FT-IR, FT-Raman and computational study of 1H-2,2-dimethyl-3H-phenothiazin- 4[10H]-one

Article abstract of DOI:10.1016/j.molstruc.2010.11.013

FT-IR and FT-Raman spectra of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one were recorded and analyzed. The vibrational wavenumbers were computed using HF/6-31G(d) and B3LYP/6-31G(d) basis. The data obtained from vibrational wavenumber calculations are used to assign vibrational bands obtained in infrared and Raman spectroscopies of the studied molecule. The first hyperpolarizability, infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non-linear optics. The geometrical parameters of the title compound are in agreement with XRD crystal structure data. The red shift of the N?H stretching wavenumber in the infrared spectrum from the computed wavenumber indicates the weakening of the N?H bond.

Full text of DOI:10.1016/j.molstruc.2010.11.013

Journal of Molecular Structure 985 (2011) 316–322
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
FT-IR, FT-Raman and computational study
of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one
R. Minitha , Y. Sheena Mary , Hema Tresa Varghese b,d, C. Yohannan Panicker c,d, , Reena Ravindran e,
a
b,f
⇑
f
f
K. Raju , V. Manikantan Nair
a
Department of Chemistry, S.N.College, Kollam, Kerala, India
b
c
d
e
f
Department of Physics, Fatima Mata National College, Kollam, Kerala, India
Department of Physics, TKM College of Arts and Science, Kollam, Kerala, India
Department of Physics, Mar Ivanios College, Trivandrum, Kerala, India
Department of Chemistry, SN College for Women, Kollam, Kerala, India
Department of Physics, University College, Trivandrum, Kerala, India
a r t i c l e i n f o
a b s t r a c t
Article history:
FT-IR and FT-Raman spectra of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one were recorded and ana-
lyzed. The vibrational wavenumbers were computed using HF/6-31G(d) and B3LYP/6-31G(d) basis. The
data obtained from vibrational wavenumber calculations are used to assign vibrational bands obtained
in infrared and Raman spectroscopies of the studied molecule. The first hyperpolarizability, infrared
intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with
the reported values of similar derivatives and is an attractive object for future studies of non-linear optics.
The geometrical parameters of the title compound are in agreement with XRD crystal structure data. The
red shift of the NAH stretching wavenumber in the infrared spectrum from the computed wavenumber
indicates the weakening of the NAH bond.
Received 17 September 2010
Received in revised form 2 November 2010
Accepted 2 November 2010
Available online 3 December 2010
Keywords:
FT-IR
FT-Raman
DFT
Hyperpolarizability
Phenothiazin
Ó 2010 Elsevier B.V. All rights reserved.
1
. Introduction
Phenothiazines are biologically active tri-cyclic compounds con-
and phenothiazine derivatives. Phenothiazines substituted in the 2
and 10 positions are used in analytical chemistry as reagents in spec-
trophotometric [16] and kinetic–catalytic determination of metals
[17,18]. Phenothiazines are also reported to form coordination com-
plexes with transition metals [19–29] and charge transfer com-
plexes with organic acceptors [30]. The ability of phenothiazines
to form well-defined ion-association products with certain organic
compounds and metal complexes forms the basis of utilizing its bin-
ary and ternary complexes in chemical and pharmaceutical analysis.
Recently phenothiazine derivatives with high electron donating
properties [31] are attracting research interest due to their potential
applications in material science. The ground state intra-molecular
charge transfer and excited state photo-induced electron transfer
properties of phenothiazine [32,33] make them serve as electro ac-
tive and photoactive materials in molecular electronics. Hence they
are widely used in industry as organic light emitting diodes [34,35],
efficient non-linear optical materials [36], acid–base dyes and pig-
ments [37], semiconductors [31], chemical sensors [38] and solar
cells [39]. The structure and interacting mechanism of biologically
active molecules can be explored using infrared and Raman
spectroscopy [40]. Computational method is at present widely used
for simulatingIR spectra. Such simulationsare indispensable tools to
perform normal coordinate analysis so that modern vibrational
spectroscopy is unimaginable without involving them. Non-linear
taining N and S as donor atoms. Drugs based on this ring system are
widely used in medicine [1–4]. Chemical modifications on phenothi-
azine ring system has led to the discovery of drugs exhibiting various
activities like neuroleptics, tranquilizers, anticholinergics, antihista-
minics, anthelmintics [2,3] antiallergics, anticarcinogenics [5], anti-
inflammatory agents, antibacterials, anticonvulsants [6] and as can-
nabinoidreceptor agonists [7]. The variety oftherapeutic activities is
believed to be due to the presence of a fold in the heterocyclic ring
along the nitrogen–sulfur axis and so phenothiazine ring system is
an essential template in medicinal chemistry research. Most of these
phenothiazinedrugs are its N-alkyl derivatives. Chlorpromazine and
ethopropazine are two such derivatives which are used to treat the
diseases of the central nervous system including schizophrenia [8]
and tremor[9–11]. The structure–activity relationship for inhibition
of human cholinesterases by alkyl amide phenothiazine derivatives
has been reported [12–14]. Bacu et al. [15] reported the synthesis of
potential drug delivery systems from maleic anhydride copolymers
⇑
Corresponding author at: Department of Physics, TKM College of Arts and
Science, Kollam, Kerala, India.
E-mail address: cyphyp@rediffmail.com (C.Y. Panicker).
0
022-2860/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.11.013

R. Minitha et al. / Journal of Molecular Structure 985 (2011) 316–322
317
optics deals with the interaction of applied electromagnetic fields in
various materials to generate new electromagnetic fields, altered in
wavenumber, phase, or other physical properties [41]. Organic mol-
ecules able to manipulate photonic signals efficiently are of impor-
tance in technologies such as optical communication, optical
computing, and dynamic image processing [42,43]. In this context,
the dynamic first hyperpolarizability of the title compound is also
and the packing of molecules in the crystal lattice is shown in Fig. 2.
Hydrogen bonds for the title compound are: DAHꢃ ꢃ ꢃA: N(1)A
H(1)ꢃ ꢃ ꢃO(1); d(DAH): 0.845(10); d(Hꢃ ꢃ ꢃA):1.982(13); d(Dꢃ ꢃ ꢃA):
2.808(3) and (DHA):166(3). In the crystalline state the compound
is hydrogen bonded (NAHꢃ ꢃ ꢃO@C) in chains, thus stabilizing the
molecular packing. Full crystallographic data (cif file) relating to
the crystal structure have been deposited with the Cambridge Crys-
tallographic Data Centre as CCDC 763279.
0
calculated in the present study. The first hyperpolarizability (b ) of
this novel molecular system is calculated using B3LYP/6-31G(d)
method, based on the finite field approach. In the presence of an ap-
plied electric field, the energy of a system is a function of the electric
field. First hyperpolarizability is a third rank tensor that can be de-
scribed by a 3 ꢀ 3 ꢀ 3 matrix. The 27 components of the 3D matrix
can be reduced to 10 components due to the Kleinman symmetry
The FT-IR spectrum (Fig. 3) was recorded using KBr pellets on a
DR/Jasco FT-IR 6300 spectrometer in KBr pellets. The spectral res-
ꢁ1
olution was 2 cm . The FT-Raman spectrum (Fig. 4) was obtained
on a Bruker RFS 100/s, Germany. For excitation of the spectrum the
emission of Nd:YAG laser was used, excitation wavelength
1064 nm, maximal power 150 mW, measurement on solid sample.
ꢁ1
[
44]. The components of b are defined as the coefficients in the Tay-
The spectral resolution after apodization was 2 cm
. Computational details
Calculations of the title compound were carried out with
.
lor series expansion of the energy in the external electric field. When
the electric field is weak and homogeneous, this expansion becomes
3
X
X
X
1
2
1
6
i
i
j
i j k
E ¼ E
0
ꢁ
liF ꢁ
a
ijF F ꢁ
b F F F
ijk
i
ij
ijk
Gaussian03 program [46] using the HF/6-31G(d) and B3LYP/6-
31G(d) basis sets to predict the molecular structure and vibrational
wavenumbers. The wavenumber values computed contain known
systematic errors [47] and we therefore, have used the scaling fac-
tor values of 0.8929 and 0.9613 for HF and DFT basis sets. Param-
eters corresponding to optimized geometry of the title compound
(Fig. 5) are given as Supplementary material in Table S2. The ab-
sence of imaginary values of wavenumbers on the calculated vibra-
tional spectrum confirms that the structure deduced corresponds
to minimum energy. The assignment of the calculated wavenum-
bers is aided by the animation option of MOLEKEL program, which
gives a visual presentation of the vibrational modes [48,49].
X
1
i
j
k l
ꢁ 2
cijklF F F F þ :::
4
ijkl
i
where E
the origin,
0
is the energy of the unperturbed molecule, F is the field at
ijkl are the components of di-pole moment,
i
l , aij, bijk and c
polarizability, the first hyper polarizabilities, and second hyperpo-
larizibilites, respectively. In the present work, the synthesis, crystal
structure data, vibrational spectroscopic analysis and the first
hyperpolarizability of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-
one is reported.
2
. Experimental
4
. Results and discussion
The title compound was synthesized by refluxing 2-aminothio-
phenol (1.25 g, 0.01 mol) and dimedone (1.4 g, 0.01 mol) in ethanol
for 5 h. The brown crystals which separated on concentrating and
cooling the reaction mixture were collected, washed with petro-
leum ether and dried over P O10 in vacuo. Yield-76%, M.P. 156 °C.
4
Good quality crystals for X-ray diffraction studies were obtained
4.1. IR and Raman spectra
The observed IR and Raman bands with their relative intensities
and calculated (scaled) wavenumbers and assignments are given in
Table 1. The NAH stretching vibrations generally give rise to bands
ꢁ
1
by slow evaporation of an ethanolic solution of the compound.
[50,51] at 3500–3400 cm . In the present study, the NAH stretch-
ꢁ
1
The electronic spectrum of the compound was measured on a
ing band split into a doublet, 3372, 3250 cm in the IR spectrum
owing to Davydov coupling between neighbouring units. A similar
type of splitting is observed in acetanilide [52,53] and N-methylac-
ꢂ
Varian Cary 5000 spectrophotometer. The compound shows
p–p
ꢂ
transitions at 288 nm and 263 nm and n–
p
transitions at 336 nm.
1
ꢁ1
The H NMR spectrum of the compound was taken in DMSO-d
6
on
etamide [54]. The splitting of about 122 cm in the IR spectrum is
Jeol GSX 400FT-NMRspectrometer and the following chemical shifts
were observed. 1d s(6H), 2.15d s(2H), 2.21d s(2H), 6.54–6.89d m(aro-
matic H), 8.878d s(–NH). Elemental analysis: Calculated%: C, 68.48;
H, 6.11; N, 5.14; S, 13.04. Found%: C, 68.38; H, 6.19; N, 5.71; S, 13.27.
Elemental analysis and spectral data agree with the formula
due to strong intermolecular hydrogen bonding. Further more the
ꢁ1
NAH stretching frequency is red shifted by 97 cm in the IR spec-
trum with a strong intensity from the computed frequency, which
indicates weakening of the NAH bond resulting in proton transfer
to the neighbouring units [55]. NAH group show bands at 1510–
ꢁ
1
ꢁ1
ꢁ1
C
14
H15NOS.
1500 cm , 1235–1165 cm
stretching modes are reported [57] in the range 1100–1300 cm
In the present case the CAN stretching modes are also observed
and 740–730 cm
[56]. The CAN
ꢁ1
The single crystals suitable for diffraction were obtained by the
slow evaporation of a solution of the compound in ethanol. The
brown crystal of the compound having appropriate dimensions of
.
ꢁ1
ꢁ1
at 1159 cm in the Raman spectrum and at 1155 and 1136 cm
0
.30 mm ꢀ 0.20 mm ꢀ 0.20 mm was mounted on a fine-focus
theoretically. According to literature if NAH is a part of a closed
ring [56,58] the CANAH deformation band is absent in the region
sealed tube for X-ray crystallographic study. A Bruker axs kappa
apex 2 CCD Diffractometer equipped with graphite monochromat-
ed Mo k
of data. The collected data were reduced using the SAINT program
and structural refinement was carried out by full – matrix least
squares on F (SHELXL-97) program package [45]. Molecular
ꢁ1
1510–1500 cm . For the title compound the CANAH deformation
0
ꢁ1
ꢁ1
a
(k = 0.71073 A ) radiation was used for the measurement
band is observed at 1313 cm in the Raman spectrum, 1306 cm
ꢁ
1
in the IR spectrum and at 1300 cm theoretically. According to
Socrates [56] the C@C stretching is expected around 1600 cm
ꢁ1
2
when conjugated with C@O. The C@O and C@C stretching bands
graphics employed includes ORTEP 3 and Mercury. The title
are observed at 1708 (IR), 1696 (Raman), 1675 (DFT) and at 1580
(IR), 1585 (Raman), 1615 (DFT) cm , respectively. The deforma-
tion bands of C@O are also identified and assigned.
ꢁ1
compound crystallizes in monoclinic p21/C with a = 17.5038,
3
b = 5.7081, c = 12.6936 A, V = 1227.12 A and Z = 4.
The crystal structure XRD data are given as Supplementary Mate-
rial In Table S1. The ORTEP diagram of the compound is given in Fig. 1
In the vibrations of the CH
, symmetric stretching
2
group, the asymmetric stretching
CH , scissoring vibration dCH
tasCH
2
t
s
2
2

3
18
R. Minitha et al. / Journal of Molecular Structure 985 (2011) 316–322
Fig. 1. ORTEP diagram of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one.
Fig. 2. Molecular Packing of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one.
Fig. 3. FT-IR spectrum of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one.
Fig. 4. FT-Raman spectrum of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one.
ꢁ
1
ꢁ1
ꢁ1
appear in the regions 2940 ± 20, 2885 ± 45, 1440 ± 10 cm
respectively [56,58]. The DFT calculation give
1159 cm in Raman and at 1290, 1273, 1230, 1155 cm theoret-
ꢁ1
tasCH
2
at
ically. The band calculated at 875, 825 cm were assigned to the
rocking modes of CH [58].
ꢁ1
ꢁ1
ꢁ1
2
982 cm , 2932 cm and
t
s
CH
2
at 2905, 2893 cm . The bands
2
ꢁ
1
observed at 2978, 2930, 2885 cm
2
in the IR spectrum and at
971, 2935, 2898 cm in the Raman spectrum are assigned as
CH stretching modes. The scissoring modes dCH are assigned at
theoretically. Absorption of hydrocarbons
twisting and wagging vibration is observed in the re-
In esters the vibrations of CH
3
are expected in the range 2900–
[58,59]. The first of these result from asymmetric
modes in which two CAH bonds of the methyl
ꢁ1
ꢁ1
3000 cm
2
2
stretching
tasCH
3
ꢁ1
1
458 and 1441 cm
group are extending while the third one is contracting and the other
result from symmetric stretching CH in which all three of the
CAH bonds extend and contract in-phase. The asymmetric stretch-
ing modes of methyl group are calculated to be at 3009, 2994,
2990, 2984 cm and the symmetric mode at 2927, 2921 cm .
due to CH
2
t
s
3
ꢁ
1
gion 1350–1150 cm . These bands are generally appreciably
weaker than those resulting from CH scissoring vibrations. These
modes are assigned at 1261, 1231 cm
2
ꢁ1
ꢁ1
ꢁ1
in IR, 1261, 1235,

R. Minitha et al. / Journal of Molecular Structure 985 (2011) 316–322
319
ents are heavy, or one of them is heavy while the other is light, or
both of them are light. In the first case the interval is 1100–
ꢁ
1
ꢁ1
1
130 cm , in the second case 1020–1070 cm , while in the third
ꢁ1
case it is between 630 and 780 cm [61]. The band observed at
ꢁ1
ꢁ1
1
083 cm in both spectra and at 1110 cm theoretically is as-
signed as the ring breathing mode in the present case. The CAH
out-of-plane deformations of the phenyl ring [58] are observed be-
ꢁ1
tween 1000–700 cm . Generally, the CAH out-of-plane deforma-
tions with the highest wavenumber have weaker intensity than
those absorbing at lower wavenumber. The CH vibrations are ob-
ꢁ1
served at 964, 936, 881, 749 cm in the IR spectrum and at 989,
ꢁ
1
9
42, 744 cm in the Raman spectrum. The DFT calculation give
ꢁ1
these modes at 993, 931, 890, 731 cm . The strong CH occurring
at 755 ± 35 cm is typical for 1,2-disubstitution and the band ob-
served at 749 cm in the IR spectrum is assigned to this mode,
ꢁ1
Fig. 5. Optimized geometry (DFT) of 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-
ꢁ1
one.
which finds support from computational results. The IR bands in
ꢁ1
the 1729–2873 cm region and their large broadening support
the intermolecular hydrogen bonding [62]. The substituent sensi-
tive modes of the phenyl ring are also identified and assigned (Ta-
ble 1).
The bands at 3014 cm 1 in the IR and 3010, 2913 cm in the Raman
spectrumof the title compound are assigned as CH stretching vibra-
ꢁ
ꢁ1
3
tions. Two bending can occur within a methyl group. The first of
these, the symmetrical bending vibration, involves out-of-phase
bending of the CAH bonds. The asymmetric deformations are ex-
4.2. Geometrical parameters and first hyperpolarizability
ꢁ1
pected in the range 1400–1485 cm [58]. The calculated values of
For the title compound the CAN bond lengths C14AN11 = 1.3771
(DFT), 1.339 (XRD) and C AN11 = 1.4108 (DFT), 1.402 Å (XRD). Dan-
3
ꢁ
1
d
asCH
3
modes are at 1482, 1475, 1465, 1460 cm . Experimentally
ꢁ1
ꢁ1
the bands are observed at 1474 cm in IR and 1472 cm in Raman
spectrum. In many molecules the symmetric deformation d CH ap-
pears with an intensityvaryingfrom medium to strong and expected
in the range of 1380 ± 25 cm [58]. Bands at 1356 cm in the IR
spectrum, 1360 cm in the Raman spectrum and at 1375 cm
dia et al. [63] reported corresponding bond lengths for CAN as 1.364
and 1.412 Å for similar derivative and Endredi et al. [64] reported
these values as 1.408 Å and 1.412 Å, and Jadeja et al. [65] reported
this as 1.428 Å, Tamasi et al. [66] reported this as 1.378 Å, 1.377 Å
and 1.397 Å. In the present case the C@O bond length is 1.237 Å
(XRD), 1.2276 (DFT). Dandia et al. [63] reported this bond length
as 1.343 Å and Jadeja et al. [65] reported this as 1.252 Å. The
s
3
ꢁ
1
ꢁ1
ꢁ1
ꢁ1
ꢁ1
and 1344 cm (DFT) are assigned as d
s
CH
3
modes for the title com-
pound. Esters display a methyl rock in the neighbourhood of
ꢁ
1
ꢁ1
1
045 cm [58]. The second rock in the region 970 ± 70 cm [58]
N11AH13 bond length of the compound is 0.845 Å (XRD), 1.0108
is more difficult to find among the CAH out-of-plane deformations.
(DFT). Dandia et al. [63] reported this value as 0.80 Å. The C@C of
cyclohexenone moiety in the compound is C14AC15 = 1.3597 (DFT),
1.360 (XRD). Dandia et al. [63] reported the C@C value as 1.364 Å.
The CAC bond lengths of cyclohexenone are C17AC15 = 1.459
For the title compound, these modes
q
CH
3
are calculated at 1016,
ꢁ1
ꢁ1
1
003, 924, 919 cm . The bands at 1018 cm
in the IR and
CH modes.
The existence of one or more aromatic ring in the structure is
normally determined from the CAH and C@C ring related vibra-
ꢁ1
9
21 cm in the Raman spectrum are assigned as
q
3
(DFT), 1.418 (XRD);
C14AC16 = 1.5116 (DFT), 1.495 (XRD);
C22AC17 = 1.5262 (DFT), 1.503 (XRD); C21AC22 = 1.5436 (DFT),
ꢁ1
tions. The CAH stretching occurs above 3000 cm and is typically
exhibited as multiplicity of weak to moderate bands, compared
with the aliphatic CAH stretching [60]. In the present case, the
1.529 (XRD); C16AC21 = 1.5456 (DFT), 1.526 (XRD). The CAH bond
lengths of cyclohexenone are C22AH23 = 1.0951 (DFT), 0.97 (XRD);
C22AH24 = 1.101 (DFT), 0.97 (XRD); C16AH19 = 1.1012 (DFT), 0.97
DFT calculations give
t
CAH modes of the phenyl rings in the range
(XRD); C16AH18 = 1.1 (DFT), 0.97 Å (XRD). The CAC bond length of
methyl groups at C21 are C21AC26 = 1.538 (DFT), 1.527 (XRD);
C21AC25 = 1.5421 (DFT), 1.527 Å (XRD). The CAH of two CH at C21
3
are C25AH28 = 1.0946 (DFT), 0.96 (XRD); C25AH27 = 1.0959 (DFT),
0.96 (XRD); C26AH30 = 1.0961 (DFT), 0.96 (XRD); C26AH32 = 1.0968
ꢁ1
3
3
092–3048 cm . The bands observed at 3195, 3157, 3106,
057 cm in the IR spectrum and at 3153, 3100, 3047 cm in
CAH modes of the phe-
ꢁ
1
ꢁ1
the Raman spectrum are assigned to the
t
nyl ring. The benzene ring possesses six ring-stretching vibrations,
of which the four with the highest wavenumbers (occurring near
(DFT), 0.96 (XRD);
26AH31 = 1.0973 (DFT), 0.96 Å (XRD). The CAC bond length of the
compound are C AC = 1.3976 (DFT), 1.381 (XRD); C AC = 1.3924
(DFT), 1.374 (XRD); AC = 1.3960 (DFT), 1.380 (XRD);
AC = 1.3959 (DFT), 1.380 (XRD); C AC = 1.397 (DFT), 1.382
(XRD); C AC = 1.4058 (DFT), 1.393 Å (XRD). The CAH bond length
of benzene ring in the compound are C AH10 = 1.0859 (DFT), 0.93
(XRD); C AH = 1.0866 (DFT), 0.93 (XRD); C AH = 1.086 (DFT),
0.93 (XRD); C AH = 1.0884 (DFT), 0.93 Å (XRD). The C14AN11AC13
AN11AH13 and C AN11AC14 bond angle of the compound for
C25AH29 = 1.097 (DFT), 0.96 (XRD);
ꢁ1
1
600, 1580, 1490 and 1440 cm ) are good group vibrations. With
C
heavy substituents, the band tends to shift to some what lower
wavenumbers. In the absence of ring conjugation, the band at
1
6
6
5
C
4
5
ꢁ
1
ꢁ1
1
580 cm is usually weaker than that at 1600 cm . In the case
C
1
2
3
4
ꢁ1
of C@O substitution, the band near 1490 cm can be very weak.
The fifth ring-stretching vibration is active near 1315 ± 65 cm
2
3
ꢁ1
,
6
a region that overlaps strongly with that of the CH in-plane defor-
mation. The sixth ring-stretching vibration, or the ring breathing
mode appears as a weak band near 1000 cm in mono, 1,3-di-
and 1,3,5-trisubstituted benzenes. In the otherwise substituted
benzenes, however, this vibration is substituent sensitive and dif-
ficult to distinguish from the ring in-plane deformation [58]. The
1
7
5
9
4
8
,
ꢁ1
C
3
3
DFT and XRD are 116.3 (119), 108.9 (115) and 124.8 (126.2°). The
asymmetry of the bond angle values is due to the interaction of
NAH with hydrogen atoms of CH
Dandia et al. [63] reported these values as 119°, 114° and 126.6°.
The C15AS12AC bond angle of the compound is 99.4 (101°). Dandia
2
of the cyclohexenone moiety.
ꢁ1
tPh mode is expected in the region 1260–1615 cm for the phe-
ꢁ1
nyl ring. The Ph modes are observed at 1514, 1425, 1287 cm in
the IR spectrum, 1569, 1501, 1417, 1284 cm in the Raman spec-
trum, 1586, 1573, 1497, 1432, 1418, 1281 cm theoretically for
the phenyl ring. In ortho disubstitution the ring breathing mode
has three frequency intervals according to whether both substitu-
2
ꢁ1
et al. [63] reported as 101.3° and Endredi et al. [64] reported this va-
lue as 96.1°, 97.9°, and 98°. The C15AC17AO20, C22AC17AO20 and
ꢁ1
C15AC17AO22 bond angle of the compound are 121.5° (121.3),
121.4° (119.6) and 117° (119.1). Dandia et al. [63] reported these

3
20
R. Minitha et al. / Journal of Molecular Structure 985 (2011) 316–322
Table 1
Calculated (scaled) wavenumbers, measured infrared and Raman band positions and assignments for 1H-2,2-dimethyl-3H-phenothiazin-4[10H]-one.
IR (cm 1
ꢁ
)
t
Raman (cm
ꢁ1
)
Assignments
HF/6-31G(d)
B3LYP/6-31G(d)
t
(cmꢁ1)
IR Intensity
Raman Activity
(Relative)
t
(cm
ꢁ1
)
IR Intensity
(Relative)
Raman Activity
(Relative)
t
(Relative)
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
9
9
9
9
9
9
8
8
8
7
7
7
6
6
6
5
5
5
5
5
4
4
4
452
030
017
007
989
933
928
919
915
909
878
865
856
851
845
758
641
606
594
507
481
475
468
464
460
449
440
425
410
393
373
313
300
282
264
251
234
203
183
157
146
126
114
079
063
026
018
010
001
87
12
9
7
1
4
15
9
10
10
7
6
7
13
4
6
100
45
9
8
18
2
23
100
30
29
20
27
48
26
19
12
19
88
22
8
17
21
26
11
13
4
0
11
1
4
9
5
5
4
1
3469
3092
3079
3069
3048
3009
2994
2990
2984
2982
2932
2927
2921
2905
2893
1675
1615
1586
1573
1497
1482
1475
1465
1460
1458
1441
1432
1418
1395
1375
1344
1300
1290
1281
1273
1254
1244
1230
1209
1155
1148
1136
1115
1110
1053
1032
1016
1003
993
931
924
919
911
900
890
875
830
825
775
731
698
676
660
633
598
566
562
535
521
483
455
441
9
9
5
0
4
10
16
6
7
5
33
100
32
21
20
14
47
11
26
14
62
15
25
27
29
27
52
5
3372 m 3250 m
3195 m
3157 m
3106 w
3057 w
3250 w
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
NH
CH
CH
CH
3153 w
3100 w
3047 m
3010 w
CH
3014 w
asMe
asMe
asMe
asMe
asCH
asCH
2978 m
2930 w
2971 m
2935 w
2
11
5
12
6
2
s
s
s
s
Me
Me
CH
CH
2913 w
2
9
2885 w
1708 w
1580 s
2898 m
1696 w
1585 s
2
65
77
2
12
25
3
C@O
C@C
Ph
Ph
Ph
16
4
0
12
2
1569 vs
1501 w
1514 w
1474 s
dasMe
dasMe
dasMe
dasMe
4
2
1472 w
38
68
1
1
2
29
3
2
6
4
12
19
2
1
58
7
0
8
7
2
2
1
2
6
1
1
5
0
1
1
0
3
2
1
1
2
13
100
22
1
2
34
4
3
2
1
39
7
13
4
1
39
7
6
0
8
2
3
2
7
1
1
2
0
0
0
6
2
1
1
1
0
0
19
2
7
5
7
3
1
2
3
14
3
4
3
1
3
6
19
3
3
2
2
9
1
7
11
3
1
0
dCH
dCH
t
t
2
2
Ph
Ph
1425 m
1384 w
1417 m
1360 m
1313 w
1284 m
1261 m
1235 s
dCH
1
2
d
d
s
Me
Me
1356 s
1306 s
s
dNH
CH
Ph
3
8
3
3
5
6
1
5
3
5
3
8
1
4
8
3
3
0
0
2
3
3
1
0
1
2
2
0
1
1
1
2
3
1
1
1
1
2
2
1
x
2
1287 w
1261 w
1231 w
t
x
x
CH
CH
2
2
dCH
CH
dCH
CN,
dCH
s
2
1159 w
t
sCH
2
1149 m
t
t
CN
CAC
1119 w
1083 w
1048 w
1122 m
1083 w
1059 w
1028 s
Ring breathing
CAS
dCH
t
1018 w
q
q
c
c
q
Me
Me
CH
CH
Me
Me
CAC
CAC
CH
964 w
936 w
989 w
942 w
48
30
25
17
08
86
65
28
76
57
19
81
65
45
94
71
1
2
2
0
921 w
q
t
t
c
q
t
0
881 w
1
1
2
1
1
1
2
1
1
4
1
1
1
1
2
5
0
879 w
845 w
802 w
CH
CC
CH
2
835 w
820 w
q
2
1
23
1
1
2
5
0
7
1
5
1
4
26
3
t
c
c
CAC
CH
Ph
749 s
698 w
674 w
744 w
687 w
0
2
3
0
5
3
4
1
dPh(X)
dPh(X)
dC@O
c
c
dC@C
c
c
640 w
600 w
572 w
558 m
536 m
517 w
478 m
450 w
644 w
623 s
590 w
555 w
Ph(X)
C@O
66
40
31
86
62
49
NH
Ph
521 w
484 s
1
26
1
dPh
c
c
NH
Ph(X)
436 s

R. Minitha et al. / Journal of Molecular Structure 985 (2011) 316–322
321
Table 1 (continued)
IR (cm 1
ꢁ
)
t
ꢁ1
Raman (cm
)
Assignments
HF/6-31G(d)
B3LYP/6-31G(d)
t
(cm 1
ꢁ
)
IR Intensity
Raman Activity
(Relative)
t
(cm
ꢁ1
)
IR Intensity
(Relative)
Raman Activity
(Relative)
t
(Relative)
4
4
3
3
3
3
2
2
2
2
2
2
1
1
1
9
6
3
25
1
1
1
1
0
0
1
0
1
0
1
0
1
1
1
0
0
0
1
1
1
1
1
1
0
1
1
1
0
0
1
1
0
1
0
1
423
411
390
364
337
302
284
266
258
248
236
214
176
147
116
92
0
1
1
1
0
0
1
0
1
0
0
0
1
1
1
0
0
0
1
1
1
1
1
1
0
0
2
0
0
6
1
1
0
1
1
1
427 m
cPh
12
88
67
37
05
88
70
63
50
38
18
82
45
21
2
407 w
tCH
tCH
tCH
3
3
2
378 w
348 w
319 w
294 w
261 w
dCAN
dPh(X)
c
CAN
dCAS
c
c
CAS
C@C
tCH
tCH
2
2
c
CASAC
skeCACAC
skeCACAC
dPh(X)
123 vs
9
4
73
26
c
c
Ph(X)
Ph(X)
t
-stretching; d-in-plane deformation;
c-out-of-plane deformation; q-rocking; s-twisting; t-torsion; x-waging; -twisting; Ph-phenyl ring; X-substituent sensitive; s-strong;
m-medium; w-weak; b-broad; sh-shoulder; sk-skeletal; subscripts: as-asymmetric; s-symmetric.
values as 122.1°, 122.3° and 115.6°. The asymmetry of the exocyclic
angle given by XRD at C17 position is due to the interaction between
tion over quinoline and hydrazone moieties [36,68] which are
responsible for the nonlinearity of the molecule. Honeybourne et
al. [36] and Badar et al. [68] reported a hyperpolarizability value
O
20 and CH
AC AC = 119.9 (DFT), 119.7 (XRD); C
18.4 (XRD); AC AC = 118.9 (DFT),
AC AS12 = 122.5 (DFT), 123.27 (XRD). Dandia et al. [63] reported
2
group. The bond angle of the compound for
AC AN11 = 119.3 (DFT),
118.9 (XRD);
ꢁ30
C
1
C
4
3
2
4
3
equal to 3.91 ꢀ 10
esu for 8-hydroxy quinolinium picrate. We
C
3
2
1
conclude that the title compound is an attractive object for future
studies of non-linear optical properties.The important thermody-
namical parameters(DFT) are: the thermal energy is 173.786 kcal/
Mol, heat capacity is 60.145 Cal/Mol-Kelvin, entropy is
121.563 Cal/Mol-Kelvin, Total energy is ꢁ978.08 a.u. and di-pole
moment is 6.27 Debye. HOMO–LUMO energies are obtained for
the optimized geometry (DFT), kmax value is obtained by the equa-
3
2
these values as 122.1°, 124.9°, and 113.0°. The three bond angles
around C given by DFT are 118.90°, 118.6° and 122.5° and by XRD
are 118.9°, 117.8° and 123.27°. The high bond angle value 123.27°
reveals the enlargement of C AC AS12 is due to the slight interaction
of the lone pairs of sulfur with H17 of aromatic ring [64].
The torsion angles of the compound are C AC AC AN11 = 180
DFT), 179.4 (XRD); C AC
AN11AC14 = 159.8 (DFT), ꢁ178.6 (XRD);
AS12 = 175.6 (DFT), ꢁ178.1 (XRD); AC AS12
15 = ꢁ162.1 (DFT), 179.79 (XRD); C21AC16AC14AN11 = ꢁ156.6
= ꢁ158.8 (DFT), ꢁ179.8
XRD); C22AC17AC15AS12 = ꢁ178.3 (DFT), ꢁ177.33 (XRD); C17
15AS12AC
= 163.7 (DFT), ꢁ179.2° (XRD). The thiazine moiety is
slightly folded along the NAS axis which is evident from the torsion
angle values 11AC14AC15AC17 = 178.4 (XRD), 179.5 (DFT),
AC AC = 177.73, S12AC AC AC AN11
AN11 = ꢁ1.1 and C
14 = ꢁ178.6. The half chair conformation of the cyclohexenone
moiety is confirmed by the torsion angles C15AC14AC16AC21 = 25.8
XRD), 24.9 (DFT); C14AC16AC21AC22 = ꢁ49.4 (XRD), ꢁ48.32 (DFT);
16AC21AC22AC17 = 51.6 (XRD), 52.8 (DFT), C26AC21AC22AC17
69.3 (XRD), 171.7 (DFT); C21AC22AC17AC15 = ꢁ30.3 (XRD), ꢁ33.0
DFT).Using the x, y and z components, the magnitude of the dy-
2
3
2
tion: k ¼ hc=
. Conclusion
The FT-IR and FT-Raman spectra of 1H-2,2-dimethyl-3H-pheno-
D
E ¼ 45:62= E ¼ 570:25 nm.
D
5
4
3
(
4
3
C AC
6
C
1
AC
2
C
1
2
A
5
(
(
DFT), ꢁ153.8 (XRD); C16AC14AN11AC
3
A
thiazin-4[10H]-one were studied. The molecular geometry and the
wavenumbers were calculated using HF and DFT methods and the
optimized geometrical parameters are in agreement with the crys-
tal structure data. The red shift of the NAH stretching wavenumber
in the infrared spectrum from the computed wavenumber indi-
cates the weakening of the NAH bond resulting in proton transfer
to the neighbouring units. The small differences between experi-
mental and calculated vibrational modes are observed. It must be
due to the fact that hydrogen bond vibrations present in the crystal
lead to strong perturbation of the infrared wavenumbers and
intensities of many other modes. Also, we state that experimental
results belong to solid phase and theoretical calculations belong to
gaseous phase.
C
2
N
S
12AC
2
3
4
2
3
4
3
A
C
(
C
=
ꢁ
(
2
x
namic first hyperpolarizability can be calculated by b ¼ ðb þ
2
y
2
1=2
z
b þ b Þ . The complete equation for calculating the magnitude
of the dynamic first hyperpolarizability from the Gaussian03 output
is given as follows [67]
Appendix A. Supplementary material
2
2
2 1=2
b ¼ ½ðbxxx þ bxyy þ bxzzÞ þ ðb þ byzz þ byxxÞ þ ðb þ bzxx þ bzyyÞ ꢄ
yyy
zzz
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.molstruc.2010.11.013.
To calculate the dynamic first hyperpolarizability, the origin of the
Cartesian coordinate system was chosen as the centre of mass of the
compound. The calculated first hyperpolarizability of the title com-
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CAN distances in the calculated molecular structure vary from
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