A double chain metal-organic framework constructed by tetrameric nickel(II) units and 1,3,5-benzenetricarboxylic trianions

Article abstract of DOI:10.1002/zaac.200700280

Hydrothermal reaction of nickel sulfate, 1,3,5-benzenetricarboxylic acid and deprotonation agent ethylenediamine yields a metal-organic framework [Ni₄(μ³-OH)₂(H₂O) ₁₀(BTC)₂] · H₂O, which consists of double chains constructed from tetrameric nicke1(11) units and 1,3,5-benzenetricarboxylic trianions. Hydrogen bonds and π-π stacking interactions among these chains result in the three-dimensional structure of the compound. Magnetic study reveals there are ferromagnetic interactions among the Ni²⁺ ions of each Ni₄ units in the compound.

Full text of DOI:10.1002/zaac.200700280

DOI: 10.1002/zaac.200700280
A Double Chain Metal-organic Framework Constructed by Tetrameric
Nickel(II) Units and 1,3,5-Benzenetricarboxylic Trianions
Linhua Xie, Shuxia Liu*, Ruige Cao, Chaoying Gao, and Jianfang Cao
Changchun/P. R. China, Key Laboratory of Polyoxometalates Science of Ministry of Education, College of Chemistry, Northeast
Normal University
Received April 14th, 2007.
Abstract. Hydrothermal reaction of nickel sulfate, 1,3,5-benzene-
the three-dimensional structure of the compound. Magnetic study
reveals there are ferromagnetic interactions among the Ni2ϩ ions
of each Ni4 units in the compound.
tricarboxylic acid and deprotonation agent ethylenediamine yields
a
metal-organic framework [Ni4(µ3-OH)2(H2O)10(BTC)2]·H2O,
which consists of double chains constructed from tetrameric nicke-
l(II) units and 1,3,5-benzenetricarboxylic trianions. Hydrogen
bonds and π-π stacking interactions among these chains result in
Keywords: Metal-organic framework; Double chain; 1,3,5-Benzene-
tricarboxylic acid; Nickel; Magnetic properties
on a Perkin-Elmer 240C elemental analyzer. IR spectrum was re-
corded in the range 400Ϫ4000 cmϪ1 on an Alpha Centaurt FT/IR
spectrophotometer using KBr pellets. TG analysis was performed
on a Perkin-Elmer TGA7 instrument in flowing N2 with a heating
rate of 10 °C/min. Powder X-ray diffraction measurement was per-
formed on a Rigaku D/MAX-3 instrument with Cu-KͰ radiation
in the angular range 2θ ϭ 3-90° at 293 K. Magnetic susceptibility
data were collected over the temperature range 2-300 K at a mag-
netic field of 5000 Oe on a Quantum Design MPMS-5 SQUID
magnetometer.
Introduction
In the last decade, metal-organic frameworks have been
investigated extensively due to their potential applications
in many areas [1Ϫ10]. 1,3,5-benzenetricarboxylic acid
(H3BTC) is one type rigid ligand and has been proved to
be versatile for construction of porous materials [11Ϫ16].
Recently, our group also reported two BTC-based porous
metal-organic frameworks Zn(BTC)·NH2(CH3)2 ·DMF
and [Ni(HBTC)(4,4Ј-bipy)·3DMF] (DMF ϭ N,NЈ-dimeth-
ylformamide, 4,4Ј-bipy ϭ 4,4Ј-bipyridine) prepared under
solvothermal conditions [17, 18]. As a part of our ongoing
research, we investigated the reactions of Ni2ϩ ions and
H3BTC under hydrothermal condition. A compound for-
mulated as [Ni4(µ3-OH)2(H2O)10(BTC)2]·H2O (1) has been
isolated, which consists of one-dimensional (1D) double
chains built up of tetrameric nickel(II) units and 1,3,5-ben-
zenetricarboxylic trianions. Synthesis, structure and mag-
netic property of the compound are reported here.
Preparation of 1
A mixture of NiSO4 ·6H2O (1.5 mmol, 0.394 g), H3BTC (1 mmol,
0.210 g), ethylenediamine (1.5 mmol, 0.1 mL) and water (10 mL)
was sealed in a Teflon-lined autoclave and heated at 160 °C for 4
days, followed by slow cooling to room temperature. Compound 1
was collected as green block crystals with a yield about 0.255 g
(77 % based on Ni). C18H30Ni4O25 (881.26); C 24.21 (calc. 24.53);
H 3.71 (3.43) %.
Experimental Section
X-ray crystallography
Materials and general methods
Diffraction intensities for compound 1 was collected on a Rigaku
R-AXIS RAPID IP diffractometer with Mo-KͰ monochromated
radiation (λ ϭ 0.71073 A) at 283 K. The linear absorption coef-
All chemicals were obtained from commercial sources and used
without further purification. Elemental analyses were performed
˚
ficients, scattering factors for the atoms, and the anomalous disper-
sion corrections were taken from International Tables for X-ray
Crystallography. The structure was solved by the direct method and
refined by the full-matrix least-squares method on F2 using the
SHELXTL crystallographic software package. Anisotropic thermal
parameters were used to refine all non-hydrogen atoms. H atoms
on C atoms are placed in calculated positions and refined in the
* Prof. Dr. Shuxia Liu
Key Laboratory of Polyoxometalates Science of Ministry of
Education, College of Chemistry, Northeast Normal University,
Changchun City, JiLin, P. R. China 130024.
Fax: ϩ86-431-85099328
E-mail: liusx@nenu.edu.cn
˚
riding model approximation with C-H ϭ 0.93 A and Uiso(H) ϭ 1.2
Ueq(C). H atoms for coordinated water molecule and hydroxide ion
Supporting information for this article is available on the
WWW under http://www.wiley-vch.de/home/zaac or from the
author
were located in a difference Fourier map, and fixed with lengths of
˚
O-H bonds in the range of 0.83 to 0.87 A and Uiso(H) ϭ 1.2
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L. Xie, S. Liu, R. Cao, C. Gao, J. Cao
Table 1 Crystal data and structure refinement parameters for 1.
Table 3 Hydrogen bond parameters for 1.
˚
˚
˚
Empirical formula
Formula weight
Temperature/K
C18H30Ni4O25
881.26
283(2)
0.71073
monoclinic
C2/c (No. 15)
19.862(4)
13.024(3)
13.120(3)
125.98(3)
2746.4(10)
4
3.12Ϫ25.00
Ϫ23ՅhՅ23, Ϫ15ՅkՅ15, Ϫ15ՅlՅ15
1800
2.131
DϪH···A
d(DϪH) /A d(H···A) /A d(D···A) /A Є(DHA) /°
O1WϪH1A···O6W 0.85
1.96
2.00
2.16
2.45
2.43
2.54
2.07
2.01
2.06
2.27
1.85
2.806 (17)
2.628 (7)
2.789 (8)
2.964 (8)
3.18 (2)
3.320 (19)
2.745 (7)
2.755 (7)
2.781 (7)
3.012 (7)
2.652 (7)
175
132
133
121
149
156
134
147
143
145
158
˚
O1WϪH1B···O3i
O3WϪH3A···O3i
O3WϪH3A···O4ii
O7ϪH1···O6W
0.84
0.83
0.83
0.84
0.84
0.87
Wavelength/A
Crystal system
Space group
˚
a /A
˚
O7ϪH1···O6Wiii
O5WϪH5A···O3iv
b /A
˚
c /A
O2WϪH2A···O5Wv 0.84
β /°
3
˚
V /A
O4WϪH4A···O1
O5WϪH5B···O1vi
O2WϪH2B···O4ii
0.84
0.85
0.84
Z
2θ range /°
Limiting indices
F(000)
Symmetry codes: (i) xϩ1/2, Ϫyϩ3/2, zϩ1/2; (ii) Ϫxϩ1/2, Ϫyϩ3/2, Ϫz;
(iii) Ϫxϩ1, y, Ϫzϩ1/2; (iv) Ϫx, Ϫyϩ1, Ϫz; (v) Ϫxϩ1/2, Ϫyϩ1/2, Ϫz;
(vi) Ϫxϩ1/2, yϪ1/2, Ϫzϩ1/2.
Dc /g cmϪ3
µ(Mo-KͰ) /mmϪ1
Total data collected
Unique data
Observed data [I > 2σ(I)]
Rint
2.814
10457
2409
1719
0.1128
2409 / 0 / 217
1.103
e-mail: deposit@ccdc.cam.ac.uk). The powder X-ray diffraction
pattern for bulk sample of 1 agrees well with that simulated from
the single-crystal data. The diffraction peaks on both experimental
and simulated patterns match well in positions, indicating its phase
purity. (see Supporting information Fig. 2S)
Data / restraints / parameters
GOF
R indexes [I > 2σ(I)]
R indexes (all data)
R1 ϭ 0.0621a), wR2 ϭ 0.1212b)
R1 ϭ 0.0924a), wR2 ϭ 0.1373b)
0.696 and Ϫ0.874
3
˚
Largest diff. peak and hole /A
a) R1 ϭ ΣʈFoΗ Ϫ ΗFcʈ/ΣΗFoΗ. b) wR2 ϭ [Σw(Fo Ϫ Fc2)2/Σw(Fo2)2]1/2; w ϭ
1/[σ2(Fo)2 ϩ (aP)2 ϩ bP], where P ϭ (Max (Fo2, 0) ϩ 2Fc2)/3, a ϭ 0.0423,
b ϭ 23.62.
2
Results and Discussion
Synthesis and structure
˚
Table 2 Selected bond lengths /A and angles /° for1.
The key for good yield of 1 is the quantity of the depro-
tonation agent ethylenediamine (en) added into the reaction
system. We noted that if excessive en was added, only
homogeneous purple solution can be obtained after reac-
tion. It may be solution of stable complex [Ni(en)3]2ϩ. We
attempted to prepare 1 with NaOH, KOH or some other
organic amine (such as piperazine and triethylene diamine)
instead of en, however, failed. It may be related the coordi-
nation peculiarity and deprotonation ability of en.
Ni(1)-O(7)
Ni(1)-O(5)
Ni(1)-O(2W)
Ni(2)-O(6)
Ni(2)-O(2)
Ni(2)-O(7)
1.994(5)
2.033(5)
2.064(5)
2.023(5)
2.054(5)
2.059(5)
Ni(1)-O(1W)
Ni(1)-O(1)
Ni(1)-O(3W)
Ni(2)-O(7)#1
Ni(2)-O(4W)
Ni(2)-O(5W)
2.074(5)
2.105(5)
2.120(5)
2.064(5)
2.070(5)
2.149(5)
O(7)-Ni(1)-O(2W)
O(5)-Ni(1)-O(2W)
O(7)-Ni(1)-O(1W)
O(5)-Ni(1)-O(1W)
O(2W)-Ni(1)-O(1W)
O(7)-Ni(1)-O(1)
O(5)-Ni(1)-O(1)
O(7)-Ni(1)-O(5)
O(6)-Ni(2)-O(2)
O(6)-Ni(2)-O(7)
O(2)-Ni(2)-O(7)
O(6)-Ni(2)-O(7)#1
O(2)-Ni(2)-O(7)#1
O(7)-Ni(2)-O(7)#1
O(6)-Ni(2)-O(4W)
88.54(19)
93.9(2)
93.9(2)
171.3(2)
88.7(2)
94.65(19)
90.72(19)
94.4(2)
174.4(2)
90.18(19)
92.01(19)
96.7(2)
88.6(2)
82.79(19)
87.7(2)
O(2W)-Ni(1)-O(1)
O(1W)-Ni(1)-O(1)
O(7)-Ni(1)-O(3W)
O(5)-Ni(1)-O(3W)
O(2W)-Ni(1)-O(3W)
O(1W)-Ni(1)-O(3W)
O(1)-Ni(1)-O(3W)
O(4W)-Ni(2)-O(5W)
O(2)-Ni(2)-O(4W)
O(7)-Ni(2)-O(4W)
174.2(2)
86.2(2)
176.4(2)
82.0(2)
91.0(2)
89.6(2)
86.2(2)
85.9(2)
86.9(2)
97.4(2)
Single-crystal X-ray diffraction study reveals that com-
pound 1 consists of 1D double chains, which are constructed
by tetrameric nickel units [Ni4(CO2)4(µ3-OH)2(H2O)10] (Ni4)
and BTC ligands. There are two crystallographic indepen-
dent nickel (Ni1, Ni2) centers and one type of BTC ligand
in the structure. Ni1 coordinate with two carboxyl O atoms
from two BTC ligands, a hydroxide ion (O7) and three ad-
ditional water molecules (O1W, O2W, O3W), adopting a
slight distorted octahedral coordination with lengths of
O(7)#1-Ni(2)-O(4W) 175.5(2)
O(6)-Ni(2)-O(5W)
O(2)-Ni(2)-O(5W)
O(7)-Ni(2)-O(5W)
O(7)#1-Ni(2)-O(5W)
87.8(2)
90.3(2)
176.0(2)
94.02(19)
˚
Ni-O bonds ranging from 1.994(5) to 2.120(5) A. (Fig. 1)
Symmetry transformations used to generate equivalent atoms: #1 Ϫxϩ1/2,
Ϫyϩ1/2, Ϫz.
Ueq(O). The lattice water (O6W) molecule is disordered at two posi-
tions and set half-occupied, hydrogen atoms on which were not
located. Details of the crystal data and final structure refinements
of the compound 1 are summarized in Table 1. Selected bond
lengths and angles for 1 are listed in Table 2 and hydrogen bond
parameters are in Table 3. Crystallographic data for the structural
analyses have been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 646309. Copies of the data can be ob-
tained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: (internat.) ϩ 44-1223-336-033;
Fig. 1 Perspective view of the Ni4 unit. All H atoms have not been
shown for clarity.
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A Double Chain Metal-organic Framework
Fig. 2 Perspective view of the double chain with Ni4 units repre-
sented by polyhedra. All H atoms have not been shown for clarity.
Ni2 coordinate with two carboxyl O atoms from two BTC
ligands, two hydroxide ions and two additional water mol-
ecules (O4W, O5W), a slight distorted octahedral coordi-
nation too, with lengths of Ni-O bonds ranging from
˚
2.023(5) to 2.149(5) A. Two Ni1 and two Ni2 atoms, which
are both related by an inversion center, respectively, are
locked by four carboxyl groups and two hydroxide ions, for-
ming a Ni4 unit. In the Ni4 unit, each carboxyl group is
chelating two Ni atoms in di-monodentate fashion and each
hydroxide ion is bridging three Ni atoms. For each BTC
ligand in 1, two carboxyl groups are coordinated with four
Ni atoms from two Ni4 units, while the other one is de-
protonated too, however, uncoordinated with any Ni atom.
Two such BTC ligands are together bridging two Ni4 units,
Fig. 3 Perspective view of 3D supramolecular structure of 1 stacked
by double chains along c axis. Lattice water molecules are repre-
sented by space filling model. All H atoms have not been shown
for clarity.
˚
with their benzene rings separated about 3.3025 A [19], and
each Ni4 unit connects four BTC ligands, resulting in a un-
ique 1D double chain along a axis. (Fig. 2) Hydrogen bond
interactions among the uncoordinated carboxyl O atoms
and water molecules from neighboring chains (O1W-O3 ϭ
˚
˚
˚
2.628(7) A, O2W-O4 ϭ 2.652(7) A, O3W-O3 ϭ 2.789(8) A,
˚
O3W-O4 ϭ 2.964(8) A) result in a two-dimensional layer
along ab plane. (see Supporting information Fig. 3S) Such
layers further stack along c axis, forming the three-dimen-
sional structure of 1 through hydrogen bonds and π-π
stacking interactions. Hydrogen bonds between adjacent
layers are among the water molecules and carboxyl O atoms
˚
from neighboring layers (O5W-O1 ϭ 3.012(7) A, O5W-
˚
O3 ϭ 2.745(7) A), and π-π stacking interactions derive from
the benzene rings among adjacent layers separated about
3.167 A. There is one type of channel along c axis in the
Fig. 4 Temperature dependence of χmT for 1.
˚
structure after the layers stacking, where one lattice water
molecule per formula (O6W) resides. (Fig. 3) It is stabilized
by hydrogen bond interactions with surrounding hydroxide
decreases, the product χmT continuously increase and reach
a maximum (6.19 cm3 K molϪ1) at 9 K, followed by an ab-
rupt drop of χmT value to 4.11 cm3 K molϪ1 at 2 K. (Fig. 4)
The maximum is obviously lower than the value (11.77 cm3
K molϪ1) of a totally populated nonuple ground state for
each Ni4 unit. These results indicate weak ferromagnetic
interactions exist among the intra-cluster Ni2ϩ ions. The
sudden decrease of χmT in low temperature range may be
for the zero-field splitting of the Ni2ϩ ions or/and weak
antiferromagnetic interactions among these Ni4 units [21,
22]. The magnetic data of 1 obey the Curie-Weiss law in the
temperature range measured, and fitting of the data gives
values of C ϭ 4.41 cm3 K molϪ1 and θ ϭ 3.12 K.
˚
ions and water molecules (O1W) (O6W-O1W ϭ 2.806(1) A,
˚
O6W-O7 ϭ 3.180(2) or 3.320 (1) A).
Magnetic property
The variation of the molar magnetic susceptibility χm was
investigated for 1 in the temperature range 2-300 K. At
room temperature, the product χmT value (4.46 cm3
K
molϪ1) is slightly lower than the expected value (4.71 cm3
K molϪ1, assuming g ϭ 2.17 [20]) of four noninteracting
S ϭ 1 Ni2ϩ ions in a tetrameric unit. When temperature
Z. Anorg. Allg. Chem. 2007, 2049Ϫ2052
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2051

L. Xie, S. Liu, R. Cao, C. Gao, J. Cao
Acknowledgements. This work was supported by the National Sci-
ence Foundation of China (Grant No. 20571014) and the Scientific
Research Foundation for Returned Overseas Chinese Scholars, the
Ministry of Education.
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