Solvothermal synthesis and crystal structure of a 1d coordination polymer: [Ni(1,4-BDC)(N-MIM)2] n (1,4-BDC = 1,4-benzenedicarboxylic acid, N-MIM = N-methylimidazole)

Article abstract of DOI:10.1134/S1070328411110029

A new metal-organic coordination polymer, namely [Ni(1,4-BDC)(N-MIM) ₂] _n (I) (1,4-BDC = 1,4-benzenedicarboxylic acid and N-MIM = N-methylimidazole), has been synthesized under solvothermal conditions by using N-MIM as solvent and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic system, space group C2/c. The 1,4-BDC ligand adopts a bis(bidentate) chelating mode to connect two adjacent Ni(II) centers to form a one-dimensional (1D) zigzag chain. The adjacent chains are further linked through hydrogen bonds and π-π stacking interactions, forming a three-dimensional (3D) supramolecular framework. The unit cell parameters for I: a = 17.250(10), b = 7.214(4), c = 16.506(7)A, β = 125.53(4)°, V = 1671.6(15)A³, Z = 4.

Full text of DOI:10.1134/S1070328411110029

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 12, pp. 926–930. © Pleiades Publishing, Ltd., 2011.
Solvothermal Synthesis and Crystal Structure of a 1D Coordination
Polymer: [Ni(1,4ꢀBDC)(NꢀMIM)2]n (1,4ꢀBDC = 1,4ꢀ
Benzenedicarboxylic Acid, NꢀMIM = N
ꢀMethylimidazole)1
Y. E. Du and Z. B. Han*
College of Chemistry, Liaoning University, Shenyang 110036, P.R. China
*eꢀmail: ceshzb@lnu.edu.cn
Received January 11, 2011
Abstract
benzenedicarboxylic acid and NꢀMIM =
tions by using NꢀMIM as solvent and characterized by elemental analysis, IR, and Xꢀray singleꢀcrystal diffraction.
The Xꢀray diffraction analysis reveals that crystallizes in the monoclinic system, space group /c. The 1,4ꢀBDC
ligand adopts a bis(bidentate) chelating mode to connect two adjacent Ni(II) centers to form a oneꢀdimensional
(1D) zigzag chain. The adjacent chains are further linked through hydrogen bonds and stacking interactions,
forming a threeꢀdimensional (3D) supramolecular framework. The unit cell parameters for I: = 17.250(10),
7.214(4), = 16.506(7) β = 125.53(4) = 4.
= 1671.6(15) Å3
—
A new metalꢀorganic coordination polymer, namely [Ni(1,4ꢀBDC)(NꢀMIM)2]n (
I) (1,4ꢀBDC = 1,4ꢀ
Nꢀmethylimidazole), has been synthesized under solvothermal condiꢀ
I
C2
π π
–
a
b =
c
Å,
°,
V
, Z
DOI: 10.1134/S1070328411110029
1
INTRODUCTION
were carried out with a PerkinElmer 240 elemental
analyzer. The FTIR spectra were recorded from KBr
pellets in the 4000–400 cm–1 range on a Nicolet 5DX
spectrometer.
The design and synthesis of metalꢀorganic frameꢀ
works (MOFs) has attracted much attention in recent
decades, not only because of their intriguing variety of
architectures and topologies but also owing to their
potential applications as functional materials, such as
Solvothermal synthesis. Compound
by the solvothermal reaction of Ni(NO3)2
I
was obtained
6H2O
⋅
porous materials, catalysis, chirality, magnetic materiꢀ (0.4361 g, 1.5 mmol), 1,4ꢀBDC (0.1661 g, 1.0 mmol),
als, etc. [1–6]. One of the successful approaches to
construct MOFs is to employ suitable multidentate
organic ligands and metal ions as building blocks.
Among them, carboxylate ligands have been demonꢀ
strated as topꢀranking candidates for the construction
of novel coordination frameworks due to the controlꢀ
lable length of ligand and the various coordination
modes of the carboxyl group [7]. In this paper, we
report the synthesis and structural characterization of
a new coordination polymer [Ni(1,4ꢀBDC)(Nꢀ
and NꢀMIM (10 mmol) in a 23ꢀmL Teflon flask at
110 C for five days followed by cooling to a needed
temperature at a rate of 5 K/h. The resulting green
block crystals of were isolated after being washed
°
I
with methanol and dried in air (the yield is
∼
40%).
For C16H16N4NiO4
anal. calcd., %:
Found, %:
C, 49.65;
C, 49.67;
H, 4.17;
H, 4.15;
N, 14.48.
N, 14.45.
MIM)2]n (
acid and NꢀMIM =
exhibits a new 1D zigzag chain structure. Adjacent
chains are further linked via strong intermolecular
hydrogen bonds and
I
)
(1,4ꢀBDC = 1,4ꢀbenzenedicarboxylic
ꢀmethylimidazole), which
IR spectrum (KBr;
, cm–1): 1557 v.s, 1536 m,
1504 s, 1440 w, 1397 v.s, 1282 m, 1240 m, 840 s, 747 s,
657 s, 530 s.
Xꢀray crystal determination. Singleꢀcrystal Xꢀray
diffraction measurements were carried out on a Bruker
P4 diffractometer at 293(2) K temperature. The data
ν
N
π
– stacking interactions to form
π
a 3D supramolecular structure.
collections were performed with Mo
( = 0.71073 Å) and a graphite monochromator using
K
radiation
α
EXPERIMENTAL
λ
the
ω
scan mode. The structure was solved by direct
Materials and methods. All reagents employed were
commercially available and used as received without
further purification. The C, H, and N microanalyses
methods and refined on F2 by fullꢀmatrix least squares
using SHELXTL [8–10]. All nonꢀhydrogen atoms
were treated anisotropically. Positions of hydrogen
atoms were generated geometrically. Crystallographic
1
The article is published in the original.
926

SOLVOTHERMAL SYNTHESIS AND CRYSTAL STRUCTURE
Table 1. Crystallographic parameters and summary of data collection for
Parameter
927
I
Value
Formula weight
Crystal system
387.02
Monoclinic
Space group
C2/c
Unit cell dimensions:
a
, Å
, Å
17.250(10)
7.214(4)
16.506(7)
125.53(4)
1671.6(15)
4
b
c
, Å
β
V
Z
, deg
, Å3
ρcalcd, mg cm–3
Absorption coefficient, mm–1
(000)
Crystal size, nm
Range, deg
1.538
1.190
F
800
0.37
×
0.31 × 0.27
θ
2.72–26.10
Limiting indeces,
h
,
k
,
l
–21
–8
≤
h
≤
21,
8
≤
≤
k
≤
–20
l
≤
20
Scan mode
ω
Reflections collected
8234
Independent reflections (Rint
Data/restraints/parameters
Goodnessꢀofꢀfit on F2
)
1657(0.0483)
1657/0/114
1.039
Final
indices (all data)
Largest diff. peak and hole,
R
indices (
I
> 2
σ
(
I
))*
R
1 = 0.0381, wR2 = 0.0904
R
R
1 = 0.0565, wR2 = 0.0982
e
/Å3
0.426 and –0.240
1/2
2
2
*
R
=
Σ Fo – Fc /Σ Fo ; wR2 = Σ[w(F2o – Fc2) ]/Σ[w(Fo2) ]
.
1
data and experimental details for structural analyses
are summarized in Table 1, and the selected bond
lengths and angles are listed in Table 2. Supplementary
material has been deposited with the Cambridge Crysꢀ
tallographic Data Centre (no. 794369; deposit@
ccdc.cam.ac.uk).
RESULTS AND DISCUSSIONS
The asymmetric unit consists of one nickel(II)
center on the 2ꢀfold axis, one molecule of 1,4ꢀBDC,
and two molecules of NꢀMIM (Fig. 1). The nickel(II)
ion is surrounded by two nitrogen atoms from two
individual NꢀMIM molecules and four oxygen atoms
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 12
2011

928
DU, HAN
Table 2. Selected lengths (Å) and angles (deg) for I*
Bond
d
, Å
Bond
d
, Å
Ni(1)–O(1)
Ni(1)–O(2)
2.186(2)
2.063(2)
Ni(1)–N(1)
2.018(2)
Angle
ω
, deg
Angle
ω
, deg
N(1)#1Ni(1)N(1)
N(1)Ni(1)O(2)#1
N(1) Ni(1)O(2)
O(2)#1Ni(1)O(2)
N(1)#1Ni(1)O(1)
N(1)Ni(1)O(1)
97.59(13)
93.99(9)
O(2)#1Ni(1)O(1)
O(2)Ni(1)O(1)
100.26(8)
61.51(8)
101.35(9)
156.68(12)
154.60(8)
94.06(10)
N(1)#1Ni(1)O(1)#1
O(2)Ni(1)O(1)#1
O(1)Ni(1)O(1)#1
94.06(10)
100.26(8)
84.64(12)
#1
* Symmetry transformations used to generate equivalent atoms:
–x, y, –z + 1/2.
from two individual chelating bisꢀbidentate 1,4ꢀBDC Ni⋅⋅⋅Ni distance of 10.562(4) Å (Fig. 2). The Ni–O
ligands with the bond lengths ranging from 2.018(2) to bond distances are in the range of 2.063(2)–
2.186(2) Å and bond angles ranging from 61.51(8)
101.35 (90) and from 154.60(8) to 156.68(12)
give a distorted octahedral geometry around of the pounds [11, 12]. Weak
mental center (Table 2). The 1,4ꢀBDC ligand acting in between the imidazole rings of the lateral NꢀMIM
bisꢀbidentate chelating mode to connect two indiꢀ ligand with a perpendicular separation of 3.6127(14) Å
°
to 2.186(2) Å for Ni
to those reported for other nickel–oxygen donor comꢀ
stacking is observed
⎯Ocarboxylic, which are comparable to
°
°
°
π π
–
a
vidual Ni(II) center to form a 1D zigzag chain with a and a centroidꢀtoꢀcentroid distance of 4.340(3) Å.
N(2)
N(1)
O(1)
O(2C)
O(2A)
Ni(1)
N(1A)
O(2)
O(1A)
O(1C)
N(2A)
Fig. 1. Coordination environment of the Ni(II) center in
I.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 12
2011

SOLVOTHERMAL SYNTHESIS AND CRYSTAL STRUCTURE
929
Fig. 2. Fragment of the zigzag [Ni(1,4ꢀBDC)(NꢀMIM) ] chain.
2
n
Fig. 3. The 3D supramolecular structure of
I
showing the hydrogen bonds and
π
– stacking interactions viewed along the y axis.
π
These values are typical of
[13]. Adjacent zigzag chains are further linked via the
hydrogen bonding to form a 3D supramolecular
π
–
stacking interactions absence of the absorption band around 1700 cm–1 conꢀ
π
firms that the carboxylate groups are completely
deprotonated [18, 19] that is in accord with the results
of the Xꢀray analysis.
framework (Fig. 3). The hydrogen bonding and
π π
–
stacking interactions enhance the stability of the comꢀ
plex [14, 15]. Parameters of bond C(9)–H(9B)⋅⋅⋅O(2)#
#
ACKNOWLEDGMENTS
(
x
+ 1/2,
⎯
y
+ 1/2,
z
– 1/2) are: D–H 0.96,
⋅⋅⋅A 143
H⋅⋅⋅A
2.46, D⋅⋅⋅A 3.276(5) Å, angle
D
⎯
H
°
.
This work supported by the National Nature Sciꢀ
ence Foundational of China (grant no. 20871063).
The IR spectrum of complex
I
shows characteristic
bands of the dicarboxylate groups in the usual region at
1557 and 1536 cm–1 for the antisymmetric stretching
and at 1440 w, 1397 vs for symmetric stretching. The
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