Indian Journal of Chemistry

Vol. 51A, July 2012, pp. 917-926

Synthesis and characterisation of arylazoimidazolium iodide and

tetraiodocadmium(II) compounds
D Mallicka, R Sahab, K K Sarkerc, P Dattad & C Sinhae, *
a
Department of Chemistry, Mrinalini Datta Mahavidyapith, Birati, Kolkata 700 051, West Bengal, India
b
Department of Physics, Jadavpur University, Kolkata 700 032, West Bengal, India
c
Department of Chemistry, Mahadevananda Mahavidyalaya, Barrackpore, Monirampore, Kolkata 700 120, West Bengal, India
d
Calcutta Institute of Engineering and Management, 24/1A Chandi Ghosh Road, Kolkata 700 040, West Bengal, India
e
Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Raja Suboth Mullick Road,
Kolkata 700 032, West Bengal, India
Email: c_r_sinha@yahoo.com

Received 9 January 2012; revised and accepted 22 June 2012

Sixteen new inorganic-organic hybrid compounds of 1,3-dialkyl-2-(arylazo)imidazolium, [RaaiR/R//]+ (R, alkyl group),
and I- or [CdI4]2- as counter ion are synthesized and characterized by spectroscopic (IR, UV-vis, 1H NMR) techniques. The
single crystal X-ray diffraction studies of representative compounds, viz., 1,3-dimethyl-2-(p-tolylazo)imidazolium iodide
[MeaaiMe2+]I- and bis- [1-methyl-3-benzyl-2-(p-tolylazo)imidazolium]tetraiodocadmium(II) [Meaai(Me)CH2Ph+]2 [CdI4]2-,
have confirmed the proposed structures. DFT computation has been used to explain the electronic structure and the
electronic spectra of the compounds.

Keywords: Coordination compounds, Inorganic-organic hybrids, Cadmium, Dialkyl-arylazoimidazolium salts,

Arylazoimidazolium salts, Iodometallates, X-ray structures, Density functional calculations

Inorganic–organic hybrid compounds have attracted
attention to generate high conducting useful ionic
materials of high mechanical and dimensional
stability1-6. The transition and non-transition
metal-halides show various coordination numbers and
structures7-9 and have generated halometallates which
are building agents to bring organic cations together
to develop sustainable hybrid materials. Iodide (I-) has
generated polymeric network with most of the metal
ions and form myriad of bridged dimers, cubanes,
chains, strands, etc.7-12 The N-heterocycle organic
cations like dialkyl imidazolium iodides are
interesting class of ionic liquids with low vapor
pressure and are important media for organic and
inorganic compound synthesis and in electrochemistry
for large potential window and separation
processes13-15. We have extensively studied the
functionalization of imidazole and have characterized
arylazoimidazoles and their derivatives16-20.
Alkylation of arylazoimidazoles has synthesized
1,3-dialkyl-2-(arylazo)imidazolium salts of different
anions like PF6¯ (ref. 21), ReO4¯ (ref. 22,23),
Cl¯ , [ZnCl4]2–, [PtCl6]2– (ref. 24), [PbI3¯ ]n (ref. 25).
Studies on the structural diversity of
arylazoimidazolium ions with different oxo and
non-oxo anions have been reported by other groups
also26,27. In this work we report arylazoimidazolium
salts of iodide and tetraiodocadmium(II) derivatives.
The compounds are characterized by different
spectroscopic studies and structural confirmation has
been carried out in representative cases by single
crystal X-ray diffraction measurements.
Materials and Methods
2-(Arylazo)imidazoles were prepared by the
reported procedure28. All other chemicals and solvents
were reagent grade and used as received. Cadmium
iodide was purchased from SD Fine Chemicals.
Microanalytical data (C, H, N) were collected on
Perkin–Elmer 2400 CHNS/O elemental analyzer.
Spectroscopic data were recorded using the following
instruments: UV-vis spectra from Perkin-Elmer
Lambda 25 spectrophotometer, IR spectra
(KBr disk, 4000–450 cm−1) on Perkin-Elmer
918 INDIAN J CHEM, SEC A, JULY 2012
RX-1 FTIR spectrophotometer and 1H NMR spectra
on Bruker (AC) 300 MHz FTNMR spectrometer.
Molar conductance was measured using Systronics-304
conductivity meter.
Preparation of compounds
/
The 1-alkyl-2-(arylazo)imidazoles (RaaiR )
were synthesized from the corresponding
2-(arylazo)imidazoles (RaaiH, 1-3) by reacting
the latter with the respective alkyl halide in the
presence of sodium hydride in dry THF16.
Preparation of 1,3-dimethyl-2 (tolaylazo)imidazolium iodide
(MeaaiMe2)+I ¯ (4b)
To a THF solution (10 ml) of 1-methyl-2-
(p-tolaylazo)imidazole (0.2 g, 1.00 mmol), MeI was
added and kept at low temperature for 30 min and
then reflux for 4 h. The solution was evaporated under
reduced pressure and the dry mass was extracted in
water and filtered. The filtrate was evaporated slowly
in air and orange crystalline products were isolated.
The orange-red needle shaped crystals were then
recrystallised from methanol-water (1:1, v/v)
yield: 0.24 g (68 %).
All other compounds were prepared by identical
procedure in the range of 65-75 % yield.
Microanalytical data of the complexes are as follows:
[HaaiMe2]+I- (4a), m. pt. 185±1 °C; Anal. (%): Found:
C, 40.31; H, 4.01; N, 17.03. Calc.: C, 40.24; H, 3.96;
N, 17.07. FT-IR (KBr disc, cm-1), ν(N=N), 1428;
ν(C=N), 1590. UV-vis spectral data in CH3CN
(λmax(nm) (10-4 ∈ (dm3 mol-1cm-1): 239(0.05),
369(2.7), 380(2.5), 452(1.6).
[MeaaiMe2]+I- (4b), m. pt. 168±1 °C; Anal. (%):
Found: C, 42.13; H, 4.43 N, 16.43. Calc.: C, 42.10; H,
4.39; N, 16.37. FT-IR (KBr disc, cm-1); ν(N=N),
1424; ν(C=N), 1592. UV-vis spectral data in CH3CN
(λmax(nm) (10-4 ∈ (dm3 mol-1cm-1) 242 (0.06),
368 (2.6), 384 (2.4), 454(1.8).
[HaaiEt2]+I- (5a), m. pt. 176 ±1 °C; Anal. (%): Found:
C, 43.90; H, 4.83 N, 15.70. Calc.: C, 43.82; H, 4.78;
N, 15.73. FT-IR (KBr disc, cm-1), ν(N=N), 1420;
ν(C=N), 1590. UV-vis spectral data in CH3CN
(λmax(nm) (10-4 ∈ (dm3 mol-1cm-1 ) 243 (0.04),
367 (2.5), 379 (2.2), 449(1.6).
[MeaaiEt2]+I- (5b), m. pt. 173±2 °C; Anal. (%):
Found: C, 42.13; H, 4.43 N, 16.43. Calc.: C, 45.78; H,
4.36; N, 15.26. FT-IR (KBr disc, cm-1), ν(N=N),
1420; ν(C=N), 1594. UV-vis spectral data in CH3CN
(λmax(nm)(10-4 ∈ (dm3 mol-1cm-1) 241 (0.06),
366(2.7), 378 (2.2), 450 (1.5).
[Haai(CH2Ph)2]+I- (6a) , m. pt. 230±1°C; Anal. (%):
Found: C, 57.43; H, 4.32; N, 11.58. Calc.: C, 57.50;
H, 4.38; N, 11.67. FT-IR (KBr disc, cm-1), ν(N=N),
1422; ν(C=N), 1592. UV-vis spectral data in CH3CN
(λmax(nm) (10-4 ∈ (dm3 mol-1cm-1): 244 (0.06),
364 (2.3), 381 (2.1), 451 (1.5).
[Meaai(CH2Ph)2]+I- (6b) , m. pt. 245±1°C; Anal. (%):
Found: C, 58.21; H, 4.60; N, 11.26. Calc.: C, 58.29;
H, 4.66; N, 11.34. FT-IR (KBr disc, cm-1), ν(N=N),
1425; ν(C=N), 1590. UV-vis spectral data
in CH3CN (λmax(nm) (10-4 ∈ (dm3 mol-1cm-1):
245 (0.07), 365 (2.3), 379 (2.0), 448 (1.7).
[HaaiMe(CH2Ph)]+I- (7a) m. pt. 235±1 °C. Anal. (%):
Found: C, 50.54; H, 4.21; N, 13.82. Calc. C, 50.51; H,
4.24; N, 13.86. FT-IR (KBr disc, cm-1), ν(N=N),
1428; ν(C=N), 1595. UV-vis spectral data
in CH3CN (λmax(nm) (10-4∈(dm3 mol-1cm-1): 238
(0.04), 368 (2.7), 378 (2.3), 449 (1.4).
[MeaaiMe(CH2Ph)]+I- (7b), m. pt. 248±1 °C Anal. (%):
Found: C, 51.75; H, 4.54; N, 13.46. Calc. C, 51.69; H,
4.58; N, 13.40 %. FT-IR (KBr disc, cm-1), ν(N=N),
1430; ν(C=N), 1588. UV-vis spectral data in CH3CN
(λmax(nm) (10-4 ∈ (dm3 mol-1cm-1):
240 (0.05), 366 (2.4), 380 (2.1), 450 (1.6).
Synthesis of [MeaaiMe(CH2Ph)+]2 [CdI4]2- (11b)
To a methanol solution (20 ml) of [MeaaiMe-
(CH2 Ph)]+ I (1-methyl-3-benzyl-2-(p-tolylazo)
imidazolium iodide) (0.105 g, 0.36 mmol), was
added CdI2 (0.132 g, 0.36 mmol) pinchwise,
with stirring and then refluxed for 8 h. The
hot solution was filtered through G4 crucible
and allowed to evaporate slowly in air. The block
shaped orange-red crystals deposited on the
wall of beaker were collected by filtration.
These crystals were ground and the 2-methoxy-
ethanol solution was prepared. Methanol (2 vol.)
was added into this solution and after a week,
bright orange-red colored block shaped crystals
were deposited at the base of the container,
which were collected and dried over CaCl2 in a
desiccator (yield 0.18 g, 62 %).
 MALLICK et al.: SYNTHESIS OF ARYLAZOIMIDAZOLIUM SALTS OF I¯ & [CdI4]2– DERIVATIVES
The other complexes were prepared by the same
procedure. In all the cases, crystalline products were
obtained. The yield varied from 60-70 %.
Microanalytical data of these complexes are as
follows:
[HaaiMe2+]2 [CdI4]2- (8a): Anal. (%): Found: C, 25.85;
H, 2.4; N, 11.03. Calc.: C, 25.84; H, 2.6; N, 11.0. FT-
IR (KBr disc, cm-1), ν(N=N), 1432; ν(C=N), 1593 cm-1.
UV-vis spectral data in CH3CN (λmax(nm)
(10-4 ∈ (dm3 mol-1cm-1): 366 (7.6), 380 (7.1), 467 (4.6).
[MeaaiMe2+]2 [CdI4]2- (8b): Anal. (%): Found: C,
27.78; H, 3.02; N, 10.73. Calc.: C, 27.80; H, 2.91; N,
10.81. FT-IR (KBr disc, cm-1), ν(N=N), 1442;
ν(C=N), 1596. UV-vis spectral data in CH3CN
(λmax(nm)(10-4 ∈ (dm3 mol-1cm-1): 370 (7.7), 382
(7.2), 464 (4.8).
[HaaiEt2+]2 [CdI4]2- (9a): Anal. (%): Found: C, 29.83;
H, 3.24; N, 10.57. Calc.: C, 29.72; H, 3.26; N, 10.67.
FT-IR (KBr disc, cm-1), ν(N=N), 1436; ν(C=N),
1597. UV-vis spectral data in CH3CN (λmax(nm)
(10-4 ∈ (dm3 mol-1cm-1): 368 (7.9), 379 (7.1),
465 (5.0).
[MeaaiEt2+]2 [CdI4]2- (9b): Anal. (%): Found: C,
31.63; H, 3.63; N, 10.51. Calc: C, 31.59; H, 3.59; N,
10.53. FT-IR (KBr disc, cm-1), ν(N=N), 1438;
ν(C=N), 1601. UV-vis spectral data in CH3CN
(λmax(nm) (10-4 ∈ (dm3 mol-1cm-1): 366 (7.4),
384 (6.7), 468 (4.7).
[Haai(CH2Ph)2+]2 [CdI4]2- (10a): Anal. (%): Found: C,
41.58; H, 3.32; N, 8.43. Calc.: C, 41.64; H, 3.20; N,
8.4. FT-IR (KBr disc, cm-1), ν(N=N), 1435; ν(C=N),
1592. UV-vis spectral data in CH3CN (λmax(nm)
(10-4∈ (dm3 mol-1cm-1): 368 (7.7), 378 (6.9),
470 (4.9).
[Meaai(CH2Ph)2+]2[CdI4]2- (10b): Anal. (%): Found:
C, 43.06; H, 3.57; N, 8.29. Calc.: C, 43.0; H, 3.5; N,
8.3. FT-IR (KBr disc, cm-1), ν(N=N), 1440; ν(C=N),
1600. UV-vis spectral data in CH3CN (λmax(nm)
(10-4∈ (dm3 mol-1cm-1): 374 (7.6), 385 (6.8),
469 (5.2).
[HaaiMe(CH2Ph)+]2[CdI4]2- (11a): Anal. (%): Found:
C, 34.38; H, 2.85; N, 9.4. Calc. C, 34.35; H, 2.9; N,
9.43. FT-IR (KBr disc, cm-1), ν(N=N), 1435; ν(C=N),
1594. UV-vis spectral data in CH3CN (λmax(nm)
(10-4∈(dm3 mol-1cm-1): 371 (7.4), 386 (7.0), 462 (5.1).
919
[MeaaiMe(CH2Ph )+]2[CdI4]2- (11b): Anal. (%):
Found: C, 35.93; H, 3.16; N, 9.29. Calc. C, 35.95; H,
3.12; N, 9.32 %. FT-IR (KBr disc, cm-1), ν(N=N),
1464; ν(C=N), 1602. UV-vis spectral data in CH3CN
(λmax(nm)(10-4 ∈ (dm3 mol-1cm-1): 373 (7.8),
390 (7.3), 463 (4.9).
X-ray crystal structure analyses
Crystals suitable for X-ray diffraction study of
(MeaaiMe2)+I- (4b) (0.12 × 0.14 × 0.22 mm) were
prepared by slow evaporation of aqueous solution in
air and for [MeaaiMe(CH2Ph)+]2 [CdI4]2- (11b)
(0.05 × 0.10 × 0.20 mm) were crystallized from a
mixture of methanol and 2-methoxy-ethanol (2:1, v/v)
at ambient condition. Diffraction data were collected
on a Bruker SMART 1K CCD area-detector
diffractometer using fine focused sealed tube
graphite-monochromatized Mo-Kα radiation
(λ = 0.71073 Å). Unit cell parameters were
determined from least-squares method in the range of
-9 ≤ h ≤ 9, -12 ≤ k ≤ 9, -13 ≤ l ≤ 13 and angle
variation 3.98 < 2θ < 55.00° for 4b and in the case of
11b, the parameters are -26 ≤ h ≤ 27, -17 ≤ k ≤ 19,
-18 ≤ l ≤ 12 and angle variation 1.92< 2θ < 56.76°.
A summary of the crystallographic data and structure
refinement parameters are given in Table 1. Data were
corrected for Lorentz and polarization effects.
Data reduction was carried out by using SAINT
programme and the structure was solved by direct
method using SHELXS-9729 and successive difference
Fourier syntheses. All non-hydrogen atoms were refined
anisotropically. Full matrix least squares refinements on
F02 were carried out using SHELXL-9730 with
anisotropic displacement parameters for all
non-hydrogen atoms. Hydrogen atoms were
constrained to ride on the respective carbon or
nitrogen atoms with anisotropic displacement
parameters equal to 1.2 times the equivalent isotropic
displacement of their parent atom in all cases. The
maximum (∆max, e Å-3) and minimum (∆min, e Å-3)
electron densities were 0.572, −0.263 (4b) and 0.680,
−0.807 (11b). All calculations were carried out using
SHELXS 9729, PLATON 9931, ORTEP-332 programs.
Computation details
All the calculations were carried out with the
density functional theory (DFT) method as
implemented in GAUSSIAN 03 (G03) program
package33 and the calculations were performed using
the B3LYP exchange correlation functional34.
920 INDIAN J CHEM, SEC A, JULY 2012

Table 1 – Crystallographic data for [MeaaiMe2+]I- (4b) and larger basis set 6-31g+(d) for H, C, N and LanL2DZ
[MeaaiMe(CH2Ph) +] 2 [CdI42-] (11b) for cadmium and iodine.
[MeaaiMe2+]I- [MeaaiMe(CH2Ph)+]2
[CdI42-] Results and Discussion
Empirical formula C12H15I N4 C36H38I4N8Cd Synthesis and characterisation of arylazoimidazolium iodides
Formula weight 342.18 1202.74 The 1,3-dialkyl-2-(arylazo)imidazolium iodides
Temperature (K) 293(2) 294(2) ([RaaiR/2]+ I- , where R = H (a), Me (b); R/ = Me (4),
Crystal system triclinic monoclinic Et (5), CH2Ph (6)] were synthesized by addition of R/I
Space group P -1 P 21/c to THF solution of 1-alkyl-2--(arylazo)imidazoles
Unit cell dimensions (RaaiR/) and purified by crystallization from
a (Å) 7.2434(14) 21.157(3) methanol-water. Unsymmetrical imidazolium iodides,
b (Å) 9.6969(19) 14.3035(17) [Raai(Me)CH2Ph]+I- (7) were synthesized by
c (Å) 10.474(2) 13.6334(16)
benzylation of 1-methyl-2-(arylazo)imidazoles
(RaaiMe). Ionic compounds of the composition,
α (°) 77.69(3)
[RaaiR/2+]2[CdI4]2- (R/ = Me (8), Et (9), CH2Ph (10))
β (°) 87.59(3) 92.135(3)
and [Raai(CH3)(CH2Ph)+]2[CdI4]2- (11) were obtained
γ (°) 74.43(3) as brown-red precipitate by mixing the aqueous
V (Å)3 692.3(2) 4122.9(9) suspension of CdI2 to the solution of [RaaiR/R//+]I- in
Z 2 4 1:2 molar ratio at room temperature, filtered and
λ (Å) 0.71073 0.71073 washed with cold water and dried in vacuuo.
µ (Mo-Kα) (mm-1) 2.298 3.560 These compounds were recrystallised from
Dcalc (mg m-3) 1.642 1.938 2-methoxyethanol-methanol (1:2, v/v) by slow
Refine parameters 166 442 evaporation in air. The composition of the compounds
Total reflections 11663 27623 is supported by elemental analyses (C, H, N) and the
Unique data [I > 2σ (I) ] 3105 10042 structures established by spectroscopic data.
R1a [ I > 2σ (I) ] 0.0289 0.0442 The single crystal X-ray diffraction data confirmed
wR2b 0.0651 0.0842 the structure of the compounds as shown in Scheme 1.
Goodness of fit 0.925 0.878
The compounds are conducting both in aqueous and
a alcohol solutions. Methanol solution of the
R = ΣF0 –Fc / Σ F0. bwR = [Σ w(F02 – Fc2)/ Σ w F04]1/2 are
general but w are different. compounds, (4 – 7) shows 1:1 conductivity
w = 1/ [σ2 (Fo2) + (0.0396P)2 + 0.3036P] for (4b); (60 - 80 Ω-1 mol-1), while the tetraiodocadmium(II)
w = 1/[σ2(F2) + ( 0.0100P)2 + (0.0000P)] for (11b) where salts (8 – 11) are also conducting molecules and show
P = (Fo2+2Fc2)/3. 2 : 1 conductivity.
The geometry of the compounds (4b) and (11b) were
Spectral studies of arylazoimidazolium iodides
fully optimized in gas phase using 6-31G* basis set
for all elements except cadmium and iodine. The Los The IR frequencies of the compounds have been
Alamos effective core potential plus double zeta assigned on comparing data with those of the free
(LanL2DZ)35 basis set was employed along with the ligand16. Moderately intense stretching at 1595–1600
corresponding pseudo-potential of cadmium and and 1435–1445 cm-1 is due to υ(C=N) and υ (N=N),
iodine without any symmetry constrain. respectively, for these compounds.
The vibrational frequency calculation was also Since the compounds are soluble in acetonitrile, the
performed for both compounds to ensure that the solution electronic spectra were recorded in
optimized geometries represent the local minima and acetonitrile in the wavelength range of 200−900 nm.
there are only positive Eigen values. The calculated There are three bands and of these, two are high
and experimental metric parameters agree well to intense (ε, 104 mol-1 dm3 cm-1) bands at 360–370 and
support proper selection of methods and functions 375–385 nm. On comparing with free ligand
used. To assign the low lying electronic transitions in spectra16, it may be concluded that these bands are
the experimental spectra, TDDFT36 calculations of the due to π-π* charge transfer transitions. A weak band
complexes were done in acetonitrile using conductor- (ε, 103 mol-1 dm3 cm-1) appears at 460–475 nm.
like polarizable continuum model (CPCM)37-39 with The electronic spectra may be assigned as the
 MALLICK et al.: SYNTHESIS OF ARYLAZOIMIDAZOLIUM SALTS OF I¯ & [CdI4]2– DERIVATIVES 921

5 4 +

N N N N I- N
N
H R 1 3 R/
(i) NaH / THF R
R
N N
N
N N +
(ii) R/I, Reflux N

11 7

10 8
9
R R
R
RaaiH, 1 - 3 RaaiR/ 2+I-, 4 - 7 RaaiR/

5 4 + 5
+

N N N
N I-
1 3 R 1 3
R R R
N N
N N [CdI4 ]2-
2 + CdI2
7 11 7
11
10 10 8
8
9 9
R R
2n

8 -11

R = H (a), Me (b), R/ = -12CH3 (1, 4, 8); -12CH2 13CH3 (2, 5 ,9), -12 CH2Ph (3, 6, 10); R/ = Me, R// = CH2Ph (7, 11)
Syntheses of ligands RaaiR/ (1-3), [RaaiR/R//]+I- (4-7) and [RaaiR/R//+]2 [CdI4]2- (8-11)
Scheme 1
admixture of charge transfer transitions azoimidazolium salts, [Raai (Me)(CH2Ph)]+I- (7) and
of π(imidazolium)/π(iodide)/π(aryl)→π*(azo)/π*(aryl) [Raai(Me)(CH2Ph)+]2[CdI4]2- show a sharp singlet at
transition and has been supported by DFT 5.70-5.80 ppm that refers to N-CH2(Ph) signal.
computation (vide infra) of optimized geometry of the Imidazole protons (4-, 5-H) appear as broad single
compounds. resonance at 7.0-7.2 ppm. The broadening may be due
The 1H NMR spectra of 1, 3-dialkyl- to rapid proton exchange between two positions. The
2-(arylazo)imidazolium iodide, [RaaiR/2]+I- (4-6) aryl protons (7-H to 11-H) are perturbed by 9-R
were recorded in CDCl3. The atom numbering substituent and 9-Me group shifts the proton signal
pattern is shown in Scheme 1. The proton upfield due to +I effect.
signals are assigned on comparing with RaaiR/ 16,
spin-spin interaction and effect of substitution. Molecular structure of [MeaaiMe2]+ I- (4b)
1,3-Dialkyl-2-(arylazo)imidazolium iodides show a The molecular structure of [MeaaiMe2]+ I- (4b) is
single resonance for two R/; 1,3-Me2 of (4) shows a shown in Fig. 1 and bond parameters are listed in
sharp singlet at 4.25 ppm; 1,3-Et2 of [RaaiEt2]+I- (5) Table 2. The p-tolyl and imidazole rings are virtually
exhibits 1-(CH2)-3-(CH2)- as quartet at coplanar as indicated by the torsion angle, C(1)-N(3)-
~4.85 ppm and methyl (-Me) shows triplet splitting N(4)-C(6) of 178.64(12)° with the dihedral angle
pattern at ~1.5 ppm. Asymmetric dialkyl between two planes being 8.80(8)°. The N(3)-N(4)
922 INDIAN J CHEM, SEC A, JULY 2012

Fig. 1 – ORTEP diagram of [MeaaiMe2+] I- (4b) with 30 %

atomic probability.

Table 2 – Selected bond lengths and bond angles of

[MeaaiMe2+]I− (4b) and [MeaaiMe(CH2Ph)+]2 [CdI42−] (11b) Fig. 2 – The 1D supramolecular chain formed by π…π
Bond lengths (Å) Bond angles (°) interactions along crystallographic a-axis of (4b).

[MeaaiMe2+]I− (4b)
charge of the species. The hydrogen bonding
N(2)-C(5) 1.462(5) C(1)-N(1) C(4) 128.1(3)
(D–H---I, D–H---N(azo) and π---π interactions build
N(1)-C(3) 1.361(4) C(1)-N(2)-C(5) 125.7(3)
up the 1D-chain (Fig. 2). I− forms three hydrogen
N(1)-C(4) 1.471(4) N(4)-N(3)-C(1) 113.1(3)
N(3)-N(4) 1.237(4) N(3)-N(4)-C(6) 112.3(3)
bonds with three MeaaiMe2+ in a triangular
N(4)-C(6) 1.439(4) arrangement where C(11)–H(11)---I(1): H(11)---I(1),
3.114 Å; C(11)----I(1), 4.031 Å; ∠C(11)–H(11)---I(1),
[MeaaiMe(CH2Ph)+]2 [CdI42−] (11b)
169.16°. C(5)–H(5B)---I(1): H(5B)---I(1), 3.125 Å;
Cd – I(1) 2.7672(9) I(2) – Cd – I(1) 109.79(3)
C(5)----I(1), 4.042 Å; ∠C(5)–H(5B)---I(1), 160.25°.
Cd – I(2) 2.7507(9) I(2) – Cd – I(4) 114.17(3)
C(3)–H(3)---I(1): H(3)---I(1), 2.966 Å; C(3)----I(1),
Cd – I(3) 2.7975(10) I(1) – Cd – I(4) 102.85(3)
Cd – I(4) 2.7851(10) I(2) – Cd – I(3) 102.03(3) 3.875 Å and ∠C(3)–H(3)---I(1), 165.91°.
N(3) – N(4) 1.215(8) I(1) – Cd – I(3) 109.28(3) The presence of intermolecular hydrogen bond
N(7) – N(8) 1.231(8) I(4) – Cd – I(3) 118.69(3) between azo-N of one molecular ion with C–H of
N(3) – C(1) 1.469(10) N(3)-N(4)-C(5) 111.2(10) imidazole-N-CH3 of neighboring ion increases the
N(4) – C(5) 1.462(11) N(4)-N(3)-C(1) 110.4(10) contact and enhances the strength of interaction. The
N(7)-N(8)-C(23) 110.5(9) hydrogen bond exists as N(3)---H(4B)–C(4),
N(8)-N(7)-C(19) 114.8(10) N(3)---H(4B) (2.682 Å); N(3)---C(4) (3.534 Å) and
N(2)-C(12) C(13) 114.9(7) ∠N(3)–H(4B)–C(4) (148.22°).
N(5)-C(30)-C(31) 112.8(8)
The packing view shows that the compound forms
bond length is 1.237(4) Å, which is shorter than that 1D chain along crystallographic a-axis through π----π
earlier reported23-25 for 1-methyl-2-(phenylazo) interactions (Fig. 3) between phenyl and imidazolyl
imidazolium perchlorate (1.252(2) Å) and 1-ethyl-2- rings. The Cg(1), C(1)-N(1)-C(3)-C(2)-N(2)
(naphthyl-α-azo)imidazolium hexafluorophosphate (imidazolyl ring) interacts with Cg(2) C(6)-C(7)-C(8)-
(1.267(3) Å). The N(azo)-C(imidazole) bond, C(9)-C(10)-C(11) (phenyl ring) at -1-x, 2-y, -z.
N(3)-C(1) (1.398(4) Å), is shorter than the N(azo)- The distance between the centroids is 3.7254(19) Å
C(phenyl) bond N(4)-C(6) (1.439(4) Å), which and the dihedral angle is 4.47(16)° Similarly, the
indicates a stronger bonding between azo and Cg(1) interacts with another Cg(2′) (neighbouring
imidazole group than between azo and phenyl group. molecule) at -x, 2-y, -z symmetry. The distances
Imidazolium ion is formed by N(1) and N(2) between the centroids is 3.8085(19) Å and the
methylation of imidazole. Presence of I− balances the dihedral angle is 4.47(16)°. In this way, 1D chains are
 MALLICK et al.: SYNTHESIS OF ARYLAZOIMIDAZOLIUM SALTS OF I¯ & [CdI4]2– DERIVATIVES
Fig. 3 – The 1D supramolecular chains packed along
crystallographic b-axis to form supramolecular channel where
guest I− gets stabilized by van der Waals interactions in (4b).
formed and packed to form channel along a-axis
where guest iodide ions are stabilized (Fig. 3) by
weak van der Waals interactions.
Azoimidazolium tetraiodocadmium(II)
The 1,3-di-alkyl-2-(arylazo)imidazolium iodides
(symmetrical: RaaiR/2+I-, R/ = Me, Me (4); Et, Et (5);
CH2Ph, CH2Ph (6) and R = H (a), Me (b);
unsymmetrical: RaaiMe(CH2Ph)+I- (7)) were used to
synthesize [RaaiR/2+]2[CdI4]2- (8-11). The molar
conductance measurements show that cadmium
complexes are 1:2 electrolyte.
Moderately intense stretching at 1595-1600 and
1435-1445 cm-1 are due to ν(C=N) and ν(N=N),
respectively for the complexes. Other stretching
frequencies are shifted to lower frequency in the
iodometallates (8-11) as compared to the free
ligand values.
The solution spectra of (8-11) were recorded in
acetonitrile in the wavelength range 230-600 nm.
The compounds show transitions at 235-245,
365-375 and 450-460 nm. On comparing with
free ligand spectra16 and that of [RaaiR/2]+I-,
it may be concluded that the bands are
associated with intramolecular charge transfer
transitions (π–π*), π(Imz/p-Tolyl/Iodine) → π*
(azo/Imz) transitions 25.
The 1H NMR spectra of [RaaiR/2+]2 [CdI4]2−
(8-11) recorded in CDCl3 reveal that the signals
in the spectra of the complexes are comparable
with those of [RaaiR/2+]I− Aryl signals shift downfield
on Me-substitution on the aryl ring. This is due to the
electron donating effect of the Me-group.
923
Fig. 4 – ORTEP diagram of [MeaaiMe(CH2Ph)]+2 CdI42- (11b).
Molecular structure of [MeaaiMe(CH2Ph)+]2 [CdI4]2− (11b)
The molecular unit of (11b) is shown in Fig. 4 and
bond parameters are listed in Table 2. The structure is
constituted from [CdI4]2− and two units of
[MeaaiMe(CH2Ph)]+. Anionic moieties [CdI4]2− are
intercalated between the layers of organic cations,
where Cd is present at the centre of a distorted
tetrahedron constituted by Cd and four I atoms.
Bond lengths are in the range of 2.7507(9) —
2.7975(10) Å.
In [MeaaiMe(CH2Ph)]+, the p-tolylazo and
imidazolyl rings are virtually coplanar as indicated by
the torsion angle, C(1)-N(3)-N(4)-C(5) (179.0(6)°)
and C(19)–N(7)–N(8)–C(23) (178.7(2)°) and the
dihedral angle of two planes 7.6(4)° and 6.8(5)°.
Nonplanarity of benzylic group (C(13) to C(18) and
C(31) to C(36)) with imidazole ring is due to –CH2
group and makes an angle of 68.1(5)° or 67.1(6)° with
the imidazole unit. The N(3)-N(4) bond length is
1.215(8) Å and that of N(7)–N(8) is 1.231(8) Å,
which are lower than in the free ligand (1.237(4) Å)
for 1-methyl-2-(phenylazo)imidazolium iodide (4b)
(Fig. 1 and Table 2). There are three types of aromatic
rings, viz., (i) imidazolyl (Imz: Cg(1), N(1)-C(1)-
N(2)-C(3)-C(2)) and Cg(2), N(5)-C(19)-N(6)-C(21)-
C(20)), (ii) p-tolyl (p-Tol: Cg(3), C(5)-C(6)-C(7)-
C(8)-C(9)-C(10) and Cg(5), C(23)-C(24)-C(25)-
C(26)-C(27)-C(28)) and (iii) benzyl (Bz: Cg(4),
C(13)-C(14)-C(15)-C(16)-C(17)-C(18) and Cg(6),
C(31)-C(32)-C(33)-C(34)-C(35)-C(36)) and a total
of six rings in two [MeaaiMe(CH2Ph)]+ units.
These rings are connected through π---π interactions
924 INDIAN J CHEM, SEC A, JULY 2012

between Imz---p-Tol, Imz---Bz and p-Tol---Bz groups

with neighbouring cations. The Cg(1) is embedded
between two Cg(3) rings of neighbouring molecular
units, i. e., Cg(1)---Cg(3), 3.743 Å (symmetry: x, y, z

Fig. 5 – The 3D supramolecular structure formed by π…π Fig. 6 – [CdI4]2- units placed within the supramolecular channel of
interactions in [MeaaiMe(CH2Ph) +] 2 [CdI4 ]2− (11b). [MeaaiMe(CH2Ph) +] in (11b).

Fig. 7 - Surface plots of some selected MOs of [MeaaiMe2]+I- (4b) and [MeaaiMe(CH2Ph)+]2[CdI4]2- (11b).
 MALLICK et al.: SYNTHESIS OF ARYLAZOIMIDAZOLIUM SALTS OF I¯ & [CdI4]2– DERIVATIVES
of Cg(1) and –x, 1-y, 1-z of Cg(3)) and 3.543 Å
(symmetry of Cg(3) is x, 3/2-y, -1/2+z). The Cg(2)
(symmetry, x, y, z) is interconnected with Cg(4)
(symmetry, x, y, z) at 3.573 Å and Cg(5)
(symmetry, 1-x, 1-y, 1-z) at 3.562 Å. The Cg(5) is
again significantly bonded with Cg(6) (symmetry,
x, ½-y, ½+z) at 3.694 Å. All these π-interactions
between aromatic rings form 1D channel along
crystallographic a-axis followed by the construction
of 3D structure (Fig. 5). The [CdI4]2- units get
stabilized within the supramolecular channel
through van der Waals interactions (Fig. 6).
DFT and TD-DFT calculations
DFT calculations were carried out to establish
the electronic structure, spectral transitions, and
redox properties of the studied compounds. The
calculated structures correlate well with the results
of their X-ray analysis. The theoretical N=N, C=N,
C=C and single bonds C–C, N–N, C–N, Cd–I are
slightly longer (0.01 – 0.05 Å) than the
experimental data.
The DFT calculations have been done using
optimized geometry of (4b) and (11b). The surface
plots of the MOs are given in Fig. 7. The composition
of MOs of [MeaaiMe2+]I- (4b) shows participation of
imidazolyl (Imz), p-tolyl (p-Tol), azo (-N=N-) and
iodide groups. The HOMO is a mixture of Imz (5 %),
p-Tol (48 %), azo (5 %) and I (42%) with HOMO-1
having 33 % I and 67 % p-tolyl function. The lower
energy occupied MOs (HOMO-2, HOMO-3, etc.)
have 70-90 % contribution from imidazolyl group. In
[MeaaiMe(CH2Ph)+]2[CdI4]2- (11b), the occupied
MOs (HOMO, HOMO-1, HOMO-2 etc.) are mainly
constituted by orbitals of iodine (>80 %) and the
unoccupied MOs are made up of functions from
organic cation (MeaaiMe(CH2Ph)+) (>90 %). The
organic cation consists of azo, p-tolyl and
imidazolium motifs. The LUMO and LUMO+1 carry
these three parts in significant amounts.
LUMO carries 38 % azo, 18 % p-tolyl and 35 %
imidazolium ion and the LUMO+1 has 40 % azo,
21 % p-tolyl and 29 % imidazolium ion while the
higher energy unoccupied MOs (LUMO+2,
LUMO+3 etc) are dominated by only imidazolium
ion function (>95 %).
The solution electronic spectra are explained on the
basis of the composition of occupied and unoccupied
MOs and their energies. The [MeaaiMe2+]I- (4b) and
[MeaaiMe(CH2Ph)+]2 [CdI4]2- (11b) exhibit intense
transitions at 350 – 380 nm and 250 – 300 nm
925
respectively and a weak band at 400 – 420 nm. In (5a),
the transition at 400 – 410 nm may be assigned to
HOMO→ LUMO, LUMO+1 which is due to π(I/Ar)
→ π*(azo), π*(Imz) and π*(p-Tol)40,41. The band at
300 – 350 nm is due to n/π(I/Imz) → π*(N=N), while
the 250 – 200 nm transitions is assigned to π(Imz) →
π*(p-Tol) /π*(imz). In (11b), the HOMO-n/HOMO →
LUMO/LUMO+1 may be observed at >400 nm, which
are assigned to I (iodine) → π*(azo) and the higher
energy transitions, HOMO-n/HOMO → LUMO+2,
LUMO+3, etc., to I (iodine) → π*(imidazole). Thus,
two classes of transitions are possible in
[RaaiR/R// +]2 [CdI4]2−, both of which are indeed observed.
Acknowledgement
Financial support from Council of Scientific and
Industrial Research (CSIR), New Delhi, India, is
gratefully acknowledged. Thanks are due to
Prof T–H Lu and Mr J Chang, Department of Physics,
National Tsing Hua University, Taiwan, ROC, for
initial crystallographic work.
Supplementary Data
Crystallographic data for the structural analysis
have been deposited with the Cambridge
Crystallographic Data Centre, under CCDC Nos
827648 for (4b) and 654252 for (11b). Copies of this
information may be obtained free of charge from the
Director, CCDC, 12 Union Road, Cambridge, CB2
1FZ, UK, Email: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk. Other supplementary
data, i. e., DFT calculations and characterization data
are available in electronic form at
http://www.niscair.res.in/jinfo/ijca/IJCA 51A(07)
917-926_Suppl Data.pdf.
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