Experimental and theoretical study of 4-cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate

Article abstract of DOI:10.1016/j.molstruc.2010.10.011

The molecular geometry, vibrational frequencies, gauge-including atomic orbital (GIAO) ¹H and ¹³C chemical shift values of 4-cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate in the ground state have been calculated by using the Hartree-Fock (HF) and density functional method (DFT/B3LYP) with 6-31++G(d,p) basis set. Furthermore, this structure has been confirmed by IR, ¹³C and ¹H spectroscopy. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The computed vibration frequencies are used to determine the types of molecular motions associated with each of the experimental bands observed. ¹³C and ¹H NMR data were calculated by means of the methods of GIAO, CSGT, and IGAIM. Calculated chemical shift values are compared with the experimental 4-cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate.

Full text of DOI:10.1016/j.molstruc.2010.10.011

Journal of Molecular Structure 984 (2010) 389–395
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Experimental and theoretical study of 4-cyanobenzaldehyde
isonicotinoyl-hydrazone monohydrate
b
c
S. Guner a, , Y. Atalay , A. Dolma
⇑
a Kocaeli University, Faculty of Art and Science, Department of Chemistry, 41380 Kocaeli, Turkey
b Sakarya University, Faculty of Art and Science, Department of Physics, 54140 Sakarya, Turkey
c Kocaeli University, Faculty of Engineering, Department of Electronics and Telecommunications, 41380 Kocaeli, Turkey
a r t i c l e i n f o
a b s t r a c t
The molecular geometry, vibrational frequencies, gauge-including atomic orbital (GIAO) 1H and 13C
chemical shift values of 4-cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate in the ground state
have been calculated by using the Hartree–Fock (HF) and density functional method (DFT/B3LYP) with 6-
31++G(d,p) basis set. Furthermore, this structure has been confirmed by IR, 13C and 1H spectroscopy. The
results of the optimized molecular structure are presented and compared with the experimental X-ray
diffraction. The computed vibration frequencies are used to determine the types of molecular motions
associated with each of the experimental bands observed. 13C and 1H NMR data were calculated by means
of the methods of GIAO, CSGT, and IGAIM. Calculated chemical shift values are compared with the exper-
imental 4-cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate.
Article history:
Received 28 June 2010
Received in revised form 5 October 2010
Accepted 5 October 2010
Available online 14 October 2010
Keywords:
4-Cyanobenzaldehyde isonicotinoyl-
hydrazone monohydrate
DFT
Ó 2010 Elsevier B.V. All rights reserved.
HF
GIAO NMR
IR spectra
Vibrational assignment
1. Introduction
noyl-hydrazone monohydrate crystalline-structure. A number of
papers have recently been appeared in the literature concerning
Tuberculosis (TB) has reemerged and infecting three million
deaths annually [1], due to the advent of multi drug resistant
strains and the association of the tuberculosis with human immu-
nodeficiency virus infection in AIDS [2]. Therefore, the search for
new drugs for tuberculosis is of the utmost importance. Treatment
regimens for tuberculosis are based on long-term basis with com-
bined chemotherapy [3]. Isoniazid (isonicotinoylhydrazine), a bac-
tericidal drug that acts both intracellular in the macrophages and
extracellular in the necrotic tissue, is main drug used in combina-
tion with other drugs for the treatment of tuberculosis [4]. The cal-
culation of NMR parameters is a recent, but extremely rapidly
progressing area of quantum chemistry [5]. During the past dec-
ade, numerous ab initio methods have been developed, imple-
mented, and tested, and several theoretical overviews [6–8] and
routinely applicable implementations of methods are currently
available [9–11]. Recently, the ab initio and density functional the-
ory (DFT) have become a powerful tool in the investigation of
chemical shift and molecular structure [14,15].
the calculation of NMR chemical shift (c.s.) by quantum-chemistry
methods [16–22]. These papers indicate that geometry optimiza-
tion is a crucial factor in an accurate determination of computed
NMR chemical shift. Moreover, it is known that the DFT (B3LYP)
method adequately takes into account electron correlation contri-
butions, which are especially important in systems containing
extensive electron conjugation and/or electron lone pairs. How-
ever, considering that, as molecular size increases, computing-time
also increases. It was proposed 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 [18].
Several methods used with ab initio calculations are now avail-
able for calculating nuclear shielding. The gauge-including atomic
orbital (GIAO) [9–11], individual gauges for atoms in molecules
(IGAIM) [13], and continuous set of gauge transformations (CSGT)
[12] methods are three of the most common approaches for calcu-
lating nuclear magnetic shielding tensors. The GIAO has been
shown to provide results that are often more accurate than those
calculated with other approaches, at the same basis set size [25].
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 highly time consuming and hence applicable only to small
The aim of the present work is to describe and characterize the
molecular structure, experimental and theoretical vibration
properties and chemical shifts on 4-cyanobenzaldehyde isonicoti-
⇑
Corresponding author. Tel.: +90 262 303 2036; fax: +90 262 303 2003.
E-mail address: seguner@kocaeli.edu.tr (S. Guner).
0022-2860/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.10.011

390
S. Guner et al. / Journal of Molecular Structure 984 (2010) 389–395
Table 1
molecular systems, and (ii) density functional theory (DFT) meth-
ods, which usually provide significant results at a relatively low
computational cost [26]. In this regard, DFT methods have been
preferred in the study of large organic molecules [27], metal com-
plexes [28] and organometallic compounds [29] and for GIAO 13C
c.s. calculations [25] in which cases the electron correlation contri-
butions were not negligible.
In the previous work, the crystal structure of the title compound
was studied experimentally [26]. To best of our knowledge, no the-
oretical results exist for the title compound. In this study, the IR
(KBr pellets), 1H and 13C (in the DMSO solvent) of the title com-
pound are analyzed. Besides, the geometrical parameters, and
GIAO [9–11], CSGT [12], IGAIM [16] 1H and 13C chemical shifts of
the title compound have been calculated in the ground state by
using the HF and DFT (B3LYP) method with 6-31++G(d,p) basis
set. A comparison of the experimental and theoretical spectra
can be very useful in making correct assignments and understand-
ing the basic chemical shift-molecular structure relationship. And
so, these calculations are valuable for providing an insight into
molecular analysis.
Optimized and experimental geometries of the ground state of the title compound.
Parameter
Experimental [26]
Calculated [6-31++G(d,p)]
HF
B3LYP
Bond lengths (Å)
C16AC15
C16AN11
C16AH
C15AC14
C15AH
C14AC13
C14AC17
C13AC12
C13AH
C12AN11
C12AH
C17AO1
C17AN17
N17AN27
N17AH
N27AC27
C27AC21
C27AH
C26AC25
C26AC21
C26AH
C25AC24
C25AH
1.383(3)
1.344(3)
0.950
1.392(3)
0.950
1.386(4)
1.505(3)
1.387(3)
0.950
1.336(3)
0.950
1.224(3)
1.356(3)
1.383(3)
0.900
1.279(3)
1.473(4)
0.950
1.372(4)
1.399(4)
0.950
1.398(3)
0.950
1.385
1.323
1.076
1.387
1.073
1.387
1.507
1.387
1.074
1.320
1.076
1.194
1.364
1.354
1.000
1.256
1.477
1.083
1.379
1.396
1.073
1.395
1.074
1.388
1.445
1.386
1.074
1.390
1.076
0.944
1.394
1.341
1.088
1.400
1.084
1.401
1.511
1.398
1.085
1.338
1.088
1.221
1.386
1.357
1.019
1.287
1.465
1.096
1.388
1.409
1.085
1.410
1.085
1.405
1.434
1.392
1.085
1.406
1.087
0.967
2. Computational details and experimental procedure
The molecular structures of 4-cyanobenzaldehyde isonicoti-
noyl-hydrazone monohydrate in the ground state (in vacuum)
are optimized HF and B3LYP with 6-31++G(d,p) basis set. Then
vibrational frequencies for optimized molecular structures were
calculated. The vibrational frequencies for these species were
scaled by 0.8929 and 0.9613 respectively. The geometry of the title
compounds, together with that of tetramethylsilane (TMS), was
fully optimized. 1H and 13C NMR chemical shifts were calculated
within GIAO, CSGT and IGAIM approach [23,24] applying B3LYP
and HF methods [27] with 6-31++G(d,p) [28] basis set. The theoret-
ical chemical shift values of 1H and 13C were obtained by subtract-
ing the GIAO, CSGT and IGAIM isotropic magnetic shielding (IMS)
C24AC23
C24AC241
C23AC22
C23AH
C22AC21
C22AH
1.397(3)
1.445(4)
1.386(4)
0.950
1.393(4)
0.950
O2 H2A
0.950
Bond angles (°)
C15AC16AN11
C15AC16AH
N11AC16AH
C16AC15AC14
C16AC15AH
C14AC15AH
C15AC14AC13
C15AC14AC17
C13AC14AC17
C14AC13AC12
C14AC13AH
C12AC13AH
C13AC12AN11
C13AC12AH
N11AC12AH
C16AN11AC12
C14AC17AO1
C14AC17AN17
O1AC17AN17
C17AN17AN27
C17AN17AH
N27AN17AH
N17AN27AC27
N27AC27AC21
N27AC27AH
C21AC27AH
C25AC26AC21
C25AC26AH
C21AC26AH
C26AC25AC24
C26AC25AH
C24AC25AH
C25AC24AC23
C25AC24AC241
C23AC24AC241
C24AC23AH
C22AC23AH
C23AC22AC21
C23AC22AH
C21AC22AH
C27AC21AC26
123.5(2)
118.2
118.2
118.7(2)
120.7
120.7
118.3(2)
117.9(2)
123.7(2)
118.8(2)
120.6
120.6
123.6(2)
118.2
123.5
120.2
116.3
118.5
121.1
120.4
118.2
118.2
123.5
118.4
121.8
119.7
123.6
120.1
116.3
117.8
121.1
114.5
124.4
119.3
120.6
119.2
119.2
120.8
122.1
117.1
120.2
120.5
119.4
120.0
120.3
119.7
120.2
119.8
119.9
120.0
120.5
120.7
119.3
120.0
121.6
123.7
120.2
116.1
119.1
121.5
119.4
117.6
116.8
125.6
118.7
122.6
118.7
124.0
120.0
116.1
116.9
121.3
115.9
122.8
119.3
121.7
119.0
117.6
120.7
121.9
117.5
120.5
120.6
118.9
120.2
120.3
119.5
119.7
120.2
120.1
119.7
120.5
120.9
119.4
119.6
121.8
118.2
117.0(2)
121.1(2)
114.6(2)
124.3(2)
118.5(2)
128.6
112.3
115.5(2)
119.0(2)
120.5
120.5
120.3(2)
119.8
119.8
120.2(2
119.9
119.9
119.9(2)
119.2(2)
121.0(2)
120.2
120.2
120.3(2)
119.8
Fig. 1. (a) The experimental geometric structure of the title compound
(C15H12N4OÁH2O) [26], (b) the theoretical (with B3LYP) geometric structure of the
title compound (C15H12N4OÁH2O).
119.8
121.5(2)

S. Guner et al. / Journal of Molecular Structure 984 (2010) 389–395
391
Table 1 (continued)
Parameter
Experimental [26]
Calculated [6-31++G(d,p)]
HF
B3LYP
C27AC21AC22
C26AC21AC22
C15AC16AN11
119.0(2)
119.6(2)
123.5(2)
119.0
119.4
123.5
119.2
119.0
123.7
Torsion angles (°)
N11AC16AC15AC14
C15AC16AN11AC12
C16AC15AC14AC13
C16AC15AC14AC17
C15AC14AC13AC12
C17AC14AC13AC12
C15AC14AC17AO1
C15AC14AC17AN17
C13AC14AC17AO1
C13AC14AC17AN17
C14AC13AC12AN11
C13AC12AN11AC16
C14AC17AN17AN27
O1AC17AN17AN27
C17AN17AN27AC27
N17AN27AC27AC21
N27AC27AC21AC26
HAC27AC21AC22
1.8(4)
0.2(4)
À1.0
À0.1
1.3
À0.2
À0.1
0.4
À2.2(4)
179.6(2)
0.9(4)
179.0(2)
25.7(4)
À153.1(2)
À152.4(3)
28.8(3)
1.1(4)
À1.6(4)
176.7(2)
À2.1(4)
179.0(2)
179.9(2)
À11.6(4)
168.0(3)
1.0(4)
179.4
À0.2
177.9
À31.9
À0.2
146.1
À34.3
À0.7
1.0
178.7
À1.7
173.1
179.4
0.2
179.8
À0.3
À179.6
À7.7
171.9
171.6
À8.8
À0.1
0.2
179.3
À1.1
178.5
180.0
0.0
0.4
0.0
0.0
0.0
C21AC26AC25AC24
C25AC26AC21AC27
C25AC26AC21AC22
C26AC25AC24AC23
C26AC25AC24AC241
C25AC24AC23AC22
N11AC16AC15AC14
C15AC16AN11AC12
C16AC15AC14AC13
C16AC15AC14AC17
C15AC14AC13AC12
C17AC14AC13AC12
C15AC14AC17AO1
C15AC14AC17AN17
C13AC14AC17AO1
C13AC14AC17AN17
C14AC13AC12AN11
C13AC12AN11AC16
C14AC17AN17AN27
O1AC17AN17AN27
C17AN17AN27AC27
176.8(3)
À2.8(4)
1.7(4)
À179.5(3)
À2.5(4)
1.8(4)
180.0
0.0
0.0
180.0
0.0
À1.0
À0.1
1.3
179.4
À0.2
177.9
À31.9
À0.2
146.1
À34.3
À0.7
1.0
179.9
0.0
0.0
180.0
0.0
À0.2
À0.1
0.4
179.8
À0.3
À179.6
À7.7
171.9
171.6
À8.8
À0.1
0.2
0.2(4)
À2.2(4)
179.6(2)
0.9(4)
179.0(2)
25.7(4)
À153.1(2)
À152.4(3)
28.8(3)
1.1(4)
À1.6(4)
176.7(2)
À2.1(4)
179.0(2)
178.7
À1.7
173.1
179.3
À1.1
178.5
Fig. 2. (a) Correlation graphs of calculated and experimental molecular bond
lengths of the title compound. (b) Correlation graphs of calculated and experimen-
tal molecular bond angles of the title compound.
values [29,30]. For instance, the average 13C IMS of TMS were taken
into account for the calculation of 13C c.s. of any X carbon atom,
and so c.s. can be calculated using the following equation:
CSx = IMSTMS À IMSx. All the calculations were performed by using
Gauss-View molecular visualization program [31] and Gaussian
03W program package on personal computer [32].
3. Results and discussion
3.1. Geometrical structure
Molecular structure of 4-cyanobenzaldehyde isonicotinoyl-
hydrazone monohydrate was determined by Wardell et al. [26].
The geometric structure of the title compound is shown in
Fig. 1a and b. The optimized parameters (bond lengths and angles,
and dihedral angles) of the title compound have been obtained at
the HF and B3LYP methods with the basis set. These results are
listed in Table 1 and compared with the experimental data of the
title compound. Geometrical parameter of the title molecule indi-
cates that hydrazone part between C14 and C21 is effectively pla-
nar and atoms are in trans-positions. Rings of the molecule are
twisted away from the hydrazone plane [26]. Geometric properties
of substituted-benzaldehyde isonicotinoyl-hydrazone are similar
to that of 4-cyanobenzaldehyde isonicotinoyl-hydrazone monohy-
drate [33–35]. In the present subject parameters of 4-cyanobenzal-
dehyde isonicotinoyl-hydrazone monohydrate bonds (lengths and
angles) optimized by HF, B3LYP methods with 6-31++G(d,p) as the
basis set are listed in Table 1. Calculated data are compared with
experimental crystal structure data of the title compound. Correla-
tion indicates that, both calculation with HF and B3LYP give agree-
ment with experimental values (Fig. 2).
4-Cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate
was obtained experimentally by the procedure [26] as follows.
Isonicotinoylhydrazine (10 mmol) and 4-cyanobenzaldehyde
(10 mmol) in tetrahydrofuran (20 ml) was heated under reflux
for 4 h. The solution was cooled and the solvent was removed un-
der reduced pressure; the residue was washed successively with
cold ethanol and recrystallized from ethanol [26]. NMR (DMSO-
d6):3.406(2H, s, H2O), 7.832 (2H, d, J = 5.5 Hz, H13 and H15),
7.928 (4H, m, H22, H23, H25 and H26), 8.512 (1H, s, H27), 8.800
(2H, d, J = 5.5 Hz, H12 and H16), 12.31 (1H, s, NH); d(C) 162.39,
150.80, 147.53, 140.5, 138.90, 133.25, 128.29, 122.03, 119.06,
112.67. IR (KBr pellets, cmÀ1):3481.27 (OH), 3165.12 (NH),
2223.77 (C„N), 1666.38 (C@O), 1299.93 (CAN). The FTIR spectra
were recorded using Shimadzu 8201 spectrometer with KBr tech-
nique, in the region 4000–400 cmÀ1 that was calibrated by polysty-
UNITY
rene. The 1H and 13C NMR spectra were obtained on Varian
INOVA 500 MHz NMR Spectrometer at 500 and 125 MHz, respec-
tively, using DMSO(d6) as solvent and TMS as internal standard.

392
S. Guner et al. / Journal of Molecular Structure 984 (2010) 389–395
Table 2
Comparison of the observed and calculated vibrational spectra of the title compound (C15H12N4OÁH2O).
Assignments
FT-IR (cmÀ1) KBr
Scaled frequencies (6-31++G(d,p)) (cmÀ1) and Rel. intensity (km/mol)
HF
Rel. intensity
B3LYP
Rel. intensity
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
(HAOAH) str.
(HAOAH) str.
(N17AH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(rings CAH) str.
(C241AN24) asym. str.
(C17AO1) str.
(N27AC27) str.
(N27AC27 + Ph ring CAC) str.
(Pyr. ring CAC) str.
(Ph ring CAC) str. + b(N17AH + HAOAH) bend.
3481
3323
3165
–
–
–
–
–
3076
–
3051
3000
2224
1666
–
1604
1577
1552
1504
1552
–
3947
3834
3493
3300
3296
3283
3280
3274
3259
3250
3250
3177
2388
1758
1702
1610
1606
1652
1639
1577
1568
1460
1458
1421
1368
1348
–
1308
1241
1224
1215
1201
1175
1090
1074
1060
–
–
1024
–
–
–
0.08003806
0.033205229
0.0908663
0.002373689
0.000747571
0.006645109
0.00383211
0.001435834
0.014354219
0.007959626
0.014318989
0.012679233
0.068930679
0.272159945
0.011754873
0.005556389
0.007618549
0.0778391
0.209221839
0.026732577
0.002460841
0.010952823
0.014130693
0.036621612
0.001762279
0.002909597
–
3914
3800
3491
3229
3225
3215
3209
3209
3184
3180
3169
3078
2330
1761
1676
1650
1640
1594
1581
1561
1528
1447
1445
1420
1362
1339
1300
1276
1250
1200
1172
1139
1122
1100
1085
1032
1012
1010
1004
966
0.176925074
0.049635638
0.200009532
0.008969576
0.003179972
0.009969053
0.003936204
0.000547794
0.018837179
0.03917278
0.051881196
0.042664025
0.163734323
0.55313509
0.016518449
0.047259163
0.009399703
0.083315057
0.737347995
0.077833561
0.049354029
0.003619591
0.037442781
0.066368063
0.013107297
0.003919196
0.0514837
b(N17AH) bend.
b(Ph ring CAH) bend.
b(Pyr. ring CAH) bend.
m
m
(rings CAC)str. + b(rings CAH) bend.
(rings CAC)str. + b(rings CAH) bend.
–
–
b(C27AH) bend.
q
q
1409
1358
1300
1280
–
(Pyr. ring CAH)rock
(Ph ring CAH)rock
m(Pyr. ring CAC) sym. str.
m(C14AC17AN17) asym. str.
1
1
b(Pyr. ring CAH) bend.
b(Pyr. ring CAH) bend.
–
0.000984308
0.014997947
0.093162995
0.003898593
0.047544745
0.005891926
0.003917699
0.000304924
0
0.050976843
0.001837778
0.484820876
0.040266983
0.026276888
0.042434031
0.024992836
0.006430939
0.003486499
0.001934285
0.001872188
0.019260384
0.036040864
0.001193676
0.001207321
0.029340973
0.040897045
0.017821882
0.004573187
0.000646476
0.009216182
0.102346435
0.002854064
0.003737455
0.195084729
0.040306733
0.000642323
0.000217535
0.004320648
0.001194467
0.000260251
–
1174
1151
–
m(N17AN27) str.
b(Ph ring CAH) bend.
b(Pyr. ring CAH) bend.
–
m
m
(Pyr. ring CAC + N17AN27) str.
(Pyr. ring CAC + C17AN17) str.
1072
1059
–
1010
1005
–
962
921
881
–
852
835
795
754
–
b(Ph ring CAC) bend.
b(Ph ring CAC) bend. +
s
(Ph ring CAH)
s
s
s
(HAC16AC15AH)
(HAC26AC25AH)
(HAC22AC23AH + C27AH)
0
0.000628812
0
0
b(N17AN27AC27) bend.
x
x
934
903
865
857
846
805
757
735
717
692
682
677
642
572
564
509
(Pyr. ring CAH) wag.
(HAC26AC25AH) wag.
0
960
890
874
807
758
750
737
695
688
673
627
577
561
505
486
459
0.014080263
0
m(Ph ring CAC) str. +
x
(Pyr. ring CAH) wag.
x
x
(HAC22AC23AH) wag.
(Pyr. ring CAC and CAH) wag.
0.02217392
0.016281781
0.001667386
0.000148023
0.011549105
0.04248882
0.001745161
0.001696507
0.086239243
0.004159905
0.002894042
0.002570153
0.001592025
0.000198382
5.69646EÀ05
–
m
s
(Ph ring CAC and C24AC241) str.
(Ph ring CAC)
x
(Pyr. ring HAC16AN11AC12AH) wag.
702
690
–
663
–
b(Pyr. ring C and N) bend.
b(Pyr. ring CAC) bend.
b(Ph ring CAC) bend.
s
x
(N17AH)
(Ph ring CAH) wag.
b(C24AC241AN24) bend.
–
557
503
480
453
422
–
x
x
(rings CAH) wag.
(rings CAH) wag.
496
475
434
397
b(N17AN27AC27) bend.
s
s
(Ph ring CAC)
(Pyr. ring CAC)
451
388
3.2. Assignments of the vibration modes
pound. Experimentally observed infrared spectrum of title com-
pound by using KBr pellets, are found; 3481.27 cmÀ1 (OH),
3165.12 cmÀ1 (NH), 2223.77 cmÀ1 (C„N), 1666.38 cmÀ1 (C@O),
1299.93 cmÀ1 (CAN). The vibrational bands assignments have been
made by using Gauss-View molecular visualization program [32].
Theoretical and experimental results of the title compound are
shown in Table 2. Infrared spectrum of title compound indicates
that NAH stretching, 3493 cmÀ1 (HF), 3491 cmÀ1 (B3LYP), C„N
stretching 2388 cmÀ1 (HF), 2330 cmÀ1 (B3LYP), C@O stretching
Based on optimized geometries, the calculation of vibrational
frequencies were performed by the same methods and basis set
as. These calculations of the title compound were compared to
the experimental results. The bands calculated in the measured
region 4000–400 cmÀ1 arise from the vibrations of OAH stretching,
N–H symmetric stretching, rings CAH stretching, C„N stretching,
C@O stretching and the internal vibrations, etc. of the title com-

S. Guner et al. / Journal of Molecular Structure 984 (2010) 389–395
393
HF-6-31++G(DP)
B3LYP-6-31++G(DP)
FT-IR (cm-1) with KBr
4000
3500
3000
2500
2000
1500
1000
500
Fig. 3. FT-IR spectrum and simulated (HF, B3LYP) IR spectra of the title compound (C15H12N4OÁH2O).
Table 3
Theoretical and experimental 13C and 1H isotropic chemical shifts (with respect to TMS all values in ppm) for the title compound (C15H12N4ÁH2O).
Atom
NMR(DMSO-d6)
HF/6-31++G(d,p)
GIAO
B3LYP/6-31++G(d,p)
IGAIM
CSGT
GIAO
IGAIM
CSGT
H(N17)
H(C16)
H(C12)
H(C27)
H(C22)
H(C26)
H(C25)
H(C23)
H(C15)
H(C13)
H(O29)
H(O30)
C17
C12
C16
C27
C14
C21
C25
C23
C26
12.315
8.800
8.800
8.512
7.928
7.928
7.928
7.928
7.832
12.31a
8.80a
8.80a
8.52a
7.94a
7.94a
7.94a
7.94a
7.83a
7.83a
–
11.83
10.04
9.76
9.39
8.20
9.79
8.82
8.70
9.53
9.97
9.59
9.41
9.03
8.30
9.71
8.70
8.57
8.80
11.71
10.11
9.92
9.74
8.59
9.98
8.98
8.86
9.34
11.12
9.32
9.05
8.67
7.45
9.08
8.11
7.99
8.82
9.25
8.87
8.70
8.31
7.58
9.00
7.98
7.85
8.08
10.99
9.40
9.91
9.03
7.87
9.27
8.26
8.14
8.63
7.832
3.406
3.406
8.97
2.92
2.92
8.17
2.71
2.63
9.07
3.60
3.58
8.26
2.20
2.21
7.45
1.99
1.91
8.35
2.87
2.88
–
162.39
150.80
150.80
147.53
140.65
138.90
133.25
133.25
128.29
128.29
122.03
122.03
119.06
112.67
161.9a
150.4a
150.4a
146.0a
140.2a
138.4a
132.8a
132.8a
127.8a
127.8a
121.5a
121.5a
118.6a
112.2a
162.2
154.4
156.1
144.16
143.74
144.90
137.61
136.43
130.53
132.45
128.3
121.97
120.29
119.08
161.97
150.44
152.51
142.06
145.89
140.79
134.58
133.72
126.59
128.72
123.63
118.75
116.80
115.34
164.81
156.10
158.21
148.63
146.13
146.41
139.96
139.03
132.53
135.51
130.81
123.61
125.38
121.18
144.66
136.83
138.54
126.64
126.22
127.36
120.12
118.92
113.04
114.95
110.81
104.47
102.77
101.38
144.50
132.93
135.05
126.50
128.41
123.27
117.00
116.24
109.08
111.17
106.06
101.21
99.33
97.80
147.26
138.54
140.71
131.11
128.62
128.88
122.41
121.52
115.00
117.98
113.27
106.15
107.88
103.67
C22
C15
C13
C32
C24
a
Taken from literature Ref. [26].
1758 cmÀ1 (HF), 1761 cmÀ1 (B3LYP) can be assigned clearly. Calcu-
lated infrared intensity (Rel. intensity) allows determination of the
strength of the transition. Note that experimental IR spectra are
generally reported in either percent transmission or absorbance
unit. Apparently, these mentioned data can be seen in Fig. 3. In
Hartree–Fock, all the vibrational frequencies are overestimated
and they are in agreement within 10–20% error for the average
of overall frequencies [36,37]. This overestimation depends on type
of the vibrational mode and the wave number range. In general, the
DFT methods have relatively close wave numbers to experimental
values. According to the different molecular structures with many
electrons, this statement can be changed. In our results, as it can be
seen in Fig. 3 and Table 2, the simulated infrared spectra are, in
general, closer to the experimental IR spectrum.
3.3. Assignments of the chemical shift values
DFT and HF methods differ in that no electron correlation ef-
fects 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. Particular
consideration was given for the investigation of the influence of

394
S. Guner et al. / Journal of Molecular Structure 984 (2010) 389–395
the level that is used in the geometry optimization on the final va-
lue of the title compound when GIAO, CSGT and IGAIM 13C and 1H
c.s. calculations were performed. One of the GIAO, CSGT or IGAIM
13C and 1H c.s. calculations is sufficient for comparison. But the
others support the result. Thus, GIAO, CSGT and IGAIM 13C and
1H c.s. calculations have been carried out using the B3LYP method
with 6-31++G(d,p) basis set for the optimized geometry. The
results of these calculations and the experimental 13C and 1H
chemical shift values are tabulated in Table 3. The theoretical 13C
and 1H chemical shift values (with respect to TMS) of the title com-
pound are generally compared to the experimental 13C and 1H
chemical shift values. The 1H chemical shift values (with respect
to TMS) have been calculated to be 11.83–2.63 ppm with HF level
and 11.12–1.91 ppm with B3LYP level. These variations are ob-
served experimentally between 12.31 and 3.41 ppm. These values
are depicted in Table 3, and so the accuracy ensures reliable inter-
pretation of spectroscopic parameters. In the title compound nitro-
gen atom which shows electronegative property, and so N17AH
atom contribute to the downfield resonance and has chemical
shifts 12.31 ppm. Besides, chemical shifts for rings-H 8.800–
7.832 ppm and HAOAH 3.406 ppm. These chemical shifts have
been obtained to be 11.83 ppm (N17AH), 8.17–11.83 ppm (rings-
H) 2.63 ppm (HAOAH) for HF calculations and 11.12 ppm
(N17AH), 9.40–7.45 ppm (rings-H) 2.88 ppm (HAOAH) for B3LYP
calculations. Furthermore, the 13C chemical shift values (with re-
spect to TMS) are observed to be 162.39–112.67 ppm range and
found to be 164.81–119.08 ppm range by HF level and 147.26–
97.80 ppm range. As can be seen from Table 3, theoretical 1H and
13C chemical shift results of the title compound are generally closer
to the experimental chemical shift data.
The correlation between the experimental and calculated chem-
ical shifts obtained by the HF and B3LYP methods is shown in
Fig. 4. (a) Correlation graphics of calculated and experimental 1H chemical shift values of the title compound (C15H12N4OÁH2O). (b) Correlation graphics of calculated and
experimental 13C chemical shift values of the title compound (C15H12N4OÁH2O).

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In this study, the results of experimental and the HF and DFT le-
vel of theory with 6-31++G(d,p) basis set are reported. Computed
and experimental geometric parameters, vibrational frequencies,
and chemical shifts of the title compound have been compared
with each other. It has noted that experimental results belong to
the solid phase in the atmospheric conditions. Compared experi-
mental, theoretical calculations belong to the gaseous phase in
the vacuum. Therefore experimental and theoretical result has
slightly different values.
To fit the theoretical frequency results with experimental ones
for HF and B3LYP levels, the data have been multiplied. Results
with multiplied factors seemed to be in good agreement with
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