Molecular structure and vibrational bands and chemical shift assignments of 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione by DFT and ab initio HF calculations

Article abstract of DOI:10.1016/j.saa.2010.05.006

The title molecule, 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4- triazole-3-thione (C₁₁H₁₁N₃OS), was synthesized and characterized by IR-NMR spectroscopy and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group is P2₁/c, a = 9.0907(5) , b = 9.1288(7) , c = 13.6222(7) , α = 90°, β = 98.442 (4), γ = 90° and V = 2683.7(6) ³, F(000) = 488, D _x = 1.386 g/cm³. In addition to the molecular geometry from X-ray experiment, the molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) ¹H and ¹³C chemical shift values of the title compound in the ground state have been calculated using the Hartree-Fock (HF) and density functional method (DFT/BLYP and DFT/B3LYP) with 6-31G(d) basis set. To determine conformational flexibility, molecular energy profile of the title compound was obtained by HF/6-31G(d) calculations with respect to selected degree of torsional freedom, which was varied from -180° to +180° in steps of 10°. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO), and several thermodynamic properties were performed by the HF and DFT methods.

Full text of DOI:10.1016/j.saa.2010.05.006

Spectrochimica Acta Part A 77 (2010) 189–198
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Molecular structure and vibrational bands and chemical shift assignments of
4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione by DFT
and ab initio HF calculations
Tuncay Karakurta,∗, Muharrem Dinc¸ era, Ahmet C¸ etinb, Memet S¸ ekercic
a Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139, Kurupelit, Samsun, Turkey
b Department of Chemistry, Faculty of Arts and Sciences Bingöl University, 12000, Bingöl, Turkey
c Department of Chemistry, Faculty of Arts and Sciences Fırat University, 23119, Elazıg˘, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The title molecule, 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione (C11H11N3OS),
was synthesized and characterized by IR-NMR spectroscopy and single-crystal X-ray diffraction. The com-
pound crystallizes in the monoclinic space group is P21/c, a = 9.0907(5) Å, b = 9.1288(7) Å, c = 13.6222(7) Å,
˛ = 90◦, ˇ = 98.442 (4), ꢀ = 90◦ and V = 2683.7(6) Å3, F(000) = 488, Dx = 1.386 g/cm3. In addition to the molec-
ular geometry from X-ray experiment, the molecular geometry, vibrational frequencies, gauge including
atomic orbital (GIAO) 1H and 13C chemical shift values of the title compound in the ground state have
been calculated using the Hartree-Fock (HF) and density functional method (DFT/BLYP and DFT/B3LYP)
with 6-31G(d) basis set. To determine conformational flexibility, molecular energy profile of the title
compound was obtained by HF/6-31G(d) calculations with respect to selected degree of torsional free-
dom, which was varied from −180◦ to +180◦ in steps of 10◦. Besides, molecular electrostatic potential
(MEP), frontier molecular orbitals (FMO), and several thermodynamic properties were performed by the
HF and DFT methods.
Received 23 December 2009
Received in revised form 3 May 2010
Accepted 13 May 2010
Keywords:
X-ray structure determination
DFT
HF
NMR
IR spectra
Molecular electrostatic potential
© 2010 Elsevier B.V. All rights reserved.
1. Introduction
important in systems containing extensive electron conjugation
and/or electron lone pairs. However, considering that as molec-
1,2,4-Triazoles are very useful ligands in coordination chem-
istry. Besides, derivatives of 1,2,4-triazole have been reported
to exhibit diverse biological activities [1–7]. Derivatives of 4,5-
disubstituted 1,2,4-triazole were synthesized by intramolecular
cyclization of 1,4-disubstituted thiosemicarbazides [8,9]. Fur-
thermore, the electronic structures and thiol-thione tautomeric
equilibrium of heterocyclic thione derivatives have been studied
previously [10–13].
The aim of the present work was to describe and characterize
the molecular structure, vibrational properties and chemical shifts
on 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-
thione crystalline-structure. A number of papers have recently
appeared in the literature concerning the calculation of NMR chem-
ical shift (c.s.) by quantum-chemistry methods [14–19]. These
papers indicate that geometry optimization is a crucial factor in an
accurate determination of computed NMR chemical shifts. More-
over, it is known that the DFT (B3LYP) method adequately takes into
account electron correlation contributions, which are especially
ular size increases, computing-time limitations are introduced
for obtaining optimized geometries at the DFT level, it was pro-
posed that the single-point calculation of magnetic shielding by
DFT methods was combined with a fast and reliable geometry-
optimization procedure at the molecular mechanics level [19].
The gauge-including atomic orbital (GIAO) [20,21] method is
one of the most common approaches for calculating nuclear mag-
netic shielding tensors. It has been shown to provide results that are
often more accurate than those calculated with other approaches,
at the same basis set size [22]. In most cases, in order to take
into account correlation effects, post-Hartree-Fock calculations of
organic molecules have been performed using (i) Møller-Plesset
perturbation methods, which are very time consuming and hence
applicable only to small molecular systems, and (ii) density func-
tional theory (DFT) methods, which usually provide significant
results at a relatively low computational cost [23]. In this regard,
DFT methods have been preferred in the study of large organic
molecules [24], metal complexes [25] and organometallic com-
pounds [26] and for GIAO 13C c.s. calculations [22] in all those cases
in which the electron correlation contributions were not negligible.
In this study, the title compound is a novel compound syn-
thesized firstly in our laboratories by us. We have calculated
∗
Corresponding author. Tel.: +90 03623121919/5260; fax: +90 03624576081.
E-mail address: tuncaykarakurt@gmail.com (T. Karakurt).
1386-1425/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2010.05.006

190
T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
Table 1
Table 3
Crystallographic data for title compound.
Selected optimized and experimental geometric parameters of 4-allyl-5-
(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione (C11H11N3OS) in the
ground state.
Formula
C11H11N3OS
Formula Weight
Temperature(K)
Wavelength (Å)
Crystal system
Space group
Unit cell
a (Å)
219.28
293
0.71073
Monoclinic
P21/c
Calculated
Parameters
Experimental
HF
BLYP
6-31G(d)
B3LYP
Bond lengths (Å)
C(8)-S(1)
1.679(14)
1.355(18)
1.372(17)
1.367(17)
1.466(18)
1.300(18)
1.375(16)
1.329(19)
1.472(18)
1.683
1.345
1.380
1.357
1.462
1.273
1.356
1.328
1.481
1.683
1.376
1.407
1.406
1.485
1.327
1.382
1.375
1.482
1.720
1.385
1.401
1.392
1.473
1.324
1.395
1.365
1.469
9.0907(5)
9.1288(7)
13.6222(7)
90
98.442(4)
90
1118.22(12)
4
1.386
O(1)-C(1)
N(1)-C(7)
N(1)-C(8)
N(1)-C(9)
N(2)-C(7)
N(2)-N(3)
N(3)-C(8)
C(6)-C(7)
b (Å)
c (Å)
␣ (◦)
␤ (◦)
␥ (◦)
V (Å3)
Z
Dcalc (g/cm3)
F(000)
RMSEa
0.011
0.012
0.015
488
Bond angles (◦)
C(7)-N(1)-C(9)
O(1)-C(1)-C(6)
C(5)-C(6)-C(7)
N(2)-C(7)-C(6)
N(1)-C(7)-C(6)
N(3)-C(8)-S(1)
N(1)-C(8)-S(1)
h, k, l Range
-11≤h≤11
-11≤k≤11
-17≤l≤17
8094
2565
0.0435
2288
2565/0/152
0.0388
0.1045
1.049
127.23(12)
117.35(12)
119.73(12)
125.06(12)
124.23(12)
128.74(11)
127.30(11)
127.73
117.39
120.51
124.63
124.28
127.64
129.11
128.48
124.42
118.00
122.46
126.56
128.76
129.41
128.22
116.19
121.34
123.09
126.08
128.31
128.87
Reflections collected
Independent reflections
Rint
Reflections observed [I≥2␴(I)]
Data/restraints/parameters
R [I>2␴(I)]
RMSEa
0.01
3.19
1.66
Rw [I>2␴(I)]
Dihedral angles (◦)
C(5)-C(6)-C(7)-N(2)
C(8)-N(1)-C(9)-C(10)
N(1)-C(7)-C(6)-C(5)
Goodness-of-fit on Indicator
Structure determination
Refinement
−75.76(13)
−77.20(19)
100.32(18)
−81.85
−88.29
96.47
−53.61
−78.94
121.15
−55.42
−79.67
120.64
Shelxs-97
Full matrix
0.333, -0.328
(ꢁ␴)max, (ꢁ␴min) (e/ Å3)
a
Between the bond lengths and the bond angles computed by the theoretical
method and those obtained from X-ray diffraction.
geometrical parameters, fundamental frequencies and GIAO 1H and
13C NMR c.s. values of the title compound in the ground state to
distinguish the fundamental from the experimental 1H c.s. values,
vibrational frequencies and geometric parameters, by using the HF
and DFT (BLYP and B3LYP) methods with 6-31G(d) basis set. A com-
parison of the experimental and theoretical spectra can be very
useful in making correct assignments and understanding the basic
c.s.-molecular structure relationship. And so, these calculations are
valuable for providing insight into molecular analysis. The prop-
erties of the structural geometry, electronic charge distribution,
molecular electrostatic potential (MEP) and the thermodynamic
properties for the title compound at the HF and DFT methods
with 6-31G(d) basis set were studied. We also make comparisons
between experiments and calculations.
mole, 1.52 g.) and the appropriate allyl isothiocyanate (0.01 mole,
0.98 ml.) in absolute ethanole (100 ml.) was refluxed for 5 hours.
The solid material obtained on cooling was filtered, washed with
diethy ether, dried and crystallized from a mixture of ethanole-
hexane (2;1). Yield 70%; m. p. 210-211 ◦C; IR ꢂ (cm-1): 3281-3131
(OH), 1668(C = O), 1641(NH), 1250(C = S), 975-910(-CH = CH2). 1H-
NMR (400 MHz, DMSO-d6, ppm): ␦ 4.08 (t, J = 5.50, 2H, NH-CH2-CH),
5.04 (dd, 1H, Jcis =7.80, 1.47, NH-CH2-CH = CH2), 5.12(dd, 1H,
Jtrans = 15.40, 1.83, NH-CH2-CH = CH2), 5.80 (dq, J= 11.13, 5.13, 1H,
NH-CH2-CH = CH2), 6.90 (q, J= 7.82, 2H, H1, H3), 7.42 (t, J = 8.05,
1H, H2,), 7.83 (d, J = 7.80, 1H, H4), 8.32 (br, 1H, S = C-NH-C), 9.48
(br, 1H, NH-CO), 10.55 (br, 1H, NH-CS), 11.90 (br, 1H, OH). 13C-
NMR (100 MHz, DMSO-d6, ppm): ␦ 182.33, 168.10, 160.13, 135.51,
134.77, 129,29, 119.47, 117.88, 116.01, 115.47, 46.64.
2. Experimental
Synthesis of 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-
1,2,4-triazole-3-thione(III): A stirring mixture of compound (II)
(10 mmole, 2.51 g.) and sodium hydroxide (40 mg, 1 mmole, as
a 2N solution) was refluxed for 6 hours. After cooling, the solu-
tion was acidified with hydrochloric acid and the precipitate was
filtered. The precipitate was then crystallized from A mixture of
ethanole-dioxane (4:1). Yield: 80%; m.p.: 298-300 ◦C, IR ꢂ (cm−1):
3281-3100 (OH), 1628 (C = N), 1260 (C = S), 975-910 (HC = CH2),
1H-NMR (400 MHz, DMSO-d6, ppm): ␦ 4.80 (d, J = 7.32, 2H, CH2-
CH = CH2), 5.20-5.22 (m, 2H Ar-CH2-CH = CH2), 5.82 (dq, J = 7.33,
1.10, 1H, Ar-CH2-CH = CH2), 6.78-6.80 (m, 2H, H1, H3), 7.21-7.23,
2H, H2, H4), 10.45 (br, 1H, OH).
2.1. Synthesis and physical properties
Melting points were determined in open capillary tubes on a
digital Gallenkamp melting point apparatus and are uncorrected.
The IR spectra were recorded for KBr disks with a Mattson 1000
FT-IR spectrometer. 1H-NMR spectra were recorded on a Varian-
Mercury-Plus 400 MHz 1H-NMR, spectrometer in DMSO-d6 with
TMS as an internal standard. Starting materials was obtained from
Fluka or Aldrich.
Synthesis of N-allyl-2-(2-hydroxybenzoyl)hydrazinecarbot-
hioamide(II): A mixture of 2-hydroxybenzohydrazide (I) (0.01
2.2. Crystallographic analysis
Table 2
Hydrogen bonding geometry (Å, ◦) for the title compound.
Data collection was performed on a STOE IPDS II image plate
detector using MoK␣ radiation (␭ = 0.71073 Å) .Intensity data were
collected in the ꢃ range 2.26◦-28.00◦ at 293 oK. Data collections:
Stoe X-AREA [27]. Cell refinement: Stoe X-AREA [27]. Data reduc-
tion: Stoe X-RED [27]. The structure was solved by direct methods
D—H· · ·A
D—H
H· · ·A
D· · ·A
D—H· · ·A
N3—H3· · ·S1i
0.840
0.847
2.45
2.03
3.28
2.87
170
173.5
O1—H1· · ·N2ii
Symmetry codes: (i)–x+1, -y, -z+2; (ii) − x, y+1/2, − z+3/2

T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
191
Table 4
Comparison of the observed and calculated vibrational spectra of 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione (C11H11N3OS) .
Assignments
FT-IR(cm-1) with KBr
Scaled frequencies (6-31G(d)) (cm-1) and relative Intensity (IIR, km/mol)) and
relative intensity (I , km/mol)
HF
IIR
BLYP
IIR
B3LYP
IIR
O-H str.
ꢄ N-H str.
ꢄas CH2 str. (Ar-CH2-CH=CH2)
ꢄ ring C-H str.
ꢄ ring C-H str.
ꢄ ring C-H str.
ꢄ C-H str. (Ar-CH2-CH=CH2)
ꢄ ring C-H str.
ꢄ CH2 str. (Ar-CH2-CH=CH2)
ꢄas CH2 str. (Ar-CH2-CH=CH2)ö
ꢄ CH2 str. (Ar-CH2-CH=CH2)
ꢄ C=C str. (Ar-CH2-CH=CH2)
ꢄ N=C + ring C-C str.
ꢄ N=C + ring C-C str.
ꢄ ring C-C str.
ꢄ ring C-C str.+ ˇ CH bend.
ꢄ N-C=S str.
ꢅw CH2 wag.(Ar-CH2-CH=CH2)
ꢅw CH2 wag.(Ar-CH2-CH=CH2)
ꢅs CH2 scis. (Ar-CH2-CH=CH2)
ꢄ N-C str.
ꢄ N-C str.
ꢅw CH2 wag.(Ar-CH2-CH=CH2)
ꢅ O-H+C-H rock.
ˇ CH bend. (Ar-CH2-CH=CH2)
ꢄ C-C str.
ꢄ C-OH str.
ꢄ N-S=C str.
ꢅ O-H+C-H rock.
ꢄ S=C str.
ꢅ O-H+C-H rock.
ꢄ S=C str.
ꢅ ring C-H rock.
ꢄ N-N str.
ꢄ ring C-C str.
ꢄ ring C-C str.
ꢀ CH out of plane bend.(Ar-CH2-CH=CH2)
ꢄ ring C-C str.+ ˇ CH bend.
ꢀ ring CH out of plane bend.
ꢀ ring CH out of plane bend.
ꢆ hetero-ring bend.
ꢀ ring CH out of plane bend.
ꢅ CH2 rock. (Ar-CH2-CH=CH2)
ꢅ CH2 rock. (Ar-CH2-CH=CH2)
ꢀ ring CH out of plane bend.
ˇ ring HC-CH-CH bend.
ꢆ hetero-ring-CH2
3281
3250
3118
3090
3066
3052
3039
3028
2984
2969
2920
3676
3508
3044
3034
3019
3011
3009
2994
2971
2968
2922
1678
1654
1612
1601
1503
1499
1457
1449
1430
1394
1354
1352
1309
1283
1269
1262
1229
1201
1186
1157
1131
1103
1091
1070
1041
1026
1014
996
0.34
0.50
0.06
0.05
0.06
0
3548
3535
3142
3119
3114
3103
3089
3087
3065
3032
2964
1655
1597
1561
1505
1469
1452
1447
1433
1419
1362
1339
1335
1301
1285
1277
1242
1228
1204
1174
1158
1154
1119
1095
1054
1035
1018
1004
951
0.53
0.47
0.09
0.08
0.09
0.07
0.03
0.01
0.04
0.02
0.07
0.01
0.16
0.16
0.26
0.56
0.27
0.09
0.09
1
0.24
0.37
0.02
0.07
0.06
0.27
0.28
0.32
0.68
0.51
0.03
0.11
0.29
0.01
0.11
0.10
0.07
0.09
0.04
0
3581
3541
3119
3112
3100
3090
3075
3071
3037
3013
2937
1647
1621
1569
1508
1462
1436
1430
1419
1396
1360
1330
1301
1291
1272
1265
1234
1210
1178
1156
1144
1141
1101
1079
1044
1015
992
0.50
0.26
0.07
0.05
0.05
0.02
0
0.03
0.04
0.02
0.04
0.01
0.16
0.08
0.10
0.28
0.11
0.23
0.07
1
0.15
0.17
0.14
0.16
0.09
0.18
0.24
0.14
0.30
0.19
0.11
0.05
0.48
0.19
0.02
0.02
0.03
0.04
0.11
0
0
0.03
0.05
0.01
0.04
0.01
0.37
0.10
0.07
0.39
1
0.14
0.24
0.04
0.19
0.41
0.11
0.41
0.01
0.06
0.04
0.30
0.10
0.20
0.12
0.11 0.10
0.20
0.07
0.03
0.02
0.01
0
1628
1584
-
1500
1309
-
-
1390
1327
-
-
-
-
1283
-
-
1260
1253
-
-
-
-
-
-
-
-
-
-
979
950
935
907
906
898
884
820
0.13
0.09
0.02
0.02
0.04
0.01
0.05
0.11
0.23
972
965
963
921
896
860
813
767
936
915
912
906
887
837
818
754
0.15
0.04
0.01
0.12
0
0.07
0.14
0.15
0.01
0.02
0.10
0.09
0
0.09
0.07
0.14
-
-
-
-
-
-
801
746
733
ꢅw ring CH wag.
748
761
744
ꢅw ring HC-C-OH wag.
719
748
0.02
711
0.03
727
0.07
ꢅw ring HC-C-OH wag.
ꢅw hetero-ring HN-S=C wag.
ˇ ring CCC bend.
ꢅt CH2 twis. (Ar-CH2-CH=CH2)
ꢅt CH2 twis. (Ar-CH2-CH=CH2)
ꢅw N-H wag.
ꢅw N-H wag.+ ring C-H wag
ꢅw N-H wag.+ ring C-H wag
ꢅw ring CH wag.
-
732
684
662
597
560
558
544
521
499
469
418
386
370
339
303
263
0.02
0.02
0.01
0.01
0.05
0.02
0.34
0.03
0.05
0.01
0.01
0.01
0.01
0.01
0.01
0.15
683
660
643
597
562
544
526
512
493
462
415
393
372
361
322
277
0.03
0.05
0.05
0.08
0.01
0.04
0.08
0.07
0.15
0.25
0.01
0.25
0.38
0.06
0.08
0.03
700
660
659
587
548
541
514
503
472
432
416
380
368
358
330
292
0.02
0.02
0.02
0.06
0.01
0.03
0.06
0.12
0.06
0.20
0.05
0.10
0.20
0.21
0.05
0.01
651
635
-
-
-
-
-
-
-
-
-
-
-
-
-
ꢅ C-OH rock.
ꢆ ring CH out of plane bend.+ ˇ HN-C=S bend.
ꢅ CH2 rock. (Ar-CH2-CH=CH2)
ˇ OH bend.
ꢅw O-H + ring C-H wag.
ˇ OH wag.
ˇ OH wag.
using SHELXS-97 [28] and anisotropic displacement parameters
were applied to non-hydrogen atoms in a full-matrix least- squares
refinement based on F2 using SHELXL-97 [28]. Molecular drawings
were obtained using ORTEP-III[29].
3. Computational methods
Molecular geometry is restricted and all the calculations are
performed without specifying any symmetry for the title molecule

192
T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
Table 5
Theoretical and experimental 13C and 1H isotropic chemical shifts (with respect to TMS, all values in ppm) for 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-
thione (C11H11N3OS).
Calculated chemical shift (ppm)
Atom
Experimental (ppm)
(DMSO-d6)
HF
BLYP
6-31G(d)
B3LYP
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H2 (Ar-H)
H3 (Ar-H)
H4 (Ar-H)
H5 (Ar-H)
168.1
153.69
111.03
137.02
115.67
134.77
107.96
151.10
178.76
44.05
129.45
116.85
7.24
8.28
7.44
7.89
3.68
4.51
6.42
5.67
145.89
108.27
124.36
111.90
124.52
104.10
142.40
159.27
50.71
122.21
115.58
6.82
7.46
6.91
7.05
3.78
4.74
6.67
5.51
150.13
110.32
128.78
115.19
127.73
106.91
151.06
170.32
50.78
128.50
111.76
6.93
7.67
7.14
7.38
3.89
4.72
6.65
5.26
117.88
135.51
116.01
134.77
115.45
160.13
182.33
46.64
129.29
119.47
6.78-7.23
6.78-7.23
6.78-7.23
6.78-7.23
4.80
H9a (Ar-CH2-CH=CH2)
H9b (Ar-CH2-CH=CH2)
H10 (Ar-CH2-CH=CH2)
H11a (Ar-CH2-CH=CH2)
H11
4.80
5.82
5.20-5.22
H11b (Ar-CH2-CH=CH2)
H(OH)
H(NH)
5.20-5.22
10.45
10.45
5.36
5.19
9.66
5.45
4.51
9.40
5.28
5.56
9.64
by using Gaussian 03w Program package [30] on a personal com-
puter. The molecular structures of the title compound in the ground
state (in vacuo) are optimized HF, BLYP and B3LYP with 6-31G(d)
basis set. Vibrational frequencies for optimized molecular struc-
tures have been calculated. Three sets of vibrational frequencies for
these species are calculated with these methods and then scaled
by 0.8929, 0.994 and 0.9613, respectively. The geometry of the
title compounds, together with that of tetramethylsilane (TMS) is
fully optimized. 1H and 13C NMR c.s. values are calculated within
GIAO approach [20,21] applying B3LYP and HF method [31] with
6-31G(d) [32] basis set. The theoretical c.s. values of 1H and 13C
were obtained by subtracting the GIAO isotropic magnetic shield-
ing (IMS) values [33,34]. For instance, the average 13C IMS of TMS
are taken into account for the calculation of 13C c.s. of any X car-
bon atom, and so c.s. can be calculated using the following equation
CSx = IMSTMS-IMSx. In order to describe conformational flexibility of
the title molecule, the selected torsion angle, T(C5–C6–C7–N2), was
varied from -180o to 180o in every 10o and the molecular energy
profile as a function of the selected torsional degree of freedom
is obtained by performing single point calculations on the calcu-
lated potential energy surface, and the molecular energy profile
was obtained at the HF/6-31G(d) level. For the calculations of the
MEP [35–38], using B3LYP/6-31G (d) level, was used. The thermo-
dynamic properties of the title compound at different temperatures
were calculated on the basis of vibrational analyses, using HF/6-
31G(d) level.
The optimized parameters of the title compound (bond lengths
and angles, and dihedral angles) by HF, BLYP and B3LYP methods
with 6-31G(d) as the basis set are listed in Table 3 and compared
with the experimental crystal structure for the title compound.
The molecular structure of the title compound is non-planar and
is shown in Fig. 2a-b-c. The hydroxyphenyl ring (C1-C2-C3-C4-
C5) form dihedral angle were observed to be 79.25◦ with the
1,2,4-triazole ring. These dihedral angle have been found to be
84.54◦ HF/6-31G(d) level, and 63.04◦ for BLYP/6-31G(d) level, and
61.781 for B3LYP/6-31G(d) level. These experimental and theo-
retical results have shown non-planar of the title compound. The
crystal structure contains intermolecular N-H. . .S and O-H. . .N
interactions. In the title compound, atom N3 in the molecule at
(x, y, z) acts as hydrogen-bond donor, via atoms H3 to atoms S1 at
(-x + 1, -y, -z + 2) and atom O1 in the molecule at (x, y, z) acts as
hydrogen-bond donor, via atoms H1 to atoms N2 at (-x, -y + 1/2,
-z + 3/2) (Fig. 3). The experimental N3. . .S1 and O1. . .N2 inter-
molecular contact distance values are 3.28, 2.87 Å, respectively,
N-H. . .S and O-H. . .N bond angle values are 170◦, 173.5◦ respec-
tively. The full geometry of intermolecular interactions is given
in Table 2.
In order to compare the theoretical results with the experi-
mental values, root mean square error (RMSE) is used. Calculated
RMSE for bond lengths and bond angles are 0.011 Å and
1.01◦ for HF 6-31G(d) method, 0.012 Å and 3.19◦ for BLYP
6-31G(d) method and 0.015 Å and 1.66◦ for B3LYP 6-31G(d),
respectively.
A logical method for globally comparing the structures obtained
with the theoretical calculations is by superimposing the molec-
ular skeleton with that obtained from X-ray diffraction, giving a
RMSE of 0.164 Å for HF, 0.274 Å for method BLYP and 0.235 for
B3LYP (Fig. 4). According to these results, it may be concluded
that the HF calculation well reproduce the geometry of the title
compound.
4. Results and discussion
4.1. Crystal and molecular structure
The atomic numbering scheme for the title compound
(C11H11N3OS) and the theoretical geometric structure of the title
compound are shown in Fig. 2a-b-c.
The orientation of the substitutents with respect to the 1,2,4-
triazole ring is determined by the experimental dihedral angles
C5-C6-C7-N2 [–75.76(13)o], C8-N1-C9-C10 [–77.20(19)o], N2-N3-
C8-S1 [–177.31(12)o], C7-C6-C1-O1 [–2.2(2)o] and C6-C7-N1-C9
[0.2(2)o]. These dihedral angles have been calculated at -81.852,
The crystal structure of the title compound is monoclinic and
space group is P21/c, Mw = 233.29, a = 9.0907 (5) Å, b = 9.1288
(7) Å, c = 13.6222 (7) Å, ␣ = 90◦, ␤ = 98.442 (4), ␥ = 90◦ and
V = 2683.7(6) Å3, F(000) = 488, Dx = 1.386 g/cm3. Additional infor-
mation for the structure determinations are given in Table 1.

T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
193
Fig. 1. Chemical structure of the title compound.
-88.289, -179.501, -0.520 and -1.268o (HF/6-31G(d)), and -53.609,
-78.935, -178.087, 1.289 and -1.162o (BLYP/6–31G(d)), and -5.419,
-79.672, -177.922, -1.286 and -2.647o (B3LYP/6-31G(d)), respec-
tively.
The different substitutents dependent on the 1,2,4-triazole ring
is defined by the experimental bond lengths N1-C9 [1.466(18)
Å], C6-C7 [1.472(18) Å] and S1 = C8 [1.679(14)]erein these bond
lengths were calculated at 1.462, 1.481 and 1.683 Å (for HF/6-
31G(d)), and 1.485, 1.482 and 1.683 Å (for BLYP/6-31G(d)), and
1.473, 1.469 and 1.720 Å (for B3LYP/6-31G(d)). In previous works,
the S = C bond length was found to be 1.6797(19) Å [39] and 1.669(2)
Å for the different substituent dependent on the 1,2,4-triazole
ring [40]. In the triazole ring, the bond lengths of C = N and N- N
were obtained to be 1.295(2) Å and 1.376(2) Å [39], and 1.313(2)
Å and 1.377(2) Å [40]. In present paper, we have calculated at
1.273 Å and 1.356 Å using HF/6-31G(d) method, and 1.327 Å and
1.382 ÅusingBLYP/6-31G(d) method, and1.324 Å and 1.395 Å using
B3LYP/6-31G(d) method and the data are shown in Table 3. For
the optimized geometric parameters. In present work, according
BLYP and B3LYP methods, the HF method for optimized geomet-
ric parameters (bond lengths, bond and dihedral angles) is much
closer to experimental data.
Molecular energy profiles with respect to rotations about the
selected torsion angle is presented in Fig. 5. According to the results,
Fig. 2. (a) The experimental geometric structure of the title compound (b) The theoretical geometric structure of the title compound (with HF/6–31G(d) level). (c) The
theoretical geometric structure of the title compound (with B3LYP/6–31G(d) level).

194
T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
Fig. 5. Molecular energy profile against the selected torsional degree of freedom at
HF/6-31G(d) level.
4.2. Assignments of the vibration modes
Harmonic vibrational frequencies of the title compound
were calculated by using both HF and DFT (BLYP and B3LYP)
method with 6-31G(d,p) basis set. Three sets of vibrational fre-
quencies for these species are calculated with these methods
and then scaled by 0.8929, 0.994 and 0.9613, respectivelyBy
using Gauss-View [41] molecular visualization program, the
vibrational bands assignments have been made. To facilitate
assignment of the observed peaks, we have analyzed vibra-
tional frequencies and compared our calculation of the title
compound with their experimental results and shown in Table 4.
The agreement between the experimental and calculated frequen-
cies is quite good in general.
Fig. 3. Part of the crystal structure of the title compound, showing the intermolec-
ular interactions (dashed lines). For the sake of clarity, H atoms not involved in the
motifs shown have been omitted.
The bands calculated in the measured region 4000-400 cm−1
arise from the vibrations of O-H, N-H stretching, and the inter-
nal vibrations, etc. of the title compound. Most bands observed
in infrared spectra of the title compound belong to hydroxy
phenyl groups’ modes, only some of them may be assigned to
group ring C-H (symmetric/asymmetric) and C-C stretching bands
were observed to be 3090-3028 and 1628-1584 as experimentally
and compares well with the value reported previously [3110-
the low energy domains for T(C5–C6–C7–N2) are located at–80 and
70◦ having energy of–1058.645 and–1058.646 a.u., respectively.
Energy difference between the most favorable and unfavorable
conformers, which arises from rotational potential barrier calcu-
lated with respect to the selected torsion angle, was calculated as
0.341 a.u.
Fig. 4. Atom-by-atom superimposition of the structures calculated (red) [a=HF; b=BLYP; c=B3LYP with 6-31G(d)] over the X-ray structure (black) for the title compound.
Hydrogen atoms omitted for clarity.

T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
195
Fig. 6. (a) Simulated (HF, BLYP and B3LYP levels) IR spectra of the title compound (b) FT-IR spectrum of the title compound.
3003, 1666-1535 cm−1, 42]. These modes have been calculated
at 3034-2994 and 1654-1503 cm−1 for HF/6-31G(d) level, and
3119-3087 and 1597-1469 cm−1 for BLYP/6-31G(d) level, 3112-
3071 and 1621-1462 cm−1 for B3LYP/6-31G(d) level and compares
well with the value reported previously [3052-3007 and 1639-
1492 cm−1 for HF/6-31G(d) level, 3130-3088 and 1597-1469 cm−1
for BLYP/6-31G(d) level, and 3107-3071 and 1609-1474 cm−1 for
B3LYP/6-31G(d) level, 42]. The twisting, wagging, rocking, and scis-
soring bands of CH2 are tabulated in Table 4.
In the triazole, the N-H and C = N stretching modes were
observed to be 3250, 1628 cm−1 as experimentally and compares
well with the value reported previously [3260,1666-1535 cm1, 42].
These modes were calculated at 3508 and 1654 cm−1 for HF/6-
31G(d), 3535 and 1597 cm−1 for BLYP/6-31G(d) level, and 3541
and 1647 cm−1 for B3LYP 6-31G(d) level and compares well with
the value reported previously [3507 and 1639-1610 cm−1 for HF/6-
31G(d) level, 3534 and 1597-1574 cm−1 for BLYP/6-31G(d) level,
and 3527 and 1609-1584 cm−1 for B3LYP/6-31G(d) level, 42].
Other essential characteristic vibrations of the title compound
are O-H, N-C = S stretching modes were observed to be 3281 and
1500 as experimentally compares well with the value reported pre-
viously [3330,1210 cm1, 42]. These modes were calculated at 3676
and 14994 cm−1 for HF/6-31G(d), 3548 and 1452 cm−1 for BLYP/6-
31G(d) level, and 3581and 1436 cm−1 for B3LYP 6-31G(d) level
and compares well with the value reported previously [3598 and
1204 cm−1 for HF/6-31G(d) level, 3579 and 1210 cm−1 for BLYP/6-
31G(d) level, and 3617 and 1222 cm−1 for B3LYP/6-31G(d) level,
42]. Also, the other levels of calculations can be seen in Table 4.
These results indicated some band shifts with regard to the differ-
ent substituent-triazole ring.
Calculated infrared intensity (Rel. intensity) allows determina-
tion of the strength of the transition. Note that experimental IR
Fig. 7. Correlation graphics of calculated and experimental frequencies of the title compound.

196
T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
iment, we present correlation graphic in Fig. 7 based on the
calculations. As we can seen from correlation graphic in Fig. 7,
experimental fundamentals are in better agreement with the scaled
fundamentals and are found to have a better correlation for DFT
than HF. Only with DFT methods are the wavenumbers relatively
close to the experimental, BLYP being the best for this purpose.
4.3. Assignments of the chemical shift values
DFT and HF methods differ in that no electron correlation effects
are taken into account in HF. DFT methods treat the electronic
energy as a function of the electron density of all electrons simul-
taneously and thus include electron correlation effect. Explicitly,
we have considered also of interest to investigate the influence of
the level used for the geometry optimization on the final value of
the title compound when GIAO 13C and 1H c.s. calculations have
been performed. Thus, GIAO 13C and 1H c.s. calculations obtained at
HF/6-31G(d), BLYP/6-31G(d) and B3LYP/6-31G(d) levels of theory
for the three optimized geometries. The 13C and 1H c.s. values (with
respect to TMS) have been calculated for the optimized structures
of the title compound and generally compared to the experimental
1H c.s. values.
Fig. 8. Molecular electrostatic potential map calculated at B3LYP/6-31G(d) level.
These results are shown in Table 5. 13C and 1H c.s. values were
experimentally observed, Therefore, 13C and 1H c.s values were
only compared to theoretical results. We have calculated 1H c.s.
values (with respect to TMS) of 9.66-3.68 ppm with HF level, 9.40-
3.78 ppm with BLYP level and 9.64-3.89 ppm with B3LYP level.,
however, the experimental results were observed to be 10.45-
4.80 ppm, these values are shown in Table 5, and so the accuracy
ensures reliable interpretation of spectroscopic parameters. As
can be seen from Fig. 1, molecular structure of the title com-
pound includes hydroxyl bounded to aromatic rings. The hydroxyl
spectra are generally reported in either percent transmission or
absorbance unit. Apparently, these mentioned can be seen in Fig. 6.
The simulated infrared spectra, where the intensity (km/mol) is
plotted against the harmonic vibrational frequencies, and experi-
mental infrared spectra are shown in Fig. 6.
In Hartree-Fock, all the vibrational frequencies are overesti-
mated and in agreement with the 10–20% error in the average of
overall the frequencies [43,44]. To make comparison with exper-
Fig. 9. Molecular orbital surfaces and energy levels given in parentheses for the HOMO – 1, HOMO, LUMO and LUMO + 1 of the title compound computed at B3LYP/6-31G(d)
level.

T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
197
Table 6
Calculated energies (a.u), zero-point vibrational energies (kcal mol-1), rotational constants (GHz), entropies (cal mol-1 K-1) and dipole moment (D) of the title compound.
Parameters
HF
BLYP
B3LYP
6-31G(d)
Dipole moment (D)
7.6840
3.5284
6.6962
Zero-point vibrational energy(kcal mol-1
Total energy (a.u.)
)
129.17902
-1058.64522
0.85705
128.62513
-1063.16906
0.82282
127.99808
-1063.42554
0.81990
Rotational constants
0.33853
0.33567
0.34101
0.28711
0.26088
0.26512
Entropy (cal mol-1 K-1
Rotational
Translational
Vibrational
Total
)
29.289
37.923
40.397
107.609
35.005
45.125
50.661
130.791
32.834
42.362
44.286
119.482
Table 7
group include oxygen atom which shows electronegative property,
and so H atom contribute to the downfield resonance. Besides,
the H c.s. of O-H and N-H was experimentally observed to be
10.45 ppm. The O-H and N-H were observed in the same band. In
different substituent-1,2,4-triazole, the H c.s. of O-H was observed
to be 10.10 ppm [42]. The other aromatic-H was observed to be
6.78–7.23, 4.80, 5.82, and 5.20-5.22 ppm. This statement was cal-
culated 7.24–8.28, 3.68–4.51, 6.42 and 5.19-5.36 using HF levels,
6.82–7.46, 3.78–4.74, 6.67 and 5.45-5.51 using BLYP levels and
6.93-7.14, 3.89-4.72, 6.65 and 5.26-5.28 using B3LYP levels. Fur-
thermore, we have calculated 13C c.s. values (with respect to TMS)
of 153.69-44.05 ppm with HF level, 159.27-50.71 ppm with BLYP
level and 150.13-50.78 ppm with B3LYP level. The c.s. values of C1
and C8 atoms bounded hydroxyl group and sulphur atom were
calculated at 153.69 and 178.76 ppm with HF level, 145.89 and
159.27 ppm with BLYP level and 150.13 and 170.32 ppm with B3LYP
level, respectively (Table 5). This statement is attributed to the
presence of delocalization between the lone pair on atom N(3)
and C(1) = S(1) double bond, and also to electronic factors associ-
ated with the large electron density substituents. As can be seen
from Table 5, theoretical 1H c.s. results of the title compound are
generally closer to the experimental c.s. data.
Thermodynamic properties of the title compound at different temperatures at HF/6-
31G(d) level.
T (K)
Cpo,m (cal.mol−1.K−1
)
Smo (cal.mol−1.K−1
)
Hmo (kcal.mol−1
)
200.0
298.1
300.0
400.0
500.0
600.0
700.0
800.0
900.0
1000.0
37.04
50.51
56.13
71.66
84.66
95.11
103.49
110.32
115.96
120.68
94.69
4.37
9.13
119.86
2125.56
144.46
162.34
179.09
194.71
209.26
222.82
235.50
10.02
16.63
24.67
33.87
44.02
54.92
66.44
78.48
puted at the B3LYP/6-31G(d) level for the title compound. The
calculations indicate that the title compound has 61 occupied
molecular orbitals. Both the highest occupied molecular orbitals
(HOMOs) and the lowest-lying unoccupied molecular orbitals
(LUMOs) are mainly localized on the rings indicating that the
HOMO-LUMO are mostly the ␲-antibonding type orbitals. As seen
from Fig. 9, in the HOMO-1 and HOMO, electrons are mainly delo-
calized on the S atom and the triazole ring. However, when electron
transitions take place, some electrons will enter into the LUMO
and LUMO + 1, then, in the LUMO and LUMO + 1, the electrons will
mainly be delocalized on triazole ring and phenyl ring. Namely,
electron transitions are corresponding to the n → ␲ * and ␲ → ␲
* electron transitions. The value of the energy separation between
the HOMO and LUMO is 4.325 eV and this large energy gap indicates
that the title structure is quite stable.
5. Other molecular properties
5.1. Molecular electrostatic potential
Molecular electrostatic potential (MEP) is related to the elec-
tronic density and is a very useful descriptor in understanding
sites for electrophilic attack and nucleophilic reactions as well as
hydrogen bonding interactions [45–47]. To predict reactive sites
for electrophilic attack for the title compound, MEP was calculated
at the B3LYP/6-31G(d) optimized geometry. The negative (red)
regions of MEP were related to electrophilic reactivity and the pos-
itive (blue) ones to nucleophilic reactivity shown in Fig. 8. As easily
can be seen in Fig. 8, this molecule has two possible sites for elec-
trophilic attack. The negative regions are mainly over the S1atom
and N3 atom. For the title compound, negative regions were calcu-
lated: the MEP value around S1 is more negative than that of N3
atom. Thus, the calculations suggested that the preferred site for
electrophilic attack is the S1 atom, followed from the N3 atom.
Namely, the title compound can act as multidentate ligand to
bind one or two metal centers, so resulting in interesting metal
complexes with different coordination geometries.
5.3. Thermodynamic parameters of the title compound
Several thermodynamic parameters were calculated using HF,
BLYP and B3LYP with 6-31G(d) basis set and calculated these
parameters of the title compound are given in Table 6. Accurate
prediction of zero-point vibrational energy (ZPVE) and the entropy
(Svib(T)) scaling the data [43]. The total energies and the change
in the total entropy of the title compound at room temperature
at different theoretical methods were also presented. In Table 6
demonstrates several thermodynamic parameters of the title com-
pound without of results of experimental.
Besides, based on the vibrational analysis at HF/6-31G(d) level
and statistical thermodynamics, the standard thermodynamic
functions: heat capacity (Cpo,m), entropy (Smo ), and enthalpy (Hmo
)
were obtained and listed in Table 7. The scale factor for frequen-
cies is 0.8929, which is a typical value for the HF/6-31G(d) level of
calculations.
5.2. Frontier molecular orbitals
The frontier molecular orbitals play an important role in the
electric and optical properties, as well as in UV–Vis spectra and
chemical reactions [48]. Fig. 9 shows the distributions and energy
levels of the HOMO − 1, HOMO, LUMO and LUMO + 1 orbitals com-
As will be seen from Table 7, the standard heat capacities,
entropies and enthalpies increase at any temperature from 200.0 K
to 1000.0 K since increasing temperature causes an increase in the
intensities of molecular vibration. For the title compound, the cor-

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T. Karakurt et al. / Spectrochimica Acta Part A 77 (2010) 189–198
relation equations between these thermodynamic properties and
temperature T are as follows:
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6. Conclusions
In this study, 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-
1,2,4-triazole-3-thione was synthesized and characterized by IR,
and X-ray single-crystal diffraction. The comparisons between to
test the different HF, BLYP and B3LYP levels of theory with 6-31
G(d) basis set reported, computed and experimental the geomet-
ric parameters, vibrational frequencies and chemical shifts of the
title compound were compared. However, these results did not
adequately reproduce the experimental pattern of vibrational fre-
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theoretical results, the results of HF method showed a better fit to
experimental ones than DFT in evaluating geometrical parameters
and vibrational frequencies, and chemical shifts.
Supplementary data
CCDC-737467 contains the supplementary crystallographic data
for the compound reported in this paper.
These data can be obtained free of charge at www.ccdc.cam.
ac.uk/conts/retrieving.html [or from the Cambridge Crystallo-
graphic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ,
UK; fax: +44(0)1223-336033; e-mail: deposit@ccdc.cam.ac.uk].
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Acknowledgement
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This study was supported financially by the Research Centre of
Ondokuz Mayıs University (Project No: F-461).
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