Spectral and crystal studies on 5-(ethoxycarbonylmethoxy)-9-(phenylazo) benzaldoxime: DFT approach

Article abstract of DOI:10.1016/j.saa.2014.01.037

Abstract 5-(Ethoxycarbonylmethoxy)-9-(phenylazo)benzaldoxime was synthesized from arylazosalicylaldehyde and characterized by IR, ¹H and ¹³C NMR spectroscopy. The crystal structure of title compound was determined by X-ray crystallog

Full text of DOI:10.1016/j.saa.2014.01.037

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Spectral and crystal studies on 5-(ethoxycarbonylmethoxy)-
9-(phenylazo)benzaldoxime: DFT approach
⇑
R. Balachander
Department of Chemistry, Achariya College of Engineering Technology, Villianur 605 110, Puducherry, India
Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamilnadu, India
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
ꢀ
2-(Ethoxycarbonylmethoxy)-5-
(phenylazo)benzaldoxime was
synthesized and characterized.
Conformation analyzed by spectral
and computational techniques.
Single crystal measurements also
support the same above
ꢀ
ꢀ
conformation.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 23 August 2013
Received in revised form 20 December 2013
Accepted 8 January 2014
Available online 21 January 2014
5-(Ethoxycarbonylmethoxy)-9-(phenylazo)benzaldoxime was synthesized from arylazosalicylaldehyde
and characterized by IR, 1H and 13C NMR spectroscopy. The crystal structure of title compound was deter-
mined by X-ray crystallography. Single crystal data reveal trans configuration of aromatic rings about
N@N bond and the two rings are nearly coplanar and oxime group adopts E configuration. The conforma-
tion of title compound was determined theoretically and NAO rotational barrier was also computed the-
oretically. HOMO–LUMO energies polarizability, hyperpolarizability, natural bond orbital (NBO), atom in
molecule (AIM) analysis and atomic charges were also calculated theoretically according to density func-
tional theory (DFT) method and analyzed.
Keywords:
5-(Ethoxycarbonylmethoxy)-9-
(phenylazo)benzaldoxime
Spectral
Ó 2014 Elsevier B.V. All rights reserved.
Computational
Crystal studies
Introduction
of compounds containing an arylazo group have been extensively
reported in the literature [4,5]. The oxidation–reduction behavior
Azo compounds are the oldest and largest class of industrial
synthesized organic dyes due to their versatile application in vari-
ous fields, such as dyeing textile fiber, biomedical studies, ad-
vanced application in organic synthesis and high technology
areas such as laser, liquid crystalline displays, electro-optical de-
vices and ink-jet printers [1–3]. The pharmaceutical importance
of these compounds play an important role in their biological
activity [6]. The preparation of new ligands is perhaps the most
important step in the development of metal complexes with un-
ique properties and novel reactivity [7]. Oximes and azo dyes have
often been used as chelating ligands and the biological importance
is also very well known [8]. Different oximes and their metal com-
plexes have shown notable bioactivity as chelating therapeutics, as
drugs as inhibitors of enzymes and as intermediates in the biosyn-
thesis of nitrogen oxides [9,10]. The present investigation focuses
on the synthesis and theoretical investigation of the molecular
⇑
Address: Department of Chemistry, Achariya College of Engineering Technol-
ogy, Villianur 605 110, Puducherry, India. Tel.: +91 9344790744.
E-mail address: svrbalu@gmail.com
1386-1425/$ - see front matter Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2014.01.037

R. Balachander / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
329
structure, charges, NBO and AIM analysis of 2-(ethoxycarbonyl-
Results and discussion
methoxy)-5-(phenylazo)benzaldoxime. HOMO–LUMO energies,
dipole moment, polarizability and first hyperpolarizability were
also determined by DFT method and analyzed.
5-(Ethoxycarbonylmethoxy)-2-(phenylazo)benzaldoxime was
synthesized as shown in Scheme 1 and characterized by 1H, 13C,
1H–1H and 1H–13C COSY spectra. The single crystal measurement
was also recorded for this compound. The labelling of the atoms
followed in the present study was indicated in Scheme 1.
Experimental
Synthesis of 5-(ethoxycarbonylmethoxy)-9-(phenylazo)benzaldoxime
NMR spectral analysis
The starting material 5-(ethoxycarbonylmethoxy)-9-(pheny-
lazo)benzaldehyde was prepared by stirring a mixture of 9-pheny-
lazosalicylaldehyde [11] (0.226 g, 1 mmol), ethylbromoacetate
(0.11 mL, 1 mmol) and potassium carbonate (0.5 g) in acetonitrile
(15 mL) for 24 h. The reaction mixture was filtered and the solvent
was evaporated to obtain 5-(ethoxycarbonylmethoxy)-9-(pheny-
lazo)benzaldehyde. The pure product was obtained by recrystalli-
zation from ethanol. Yield: 70%; m.p. 86 °C.
The signals in the 1H NMR spectrum (Fig. S1) were assigned
based on their positions, integrals and multiplicities. The triplet
and quartet appeared at 1.31 and 4.30 ppm are due to methyl
and methylene protons of the ethyl group attached to the COO
moiety. A singlet observed at 4.81 ppm is corresponding to meth-
ylene proton attached to the oxygen atom O–15. The singlet exhi-
bit at 8.64 ppm is due to the H–7 proton.
A mixture of 5-(ethoxycarbonylmethoxy)-9-(phenylazo)benzal-
dehyde (0.312 g, 1 mmol) and sodium acetate (0.5 g) was dissolved
in boiling ethanol and hydroxylamine hydrochloride (0.13 g,
2 mmol) was added. The mixture was refluxed for 3 h. The reaction
mixture was poured into water. The 5-(ethoxycarbonylmethoxy)-
9-(phenylazo)benzaldoxime separated out was filtered and recrys-
tallized from ethanol. Yield: 70%, m.p. 153 °C. IR (KBr, cmÀ1): 1605
The downfield doublet resonated at 6.93 ppm is corresponding
to the ortho proton with respect to OCH2COO moiety i.e., H–11. The
doublet seems at 8.37 ppm (integral corresponds to one proton)
and doublet of doublet observed at 7.97 ppm (integral corresponds
to one proton) are could be attributed to the ring proton H–8 and
H–10 respectively. The doublet nature of the signal for H–8 is due
to meta coupling (J8,10 = 5.00 Hz) and this coupling is also observed
in the signal for H–10 which appears as doublet of doublet due to
J8,10 (5.00 Hz) and J9,10 (10.00 Hz). The 1H NMR spectrum further
reveals that the downfield doublet at 7.89 ppm for ortho protons
of the phenyl ring attached to the nitrogen atom N–3 i.e., (H–13
and H–17). Two triplets at 7.50 (integral corresponds to two pro-
tons) and 7.47 ppm (integral corresponds to one proton) are also
observed for meta (H–14 and H–16) and para (H–15) protons of
the phenyl ring attached to nitrogen atom N–3. This assignment
is further confirmed by the correlations observed in the 1H–1H
COSY spectrum as shown in Fig. 1.
(mC@N), 1752 (mCOO), 3251 (mOH), 1316 (mN@N) and 1218 (dOH).
Spectral measurements
The 1H NMR (500 MHz) and 13C NMR (125 MHz) were recorded
at room temperature on Bruker 500 MHz instrument using 10 mm
sample tube. Samples were prepared by dissolving about 10 mg of
the sample in 2.5 mL of chloroform-d containing 1% TMS for 1H and
50 mg of the sample in 2.5 mL of chloroform-d containing a few
drops of TMS for 13C. The solvent chloroform-d also provided the
internal field frequency lock signal. The 1H–1H and 1H–13C COSY
spectra were performed on a Bruker 500 NMR spectrometer.
In 13C NMR spectrum (Fig. S2), the signals at 14.2 and 61.7 ppm
are due to the methyl and methylene carbon of ethyl group at-
tached to oxygen atom O–1. The methylene carbon attached to
oxygen O–3 resonates at 66.1 ppm. The low intense signal at
168.12 ppm is due to ester carbonyl carbon C–3 [14]. The signal
at 112.5 ppm is corresponding to ortho carbon with respect to oxy-
gen atom O–3 i.e., C–11. The high intense signals at 123.0 and
129.0 ppm are should be attributed to ortho (C–13 and C–17) and
meta (C–14 and C–16) carbons of the phenyl ring attached to nitro-
gen atom N–3.
Computational study
Geometry optimizations were carried out according to density
functional theory available in Gaussian-03 package using B3LYP/
6-31G(d,p) basis set [12] and also according to MP2 method using
the [CHELPG] basis set 6-31G(d) available in Gaussian-03 package.
The polarizabilities and hyperpolarizabilities were determined
from the DFT optimized structure by finite field approach using
B3LYP/6-31GÃ basis set, NBO calculations using the basis set
B3LYP/6-311+G(d,p) available in Gaussian-03 and AIM calculations
were done using B3LYP/6-31G(d,p) basis set. Charges, were also
calculated according to MP2 method using the [CHELPG] basis
set 6-31G(d) available in Gaussian-03 package.
The 13C NMR spectrum reveals four signals for quaternary car-
bons (C–6, C–5, C–9 and C–12) at 123.1, 157.7, 147.3 and
152.4 ppm [15–20] which can easily be distinguished from other
carbons based on small intensities. Among the signals for quater-
nary carbons, the downfield signal at 157.7 ppm is due to the ipso
carbon C–5 and this conformation is based on the deshielding nat-
ure of the oxygen atom compared to nitrogen and carbon atoms.
The signal at 123.1 ppm is assigned to ipso carbon C–6. Further-
more, the signal at 152.4 ppm is assigned to the ipso carbon C–12
which is attached to the nitrogen atom N–3. Obviously, the signal
at 147.3 ppm is assigned to the carbon C–9 which is para with re-
spect to the OCH2 moiety.
X-ray analysis
A
single crystal of title compound with the dimensions
0.30 Â 0.25 Â 0.20 mm was chosen for X-ray diffraction study.
Crystallographic measurements were done at 293(2) K with Bruker
axis Kappa CCD diffractometer using graphite monochromated Mo
The spectrum further reveals four signals at 146.0, 130.8, 126.3
and 121.8 ppm. Among these signals the high frequency signal
(146.07 ppm) is obviously due to carbon attached to NOH group
(C–7). The signals at 121.8 and 126.3 ppm are due to ortho carbons
(C–8 and C–10) of phenyl ring with respect to nitrogen atom N–2.
The para (C–15) carbon of the phenyl ring attached to the nitrogen
atom N–3 resonate at 130.8 ppm. This assignment is further con-
firmed by the correlations observed in the 1H–13C COSY spectrum
as shown in Fig. 2. Table 1 lists the NMR data of oxime.
Ka radiation (k = 0.71073 Å). The crystal structure was solved by
direct method and refined by full-matrix least square technique
on F2 using the SHELX-97 set of program [13]. The parameters in
the CIF form are available as electronic supplementary information
from the Cambridge Crystallographic Database Centre [CCDC
846567].

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R. Balachander / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
Scheme 1. Steps involved in the synthesis of oxime.
Fig. 1. 1H–1H COSY spectrum of oxime.
Conformational analysis
age [12] and the relative energies determined are found to be 0.0
(A), 1.757 (B), 0.126 (C) and 1.945 (D) kcal molÀ1. Thus, the theoret-
ical study predicts the favoured conformation as A (E configuration)
only. Potential energy scan over NAO bond in E configuration was
also carried out to predict the orientation of OH group of oxime moi-
ety in conformation A. The torsional angle C(7)AN(1)AO(4)AH(4)
was varied in steps of 10° from 0° to 180° and potential energy scan
diagram thus obtained is illustrated in Fig. 3. From the scan diagram
it is concluded that OAH bond is anti to C@N bond
[C(7)AN(1)AO(4)AH(4) = 180°] and this arrangement is favoured
the syn arrangement (torsional angle = 0°) and the barrier for this
process is determined to be 8.227 kcal molÀ1 (0.0131 Hartree). From
the favoured structure selected geometric parameters were derived.
The optimized structure of the favoured confirmation of oxime is
shown in Fig. 4. Single crystal measurements were also made for
the oxime and it also supports the same conformation. The ORTEP
structure and close packed diagram are shown in Fig. 5.
There are four possible conformations for the title compound as
shown in Scheme 2. The oxime moiety adopts E configuration in
conformations A and C and Z configuration in conformations B
and D. The conformers A and C differ in the conformation of
COOCH2CH3 group only, so also conformers B and D. The carbonyl
oxygen of ethoxycarbonyl group i.e., O–2 is on the same side as that
of alkoxy oxygen O–3 in conformations A and C whereas it is on
opposite side in conformations B and D. It is seen from Scheme 2
that steric interaction exists between oxime moiety and alkoxy moi-
ety in conformations C and D and hence not favoured in the present
study. Further E configuration of oxime is favoured over the Z con-
figuration generally and hence the favoured conformation is pre-
dicted to be A. In order to confirm the favoured conformation
computational calculations were performed according to DFT meth-
od using B3LYP/6-31G(d,p) basis set available in Gaussian-03 pack-

R. Balachander / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
331
Fig. 2. 1H–13C COSY spectrum of oxime.
Table 1
1H and 13C NMR chemical shifts (ppm) of oxime.
1H chemical shift
13C chemical shift
Carbon
Proton
d
d
H–11
H–10
H–8
H–7
6.93 (d, 10.00 Hz)
7.97 (dd)
8.37 (d, 5.00 Hz)
8.64
C–11
C–10
C–8
C–7
112.5
126.3
121.8
146.0
66.1
H–4
4.81
C–4
H–2
H–1
H–13 and H–17
H–14 and H–16
H–15
4.30 (q, 10.00 Hz)
1.31 (t, 10.00 Hz)
7.89 (d, 7.50 Hz)
7.50
C–3
C–2
C–1
C–6
C–5
C–9
C–12
C–13 and C–17
C–14 and C–16
C–15
168.1
61.7
14.2
123.1
157.7
147.3
152.4
123.0
129.0
130.8
7.47
XRD analysis
A summary of crystallographic data, experimental details and
refinement results for title compound are given in Table 2. The aro-
matic rings adopt a trans configuration about the N@N double
bond and are nearly coplanar with a dihedral angle of À179.2°. A
weak intramolecular interaction involving oxime OH and azo
nitrogen N2 (O4AH4Á Á ÁN2) i.e., hydrogen bond was also observed
and the values are also listed in Table 2 itself.
Molecular properties
Geometric parameters
Scheme 2. Possible conformations of oxime.
From the optimized geometrical parameters were derived from
DFT and MP2 method (Table S1). The selected XRD and computed
bond distances, bond angles and torsional angles for title com-
pound. The theoretical bond lengths and bond angles are closer
to the XRD values. However, for the torsional angles deviation is
noticed and the maximum deviation in torsional angles is found
to be 7°. The small differences between the theoretical and exper-
imental parameters can be attributed to the fact that the DFT

332
R. Balachander / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
Table 2
Crystal data and structural refinement for 5-(ethoxycarbonylmethoxy)-9-
(phenylazo)benzaldoxime.
Empirical formula
Formula weight
Temperature (K)
Wave length (Å)
Crystal system
Space group
a (Å)
C17H17N3O4
327.34
293(2)
0.71073
Monoclinic
P-21/c
7.4640(11)
b (Å)
22.034(3)
c (Å)
10.5312(17)
a
(°)
90
b (°)
108.709(4)
c
(°)
90
1640.4(4)
Volume (Å3)
Z
4
Dx (g cmÀ3
)
1.325
0.096
688
l
(mmÀ1
F (000)
)
Crystal size
h Range (°)
0.30 Â 0.25 Â 0.20 mm
1.85–27.50
Fig. 3. Potential energy scan diagram of oxime.
Index ranges
À5 6 h 6 9; À28 6 k 6 28; À13 6 l 6 13
18,653
3757
Semi-empirical from equivalents
0.9810 and 0.9717
Full-matrix least-squares on F2
3758/0/219
Reflections collected
Independent reflections
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices (all data)
1.055
R1 = 0.0508, wR2 = 0.1602
R1 = 0.0702, wR2 = 0.1832
0.510 and À0.274
R indices [I > 2
r(I)]
Largest diff. peak and hole (e ÅÀ3
)
Hydrogen-bonding geometry (Å) of oxime
DAHÁ Á ÁA
O4AH4
0.82
H4Á Á ÁN2
O4Á Á ÁN2
O4AH4Á Á ÁN2
O4AH4Á Á ÁN2
2.12
2.935(2)
170.6
Àx + 1, Ày, Àz + 1.
calculation was carried out with isolated molecule in the gaseous
phase, whereas the X-ray parameters were based on molecules in
the solid state.
Fig. 4. Optimized structure of oxime.
Energies, dipole moment and polarizabilities
HOMO–LUMO energies, electronic dipole moment, polarizabili-
ties and hyperpolarizabilities were also derived and the values are
listed in Table 3 and the HOMO–LUMO plots are given in Fig. 6. The
HOMO orbital is mainly derived from pz orbitals of carbon, nitro-
gen and oxygen atoms except those of COOCH2CH3 group [C3,
O2, O1, C2 and C1]. The formation of LUMO orbital does not involve
the participation of pz orbitals of carbon (C14), carbon (C7) and
oxygen (O4) of CH@NOH group and CH2COOCH2CH3 group [C4,
C3, O2, O1, C2 and C1].
Table 3
HOMO–LUMO energy (eV), dipole moment
ability of oxime.
l (D), polarizability and hyperpolariz-
HOMO–LUMO
Dipole moment
LUMO
HOMO
À5.73
D
E
lx
ly
lz
ltot
À2.08
3.65
1.62
À2.59
0.23
3.06
Polarizability
Hyperpolarizability
axx
axy
ayy
axz
ayz
azz
418.0532
0.0415
bxxx
bxxy
bxyy
byyy
bxxz
bxyz
byyz
bxzz
2005.8278
À3.8112
À10.3233
2.2064
À785.7970
À1.1818
58.9065
494.7646
À1.2076
À20.6832
225.0367
89.7557
À58.8608
À0.0555
276.1727
38.7228
atot (esu) Â 1024
byzz
bzzz
btot (esu) Â 1035
Fig. 5. ORTEP and close packed structures of oxime.

R. Balachander / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
333
delocalized on to the pure non-bonding p-orbitals available on
C–9 carbon atom, which in turn delocalized on to the nearby anti-
bonding orbitals of the vicinal C6AC8, N2AN3 and C10AC11 bonds.
This hyperconjugative interactions energy is found to be very high
(67.20, 73.50 and 73.95 kcal molÀ1) and this is the primary delocal-
ization seen in the oxime.
AIM analysis
We have calculated at DFT level the charge density
q(r) Lapla-
cian of (r) [
q
D
2q(r)] and ellipticity (e) at the position of the bond
critical points and charge density of the ring critical point in oxime
(Table S2). Atoms in molecules electron density topological analy-
sis revealed the existence of 41 bcp with a (3, À1) topology be-
tween the atoms connected by covalent bond. The negative
values obtained for the Laplacian except for C@O group are a clear
indication that the corresponding bonds are covalent bonds. Be-
sides these one more bond critical point is observed between C3
and O2 atoms (ester carbonyl group). The positive Laplacian of
the density at the BCP and high qBCP values for carbonyl group indi-
cate the ionic nature of the carbonyl group. Ring critical point of
phenyl ring attached to N–3 is slightly having higher electron den-
sity compared to the phenyl ring of the benzaldoxime moiety.
Charges
Charges calculated from NBO calculations and MP2 method
[CHELPG 6-31G(d) as basis set] (Table S3). From Table S3 it is in-
ferred that all hydrogens and sp2 carbons attached to electronega-
tive atoms such as oxygen and nitrogen [C–5, C–9, C–12, C–7 and
C–3] alone attain positive charge according to both the methods.
However for sp3 hybridized carbons attached to electronegative
atom oxygen [C–4 and C–2] the sign of charge predicted by MP2
method (positive charge) is opposite to that of NBO method (neg-
ative charge).
Fig. 6. HOMO–LUMO pictures of oxime.
NBO analysis
NBO analysis at B3LYP/6-311+G(d,p) level were carried out for
the oxime and the important second order perturbative estimates
of donor-acceptor interactions are displayed in Table 4. The occu-
pancies and the energies of the orbitals involved in primary delo-
calization are also reported in Table 4. The interaction between
filled and empty NBO’s can be described as a hyperconjugative
electron transfer process from the donor (filled) to the acceptor
(vacant) orbital and the energy lowering due to this interaction is
Conclusions
Structure of 5-(ethoxycarbonylmethoxy)-9-(phenylazo)ben-
zaldoxime was analyzed by NMR, single crystal measurement and
computational techniques. Oxime group adopts E configuration
expressed as E2. The
p-bonded electrons of C6AC8 bond are
Table 4
Energies, occupancies of primary donor and acceptor orbitals and their delocalization energies of oxime.
Donor NBO
Occupancy
Energy (a.u.)
Acceptor NBO
Occupancy
Energy
E2 (kcal molÀ1
)
BD(2)C6AC8
BD(2)C6AC8
BD(2)C6AC8
BD(2)C11AC10
BD(2)C11AC10
BD(2)N2AN3
BD(2)N2AN3
BD(2)C13AC14
BD(2)C13AC14
BD(2)C12AC17
BD(2)C12AC17
BD(2)C12AC17
BD(2)C15AC14
BD(2)C15AC14
LPÃ(1)C5
1.64084
1.64084
1.64084
1.70583
1.70583
1.91150
1.91150
1.67460
1.67460
1.61512
1.61512
1.61512
1.65995
1.65995
0.96579
0.96579
1.04304
1.04304
1.04304
1.83460
1.97871
1.83683
1.83683
1.79626
1.89819
À0.25420
À0.25420
À0.25420
À0.26446
À0.26446
À0.36446
À0.36446
À0.25152
À0.25152
À0.25028
À0.25028
À0.25028
À0.25227
À0.25277
À0.13283
À0.13283
À0.11451
À0.11451
À0.11451
À0.33454
À0.70101
À0.27465
À0.27465
À0.34183
À0.31587
LPÃ(1)C5
0.96579
1.04304
0.15597
0.96579
1.04304
1.04304
0.37241
0.37241
0.32614
0.21747
0.28890
0.32614
0.28890
0.37241
0.35384
0.31702
0.35384
0.31702
0.21747
0.96579
0.01930
0.07394
0.09849
0.21391
0.15597
À0.13283
À0.11451
0.01971
À0.13283
À0.11451
À0.11451
0.03130
0.03130
0.02981
À0.02188
0.03531
0.02981
0.03531
0.03130
0.03104
0.02257
0.03104
0.02257
À0.02188
À0.13283
0.91380
0.33961
0.36094
À0.00270
0.01971
65.25
45.13
15.85
58.12
38.87
17.66
10.58
19.65
20.87
20.30
19.21
19.52
18.55
21.08
51.02
53.59
73.50
73.95
67.20
54.21
15.33
20.98
31.07
47.18
17.80
LP((1)C9
BDÃ(2)C7AN1
LPÃ(1)C5
LP(1)C9
LP(1)C9
BDÃ(2)C12AC17
BDÃ(2)C12AC17
BDÃ(2)C15AC16
BDÃ(2)N2AN3
BDÃ(2)C14AC13
BDÃ(2)C15AC16
BDÃ(2)C14AC13
BDÃ(2)C12AC17
BDÃ(2)C6AC7
BDÃ(2)C11AC10
BDÃ(2)C6AC7
BDÃ(2)C11AC10
BDÃ(2)N2AN3
LPÃ(1)C5
LPÃ(1)C5
LPÃ(1)C9
LPÃ(1)C9
LPÃ(1)C9
LPÃ(2)O3
LPÃ(1)O2
RYÃ(1)C3
LPÃ(2)O2
BDÃ(1)C4AC3
BDÃ(1)C3AO1
BDÃ(2)C3AO2
BDÃ(2)C7AN1
LPÃ(2)O2
LPÃ(2)O1
LPÃ(2)O4

334
R. Balachander / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 125 (2014) 328–334
and NAO rotational barrier was computed to be 8.227 kcal molÀ1
Several molecular properties were determined from optimized
structure. Theoretically derived geometric parameters are com-
pared with the experimentally determined values.
.
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Acknowledgement
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The authors thank the NMR Research Centre, Indian Institute of
Science, Bangalore for recording the NMR spectra.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2014.01.037.
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