Inorganica Chimica Acta 358 (2005) 1927–1933

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Difference in bonding behaviour of azide and thiocyanate to

Hg(II)-azoimidazoles
B.G. Chand a, U.S. Ray a, G. Mostafa b, J. Cheng c, T.-H. Lu c, C. Sinha d,*

a
Department of Chemistry, The University of Burdwan, Burdwan 713104, India
b
Department of Physics, Jadavpur University, Kolkata 700 032, India
c
Department of Physics, National Tsing Hua University, Hsinchu 300, Taiwan, ROC
d
Department of Chemistry, Inorganic Section, Jadavpur University, Kolkata 700032, India

Received 20 August 2004; accepted 30 December 2004

Available online 7 February 2005

Abstract

Mercury(II) acetate reacts with the 1-alkyl-2-(arylazo)imidazoles [RaaiR 0 where R = H (a), Me (b); R 0 = Me (1/3/5), Et (2/4/6)]
and sodium azide in methanol solution to afford azido bridged polymeric complexes [Hg(RaaiR 0 )(N3)2]n (3/4). On setting up similar
reaction condition, the reaction of Hg(OAc)2 with RaaiR 0 and NH4SCN has yielded, instead of polymer, an ion-pair
[Hg(RaaiR 0 )4][Hg(SCN)4] (5/6). The complexes are characterised by elemental analysis, IR, UV–Vis, 1H NMR spectral data and
single-crystal X-ray structures of [Hg(HaaiEt)(l-1,1-N3)2]n (4a) and [Hg(HaaiEt)4][Hg(SCN)4] (6a). The complex 4a is a coordina-
tion polymer with end-on (l-1,1) azido bridge and 6a has tetrahedral structure.

2005 Elsevier B.V. All rights reserved.

Keywords: Arylazoimidazole; End-on azide bridge; Ion-pair thiocyanate complex; Hg(II)-complexes; Crystal structures

1. Introduction Our interest is currently engaged with exploration of

Azide ðN3
Þ and thiocyanate (SCN
) are versatile
bridging agents. Their bonding in transition metal cen-
tres has generated varieties of magnetic materials [1–5].
Non-transition metal complexes of N3
, SCN
are less
developed [6–10] compared to that of transition metal
complexes. The dimensionality of the complexes has
been controlled by the nature of end capping ligands
[11,12]. SCN
is an ambidentate ligand [6]. It binds to
soft/boarder line metal ions by the S-donor centre that
makes the metal ions more soft than its precursor. The
symbiosis is the leading force for redistribution of li-
gands (Eq. (1))
2L2 MðSCNÞ2 ¼ ½ML4 ½MðSCNÞ4 
*
Corresponding author. Tel. +91 98306 32450; fax: +91 33
24146584/+91 342 2530452.
E-mail address: c_r_sinha@yahoo.com (C. Sinha).
coordination chemistry of 1-alkyl-2-(arylazo)imidazoles
(RaaiR 0 ) with transition [13–17] and non-transition
[18–21] metals. The ligands are unsymmetric bidentate
N,N 0 -chelating donor systems. The Group 12 (Zn, Cd,
Hg) metal complexes of RaaiR 0 using different counter
anions, viz., Cl
; NO3
; ClO4
; N3
; and SCN
have
been reported by us [21]. It is observed that Cl
forms
a tetrahedral M(RaaiR 0 )nCl2 (n = 1 for monodentate;
n = 2, bidentate chelate) type compounds. The ClO4

and NO3
have synthesised tetrahedral [M(RaaiR 0 )4]2+
(M = Cd(II)) ionic species; the NO3
has created
hydrogen bonded supramolecular networks. The N3

and SCN
form bridged 1D chain [Cd(RaaiR 0 )(N3/
ð1Þ SCN)2]n [22]. Cadmium and mercury are chemically sim-
ilar [23] and we could apprehend structurally identical
compounds of RaaiR 0 with same anions. However, the
X-ray diffraction studies of N3
and SCN
compounds
of Hg-RaaiR 0 show structurally different compounds.

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2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.12.046
1928 B.G. Chand et al. / Inorganica Chimica Acta 358 (2005) 1927–1933
Azido forms usual bridge coordination polymer
[Hg(RaaiR 0 )(l-1,1-N3)2]n, while SCN
gives complex
ion pair [Hg(RaaiR 0 )4]2+ [Hg(SCN)4]2
. Detail spectral
and structural studies are reported in this work.
2. Experimental
2.1. Materials
Imidazole was purchased from Aldrich. Hg(OAc)2,
NaN3, and NH4SCN were obtained from Loba Chemi-
cals, Bombay, India. All other chemicals and solvents
were reagent grade and used as received. 1-Alkyl-2-(ary-
lazo)imidazole (RaaiR 0 ) were prepared by reported pro-
cedure [13].
2.2. Physical measurements
Microanalytical (C, H, N) data were obtained from a
Perkin–Elmer 2400 CHNS/O elemental analyser. Spec-
troscopic data were obtained using the following instru-
ments: UV–Vis, JASCO UV/Vis/NIR Model V-570; IR
(KBr disk, 4000–200 cm
1), JASCO FT-IR Model 420
spectrophotometer, and 1H NMR, Bruker 300 MHz
FT-NMR spectrometer.
2.3. Synthesis of [Hg(HaaiEt)(N3)2]n (4a)
1-Ethyl-2-(phenylazo)imidazole (0.2 g, 1 mmol) in
MeOH (20 ml) was added dropwise to a stirred methan-
olic solution (20 ml) of Hg(OAc)2 (0.32 g, 1 mmol) at
room temperature. NaN3 (0.28 g, 4.4 mmol) was added
to the brownish-orange solution. The colour was chan-
ged to red-orange. The solution was filtered and left
undisturbed for 2 weeks. Bright red-orange crystals were
obtained by slow evaporation process. The crystals were
collected by filtration, washed with cold water–methanol
(1:1, v/v) and dried over CaCl2 in vacuo. The yield was
0.3 g (64%). The microanalytical data of the complex are
as follows, [Hg(HaaiEt)(l-1,1-N3)2]n (4a): Anal. Calc.
for C11H12N10Hg: C, 27.24; H, 2.49; N, 28.88. Found:
C, 27.11; H, 2.40; N, 28.83%.
All other complexes were prepared by the same pro-
cedure. In all cases, crystalline products were obtained.
The yield varied from 60% to 75% and microanalytical
data of the complexes are as follows.
[Hg(HaaiMe)(l-1,1-N3)2]n (3a): Anal. Calc. for
C10H10N10Hg: C, 25.50; H, 2.14; N, 29.74. Found: C,
25.34; H, 2.00; N, 29.90%. [Hg(MeaaiMe)(l-1,1-N3)2]n
(3b): Anal. Calc. for C11H12N10Hg1: C, 27.24; H, 2.49;
N, 28.88. Found: C, 27.10; H, 2.38; N, 28.72%.
[Hg(MeaaiEt)(l-1,1-N3)2]n (4b): Anal. Calc. for
C12H14N10Hg: C, 28.88; H, 2.81; N, 28.07. Found: C,
28.73; H, 2.85; N, 28.16%.
2.4. Synthesis of [Hg(HaaiEt)4][Hg(SCN)4] (6a)
Ammonium thiocyanate (0.32 g, 4.2 mmol) in MeOH
(20 ml) was added dropwise to a stirred mixture of
Hg(OAc)2 (0.32 g, 1 mmol) and 1-ethyl-2-(pheny-
lazo)imidazole (0.2 g, 1 mmol) in MeOH (15 ml) at
room temperature. The colour was red-orange. The
solution was filtered and left undisturbed for 2 weeks.
The bright red-orange crystals were obtained by slow
evaporation process. The crystals were collected by fil-
tration, washed with cold water–methanol (1:1, v/v)
and dried over CaCl2 in vacuo. The yield was 0.5 g
(70%). The microanalytical data of the complex is as fol-
lows, [Hg(HaaiEt)4][Hg(SCN)4] (6a): Anal. Calc. for
C48H48N20S4Hg2: C, 40.19; H, 3.35; N, 19.54. Found:
C, 40.26; H, 3.33; N, 19.49%.
All other complexes were prepared by the same pro-
cedure. In all cases, crystalline products were obtained.
The yield varied from 65% to 75% and microanalytical
data of the complexes are as follows.
[Hg(HaaiMe)4][Hg(SCN)4] (5a): Anal. Calc. for
C44H40N20S4Hg2: C, 38.33; H, 2.90; N, 20.33. Found:
C, 38.27; H, 2.82; N, 20.15%. [Hg(MeaaiMe)4][Hg
(SCN)4] (5b): Anal. Calc. for C48H48N20S4Hg2: C,
40.19; H, 3.35; N, 19.54. Found: C, 40.03; H, 3.35; N,
19.42%. [Hg(MeaaiEt)4][Hg(SCN)4] (6b): Anal. Calc.
for C52H56N20S4Hg2: C, 41.90; H, 3.76; N, 18.79.
Found: C, 41.80; H, 3.84; N, 18.70%.
2.5. X-ray crystal structure analyses
Suitable single crystals of the complexes 4a and6a
were mounted on a Siemens CCD X-ray diffractometer
equipped with graphite monochromated Mo Ka
(k = 0.71073 Å) radiation. The crystallographic data
are listed in Table 1. The unit cell parameters and crys-
tal-orientation matrices were determined for two com-
plexes by least squares refinements setting angles with
2h in the range 3–56 and hkl range 8 P h P
9,
29 P k P
13, 12 P l P
11 for 4a and 20 P
h P
20, 16 P k P
30, 20 P l P
20 for 6a. The
intensity data were corrected for Lorentz and polarisa-
tion effects and an empirical absorption correction was
also employed using the SAINT program for complexes.
During refinement, it was observed that C(3) and C(4) in
N(1)–C(3)H2C(4)H3 of 4a were disordered over two
positions with 50% occupancy. All these structures were
solved by direct methods and followed by successive
Fourier and difference Fourier syntheses. Full-matrix
least-squares refinements on F 2o were carried out using
SHELXL -97 [24]with anisotropic displacement parame-
ters for all non-hydrogen atoms. Hydrogen atoms were
constrained to ride on the respective carbon or nitrogen
atoms with an isotropic displacement parameters equal
to 1.2 times the equivalent isotropic displacement of
their parent atom in all cases. In the final difference Fou-
 B.G. Chand et al. / Inorganica Chimica Acta 358 (2005) 1927–1933 1929

Table 1
Summarised crystallographic data for [Hg(HaaiEt)(l-1,1-N3)2]n (4a) and [Hg(HaaiEt)4][Hg(SCN)4] (6a)
[Hg(HaaiEt)(l-1,1-N3)2]n (4a) [Hg(HaaiEt)4][Hg(SCN)4] (6a)
Empirical formula C11H12N10Hg C48H48N20S4Hg2
Formula weight 484.90 1434.48
T (K) 295(2) 293(2)
Crystal system monoclinic orthorhombic
Space group P21/n Pna21
Crystal size (mm)3 0.28 · 0.20 · 0.18 0.50 · 0.45 · 0.38
Unit cell dimensions
a (Å) 7.1144(7) 15.7015(7)
b (Å) 22.386(2) 23.7769(11)
c (Å) 9.3308(9) 15.1804(7)
b () 93.818(2) 90
V (Å3) 1482.8(2) 5667.3(4)
Z 4 4
k (Å) 0.71073 0.71073
l (Mo Ka) (mm
1) 10.394 5.611
qcalc (mg m
3) 2.172 1.681
Reflection collected 8726 9908
Unique data (Rint) 3320 (0.0424) 9908 (0.0678)
Observed data 2345 5826
Refinement parameters 219 667
R1a [I > 2r(I)] 0.0335 0.0492
wR2b (all data) 0.0753 0.1056
Goodness-of-fit 0.959 0.908
a P P
R1 = |F Po
F c|/ F o . P
b
wR2 ¼ ½ wðF 2o
F 2c Þ= wF 4o 1=2 are general but w are different, w ¼ 1=½r2 ðF 2o Þ þ ð0:0366P Þ2  where P ¼ ðF 2o þ 2F 2c Þ=3 for 4a and
2
w ¼ 1=½r ðF o Þ þ ð0:0548P Þ  for 6a where P ¼ ðF 2o þ 2F 2c Þ=3.
2 2

rier maps, the residual maximum and minimum were HgðOAcÞ2 þ RaaiR0 þ nNH4 SCN
1.746 and
0.946 e Å
3 for 4a, and 1.795 and
1.065 ðn>4Þ

e Å
3 for 6a. All calculations were carried out using
SHELXS -97 [25], PLATON -99 [26], and ORTEP -3 [27]
programs.
3. Result and discussion
3.1. Synthesis and formulation
Ligands used are 1-alkyl-2-(arylazo)imidazole
[RaaiR 0 , where R = H (a), Me (b); R 0 = Me (1), Et
(2)], they are unsymmetrical N,N 0 -bidentate chelator
[13–17] where N and N 0 refer to N(imidazole) and
N(azo) donor centres, respectively. It can also act as a
monodentate ligand through N(imidazole) binding with
the metal ion [18,21]. Under the same reaction condition
(solvent, temperature and composition) and metal–
ligand–pseudohalide ratio, these two types of com-
pounds, polynuclear l-(1,1) (EO) azido bridged
bischelated [Hg(RaaiR 0 ){(l-1,1)N3}2]n (3, 4) and mono-
nuclear ion pair [Hg(RaaiR 0 )4][Hg(SCN)4] (5, 6), have
been isolated.
HgðOAcÞ2 þ RaaiR0 þ nNaN3
ðn>4Þ
MeOH 1
! ½HgðRaaiR0 Þfðl-1; 1ÞN3 g2 n
298 K 2
3=4
MeOH
! ½HgðRaaiR0 Þ4 ½HgðSCNÞ4  ð3Þ
298 K 5=6
The complexes 3, 4 have been prepared by mixing
Hg(OAc)2, RaaiR 0 and NaN3 in 1:1:excess (>4 mol) mole
proportion in MeOH (Eq. (2)). When similar reaction is
carried out using NH4SCN, ion pair complexes of the type
[Hg(RaaiR 0 )4][Hg(SCN)4] (5, 6) are obtained. This may
be due to the greater affinity of Hg(II) towards the S-
donor centre of SCN
ion and the symbiotic effect makes
[Hg(SCN)4]2
ionic species. On the other hand, the coor-
dination of one RaaiR 0 to Hg(II) enhances further coordi-
nation of RaaiR 0 giving tetrahedral [Hg(RaaiR 0 )4]2+. The
formation of Hg(RaaiR 0 )2 (SCN)2 has not been ruled out,
which upon ligand distribution between two moles may
prepare [Hg(RaaiR 0 )4][Hg(SCN)4]. In both cases, the
complexes are isolated from the reaction mixture on slow
evaporation under ambient condition. The azido com-
plexes are non-electrolyte but thiocyanato complexes
are 1:1 electrolyte in MeCN. Microanalytical data sup-
port the composition of complexes and the structures
are established by the single-crystal X-ray diffraction
study in representative cases.
3.2. Spectral studies
ð2Þ IR bands were assigned on comparing with free
ligand data [28]. Most significant observation in 3 and
1930
4 is the appearance of very strong band in the range of
2030–2060 cm
1 corresponding to mas(N3). The bridging
nature of N3
is assigned by weak doublet splitting pat-
tern of this band [1,13]. The strong sharp single stretch-
ing at 2111–2115 cm
1 is due to m(SCN
) in the infrared
spectra of 5, 6. This band confirms the thiocyanato-S
coordination with the mercury atom [1,11]. Moderately
intense stretching at 1595–1600 and 1435–1445 cm
1 is
due to m(C@N) and m(N@N), respectively, for both types
of complexes.
Very low solubility of 3 and 4 in methanol has ruled
out to carry out solution spectral studies. However, they
are soluble in CHCl3 and spectra are recorded in this
solvent. Solution electronic spectra of 5, 6 were recorded
in methanol solution in the wavelength range 250–900
nm. There are three bands and out of them two are high
intense (e  104 mol
1 dm3 cm
1) band at 350–360 and
370–380 nm. On comparing with free ligand spectra
[29], we may conclude that these bands are due to intra-
molecular charge transfer transitions. A weak band
(e  103 mol
1 dm3 cm
1) appears at 440–455 nm. This
may be due to MLCT transition from
Hg(II) ! p*(azoimine).
The 1H NMR spectra of [Hg(RaaiR 0 ){(l-1,1)N3}2]n
(3, 4) and [Hg(RaaiR 0 )4][Hg(SCN)4] (5, 6) are recorded
in CDCl3. The NMR signals have been assigned to indi-
vidual protons in the complexes on comparing with the
free ligand values, Hg(RaaiR 0 )Cl2 [29] and on looking
into the spin-spin interaction to each proton. The atom
numbering pattern is shown in Scheme 1. Data reveal
that the signals in the spectra of the complexes are
shifted to downfield side relative to free ligand values.
This supports the coordination of ligand to Hg(II).
There is no significant difference in the chemical shift
data of azido complex 3, 4 and thiocyanato derivatives
5, 6. Important feature of the spectra is the shifting of
imidazole protons 4-H and 5-H to lower d-values, in
general, relative to aryl protons (7-H–11-H). Imidazole
protons suffer downfield shifting by 0.3–0.4 ppm com-
pared to the free ligand position. This supports the
strong preference of imidazole-N to Hg(II). This prop-
erty has been used to remove mercury from polluted
water passing through azoimidazole resin [30,31]. Aryl
signals shift to the lower field side on Me– substitution
5
N
4 N
N N
N N
R' N
Hg
N N'
N' N
N
N
N
N N N NN
N N
11 7 N'
10 8
9 5/6
R 3/4
1/2
Scheme 1. R = H (a), Me (b); R 0 = Me (1/3/5), Et (2/4/6).
B.G. Chand et al. / Inorganica Chimica Acta 358 (2005) 1927–1933
to the aryl ring. This is due to electron donating effect
of the Me– group.
The 13C NMR spectra of RaaiR 0 and
[Hg(RaaiR 0 )(N3)2]n are recorded in CDCl3. Low solubil-
ity of [Hg(RaaiR 0 )4][Hg(SCN)4] in the same solvent has
prevented to run their 13C NMR spectra. The assign-
ment has been made on comparing the spectra of free li-
gands, complexes and following the intensity of lines.
The DEFT study has also distinguished the primary
(1), secondary (2), tertiary (3) and quaternary (4)
C-centres. There are two 4 C-centres (C-2, C-6) and se-
ven 2 C-centres (C-4, C-5, C-7, C-8, C-9, C-10, and C-
11) in 3a and 4a; in 3b and 4b three 4 C-centres (C-2,
C-6, C-9) and six 2 C-centres (C-4, C-5, C-7, C-8, C-
10, and C-11) are present. The resonances for aromatic
carbons usually appear within the range of 130–160
ppm. The 1-R group resonates at low d value, 45–80
ppm. Data reveal (see Section 2) that resonances are
shifted to higher d value on going from free ligand to
Hg-compounds. This may be due to charge drifting by
Hg(II) from coordinated ligand. The 1-R has little influ-
ence on the aryl C-centre resonances. Some of the 13C
NMR data are either same or very closely spaced, which
reflect their resemblances in chemical and electronic
environment.
3.3. Molecular structure
The crystals of complexes 4a and 6a were grown by
slow evaporation of the reaction mixture in methanol
under ambient condition for a week.
3.3.1. [Hg(HaaiEt){(l-1,1)N3}]n (4a)
Monomeric unit of 1D chain of the complex 4a is
shown in Fig. 1 and the bond parameters are listed in
Table 2. The structure shows an end-on (l-1,1-N3) azido
bridged Hg-HaaiEt polymer. The Hg is sitting in a dis-
torted octahedral environment with HgN6 coordination;
four N-centres are coming from bridged four-N3 and
two-N donor centres, N(imidazole), N(azo) are coming
from chelated HaaiEt unit. The unsymmetrical nature
of the ligand is reflected from the Hg–N bond distance
data in the chelated structure: the Hg–N(imidazole),
2.394(6) Å is shorter than Hg–N(azo), 2.783(5) Å length.
The distortion may be originated from small chelate an-
gle \N(7)–Hg–N(10), 63.29(18) and long Hg–N(azo)
N'
2+ distance. In the HgN6 coordination, four azido-Ns are
N bridged in pairs with adjacent Hg(II) centres on either
Hg side of the central unit. There are two Hg2N2 bridging
N
N
N units. They are distinguished in terms of their bond
N'
parameters. Bridged angles are 90.57(19) and
108.7(2) (symmetry: 1
x, 2
y, 1
z); 91.64(19)
and 104.2(2) (symmetry:
x, 2
y, 1
z). The Hg–N
distances in Hg2N2 bridge unit are 2.855 Å (symmetry:
1
x, 2
y, 1
z) and 2.822 Å (symmetry:
x, 2
y,
1
z). Two neighbouring Hg centres are in angular
 B.G. Chand et al. / Inorganica Chimica Acta 358 (2005) 1927–1933 1931

Å, which is slightly elongated than that of free ligand va-

lue [19]. The Hg–N(azo) (Hg–N(10) 2.783(5) Å) is longer
than Hg–N(imidazole) (Hg–N(7), 2.394(6) Å). The cov-
alency of the Hg–N(azo) is doubtless because it is less
than the sum of van der Waals radii of N(azo) and
Hg(II) [32]. However, the short Hg–N(imidazole) bond
length compared to Hg–N(azo) distance is in support
of preferential interaction of Hg(II) with N(imidazole).
Mercury(II) is one of the heavy metals exhibiting very
high biochemical toxicity and carcinogenicity due to
its binding to –SH group to a class of thiol proteins
[33]. Imidazole is present as such in most of the biomo-
lecular nucleic acids, proteins, DNA and the preferential
binding of Hg(II) to imidazole–N may be the reason for
very high toxic efficiency of mercury(II). The azido N–N
distances lie between 1.15 and 1.20 Å. The \N–N–N is
slightly deviated from linearity (av. 176.2). The 1D neu-
tral chain is running by repeating Hg2N2 unit. The pen-
dant phenyl ring of each chelated HaaiEt in the 1D

Fig. 1. Monomeric unit of 1D chain of [Hg(HaaiEt)(l-1,1-N3)2]n (4a)

with 30% probability for ellipsoids.

Table 2
Bond distance (Å) and bond angle () of [Hg(HaaiEt)(l-1,1-N3)2]n (4a)
Bond distance (Å) Bond angle ()
Hg–N(1) 2.140(5) N(1)–Hg–N(4) 144.0(2)
Hg–N(4) 2.179(5) N(1)–Hg–N(7) 119.92(18)
Hg–N(7) 2.394(5) N(4)–Hg–N(7) 92.31(19)
Hg–N(10) 2.783(5) N(1)–Hg–N(10) 89.17(18)
N(9)–N(10) 1.260(7) N(7)–Hg–N(10) 63.29(18)
N(1)–N(2) 1.179(8) N(4)–Hg–N(10) 121.91(19)
N(2)–N(3) 1.166(8) N(1)–N(2)–N(3) 175.9(7)
N(4)–N(5) 1.204(7) N(4)–N(5)–N(6) 176.5(6)
N(5)–N(6) 1.148(8) N(2)–N(1)–Hg 117.6(4)
Hg–N(4_c)a 2.855(5) N(5)–N(4)–Hg 113.8(4)
Hg–N(1_c)b 2.822(5) N(1)–Hg–N(1)b 75.8(2)
Fig. 2. Supramolecular sheet generated by p  p interaction of
Hg  Hg(_3) 3.936(6) N(4)–Hg–N(1)b 91.64(18)
aromatic rings running in a 1D chain of 4a.
N(7)–Hg–N(1)b 86.77(18)
N(10)–Hg–N(1)b 133.84(15)
N(1)–Hg–N(4)a 90.57(19)
N(4)–Hg–N(4)a 71.3(2)
N(7)–Hg–N(4)a 139.24(18)
N(10)–Hg–N(4)a 93.49(16)
N(1)b–Hg–N(4)a 129.31(17)
Hg–N(4)a–Hga 108.7(2)
a
Symmetry: 1
x, 2
y, 1
z.
b
Symmetry:
x, 2
y, 1
z.

arrangement with the central Hg and make 124.2(5)

and the intermolecular Hg  Hg distance is 3.93(6) Å.
Each chelating ligand, HaaiEt, about Hg in the bridged
dimer is oriented in such a fashion that two N(azo) cen-
tres are either coming closer or away from each other.
The distorted HgN6 coordination is exhibited by six
non-equivalent Hg–N bond distances (Table 2). The Fig. 3. Perspective view of [Hg(HaaiEt)4][Hg(SCN)4] (6a) with 30%
azo N@N bond length in chelated HaaiEt is 1.262(7) probability for ellipsoids.
1932 B.G. Chand et al. / Inorganica Chimica Acta 358 (2005) 1927–1933

Table 3
Bond distance (Å) and bond angle () of [Hg(HaaiEt)4][Hg(SCN)4] (6a)
Bond distance (Å) Bond angle ()
Hg(2)–S(1) 2.560(4) S(1)–Hg(2)–S(2) 98.26(18)
Hg(2)–S(2) 2.532(3) S(1)–Hg(2)–S(3) 114.34(16)
Hg(2)–S(3) 2.518(3) S(1)–Hg(2)–S(4) 110.21(15)
Hg(2)–S(4) 2.554(4) S(2)–Hg(2)–S(3) 113.72(14)
Hg(1)–N(1C) 2.261(7) S(2)–Hg(2)–S(4) 109.69(17)
Hg(1)–N(1A) 2.239(8) S(3)–Hg(2)–S(4) 110.08(15)
Hg(1)–N(1B) 2.288(8) N(1A)–Hg(1)–N(1D) 99.4(3)
Hg(1)–N(1D) 2.262(7) N(1A)–Hg(1)–N(1B) 130.4(3)
N(1A)–C(3A) 1.317(12) N(1A)–Hg(1)–N(1C) 96.2(3)
N(1B)–C(3B) 1.343(12) N(1C)–Hg(1)–N(1D) 132.5(3)
N(1C)–C(3C) 1.304(12) N(1B)–Hg(1)–N(1C) 95.9(3)
N(1D)–C(3D) 1.358(13) N(1B)–Hg(1)–N(1D) 106.9(3)
N(3A)–N(4A) 1.263(10) Hg(1)–N(1A)–C(3A) 125.7(6)
N(3B)–N(4B) 1.255(13) Hg(1)–N(1B)–C(3B) 126.3(7)
N(3C)–N(4C) 1.244(10) Hg(1)–N(1C)–C(3C) 128.0(7)
N(3D)–N(4D) 1.274(10) Hg(1)–N(1D)–C(3D) 125.4(7)
N(1)–C(1) 1.122(15) N(4A)–N(3A)–C(3A) 113.0(8)
N(2)–C(2) 1.14(2) N(4B)–N(3B)–C(3B) 113.8(9)
N(3)–C(3) 1.124(16) N(4C)–N(3C)–C(3C) 112.2(8)
N(4)–C(4) 1.12(2) N(4D)–N(3D)–C(3D) 114.7(8)
C(1)–S(1) 1.651(15) S(1)–C(1)–N(1) 172.8(15)
C(2)–S(2) 1.54(2) S(2)–C(2)–N(2) 177.4(18)
C(3)–S(3) 1.695(17) S(3)–C(3)–N(3) 176.0(15)
C(4)–S(4) 1.66(2) S(4)–C(4)–N(4) 174(2)

D–H  A d(D–H) (Å) d(H  A) (Å) d(D  A) (Å) \(DHA) ()
Hydrogen-bonds
C(1C)–H(1C)  N(1) 0.93 2.534 3.412(19) 157.67
C(2D)–H(2D)  N(3)i 0.93 2.626 3.443(18) 147.18
C(10A)–H(10A)  N(3A) 0.97 2.513 2.942(15) 106.68
Line missing

chain of alternate molecular fragment, Hg(HaaiEt), pen-
etrates into the groove of neighbouring 1D chain. This
ascertains a p  p interaction with pendant phenyl rings
and imidazole groups. Although the interaction is weak
(>4 Å) but disposition of rings warrant to consider that
the arrangement is a 2D network (Fig. 2).
3.3.2. [Hg(HaaiEt)4][Hg(SCN)4] (6a)
The structure of the complex, 6a is shown in Fig. 3
and the bond parameters are listed in Table 3. Each dis-
crete molecular unit consists of tetrahedral cationic
complex [Hg(HaaiEt)4]2+ and by four SCN ions in
[Hg(SCN)4]2
. Both the complex ions are asymmetric
in nature as evident from bond length data (Table 3).
In the cationic complex, Hg is sitting at the centre of
asymmetric tetrahedron and is coordinated by imidaz-
ole–N centre of HaaiEt.
Two of the Hg–N distances are closely spaced;
Hg(1)–N(1C), 2.261(7) Å and Hg(1)–N(1D), 2.262(7)
Å. Other two Hg–N distances differ significantly
Hg(1)–N(1A), 2.239(8) Å and Hg(1)–N(1B), 2.288(8)
Å. The Hg–N(imidazole) distances are unequal and lie
in the range 2.239–2.262 Å. The geometry is compressed
along the crystallographic c-axis in such a way that two
of N–Ng–N angles are higher than the tetrahedral angle
with a value of N(1A)–Hg(1)–N(1B), 130.4(3) and
N(1C)–Hg(1)–N(1D), 132.5(3). The N@N distances
are varied from 1.244(10) to 1.274(10) Å. In the counter
complex ion [Hg(SCN)4]2
, the thiocyanate is bonded
through S donor centre which softens the mercury(II)
and may be the reason for not acting as bridging agent
unlike azide. The Hg–S(CN) distances (2.518(3)–
2.560(4) Å) are lying in the range of reported values
[34]. Cadmium, preceding member of Group 12, shows
polymeric interaction with N3
and SCN
[22]. The
limitation of mercury may be due to inclusion of lantha-
nide contraction and some relativistic effect of heavy
metals [23].
4. Conclusion
The work describes structural differences of Hg(II)-
arylazoimidazoles when two different pseudohalides,
N3
and SCN
, are used as counter ions under identical
reaction condition. The azide forms bridged 1D poly-
mer, [Hg(RaaiR 0 )(l-1,1-N3)2]n, while thiocyanate gives
monomeric complex system, [Hg(RaaiR 0 )4][Hg(SCN)4].
 B.G. Chand et al. / Inorganica Chimica Acta 358 (2005) 1927–1933
Both spectroscopic and X-ray structural studies support
the bonding differences.
5. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 224571 for [Hg(HaaiEt)(l-
1)N3{(l-1,1)N3}]2 (4a) and CCDC No. 231712 for
[Hg(HaaiEt)4][Hg(SCN)4] (6a), respectively. Copies of
this information may be obtained free of charge from
the Director, CCDC, 12 Union Road, Cambridge CB2
1FZ, UK.
Acknowledgements
Financial supports (C.S.) from the University Grants
Commission (UGC, Major project and DSA Phase-II),
New Delhi are gratefully acknowledged. One of us
(U.S.R.) also thanks UGC for a fellowship.
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