The synthesis, molecular structure, FT-IR and XRD spectroscopic investigation of 4-[(2-{[(2-furylmethyl)imino]methyl}-4-methoxyphenoxy)methyl] benzonitrile: A comparative DFT study

Article abstract of DOI:10.1016/j.molstruc.2010.12.049

4-[(2-{[(2-Furylmethyl)imino]methyl}-4-methoxyphenoxy)methyl]benzonitrile, a novel Schiff base compound, was prepared for the first time and its structural and vibrational properties were studied both experimentally and theoretically using FT-IR and XRD s

Full text of DOI:10.1016/j.molstruc.2010.12.049

Journal of Molecular Structure 991 (2011) 12–17
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
The synthesis, molecular structure, FT-IR and XRD spectroscopic investigation
of 4-[(2-{[(2-furylmethyl)imino]methyl}-4-methoxyphenoxy)methyl]benzonitrile:
A comparative DFT study
c
c
d
b
Özgür Alver a,b, , Zeliha Hayvalı , Hüseyin Güler , Hakan Dal , Mustafa Sßenyel
⇑
a Plant, Drug and Scientific Research Centre, Anadolu University, Eskißsehir, Turkey
b Department of Physics, Science Faculty, Anadolu University, Eskißsehir, Turkey
c Department of Chemistry, Ankara University, Ankara, Turkey
d Department of Chemistry, Science Faculty, Anadolu University, Eskißsehir, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 26 October 2010
Received in revised form 25 December 2010
Accepted 31 December 2010
Available online 4 February 2011
4-[(2-{[(2-Furylmethyl)imino]methyl}-4-methoxyphenoxy)methyl]benzonitrile, a novel Schiff base com-
pound, was prepared for the first time and its structural and vibrational properties were studied both
experimentally and theoretically using FT-IR and XRD spectroscopic methods. FT-IR spectrum was
recorded in the region of 4000–400 cmÀ1. The optimized geometric structures concerning to the mini-
mum on the potential energy surface was investigated by Becke-3-Lee–Yang–Parr (B3LYP) hybrid density
functional theory method together with 6-31(d) basis set. Vibrational wavenumbers were calculated
using B3LYP/6-31G(d) level of theory. Comparison between the experimental and theoretical results indi-
cates that density functional B3LYP method is able to provide satisfactory results for predicting vibra-
tional wavenumbers and structural parameters of the prepared Schiff base compound. Furthermore,
reliable vibrational assignments were made on the basis of total energy distribution (TED) calculated
with scaled quantum mechanical (SQM) method.
Keywords:
Schiff base compound
Infrared spectra
Conformational analysis
XRD
DFT
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
chemical investigation will aid in making assignments to the fun-
damental normal modes and clarifying the obtained experimental
Compounds with the structure XC@NY are known as Schiff
bases, which are usually synthesized from the condensation of pri-
mary amines and active carbonyl groups. Some Schiff bases, are
used as starting materials in the reactions of important drugs, such
as antibiotics and antiallergic and antitumor substances [1–4].
Major advances have been made in these materials due to their
interesting properties and potential in various applications, such
as host guest chemistry, biochemical relevant studies of metal
complexes, ion exchange, non-linear optics, electrical conductivity
[5–8]. Synthesis of new Schiff bases and their metal complexes are
still in the center of many recent investigations. 2-Furylmethyl-
amine Schiff base derivatives are very useful biochemical materials
having biological activities [9].
results for the investigated molecules.
In this study, first; 4-[(2-formyl-4-methoxyphenoxy)methyl]-
benzonitrile (I) was obtained by the reaction of 2-hydroxy-5-meth-
oxy-benzaldehyde with 4-bromomethyl-benzonitrile. Later, 4-[(2-
{[(2-furylmethyl)imino]methyl}-4-methoxyphenoxy)methyl]ben-
zonitrile (II) was prepared by the condensation of compound (I)
with 2-furylmethylamine in absolute ethanol (Scheme 1). Further-
more, X-ray crystallographic characterization, FT-IR vibrational
wavenumbers and structural parameters were identified both
experimentally and theoretically for compound (II) at B3LYP level
of theory using 6-31G(d) basis set.
2. Experimental
The B3LYP density functional model exhibits good performance
on electron affinities, excellent performance on bond energies and
reasonably good performance on vibrational frequencies and
geometries of organic compounds [10–15]. A detailed quantum
2.1. Instrumentation
FT-IR spectrum (4000–400 cmÀ1) was recorded KBr pellet tech-
nique using Perkin–Elmer FT-IR 2000 spectrometer with single
scan at a resolution of 4 cmÀ1. Crystallographic data were recorded
on a Bruker Kappa APEXII CCD area detector diffractometer using
⇑
Corresponding author at: Department of Physics, Science Faculty, Anadolu
University, Eskißsehir, Turkey. Tel.: +90 (222) 335 05 80/3668; fax: +90 (222) 320 49
10.
E-mail address: ozguralver@anadolu.edu.tr (Ö. Alver).
Mo Ka radiation (k = 0.71073 Å) at T = 100(2) K.
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.12.049

Ö. Alver et al. / Journal of Molecular Structure 991 (2011) 12–17
13
Scheme 1. The structures of the new compounds (I and II).
Fig. 1. The optimized structure of compound II.
2.2. Synthesis of 4-[(2-formyl-4-methoxyphenoxy)methyl]-
benzonitrile (I)
2.3. Synthesis of 4-[(2-{[(2-furylmethyl)imino]methyl}-4-methoxy-
phenoxy) methyl] benzonitrile (II)
2-Hydroxy-5-methoxy-benzaldehyde (0.388 g, 2.55 mmol), dis-
solved in 15 ml of DMF was added into 100 ml reaction flask
equipped with a condenser and magnetic stir bar. Anhydrous
NaOH (0.102 g, 2.55 mmol) was added to flask. After the mixture
was stirred for 1 h and then 4-bromomethyl-benzonitrile (0.5 g,
2.55 mmol) was dissolved in 10 ml DMF and added into the reac-
tion mixture. The resulting solution was heated for 6 days at
150 °C with continuous stirring, then the complete consumption
of the starting material was observed by TLC (silica, eluent; CHCl3).
After cooling, the product was poured into 250 ml cold water until
the solution turned cloudy. The beige precipitate formed was iso-
lated and recrystallized from ethanol. Yield 0.62 g, 73%, m.p.
110 °C.
The compound I (0.681 g, 2.55 mmol) was dissolved in 10 ml
EtOH. 2-Furylmethylamine (0.171 g, 2.55 mmol) was added slowly
dropwise to the reaction mixture. The resulting solution was stir-
red under reflux for 2 h and the reaction mixture was allowed to
stand 2 h at room temperature. Yellow crystals formed and these
were recrystallized from EtOH. Single crystals of compound II,
suitable for X-ray analysis, were obtained by slow evaporation of
ethanol at room temperature. Yield 0.40 g, 62%, m.p. 99 °C.
3. Calculations
For the calculations, compound II (Fig. 1) was first optimized at
B3LYP/6-31G(d) level in the gas phase. The optimized geometric

14
Ö. Alver et al. / Journal of Molecular Structure 991 (2011) 12–17
structures concerning to the minimum on the potential energy sur-
face were provided by solving self-consistent field (SCF) equation
iteratively. Basic molecular structure was drawn considering the
XRD data but no molecular restrictions were applied. For the vibra-
tional calculations, the vibrational frequencies were calculated
using the same method and the basis set under the keyword freq.
No imaginary frequencies were observed, therefore; the optimized
structure is not in the transition state for the investigated form.
TED calculations, which show the relative contributions of the
redundant internal coordinates to each normal vibrational mode
of the molecule and thus make it possible to describe the character
of each mode numerically, were carried out by the scaled quantum
mechanical (SQM) program [16,17] using the output files created at
the end of the wavenumber calculations. All the calculations were
performed with Gaussian 03 program on a personal computer [18].
Fig. 2. The structure obtained from XRD result.
4. Results and discussion
176.14°. In general geometric parameters seem to an agreement
with experimental findings. Possible differences could be due to
the fact that while experimental findings were obtained at very
low temperature and so the molecular rotations were restricted,
the theoretical results were obtained for a single molecule in the
gas phase without any intermolecular interactions.
4.1. Geometrical structures
The optimized geometric parameters (bond lengths, bond and
dihedral angles) calculated by B3LYP/6-31G(d) are listed in Table 1.
Obtained experimental XRD structure of compound II is given in
Fig. 2. Some critical calculated/experimental geometric parameters
are as following: R(10,12), R(11,16), R(16,19), R(29,30) and
R(26,29) are found as 1.419/1.428 Å, 1.416/1.417 Å, 1.512/1.498 Å,
1.163/1.144 Å and 1.434/1.440 Å. A(6,10,12), A(3,11,16), A(2,31,33)
and A(26,29,30) are found as 117.81/117.22°, 119.03/118.45°,
121.62/121.26° and 179.94/178.99°. D(4,3,11,16), D(3,11,16,17),
D(6,10,12,13), D(31,33,34,36), D(33,34,37,38), D(19,20,22,26) and
D(11,16,19,20) are found as 1.97/4.90°, 57.64/57.36°, 179.88/
179.96°, 126.48/124.33°, 99.22/103.12°, 0.43/0.20° and 161.94/
4.2. FT-IR study
Compound II consists of 44 atoms, so it has 126 normal vibra-
tional modes and it belongs to the point group C1 with only identity
(E) symmetry operation. It is difficult to determine the vibrational
assignments of compound II in the observed spectrum due to its
low symmetry. According to the calculations, 24 normal vibrational
modes of the title molecule are below the 200 cmÀ1. All the
Table 1
The magnitude of the optimized geometry parameters of compound II calculated by B3LYP method using 6-31G(d) basis set.
Coordinatea
Calc.
Exp.
Coordinatea
Calc.
1.098
1.097
1.497
1.365
1.082
1.434
1.081
1.361
1.079
Exp.
0.970
0.970
1.482
1.343
0.930
1.426
0.930
1.341
0.930
Coordinatea
Calc.
Exp.
R(1,2)
R(2,3)
R(3,4)
R(4,5)
1.404
1.409
1.401
1.391
1.402
1.367
1.419
1.092
1.098
1.098
1.083
1.084
1.085
1.373
1.416
1.102
1.100
1.512
1.401
1.390
1.085
1.405
1.434
1.163
1.404
1.085
1.392
1.083
1.399
1.474
1.093
1.393
1.397
1.395
1.376
1.391
1.372
1.428
0.960
0.960
0.960
0.930
0.930
0.930
1.369
1.417
0.970
0.970
1.498
1.392
1.379
0.930
1.398
1.440
1.144
1.391
0.930
1.380
0.930
1.391
1.475
0.986
R(34,35)
R(34,36)
R(34,37)
R(37,38)
R(38,40)
R(38,39)
R(39,42)
R(39,41)
R(41,43)
R(41,44)
R(37,44)
A(6,10,12)
A(1,6,5)
A(6,1,2)
A(1,2,3)
A(2,3,4)
A(3,4,5)
A(4,5,6)
A(6,1,7)
A(6,5,9)
A(3,4,8)
A(3,11,16)
A(17,16,18)
A(11,16,19)
A(20,19,21)
A(19,20,22)
A(20,22,26)
A(19,21,24)
A(21,24,26)
A(22,26,24)
A(19,20,23)
A(19,21,25)
A(26,24,28)
A(26,22,27)
A(26,29,30)
A(2,31,32)
119.78
119.80
119.72
179.94
115.72
121.62
122.66
119.78
119.21
105.87
117.19
109.35
107.35
105.95
106.86
125.97
127.43
179.86
1.97
119.70
120.10
120.30
178.99
115.50
121.26
123.20
119.48
118.90
107.00
116.89
109.79
106.27
106.31
106.95
126.50
126.80
174.46
4.90
R(5,6)
R(6,10)
R(10,12)
R(12,13)
R(12,14)
R(12,15)
R(1,7)
A(2,31,33)
A(32,31,33)
A(31,33,34)
A(33,34,37)
A(35,34,36)
A(34,37,44)
A(38,37,44)
A(37,44,41)
A(38,39,41)
A(37,38,39)
A(37,38,40)
A(38,39,42)
D(5,6,10,12)
D(4,3,11,16)
D(11,16,19,20)
D(3,11,16,17)
D(6,10,12,13)
D(1,2,31,32)
D(3,2,31,33)
D(2,31,33,34)
D(31,33,34,37)
D(31,33,34,36)
D(33,34,37,38)
D(38,39,41,44)
D(1,2,3,4)
1.363
1.374
1.365
1.377
R(4,8)
R(5,9)
117.81
119.27
120.88
119.32
119.73
120.18
120.62
122.26
118.73
120.90
119.03
107.26
109.28
119.14
120.89
119.75
120.50
120.14
119.58
119.83
117.22
120.01
120.06
119.38
120.35
119.57
120.63
120.00
119.70
120.20
118.45
108.40
108.07
119.13
120.91
119.35
120.68
119.75
120.18
119.50
R(3,11)
R(11,16)
R(16,17)
R(16,18)
R(16,19)
R(19,20)
R(20,22)
R(22,27)
R(22,26)
R(26,29)
R(29,30)
R(24,26)
R(24,28)
R(21,24)
R(21,25)
R(19,21)
R(2,31)
R(31,32)
161.94
57.64
176.14
57.36
179.88
178.29
178.07
179.59
3.70
126.48
99.22
0.03
179.96
176.19
177.77
178.46
1.80
124.33
103.12
0.11
0.04
0.43
1.10
0.20
D(19,20,22,26)
a
Coordinate descriptions are carried out by the numbers in Fig. 1. R, A, and D characters represent bond length (Å), angle (°) and dihedral angle (°) type of coordinates,
respectively.

Ö. Alver et al. / Journal of Molecular Structure 991 (2011) 12–17
15
Table 2
Comparison of the experimental and calculated vibrational wavenumbers (cmÀ1) of compound II.
Mode
TEDa (P10%)
Exp.b
IR
Scaled waven.
B3LYP/6-31G(d)
ma
mb
mt
IIR
m1
m3
m7
m
m
m
m
m
m
m
m
m
m
m
m
m
43-41 (89) +
42-39 (51) +
27-22 (94)
m
m
42-39 (10)
40-38 (45)
3146
3108
3075
3023
2957
2928
2903
2864
2826
2224
1646
1611
1590
1510
1496
1453
3146
3106
3069
3008
2940
2932
2890
2884
2855
2238
1653
1601
1572
1504
1486
1458
3153
3113
3076
3015
2947
2939
2897
2891
2861
2241
1671
1612
1583
1507
1493
1454
3302
3260
3221
3157
3086
3078
3034
3027
2996
2347
1728
1667
1637
1558
1544
1504
0.92
4.22
5.50
m11
m13
m14
m16
m17
m18
m19
m20
m22
m24
13-12 (91)
32.72
41.29
12.95
29.54
51.03
34.19
39.74
86.03
9.79
15-12 (50) +
36-34 (72) +
18-16 (77) +
15-12 (46) +
17-16 (78) +
30-29 (89) +
33-31 (72)
m
m
m
m
m
m
14-12 (50)
35-34 (28)
17-16 (22)
14-12 (45)
18-16 (22)
29-26 (11)
5-4 (19) +
6-5 (22) +
m
m
2-1 (15) +
3-2 (20) +
m
m
6-1 (11)
4-3 (14) +
m
6-1 (12)
3.48
c
m26
m28
m32
d 27-22-20 (7) + d 28-24-21 (7)
d 14-12-15 (40)
d 13-12-10 (15) + d 13-12-14 (15)
d 13-12-15 (13) + d 14-12-10 (11)
d 15-12-10 (11) + d 14-12-15 (10)
69.26
14.22
17.41
m34
m36
m38
m
2-1 (16) + d 6-5-9 (11) +
d 32-31-33 (31) + d 32-31-2 (20)
24-21 (9) + d 18-16-11 (9) + d 18-16-19 (8)
m
5-4 (10)
1421
1389
1375
1419
1393
1376
1420
1391
1379
1469
1439
1426
70.42
59.40
102.96
c
m
d 17-16-11 (8) + d 17-16-19 (7)
d 35-34-33 (17) + d 36-34-33 (15)
d 35-34-37 (14) + d 36-34-37 (11)
m39
1319
1322
1326
1371
74.44
c
m40
m
m
m
m
m
m
m
m
m
m
m
m
m
3-2 (8) +
26-24 (18) +
20-19 (11)
2-1 (10) + d 5-4-8 (10)
11-3 (24) + 4-3 (17) +
11-3 (21) + d 2-1-7 (16) +
19-16 (17) +
5-4 (10)
29-26 (13) +
44-41 (29) + d 43-41-44 (19) +
24-21 (10)
44-41 (40) +
16-11 (45) +
m
5-4 (7)
m 26-22 (17) + m 21-19 (15)
1312
1299
1305
1280
1312
1294
1357
1338
42.03
4.86
m42
m43
m45
m47
m49
m53
m54
m56
m57
m59
m60
m62
m63
1277
1258
1217
1187
1161
1147
1119
1111
1080
1049
1032
1015
991
1278
1253
1215
1192
1165
1160
1140
1113
1074
1048
1016
1009
1007
1281
1264
1218
1194
1168
1166
1146
1115
1081
1057
1021
1011
1004
1325
1307
1260
1235
1208
1206
1185
1153
1118
1093
1056
1046
1038
109.06
89.01
463.85
10.81
13.02
24.69
18.06
5.67
4.25
162.89
1.39
19.83
10.67
m
m
10-6 (14)
10-6 (10)
m
m
29-26 (10)
m
19-16 (11)
m
41-39 (14)
m
m
41-39 (14) +
12-10 (25)
m
39-38 (10)
d 17-16-19 (12) + d 18-16-19 (10)
m
m
39-38(30)+ d 39-38-40(18)+ d 40-38-37(10)
21-19 (9) + d 24-21-19 (8) + d 26-22-20 (8)
c
m64
d 26-24-21 (7) + d 26-24-28 (7) + d 23-20-19 (7)
d 22-20-19 (7) + 26-22 (7) + 26-24 (7)
12-10 (10)
27-22-20-23 (42) + 29-26-22-27 (11)
44-37 (12) + 34-33 (11)
9-5-4-8 (34) + 10-6-5-9 (12) +
m
m
m66
m69
m70
m71
m72
m74
m75
m76
m78
m79
m81
m82
m
s
m
s
31-2 (10) +
m
973
934
926
893
884
865
850
837
819
805
966
929
924
894
884
865
842
833
817
805
968
938
924
902
888
868
844
839
820
811
1001
970
956
933
918
898
873
868
848
839
2.12
0.16
6.47
3.27
27.98
4.24
6.60
7.25
7.48
42.20
s
m
s
s
1-6-5-9 (10)
44-37 (13)
31-2-1-7 (10)
21-19 (8) + d 19-16-11 (7)
42-39-38-40 (31) + 43-41-39-42 (17)
19-16 (7) + 21-19 (7)
d 41-39-38 (21) + d 44-41-39 (15) +
m
s
m
s
m
s
s
s
s
s
m
s
s
s
10-6-1-7 (16) +
4-3 (9) +
s 3-2-1-7 (10) + s
c
m
s
c
m
26-20-22-23 (14) +
23-20-19-16 (10)
8-4-3-11 (22) +
10-6-5-9 (14) +
40-38-37-44 (12)
29-26 (7)
43-41-39-38 (31) +
44-41-39-42 (12) +
42-39-38-37 (10)
s 29-26-22-27 (13)
s
s
6-5-4-8 (18)
9-5-4-3 (13)
782
787
794
821
19.80
757
712
703
772
727
714
772
726
718
798
751
743
37.13
34.86
22.62
c
m83
m84
s
s
37-44-41-43 (18)
43-41-39-42 (10)
c
m89
d 5-4-3 (9) + d 6-5-4 (8) + d 34-33-31 (8) d 3-2-1 (7)
d 4-3-11 (11) + d 10-6-1 (10)
632
603
588
548
466
633
593
576
553
458
629
595
588
552
468
651
615
608
571
484
2.18
7.47
4.58
14.36
5.77
m91
m92
m94
m98
s
s
m
1-6-5-9 (13) +
30-26-29-24 (12) +
37-34 (12)
s
1-6-5-4 (11)
s
30-26-29-22 (12)
ma: Wavenumbers are scaled by SQM methodology, b: dual scaling factors were used, 0.955 above 1800 cmÀ1, 0.967 under 1800 cmÀ1 [10], t: unscaled wavenumbers, IR:
m m
infrared, IIR: infrared intensities, waven.: wavenumbers, Exp.: experimental.
a
Our vibrational wavenumbers assignments on the basis of total energy distribution (TED) calculations.
Our experimental IR wavenumbers, m, d, s: Stretching, bending and torsion, respectively.
TED P 7.
b
c
experimental and theoretical vibrational modes obtained in this
study are given in Table 2. The assignments of the vibrational modes
of the title molecule are provided by animation option of the Gauss-
View package program for the B3LYP/6-31G(d) level of calculation.

16
Ö. Alver et al. / Journal of Molecular Structure 991 (2011) 12–17
Fig. 3. FT-IR spectrum of compound II.
Using the animation we identified vibrational motions of the studied
molecule. For a heteroaromatic structure CH stretching vibrations
are commonly appeared in the region of 3000–3200 cmÀ1. Experi-
mental/theoretical (SQM methodology/with dual scaling factor)
CH stretching modes were found as 3146/(3146/3153) cmÀ1
,
3108/(3106/3113) cmÀ1 and 3075/(3069/3076) cmÀ1 (Fig. 3). CH3
stretching modes were found as 3023/(3008/3015) cmÀ1, 2957/
(2940/2947) cmÀ1 and 2864/(2884/2891) cmÀ1. CH2 stretching
modes were observed at 2928/(2932/2939) cmÀ1, 2903/(2890/
2897) cmÀ1 and 2826/(2855/2861) cmÀ1. C„N and C@N stretching
vibrations were observed at 2224/(2238/2241) cmÀ1 and 1646/
(1653/1671) cmÀ1
, respectively. The carbon–carbon stretching
modes of the phenyl group occur in the range of 1620–1320 cmÀ1
[19]. In this study, the carbon–carbon stretching vibrations were
observed at 1611 cmÀ1
, , , ,
1590 cmÀ1 1421 cmÀ1 1312 cmÀ1
1299 cmÀ1, 1277 cmÀ1 and 1258 cmÀ1. The corresponding scaled
theoretical values (SQM methodology/dual scaling) of these vibra-
tions are 1601/1612 cmÀ1
, , ,
1572/1583 cmÀ1 1419/1420 cmÀ1
1305/1312 cmÀ1 1280/1294 cmÀ1 1278/1281 cmÀ1 and 1253/
, ,
1264 cmÀ1. We also made measurements in the frequency region
of 1300–400 cmÀ1. These vibrations have revealed to be mixed type
of vibrations as given in Table 2. In general, B3LYP/6-31G(d) level of
calculation with the dual scaling factors [10] and SQM [16,17] meth-
odology used in this study provided reasonable agreement with the
experimental findings. The correlation values between the experi-
mental and calculated vibrational wavenumbers are found to be
0.99983 (ma) and 0.99985 ( b) and presented in Fig. 4. The results
m
obtained in this study also indicate that B3LYP/6-31G(d) method is
reliable and it is helpful for the understanding of vibrational spec-
trum and structural parameters of prepared Schiff base compound.
5. Conclusion
We prepared a novel Schiff base compound and conducted the
experimental–theoretical structural and vibrational analysis of this
compound for the first time. The structural parameters, IR wave-
numbers and activities of vibrational bands were calculated with
Fig. 4. Plot of calculated vs. experimental wavenumbers of compound II.

Ö. Alver et al. / Journal of Molecular Structure 991 (2011) 12–17
17
[5] D. Gatteschi, O. Kahn, J. Miller, Molecular Magnetic Materials, Nato ASI Series
E198, Kluwer, Dordrecht, The Netherlands, 1991.
[6] O.M. Yaghi, G. Li, H. Li, Nature 378 (6558) (1995) 703.
[7] C.T. Chen, K.S. Suslick, Coord. Chem. Rev. 128 (1–2) (1993) 293.
[8] M. Jalali-Heravi, A.A. Khandar, I. Sheikshoaie, Spectrochim. Acta, Part A 55
(1999) 2537.
[9] L. Juhasz, Z. Dinya, S. Antus, T.E. Gunda, Tetrahedron Lett. 41 (2000) 2491.
[10] K. Balcı, S. Akyüz, Vib. Spectrosc. 48 (2008) 215.
[11] A.P. Scott, L. Radom, J. Phys. Chem. 100 (1996) 16502.
[12] J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure
Methods, second ed., Gaussian, Inc., Pittsburgh, 1996.
[13] Ö. Alver, C. Parlak, M. Sßenyel, Spectrochim. Acta A 67 (2007) 793.
[14] Ö. Alver, C. Parlak, M. Sßenyel, J. Mol. Struct. 923 (2009) 120.
[15] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
B3LYP methods and 6-31G(d) basis set. Calculated bond lengths
are, in general, slightly bigger than experimental ones which are
possibly due to the shortening of the bond lengths of the title mol-
ecule during the experimental measurements conducted at very
low temperature. However, similar generalizations are not possible
for bond-dihedral angles. In order to make a comparison with
experimental wavenumbers, we calculated root mean square devi-
ation (RMSD) based on the calculation. The following mean abso-
lute error values were found for vibrational wavenumbers:
7.80 cmÀ1 for SQM methodology and 7.63 cmÀ1 for dual scaling
factor. Any differences observed between the experimental and
the calculated wavenumbers could be due to the fact that the cal-
culations have been performed for single molecule in the gaseous
state contrary to the experimental values recorded in the presence
of intermolecular interactions. Henceforth, the assignments made
at B3LYP/6-31G(d) level of theory with only reasonable deviations
from the experimental values seem feasible.
[16] G. Rauhut, P. Pulay, J. Phys. Chem. 99 (1995) 3093.
[17] J. Baker, A.A. Jarzecki, P. Pulay, J. Phys. Chem. A102 (1998) 1412.
[18] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, J.T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J.
Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson,
H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian,
J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J.
Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A.
Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels,
M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman,
J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A.
Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-
Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W.
Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03 Revision C.02, Gaussian
Inc., Pittsburgh PA, 2003.
References
[1] S.Y. Yu, S.X. Wang, Q.H. Luo, L.F. Wang, Polyhedron 12 (1993) 1093.
[2] S. Rekha, K.R. Nagasundara, Indian J. Chem. A45 (2006) 2421.
[3] A.A. Jarrahpour, M. Motamedifar, K. Pakshir, N. Hadi, M. Zarei, Molecules 9
(2004) 815.
[19] J.A. Faniran, H.F. Shurvell, Can. J. Chem. 46 (1968) 2089.
[4] P.G. Ramappa, K.B. Somasekharappa, Indian J. Chem. A33 (1994) 66.