Coordination compounds of ambidentate 1-(H)Alkyl-2-(2-pyridyl) benzimidazoles. Synthesis and crystal structure

Article abstract of DOI:10.1134/S1070328410120079

Mono-and binuclear complexes of 2-(2-pyridyl)benzimidazole and its 1-alkyl-substituted deriv-atives with zinc dichloride were synthesized and structurally characterized. In terms of the competitive coordination problem, it was shown that pyridylbenzimidazole is an N,N-chelating ligand. The binuclear complex is formed through a dichloride bridge. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070328410120079

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2010, Vol. 36, No. 12, pp. 906–912. © Pleiades Publishing, Ltd., 2010
Original Russian Text © A.S. Burlov, A.S. Antsyshkina, G.G. Sadkov, V.V. Chesnokov, Yu. V. Koshchienko, D.A. Garnovskii, I.S. Vasil’chenko, A.I. Uraev, G.S. Borodkin, V.S. Serꢀ
gienko, A.D. Garnovskii, 2010, published in Koordinatsionnaya Khimiya, 2010, Vol. 36, No. 12, pp. 918–924.
Coordination Compounds of Ambidentate 1ꢀ(H)Alkylꢀ2ꢀ
(2ꢀpyridyl)benzimidazoles. Synthesis and Crystal Structure
A. S. Burlova, A. S. Antsyshkinab, G. G. Sadkovb, V. V. Chesnokova, Yu. V. Koshchienkoa,
D. A. Garnovskiic, I. S. Vasil’chenkoa, A. I. Uraeva, G. S. Borodkina,
V. S. Sergienkob, and A. D. Garnovskiia, *
a Institute of Physical and Organic Chemistry, Southern Federal University, pr. Stachki 194/3, RostovꢀonꢀDon, 344104 Russia
b Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 117907 Russia
c Southern Scientific Center, Russian Academy of Sciences, RostovꢀonꢀDon, Russia
*Eꢀmail: garn@ipoc.rsu.ru
Received April 7, 2010
Abstract—Monoꢀ and binuclear complexes of 2ꢀ(2ꢀpyridyl)benzimidazole and its 1ꢀalkylꢀsubstituted derivꢀ
atives with zinc dichloride were synthesized and structurally characterized. In terms of the competitive coorꢀ
dination problem, it was shown that pyridylbenzimidazole is an
is formed through a dichloride bridge.
N,Nꢀchelating ligand. The binuclear complex
DOI: 10.1134/S1070328410120079
The metal complexes based on 2ꢀ(2ꢀpyridyl)benzimiꢀ
As a continuation of this subject matter, we syntheꢀ
with zinc chloride and
studied them in view of the potential luminescence
activities [24].
dazoles ( ) occupy an important place among the coordiꢀ sized complexes of ligands
I
I
nation compounds of bisꢀheterocyclic ligands [1–6].
N
N
N
N
R
EXPERIMENTAL
Cl
N
N
N
M
R
2ꢀ(2ꢀPyridyl)benzimidazole (Ia, R = H) was preꢀ
pared by a reported procedure [25].
R
N
N
Cl
Synthesis of 1ꢀalkylꢀ2ꢀ(2ꢀpyridyl)benzimidazoles
(R = CH3 (Ib), C4H9 (Ic), CH2ꢀCH=CH2 (Id),
CH2C6H5 (Ie)). 2ꢀ(2ꢀPyridyl)benzimidazole (5.86 g,
0.03 mol)) and acetone (30 mL) were added to 40%
aqueous KOH (12 mL). To the resulting mixture, alkyl
(
I
): R = H, Alk, Ar
(II)
R
N
N
halide (for Ib, CH3I; for Ic, C4H9Br; for Id
,
N
CH2CHCH3Br; and for Ie, CH2C6H5Cl) (0.033 mol)
was added dropwise with stirring over a period of
10 min. The mixture was refluxed for 2 h. The acetone
layer was separated and treated with water (50 mL).
The precipitate that formed was filtered off, washed
with water, and dried. The product was dissolved in
15% HCl (30 mL) and refluxed with activated carbon,
and pH was brought to 7 by adding a 22%solution of
ammonia. The precipitate was filtered off, washed
with water, and dried. Then the product was purified
by chromatography on a column with Al2O3 (chloroꢀ
form as the eluent), chloroform was distilled off from
N
N
N
M/2
M
(
Cl
Cl
III)
(IV)
These potentially tridentate ligand systems form
complexes with different types of metal binding:
molecular adducts where they function as monoꢀ (II
[7] or bidentate (III) ligands [5–12] or bisꢀchelates
IV) [2, 3, 13] formed upon deprotonation of the imiꢀ
dazole N–H group. Both monoꢀ [1–13] and oligonuꢀ
clear [6, 11, 14–18] complexes have been isolated.
These are of interest as polyfunctional materials (for
example, luminescence materials [8, 9, 19], catalysts
)
(
the eluate to give
colorless oil in the case of Ic).
I (R = Alk) as colorless crystals (or
The elemental analysis data, the yields, and the
[7, 10, 13, 20, 21], and other practically valuable comꢀ melting points of compounds Ib–Ie are summarized
pounds [22, 23]). in Table 1.
906

COORDINATION COMPOUNDS OF AMBIDENTATE
Table 1. Elemental analysis data, yields, and melting points of compounds Ib–Ie* and IIIa–IIIe
Content (found/calculated), %
907
Comꢀ
pound
Molecular
formula
Тmp
,
°С
Yield, %
C
H
N
Zn
Cl
Ib
C13H11N3
74.64/74.62 5.21/5.30 20.01/20.08
72.43/72.48 6.46/6.54 21.11/21.17
76.57/76.61 5.57/5.60 17.86/17.77
79.89/79.98 5.28/5.30 14.47/14.73
62–63
oil
49
57
62
66
41
45
32
38
46
Ic
C16H17N3
C15H13N3
C19H15N3
Id**
Ie
60–61
116–118
IIIa
IIIb
IIIc
IIId
IIIe
C12H9Cl2N3Zn 43.50/43.48 2.71/2.74 12.82/12.67 19.83/19.72 21.42/21.39
C26H22Cl4N6Zn2 45.19/45.21 3.21/3.18 12.16/12.26 18.92/19.01 20.46/20.32
C16H17Cl2N3Zn 47.85/47.89 4.27/4.38 13.95/13.89 16.28/16.31 17.66/17.58
C15H13Cl2N3Zn 48.49/48.51 3.53/5.48 11.71/11.28 17.60/17.62 19.08/19.17
>250
>250
>250
>250
>250
C19H15Cl2N3Zn 54.12/54.18 3.59/3.61
9.97/9.84 15.51/15.45 16.82/16.94
Notes: * For Ib: yield 49%, T = 62–63°C (higher than published value [26]), for Ie: yield 66%, T = 116–118° (corresponds to the pubꢀ
mp
mp
lished value [26]).
** Recrystallized from hexane.
Ib: IR (
ν
, cm–1): 1588 w, 1564 w (benzimidazole filtered off, washed with methanol (
ring). H NMR (DMSOꢀd6; , ppm): 4.30 (s 3H, and dried in a vacuum drying chamber. The crystals
CH3), 7.21–7.51 (m, 4H, CAr–H), 7.65–7.95 (m, 2H, for Xꢀray diffraction analyasis were grown from a
CAr–H), 8.36 (d, 1H, = 8.1 Hz, CAr–H), 8.69 (d, methanol–chloroform mixture (2 : 1).
1H, = 4.8 Hz, CAr–H).
Ic: IR (
, cm–1): 1587 m, 1563 w (C=N). 1H NMR idazole ring). H NMR (DMSOꢀd6;
, ppm): 0.94 (t, 3H, = 7.4 Hz, СН3), 2H, CAr–H), 7.56–7.63 (m, 3H, CAr–H), 8.08–8.10
= 7.8 Hz, СН2СН2СН2СН3), 1.83 (2H, (m, 1H, CAr–H), 8.40 (d, 1H, = 7.8 Hz, CAr–H),
8.64 (s, 1H, CAr–H), 13.58 (br.s. 1H, NH).
IIIb: IR (
, cm–1): 1595 m, 1585 w (benzimidazole
ring). H NMR (DMSOꢀd6; ppm): 4.26 (s, 3H,
CH3), 7.27–7.38 (m, 2H, CAr–H), 7.57–7.59 (m, 1H,
, cm–1): 1589 m, 1563 w (C=N). 1H NMR CAr–H), 7.69 (d, 1H,
= 7.8 Hz, CAr–H), 7.77 (d,
(DMSOꢀd6; , ppm): 4.95 (d, 1H, = 17.1 Hz, CH2), 1H, = 7.8 Hz, CAr–H), 8.05 (t, 1H, = 7.8 Hz,
5.08 (d, 1H, = 10.2 Hz, CH2), 5.54 (d, 2H, CAr⎯H), 8.34 (d, 1H, = 8.1 Hz, CAr–H), 8.76 (d,
5.1 Hz, CH2), 6.00–6.09 (m, 1H, CH), 7.25–7.54 (m, 1H,
2 × 2 mL),
1
δ
J
IIIa: IR (ν
, cm–1): 3256 br (NH), 1601 m (benzimꢀ
J
1
ν
δ ppm): 7.25 (s
(DMSOꢀd6;
1.40 (q, 2H,
δ
J
J
J
q,
7.4 Hz, СН2СН2СН2СН3), 7.20–7.48 (m, 4H,
CAr⎯H), 7.64–7.92 (m, 2H, CAr–H), 8.38 (d, 1H,
8.1 Hz, CAr–H), 8.68 (d, 1H, = 4.2 Hz, CAr–H).
Id: IR (
J = 7.7 Hz, СН2СН2СН2СН3), 4.86 (t, 2H, J =
ν
1
J
=
δ
J
ν
J
δ
J
J
J
J
J
=
J
J
= 4.5 Hz, CAr–H).
IIIc: IR (
ν
, cm–1): 1597 m, 1587 w (benzimidazole
, ppm): 0.83 (t, 3H,
4H, CAr–H), 7.61 (d, 1H,
1H, = 6.9 Hz, CAr–H), 7.97–8.03 (m, 1H, CAr–H),
8.33 (d, 1H, = 7.8 Hz, CAr–H), 8.73 (d, 1H,
4.2 Hz, CAr–H).
Ie: IR (
J= 7.5 Hz, CAr–H), 7.74 (d,
ring). 1H NMR (DMSOꢀd6;
δ
J =
J
J
J =
7.3 Hz, CH3), 1.26 (q, 2H,
CH2CH2CH2CH3), 1.74 (q, 2H,
J= 7.5 Hz,
J= 7.4 Hz,
ν
, cm–1)): 1585 m, 1565 w (benzimidazole CH2CH2CH=CH3), 4.83 (t, 2H,
J = 7.3 Hz,
⎯CH2CH2CH2CH3), 7.24–7.36 (m, 2H, CAr–H),
1
ring). H NMR (DMSOꢀd6;
CH2), 7.11–7.28 (m, 7H, m, CAr–H), 7.48–7.58 (m, 7.52–7.56 (m, 1H, CAr–H), 7.68–7.76 (m, 2H,
2H, CAr–H), 7.74–7.77 (m, 1H, CAr–H), 7.97–8.03 CAr⎯H), 7.99–8.05 (m, 1H, CAr–H), 8.31 (d, 1H,
(m, 1H, CAr–H), 8.36 (d, 1H, = 8.1 Hz, CAr–H), 8.1 Hz, CAr–H), 8.74 (d, 1H, = 4.1 Hz, CAr–H).
, cm–1): 1598 m, 1588 m (benzimidazole
δ, ppm): 6.22 (s, 2H,
J
=
J
J
8.69 (d, 1H, J = 4.8 Hz, CAr–H).
IIId: IR (
ν
Synthesis of complexes III. Zinc chloride ring). 1H NMR (DMSOꢀd6;
δ, ppm): 5.01 (d, 1H,
J =
(0.01 mol) was added to a solution of specified 17.1 Hz, CH), 5.10 (d, 2H,
J = 10.3 Hz, CH2), 5.55
1ꢀalkyl(H)ꢀ2ꢀ(2ꢀpyridyl)benzimidazole (0.01 mol) in (d, 2H,
J = 4.4 Hz, CH2), 6.00–6.12 (m, 1H, CH),
absolute methanol (10 mL). The mixture was refluxed 7.19–7.28 (m, 2H, CAr–H), 7.42–7.49 (m, 2H,
for 1 h. The precipitated crystals of the complexes were CAr⎯H), 7.69–7.72 (m, 1H, CAr–H), 7.91–7.97 (m,
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
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2010

908
Table 2. Crystallographic data and Xꢀray experiment details for compounds IIIb–IIIe
Value
BURLOV et al.
Parameter
IIIb
IIIc
IIId
IIIe
М
691.04
387.60
371.55
421.61
System
Triclinic
Triclinic
Monoclinic
Monoclinic
P
21/
n
P21/c
Space group
P1
P1
9.380(5)
10.261(5)
10.427(5)
61.67(3)
85.33(2)
74.82(2)
853.2(4)
2
a
, Å
, Å
, Å
8.962(3)
9.2651(3)
9.351(3)
105.79(3)
107.25(4)
106.41(4)
655.47(11)
1
9.792(4)
14.294(3)
11.105(4)
90
9.698(4)
13.965(4)
14.148(5)
90
b
c
α
,
deg
deg
deg
Å3
β,
101.25(3)
90
108.25(3)
90
γ,
V,
1524.6(2)
4
1819.8(3)
4
Z
ρ(
calcd), g/cm3
1.751
1.509
1.619
1.539
F
(000)
μMo, mm–1
range, deg
348
396
752
856
2.267
1.751
1.956
1.649
θ
2.48–29.97
2.22–29.97
2.35–29.98
2.10–25.72
Range of indices
–11
≤
h
≤
–11
11, 0
≤
11
k
≤
11, –12
≤
h
–12
≤
12, 0
≤k ≤13, –12 ≤h ≤ 8, 0 ≤k ≤18, –10 ≤ h ≤ 0, 0 ≤ k ≤ 15,
–15 ≤ l ≤ 15
≤
l
≤
≤
l
≤
13
–14
≤
l
≤
14
The number of independent
reflections
3087
1289
216
4862
2112
196
4324
1306
190
3162
1515
286
The number of reflections
(I ≥ 2σ(I))
The number of refined
parameters
GOOF
1.028
1.028
1.036
1.032
R1
/
wR2
(
I
≥
2
σ
(
I
))
0.0555/0.1331
–1.641/1.299
0.0431/0.0970
–0.478/0.575
0.0539/0.0772
–0.498/0.658
0.0424/0.1105
–1.804/0.124
Δρmin/Δρmax
,
e
Å–3
1
1H, CAr–H), 8.36 (d, 1H,
J
= 8.0 Hz, CAr–H), 8.67
The H NMR spectra were recorded on a Varian
Unity 300 (300 MHz) instrument in the internal stabiꢀ
lization mode of 2H resonance line in DMSOꢀd6. The
IR spectra were recorded for solid samples of ligands
and complexes on a VarianꢀExcalibur 3100 FTꢀIR
instrument in the frustrated total internal reflection
mode for powders. IR spectra were recorded on a
Varian Cary 100 spectrophotometer.
(d, 1H, = 4.8 Hz, CAr–H).
J
IIIe: IR (ν
, cm–1): 1599 m, 1585 w (benzimidazole
ring). H NMR (DMSOꢀd6; , ppm): 6.22 (s, 2H,
δ
1
CH2), 7.11–7.29 (m, 7H, CAr–H), 7.49–7.60 (m, 2H,
CAr–H), 7.75–7.78 (m, 1H, CAr–H), 7.98–8.04 (m,
1H, CAr–H), 8.36 (d, 1H, J= 7.8 Hz, CAr–H), 8.70 (d,
1H,
J = 4.8 Hz, CAr–H).
XꢀRay diffraction analysis. The experimental data
for crystal structure determination of ZnCl2 with
pyridylbenzimidazole containing different substituꢀ
The results of elemental analysis, the yields, and
melting points of compounds IIIa–IIIe are summaꢀ
rized in Table 1.
ents R (Alk, Ar) at the imidazole nitrogen (type III)
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COORDINATION COMPOUNDS OF AMBIDENTATE
909
were collected on a CAD4 EnrafꢀNonius diffractomeꢀ anisotropically, the hydrogen atoms were partly
ter (МоКα radiation, graphite monochromator,
scan mode).
Crystallographic characteristics and Xꢀray experiꢀ
ment details are summarized in Table 2 and deposited
with the Cambridge Crystallographic Data Centre
θ
/2
θ
located from difference Fourier syntheses and refined
with the isotropic thermal parameter
H = 0.08 Å2, the
lacking ones were specified geometrically and refined
by the riding model with fixed
H = 0.08 Å2.
U
U
(nos.
(C16H17Cl2N3Zn),
3770420
(C19H15Cl2N3Zn),
770422 (C15H13Cl2N3Zn),
770421
RESULTS AND DISCUSSION
771 080 (C26H22Cl4N6Zn2); deposit@icdc.cam.ac.uk
or http://www.ccdc.cam.ac.uk).
2ꢀ(2ꢀPyridyl)benzimidazole was synthesized by the
procedure commonly used to prepare 2ꢀ(2ꢀ
The structures of compounds Ia
⎯IIIe were solved pyridyl)benzazoles based on the reaction of anilines
by the direct method using SHELXSꢀ86 program containing a protonꢀdonor group in the orthoꢀposition
package [27] and refined by the SHELXLꢀ97 program
package [28]. Nonꢀhydrogen atoms were refined
(
(
V
) with pyridineꢀ2ꢀcarbaldehyde (
VII):
VI) [10] to give
XH
N
X
+
O
N
N
NH2
H
(V): X = NR, O, S
(
VI)
(VII)
Nꢀsubstituted VII were prepared by alkylation of of structures II–IV. These structures are important for
2ꢀ(2ꢀpyridyl)benzimidazole.
Complex compounds of type III (M = Zn, R =
C4H9, CH2–CH=CH2, CH2C6H5) were isolated upon
development of the competitive coordination probꢀ
lem. To our knowledge, complexes of nitrogen bishetꢀ
erocycles have not been considered previously from
this standpoint [3, 31].
The Xꢀray diffraction data indicate that the comꢀ
pounds have type III chelate structure with zinc coorꢀ
dination to both sp2 hybridized nitrogen atoms of the
imidazole and pyridine fragments. As a result, irreꢀ
spective of the nature (Alk, Ar) and the length of subꢀ
stituent R, a fairly planar system of four conjugated
rings including the metal ring is formed (Figs. 1–4).
The metal rings of all four compounds are slightly
folded at the N(1)–N(3) line to form a dihedral angle
the reaction of
The binulear complex IIIb (R = СН3) was prepared in
a similar way.
I with zinc dichloride in methanol.
Cl
N
N
N
N
N
Cl
Cl
R
Zn
Zn
Cl
R
N
of
2°–9° between the corresponding planes. In the
(pyridyl)benzimidazole fragment, the bond length
distribution order typical of free molecule
retained.
I is
(
IIIb)
The Zn coordination unit in IIIc
The complex formation induces an increase in the is a somewhat distorted tetrahedron. The dihedral
IR stretching frequencies of the benzimidazole ring at angles
between the N(1)Zn(1)N(3) and
1590–1600 cm–1, which is consistent with published Cl(1)Zn(1)Cl(2) planes are 96.3
, 93.2 and 91.7
respectively (the ideal value is 90 ). The linear and
–IIIe (Figs. 2–4)
°
°,
°,
data for molecular complexes [29].
°
angular parameters in the coordination polyhedron of
these three compounds are almost identical (Table 3).
The Zn–N bond with the pyridine nitrogen atom is
0.1 Å longer than that for the imidazole atom. The
Zn–Cl bonds are equal (average length 2.203 Å).
Unlike the previous compounds in which the effect
of substituent R on the structure of the complex was
minor, in compounds like IIIb (Fig 1), the practically
According to Xꢀray diffraction data, 2ꢀ(2ꢀ
pyridyl)benzimidazoles
I and analogs VII exist most
often as transꢀisomers as regards the arrangement of
pyridine type nitrogen atoms of the azole and azine
substituents relative to the C(2)–C(2)' bond. [25].
Only one example is known where 2ꢀ(2ꢀpyridyl)benzꢀ
imidazole containing a bulky dioxyribose substituent
in position 1 exists as the cisꢀisomer [30].
The higher stability of transꢀisomers and the monoatomic substituent does not create hindrance
chelating effect determine the possibility of existence that would prevent approach to the neighboring moleꢀ
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
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910
BURLOV et al.
C(13)
N(2)
C(16)
C(10)
C(12)
C(9)
C(8)
C(5)
C(4)
C(6)
C(7)
C(15)
C(14)
C(11)
N(3)
C(1)
C(3)
N(1)
C(2)
C(9)
Zn(1)
C(13)
C(10)
C(11)
N(3)
C(6)
Cl(1)
C(8)
Cl(2)
C(7)
C(5)
Cl(2A)
C(4)
C(3)
C(12)
Fig. 1. Molecular structure of binuclear complex IIIb
.
N(2)
C(1)
N(1)
C(2)
cule to a distance sufficient for interaction. The moleꢀ
cule is dimerized through sharing a chlorine atom of
the neighboring molecule to form a fourꢀmembered
Zn2Cl2 ring and an additional elongated Zn–Cl bond
Zn(1)
Cl(1)
Cl(2)
(
2.646 Å). The main Zn–Cl bonds and the Zn–N(3)
bonds are also elongated (Table 3).
The insertion of an additional chlorine atom to the
coordination sphere of the central atom results in a
pronounced rearrangement of the polyhedron, which
can rather be classified as a trigonal bipyramid with
Fig. 2. Molecular structure of complex IIIc
.
groups, these groups play a key role in the choice of the
packing pattern of structural units; as a consequence,
compounds with nearly the same structure of the comꢀ
plex form different crystal packings.
elongated axial Zn
shorter equatorial Zn–N(3), Zn–Cl(1), and
Zn Cl(2) bonds (Table 3).
In the considered compound IIIb, the small subꢀ
stituent plays rather a passive role in structure formaꢀ
⎯Cl(2А) and Zn–N(3) bonds and
⎯
The structures with dichloride bridges have not
tion, while in compounds with longer or more bulky been known previously among 2ꢀ(2ꢀpyridyl)benzazole
Table 3. Parameters of Zn coordination polyhedron in the complexes IIIb–IIIe
Bond
,
d,
Å
Angle, ω, deg
Comꢀ
pound
Zn–Cl(2)
Zn–Cl(2
Zn–Cl(1)
2.239(2)
Zn–N(1)
2.044(5)
Zn–N(3)
2.216(6)
Cl(1)ZnCl(2) N(1)ZnN(3) Cl(1)ZnCl(2А)
А)
IIIb
2.337(2)
2.646(3)
97.63(7)
76.4(2)
119.83(8)
IIIc
IIId
IIIe
2.208(2)
2.214(2)
2.194(2)
2.193(1)
2.210(2)
2.202(2)
2.036(5)
2.016(5)
2.030(4)
2.106(4)
2.102(5)
2.098(4)
116.4(7)
114.0(8)
119.70(7)
79.3(2)
80.2(3)
79.2(2)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
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COORDINATION COMPOUNDS OF AMBIDENTATE
911
more bulky ligands containing pyridylbenzimidazole
fragments [11, 15,17, 18,32ꢀ36].
C(15)
ACKNOWLEDGMENTS
C(14)
This work was supported by a Russian Federation
President grant (NSh 3233.2010.3) and the Ministry
of Science and Education of the Russian Federation
(project no. 2.1.1/2371).
C(10)
C(9)
C(11)
C(13)
C(8)
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N(2)
C(6)
C(12)
N(3)
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Chem. Soc., 1992, vol. 114, no. 19, p. 7440.
C(7)
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