Synthesis and crystal structure of bis[4-(imidazol-1-yl)phenyl]methane

Article abstract of DOI:10.14233/ajchem.2014.15781

A bidentate imidazole derivative with the molecular formula C ₁₉H₁₆N₄, has been synthesized according to modified Ullmann-type coupling method involving C-N coupling reaction under the catalysis of copper and characterized by the ¹H NMR, ¹³C NMR, elemental analysis and X-ray single-crystal diffraction. In the crystal structure, the two mean plans of benzene rings make dihedral angels of 83.05 (0.07)°. N-H···N hydrogen bonds link the molecules into a 1D supramolecular structure. In addition, weak C- H···π(Ph) stacking interactions are also observed.

Full text of DOI:10.14233/ajchem.2014.15781

Asian Journal of Chemistry; Vol. 26, No. 7 (2014), 2062-2064
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.15781
Synthesis and Crystal Structure of bis[4-(Imidazol-1-yl)phenyl]methane
1,*
1
2
KUN HUANG , BING-XIN DU and DA-BIN QIN
1Department of Chemistry and Chemical Engineering, Sichuan University ofArts and Science, Dazhou 635000, Sichuan Province, P.R. China
2China West Normal University, Nanchong 637002, Sichuan Province, P.R. China
*Corresponding author: E-mail: greatwall520@163.com; angel-dog1@126.com
Received: 16 May 2013;
Accepted: 10 September 2013;
Published online: 22 March 2014;
AJC-14961
A bidentate imidazole derivative with the molecular formula C19H16N4, has been synthesized according to modified Ullmann-type coupling
method involving C-N coupling reaction under the catalysis of copper and characterized by the 1H NMR, 13C NMR, elemental analysis
and X-ray single-crystal diffraction. In the crystal structure, the two mean plans of benzene rings make dihedral angels of 83.05 (0.07)°.
N-H···N hydrogen bonds link the molecules into a 1D supramolecular structure. In addition, weak C-H···π(Ph) stacking interactions are
also observed.
Keywords: Imidazole, Coupling reaction, Crystal Structure.
automatic elemental analysis instrument. X-Ray single crystal
structure determination was carried out on a rigaku saturn CCD
area detector diffractometer. Melting point were determined
with a KY-XT6B.
INTRODUCTION
As an important member of five-membered heterocyclic
rings, imidazole moieties are commonly found in natural
compound structures, which attract many scientists' attention1.
Nitrogen-containing heterocycles such as N-arylimidazoles
have been found extensive applications in medicinal2, biolo-
gical3, natural products4, and N-heterocyclic carbene chemistry5.
In recent years, as the development of green chemistry and
metal organic chemistry, imidazoles and its derivatives have
been widely used in ionic liquid and nitro heterocyclic carbenes,
most of which show efficiency of catalysis6. In addition, it is
of great interest to build supramolecular architectures involving
imidazole skeleton in areas of coordination and supermolecular
chemistry7. Arylimidazoles have attracted much attention due
to the rigidity and block of aromatic rings so as to facilitate
building the structure of supramolecular MOF8. Herein, a new
A bidentate imidazole derivative, bis[4-(imidazol-1-yl)-
phenyl]methane, was synthesized and the single crystal
structure was also determined.
Imidazole, copper powder, sodium hydride and all other
reagents were purchased from Alfa Aesar and used without
further purification. Bis(4-iodophenyl)methane was synthe-
sized according to an analogous method reported earlier9. DMF
were distilled from appropriate drying agents prior to use.
1H and 13C NMR spectra were recorded on a BrukerAvance
III 400 spectrometer at 400 HZ and 100 HZ, respectively. C,
H and N analyses were obtained using a GmbHVarioELV3.00
EXPERIMENTAL
bis[4-(Imidazol-1-yl)phenyl]methane synthesized accor-
ding to an analogous method reported earlier10. A suspended
solution of imidazole (1.36g, 20 mmol) and sodium hydride
(1.2 g, 30 mmol, 60 % activity) in DMF was stirred in nitrogen
atmosphere for about 12 h at room temperature, then powder
of copper (0.064 g, 1 mmol) and bis(4-iodophenyl)
methane (4.22 g, 10 mmol) was added. The mixture was stirred
under reflux for 48 h and cooled to room temperature. Then
water was added and filtrated to remove solid. The filtrate was
extracted by ethyl acetate and extracted solution was washed
by saturated salt water for several times and desiccated by
anhydrous magnesium sulfate in sequence. Purified white solid
was obtained through column chromatography (silica gel),
petroleum ether/ethyl acetate = 2:1. yield: 58.3 %, m.p.: 176-
178 °C. Anal. Calc. (%) for C38H32N8: C, 75.47; H, 6.00; N,
1
18.53; Found (%): C, 75.40; H, 6.05; N, 18.50 %. H NMR
(CDCl3, 25 °C,TMS, δ ppm) 4.08 (s, 2H, ArCH2Ar), 7.21 (d,
2H, J = 0.90 Hz, CH=CHim), 7.27-7.36 (m, 10H, ArH), 7.85
(s, 2H, NCHN) 13C NMR (CDCl3, 25 °C, δ ppm) 139.90,
135.70, 135.47, 130.19, 121.70, 118.20, 40.63.
The crystal data and structure refinement for the titled
compound are given in Table-1.

Vol. 26, No. 7 (2014)
Synthesis and Crystal Structure of bis[4-(Imidazol-1-yl)phenyl]methane 2063
TABLE-1
CRYSTAL DATA AND STRUCTURE
REFINEMENT FOR THE TITLE COMPOUND
atoms were refined anisotropically. In general, hydrogen atoms
were fixed at calculated positions and their positions were
refined by a riding model. The selected bond lengths and bond
angles are listed in Table-2.
Empirical formula
Formula weight
Temperature
Crystal system,
Space group
C19H16N4
300.36
296(2) K
Monoclinic
C2/c
Cell dimensions
a = 13.828(8) Å, b = 12.923 (8) Å,
c = 18.270(9) Å, β = 111.84 (3)°
V
3030(3) Å3
Z
Dcalc
Absorption coefficient
F(000)
4
1.317 g cm-3
0.081 mm-1
1264
Index ranges
-15 ≤ h ≤ 16, -12 ≤ k ≤ 15, -21 ≤ l
≤ 21
8477/2559 [Rint = 0.0380]
2135
2559/0/208
Fig. 1. Molecule structure of bis[4-(imidazol-1-yl) phenyl] methane with
atom numbering scheme. Displacement ellipsoids for non-hydrogen
atoms are drawn at the 30 % probability level
Reflections collected/unique
Independent reflections
Data/restraints/parameters
Goodness of fit indicator
Final R indices [I>2σ(I)]a,b
Largest difference peak and
hole (e Å-3)
1.032
RESULTS AND DISCUSSION
R1 = 0.0488 wR2 = 0.1600
0.199 and -0.222
X-Ray crystal diffraction analysis: In the crystal struc-
ture of 2a, both bond distance and bond angles are in normal
range. The mean plan of benzene rings in 2a make dihedral
angels with each other of 83.05 (0.07)° and with attached
imidazole rings of 27.67 (0.06)° and 39.06 (0.10)°, respec-
tively. Extensive intermolecular hydrogen bonds, C2-H2 …N4i
and C17-H17…N4ii (d(C2-H2) = 0.93 Å, d(H2··N4) = 2.48Å,
d(C2···N4) = 3.238(4) Å, C2-H2···N4 = 139º; d(C17-H17) =
0.93 Å, d(H17··N4) = 2.60 Å, d(C17···N4) = 3.474 (4) Å, C17-
H17···N4 =160º. Symmetry code: i: 1-x, y, 1/2-z; ii: -1 + x, y,
z) link molecules into infinite 1D supramolecular structure,
which may contribute to stabilize the crystal structure.
X-ray structure determination: Colourless block-shaped
single crystals suitable for X-ray diffraction studies were obtained
after several weeks by slow evaporation from an acetate
solution of the title compound.A crystal of dimensions 0.20 ×
0.20 × 0.19 mm was used to determine the crystal structures
by X-ray diffraction technique on Rigaku saturn CCD area
detector diffractometer with graphite-monochromated MoKα
radiation (λ = 0.71073 Å, T = 296 (2) K) by ω/2θ multi-scan
mode. All calculations were performed using the SHELXL-
97 crystal graphic software package11. All the non-hydrogen
Fig. 2. Part of the 1D chain supramolecular structure of bis[4-(imidazol-1-yl)phenyl]methane Intermolecular hydrogen bonds are shown as dashed lines
TABLE-2
SELECTED BOND DISTANCES (Å) AND ANGLES (º) FOR THE TITLE COMPOUND
Bond
Length
Bond
C(2)-N(1)
C(1)-C(3)
C(5)-C(6)
C(7)-C(10)
Bond
N(4)-C(2)-N(1)
C(9)-C(4)-N(1)
C(7)-C(6)-C(5)
C(8)-C(7)-C(10)
C(7)-C(10)-C(11)
Length
Bond
Length
1.293(3)
1.408(3)
1.365(3)
1.365(3)
Angles
105.9(2)
121.2(2)
117.7(2)
122.4(2)
-
C(3)-N(1)
C(1)-N(4)
C(4)-C(5)
C(7)-C(8)
Bond
1.372(3)
1.356(3)
1.378(3)
1.379(3)
Angles
110.2(2)
120.0(2)
120.3(2)
121.7(2)
118.8(2)
1.337(3)
1.331(3)
1.364(3)
1.496(3)
Angles
111.7(2)
118.82(19)
120.8(2)
120.6(2)
115.64(19)
C(2)-N(4)
C(4)-N(1)
C(6)-C(7)
C(8)-C(9)
Bond
C(1)-C(3)-N(1)
C(5)-C(4)-N(1)
C(6)-C(7)-C(8)
C(9)-C(8)-C(7)
-
C(3)-C(1)-N(4)
C(9)-C(4)-C(5)
C(6)-C(5)-C(4)
C(6)-C(7)-C(10)
C(4)-C(9)-C(8)

2064 Huang et al.
ACKNOWLEDGEMENTS
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