The synthesis of some new imidazole and triazole derivatives: Crystal Structure and DFT-TDDFT investigation on electronic structure

Article abstract of DOI:10.1007/s10847-009-9714-7

A series of new N′-3-(1H-imidazol-1-yl)propylcarbamoyl-4-halogenebenzo hydrazonate (3a-b) were obtained by reaction Ethyl 2-((4-halogene phenyl) (ethoxy) methylene) hydrazinecarboxylate (1) and N-(3-aminopropyl)imidazole (2) at 120-140 °C. Compounds (4a-b) were obtained by the reaction compound 1 and N-(3-aminopropyl)imidazole (2) at 160-180 °C. The structures of compounds 3,4 have been inferred through UV-Vis, IR, ¹H/¹³C NMR, mass spectrometry, elemental analyses, and X-ray crystallography. DFT level 6-31G (d) calculations provided structural information. The electronic structure of compound 3a has been studied by DFT level 6-31G (d) calculations using the X-ray data. The results are accordance with X-ray data. Springer Science+Business Media B.V. 2009.

Full text of DOI:10.1007/s10847-009-9714-7

J Incl Phenom Macrocycl Chem (2010) 67:325–334
DOI 10.1007/s10847-009-9714-7
ORIGINAL ARTICLE
The synthesis of some new imidazole and triazole derivatives:
crystal Structure and DFT-TDDFT investigation on electronic
structure
¨
Kemal Sancak Yasemin Unver Hasan Tanak
•
•
•
•
•
˘
˘
Ismail Degirmencioglu Esra Du¨gdu¨
•
Mustafa Er S¸amil Is¸ik
Received: 22 July 2009 / Accepted: 19 November 2009 / Published online: 10 December 2009
ꢀ Springer Science+Business Media B.V. 2009
Abstract A series of new N0-3-(1H-imidazol-1-yl)pro-
pylcarbamoyl-4-halogenebenzo hydrazonate (3a–b) were
obtained by reaction Ethyl 2-((4-halogene phenyl) (ethoxy)
methylene) hydrazinecarboxylate (1) and N-(3-aminopro-
pyl)imidazole (2) at 120–140 ꢁC. Compounds (4a–b) were
obtained by the reaction compound 1 and N-(3-aminopro-
pyl)imidazole (2) at 160–180 ꢁC. The structures of com-
pounds 3,4 have been inferred through UV–Vis, IR, 1H/13C
NMR, mass spectrometry, elemental analyses, and X-ray
crystallography. DFT level 6-31G (d) calculations provided
structural information. The electronic structure of com-
pound 3a has been studied by DFT level 6-31G (d) cal-
culations using the X-ray data. The results are accordance
with X-ray data.
addition, primary and opportunistic fungal infections con-
tinue to increase rapidly because of the increased number
of immuno compromised patients (AIDS, cancer and
transplants). Several reviews have appeared illustrating the
problems encountered by today’s infectious disease clini-
cians [1–3]. As known, not only biochemical similarity of
the humancell and fungi forms a handicap for selective
activity, but also the easily gained resistance is the main
problem encountered in developing safe and efficient
antifungals. The azole antifungals may be regarded as a
new class providing truly effectivedrugs those are reported
to inhibit fungi by blocking the biosynthesis of certain
fungal lipids, especially ergosterol incell membranes, and
by additional mechanisms [4, 5]. The imidazole antifun-
gals, such as clotrimazole, miconazole, and ketoconazole,
showed good topical activity, but were only oflimited value
for systematic administration. Triazole derivatives are the
other major chemical group of antifungal azole derivatives.
The most frequently used triazoles are fluconazole and
itraconazole. They posses a broad spectrum of antifungal
activity and reduced toxicity when compared with the
imidazole antifungals [6–11].Triazoles are among the
various heterocycles that have received the mostattention
during the last two decades as potential antimicrobial
agents [12–29]. Substitutions including thio [30–32], alkyl
thio and alkenylthio [33–35] derivatives have been carried
out primarily at the 3-position of the 1,2,4-triazole ring, as
potential antimicrobial agents those will overcome the
above mentioned resistance problems.
Keywords 1, 2, 4-triazoles ꢀ Imidazole ꢀ
DFT calculations ꢀ UV–Vis ꢀ X-ray crystallography
Introduction
The development of resistance to current antibacterial
therapy continues to search for more effective agents. In
¨
˘
˘
K. Sancak (&) ꢀ Y. Unver ꢀ I. Degirmencioglu ꢀ E. Du¨gdu¨
Department of Chemistry, Faculty of Arts and Sciences,
Karadeniz Technical University, 61080 Trabzon, Turkey
e-mail: ksancak@ktu.edu.tr
Recently, the interest in triazol and imidazol heterocy-
clic system has widened as it is a precursor to a class of
compounds called ‘room temperature ionic liquids’ (For
reviews, see [36–40]). Ionic liquids have high ion content,
high ionic conductivity, low viscosity, nonvolatility, flame
resistance, and other surprising properties as a polar liquid,
H. Tanak ꢀ S¸. Is¸ik
Department of Physics, Ondokuz Mayis University, Samsun,
Turkey
M. Er
Department of Chemistry, Karabu¨k University, 78200 Karabu¨k,
Turkey
123

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J Incl Phenom Macrocycl Chem (2010) 67:325–334
and have therefore been investigated as novel ion con-
ductive matrix [41, 42], as well as reaction solvent [39] and
a ‘green solvent’ [43].
9.43 (s, 1H, NH-C=O). 13C NMR (200 MHz, DMSOd6):
14.91 (CH3); 31.33 (NHCH2-CH2); 36.38 (CH2-N); 43.73
(NH-CH2); 66.02 (OCH2); arom. C [119.13 (CH), 119.78
(CH), 125.93 (C), 134.87 (C)]; imid. C [128.16 (CH),
128.98 (CH), 129.55 (CH)]; 145.24 (C=N); 155.39 (C=O).
Anal. calc. for C16H20ClN5O2: C, 54.94; H, 5.76; N, 20.02.
Found: C, 54.90; H, 5.81; N, 20.06. EI -MS: 350.21 [M]?.
UV–vis (Me2CO, kmax, nm) (10-4 loge/dm3 mol-1 cm-1):
252(1704), 274 (1754), 287(9570), 299 (7690), 319
(10280), 334 (2220).
Ionic liquids, of which imidazolium salts are most
widely used, have gained initial notice of synthetic chem-
ists as enviromentally friendly organic solvents, and
continue to hold their attention as reaction catalysts or
promoters (Recent examples [44–49]). Additionally, they
have the ability to dissolve an enormous range of inor-
ganic, organic and polymeric materials at very high con-
centrations, are noncorrosive, and have low viscosities and
no significant vapor pressures [50, 51].
N0-3-(1H-imidazol-1-yl)propylcarbamoyl-4-
fluorobenzohydrazonate (3b)
In view of these facts, the aim of the present study is to
synthesize the compounds containing imidazol and triazole
ring which are fundamental compounds in the preparation
of ionic liquids and used as a antimicrobial substance.
Yield: 285 mg (78%). Colorless crystals. M.p. 105–
106 ꢁC. IR (KBr, cm-1): 3162 (NH), 1621 (C=N); 1664
(C=O). H-NMR (200 MHz, DMSOd6): 1.28 (t, 3H, CH3);
1
1.89–1.93 (m, 2H, NHCH2-CH2); 3.10 (t, 2H, OCH2);
3.88–4.01 (m, 4H, NH-CH2?CH2-N); 6.88 (s, 1H, imid.H);
7.15 (t, 1H, NH); 7.21 (s, 1H, imid.H); 7.23–7.32 (m, 3H,
imid.H?arom.H); 7.61–7.66 (m, 3H, arom.H); 9.32 (s, 1H,
NH-C=O). 13C NMR (200 MHz, DMSOd6): 14.90 (CH3);
31.57 (NHCH2-CH2); 36.36 (CH2-N); 43.69 (NH-CH2);
65.91 (OCH2); arom. C [115.21 (CH), 115.64 (CH), 119.27
(C), 137.20 (C)]; imid. C [128.20 (CH), 129.09 (CH),
129.25 (CH)]; 145.32 (C=N); 155.43 (C=O). Anal. calc. for
C16H20FN5O2: C, 57.65; H, 6.05; N, 21.01. Found: C,
57.61; H, 6.09; N, 21.08. EI -MS: 334.01 [M]?.
Experimental
1H-NMR and 13C-NMR spectra were recorded on a Varian
XL-200 NMR spectrophotometer in (DMSO-d6). IR spec-
tra were recorded on a Perkin-Elmer Spectrum one FT-IR
spectrometer in KBr pellets. The MS spectra were mea-
sured with an Micromass Quattro LC/ULTIMA LC-MS/
MS spectrometer with EtOH as solvent. The experiment
was performed in the positive ion mode. Elemental anal-
yses were performed on a Hewlett-Packard 185 CHN
analyzer. UV/Vis spectra were recorded by means of a
Unicam UV2-100 spectrophotometer. M.p. were measured
on an electrothermal apparatus and are uncorrected. The
compound (1) was prepared as described by Ikizler and
Sancak [52].
Synthesis of compound 4a–b
Ethyl 2-((4-chlorophenyl)(ethoxy)methylene]hydrazinecarb-
oxylate (1) (10 mmol) together with N-(3-aminopropyl)
imidazole (2) (1.25 g, 10 mmol) were heated without solvent
in a sealed tube for 2 h at 160–180 ꢁC. Then, the mixture was
cooled to r.t. and a solid formed. The crude product was re-
crystallized using acetone/petroleum ether (1:2) to afford the
desired compound.
Synthesis of compound 3a–b
Ethyl 2-((4-halogenophenyl)(ethoxy)methylene)hydrazine-
carboxylate (1) (10 mmol) together with N-(3-aminopro-
pyl)imidazole (2) (1.25 g, 10 mmol) were heated without
solvent in a sealed tube for 2 h at 120–140 ꢁC. Then, the
mixture was cooled to r.t. and a solid formed. The crude
product was recrystallized using acetone/petroleum ether
(1:2) to afford the desired compound.
4-(3-(1H-imidazol-1-yl)propyl)-5-(4-chlorophenyl)-
2H-1,2,4-triazol-3(4H)-one (4a)
Yield: 221 mg (72%). Colorless crystals. M.p. 194–195ꢁC.
IR (KBr, cm-1): 3116 (NH), 1606 (C=N); 1712 (C=O).
1H-NMR (200 MHz, DMSOd6): 1.91–2.09 (m, 2H,
NHCH2-CH2); 3.66 (t, 2H, NCH2); 3.98 (t, 2H, CONCH2);
6.88 (s, 1H, imid.H); 7.13 (s, 1H, imid.H); 7.58 (s, 5H,
imid.H ? arom.H); 12.09 (s,1H, NH). 13C NMR (200
MHz, DMSOd6): 29.90 (NHCH2-CH2); 38.05 (N-CH2);
43.13 (CON-CH2); arom. C [115.28 (CH), 119.11 (CH),
125.93 (C), 134.86 (C)]; imid. C [128.31 (CH), 129.98
(CH), 129.55 (CH)]; 145.24 (C=N); 155.06 (C=O). Anal.
N0-3-(1H-imidazol-1-yl)propylcarbamoyl-4-
chlorobenzohydrazonate (3a)
Yield: 250 mg (75%). Colorless crystals. M.p. 139–140 ꢁC.
IR (KBr, cm-1): 3156 (NH), 1616 (C=N); 1666 (C=O).
1H-NMR (200 MHz, DMSOd6): 1.32 (t, 3H, CH3); 1.87–1.93
(m, 2H, NH -CH2-CH2); 3.12 (q, 2H, OCH2); 3.63 (t, 2H,
CH2-N); 3.92–3.98 (m, 2H, NH -CH2); 6.89 (s, 1H, imid.H);
7.12 (t, 1H, NH); 7.21–7.78 (m, 6H, imid.H ? arom.H);
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J Incl Phenom Macrocycl Chem (2010) 67:325–334
327
calc. for C14H14ClN5O: C, 55.36; H, 4.65; N, 23.06. Found:
C, 55.40; H, 4.61; N, 25.01. EI -MS: 304.25 [M]?.
which also indicate the anti configuration of the NH groups
relative to each other [53]. The D2O exchangeable NH
protons of compounds 3a–b were measured at 7.12–7.15,
9.43–9.32 8.38 ppm. The addition of D2O cause the dis-
4-(3-(1H-imidazol-1-yl)propyl)-5-(4-fluorophenyl)-2H-
1,2,4-triazol-3(4H)-one (4b)
1
appearance of the NH peak. In the H-NMR spectra of
compounds 3a–b signals from OCH2CH3 group were
observed at 1.32–1.28 ppm (OCH2CH3) and 3.12–3.10
ppm (OCH2CH3) integrating for two protons and three
protons, respectively. The structure of compounds 3a–b
was provided by the 13C-NMR spectra. The signals for the
triazole C=N and the C=O group are found at 145.24–
145.32 and 155.39–155.43 ppm, respectively [54].
Synthesis of the compounds 4a–b was performed from
condensation of compound 1 with compound 2 in reason-
ably at temperature 160–180 ꢁC (Scheme 1).
The IR data indicated the formation of compounds 4a–b
by the disappearance of COCH2 (esteric) band of 1 at
1247 cm-1, and the new band at 1712–1716 cm-1
belonging to the triazole C=O. The EI-MS of compounds
4a–b confirmed the proposed structures with a molecular
ion peak at m/z = 304.25 and 285.56 respectively.
In the 1H-NMR spectra, the existence of 4a–b was
revealed by the disappearance of form of the ester CH2O
groups (4.18–4.24 ppm) in the precursor 1 after the cycli-
zation and the appearance of a new peak at 12.09–
12.07 ppm integrating for one H-atom (exchangeable with
D2O) belonging to H–N [53].
Yield: 201 mg (69%). Colorless crystals. M.p. 185–186ꢁ C.
IR (KBr, cm-1): 3118 (NH), 1601 (C=N); 1716 (C=O).
1H-NMR (200 MHz, DMSOd6): 1.86–2.01 (m, 2H, NHCH2-
CH2); 3.61 (t, 2H, NCH2); 3.82 (t, 2H, CONCH2); 6.85
(s, 1H, imid.H); 7.19 (s, 1H, imid.H); 7.63 (s, 5H, imid.H ?
arom.H); 12.07 (s,1H, NH). 13C NMR (200 MHz, DMSOd6):
29.80 (NHCH2-CH2); 38.11 N-CH2); 44.21 (CON-CH2);
arom. C [115.30 (CH), 119.21 (CH), 125.90 (C), 134.81 (C)];
imid. C [128.22 (CH), 129.90 (CH), 129.67 (CH)]; 145.20
(C=N); 155.01 (C=O). Anal. calc. for C14H14FN5O: C,
58.53; H, 4.91; N, 24.38. Found: C, 58.57; H, 4.87; N, 24.45.
EI -MS: 285.56 [M]?.
Results and discussion
The synthesis of compounds 3 was obtained by the reaction
of compound (1) and compound (2) (Scheme 1). X-ray,
analytical and spectroscopic data of the products 3a and 3b
confirmed the success of the substution reaction.
1
1
In the H-NMR spectra of the compound 3, In the H
NMR spectra of the compounds 3, two peaks are present
for the NH protons. These two deuterium exchangeable
singlets correspond to two nonequivalent NH protons,
The NHCH2-CH2 groups of the propyl residue attached
to the triazol and imidazol rings resonate as a multiplet
between 1.91–2.09 and 1.86–2.01 ppm, while NCH2CH2,
linked to the imidazol ring, was recorded at 3.66–3.61 ppm
as a triplet, and CONHCH2 linked to the triazol ring was
observed at 3.98–3.81 ppm as triplet respectively. In
(DMSO-d6), H–C protons of the imidazol ring of compo-
uns 4a–b resonate at 6.88, 7.13, 7.58 and 6.85, 7.19,
7.63 ppm, respectively [55].
NH2
O
C
N
OCH2CH3
NH
X
+
N
OCH2CH3
N
1
More detailed information about the structure of
compounds 4a–b was provided by the 13C-NMR spectra.
The signals for the triazole C=N and the C=O group
are found at 145.24–145.20 and 155.06–155.01 ppm,
respectively.
2
oil bath
160-180°C
°C
oil bath
120-140
O
H
NH
N
X
C
N
N
NH
N
X
O
N
N
Crystal-structure determination of 3a
N
The crystal structure of the compound 3a, C16H20ClN5O2,
was determined by single crystal X-ray diffraction tech-
nique, Fig. 1. The compound 3a crystallizes in the triclinic
space group in the asymmetric unit, with the following
3
N
4
X
3
a
b
F
F
Cl
Cl
˚
unit-cell parameter: a = 7.5513(7) A, b = 9.1809(9) A,
˚
˚
˚
˚
4
c = 14.6989(13) A, a = 74.409(8), b = 87.525(7), c =
3
70.346(7) and V = 923.11(15) A , with Z = 2, crystallo-
˚
˚
Scheme 1 Synthetic route to target compounds 3 and 4
graphic data shown in Table 1.
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reflections 9720 (3619 unique) were performed within 2h
˚
range 1.44 and 28.49.
Correction for absorption ðl ¼ 0:225Þ; by comparison
of the intensities of equivalent reflections, was applied
using X-RED software [56] and cell parameters were
determined by using X-AREA software [56].The initial
partial solution obtained by direct methods as implemented
in the program SHELXS-97 [57] was expanded and refined
by means of the program SHELXL-97 [57]. The program
ORTEP-3 for windows [58] has been used in the prepara-
tion of the figure. All non-hydrogen atoms were refined
anisotropically. The refinement carried out by full matrix
least squares method on the positional and anisotropic
temperature parameters of non-hydrogen atoms corre-
sponding to 217 crystallographic parameters. All H atoms
were included in calculated positions and refined using a
riding model. The structure was refined to Rint ¼ 0:0460
with 2434 observed reflections by the condition of
I [ 2rðIÞ threshold. The absorption correction is applied
with integration type (Tmin ¼ 0:9001and Tmax ¼ 0:9563).
In the compound 3a, C16H20ClN5O2, molecular struc-
ture is not planar but the ring systems are perfect planar.
Fig. 1 Ortep III diagram of the compound 3a. Displacement
ellipsoids are drawn at the 50% probability level and H atoms are
shown as small spheres of arbitrary radii
Table 1 Crystal and experimental data
Formula: C16H20ClN5O2
Formula weight: 349.82
Crystal system: triclinic
ꢀ
Space group: P1
Z = 2
˚
The maximum deviations are 0.006(3) A for atom C21 in
˚
the imidazol ring and -0.005(3) A for atom C16 in the
˚
a = 7.5513(7) A
˚
b = 9.1809(9) A
phenyl ring. The dihedral angle between the imidazol ring
(N1/N2/C18/C21/C22) and phenyl ring (C10/C13/C14/
˚
C16/C17/C19) is 63.7(1). The bond lengths and the
˚
c = 14.6989(13) A
˚
˚
˚
a = 74.409(8), b = 87.525(7), c = 70.346(7)
3
˚
and V = 923.11(15) A
bond angles in the molecule 3a are in good agreement
with our previous work, Experimental and DFT studies of
ethyl N-3-(1H-imidazol-1-yl)propylcarbamoyl benzohyd-
razonate monohydrate [59].
No. of reflections used = 9720
˚
˚
hmin = 1.44 hmax = 28.49
Absorption correction type = integration with Tmin = 0.9001
and Tmax = 0.9563
The molecular conformation of the compound can be
defined in terms of two torsion angles, which are defined as
s1ðC10=C7=N5=N4Þ and s2ðN2=C15=C12=C9Þ: The tor-
sion angles s1ðC10=C7=N5=N4Þ and s2ðN2=C15=C12=
C9Þ shows that for the title compound, the molecular
conformation induced by the anti and gauche conforma-
tions in s1 ands2, respectively.
wr2 = 0.143
R1 = 0.083
(D/r)max = 0.000
-3
˚
(Dq)max = 0.471 eA
-3
˚
(Dq)min = -0.481 eA
F(000) = 368
ðl ¼ 0:225Þ
In the molecular structure, the organic compound forms
N–H…N, N–H…O and C–H…O type intramolecular
hydrogen bonds, namely N3-H3…N5, N4-H4…O2, which
are producing S(5) motif [60], and C19-H19…O2, Fig. 2.
The molecules are connected via N–H…N, N–H…O and
C–H…O intermolecular interactions link the molecules
infinite chains. Namely, N3-H3…N1 (symmetry code: -x,
-y ? 1,-z ? 2), N4-H4…O1 (symmetry code: -x ? 2,
-y,-z ? 2) producing R22ð8Þ motif [5] and C15-
H15A…O2 (symmetry code: -x ? 1,-y, z ? 2). N3-H3
and N4-H4 bonds form bifurcated contact to two acceptors,
namely N5/N1 and O1/O2. The bifurcated nature of the
contact explains the relatively large H…A distances and
relatively small D-H…A angles, the detail of the hydrogen
bonds shown in Table 2.
Measurement: STOE IPDS II
Program system: STOE X-RED
Structure determination: direct methods
Refinement: full matrix
Data collection
A block single crystal with dimensions 0.550 9 0.380 9
0.240 mm was mounted on goniometer and data collection
was performed on a STOE IPDS II [56] diffractometer by
the x scan technique using graphite-monochromatic MoKa
˚
radiation (k = 0.71073 A) at 296 K. The intensity sym-
ꢀ
metries indicate the triclinic P1 space group. A total of
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J Incl Phenom Macrocycl Chem (2010) 67:325–334
329
Fig. 2 Packing diagram of the
title compound
˚
Table 2 Hydrogen-bond geometry (A, 8)
D-H…A
D-H
H…A
D…A
D-H…A
N3-H3…N5
0.86
0.86
0.86
0.86
0.97
0.93
2.25
2.30
2.37
2.03
2.54
2.52
2.623(3)
2.999(3)
2.671(2)
2.871(2)
3.383(3)
2.842(3)
105.8
138.7
100.9
166.7
145.6
100.7
N3-H3…N1i
N4-H4…O2
N4-H4…O1ii
C15-H15A…O2iii
C19-H19…O2
Symmetry codes: (i) -x,-y ? 1,-z ? 2 (ii) -x ? 2,-y,-z ? 2
(iii) -x ? 1,-y, z ? 2
Crystal-structure determination of 3b
The crystal structure of the compound 3b, C16H20FN5O2,
was determined by single crystal X-ray diffraction tech-
nique, Fig. 3. The compound 3b crystallizes in the triclinic
ꢀ
space group P1with two molecules in the asymmetric unit,
˚
with the following unit-cell parameters: a = 11.1443(6) A,
Fig. 3 Ortep III diagram of the compound 3b. Displacement
ellipsoids are drawn at the 50% probability level and H atoms are
shown as small spheres of arbitrary radii
˚
˚
˚
3
b = 12.8632(7) A, c = 14.1440(7) A, a = 65.472(4), b =
˚
˚
˚
72.503(4), c = 75.253(4) and V = 1739.47(16) A , with
Z = 4, crystallographic data shown in Table 3. The crystal
structure has crystallographic inversion center and stabilized
by N–H…N, C–H…O and N–H…O type intramolecular
hydrogen bonds and N–H…N, C–H…N, C–H…F and
C–H…O type intermolecular hydrogen bonds.
ꢀ
symmetries indicate the triclinic P1 space group. A total of
reflections 20386 (6831 unique) were performed within
˚
˚
2h range 1.62 and 28.42.
Correction for absorption ðl ¼ 0:095Þ; by comparison
of the intensities of equivalent reflections, was applied
using X-RED software [56] and cell parameters were
determined by using X-AREA software [56].The initial
partial solution obtained by direct methods as implemented
in the program SHELXS-97 [57] was expanded and refined
by means of the program SHELXL-97[57]. The program
ORTEP-3 for windows [58] has been used in the prepara-
tion of the figure. All non-hydrogen atoms were refined
Data collection
A block single crystal with dimensions 0.800 9 0.593 9
0.310 mm was mounted on goniometer and data collection
was performed on a STOE IPDS II [56] difractometer
by the x scan technique using graphite-monochromatic
˚
MoKa radiation (k = 0.71073 A) at 296 K. The intensity
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J Incl Phenom Macrocycl Chem (2010) 67:325–334
Table 3 Crystal and experimental data
Formula: C16H20FN5O2
Formula weight: 333.37
Crystal system: triclinic
ꢀ
Space group: P1
Z = 4
˚
a = 11.1443(6) A
˚
b = 12.8632(7) A
˚
c = 14.1440(7) A
˚
˚
˚
a = 65.472(4), b = 72.503(4), c = 75.253(4)
3
˚
and V = 1739.47(16) A
No. of reflections used = 20386
˚
˚
hmin = 1.62 hmax = 28.42
Absorption correction type = integration with Tmin = 0.9401
and Tmax = 0.9770
wr2 = 0.148
R1 = 0.072
(D/r)max = 0.000
-3
˚
(Dq)max = 0.542 eA
-3
˚
(Dq)min = -0.403 eA
F(000) = 704
ðl ¼ 0:095Þ
Fig. 4 Packing diagram of the compound 3b (H atoms are omitted
for clarity)
Measurement: STOE IPDS II
Program system: STOE X-RED
Structure determination: Direct methods
Refinement: Full matrix
ring motif [60], N6-H6…N9, N9-H9…N6, C19-H19…O4]
and molecules are linked trough N–H…N, C–H…N,
C–H…F and C–H…O type intermolecular hydrogen bonds
[namely, N3-H3…N11 (symmetry code: x ? 1,y - 1,z),
N9-H9…N5 (symmetry code: x - 1,y ? 1,z), C16-H16
…N1 (symmetry code: -x?2,-y?1,-z?1), C22-H22…F1
(symmetry code: x - 1,y ? 1,z - 1) and C29-H29B…O4
(symmetry code: -x?1,-y?2,-z?1)], Fig. 4. N2-H2, N3-H3
and N9-H9 bonds form bifurcated contact to two acceptors,
namely O1/O3, N1/N11 and N5/N6, respectively. The
bifurcated nature of the contact explains the relatively large
H…A distances and relatively small D-H…A angles, the
detail of the hydrogen bonds shown in Table 4.
anisotropically. The refinement carried out by full matrix
least squares method on the positional and anisotropic
temperature parameters of non-hydrogen atoms corre-
sponding to 434 crystallographic parameters. All H atoms
were included in calculated positions and refined using a
riding model. The structure was refined to Rint ¼ 0:0355
with 4718 observed reflections by the condition of
I [ 2rðIÞ threshold. The absorption correction is applied
with integration type (Tmin ¼ 0:9401and Tmax ¼ 0:9770).
In the compound 3b, C16H20FN5O2, the imidazol and
triazole ring systems are bridged by propyl moiety for both
independent molecules and the crystal structure utilizes the
symmetry of the crystallographic inversion center.
Method of calculations
Both molecules in the asymmetric unit are not planar but
Computational details
ring systems are almost perfect planar. The dihedral angles
˚
between the triazole and imidazol ring systems are 60.16(8)
˚
and 63.07(9), respectively for molecule A and B. The bond
To better understanding experimental data for compound
3a, theoretical calculations in B3LYP/6-31G(d) level were
performed. The molecular geometry is directly taken from
the X-ray diffraction experimental result without any
constrained. The molecular structure of ligand in the
ground state was optimized by density functional using
Becke’s three-parameter hybrid method (B3) with the Lee,
Yang and Parr correlation functional methods (LYP) with
the Standard 6-31G(d) basis set [61, 62]. The optimized
lengths and bond angles in the title molecule are in good
agreement with in those related structure Ethyl N0-3-
(1Himidazol-1-yl) propylcarbamoyl benzohydrazonate
monohydrate [59].
In the molecular structure, the organic molecule forms
N–H…O, N–H…N and C–H…O intramolecular hydrogen
bonds [namely, N2-H2…O3, N2-H2…O1 producing S(5)
123

J Incl Phenom Macrocycl Chem (2010) 67:325–334
331
˚
imidazole ring with some contribution of C=N/N–C, -NH
and related –CH2 groups.
Table 4 Hydrogen-bond geometry (A, 8)
D-H…A
D-H
H…A
D…A
D-H…A
TD-DFT studies have been very useful in order to assign
the electronic absorption transitions of the compounds.
The low-energy excitations obtained by this method are
in good/moderate agreement with the experimental results.
Specifically, the HOMO is composed of the p-bonding-
2pz-orbitals of the chelating benzene ring, 3px orbitals
with antibonding interaction of the chlorine, 2pz orbitals
with antibonding interaction of the oxygen, orbitals with
p-symmetry of C=N/N–C chromophores and p - py orbi-
tals of –NH group. The HOMO - 1 is also a chlorine/
benzene/C=N/N–C based orbital teams and partially non-
bonding orbitals of imidazole moiety. The HOMO - 2 is
related p orbitals of chlorine and oxygen atoms and orbitals
with p-symmetry of imidazole ring (mixed p - py/pz
orbitals of nitrogen and benzene carbons). The HOMO - 3
is also antibonding p - px orbitals of chlorine and non-
bonding orbitals of arene carbons and HOMO - 4 is a set
of degenerated orbitals as those of other HOMOs [64].
The LUMO and LUMO ? 3 are also a set of quasi
degenerated orbitals. These orbitals show a predominant
character of the chlorine/oxygen/benzene/C=N/N–C based
orbital combinations and mixed with less character of
–CH2 group. On the other hand, the LUMO ? 2 is com-
posed of orbital sets with p-symmetry of imidazole annular
and related –CH2 group. The LUMO ? 1 has an important
contribution of the arene carbons and chlorine and the
LUMO ? 4 has also a noticeable contribution of the
imidazole and presents a decrease of the electronic density
of the –NH group. The intensity of these transitions has
been assessed from the oscillator strength (f). All these
transitions are of intra-ligand p ? p* charge transfer
origin (LLCT) mainly arene with some contributions
of carbonyl oxygen/chlorine/imidazole ? arene/chlorine,
imidazole and arene/chlorine/oxygen in nature mixed with
LLCT (arene/chlorine ? arene/chlorine) transitions [65].
The involved orbitals in these transitions are presented in
Fig. 5 and the most relevant electronic transitions are
present in Table 5.
N3-H3…N11i
N9-H9…N5ii
C16-H16.. N1iii
C29-H29B…O4iv
C22-H22…F1v
N2-H2…O1
N2-H2…O3
N3-H3…N1
N6-H6…N9
C19-H19…O4
0.86
0.86
0.93
0.97
0.93
0.86
0.86
0.86
0.86
0.93
2.30
2.31
2.55
2.59
2.45
2.36
2.11
2.22
2.29
2.51
3.031(2)
3.002(3)
3.437(2)
3.378(2)
3.335(3)
2.6470(18)
2.9044(19)
2.605(2)
2.623(2)
2.830(2)
142.7
138.2
159.5
138.1
158.5
100.2
153.7
106.9
103.1
100.7
Symmetry code: (i) x ? 1, y - 1,z (ii) -x ? 2,-y ? 1,-z ? 1 (iii)
-x ? 2,-y ? 1,-z ? 1 (iv) -x ? 1,-y ? 2,-z ? 1
(v) x - 1, y ? 1, z - 1
structural parameters were used in the vibrational fre-
quency calculations at DFT level to characterize all sta-
tionary points as minima. 6-31G(d) basis set was used for
all elements. All calculations were performed with the
Gaussian 03 W program package [63]. In calculations,
tight converge criteria was used. By allowing that all the
parameters could relax, all the calculations converged to
optimized geometries, which corresponded to true energy
minima. On the basis of the optimized ground state struc-
ture, the spectroscopic properties and UV–vis absorption
calculations in vacuum have been carried out by using the
time-dependent density functional theory (TD-DFT) at
B3LYP level, providing an accurate description of UV–vis
transitions of ligand system. This method was used to
compute the 20 singlet ? singlet transitions in vacuum.
Interpretation of UV–vis absorption spectrum of ligand
molecule via DFT and TD-DFT calculations
UV absorption spectrum of compound 3a was calculated
using time-dependent density functional theory (TD-DFT)
method based on B3LYP/6-31G(d) basis set in order to
compare with experimental results. This strategy leads to
an average discrepancy of 1–25 nm between theoretical
and experimental kmax due to several influencing factors,
such as solvent effect and intermolecular interaction, etc.
DFT calculations were carried out in order to know the
geometry of the frontier orbitals of the related compound.
The highest four energy occupied orbitals are mainly
localized on the chlorine and carbonyl oxygen atoms,
benzene carbons, imidazole ring and C=N/N–C groups
with small contribution of related –CH2 groups. Similarly,
the lowest four energy unoccupied orbitals are mainly
located on the chlorine and carbonyl oxygen atoms,
Conclusions
In this study, It has been synthesized and characterized
new triazol and imidazol derivatives.In addition, these
1
key compounds were characterized UV–Vis, IR, H and
13C NMR, mass spectrometry, elemental analyses, and
X-ray crystallography. The investigations of ionic liquid
derivatives and pharmacology properties of these synthe-
sized key compounds are thought to be next studies.
123

332
J Incl Phenom Macrocycl Chem (2010) 67:325–334
Fig. 5 The energy (eV) and
some contours of the occupied
and unoccupied molecular
orbitals of compound 3a
123

J Incl Phenom Macrocycl Chem (2010) 67:325–334
333
Table 5 Calculated TD-DFT
Orbital (transitions)
Oscillator (f)
Assignment
kexp (nm)
kcalc (nm)
wavelengths, oscillator
strengths (f), allowed transitions
and experimental data for ligand
aHOMO - 3 ? LUMO
0.523
p ? p*
p ? p*
334
319
339.9
316.6
HOMO - 2 ? LUMO ? 4
0.0017
HOMO - 1 ? LUMO ? 1
HOMO - 4 ? LUMO
0.5292
p ? p*
299
274.3
HOMO - 1 ? LUMO
HOMO - 1 ? LUMO ? 4
HOMO ? LUMO ? 2
0.1861
0.0009
p ? p*
p ? p*
287
274
262.3
258.5
HOMO - 1 ? LUMO ? 2
HOMO - 1 ? LUMO ? 3
HOMO - 2 ? LUMO ? 1
0.1982
p ? p*
252
253.9
a
HOMO is No. 92 orbital
Acknowledgements This study was supported by grants from
Karadeniz Technical University (proje no: 2007.111.002.11) and the
scientific and technological research council (TUBITAK proje no:
107T065) of Turkey.
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