Synthesis, infrared spectral studies and theoretical calculations of 4-phenyl-4,5-dihydrobenzo[f][1,4]oxazepin-3(2H)-one (thione)

Article abstract of DOI:10.1016/j.molstruc.2008.05.023

Salicylaldehyde (1) was reacted with aniline to afford 2-[(E)-(phenylimino)methyl]phenol (2). The reduction of (2) by NaBH₄ gave 2-((phenylamino)methyl)phenol (3) which was reacted with chloroacetyl chloride to give 2-chloro-N-(2-hydroxybenzyl)

Full text of DOI:10.1016/j.molstruc.2008.05.023

Journal of Molecular Structure 892 (2008) 132–139
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, infrared spectral studies and theoretical calculations
of 4-phenyl-4,5-dihydrobenzo[f][1,4]oxazepin-3(2H)-one (thione)
b
a
a
Hikmet Agirbas a, , Seda Sagdinc , Fatma Kandemirli , Berat Kemal
*
a Department of Chemistry, Kocaeli University, 41300 Izmit, Turkey
b Department of Physics, Kocaeli University, 41300 Izmit, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Salicylaldehyde (1) was reacted with aniline to afford 2-[(E)-(phenylimino)methyl]phenol (2). The reduc-
tion of (2) by NaBH4 gave 2-((phenylamino)methyl)phenol (3) which was reacted with chloroacetyl chlo-
ride to give 2-chloro-N-(2-hydroxybenzyl)-N-phenylacetamide (4). Compound (4) was cyclized to 4-
phenyl-4,5-dihydrobenzo[f][1,4]oxazepin-3(2H)-one (5) by NaOH in ethanol solution. The treatment of
compound (5) with P2S5 gave corresponding 4-phenyl-4,5-dihydrobenzo[f][1,4]oxazepin-3(2H)-thione
(6). The structures of (5) and (6) were determined by 1H NMR and IR spectra. The optimized structural
parameters and vibrational frequencies of (5) and (6) were calculated by DFT with 6-31G(d,p) basis
set. The mechanism of the cyclization reaction was studied by RHF with the standard 3-21G basis set.
Ó 2008 Elsevier B.V. All rights reserved.
Received 23 November 2007
Received in revised form 18 April 2008
Accepted 1 May 2008
Available online 20 May 2008
Keywords:
Benzoxazepine
Chloroacetyl chloride
IR spectra
MO calculations
1. Introduction
(4) to obtain 4-phenyl-4,5-dihydrobenzo[f][1,4] oxazepin-3(2H)-
one (5). The electronic structures of the reactants, their transition
Benzoxazepines have a wide range of biological activities. The
application of benzoxazepine and its derivatives is found in the re-
search areas as having hypnotic muscle relaxation [1], antiemetic,
antagonistic [2] and anti-inflammatory [3] effects. These com-
pounds are also used as anxiolytics [4] antiallergic and antihista-
minic agents [5]. The benzoxazepines with carbonyl groups have
shown anxiolytic [6], central depressant [7], analgesic [8], local
anesthetic [9], anti-inflammatory [10], and antihistaminic [11] ef-
fects. Additionally, benzoxazepines have also shown the stabilizing
property in photography [12].
In this study, we have synthesized 4-phenyl-4,5-dihydro-
benzo[f][1,4]oxazepin-3(2H)-one (5) and 4-phenyl-4,5-dihydro-
benzo[f][1,4]oxazepin-3(2H)-thione (6) (Scheme 1) and report the
complete assignments of their IR spectra.
With the recent advances in computer, chemical properties of
small molecules can be described correctly [13–15]. Raw frequency
values computed at the Hartree–Fock level contain systematic er-
rors due to the neglect of electron correlation, resulting overesti-
mates of about 10–12% [15]. Therefore, we selected density
functional theory (DFT)(B3LYP/6-31G(d,p)) method for the vibra-
tional frequency calculations of compounds (5) and (6).
states, intermediate states and final products of the cyclization reac-
tion were investigated.
2. Synthesis
Compounds (2–6) were synthesized as illustrated in Scheme 1.
Salicylaldehyde (1) was reacted with aniline to afford 2-[(E)-(phe-
nylimino) methyl]phenol (2). Then the imine (2) was reduced
by NaBH4 to give 2-((phenylamino)methyl)phenol (3). Compound
(3) was reacted with chloroacetyl chloride to have the
corresponding amide (4). The cyclic ether, 4-phenyl-4,5-dihydro-
benzo[f][1,4]oxazepin-3(2H)-one (5) was obtained in quantitative
yield under the basic treatment of (4). Compound (5) was
treated with P2S5 to give corresponding 4-phenyl-4,5-dihydro-
benzo[f][1,4]oxazepin-3(2H)-thione (6). The compounds (3–6)
were identified by their IR and 1H NMR spectra.
3. Experimental
Melting points were determined in open capillaries in Electro-
thermal 9200 apparatus and are uncorrected. The FTIR spectra
were recorded on Shimadzu 8201 spectrometer with KBr tech-
nique, in the region of 4000–400 cmꢀ1 that was calibrated by poly-
styrene. 1H NMR spectra were recorded on Bruker DPX-400
(400 MHz) High Performance Digital FT-NMR Spectrometer in
CDCl3 with Me4Si as an internal standard. Silica Gel (Fluka or
Merck) were used for column chromatography.
We also report here the ab initio (RHF/3-21G) calculations for the
cyclization of 2-chloro-N-(2-hydroxybenzyl)-N-phenylacetamide
* Corresponding author.
E-mail address: agirbas@kou.edu.tr (H. Agirbas).
0022-2860/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2008.05.023

H. Agirbas et al. / Journal of Molecular Structure 892 (2008) 132–139
133
Ph
Ph
O
N
N
H
H2N
Ph
NaBH4
OH
OH
OH
(1)
(2)
(3)
Cl
Ph
Ph
N
N
C
Cl
C
O
NaOH
H2
O
O
OH
O
Cl
(4)
(5)
Ph
N
P2S5
S
O
(6)
Scheme 1. Synthesis of 4-phenyl-4,5-dihydrobenzo[f][1,4]oxazepin-3(2H)-one (5) and 4-phenyl-4,5-dihydrobenzo[f][1,4]oxazepin-3(2H)-thione (6).
Table 1
Schiff base (2) (Scheme 1) was synthesized according to the lit-
0
Selected optimized geometrical parameters (bond length (AÅ), bond angles (°), dihedral
angles (°)) of compounds (5) and (6)
erature [16]. A band for the azomethine group was observed in IR
spectrum at about 1620 cmꢀ1. For the synthesis of compounds (3–
5), literature methods [17,18] were applied with slight
modifications.
Compounds
(5)
(6)
(5)
(6)
0
Bond length (ÅA)
C(6)–C(7)
C(6)–C(8)
C(7)–C(11)
C(8)–C(9)
C(8)–C(12)
C(9)–O(15)
C(9)–C(10)
C(10)–C(11)
C(12)–N(13)
N(13)–C(17)
C(14)–O(16)
C(14)–S(16)
C(14)–N(13)
O(15)–C(18)
Bond angles(°)
C(6)–C(8)–C(12)
C(9)–C(8)–C(12)
1.392
1.403
1.396
1.407
1.517
1.371
1.401
1.390
1.476
1.433
1.222
–
1.392
1.402
1.396
1.407
1.517
1.370
1.401
1.390
1.480
1.442
–
118.87
123.28
115.58
119.32
118.87
121.36
119.08
115.10
112.75
–
125.37
114.34
124.51
120.36
–
118.51
123.55
114.87
121.33
116.85
119.47
119.89
114.44
–
125.14
112.66
125.39
114.37
–
3.1. Calculation methods
C(8)–C(12)–N(13)
C(12)–N(13)–C(14)
C(12)–N(13)–C(17)
N(13)–C(17)–C(5)
N(13)–C(17)–C(1)
N(13)–C(14)–C(18)
N(13)–C(14)–O(16)
N(13)–C(14)–S(16)
C(14)–C(18)–O(15)
O(15)–C(9)–C(8)
O(15)–C(9)–C(10)
O(16)–C(14)–N(13)
S(16)–C(14)–N(13)
O(16)–C(14)–C(18)
C(2) –C(1)–C(17)
C(18)–O(15)–C(9)
3.1.1. Calculation methods for IR studies
The geometries were first determined at the B3LYP exchange-
correlation functional [19,20] with 3-21G basis set using Hyper-
Chem package [21]. All other calculations were then performed
using Gaussian 03W program package [15], utilizing gradient
geometry optimization [22]. Calculations on the molecules by this
program were carried out on the basis of B3LYP exchange-correla-
tion functional with 6-31G(d,p) basis set.
Vibrational frequencies, calculated at B3LYP/6-31G(d,p) level
scaled by 0.96[23]. All the calculations have been carried out with
the restricted closed-shell formalism.
1.663
1.356
1.430
1.380
1.428
125.14
120.41
119.60
120.87
120.21
120.56
120.97
3.1.2. Calculation methods for the cyclization reaction
The calculations were performed by using the Gaussian03 Revi-
sion-B.04s by means of RHF with the standard 3-21G basis set. Nat-
ural bond analysis (NBO) (RHF/3-21G) was carried out only for
chloroacetyl chloride and. 2-((Phenylamino)methyl) phenol to
determined the reacting atoms in the molecules.
ment of oxygen O(16) atom by sulfur S(16) atom. The C(14)–
O(16) and C(14)–S(16) bond lengths are found 1.222 and 1.663,
respectively. Calculated bond length of C(14)–S(16) is in agree-
ment with reported value of 1.668 [24].
The energies and the dipole moments of (5) and (6) are given in
Table 2.
4. Results and discussion
The energy values of these two molecules were found to be
ꢀ784.64 and ꢀ1107.59 au, respectively. According to this result,
molecule (6) is more stable than molecule (5).
4.1. Geometrical parameters
The optimized structure parameters of compounds (5) and (6)
were calculated by DFT with 6-31G(d,p) basis set (Table 1). The
compounds consist of benzene ring (Ring1), oxazepine ring (Ring2)
and phenyl ring (Ring3), as seen in Fig. 1.
The calculated bond lengths of (5) are longer than bond lengths
of (6) (except C(14)–N(13) bond length), because of the replace-
Mulliken atomic charges of C, O, N, and S atoms of mole-
cules (5) and (6) are also given in Table 2. The N(13), O(15),
C(12), O(16), and S(16) atoms, which exhibit a substantial neg-
ative charges, are the donor atoms in both of the molecules.
C(17), C(14), and C(9) atoms which exhibit positive charges
are the acceptor atoms.

134
H. Agirbas et al. / Journal of Molecular Structure 892 (2008) 132–139
Fig. 1. Optimized geometries of compounds (5) and (6) calculated with DFT (B3LYP/6-31G(d,p)).
4.2. FT-IR spectroscopy
Table 2
The Mulliken atomic charges, dipole moments (D) and energies (a.u) obtained by
B3LYP/6-31G(d,p) method
The wavenumbers (in the range of 1800–400cmꢀ1) and the
intensities of the peaks in the IR spectra (Fig. 2) were compared
with the calculated values (Table 3).
Atoms
B3LYP/6-31G(d,p)
Compound (5)
Compound (6)
The correlation of calculated vibrational wavenumbers of (5)
and (6) with the experimentally values gave the correlation coeffi-
cients to be 0.9993 and 0.9996, respectively (Fig. 3).
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
ꢀ0.103
ꢀ0.099
ꢀ0.078
ꢀ0.104
ꢀ0.064
ꢀ0.136
ꢀ0.087
0.109
ꢀ0.059
ꢀ0.098
ꢀ0.073
ꢀ0.097
ꢀ0.059
ꢀ0.134
ꢀ0.088
0.104
The strong and sharp band at 1661 cmꢀ1 in the IR spectrum of
molecule (5) was assigned as m(C@O) mode, This band was not ob-
served in the IR spectrum of molecule (6). Dreig and Sternbach [17]
reported the wavenumber of this C@O stretching band as
1675 cmꢀ1. We calculated this mode as 1743 cmꢀ1 with B3LYP/6-
31G(d,p) method.
The C@S group does not give a band as characteristic as the C@O
group due to the complication of interactions. The C@S vibration is
expected to occur at considerably lower frequencies than the C@O
vibration because of the greater mass of sulfur [25]. The medium
strong band observed at 1161 cmꢀ1 in IR spectrum of molecule
C(9)
0.308
0.308
C(10)
C(11)
C(12)
N(13)
C(14)
ꢀ0.118
ꢀ0.087
ꢀ0.154
ꢀ0.511
0.552
ꢀ0.118
ꢀ0.087
ꢀ0.138
ꢀ0.447
0.131
O(15)
O (16)
S(16)
ꢀ0.525
ꢀ0.489
–
ꢀ0.522
–
(6) was assigned as
m(C@S) mode. Calculated value of this band, to-
ꢀ0.228
0.205
gether with CH band (Ring3) was found at 1159 cmꢀ1
.
C(17)
0.250
C(18)
Dipole moments (D)
Energies (a.u)
ꢀ0.024
3.5454
ꢀ784.64
0.014
4.8116
ꢀ1107.59
In the oxazine rings of both molecules, the very strong
stretching tC(14)–N(13) band and the in-plane deformation
xC(14)–H(2) band were observed at 1425 cmꢀ1. We have calculated

H. Agirbas et al. / Journal of Molecular Structure 892 (2008) 132–139
135
Fig. 2. A comparison of FT-IR spectra of compounds (5) and (6).
this band at 1412 cmꢀ1 and 1443 cmꢀ1 for molecules (5) and (6),
respectively. The bands in the 1629-1493 cmꢀ1 region were
assigned as ring stretch and in-plane CH deformation modes of
the molecules.
Contrarily, p* antibonding orbital of the same carbonyl group
(Fig. 4) is polarized towards the carbon atom. The results of NBO
calculation yield (0.802p)C25 + (ꢀ0.598p)O35. The larger coefficient
of the carbon 2p orbital means that the carbonyl p* antibonding
orbital will interact strongly to the nitrogen atom (N13) of 2-((phe-
nylamino)methyl) phenol, 2 (Fig. 4). The orbital of lone pair
electrons of nitrogen atom in 2-((phenylamino)methyl) phenol
consists of 2.075% s orbital and 97, 93% p orbital. The density of
electrons is 1.84eꢀ.
The bands at 974 cmꢀ1, 893 cmꢀ1, and 745 cmꢀ1 in the IR
spectrum of (5) were assigned as d(C@O) modes together with
d(C12H2), d(C27H2) and d(Ring2) modes. The same bands were pre-
dicted by B3LYP/6-31G(d,p) calculations as 964 cmꢀ1, 878 cmꢀ1
and 740 cmꢀ1, These bands were not observed in the IR spectrum
of (6).
The approach of N13 (as a nucleophile) is towards the C25 atom
in a perpendicular direction to the plane of the carbonyl group.
Firstly, N13 atom of molecule 1 reacts with C25 of molecule 2. As
the reacting molecules, 1 + 2 are far from each other (C25–
N13 = 2.95 Å), the bond lengths of C25–O35, C25–Cl26 and C9–
N13 are 1.163 Å, 1.954 Å, and 1.479 Å, respectively. The Mulliken
charges of C25, N13, and O35 are 0.515 e, ꢀ0901 e, and ꢀ0431 e,
4.3. Calculations of the cyclization reaction
Quantum chemical calculations of the cyclization reaction have
been carried out for the theoretical study on reactants, intermedi-
ates and final products. Vibrational analysis has also been per-
formed for transition states. The stationary points were
characterized by frequency calculations in order to verify that
TSs had only one imaginary frequency. Intrinsic reaction coordi-
nate (IRC) calculations have also been performed for transition
states. (IRC) path was traced in order to check the energy profiles
connecting each TS to the two associated minima of the proposed
mechanism.
The atoms spatial arrangements in reactants, intermediates,
transition states (TS) and product are shown in Fig. 4 and
Fig. 5.
The charge distribution on atoms, bond lengths and bond angles
of the systems participating in the reaction are given in Table 4.
The determination of reacting atoms in the reactants was done
by natural bond analysis (NBO). All the other calculations for the
cyclization reaction mechanism have been carried out by RHF
method at the level of 3-21G basis set.
¯
¯
¯
respectively. In the first intermediate, the bond C25–N13 is
formed. In TS1 structure, bond is formally broken. The N13 is
p
in a tetrahedral state, but the C25 forms a trigonal pyramid (the an-
gles of C9–N13–H24, C9–N13–C14, C9–N13–C25 and N134–H24–
Cl26 are 112.91o, 120.85o, 116.64o, 118.94o). The negative charge
on N13 (ꢀ0.902 e) for 1 + 2 decreases to ꢀ0.849 e for TS1. Imagi-
¯
¯
nary frequency for TS1 is ꢀ251.63 cmꢀ1. The system transition to
the intermediate state In_1 happens under the lengthen of the
bond C25ꢁꢁꢁCl26. In_2 happens under the full breakage of the bond
C25ꢁꢁꢁCl26 and proton H24 transfer to the Cl26 atom. Imaginary
frequency is ꢀ341.81 cmꢀ1 for TS2. In TS3 stage, the O11ꢁC24 dis-
tance becomes equal to 2.235 Å. This stage is a cyclization stage
resulting from the product 3. In this stage full breakage of Cl26
occurs.
For reagents 1 + 2, the total of electronic energy is
ꢀ1691,16348249 au. For intermediates In_1, In_2 and In_3, the to-
tals of those are equal to ꢀ1691,17534961 au, ꢀ1691,18819311 au,
and ꢀ1232,74492990 au, respectively. The total of the electronic
energies for TS1, TS2, TS3, and TS4 are ꢀ1691,15693545 au,
ꢀ1691,18441118 au, and ꢀ1232,74241793 au, respectively.
The
ride, 1 is polarized towards the oxygen atom. The results of NBO
(RHF/3-21G) calculation yield (0.598p)C25 + (0.8017p)O35 The
coefficient of the carbon 2p orbital is smaller than that of oxygen.
p bonding orbital of carbonyl group in chloroacetyl chlo-
.

136
H. Agirbas et al. / Journal of Molecular Structure 892 (2008) 132–139
Table 3
Observed and calculated wavenumbers (cmꢀ1), peak intensities (km molꢀ1) and the peak assignments of IR spectra of compounds (5) and (6)
Compounds
Assignments
(5)
(6)
IRa
Calcb
I
IRa
Calcb
I
m
(C@O)
1661s
1629vw
1611w
1595w
1581vw
1541vw
1493vs
1472vw
1458mw
1449w
1425vs
1364vw
1348mw
1339vw
1321w
1306vw
1290vw
1276vw
1238m
1221ms
1213vw
–
1192w
1180vw
1163vw
–
1135vw
1115m
–
1074w
1053w
–
1030m
1001vw
–
1743
1631
1624
1607
1600
1509
1505
1492
1469
1468
1412
1366
1354
1337
1324
1319
1289
1275
1245
1223
1208
–
1191
1186
1164
–
1122
1118
–
1088
1055
1039
1033
997
974
964
–
952
1039
1033
997
974
964
–
283
25
30
3
22
78
86
9
19
7
161
13
68
8
–
–
–
d(CH)Ring1,
d(CH)
d(CH)
d(CH)Ring1
d(CH)
d(CH)
d(C12H2), d(C18H2)
d(C12H2), d(C27H2), d(CH)Ring1
t
s(Ring1)
s(Ring3)
s(Ring2)
s(Ring1)
s(Ring3)
1624vw
1606w
1589vw
1578w
1554vw
1493vs
–
1631
1622
1610
1601
1506
1505
1497
1468
1464
1443
1374
1352
1328
1325
1316
1306
1286
1251
1233
–
28
12
3
,
t
Ring3
,
t
Ring3
,
t
24
32
111
17
49
14
243
2
193
1
26
5
,
,
t
t
Ring3
s(Ring3), d(C12H2)
Ring1
,
t
s(Ring1)
–
d(C12H2),
(C14N13),
d(C14H2), d(C18C14
t
(C14N13
x
)
1456w
1425vs
1364vw
1346vs
–
1327vw
1304vw
1294vw
1279vw
1236ms
1219ms
–
t
(C14H2)
)
t
(C14N13),
x
(C18H2)
d(CH)
t
d(C12H2),
d(CH)
d(C12H2), d(C18H2),
t(C18H2),
t(C18H2)
t(C12H2)
d(CH)Ring1,
t
,
ts(Ring3)
Ring3
s(Ring1), d(C12H2),
t
s(Ring2)
2
7
t
s(Ring2)
s(Ring3)
,
t
17
24
139
8
103
–
8
3
0.1
–
–
34
–
5
20
6
39
0.3
0.4
11
–
1
7
Ring3
t
s(Ring1)
t
(CO15
)
138
62
–
38
4
t
s(Ring1)
1201w
–
–
1207
1192
1175
1164
1159
–
(CC)Ring2, d(CH)Ring1,
t
s(Ring1)
d(CH)Ring3
d(CH)Ring3
t
t
5
–
0.02
30
–
–
37
6
(CS), d(CH)Ring3
(CO), Ring3(CH)
1161ms
–
–
d(CH)Ring1
(C14N13),
d(CH)
–
t
t
,
(CS)
a(Ring3),
1113m
1078w
1064vw
1045m
1028w
1005vw
995m
–
964m
945w
1045m
1028w
1005vw
995m
–
964m
945w
–
910w
–
866mw
849vw
837mw
–
758vs
–
1118
1082
1069
1049
1033
1002
998
–
957
952
1049
1033
1002
998
–
957
952
926
910
–
861
841
835
770
755
–
t
Ring3
t
t
a(Ring1),
a(Ring1),
t
t
(C12N13), d(C27H2)
(Ring2),
5
22
10
14
7
d(Ring1),
d(C18H2), d(C12H2),
d(Ring3)
d(C@O), d(C12H2), d(C18H2)
d(C18H2), d(C12H2), d(CS)
c
t
d(Ring1),
d(C18H2), d(C12H2),
d(Ring3)
d(C=O), d(C12H2), d(C18H2)
d(C18H2), d(C12H2), d(CS)
c
c
c
t
(C27O15
)
t(Ring2)
974m
–
939w
–
1030m
1001vw
–
974m
–
–
17
0.03
22
10
14
7
(CH)Ring3
a(Ring1),
0.4
6
t
(Ring2),
t
(C27O15
)
39
0.3
0.4
11
–
0.4
3
4
17
8
5
0.5
11
25
45
14
4
t(Ring2)
–
17
0.03
3
0.4
–
4
7
3
9
(CH)Ring3
(CH)Ring1
(CH)Ring3
939w
–
952
927
906
918w
893mw
870vw
847mw
–
779w
768m
755m
745m
732vw
–
d(C=O), d(Ring2)
(CH)Ring1
d(Ring1), d(C8C12N13
878
856
839
831
767
757
752
740
733
–
698
–
c
)
c
(CH)Ring3
(CH)Ring3
(CH)Ring1
(Ring2), d(CH)Ring3
x
x
x
37
–
–
C@O,
Skeletal
d(CH)Ring1
d(Ring2)
CNS
x
(Ring2)
–
–
729mw
717vw
689vs
656m
733
724
695
645
–
2
–
17
–
17
25
11
–
698s
–
646vw
d(Ring1), d(Ring2), d(Ring3)
640
1
CNS
r(Ring3),
r(C18H2), r(C12H2),
r(C18H2), r(C12H2), d(CS), d(CN)
d(C18H2), d(C12H2), d(Ring3), d(CO)
d(C18H2), d(C12H2), d(CS), d(CN)
d(C=O), d(C27H2)
636w
613w
630
617
–
582
–
562
–
534
513
–
7
2
–
8
–
12
–
2
1
615vw
590mw
–
577w
–
552mw
525vw
–
511mw
–
618
586
–
571
–
545
522
–
504
461
444
1
6
–
9
x
(CO), d(CN)
583vw
–
565m
–
532w
517vw
–
463w
448vw
–
10
0.3
–
6
1
c
c
(Ring1),
(Ring1),
c
c
(Ring2)
(Ring2),
c
(Ring2)
r(Ring3), r(Ring2),
d (C18O15
r(C12H2)
c
(C@O)
–
1
3
)
459
450
437vw
8
Vibrational modes:
m
, stretching; d, in-plane deformation;
c
, out-of-plane deformation; t, twisting;
x
, wagging Superscript s, strong; m, medium; w, weak; vw, very weak.
a
IR (in KBr).
b
Scaled by 0.96.

H. Agirbas et al. / Journal of Molecular Structure 892 (2008) 132–139
137
Fig. 3. Graphic correlation between the experimental and calculated wavenumbers obtained by DFT (B3LYP/6-31G(d,p)) method for compounds (5) and (6).
Fig. 4. Optimized forms for I+2, TS1, In_1, TS2, In_2 calculated with RHF/3-21G.
Fig. 5. Optimized forms for I+2, TS1, In_3, TS3, 3 calculated with RHF/3-21G.

138
H. Agirbas et al. / Journal of Molecular Structure 892 (2008) 132–139
Table 4
Geometric and electronic values of reactants, intermediates, transition states and product
1+2
TS1
1n_1
1n_1a
TS2
1n_2
In_3
TS3
3
0
Bond length (ÅA)
C3–C9
1.516
1.513
1.504
1.501
1.075
1.074
1.550
1.477
1.389
1.385
0.977
1.522
1.912
1.065
1.070
1.505
1.193
2.820
1.033
2.033
1.502
1.513
1.081
1.075
1.474
1.438
1.388
1.382
0.965
1.359
1.890
1.070
1.072
1.515
1.515
4.319
3.866
1.301
1.505
1.516
1.518
1.079
1.082
1.478
1.415
1.392
1.368
C9–H10
C9–H27
C9–N13
N13–C14
C3–C2
1.078
1.080
1.479
1.407
1.388
1.391
0.965
2.950
1.865
1.074
1.076
1.486
1.163
1.954
1.001
2.912
1.077
1.075
1.520
1.450
1.389
1.386
0.965
1.986
1.891
1.069
1.072
1.494
1.167
2.206
1.009
2.498
1.076
1.074
1.536
1.476
1.388
1.384
0.965
1.561
1.927
1.068
1.069
1.506
1.192
2.400
1.020
2.343
1.078
1.072
1.536
1.472
1.386
1.385
0.969
1.452
1.890
1.071
1.073
1.50826
1.19440
3.362
1.263
1.688
1.083
1.078
1.489
1.430
1.426
1.282
1.081
1.082
1.478
1.377
1.423
1.291
C2–O11
O11–H12
C25–N13
C31–Cl34
C31–H32
C31–H33
C31–C25
C25–O35
C25–Cl26
N13–H24
Cl26–H24
C31–O11
1.361
1.934
1.069
1.071
1.510
1.220
1.377
2.045
1.056
1.063
1.509
1.215
1.379
3.000
1.066
1.074
1.520
1.216
2.600
2.235
1.468
Mulliken charges
C3
C9
H10
H27
N13
C14
C2
O11
H12
C25
C31
H32
H33
O35
Cl26
–0.101
–0.180
0.238
0.252
–0.902
0.344
0.388
–0.758
0.409
0.515
–0.674
0.385
0.328
–0.431
–0.173
5.75
–0.114
–0.219
0.259
0.288
–0.849
0.259
0.396
–0.759
0.417
0.692
–0.611
0.345
0.354
–0.506
–0.506
8.27
–0.120
–0.218
0.278
0.323
–0.927
0.272
0.401
–0.766
0.429
–0.130
–0.224
0.279
0.324
–0.952
0.258
0.390
–0.771
0.447
0.817
–0.616
0.349
0.366
–0.092
–0.794
9.18
–0.121
–0.215
0.273
0.311
–0.965
0.250
0.422
–0.763
0.433
0.829
ꢀ0.662
0.351
0.344
ꢀ0.497
–0.648
6.18
–0.098
–0.151
0.247
0.270
–0.971
0.303
0.400
–0.774
0.423
0.912
–0.657
0.324
0.315
–0.614
–0.260
4.73
–0.182
–0.156
0.205
0.248
–0.964
0.317
–0.179
–0.156
0.220
0.230
–1.003
0.372
–0.080
–0.215
0.228
0.357
–1.010
0.383
0.488
–0.819
0.477
–0.807
0.430
–0.743
0.768
0.918
–0.588
0.377
0.281
–0.640
–0.217
6.24
0.960
–0.423
0.294
0.321
–0.652
–0.375
6.62
0.910
–0.214
0.328
ꢀ0.566
0.316
0.366
0.260
ꢀ0.531
–0.708
11.317
–0.639
–0.911
14.04
Dipole moment (D)
Bond angles (°)
1+2
TS1
1n_1
1n_1a
TS2
1n_2
C9–N13–H24
C9–N13–C14
C9–N13–C25
N13–H24–Cl26
112.91
120.85
116.64
118.94
108.56
112.96
118.47
107.30
In_3
106.25
111.51
113.18
106.66
107.76
112.43
114.03
137.10
TS3
110.08
110.53
114.92
171.45
116.69
115.96
125.57
136.08
3
C14–C18–O15
C14–C18–Cl32
C14–C18–H31
C14–C18–H30
83.50
107.84
108.45
113.13
76.07
103.55
111.03
121.97
105.80
91.05
107.88
115.05
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