Synthesis and characterization of coordination polymers with interpenetrated frameworks: M(adipate)(1,2-bis(4-pyridyl)ethane) and M(adipate)(trans-1,2-bis(4-pyridyl)ethene), M=Co, Mn

Article abstract of DOI:10.1016/S0020-1693(02)00905-2

Four novel coordination polymers: M(adipate)(1,2-bis(4-pyridyl)ethane) (1, 2) and M(adipate)(trans-1,2-bis(4-pyridyl)ethene) (3, 4), M=Co (1, 3) or Mn (2, 4), were synthesized by the self-assembly of Co²⁺ or Mn²⁺, adipate, and 1,2-bi

Full text of DOI:10.1016/S0020-1693(02)00905-2

Inorganica Chimica Acta 338 (2002) 1ꢂ6
/
www.elsevier.com/locate/ica
Synthesis and characterization of coordination polymers with
interpenetrated frameworks: M(adipate)(1,2-bis(4-pyridyl)ethane)
and M(adipate)(trans-1,2-bis(4-pyridyl)ethene), Mꢀ
/
Co, Mn
Ju-Hsiou Liao a,*, Shi-Hao Cheng a, Hui-Lien Tsai b, Chen-I Yang b
a Department of Chemistry, National Chung Cheng University, 160 San-Hsing, Min-Hsiung, Chia-Yi 621, Taiwan, ROC
b Department of Chemistry, National Cheng Kung University, 1 Ta-Hsueh, Tainan 701, Taiwan, ROC
Received 25 August 2001; accepted 18 March 2002
Abstract
Four novel coordination polymers: M(adipate)(1,2-bis(4-pyridyl)ethane) (1, 2) and M(adipate)(trans-1,2-bis(4-pyridyl)ethene) (3,
4), Mꢀ
Co (1, 3) or Mn (2, 4), were synthesized by the self-assembly of Co2ꢁ or Mn2ꢁ, adipate, and 1,2-bis(4-pyridyl)ethane or
trans-1,2-bis(4-pyridyl)ethene. Their crystal structures were determined by X-ray diffraction, showing that they have similar
structures. Each structure of 1ꢂ4 contains two sets of interpenetrated open frameworks, which are built by M(adipate) 2-D networks
connected by N,N?-dipyridyl ligands. Magnetic studies indicate 1ꢂ4 follow CurieꢂWeiss law and become antiferromagnetic at low
/
/
/
/
temperatures.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Coordination polymers; Crystal structure; Self-assembly; Interpenetrated; Antiferromagnetic
1. Introduction
products, we compare the self-assemblies of metal ions
with a long and flexible polycarboxylate, adipate [9],
and one of the two N,N?-bidentate ligands with similar
structures, 1,2-bis(4-pyridyl)ethane and trans-1,2-bis(4-
pyridyl)ethene (Scheme 1). In this work we report such
combinations resulted in the formation of similar
interpenetrated frameworks under the same synthetic
conditions. By choosing the two N,N?-bidentate ligands
with different p-conjugation system, we attempted to
investigate if the subtle structural difference of ligands
imposes any effect on the coupling of the magnetic
centers. A variable temperature magnetic susceptibility
investigation shows that the metal centers in the
complexes are antiferromagnetically coupled.
Crystal engineering has become an intriguing field,
continuing to generate new materials [1]. To date, self-
assembly of metal ions and multidentate organic ligands
have achieved great success in forming coordination
polymers [2ꢂ8] that can be potentially applied as
/
catalysts [3], or possess interesting properties such as
molecular sorption [4], electric conductivities [5], mag-
netism [6] and optical properties [7]. The architecture of
the hybrid inorganic-organic networks is determined by
the geometrical preference of the metal ions as well as
organic ligand building blocks, which exhibit remark-
able variety in their molecular structures. Rigid poly-
carboxylates, such as 1,3,5-benzenetricarboxylates,
1,3,5-cyclohexanetricarboxylates, 1,4-benzenedicarbox-
ylate and 4,4?-biphenyldicarboxylate, have been used
as anionic linkers to stabilize many structures with open
frameworks [8]. In order to verify if the length and shape
of building blocks determines the topologies of the
2. Experimental
Co(NO3)2×
/
6H2O, Mn(NO3)2×
/
4H O (Riedel-de Haen),
¨
2
CoCl2×6H2O (Showa), MnCl2×
/
/
4H2O (Showa), 1,2-bis(4-
pyridyl)ethane (Aldrich), trans-1,2-bis(4-pyridyl)ethene
(Aldrich), were used as obtained, without further
purification. Infrared spectra (IR) were recorded from
* Corresponding author. Tel.: ꢁ
040
E-mail address: chejhl@ccunix.ccu.edu.tw (J.-H. Liao).
/
886-52-428 168; fax: ꢁ886-52-721
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 9 0 5 - 2

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J.-H. Liao et al. / Inorganica Chimica Acta 338 (2002) 1ꢂ6
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1126(s), 1068(w), 1012(s), 920(m), 876(w), 832(s),
814(m), 772(w), 694(w), 632(s), 550(s), 494(m). Anal.
Calc. for MnO4N2C18H20: C, 56.40; H, 5.26; N, 7.31.
Found: C, 55.99; H, 5.25; N, 7.41%.
2.1.3. Co(adipate)(trans-1,2-bis(4-pyridyl)ethene)
CoCl2×
solved in 5 ml distilled water and a mixture of adipic
acid (0.073 g, 0.500 mmol)ꢂtrans-1,2-bis(4-pyri-
dyl)ethene (0.364 g, 2.00 mmol) were first dissolved in
5 ml distilled waterꢂ5 ml ethanol at 80 8C. The two
/6H2O (0.119 g, 0.500 mmol) were first dis-
/
/
solutions were mixed and sealed in a 30 ml test tube,
forming a clear pink solution with pH 4.50. The solution
was kept at 80 8C for 3 days until many parallelepiped
red crystals of 3 were observed. The final pH value was
5.31. Crystals (0.169 g) were collected after filtration and
several washings with distilled water and acetone in
87.7% yield (based on Co). IR(KBr, cmꢃ1): 3066(w),
3040(w), 3008(w), 2948(m), 2854(w), 1600(s), 1564(s),
1500(w), 1458(m), 1424(s), 1330(w), 1294(w), 1248(m),
1208(m), 1128(w), 1066(w), 1012(m), 988(m), 922(w),
862(m), 832(s), 802(w), 762(w), 624(m), 554(s), 506(w),
470(w), 426(w). Anal. Calc. for CoO4N2C18H18: C,
56.12; H, 4.71; N, 7.27. Found: C, 55.91; H, 4.69; N,
7.24%.
Scheme 1.
KBr pellets on a PerkinꢂElmer PC 16 FTIR spectro-
/
meter. Thermogravimetric analysis (TGA) was per-
formed under air flow at a heating rate of 10 8C
minꢃ1 using a Shimadzu TGA-50 system. X-ray powder
diffraction (XRPD) data were recorded on a Shimadzu
XRD-6000 diffractometer.
2.1. Synthesis
2.1.1. Co(adipate)(1,2-bis(4-pyridyl)ethane)
Co(NO3)2×
/
6H2O (0.145 g, 0.500 mmol) and a mixture
1,2-bis(4-pyri-
of adipic acid (0.073 g, 0.500 mmol)ꢂ
/
dyl)ethane (0.276 g, 1.50 mmol) were first dissolved in 5
and 10 ml distilled water, respectively, at 80 8C. The
two solutions were mixed and sealed in a 30 ml test tube,
forming a clear pink solution with pH 3.84. The solution
was kept at 80 8C for 4 days until many parallelepiped
purple crystals of 1 were observed. The final pH value
was 4.90. Crystals (0.168 g) were collected after filtration
and several washings with distilled water and acetone in
86.8% yield (based on Co). IR(KBr, cmꢃ1): 3064(w),
2944(m), 2856(w), 1602(s), 1568(s), 1552(m), 1498(w),
1456(m), 1422(s), 1330(w), 1296(w), 1218(m), 1128(m),
1072(w), 1016(m), 922(w), 872(w), 834(s), 816(w),
802(w), 634(m), 554(s), 500(w), 418(w), 404(w). Anal.
Calc. for CoO4N2C18H20: C, 55.82; H, 5.20; N, 7.23.
Found: C, 55.57; H, 5.18; N, 7.32%.
2.1.4. Mn(adipate)(trans-1,2-bis(4-pyridyl)ethene)
MnCl2×
solved in 5 ml distilled water and a mixture of adipic
acid (0.073 g, 0.500 mmol)ꢂtrans-1,2-bis(4-pyri-
dyl)ethene (0.364 g, 2.00 mmol) were first dissolved in
5 ml distilled waterꢂ5 ml ethanol at 80 8C. The two
/
4H2O (0.099 g, 0.500 mmol) were first dis-
/
/
solutions were mixed and sealed in a 30 ml test tube,
forming a colorless solution with pH 2.94. The solution
was kept at 80 8C for 3 days until many parallelepiped
yellow crystals of 4 were observed. The final pH value
was 4.35. Crystals (0.096 g) were collected after filtration
and several washings with distilled water and acetone in
50.1% yield (based on Mn). IR(KBr, cmꢃ1): 3064(w),
3008(w), 2948(m), 2858(w), 2362(w), 1704(w), 1592(s),
1562(s), 1456(w), 1424(s), 1330(w), 1294(m), 1248(w),
1210(m), 1128(m), 1064(w), 1010(s), 988(s), 920(m),
892(w), 866(w), 830(s), 802(m), 764(m), 628(s), 554(s),
504(w). Anal. Calc. for MnO4N2C18H18: C, 56.70; H,
4.76; N, 7.35. Found: C, 56.61; H, 4.77; N, 7.39%.
2.1.2. Mn(adipate)(1,2-bis(4-pyridyl)ethane)
Mn(NO3)2×
/
4H2O (0.126 g, 0.500 mmol) and a mixture
of adipic acid (0.073 g, 0.500 mmol)ꢂ
/1,2-bis(4-pyri-
dyl)ethane (0.368 g, 2.00 mmol) were first dissolved in 5
and 10 ml distilled water, respectively, at 80 8C. The
two solutions were mixed and sealed in a 30 ml test tube,
forming a colorless solution with pH 3.69. The solution
was kept at 80 8C for 4 days until many colorless
crystals of 2 were observed. The final pH value was 5.29.
Crystals (0.096 g) were collected after filtration and
several washings with distilled water and acetone in
86.8% yield (based on Mn). IR(KBr, cmꢃ1): 3062(w),
3034(w), 2944(s), 2856(w), 1596(s), 1564(s), 1500(w),
1456(w), 1422(s), 1330(w), 1294(m), 1216(m), 1186(m),
2.2. Structure determination
Single crystals of 1ꢂ4 were mounted on the tops of
/
glass fibers. The crystallographic works were performed
on a Bruker P4 automatic diffractometer with graphite
˚
0.71073 A).
monochromated Mo Ka radiation (lꢀ
/
Initial unit cells for 1ꢂ4 were determined from 20
/
reflections randomly located from hemisphere search.
Unit cell constants and orientation matrices for data
collection were refined from 25 carefully centered

J.-H. Liao et al. / Inorganica Chimica Acta 338 (2002) 1ꢂ
/6
3
reflections around 2uꢀ
/
258. Three standard reflections
acid:bpeꢀ1:1:1, under the same reaction parameters
/
were measured periodically every 97 reflections. No
significant decay was observed. An empirical c-scan
absorption correction was applied to all the data. The
structures were solved with direct method (SHELXS-86)
[10], and were refined by a full-matrix least-square
technique available in the SHELXL-93 [11] crystallo-
graphic software package. All the non-hydrogen atoms
were refined with anisotropic thermal parameters. All
the hydrogen atoms bonded to carbon atoms at
calculated idealized positions were included in structure
factor calculation but were not refined. The crystal-
lographic data and detailed information of structure
solution and refinement are listed in Table 1.
mentioned in the experimental section. However the
yield obtained from such ratio was very low at 24.8%.
During the efforts to optimize the yield, we found the
yield can be improved significantly to 86.8% by increas-
ing the amount of N,N?-dipyridyl ligands to more than
3 equiv. The addition of more dipyridyl ligands was
observed to increase the crystal growing rates at the
sacrifice of crystallinity and crystal size. During the
preparation of 3 and 4, appropriate amount of ethanol
was added in order to promote the crystallization of the
products. The addition of too much ethanol resulted in
the formation of polycrystalline products in a shorter
reaction period.
2.3. Magnetic measurement
3.2. Crystal structures
Variable-temperature dc magnetic susceptibility data
Compounds 1, 2 and 3, 4 are two pairs of isostruc-
tures, with similar three-dimensional frameworks. Each
3-D framework is formed by two sets of interpenetrated
networks offset by (1/2, 1/2, 1/2), as shown in Fig. 1.
Each set of 3-D network is composed of parallel 2-D
were collected for polycrystalline samples of 1ꢂ
applied filed of 1.0 kG, and in the temperature range of
2.0ꢂ300.0 K, which were measured by a SQUID magnet-
/4 in an
/
ometer (Quantum Design, MPMS-7). The samples were
embedded in eicosane wax to prevent any torquing of
the polycrystalline in the magnetic field. Pascal’s con-
stants [12] were used to estimate the diamagnetic
corrections.
¯
M(adipate) nets perpendicular to [/1/11] direction, as
shown schematically in Fig. 2, cross-linked by bridging
1,2-bis(pyridyl)ethane in 1 and 2, or by bridging trans-
1,2-bis(pyridyl)ethene in 3 and 4. All the dipyridyl rings
are parallel, with the bpe ligands running along the [011]
direction. The linkage of M2ꢁ ions, adipates and
3. Results and discussion
dipyridyl ligands results in large parallelepipeds with
˚
dimensions of 13.7ꢄ
/
10.8ꢄ
10.8ꢄ
13.9 A for 4, respectively, whereas little void
/
13.7 A for 1, 13.7ꢄ
/
10.9ꢄ
/
˚
˚
3.1. Synthesis
13.9 A for 2, 13.3ꢄ
/
/
13.6 A for 3 and 13.4ꢄ
/
˚
10.9ꢄ
/
The crystals of 1 suitable for single-crystal X-ray
diffraction studies were obtained from a reaction with
stoichiometric amount of starting reagents, Co2ꢁ:adipic
space is obtained due to interpenetration. Fig. 3(a) and
(b) show the distorted octahedral coordination environ-
ment of the metal centers. Among the four oxygen
Table 1
Crystallographic data for 1ꢂ4
/
1
2
3
4
Formula
Formula weight
Space group
CoO4N2C18H20
387.29
MnO4N2C18H20
383.30
CoO4N2C18H18
385.27
MnO4N2C18H18
381.28
¯
P/1 (number 2)
¯
1 (number 2)
¯
1 (number 2)
¯
P/1 (number 2)
P/
P/
˚
a (A)
8.482(1)
9.374(1)
11.409(1)
98.42(1)
95.17(1)
106.07(1)
854.1(2)
2
8.433(1)
9.406(1)
11.476(2)
97.02(1)
94.66(2)
105.15(1)
866.0(2)
2
8.297(1)
9.096(2)
11.343(2)
96.96(1)
96.24(2)
103.40(1)
818.3(3)
2
8.217(1)
9.150(1)
11.384(3)
95.88(1)
95.65(2)
102.54(1)
824.6(2)
2
˚
b (A)
˚
a (A)
a (8)
b (8)
g (8)
3
˚
V (A )
Z
Temperature (K)
298
298
298
298
˚
l (A) (Mo Ka)
0.71073
1.506
10.30
0.71073
1.470
7.87
0.71073
1.564
10.75
0.71073
1.524
8.20
rcalc (g cmꢃ3
)
m (Mo Ka, cmꢃ1
)
R1 a/wR2 (I ꢀ2s(I))
0.0484/0.0690
0.0478/0.0761
0.0944/0.1430
0.0425/0.0592
b
a
R1ꢀajjFojꢃjFcjj/ajFoj.
b
wR2(F)ꢀ[a w(Fo2ꢃFc2)2/a w(Fo2)2]1/2
.

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J.-H. Liao et al. / Inorganica Chimica Acta 338 (2002) 1ꢂ6
/
Fig. 1. (a) Packing diagram of a single set of interpenetrated frameworks. (b) Schematic presentation of two sets of interpenetrated frameworks.
atoms bound to M, two are from a bidentate COOꢃ
group and two are from two monodentate COOꢃ of
three different adipates. Selected bond lengths and
angles are given in Table 2. M and the four oxygen
atoms bound to it are almost in the same plane. The
ethane and trans-1,2-bis(pyridyl)ethene are building
blocks of similar size and shape in constructing these
frameworks.
3.3. Thermal analysis
O(1)Ã
/
MÃ
/
O(2) angles of the oxygen atoms from the
MÃ
bidentate COOꢃ are close to 608 while the O(3)Ã
/
/
TGA experiments performing under air flow indicate
O(4) angles of the oxygen atoms from two monodentate
COOꢃ are close to 1208 The bond lengths of the metal
to the oxygen atoms of the bidentate COOꢃ are longer
than those between the metal and the oxygen atoms of
the monodentate COOꢃ. Two dipyridyl ligands are at
1ꢂ
/
4 are thermally stable up to 274, 237, 292 and 276 8C
for 1ꢂ
/
4, respectively, followed by one-step exothermic
decomposition, resulting in Co3O4 or Mn2O3 residues
based on XPRD measurements.
trans positions with nearly linear N(1)Ã
(177.4(1)8 1, 174.44(9)8 2, 176.4(3)8 3, 173.21(9)8 4) and
average CoÃN and MnÃN distances of 2.156 and 2.281
A, respectively. The similarity of these bond lengths and
angles data in 1ꢂ4 reflects the fact that 1,2-bis(pyridyl)
/
MÃ
/
N(2) angles
3.4. Magnetic studies
/
/
The magnetic susceptibilities of complexes were
˚
measured in the range of 2.0ꢂ300.0 K. The inverse
magnetic susceptibilities (xꢃ1) and effective magnetic
/
/

J.-H. Liao et al. / Inorganica Chimica Acta 338 (2002) 1ꢂ
/6
5
Table 2
Selected bond lengths (A) and angles (8) for 1ꢂ
˚
/4
1
2
3
4
MÃO(1)
MÃO(2)
MÃO(3)
MÃO(4)#1
MÃN(1)
MÃN(2)
2.164(3) 2.231(2)
2.261(3) 2.341(2)
2.023(2) 2.106(2)
2.023(2) 2.101(2)
2.156(2) 2.277(2)
2.158(3) 2.295(2)
2.122(7) 2.216(3)
2.283(7) 2.342(3)
2.011(6) 2.103(3)
2.009(6) 2.094(3)
2.152(7) 2.269(3)
2.156(7) 2.283(3)
O(1)ÃMÃO(2)
O(1)ÃMÃO(3)
O(1)ÃMÃO(4)#1
O(1)ÃMÃN(1)
O(1)ÃMÃN(2)
O(2)ÃMÃO(3)
O(2)ÃMÃO(4)#1
O(2)ÃMÃN(1)
O(2)ÃMÃN(2)
O(3)ÃMÃO(4)#1
O(3)ÃMÃN(1)
O(3)ÃMÃN(2)
O(4)#1ÃMÃN(1)
O(4)#1ÃMÃN(2)
N(1)ÃMÃN(2)
58.7(1)
92.5(1)
147.3(1) 144.63(9)
56.68(8)
92.64(9)
57.9(3)
92.2(3)
145.3(3) 142.8(1)
56.7(1)
91.8(1)
91.5(1) 93.67(9)
88.3(1) 88.21(9)
150.9(1) 149.09(9)
92.8(3) 95.8(1)
88.9(3) 88.2(1)
149.8(3) 148.3(1)
88.7(1)
93.3(1)
88.8(1)
88.09(9)
95.81(9)
89.60(9)
87.6(3)
94.3(3)
89.3(3)
86.3(1)
96.4(1)
90.3(1)
119.8(1) 122.15(9)
122.0(3) 124.7(1)
91.0(1)
86.4(1)
93.1(1)
88.6(1)
89.36(8)
85.32(8)
92.95(9)
88.52(9)
90.5(3)
86.2(3)
92.8(3)
87.7(3)
89.5(1)
85.0(1)
92.3(1)
87.8(1)
Fig. 2. ORTEP diagram of the 2-D framework of M(adipate), Mꢀ
Mn.
/
Co,
177.4(1) 174.44(9)
176.4(3) 173.21(9)
Symmetry transformations used to generate equivalent atoms: #1,
ꢃx, ꢃy, ꢃz; #2, x, yꢃ1, zꢃ1; #3, x, yꢁ1, zꢁ1; #4, ꢃxꢁ1, ꢃy,
ꢃzꢁ1; #5, ꢃxꢁ1, ꢃyꢁ1, ꢃz.
Fig. 4. Magnetic effective moment vs. temperature plots for 1(k),
2(I), 3(^), and 4(2) and inverse magnetic susceptibility vs.
temperature plots for 1(m), 2(j), 3('), and 4("). The solid lines
represent the best fitting to the Curieꢂ
/
Weis law for data of 60ꢂ300 K.
/
Fig. 3. ORTEP diagram and labeling scheme of 1 (a) and 3 (b). Note
that 2 and 4 are isostructural to 1 and 3, respectively, and are not given
here.
coupling between magnetic centers. For cobalt com-
plexes 1 and 3, the meff values at 300 K are 4.32 and 4.48
mB, and decrease smoothly upon cooling to about 30 K,
and then decrease rapidly to 1.37 and 1.67 mB at 2.0 K,
respectively. For manganese complexes 2 and 4, the meff
values at 300 K are 5.80 and 5.78 mB, and decrease
moment (meff) versus temperature plots are shown in
Fig. 4. When the temperature is lowered, the value of
meff is decreased, indicative of overall antiferromagnetic

6
J.-H. Liao et al. / Inorganica Chimica Acta 338 (2002) 1ꢂ6
/
O’Connor, R.S. Rarig, K.M. Johnson, R.L. LaDuca, J. Zubieta,
Chem. Mater. 10 (1998) 3294;
smoothly upon cooling to about 30 K, and then decrease
rapidly to 1.54 and 1.51 mB at 2.0 K, respectively. From
the magnetic properties of complexes 1, 2, 3, and 4, the
different p-conjugation system in the two N,N?-biden-
tate ligands does not play an important role in the
pathway of magnetic coupling interaction.
(g) Y.B. Dong, R.C. Layland, M.D. Smith, N.G. Pschirer, U.H.F.
Bunz, H.C. zur Loye, Inorg. Chem. 38 (1999) 3056;
(h) J. Lu, T. Paliwala, S.C. Lim, C. Yu, T. Niu, A.J. Jacobson,
Inorg. Chem. 36 (1997) 923;
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(1999) 4608.
In Fig. 4, the plots of xꢃ1 versus T for complexes 1ꢂ
give straight lines, which can be fitted to the Curieꢂ
Weiss law. The best linear fits of xꢃ1(T) data above
60 K yield Cꢀ
2.446, 4.067, 2.623 and 4.307 emu molꢃ1
and uꢀ 14.3, ꢃ7.9, ꢃ14.9, and ꢃ9.4 K for com-
plexes 1ꢂ4, respectively. The values of u indicate the
/
4
[3] J.S. Seo, D. Whang, H. Lee, S.I. Jun, J. Oh, Y. Jin, K. Kim,
Nature 404 (2000) 982.
/
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Am. Chem. Soc. 121 (1999) 8204;
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(b) G.B. Gardner, Y.H. Kiang, S. Lee, A. Asgaonkar, D.J.
Venkataraman, J. Am. Chem. Soc. 118 (1996) 6946;
(c) M. Eddaoudi, H. Li, O.M. Yaghi, J. Am. Chem. Soc. 122
(2000) 1391;
/
ꢃ
/
/
/
/
/
antiferromagnetic interactions between the metal cen-
ters, and there is stronger antiferromagnetic coupling
between two Co than Mn.
(d) O.M. Yaghi, C.E. Davis, G. Li, H. Li, J. Am. Chem. Soc. 119
(1997) 2861;
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¨
4. Supplementary material
Schutz, H.C. Wolf, R.K. Kremer, T. Metzenthin, R. Bau, S.I.
¨
Khan, A. Lindbaum, C.L. Lengauer, E. Tillmanns, J. Am. Chem.
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The X-ray crystallographic files in CIF format is
available free of charge via the internet.
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Acknowledgements
We thank the National Science Council of Taiwan for
financial support.
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