
740
716
25
(continued on next page)

362
Y.S. Kara et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 110 (2013) 351–363
Table 6 (continued)
Obs. IR.
Obs. R.
Aa
Ba
IR inten.
Rel
Raman act
Rel Abs
Assignments
Abs
3.20
3.20
–
–
–
1.92
–
3.45
5.63
–
5.88
4.09
–
0.64
–
0
730
707
25
53
–
–
–
15
–
27
44
–
46
32
–
5
–
–
27
54
–
23
–
–
–
x
x
x
x
(CC)ring1 ring1
,
669(w)
672(vw)
638(vw)
727
723
717
683
679
654
653
640
602
601
593
593
571
571
539
536
515
505
491
490
467
465
463
460
423
375
370
353
350
325
319
311
305
290
267
252
237
234
203
179
127
100
704
700
694
661
657
633
632
620
583
582
574
574
553
519
522
519
499
489
475
474
452
450
448
445
409
363
358
342
339
315
309
301
295
281
259
244
229
227
197
173
123
97
–
2
2
28
–
–
(CC),
(CON),
(OH),
x
(CO),
x
(CO)
0.4
0.4
6
x
(CON)0
x
(OH)0
t(N1C7N2)
Skeletal
638(vw)
–
7
1
c
c
(CC),
(CC),
c
c
(C7N2C8),
(C7N2C8),
c
c
(CC)0,
(CC)0,
0
c
c
(C7N2C8)0
(C7N2C8)0
621(mw)
591(vw)
0
0
594(vw)
0
0
d(CCCC)ring2, d(CCCC)ring2
42
–
9
–
c
c
c
c
(N2H4),
(N2H4),
(CCCC)ring2
c
c
(N2H4)0
579 (m)
561(vw)
(N2H4)0
0
0
–
–
,
,
c
c
(CCCC)ring2
(CCCC)ring2
9
2
(CCCC)ring2
0
0
t(ring1), t(ring1)0
t(ring1), t(ring1)0
t(ring2), t(ring2)0
t(ring2), t(ring2)0
2
11
–
0.4
2
–
–
513(m)
488(w)
3.45
6.91
–
2.94
–
–
1.15
2
5.75
–
–
1.54
1.28
–
–
1.79
–
2.69
–
0.38
–
2.81
0.90
–
0.51
–
490(w)
455(w)
413(w)
–
–
s(CNOH),
(CNOH),
s
s
(CNOH)0
(CNOH)0
10
–
2
–
s
459(w)
Skeletal
Skeletal
8
13
–
1.7
2.7
–
–
9
0
45
–
c
c
c
c
c
(ring1),
(ring1),
(ring1),
(skeletal)
(ring2),
c
c
c
(ring1)0,
(ring1)0
(ring1)0
c(ring2), c
(ring2)0
445(m)
2
–
0.4
–
407(vw)
373(w)
349(w)
5
1
c
(ring2)0
–
9
2
s(C7N1O1H1), s
(C7N1O1H1)0
12
10
–
–
14
–
21
–
3
–
22
7
–
–
c
c
(ring2),
(ring2)
c
(ring2)0
–
–
320(m)
14
25
0
3
5
0
s(C7N1O1H1),
s
s
(C7N1O1H1)0
(C7N1O1H1)0
s(C7N1O1H1),
OH,
c
(ring2)
(ring1), (ring1)
(CH3)0
278(w)
21
0
4
0
s
s
s
s
s
s
s
s
s
s
s
s(CH3), s
(CH3)0
(CH3), s
(O1H1N1),
250(vw)
215(mw)
4
1
s
(O1H1N1)0
0
0
(CH3),
(CH3),
(CH3),
(CH3),
(CNOH),
(CH3), (ring1),
(ring2),
(ring2)0,
(skeletal)
s
s
s
s
(CH3)0
(CH3)0
(CNOH),
(CH3)0
3
–
0.6
–
s , s
(CH3)0 (CNOH)0
–
–
173(mw)
–
4
–
–
9
2
s
(CNOH)0
(ring1)0
(ring1), s
(ring1)0
0
0
s
s
s
136(m)
98(vs)
5
1
s
–
6
1
c
Vibrational modes:
m, stretching; d, in-plane deformation; x, wagging; c, out-of-plane deformation; s, torsion ; q, rocking; s, strong; m, medium; mw, mediumweak, w, weak;
vw, very weak; sh, shoulder.
a
A: unscaled wavenumber and B: scaled wavenumber.
bands observed at 943, 905, 837 and 712 cmꢂ1. The corresponding
calculated wavenumbers are 941, 823, 822 and 729 cmꢂ1 by the
B3LYP/6-311G (d,p) level, respectively. They show close agreement
with observed bands of the title molecule. The aromatic CH in-
plane and out-of-plane bending vibrations have substantial over-
lapping with the ring CC in-plane and out-of-plane bending modes,
respectively. Only the calculated IR frequencies of the CMB dimer
below 400 cmꢂ1 are given in Table 6 because the lowest frequency
modes of the IR spectrum are not observed due to instrumental
restrictions.
CMB dimer were investigated in detail using the same method.
As a result, all the calculated and scaled vibrational frequencies
are in agreement with the FT-IR and FT-Raman spectra.
Acknowledgements
We would like to thank the Research Fund of Kocaeli University
(2011/007) for financial support of this research. The authors
acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs Uni-
versity, Turkey, for the use of the Stoe IPDS II diffractometer (pur-
chased under Grant F.279 of the University Research Fund). We
wish to thank O. Büyükgüngör (Department of Physics, Faculty of
Arts and Sciences, Ondokuz Mayıs University, Turkey) for the valu-
able contribution on the X-Ray analysis.
Conclusion
The crystal structure analysis of a novel N-Substituted amidox-
ime by using X-ray crystallography was confirmed the compound
as 4-chloro-N-(2-methoxyphenyl)benzamidoxime (CMB). FT-IR,
FT-Raman, 1H NMR and 13C NMR spectra of the CMB compound
were recorded and compared with theoretical calculations. The
calculated 1H NMR and 13C NMR chemical shifts by the B3LYP/6-
311G (d,p) method are in accordance with experimentally mea-
sured values. The vibrational frequencies and intensities of the
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