Synthesis, crystal structure, and characterization of a novel coordinated polymer [HgI2L]2 [L = ethanediyl bis(isonicotinate)]

Article abstract of DOI:10.1080/15533174.2011.591336

A novel coordinated polymer [HgI₂L]₂ was synthesized through the reaction of ethanediyl bis(isonicotinate) and HgI₂ in mixed MeOH-THF (5:2). The crystal structural analysis indicated that the complex crystallized in the monoclinic space group P2₁/c, a= 10.8575(10), b = 19.8946(19), c = 8.8408(8), = 95.4690(10), V = 1901.0(3) 3, Z = 4. The complex possessed a novel three-dimensional supramolecular framework formed by hydrogen bonds among repeating [HgI₂L]₂ dimeric units. Its decomposition process is very simple, and decomposition with an apparently endothermal process takes place at the same time. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.591336

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Synthesis, Crystal Structure, and Characterization of
a Novel Coordinated Polymer [HgI2L]2 [L = Ethanediyl
bis(isonicotinate)]
Hong-Mei Wang a , Mei Liu b , Qing-Li Wang a & Yun-Yin Niu a
a Department of Chemistry , Zhengzhou University , Zhengzhou, P. R. China
b Physical, Chemical and Biological Department , Henan Jiaozuo Teacher's College ,
Jiaozuo, P. R. China
Published online: 04 Oct 2011.
To cite this article: Hong-Mei Wang , Mei Liu , Qing-Li Wang & Yun-Yin Niu (2011) Synthesis, Crystal Structure, and
Characterization of a Novel Coordinated Polymer [HgI2L]2 [L = Ethanediyl bis(isonicotinate)], Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:8, 1014-1017, DOI: 10.1080/15533174.2011.591336
To link to this article: http://dx.doi.org/10.1080/15533174.2011.591336
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:1014–1017, 2011
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.591336
Synthesis, Crystal Structure, and Characterization
of a Novel Coordinated Polymer [HgI2L]2 [L = Ethanediyl
bis(isonicotinate)]
Hong-Mei Wang,1 Mei Liu,2 Qing-Li Wang,1 and Yun-Yin Niu1
1Department of Chemistry, Zhengzhou University, Zhengzhou, P. R. China
2Physical, Chemical and Biological Department, Henan Jiaozuo Teacher’s College, Jiaozuo, P. R. China
In this study, a novel three-dimensional metallosupramolec-
ular complex [HgI2L]2 was obtained through the reaction of
ethanediyl bis(isonicotinate) and HgI2 in mixed MeOH-THF
(5:2). The crystal structural analysis indicated that the complex
crystallized in the monoclinic space group P21/c and was a bin-
uclear metal macrocyclic complex with center of symmetry. Its
decomposition process is very simple, and decomposition with
A novel coordinated polymer [HgI2L]2 was synthesized through
the reaction of ethanediyl bis(isonicotinate) and HgI2 in mixed
MeOH–THF (5:2). The crystal structural analysis indicated that
the complex crystallized in the monoclinic space group P21/c, a =
10.8575(10), b = 19.8946(19), c = 8.8408(8), β = 95.4690(10),
V = 1901.0(3) Å3, Z = 4. The complex possessed a novel
three-dimensional supramolecular framework formed by hydro-
gen bonds among repeating [HgI2L]2 dimeric units. Its decomposi- an apparent absorption process takes place at the same time.
tion process is very simple, and decomposition with an apparently
endothermal process takes place at the same time.
EXPERIMENTAL
Keywords coordinated polymer, HgI2 adducts, metallamacrocycle,
General Information and Materials
crystal structure, thermogravimetric analysis
Iso-nicotinic acid and anhydrous ethanediol were obtained
from Aldrich Chemical Company. All other chemicals were of
analytical reagent grade and used without further purification.
The infrared (IR) spectrum was recorded on a Shimazu IR435
spectrometer as KBr disk (4000–400 cm−1).
INTRODUCTION
Metallosupramolecular species with fascinating structures
and topology have become one of the most active areas of
material science and chemical research, because of their po-
tential applications on magnetism, electrical, conductivity, ion Syntheses of the Ligand L
exchange, separation, and catalysis.[1–3] In the supramolecular
The ligand L is obtained by the simple reaction of heating
the isonicotinic acid chloride with ethanediol.[15]
compounds, coordination interactions between metal centers
and multidentate organic ligands formed the primary structure,
which could be further organized to supramolecular frame-
works through weak noncovalent interactions, such as hydro-
gen bonding, halogen bonding, and π–π interactions.[4,5] It was
found that the metallosupramolecule of mercuric iodide pre-
sented important utility in fields such as optical detection and
superconducting materials, and the self-assembly of the metallo-
supramolecule of mercuric iodide attracted much attention.[6–8]
Recently, some macrocyclic coordination polymers of mercuric
iodide were designed and constructed with the introduce of the
organic nitrogen-containing heterocyclic bridging ligands.[9–14]
Syntheses of the Complex [HgI2L]2
A solution of L (0.1 mmol) in CH3OH (5 ml) was added to
a solution of HgI2 (45.4 mg, 0.1 mmol) in THF (2 ml). The so-
lution was then filtered and slowly evaporated in a vial at room
temperature. Colorless crystals of the complex were obtained
after approximately 3 days in about 51% yield. Analysis cal-
culated for [HgI2L]2: C, 23.12; H, 1.65; N, 3.85%. Found: C,
23.15; H, 1.67; N, 3.89%.
X-Ray Crystallography
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 using
MoKα radiation (0.071–0.073 nm). Data collection and reduc-
tion were performed using the SMART and SAINT software.[16]
The structures were solved by direct methods, and the non-
hydrogen atoms were subjected to anisotropic refinement by
Received 22 February 2011; accepted 1 March 2011.
The authors gratefully acknowledge the financial support of the
National Science Foundation of China (number 20671083).
Address correspondence to Yun-Yin Niu, Department of Chem-
istry, Zhengzhou University, Zhengzhou 450052, P. R. China. E-mail:
niuyy@zzu.edu.cn
1014

NOVEL COORDINATED POLYMER [HgI2L]2
1015
TABLE 1
Crystallographic data and structural refinement for compound
[HgI2L]2
Empirical formula
C14H12Hg I2N2O4
726.65
Formula weight
Crystal system
Monoclinic
Space group
P2(1)/c
Crystal size(mm)
a, Å
0.31 × 0.29 × 0.18
10.8575(10)
b, Å
19.8946(19)
c, Å
8.8408(8)
90
95.4690(10)
90
1901.0(3)
2.539
4
α, ◦
ß, ◦
γ , ◦
V, Å3
Dc, mg·cm−3
Z
FIG. 1. The binuclear metallamacrocycle of the complex [HgI2L]2. The hy-
drogen atoms are not displayed, for clarity.
µ, mm−1
11.362
Reflections collected/unique
R(int)
14334/3531
0.0249
RESULTS AND DISCUSSION
Final R indices
R indices (all data)
Goodness-of-fit on F2
R1 = 0.0218, wR2 = 0.0425
Crystal Structure of the Complex [HgI2L]2
R1 = 0.0276, wR2 = 0.0443
Single-crystal x-ray diffraction analysis revealed that the
complex was a novel neutral binuclear metallamacrocycle with
a crystallographic center of symmetry. As shown in Figure 1, the
binuclear metallamacrocycle was composed of two Hg(II) ions,
two bridging L ligands, and four terminal I anions. The distorted
tetrahedral coordination center Hg(II) was bound to two iodide
atoms and two N-donors from two L ligands, and the Hg1–I1,
Hg1–I2, Hg1–N1, and Hg1–N2 bond lengths were 2.6462(4),
2.6498(4), 2.462(4), and 2.455(3) Å, respectively, which were
similar to those of the related polymers [HgI2(4-bped)]2 (Hg–I
ranging from 2.6425(5) to 2.6391(5) Å and Hg–N from 2.457(5)
to 2.454(4) Å). Additionally, the angles around Hg center ranged
from 98.67(12) to 143.539(14)◦. Two bridging L ligands and two
1.014
0.721, –0.816
1312
Largest peak, hole (e· Å−3
)
F(000)
Temperature, K
291(2) K
aR1 = ꢁFo| −|Fcꢁ/|Fo|.
bwR2 = [w(Fo2 – Fc2)2/w(Fo2)2]1/2
.
full-matrix least squares on F2 using the SHELXTXL pack-
age.[17] The hydrogen atoms were generated geometrically and
included in structure factor calculations. Crystal data and refine-
ment details were summarized in Table 1. Selected bond lengths
and bond angles were listed in Table 2.
TABLE 2
Selected bond lengths (Å) and angles (◦) for compound [HgI2L]2
Hg(1)–N(1)
Hg(1)–N(2)#1
Hg(1)–I(1)
Hg(1)–I(2)
O(1)–C(6)
2.462 (4)
2.455 (3)
2.6462 (4)
2.6498 (4)
1.197 (5)
O(3)–C(9)
O(3)–C(8)
O(4)–C(9)
N(1)–C(5)
N(1)–C(1)
N(2)–C(12)
N(2)–C(13)
1.339 (5)
1.450 (5)
1.193 (5)
1.328 (5)
1.336 (5)
1.329 (5)
1.329 (5)
O(2)–C(6)
O(2)–C(7)
1.321 (5)
1.445 (5)
N(1)–Hg(1)–I(1)
N(1)–Hg(1)–I(2)
N(2)#1—Hg(1)–N(1)
N(2)#1—Hg(1)–I(1)
N(2)–Hg(1)–I(2)
I(1)–Hg(1)–I(2)
C(6)–O(2)–C(7)
102.55 (8)
100.76 (8)
98.67 (12)
100.27 (8)
103.48 (8)
143.539 (14)
116.5 (3)
C(9)–O(3)–C(8)
C(5)–N(1)–C(1)
C(1)–N(1)–Hg(1)
C(5)–N(1)–Hg(1)
C(12)–N(2)–C(13)
C(12)–N(2)–Hg(1)#1
C(13)–N(2)–Hg(1)#1
116.6 (3)
117.5 (4)
119.8 (3)
122.5 (3)
117.7 (4)
122.3 (3)
120.0 (3)
Symmetry transformations used to generate equivalent atoms: #1, –x + 1, –y + 2, –z + 1.

1016
H.-M. WANG ET AL.
TABLE 3
Indeed, all these intermolecular interactions are weak, we can’t
deny, but they may make this binuclear complex increase its
melting point and become stable.
D–H···A interactions and their distances and angles parameters
for the compound [HgI2L]2
D–H···A interaction
C(11)–H(11A)···O(1)
C(8)–H(8B)···O(4)
C(8)–H(8A)···I(1)
D D···A (Å) D H···A (Å) ∠DHA (◦) Thermogravimetric Properties
From DTG (Figure 3), it is observed that the decomposition
process of the compound [HgI2L]2 is very simple. At 107.8◦C,
compound [HgI2L]2 reaches decomposition and the peak value
of weightlessness rate appears at 167.1◦C in the process of
decomposition. On the basis of TG graphs, the complex begins
to decompose at 107.8◦C, indicating that its stablility is very
poor. Decomposition temperature of the complex is between
107.8 and 241.0◦C. In this temperature range, the bonds,
Hg–I and Hg–N break. Total weightlessness is 70.19% when
the temperature reaches 700◦C, with the last product HgO.
Decomposition of the compound with an endothermic process
occurs at the same time.
3.405
3.670
3.964
2.571
2.718
3.165
149.39
167.02
140.76
Hg atoms made up an interesting, ring-like structure unit with
dimensions of 13.05 Å (Hg1–Hg1), which is smaller than that
in its HgCl2 complex (13.29 Å).[18]
In the solid-state structure, there existed three types of outer
sphere intermolecular interactions: The terminal I1 atom had a
C–H···I hydrogen bonding with the aliphatic C(8)H(8A)s group
from the L ligand of the neighboring dimeric unit; on the other
hand, there were aromatic C(11)–H(11A)···O(1) bonding and
aliphatic C(8)–H(8B)···O(4) hydrogen bonding between L lig-
ands of the neighboring dimeric unit. Although the C–H···I(O)
hydrogen bonds (Table 3) were relatively weak, they were very
important in holding crystal framework. As a result of these
C–H···I(O) inducing contacts, the repeating [HgI2L]2 dimeric
units grow infinitely in the a, b, c directions, and then a final
three-dimensional supramolecular structure was built (Figure 2).
SUPPLEMENTAL MATERIAL
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Cen-
ter, CCDC number 813846. Copies of this information may
be obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (e-mail: HYPERLINK
“mailto:deposit@ccdc.cam.ac.uk” deposit@ccdc.cam.ac.uk, or
URL: http://www.ccdc.cam.ac.uk).
FIG. 2. Three-dimensional supramolecular framework of compound [HgI2L]2 (along c axis), with CH. . .O(I) interaction showed by dotted lines.

NOVEL COORDINATED POLYMER [HgI2L]2
1017
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