Zn(II) and Cu(II) complexes of 2-(2-hydroxy-5-methylphenyl)-1H- benzimidazole and crystal structure of 2-(2-hydroxy-5-methylphenyl)-1H- benzimidazolium chloride

Article abstract of DOI:10.1134/S0036023610030137

2-(2-Hydroxy-5-methylphenyl)-1H-benzimidazole ligand (HL) and its complexes with Cu(NO₃)₂, Zn(NO₃)₂ have been synthesized and characterized. The structures of the compounds were confirmed on the basis of element

Full text of DOI:10.1134/S0036023610030137

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 3, pp. 377–383. © Pleiades Publishing, Ltd., 2010.
COORDINATION COMPOUNDS
Zn(II) and Cu(II) Complexes of 2ꢀ(2ꢀHydroxyꢀ5ꢀmethylphenyl)ꢀ
1Hꢀbenzimidazole and Crystal Structure of 2ꢀ(2ꢀHydroxyꢀ5ꢀ
methylphenyl)ꢀ1
H
ꢀbenzimidazolium Chloride1
Aydin Tavman
Istanbul University, Faculty of Engineering, Chemistry Department, Avcilar, 34320, Istanbul, Turkey
eꢀmail: atavman@istanbl. edu. tr
Received July 21, 2008
Abstract—2ꢀ(2ꢀHydroxyꢀ5ꢀmethylphenyl)ꢀ1Hꢀbenzimidazole ligand (HL) and its complexes with
Cu(NO3)2, Zn(NO3)2 have been synthesized and characterized. The structures of the compounds were conꢀ
firmed on the basis of elemental analysis, molar conductivity, magnetic moment, FTꢀIR, 1Hꢀ and 13C NMR.
Cu(II) complex has 1 : 2 metal : ligand ratio, while Zn(II) complex is 1 : 1. Crystal structure of 2ꢀ(2ꢀhydroxyꢀ
5ꢀmethylphenyl)ꢀ1Hꢀbenzimidazolium chloride (HL · HC1) was determined by singleꢀcrystal Xꢀray diffracꢀ
tion. It crystallizes in the orthorombic, space group P212121and Z = 4.
DOI: 10.1134/S0036023610030137
1
2ꢀSubstituted benzimidazoles have varied pharmaꢀ purification. Melting points were determined using an
cological activities, such as antitumor, antiverminous, Electrothermal meltingꢀpoint apparatus. Analytical
antiviral, hypotensive, spasmolytic etc. [1].
2ꢀHydroxyphenylꢀ ꢀbenzimidazole and its
derivatives are known to be strong chelating agents.
Various transition metal complexes of hydroxyphenylꢀ
data were obtained with a Thermo Finnigan Flash EA
1112 analyzer. Atomic absorption data were obtained
with a Perkin Elmer Analyst 200 flame spectrometer
for Cu and Zn analysis. Molar conductivity of the
complexes was measured on a WPA CMD750 conꢀ
ductivity meter in dimethylsulfoxide (DMSO) at
1H
1Hꢀbenzimidazole type ligands are reported [2, 3].
These ligands are potential N, O donors and they react
easily with the metal ions to give stable chelate comꢀ
plexes.
There are a lot of crystal structure of benzimidazole
derivatives and their salts in the literature. For examꢀ
ple, crystal structure of 2ꢀ(3ꢀmethoxyꢀ2ꢀhydroxypheꢀ
nyl)benzimidazole [4], 1,3ꢀbis(4ꢀmethylbenzyl)benzꢀ
imidazolium chloride monohydrate [5], 2,2'ꢀ(proꢀ
25°
C. 1Hꢀ and 13C NMR spectra were run on a Varian
Unity Inova 500 NMR spectrometer. The residual
DMSOꢀd6 signal was also used as an internal referꢀ
ence. UVꢀVisible spectra were performed on a Perkin
Elmer Lambda 25 UV/Visible Spectrometer. FTꢀIR
spectra were recorded in KBr disks on a Mattson 1000
FTꢀIR spectrometer. Magnetic measurements were
carried out on a Sherwood Scientific apparatus at
room temperature by Gouy’s method.
paneꢀ1,3ꢀdiyl)bis(benzimidazolium)
dihydrate [6], 2,2'ꢀ(iminodimethylene)bis(1
dichloride
ꢀbenzꢀ
H
imidazolium)(1+) chloride [7] and 2,2'ꢀ(butaneꢀ1,4ꢀ
diyl)dibenzimidazolium dichloride dihydrate [8] were
reported. However, studies on crystal structures of
2ꢀhydroxyphenyl benzimidazole derivatives and their
hydrochloride salts are very limited. In this study,
Synthesis of HL. The ligand was prepared accordꢀ
ing to literature procedures [9, 10], by reacting
2ꢀhydroxyꢀ5ꢀmethylbenzaldehyde (1.36 g, 10 mmol)
and an equivalent amount of NaHSO3 (1.04 g,
10 mmol) at room temperature in EtOH (25 mL) for
2ꢀ(2ꢀhydroxyꢀ5ꢀmethylphenyl)ꢀ1Hꢀbenzimidazole
several h. The mixture was treated with oꢀphenyleneꢀ
ligand (HL) and its complexes with Cu(NO3)2,
Zn(NO3)2 have been synthesized and characterized.
Crystal structure of 2ꢀ(2ꢀhydroxyꢀ5ꢀmethylphenyl)ꢀ
1Hꢀbenzimidazolium chloride (HL ⋅ HC1) was deterꢀ
mined by singleꢀcrystal Xꢀray diffraction.
diamine (1.08 g, 10 mmol) in dimethylformamide
(15 mL) and gently refluxed for 2 h. The reaction mixꢀ
ture was then poured into iced H2O (500 mL), filtered
and crystallized from EtOH.
Synthesis of the Complexes
EXPERIMENTAL
[Cu(L)2]
133 mg Cu(NO3)2
10 mL methanol. After 4 h reflux the precipitate was
filtered and dried at 80–90
⋅
3H2O. 112 mg ligand (0.5 mmol) and
Chemistry. All chemicals and solvents were reagent
⋅
3H2O (0.55 mmol) were reacted in
grade and were used as purchased without further
1
The article is published in the original.
°C.
377

378
TAVMAN
Table 1. The analytical data and physical properties of the ligand and the complexes
Elemental analysis
Found (Calcd), %
Yield,
%*
M.P.,
°C
Compound
Colour
C
H
N
M
–
HL
C14H12N2O
75.3
(75.0)
5.7
(5.4)
12.2
(12.5)
70
75
65
257
>350
>350
colorless
dark green
dark yellow
[Cu(
L
)2]
⋅
3H2O 1, 2
C28H28CuN4O5
58.8
(59.6)
4.6
(5.0)
9.6
(9.9)
10.8
(11.3)
1
[Zn(
C14H15N3O6Zn
L)(H2O)2]NO3
42.9
(43.5)
3.6
(3.9)
10.8
(10.9)
16.0
(16.9)
1
2
–1
2
–1
Molar conductivity of the Cu(II) and Zn(II) complexes are 9.5 and 47
value for [Cu( ) ] 3H O is 1.61 BM. * approximately values.
Ω
cm mol (25°C), respectively.
μ
L
⋅
2
eff
2
Table 2. IR and UVꢀVis. spectral data of the ligand and the complexes
Compound
Frequency (cm–1), KBr pellets
Wavelength, nm (in methanol)
HL
3330 s, 3284 s, 3057 w, 2918 w, 1640 m, 1613 m, 1590 m, 1569 s, 1455 m, 242, 289, 297, 324, 335
1397 m, 1286 s, 1262 s, 1235 m, 808 s, 731 m, 643 m
[Cu(L
)2]
⋅
3H2O
3431 m, br, 3038 m, 2915 m, 1631 m, 1623 m, 1554 m, 1492 s, 1383 m, 251, 294, 304, 344, 417, 641
1308 m, 1262 s, 1138 m, 1046 m, 831 m, 808 m, 600 m
[Zn(L)(H2O)2]NO3 3430 m, br, 3322 m, br, 3064 w, 2922 w, 1632 m, br, 1513 s, 1470 m, 264, 270 sh, 284, 365, 409 br
1386 s, 1355 m, 1259 m, 1035 m, 827 m, 747 m, 623 m
[Zn(L)(H2O)2]NO3. 112 mg ligand (0.5 mmol) susꢀ reflections were merged. An empirical absorption corꢀ
pended in ethylacetate (5 mL), 164 mg Zn(NO3)2 rection was applied which resulted in transmission
⋅
6H2O (0.55 mmol) in 10 mL ethylacetate was added to factors ranging from 0.74 to 1.00. The data were corꢀ
the ligand solution. The mixture was refluxed for 2 h. rected for Lorentz and polarization effects.
The dark yellow precipitate was filtered and dried at
80–90
Preparation of HL · HCl. HL was synthesized
according to above method. It was crystallized from
ethanol : HCl (10%) mixture (v : v, 95 : 5). The colorꢀ
less crystals (mp 286–313°C), suitable for Xꢀray anaꢀ
lysis, were obtained at room temperature by slow evaꢀ
poration.
The structure was solved by direct methods
(SIR92) and expanded using Fourier techniques [11].
The nonꢀhydrogen atoms were refined anisotropically.
H atoms were treated as riding, with C–H = 0.95(6) Å
and Uiso(H) = 1.2Ueq(C) and were constrained refineꢀ
ment. All calculations were performed using the Crysꢀ
talStructure [12] crystallographic software package.
°C.
Xꢀray crystallography. Diffraction measurements
were carried out at 20 1°C on a Rigaku RAXIS
RESULTS AND DISCUSSIONS
The analytical data and physical properties of the
ligand and the complexes are summarized in Table 1.
The molar conductivity value of Zn(II) complex,
47 Ω–1 cm2 mol–1, is indicative for 1 : 1 electrolyte
complexes. Cu(II) complex has nonꢀionic character
RAPID imaging plate area detector with graphite
monochromated MoKα) radiation ( = 0.71070 Å), at
the 127.40 mm distance between the crystal and the
detector (Istanbul University Advanced Analyses Laboꢀ
ratory).
λ
For the structure solution, 4790 reflections were according to the molar conductivity. Magnetic
collected, 2395 were unique (Rw = 0.034); equivalent moment value of [Cu( )2] 2H2O complex is 1.61 BM,
L
⋅
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 3 2010

Zn(II) AND Cu(II) COMPLEXES
379
Table 3. 1H NMR spectral data (the chemical shift values, δH, ppm, with coupling constants,
J, Hz, in DMSOꢀd6)
The benzimidazole protons
The phenolic protons
Compound
H4
H5
H6
H7
NH
H3’
H5’
H6’
OH
CH3
HL
7.70
m
7.27
s, br
7.27
s, br
7.60
13.12 7.88 d
7.19 dꢀd
6.93 d
12.86 2.33
s
s, br
7.63 d, br 13.25 7.95
= 1.8 s, br s, br
s
J
= 1.5
J
= 8.3, 2.4
7.57 d, br 7.30 d, br
= 7.3 = 7.3
J
= 8.3
s
[Zn(L)(H2O)2]NO3
7.95
s, br
7.26
s, br
7.26
s, br
–
2.30
s
J
J
J
Table 4. 13C NMR
(
APT) spectral data of the ligand and its Zn(II) complex (δC, ppm; in DMSOꢀd6)
Quaternary carbons Hꢀbonded carbons
156.59, 152.47, 128.39, 112.92 133.14, 126.89, 117.71, 20.92
L)(H2O)2](NO3) 161.87, 152.33, 143.74, 140.58, 132.92, 120.57, 117.09 133.44, 128.37, 124.47, 123.31, 112.08, 20.28
Compound
HL
[Zn(
which is in the expected range for a typical d9 Cu(II) and subsequent involvement of the phenoxyl group in
metal coordination.
complex. The high melting points of the complexes
>350 ) show their high thermal stabilities.
(
°C
The 3431 cm–1 medium broad band at the Cu(II)
complex spectra is assigned to the imine proton
remains attached at the Nꢀ1 position (NH) and uncoꢀ
ordinated water molecules stretching vibrations, while
at Zn(II) complex 3430 cm–1 band is assigned to
IR Spectra. FTꢀIR spectral data of the ligand and
the complexes are given in Table 2. In the IR spectra of
HL the bands at 3330 and 3284 cm–1 are due to OH
and NH stretching vibration frequencies, respectively.
These bands appear closer to each other due to
intramolecular hydrogen bonding between the pheꢀ
noxyl hydrogen atom and one of the imine nitrogen
atoms [3, 13, 14]. These bands change significantly
ν(NH) only. The 3322 band at Zn(II) complex is
assigned to the coordinated water molecules stretchꢀ
ing vibrations.
The characteristic
ν(C–H) modes of ring residues are
observed in the wave region between 3038 and 3064 cm–1.
upon metal complexation indicating deprotonation The sharp or medium bands at the 830–730 cm–1
H
CH3
7
4
3' 4'
8
9
N
6
5
2
2'
1
5'
3
N
6'
1'
HO
Fig. 1. Structure of the ligand.
CH3
H
N
+
CH3
H
N
N
3H2O
O
Cu
O
NO–3
N
N
Zn O
N
H2O
[Zn(
OH2
L)(H2O)2]NO3
H
H3C
[Cu(L)2]
⋅
3H2O
Fig. 2. The proposal structures for the Cu(II) and Zn(II) complexes in the present study.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 3 2010

380
TAVMAN
O(1)
C(10)
C(9)
C(6)
C(5)
N(1)
C(11)
C(1)
C(8)
C(7)
C(13)
C(12)
C(2)
N(2)
C(4)
C(3)
C(14)
Cl(1)
Fig. 3. The molecular structure of HL · HCl showing the atomꢀlabelling scheme and 50% probability displacement ellipsoids.
Broken line shows hydrogen bond.
Fig. 4. Packing diagram of HL · HCl along the a axis (the broken lines show hydrogen bonds).
range are due to the outꢀofꢀplane deformation bands
for the aromatic C–H.
[Zn(L)(H2O)2]NO3 complex shows a strong band at
1
1386 cm− in IR spectra, supporting the presence of
uncoordinated nitrate ion, which was also confirmed
by conductivity data [15–17].
The ν(C=C) frequencies for the ring residues are
1
expected to appear at ca. 1640 cm− with their own
characteristics for the ligand in the IR spectra. These
frequencies are expected to shift at lower frequency (240–300 nm) in the electronic spectra of the ligand
Electronic spectra. The lower wavelength bands
upon complex formation. Similarly the (C=N) asymꢀ and the complexes correspond to
π
π*
transition
metric stretching frequencies are expected to appear at of the aromatic rings. The other bands at the UV
1
ca. 1590 cm−
.
region are due to
n
π* transitions. The bands at the
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 3 2010

Zn(II) AND Cu(II) COMPLEXES
381
Fig. 5. Packing diagram of HL · HCl along the b axis (the broken lines show hydrogen bonds).
visible region (>350 nm) in the Zn(H) complex are observation is an evidence for the OH hydrogen’s
due to L Zn (oxygen zinc) charge transfer eliminating and the phenolic oxygen’s coordinating to
(reason of the dark yellow color of the complex).
The electronic spectra of the Cu(II) complex showed
three bands at 641, 417 and 344 nm. The 344 nm band is
the Zn(II) ion (Fig. 2).
13C NMR (APT) spectral data of HL and its Zn(II)
complex are given in Table 4. In the APT spectra of HL
spectra only eight carbons were determined; in the
Zn(II) complex spectra all of the carbon atoms were
observed. 156.59 and 159.87 ppm signals are attributed
to Cl’ carbon atom (OH bonded carbon) in HL and its
Zn(II) complex, respectively. 152.47 and 152.33 ppm
signals are assigned C2 carbon atom (C=N). C8 and
C9 carbons were seen at 142.25 ppm in the ligand
spectra, however they appear separately at 143.74 and
140.58 ppm values at the APT spectra of
assigned to a ligandꢀtoꢀmetal charge transfer. The
2
other two bands are assigned to B1g
2A1g and
2B1g
2Eg transitions, respectively. These assignꢀ
ments are typically characteristic for squareꢀplanar
geometry for Cu(II) complex (Fig. 2) [18, 19].
NMR Spectra. 1H NMR spectral data of HL and
its Zn(II) complex, and the assignments of the peaks
are presented in Table 3. The ligand gives two singlets
at 13.12 and 12.86 ppm for NH and OH protons,
respectively. These signals are very closer to each other
because of intramolecular hydrogen bonding between
the OH hydrogen and the C=N nitrogen atoms.
The characteristic of the phenolic and benzimidaꢀ
zole protons of the Zn(II) complex have changed
according to the ligand. For instance, in the Zn(II)
complex, multiplet and doublets change to broad sinꢀ
glets or broad doublets because of the metal ion’s
strong perturbing effect. It can be said that, on comꢀ
plexation, acidic character of the benzimidazole and
[Zn(L)(H2O)2](NO3), respectively. The low ppm sigꢀ
nals of the ligand and its Zn(II) complex, 20.92 and
20.28 ppm, are due to methyl carbon atoms, respecꢀ
tively. The other assignments are given in Table 4.
The proposal structures of the Cu(II) and Zn(II)
complexes in Fig. 2, are in best accord with the experꢀ
imental data obtained from the analytical data, molar
conductivity, magnetic moments, UVꢀvisible, FTꢀIR
and NMR spectroscopic measurements.
Xꢀray crystallography. The crystal structure of HL ·
HCl is shown in Fig. 3. The packing diagrams along a
the phenol moiety protons is increased.
1
The OH proton signal in the H NMR spectra of and b axes are given in Figs. 4 and 5. Because of the
the Zn(II) complex is removed as expected. This deposits of the complexes are in the small disperse
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 3 2010

382
TAVMAN
Table 5. Crystallographic characteristics and experimental and Table 7. Atomic coordinates and temperature factors (Å2
)
refinement details for the structure of HL
Formula: C14H13N2OCl
⋅
HCl
for HL
Atom
⋅ HCl
x
y
z
Beq
Formula weight = 260.72
Cl(1)
O(1)
N(1)
N(2)
C(7)
C(13)
C(8)
C(1)
C(12)
C(2)
C(10)
C(5)
C(11)
C(9)
C(3)
C(4)
C(6)
C(14)
0.49172(13) 0.1806(4) 1.0712(2) 4.55(4)
0.1269(9) –0.079(1) 0.8902(8) 6.7(2)
Crystal system: orthorombic
0.1775(4)
0.3069(5)
0.2496(6)
0.2314(12) 0.9954(6) 4.08(12)
Space group:
P212121
Z
= 4
= 1408.93(8) Å3
D
x = 1.229 g/cm3
0.2366(11) 1.0320(5) 3.88(11)
0.1295(13) 0.9815(5) 4.04(13)
a
b
c
= 16.2919(5)
Å
V
= 6.3302(2)
Å
0.3411(6) –0.134(2) 0.9196(6) 4.4(1)
0.2639(8) –0.063(1) 0.9321(7) 4.8(2)
0.1929(10) 0.4132(13) 1.0632(6) 5.2(2)
0.3584(9) –0.322(2) 0.8690(7) 5.5(2)
= 13.6616(4)
Å
Crystal size = 0.50
(000) = 544
No. of observations (
No. of parameters = 176
Refinement on : Fullꢀmatrix leastꢀsquares on
× 0.30 × 0.20 mm
F
I
> 3.00 σ(I)) = 2298
0.2749(9)
0.420(2) 1.0752(7) 5.1(2)
0.2089(11) –0.356(2) 0.8338(11) 6.1(3)
0.1794(12) 0.727(2) 1.1524(10) 6.4(3)
0.2937(8) –0.450(2) 0.8283(8) 5.2(2)
F
F
Data collection: CRYSTALCLEAR
Structure solution: Direct Methods (SIR92)
Goodnessꢀofꢀfit: 1.088
0.2017(12) –0.172(2) 0.889(2)
0.3094(11) 0.589(3) 1.1270(9) 7.8(3)
0.259(2) 0.737(3) 1.171(2) 8.5(5)
0.1309(13) 0.561(2) 1.0959(8) 6.3(3)
7.7(4)
Least squares weights: Chebychev polynomial with 3 parameꢀ
ters, 27.2025, 31.9192, 17.9013
0.449(2)
–0.398(4) 0.880(3) 11.9(8)
R
(I
> 3.00
σ
(
I
)) = 0.297
2
2
2
2
B
2
=
8/3π
(
U
(aa*)
+
U
(bb*)
+
U (cc*)
33
+
eq
11
22
Rw
(I
> 3.00
σ(I)) = 0.308
U (aa*bb*)cos γ + 2U (aa*cc*)cos β + 2U (bb*cc*)cos α).
12 13 23
CCDC 692344 contains the supplementary crystallograꢀ
phic data for this paper.
powders forms; the crystal structure of the complexes
was not obtained. It was not accomplished to grow up
crystals of complexes from methanol or other any
other organic solvent.
Table 6. Hydrogenꢀbond geometry (Å
study and in some literatures
,
o) in the present
Crystallographic characteristics and experimental
and refinement details are given in Table 5; hydrogen
bonding geometry is in Table 6 and the bond lengths,
bond angles and torsion angles are given in Tables 7–9.
D
−
H···A
D–H
H···A
D···A
D−H···A
N2
[6]
[7]
[8]
−
H12···Cl i
0.88
0.86
0.86
0.88
2.225
2.308
2.31
3.079
3.135
3.146
3.117
163.5
160
The N1–C7 and N2–C7 distances of HL
.35(1) and 1.34(1) Å, are in the between the C–N and
⋅ HCl,
1
C=N bond lengths because of the hydrochloride
bonded to the N2 atom. These lengths were reported
1.371 and 1.325 Å, respectively, for 2ꢀ(3ꢀmethoxyꢀ2ꢀ
164
hydroxyphenyl)benzimidazole [4]; 1.3346 and 1.3337
Å
for 2,2'ꢀ(butaneꢀ1,4ꢀdiyl)dibenzimidazolium dichloꢀ
ride dihydrate [8]; 1.342 and 1.322 Å for 2,2'ꢀ(proꢀ
2.280
159
paneꢀ1,3ꢀdiyl)bis((benzimidazolium)
dihydrate [6], 1.334 and 1.315 Å for 2,2'ꢀ(iminodimeꢀ
thylene)bis(1 ꢀbenzimidazolium)(1+) chloride [7],
dichloride
Symmetry code: (i) +x, +y, +z.
H
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 3 2010

Zn(II) AND Cu(II) COMPLEXES
383
Table 8. Bond lengths (Å) bond angles (deg) for HL
⋅
HCl
HL · HCl is stabilized by NꢀH⋅⋅⋅Cl (intramolecular)
and Cꢀ
H
⋅⋅⋅Cl (intermolecular) hydrogenꢀbonding
O(1)–C(9)
N(1)–C(1)
N(2)–C(2)
1.35(2)
1.50(1)
1.40(1)
1.35(2)
1.36(2)
1.45(2)
1.56(3)
1.50(2)
1.32(3)
1.38(3)
N(1)–C(7)
N(2)–C(7)
C(7)–C(8)
C(13)–C(12)
C(1)–C(2)
C(12)–C(11)
C(2)–C(3)
C(10)–C(9)
C(5)–C(6)
1.35(1)
1.34(1)
1.41(1)
1.40(1)
1.35(2)
1.44(2)
1.40(2)
1.40(2)
1.52(2)
interactions as mentioned above. Consequently, meltꢀ
ing point of HL · HCl is higher than that of HL (286–
313 > 257°C) as a result of hydrogen bondings.
C(13)–C(8)
C(8)–C(9)
C(1)–C(6)
ACKNOWLEDGMENTS
This work was supported by Istanbul University
Research Fund.
C(12)–C(14)
C(10)–C(11)
C(5)–C(4)
C(3)–C(4)
REFERENCES
C(7)N(1)C(1)
C(8)C(7)N(1)
N(1)C(7)N(2)
C(9)C(8)C(7)
C(7)C(8)C(13)
C(2)C(1)N(1)
107.9(8) C(7)N(2)C(2)
128.4(9) C(8)C(7)N(2)
106.9(7) C(8)C(13)C(12) 122(1)
112.0(9)
124.5(9)
1. N. Rashid, M. K. Tahir, N. M. Yusof, and B. M. Yamin,
Acta Crystallogr., Sect. E 63, o1260 (2007).
2. C. G. Wahlgren, A. W. Addison, S. Burman, et al.,
121(1)
120(1)
105.4(9) C(6)C(1)N(1)
C(9)C(8)C(13)
C(2)C(1)C(6)
118(1)
129(1)
124(1)
Inorg. Chim. Acta 166, 59(1989).
3. A. Tavman, N. M. AghꢀAtabay, S. Guner, et al., Transit.
Met. Chem. 32, 172 (2007).
C(11)C(12)C(14) 123(1)
C(14)C(12)C(13) 113(1)
C(11)C(12)C(13) 121(1)
4. Y. Elerman and M. Kabak, Acta Crystallogr., Sect.
C
53, 372 (1997).
C(3)C(2)N(2)
N(2)C(2)C(1)
C(4)C(5)C(6)
O(1)C(9)C(8)
C(8)C(9)C(10)
C(5)C(4)C(3)
134(1)
107.0(9)
129(1)
116(1)
126(1)
117(1)
C(3)C(2)C(1)
118(1)
5. S¸. P nar, M. Akkurt, H. Küçükbay, et al., Acta Crystalꢀ
i
logr., Sect. E 62, o2223 (2006).
C(11)C(10)C(9) 115(1)
C(12)C(11)C(10) 115(1)
6. B. Hu, X. T. Deng, C. G. Wang, and X. Y. Wang, Acta
Crystallogr., Sect. E 62, m3477 (2006).
O(1)C(9)C(10)
C(4)C(3)C(2)
C(1)C(6)C(5)
116(1)
119(1)
103(1)
7. S. R. Zheng, Y. P. Cai, X. L. Zhang, and C. Y. Su, Acta
Crystallogr., Sect. C 61, o642 (2005).
8. L. Dobrzanska and G. O. Lloyd, Acta Crystallogr.,
Sect. E 62, o1205 (2006).
Table 9. Selected torsion angles (deg) for HL ⋅ HCl
9. H. F. Ridley, G. W. Spickett, and G. M. Timmis, J. Het.
Chem. 2, 453 (1965).
C(1)N(1)C(7)N(2)
C(8)C(9)O(1)(H13)
N(1)C(7)C(8)C(9)
C(1)N(1)C(7)C(8)
C(10)C(9)O(1)H(13)
–1.8(9)
–2(2)
10. A. Tavman, B. Ülküseven, Main Group Met. Chem.
24, 205 (2001).
1(1)
11. A. Altomare, G. Cascarano, C. Giacovazzo, et al.,
172.6(8)
–174(1)
J. Appl. Cryst. 27, 435 (1994).
12. Rigaku/MSC,
CrystalStructure.
Version
3.5.1
(Rigaku/MSC, 2003).
and were to be found 1.357 and 1.311 Å for
1,4ꢀbis(benzimidazolꢀ2ꢀyl)butane [20].
13. V. M. Leovac, L. S. Jovanovic, V. S. Cesljevic, et al.,
Polyhedron 13, 3005 (1994).
N1–C1 and N2–C2 distances are to be found
1.50(1) and 1.40(1) Å, respectively, as expected
because of two nitrogen atoms have different chemical
environments.
14. R. A. Nyquist and R. O. Kagel, Infrared Spectra of Inorꢀ
ganic Compounds (Academic Press, New York/London,
1971).
15. K. Nakamoto, Infrared and Raman Spectra of Inorganic
and Coordination Compounds, 5th Edn. (Wiley, New
York, 1997), Part B, p. 87.
Dihedral angle between phenol and imidazol rings
(torsion angle of N(1)C(7)C(8)C(9)) is 1(1) Å shows
that the molecule is almost planar.
16. D. Y. Kong and Y. Y. Xie, Polyhedron 19, 1527 (2000).
17. A. Tavman, Spectrochim. Acta A 63, 343 (2006).
There is a strong intramolecular hydrogen bonding
in the molecule between Cl and H12 atoms,
H⋅⋅⋅Cl
18. M. M. AbdꢀElzaher, Appl. Organometal. Chem. 18
,
bond length is 2.225(8) Å and ⋅⋅⋅A (N2⋅⋅⋅Cl) distance
D
149 (2004).
is 3.079 Å. These values are compared with the literaꢀ
ture values and it is seen that they are in the line with
the literatures (Table 6). In addition, a weak intermoꢀ
lecular interaction is observed between Cl and Cl3
atoms (D⋅⋅⋅A distance: 3.81 Å). The crystal structure of
19. A. B. P. Lever, Inorganic Electronic Spectroscopy
(Elsevier, Amsterdam 1984), p. 555.
20. C. Chen, C. Su, A. Xu, et al., Acta Crystallogr., Sect.
E
58, o916 (2002).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 3 2010