Preparation and crystal structural study of a novel coordinated polymer [HgI2(4-bped)2] (bped = bis(4-pyridyl)ethylene diamine)

Article abstract of DOI:10.1007/s10870-010-9970-9

A novel coordinated polymer [HgI₂(4-bped)₂] was synthesized through the reaction of bis(4-pyridyl)ethylene diamine and HgI ₂ in mixed MeOH-THF (5:2). The crystal structural analysis indicated that the complex crystallized in a monoclinic space group P2₁/c, a = 10.8392(12), b = 19.841(2), c = 8.8279(10), β = 95.452(2), V = 1889.9(4) A³, Z = 4. The complex possessed a novel three-dimensional supramolecular framework formed by hydrogen bonds among repeating [HgI ₂(4-bped)]₂ dimeric units.

Full text of DOI:10.1007/s10870-010-9970-9

J Chem Crystallogr (2011) 41:763–766
DOI 10.1007/s10870-010-9970-9
ORIGINAL PAPER
Preparation and Crystal Structural Study of a Novel Coordinated
Polymer [HgI (4-bped) ] (bped 5 bis(4-pyridyl)ethylene diamine)
2
2
Yu Liang
Yunyin Niu
•
Fukai Zhao
•
Qingli Wang
•
Received: 13 June 2009 / Accepted: 31 December 2010 / Published online: 21 January 2011
Ó Springer Science+Business Media, LLC 2011
Abstract A novel coordinated polymer [HgI (4-bped) ]
2
noncovalent interactions, such as hydrogen bonding, hal-
2
was synthesized through the reaction of bis(4-pyridyl)
ogen bonding, and p–p interactions [11–14]. It was found
that metallosupramolecule of mercuric iodide presented
the important utility in the fields such as optical detector
and superconducting materials, and the self-assemble of
metallosupramolecule of mercuric iodide had attracted
much attention [15–17]. Recently, some macrocyclic
coordination polymers of mercuric iodide were designed
and constructed with the introduce of the organic nitrogen-
containing heterocyclic bridging ligands [18–23].
ethylene diamine and HgI in mixed MeOH–THF (5:2). The
2
crystal structural analysis indicated that the complex crys-
tallizedin amonoclinic space group P2 /c, a = 10.8392(12),
1
b = 19.841(2), c = 8.8279(10), b = 95.452(2), V =
3
889.9(4) A , Z = 4. The complex possessed a novel three-
˚
1
dimensional supramolecular framework formed by hydro-
gen bonds among repeating [HgI (4-bped)] dimeric units.
2
2
Keywords Coordinated polymer Á Crystal structure Á
In the study, a novel three-dimensional metallosupra-
molecular complex [HgI (4-bped) ] was obtained through
HgI adducts Á Metallamacrocycle
2
2
2
the reaction of bis(4-pyridyl)ethylene diamine and HgI in
2
mixed MeOH–THF (5:2). The crystal structural analysis
indicated that the complex crystallized in a monoclinic
Introduction
space group P2 /c, and was a binuclear metal macrocyclic
1
Metallosupramolecular species with fascinating structures
and topology had become one of the most active areas of
material science and chemical research, because of their
potential applications on magnetism, electrical, conduc-
tivity, ion exchange, separation and catalysis [1–10]. In the
supramolecular compounds, coordination interactions
between metal centers and multidentate organic ligands
formed the primary structure, which could be further
organized to supramolecular frameworks through weak
complex with symmetry of center.
Experimental
General Information and Materials
Iso-Nicotinic acid and Ethylene diamine anhydrous were
obtained from Aldrich Chemical Company. All other
chemicals were of A. R. Grade and used without further
purification. The IR spectrum was recorded on a Shimazu
-
1
IR435 spectrometer as KBr disk (4000–400 cm ).
Y. Liang
College of Chemistry and Chemical Engineering,
Xinxiang University, Xinxiang 453000,
People’s Republic of China
Syntheses of the Ligand Bped
A solution of 0.1 mol ethylene diamine anhydrous (6 g) in
pyridine anhydrous was added to a solution of 0.2 mol iso-
Nicotinic acid (24.6 g) in pyridine anhydrous, and then
2 mL triphenyl phosphate was added to the mixture. The
F. Zhao Á Q. Wang Á Y. Niu (&)
Department of Chemistry, Zhengzhou University,
Zhengzhou 450052, Henan, People’s Republic of China
e-mail: niuyy@zzu.edu.cn
123

7
64
J Chem Crystallogr (2011) 41:763–766
mixture was stirred while heating at reflux for 40 min. The
resultant precipitate was collected by suction filtration,
rinsed with water to remove pyridine and washed with
acetone to remove triphenyl phosphate. The product was
recrystallized from a methanol–water mixture in about
Table 1 Crystal data and structure refinement for [HgI (4-bped) ]
2
2
CCDC deposit no.
Compound
628787
[HgI (4-bped)
14HgI
724.68
Monoclinic
P2 /c
2
2
]
Formula
C
14
H
2 4 2
N O
Formula weight
Crystal system
Space group
7
1% yield.
1
Syntheses of the Complex [HgI (4-bped) ]
2
2
˚
a (A)
10.8392(12)
19.841(2)
8.8279(10)
90
˚
b (A)
A solution of bped (0.1 mmol) in CH OH (5 mL) was added
3
˚
c (A)
to a solution of HgI (45.4 mg, 0.1 mmol) in THF (2 mL).
2
a (°)
b (°)
c (°)
The solution was then filtered and slowly evaporated in a vial
at room temperature. Colorless crystals of the complex were
obtained after approximate 3 days in about 51% yield. IR
95.452(2)
90
3
˚
Volume (A )
1889.9(4)
4
(
KBr): 2942.0(m), 1608.9(vs), 1426.6(s), 1221.5(s),
-
067.3(m), 1010.7(s), 813.7(s), 608.2(m), 514.8(s) cm .
1
Z
1
-
3
)
Calculated density (Mg m
-
2.547
1
)
l (mm
F(000)
11.423
1312
X-ray Crystallography
Crystal size (mm)
Crystal color
0.20 9 0.17 9 0.16
White
Suitable crystals were selected for the structure analysis.
The diffraction data were collected on a Bruker APEX-II
area-detector diffractometer operating at 50 kV and 40 mA
Temperature (K)
297(2)
˚
Wavelength (A)
˚
0.71073
28.25
using MoKa radiation (0.71073 A). Data collection and
2hmax (°)
reduction were performed using the SMART and SAINT
softwares [24]. The structures were solved by direct
methods, and the non-hydrogen atoms were subjected to
anisotropic refinement by full-matrix least squares on F2
using SHELXTXL package [25]. The hydrogen atoms
were generated geometrically and included in structure
factor calculations. Crystal data and refinement details
were summarized in Table 1. Selected bond lengths and
bond angles were listed in Table 2.
Reflections collected
12932
Independent reflections
4477
R
int
0.0355
Data/restraints/parameters
2
Goodness-of-fit on F
4477/0/208
1.036
Final R indices [I [ 2r(I)]
R indices (all data)
R1 = 0.0354, wR2 = 0.0819
R1 = 0.0440, wR2 = 0.0857
0.999 and -1.244
-
3
)
Largest diff. peak and hole (e A
˚
Table 2 Selected geometric parameters (in A and °) for [HgI
2
(4-
Results and Discussion
bped)
2
]
Complex [HgI
2 2
(4-bped) ]
Infrared Spectrum Analysis
Hg(1)–N(4)#1
Hg(1)–N(1)
Hg(1)–I(2)
2.454(4)
2.457(5)
2.6391(5)
2.6425(5)
98.52(6)
100.31(1)
102.42(1)
103.52(1)
100.95(1)
143.52(7)
122.5(4)
119.9(4)
119.9(4)
122.1(4)
The IR spectra of [HgI (4-bped) ]exhibits characteristic
2
2
-
1
strong absorption around 1608 cm
for the carbonyl
-
1
groups, and 1221.5(s)–1010.7 cm belong to the –NH–
Hg(1)–I(1)
groups. The strong bands centered at 813.7, 608.2, and
N(4)#1–Hg(1)–N(1)
N(4)#1–Hg(1)–I(2)
N(1)–Hg(1)–I(2)
-
14.8(s) cm are attributed to the ring of pyridines, and
1
5
-
the moderate bands at 2942.0 and 1426.6 cm is attrib-
1
uted to –CH – in the title compound.
2
N(4)#1–Hg(1)–I(1)
N(1)–Hg(1)–I(1)
Crystal Structure of the Complex [HgI (4-bped) ]
2
2
I(2)–Hg(1)–I(1)
C(1)–N(1)–Hg(1)
C(5)–N(1)–Hg(1)
C(14)–N(4)–Hg(1)#1
C(10)–N(4)–Hg(1)#1
Single crystal X-ray diffraction analysis revealed that the
complex was a novel neutral binuclear metallamacrocycle
with a crystallographic center of symmetry. As was shown
in the Fig. 1, the binuclear metallamacrocycle was com-
posed of two Hg(II) ions, two bridging 4-bped ligands and
Symmetry for compound: #1 -x ? 1, -y, -z ? 1
1
23

J Chem Crystallogr (2011) 41:763–766
765
Fig. 2 Three-dimensional supramolecular framework of complex
2
[HgI (4-bped)
lines
2
] with CHÁÁÁO, CHÁÁÁI interaction indicated by dotted
Fig. 1 The ORTEP diagram (50% probability ellipsoids) showing the
binuclear metallamacrocycle of the complex [HgI
hydrogen atoms were omitted for clarity
C–HÁÁÁI(O) inducing contacts, the repeating [HgI (4-
2
(4-bped)
2
] 1. The
2
bped) ] dimeric units grow infinitely in the a, b, c direc-
2
2
tions, and then a final supramolecular structure was built
Fig. 2). Indeed all these intermolecular interactions are
(
Table 3 D–HÁÁÁA interactions and their distance and angle parame-
weak, which can be proved that this binuclear complex
become melting state at 140 °C, and begin continuous
decomposition at 162 °C. The melting/decomposition
temperatures are comparable to the related mononuclear
Hg complex [27].
2 2
ters for the complex [HgI (4-bped) ]
˚
˚
D–HÁÁÁA interaction
D
DÁÁÁA (A)
D
HÁÁÁA (A)
\DHA (°)
C(11)–H(11A)ÁÁÁO(1)
C(8)–H(8B)ÁÁÁO(2)
C(8)–H(8A)ÁÁÁI(2)
3.661
3.410
3.968
2.707
2.577
3.177
167.90
149.36
139.86
Supplemental Material
four terminal I anions. The distorted tetrahedral coordina-
tion center Hg(II) was bound to two iodide atoms and two
N-donors from 4-bped ligands, and the Hg1–I1, Hg1–I2,
Hg1–N1 and Hg1–N4 bond lengths were 2.6425(5),
CCDC-628787 contains the supplementary crystallo-
graphic data for this article. These data can be obtained free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or
from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; Fax: ?44-1223-
336033; E-mail:deposit@ccdc.cam.ac.uk].
˚
.6391(5), 2.457(5) and 2.454(4) A, respectively, which
2
were similar to those of the related polymers [HgI (L)]
2
n
˚
Hg–I ranging from 2.6377(0) to 2.7125(8) A and Hg–N
(
˚
from 2.3626(6) to 2.5917(0) A) [26–29]. Additionally, the
angles around Hg center ranged from 98.52(6) to
Acknowledgment We gratefully acknowledge the financial support
of The National Science Foundation of China (20671083).
143.52(7)°. Two bridging 4-bped ligands and two Hg
atoms consisted of an interesting, ring-like structure unit
˚
with dimensions of 13.0255 9 12.7413 A (Hg1–Hg1 9
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