Coordination polymers of macrocyclic oxamide with 1,3,5- benzenetricarboxylate: Syntheses, crystal structures and magnetic properties

Article abstract of DOI:10.1039/c0dt01584a

Solvothermal reactions of mixed ligands H₃BTC and macrocyclic oxamide complexes (ML, M = Cu, Ni) with M(ClO₄)₂· 6H₂O (M = Co, Zn, Ni and Cd) afford six new complexes, including [M′₄(BTC)₂(ML)₂(OH)₂(H ₂O)₂]·2H₂O (M′ = Co, M = Ni, for (1); M′ = Zn, M = Ni, for (2); M′ = Zn, M = Cu, for (3)), [Ni ₃(BTC)₂(NiL)₂(H₂O) ₆]·2CH₃OH·2H₂O (4), [Cd ₄(BTC)₂(HBTC)(NiL)₄(H₂O)] ·3H₂O (5) and [Cd(HBTC)(CuL)]·H₂O (6) (ML, H₂L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1,4,8,12-tetraazacyclo- pentadeca-7,13-dien; H₃BTC = 1,3,5-benzenetricarboxylic acid). Complexes 1-3 consist of a 2D layer framework formed by the linkage of M(ii)(M = Ni, Cu) and M′₄ (M′ = Co, Zn) cluster via the oxamide and BTC^3- bridges and display a (3,6)-connected network with a (4³)₂(4⁶.6⁶.8³) topology. The structure of 4 consists of pentanuclear [Ni^II₅] units and arranges in a 1D cluster chain. Complex 5 exhibits a 2D layered structure characterized by 3,4,3-connected (4.6²)₃(4.6 ³.8²)(4².6³.8)(4².6) topology. Complex 6 possesses a 3D network with sra topology. The magnetic properties of complexes 1 and 4 were investigated. The Royal Society of Chemistry.

Full text of DOI:10.1039/c0dt01584a

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PAPER
Coordination polymers of macrocyclic oxamide with
1,3,5-benzenetricarboxylate: syntheses, crystal structures and magnetic
properties†
Ya-Qiu Sun,*a Dong-Zhao Gao,a Yan-Yan Xu,a Guo-Ying Zhang,a Lan-Lan Fan,a Cheng-Peng Li,a
Tong-Liang Hu,b Dai-Zheng Liaob and Chen-Xi Zhangc
Received 15th November 2010, Accepted 17th March 2011
DOI: 10.1039/c0dt01584a
Solvothermal reactions of mixed ligands H3BTC and macrocyclic oxamide complexes (ML,
M = Cu, Ni) with M(ClO4)2·6H2O (M = Co, Zn, Ni and Cd) afford six new complexes, including
[M¢4(BTC)2(ML)2(OH)2(H2O)2]·2H2O (M¢ = Co, M = Ni, for (1); M¢ = Zn, M = Ni, for (2); M¢ = Zn,
M = Cu, for (3)), [Ni3(BTC)2(NiL)2(H2O)6]·2CH3OH·2H2O (4), [Cd4(BTC)2(HBTC)(NiL)4(H2O)]·3H2O
(5) and [Cd(HBTC)(CuL)]·H2O (6) (ML, H2L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1,4,8,12-
tetraazacyclo-pentadeca-7,13-dien; H3BTC = 1,3,5-benzenetricarboxylic acid). Complexes 1–3 consist
of a 2D layer framework formed by the linkage of M(II)(M = Ni, Cu) and M¢4 (M¢ = Co, Zn) cluster via
the oxamide and BTC3- bridges and display a (3,6)-connected network with a (43)2(46.66.83) topology.
The structure of 4 consists of pentanuclear [NiII5] units and arranges in a 1D cluster chain. Complex 5
exhibits a 2D layered structure characterized by 3,4,3-connected (4.62)3(4.63.82)(42.63.8)(42.6) topology.
Complex 6 possesses a 3D network with sra topology. The magnetic properties of complexes 1 and 4
were investigated.
architectures.6 The other synthetic approach is given by the
Introduction
concept of ‘complex ligand’, i.e., utilizing a metal complex as a
ligand to coordinate an appropriate additional metal ion.7–10
A
Coordination polymers have recently attracted much attention
because of their fascinating structures and their potential ap-
plication in magnetism, luminescence, adsorption, catalysis, etc.1
Research has mainly focused on homometallic systems. However,
heterometallic coordination polymers, which often exhibit novel
electromagnetic properties, remain relatively scarce because of the
coordinative complexity of the heterometallic ions involved in the
self-assembly process.2 Up to date, there are two main synthetic
approaches to obtain the heterometallic coordination polymers.
One is a one-pot synthetic approach. Adopting this synthetic
approach, the ligand design strategy is very important in the con-
struction of unusual heterometallic coordination frameworks.3–5
However, the design and synthesis of heterometallic polymers
is still a challenge to chemists, especially in the case of 3d–3d
heterometallic polymers, because a one-pot synthetic approach
can lead to a statistical mixture of homo- and heterometallic
good example is represented by the use of mononuclear oxamide
group complexes.9
The macrocyclic oxamides, in which the exo–cis conformation
of the oxygen donors is enforced, allow us to synthesize
heterobimetallic systems and model magnetic systems in a
more controlled fashion via the stepwise complexation of
the macrocyclic and exo donors (Scheme 1a).11 However,
heterobimetallic coordination polymers based on macrocyclic
oxamides are rarely obtained, because of the limitations
of the coordination modes of the macrocyclic oxamide. So
the construction of heterobimetallic coordination polymers
containing macrocyclic oxamides requires other co-ligands with
one or more bridges. Recently, our groups have succeeded in the
synthesis of some oxamido-bridged macrocyclic coordination
-
-
-
polymers with N3 , SCN-, N(CN)2 , ClO4 and 5-sulfosalicylic
acid co-ligands.12 Although some oxamido-bridged coordination
polymers have been synthesized, rational control in the
aTianjin Key Laboratory of Structure and Performance for Functional
Molecule, College of Chemistry, Tianjin Normal University, Tianjin, 300387,
P. R. China. E-mail: hxxysyq@mail.tjnu.edu.cn; Tel: (86)-22-81585464
construction of polymeric networks still remains
a great
challenge in crystal engineering. Heterometallic polymers
with multi-dimension have been made rarely.12 Therefore, in
order to design and construct the diverse multi-dimension
oxamido-bridged heteropolynuclear network, we have chosen
the 1,3,5-benzenetricarboxylic acid as co-ligand, because it has a
great ability to adopt different bonding modes and satisfy many
bDepartment of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
E-mail: liaodz@nankai.edu.cn
cTianjin University of Science & Technology, Sch Sci, Tianjin, P. R. China
† Electronic supplementary information (ESI) available. CCDC reference
numbers 800812–800817. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c0dt01584a
5528 | Dalton Trans., 2011, 40, 5528–5537
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X-Ray crystallography
Single crystal X-ray diffraction analyses of 1–6 were carried
out on a Bruker Smart Apex II CCD diffractometer equipped
with a graphite monochromated Mo–Ka radiation (l = 0.71073
˚
A) by using a f/w scan technique at room temperature. Semi-
empirical absorption corrections were applied using SADABS.
All structures were solved by direct methods using the SHELXS
program of the SHELXTL package and refined with SHELXL.
The crystallographic data and selected bond lengths and angles
for 1–6 are listed in Table 1–3. CCDC reference numbers: 800812–
800817.
Preparation of complexes of 1–6
Caution! Perchlorate salts of metal complexes with organic ligand
are potentially explosive and should be handled with care in small
quantities.
Synthesis of [M4(BTC)2(NiL)2(OH)2(H2O)2]·2H2O (M = Co, 1;
Zn, 2). A mixture of M(ClO4)2·6H2O (0.05 mmol, M = Co, 1;
Zn, 2), H3BTC (0.05 mmol, 10.5 mg), NiL (0.025 mmol, 9.8 mg),
H2O (10 mL) and CH3OH (3 mL) was stirred for 40 min at
room temperature, and the pH value of the solution was adjusted
to about 7–8 with triethylamine. After stirring, the mixture was
transferred to an 18 ml Teflon-lined reactor, and heated at 150 ◦C
for 72 h. Then the reaction system was cooled to room temperature
during 36 h, and deep red crystals for 1 and brown red crystals for
2 were isolated (for 1, yield = 63.5% based on Co; for 2, yield =
53.8% based on Zn) by filtering and washing with water. Calcd
for C28H24Co2N4NiO11 1: C, 43.69; H, 3.12; N, 7.28%. Found: C,
43.66; H, 3.09; N, 7.31%. Calcd for C28H24NiN4O11Zn2 2: C, 42.97;
H, 3.07; N, 7.16%. Found: C, 42.96; H, 3.05; N, 7.14%. Main IR
bands (KBr, cm-1): 3428 s (br), 1629 s, 1576 s, 1486 w, 1442 m,
1368 s, 1274 w, 1219 w, 1168 w, 1090 w, 767 m, 718 m, 562 w,
459 w.
Scheme 1 The macrocyclic oxamide complex ligands and coordinated
modes of the 1,3,5-benzenetricarboxylate.
metal coordination preferences.13 Meanwhile, the employment of
the metal ions CuII, CoII, ZnII, NiII, CdII, which have different
electronic structures, sizes, hard/soft behaviours, could lead
to the diversity and complexity of the resulted heterometallic
assemblies and new functional properties. The results show that
the marrying of the ML macrocyclic units with the tritopic
BTC3- and/or HBTC2- ligands has indeed led to interesting
and novel 1, 2 and 3D extended networks. Herein, we report
the syntheses, structures, topological analysis, and properties of
six coordination polymers [M¢4(BTC)2(ML)2(OH)2(H2O)2]·2H2O
(M¢ = Co, M = Ni, for (1); M¢ = Zn, M = Ni, for (2); M¢ = Zn,
M = Cu, for (3)), [Ni3(BTC)2(NiL)2(H2O)6]·2CH3OH·2H2O
Synthesis of [Zn4(BTC)2(CuL)2(OH)2(H2O)2]·2H2O (3). The
synthetic procedure was similar to that described for the prepara-
tion of 2 except using CuL (0.025 mmol, 9.9 mg) instead of NiL.
Deep brown–green crystals of 3 were obtained (yield = 63.5%
based on Zn). Calcd for C28H24CuN4O11Zn2 3: C, 42.71; H, 3.05;
N, 7.12%. Found: C, 42.69; H, 3.02; N, 7.08%. Main IR bands
(KBr, cm-1): 3432 s (br), 1613 s, 1568 s, 1482 w, 1437 m, 1364 s,
1164 m, 1105 m, 767 s, 714 s, 584 m, 454 w.
(4),
[Cd4(BTC)2(HBTC)(NiL)4(H2O)]·3H2O
(5)
and
[Cd(HBTC)(CuL)]·H2O (6).
Synthesis of [Ni3(BTC)2(NiL)2(H2O)6]·2CH3OH·2H2O (4).
A
mixture of Ni(ClO4)2·6H2O (0.05 mmol, 18.3 mg), H3BTC
(0.03 mmol, 6.3 mg), NiL (0.03 mmol, 11.8 mg), H2O (10 mL)
and CH3OH (3 mL) was stirred for 40 min at room temperature,
and the pH value of the solution was adjusted to about 7–8 with
triethylamine. After stirring, the mixture was◦transferred to an
18 ml Teflon-lined reactor, and heated at 150 C for 72 h. Deep
brown–red crystals of 4 were obtained (yield = 63.5% based on
Ni). Calcd for C29H31N4Ni2.50O13 4: C, 44.03; H, 3.92; N, 7.09%.
Found: C, 44.06; H, 3.97; N, 7.08%. Main IR bands (KBr, cm-1):
3443 s (br), 1622 s, 1563 s, 1484 m, 1436 s, 1366 s, 1279 w, 1222 w,
1107 w, 1097 w, 1014 w, 970 w, 930 w, 769 s, 718 s, 590 w, 507 w,
459 w.
Experimental
Materials and physical measurements
All the starting reagents were of A. R. grade and were used as
purchased. The complex ligand ML(M = Cu, Ni) was prepared as
described elsewhere.14 Analyses of C, H and N were determined
on a Perkin–Elmer 240 Elemental analyzer. IR spectrum was
recorded as KBr discs on a Shimadzu IR-408 infrared spec-
trophotometer in the 4000–600 cm-1 range. XRPD spectra for
the power were recorded with a Model D/MAX-2550V, Rigaku,
Japan. Variable-temperature magnetic susceptibilities of single
crystals were measured on an MPMS-7 SQUID magnetometer.
Diamagnetic corrections were made with Pascal’s constants for all
the constituent atoms.15
Synthesis of [Cd4(BTC)2(HBTC)(NiL)4(H2O)]·3H2O (5).
A
mixture of Cd(ClO4)2·6H2O (0.05 mmol, 20.9 mg), H3BTC
Dalton Trans., 2011, 40, 5528–5537 | 5529
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Table 1 Crystal data and structure refinement for complexes 1–3
Complexes
1
2
3
Formula
Fw
C28H24Co2N4NiO11
769.08
C28H24N4NiO11Zn2
781.96
C28H24CuN4O11Zn2
786.79
Crystal system
Space group
Triclinic
P1
Triclinic
P1
Triclinic
P1
¯
¯
¯
a
10.149(7)
12.422(9)
13.888(10)
100.960(13)
108.179(12)
109.137(12)
1485.8(18)
2
1.719
0.71073
0.28 ¥ 0.22 ¥ 0.20
296(2)
0.980
7420/5175
0.0477
0.0721
0.1844
10.1145(5)
12.3815(6)
13.7981(6)
100.4750(10)
107.9830(10)
109.2310(10)
1472.49(12)
2
1.764
0.71073
0.32 ¥ 0.22 ¥ 0.20
296(2)
1.074
7648/5166
0.0146
0.0298
0.0722
10.1376(6)
12.3611(8)
13.8352(8)
100.5220 (10)
107.4860(10)
109.1880(10)
1483.59(16)
2
1.761
0.71073
0.20 ¥ 0.10 ¥ 0.08
296(2)
1.039
7594/5196
0.0115
0.0267
0.0660
b
c
a (◦)
b (◦)
g (◦)
3
˚
V (A )
Z
rcaled (g cm-3)
v (Mo–Ka) (mm-1)
Crystal size (mm)
T (K)
Goodness-F2
Reflections collected/unique
R(int)
R1a [I > 2s(I)]
wR2b [I > 2s(I)]
CCDC numbers
800816
800812
800817
ꢀ
ꢀ
ꢀ
ꢀ
2
1/2
a R1 = ꢀFo| - |Fcꢀ/ |Fo|. b wR2 = { [w(Fo - Fc2)2]/ [w(Fo)2]}
Table 2 Crystal data and structure refinement for complexes 4–6
Complexes
4
5
6
Formula
Fw
Crystal system
Space group
C29H31N4Ni2.50O13
790.35
C103H82Cd4N16Ni4O30
2708.29
Monoclinic
P21
18.4200(7)
14.3984(6)
18.8098(8)
90
97.4300(10)
90
4946.8(3)
2
C28.5H22CdCuN4O8.5
732.44
Monoclinic
Triclinic
¯
P1
P21/n
a
9.7772(6)
12.0096(7)
14.0441(9)
88.6690(10)
82.8440(10)
71.6580(10)
1552.87(16)
2
10.021(3)
13.739(4)
18.812(5)
90
b
c
a (◦)
b (◦)
91.981(4)
90
2588.6(12)
4
g (◦)
3
˚
V (A )
Z
rcaled (g cm-3)
1.690
0.71073
0.28 ¥ 0.22 ¥ 0.20
296(2)
1.027
8054/5464
0.0157
0.0335
0.0758
1.818
1.879
v (Mo–Ka) (mm-1)
Crystal size (mm)
T (K)
0.71073
0.28 ¥ 0.22 ¥ 0.20
296(2)
1.044
25658/13515
0.0186
0.0310
0.0794
0.489(16)
800815
0.71073
0.38 ¥ 0.32 ¥ 0.22
296(2)
1.031
16858/7003
0.0210
Goodness-F2
Reflections collected/unique
R(int)
R1a [I > 2s(I)]
wR2b [I > 2s(I)]
Flack parameter
CCDC numbers
0.0289
0.0623
800814
800813
ꢀ
ꢀ
ꢀ
ꢀ
2
1/2
a R1 = ꢀFo| - |Fcꢀ/ |Fo|. b wR2 = { [w(Fo - Fc2)2]/ [w(Fo)2]}
(0.04 mmol, 8.4 mg), NiL (0.05 mmol, 19.6 mg), H2O (10 mL)
and CH3OH (3 mL) was stirred for 40 min at room temperature,
and the pH value of the solution was adjusted to about 6–7 with
triethylamine. After stirring, the mixture was◦transferred to an
18 ml Teflon-lined reactor, and heated at 150 C for 72 h. Then
the reaction system was cooled to room temperature during 36 h,
and brown–red crystals of the compound 5 were isolated (yield =
73.5% based on Cd) by filtering and washing with water. Calcd
for C103H82Cd4N16Ni4O30 5: C, 45.64; H, 3.03; N, 8.27%. Found:
C, 45.66; H, 3.07; N, 8.28%. Main IR bands: 3416 s (br), 1718 m,
1629 s, 1588 s, 1565 s, 1478 m, 1433 s, 1368 s, 1319 m, 1278 m,
1162 w, 1099 w, 1074 w, 976 w, 914 w, 813 w, 767 s, 730 s.
Synthesis of [Cd(HBTC)(CuL)]·H2O (6).
A mixture of
Cd(ClO4)2·6H2O (0.05 mmol, 20.9 mg), H3BTC (0.05 mmol,
10.5 mg), CuL (0.05 mmol, 20.4 mg), H2O (10 mL) and CH3OH
(3 mL) was stirred for 40 min at room temperature, and the pH
value of the solution was adjusted to about 6–7 with triethylamine.
After stirring, the mixture was sealed in an 18 mL Teflon-lined
reactor which was kept at 150 ◦C for 72 h. Deep brown–green
5530 | Dalton Trans., 2011, 40, 5528–5537
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◦
a
˚
Table 3 Selected bond distances (A) and angles ( ) for 1, 4–6
Compound 1
Ni(1)–N(4)
Co(1)–O(10)
Co(1)–O(9)
1.877(7)
2.084(5)
2.090(5)
2.097(5)
1.944(6)
1.949(6)
165.9(3)
82.1(2)
Ni(1)–N(1)
Co(1)–O(9)#1
Co(1)–O(2)
Co(1)–O(1)
Co(2)–O(9)
Co(2)–O(6)#2
N(2)–Ni(1)–N(1)
O(10)–Co(1)–O(5)#2
O(8)#3–Co(2)–O(6)#2
O(9)–Co(2)–O(6)#2
1.909(6)
2.087(5)
2.090(5)
2.112(5)
1.946(4)
1.974(5)
86.7(3)
176.5(2)
102.1(2)
107.1(2)
Co(1)–O(5)#2
Co(2)–O(8)#3
Co(2)–O(3)
N(4)–Ni(1)–N(2)
O(2)–Co(1)–O(5)#2
O(10)–Co(1)–O(9)
O(9)–Co(2)–O(3)
Compound 4
Ni(1)–O(3)
Ni(1)–O(9)
Ni(2)–O(1)
Ni(3)–N(4)
91.4(2)
116.4(2)
2.0558(19)
2.1452(18)
2.067(2)
Ni(1)–O(6)#2
Ni(2)–O(5)#2
Ni(2)–O(9)
2.0718(18)
2.009(2)
2.0888(18)
1.908(3)
1.877(3)
Ni(3)–N(1)
O(3)–Ni(1)–O(3)#1
O(1)–Ni(2)–O(11)
O(5)#2–Ni(2)–O(9)
N(4)–Ni(3)–N(1)
Compound 5
180.00(16)
82.86(9)
95.62(8)
O(3)–Ni(1)–O(9)#1
O(2)–Ni(2)–O(9)
N(2)–Ni(3)–N(1)
N(4)–Ni(3)–N(2)
88.34(7)
174.27(8)
90.96(12)
166.56(12)
94.54(12)
Cd(1)–O(9)
2.228(4)
2.193(5)
2.198(4)
2.211(4)
1.880(8)
80.52(16)
85.59(16)
165.27(17)
80.21(19)
86.8(2)
Cd(1)–O(13)#1
Cd(2)–O(21)
Cd(3)–O(12)
Cd(4)–O(26)#3
Ni(1)–N(3)
O(9)–Cd(1)–O(2)
O(16)–Cd(2)–O(3)
O(18)#2–Cd(3)–O(11)
O(24)–Cd(4)–O(6)
N(4)–Ni(1)–N(2)
2.567(5)
2.521(5)
2.428(4)
2.529(5)
Cd(2)–O(16)
Cd(3)–O(23)
Cd(4)–O(24)
Ni(1)–N(4)
1.892(8)
O(9)–Cd(1)–O(1)
O(16)–Cd(2)–O(4)
O(18)#2–Cd(3)–O(7)
O(25)#3–Cd(4)–O(27)
N(2)–Ni(1)–N(1)
Compound 6
Cd(1)–O(7)#1
Cd(1)–O(8)#1
Cu(1)–N(1)
O(4)–Cd(1)–O(3)
O(7)#1–Cd(1)–O(2)
O(2)–Cd(1)–O(1)
O(2)–Cd(1)–O(3)
N(1)–Cu(1)–N(2)
149.05(18)
156.44(17)
90.85(18)
143.25(18)
163.8(3)
2.2448(18)
2.515(2)
1.962(2)
52.63(6)
139.61(8)
70.27(6)
81.64(7)
82.96(8)
Cd(1)–O(2)
Cd(1)–O(3)
Cu(1)–N(4)
O(8)#1–Cd(1)–O(3)
O(7)#1–Cd(1)–O(3)#2
O(2)–Cd(1)–O(8)#1
N(1)–Cu(1)–N(3)
N(3)–Cu(1)–N(4)
2.2531(18)
2.6283(19)
2.021(2)
162.42(6)
110.69(7)
94.11(7)
172.61(9)
95.56(10)
a Symmetry transformations:1:#1 -x, -y, -z; #2 x - 1, y, z; #3 -x + 1, -y + 1, -z. 4: #1 -x + 2, -y, -z; #2 x - 1, y, z. 5: #1 -x + 1, y - 1/2, -z + 1; #2 x,
y + 1, z; #3 -x, y + 1/2, -z + 2. 6: #1 x - 1, y, z; #2 -x, -y + 1, -z.
crystals of 6 were obtained (yield = 60.3% based on Cd). Calcd
for C28H22CdCuN4O9 6: C, 46.69; H, 3.00; N, 7.63%. Found: C,
46.70; H, 3.02; N, 7.66%. Main IR bands (KBr, cm-1): 3432 s (br)
1689 m, 1613 s, 1572 s, 1485 w, 1438 m, 1362 m, 1275 w, 1162 w,
1101 w, 976 w, 914 w, 750 m, 720 m, 681 w, 592 w, 466 w.
that complexes for 1–4 were obtained at relatively higher pH
(7–8), whereas compounds 5 and 6 were obtained at relatively
lower pH (6–7). In order to explore the effect of the other
reaction parameters in preparing complexes 1–6, a large numbers
of experiments were also carried out via varying the reaction
temperature (100 to 180 ◦C) and time (1 to 4 days), and the results
show that single-crystal products suitable for X-ray analysis can
only be readily obtained at 150 ◦C for 3 days.
Results and discussion
For complexes 1–6, the spectra exhibit strong absorption bands
in the region 1629–1613 cm-1 and 1588–1563 cm-1 due to the
u(C O) and the u(C N) vibrations, respectively.16,17 The IR
spectra of 1, 2, 3 and 4 show no bands in the region 1680–
1720 cm-1, indicating complete deprotonation of the carboxyl
groups. While the IR spectra of the complexes 5 and 6 show
one band around 1718 cm-1 in 5, and around 1689 cm-1 in
6, which are characteristic of the protonation of the carboxyl
groups.17 The IR spectra of 1, 2, 3, 4 and 5 exhibit broad
absorption bands in the range 3260–3450 cm-1, indicating the
existence of coordinated water.17 To confirm the phase purity of
the obtained complexes, the original samples were characterized
Synthetic and spectral aspects
By using 1,3,5-benzenetricarboxylic acid and macrocyclic oxamide
mixed ligands as the metal linker, six new complexes have been syn-
thesized under solvothermal conditions. The results reported here
and previously reported12g,12h clearly show that the solvothermal
synthesis is a powerful and versatile tool for preparing macrocyclic
oxamide and organic acid bridged heterometallic coordination
polymers. Considering that the deprotonated degree of H3BTC
may play a vital role in constructing the extended structures,
a series of experiments were performed varying the pH values
of the reaction system in the range of 4–9. The results show
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by XRPD at room temperature. The experimental spectra (Fig.
S1†) of complexes 1, 2, 4 and 5 are almost consistent with those
simulated based on the structure models derived from single-
crystal X-ray diffraction data, indicating the phase purity of the
products.
Structural description
The ligands involved in this research and coordination modes of
1,3,5-benzenetricarboxylate ligand are listed in Schemes 1.
[Co4(BTC)2(NiL)2(OH)2(H2O)2]·2H2O (1)
Compounds 1–3 are isomorphous, hence only the structure of
1 will be discussed in detail as a representative. Single-crystal
X-ray analyses revealed that the complex 1 crystallizes in the
¯
triclinic space group P1. The asymmetric unit of 1 consists of one
copper(II) ion, two cobalt(II) ions, one macrocyclic oxamide group,
one BTC3-, two water molecules, and one hydroxyl (Fig. S2†). The
complex 1 is a 2D layer coordination polymer composed of hex-
anuclear Co4Ni2 building unit [Co4(BTC)2(NiL)2(OH)2(H2O)2].
As shown in Fig. 1a, in the hexanuclear structure of 1, the
nickel ion is coordinated by four nitrogen atoms from the
macrocyclic organic ligand, with the [NiN4] geometry exhibiting
a distorted square planarity. The Co(1) ion is six-coordinated
by two oxygen atoms from one oxamido ligand (Co(1)–O(1) =
˚
2.113(5) and Co(1)–O(2) = 2.091(5) A), one oxygen atom from
a BTC3- (Co(1)–O(5) = 2.097(5) A), one oxygen atom from a
˚
˚
water molecule (Co(1)–O(10) = 2.084(5) A), and two oxygen
atoms from two m3-OH groups (Co(1)–O(9) = 2.090(5) and Co(1)–
˚
O(9A) = 2.087(5) A). However, the Co(2) ion is tetrahedrally
˚
surrounded by one m3-OH group (Co(2)–O(9) = 1.946(4) A)
and three oxygen atoms (Co(2)–O(3) = 1.949(6), Co(2)–O(6B) =
˚
1.974(5) and Co(2)–O(8C) = 1.944(6) A) belonging to three
different carboxylate groups from three separated BTC3- ligands.
˚
The Co(2)–O average bond length (1.953(5) A) is somewhat
˚
shorter than those of Co(1)–O (2.093(5) A) and this is consistent
with the fact that bond lengths in a tetrahedral geometry are
generally shorter than those in other geometries. Four adjacent
metal ions (Co(1), Co(2), Co(1A), Co(2A)) are connected by
two bridging m3-OH groups to construct a tetrametallic cluster
[Co4(m3-OH)2], in which the non-bonding distances of Co ◊ ◊ ◊ Co
˚
˚
˚
are 3.359(6) A (Co(1) ◊ ◊ ◊ Co(2)), 3.543(4) A (Co(1) ◊ ◊ ◊ Co(2A)),
Fig. 1 (a) Portion of the crystal structure of 1 showing the coordinate
environments of Co(II) and Ni(II) ions; all H atoms are omitted for
clarity (symmetry code: A -x, -y, -z; B x - 1, y, z; C -x + 1, -y +
1, -z). (b) View of the self-assembly 2D sheet structure constructed by
[Co4(BTC)2(NiL)2(OH)2(H2O)2]; hydrogen atoms, coordinated water and
NiL ligands were removed for clarity. (c) The topological representation of
the 2D sheet; the green and red balls represent [Co4(m3-OH)2] and BTC3-
units, respectively.
and 3.102(4) A (Co(1) ◊ ◊ ◊ Co(1A)), respectively. Nickel ions and
the [Co4(m3-OH)2] cluster are interlinked through the macrocyclic
oxamide ligand to form a hetero-hexanuclear Co4Ni2 unit. The
structural Co4Ni2 building units are further linked with each other
through the BTC3- to create an infinite 2D layer with the formula
[Co4(BTC)2(NiL)2(OH)2(H2O)2]·2H2O (Fig. 1b). In the 2D layer
structure, the BTC3- act as a tetradentate connector to bridge four
Co(II) ions (Scheme 1b).
From the topological view of the complex 1, the 2D layer
consists of [Co4(m3-OH)2] clusters, and each Co4 unit is connected
through six carboxylate groups. Consequently, the Co4 unit can
be viewed as an irregular six-connected node. Each BTC3- ligand
connects three Co4 units, so BTC3- ligands are 3-connected nodes.
Thus, as illustrated in Fig. 1c, polymer 1 affords a (3,6)-connected
dinodal two-dimensional (2D) network with a (43)2(46.66.83)
topology.
[Ni3(BTC)2(NiL)2(H2O)6]·2CH3OH·2H2O (4)
¯
Complex 4 crystallizes in the triclinic space group P1. The
asymmetric unit of 4 consists of two and half nickel(III) ions, one
macrocyclic oxamide group, one BTC3-, four water molecules, and
one methanol molecule (see Fig. S3†). The structure of 4 is a 1D
double chain coordination polymer consisting of pentanuclear Ni5
building blocks. As shown in Fig. 2a, the Ni(1) ion is coordinated
5532 | Dalton Trans., 2011, 40, 5528–5537
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direction (Fig. S4†). The d(H ◊ ◊ ◊ O) and d(O ◊ ◊ ◊ O) distances between the
˚
chains are 1.75 and 2.6007 A, respectively.
[Cd4(BTC)2(HBTC)(NiL)4(H2O)]·3H2O (5)
Complex 5 crystallizes in the monoclinic space group P21. The
asymmetric unit of 5 consists of four cadmium(II) ions, four
nickel(II) ions, four macrocyclic oxamide groups, two BTC3-, one
HBTC2-, and four water molecules (Fig. S5†). As shown in Fig. 3a,
in the octanuclear structure of 5 each Cd(II) ion is linked to a Ni(II)
ion via the exo–cis oxygen donors of the macrocyclic oxamide
ligand. The Ni(II) ion is coordinated by four nitrogen atoms
from the macrocyclic organic ligand, with the [NiN4] geometry
exhibiting a distorted square planarity. The Cd(1) ion is six-
coordinated by two oxygen atoms from one oxamide ligand, and
four carboxylate oxygen atoms from two different BTC3- and one
HBTC2-. The coordination sphere of the Cd(1) ion is a distorted
octahedral geometry, which can be seen from the bond angles O–
Cd(1)–O varying from 53.18(15) to 149.05(18)◦. The Cd(4) ion
coordinates with two oxygen donors of the macrocyclic oxamide
ligand, three carboxylate oxygen atoms from two different BTC3-
and one oxygen atom from a water molecule, with the [Cd(1)O6]
unit exhibiting a distorted octahedral geometry. The coordination
environment of Cd(2) and Cd(3) is similar to that of Cd(1). The
adjacentCd(1) andCd(2) centers are connectedbytwocarboxylate
1
1
from one HBTC2- and one BTC3-, adopting a m2-h : h bridging
mode to construct a bimetallic unit [Cd2(CO2)2], in which the
˚
non-bonding distance of Cd(1) ◊ ◊ ◊ Cd(2) is 3.890(8) A. While the
adjacent Cd(3) and Cd(4) ions are connected by a carboxylate
from one BTC3-, adopting a m2-h : h bridging mode to construct
1
1
a bimetallic unit [Cd2(CO2)], in which the non-bonding distance of
Fig. 2 (a) Portion of the crystal structure of 4 showing coordinate
environments of Ni(II) ions; all H atoms are omitted for clarity (symmetry
code: A -1 + x, y, z). (b) The polyhedral view of the self-assembly 1D chain
structure constructed by [Ni3(BTC)2(NiL)2(H2O)6]; the blue polyhedrons
represent Ni(II) atoms.
˚
Cd(3) ◊ ◊ ◊ Cd(4) is 4.195(5) A. The bimetallic units [Cd2(CO2)2] and
[Cd2(CO2)] are connected by bridging ligands BTC3- and HBTC2-
to form a 2D layer framework, as shown in Fig. 3b.
In the 2D frameworks, each HBTC2- ligand connects three
0
1
Cd(II) ions with carboxylate groups, adopting m1-h : h mon-
1
1
odentate, and m2-h : h -bridging coordination modes, as shown
by four carboxylate oxygen atoms from four BTC3- ligands with
in Scheme 1e and Fig. 3b. While each BTC3- ligand connects four
1
1
˚
Ni–O distances 2.0558(19)–2.0718(18) A, and two oxygen atoms
Cd(II) ions with carboxylate groups, adopting m1-h : h -chelating
1 1
˚
from two water molecules (Ni(1)–O(9) = 2.1452(18) A), showing
and m2-h : h -bridging coordination modes (see Scheme 1d).
Topologically, the structure is composed of 3-connecting HBTC2-
anions, 4-connecting BTC3- anions, and 3-connecting Cd(II) ions.
The complicated 3,4,3-connected 6-nodal 2D network is shown
Fig. 3c. The Schla¨fli symbols are (4.62)3(4.63.82)(42.63.8)(42.6).
a distorted octahedral coordination environment. The Ni(2) ion
also has a distorted octahedral geometry with two oxygen atoms
from one oxamido ligand, three oxygen atoms from three water
molecules, a carboxylate oxygen atom from a BTC3-. While
the Ni(3) ion is coordinated by four nitrogen atoms from the
macrocyclic organic ligand, with the [NiN4] geometry exhibiting
a distorted square planarity. Three adjacent metal ions (Ni(1),
Ni(2), Ni(2A)) are connected by two bridging m2-OH2 groups to
construct a linear trimetallic cluster [Ni3(m2-OH2)2], in which the
[Cd(HBTC)(CuL)]·H2O (6)
Single-crystal X-ray analysis revealed that 6 is a complicated
3D framework consisting of crystallographically independent
cadmium(II) and copper(II) ions (Fig. S6†), and crystallizes in
the monoclinic space group P2(1)/n. As shown in Fig. 4a, the
Cu(II) ion is five-coordinated by four nitrogen atoms from the
macrocyclic organic ligand with Cu–N distances 1.962(2)–2.021(2)
˚
non-bonding distances of Ni ◊ ◊ ◊ Ni are 3.7166(4) A (Ni(1) ◊ ◊ ◊ Ni(2)
or Ni(1) ◊ ◊ ◊ Ni(2A)). Ni(3) (Ni(3A)) and the [Ni3(m2-OH2)2] cluster
are interlinked through the macrocyclic oxamide ligand to form a
pentanuclear Ni5 unit. Adjacent pentanuclear units are connected
by two BTC3- bridging ligands to form a 1D infinite chain, as
shown in Fig. 2b. In the 1D chain structure, the BTC3- acts as a
tridentate connector to bridge three Ni(II) ions (Scheme 1c), and
the relationship of the adjacent BTC3- with respect to each other is
anti. Furthermore, the 1D infinite chains are linked together with
O–H ◊ ◊ ◊ O hydrogen bonding to form a 2D framework along the c
2-
˚
˚
A, and one oxygen atom from a HBTC (Cu–O = 2.5602(21)
A) to complete the distorted tetragonal pyramidal coordination
geometry. The apical position is occupied by a carboxylate oxygen
atom. The Cd(II) ion is seven-coordinated by two oxygen atoms
from one oxamido ligand, and five carboxylate oxygen atoms from
three different HBTC2-, with the [CdO7] unit exhibiting a distorted
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Fig. 4 (a) Portion of the crystal structure of 6 showing coordinate
environments of Cd(II) and Cu(II) ions; all H atoms are omitted for
clarity. (b) Portion of the crystal structure of 6 showing the coordinate
environments of HBTC2- ligands; some C atoms of NiL ligands were
removed for clarity. (c) The topological representation of the sra net; the
green and red sticks represent Cd(II) atoms and HBTC2-, respectively.
2
1
adopting a m2-h : h bridging mode to construct a bimetallic
cluster [Cd2O2], in which the non-bonding distances of Cd ◊ ◊ ◊ Cd
˚
are 3.7602(7) A. Two Cu(II) ions and a [Cd2O2] cluster are
interlinked through the macrocyclic oxamide ligand to form a
tetranuclear Cu2Cd2 unit. Adjacent tetranuclear Cu2Cd2 units are
connected by bridging ligands HBTC2- to form 3D frameworks. In
the 3D frameworks, each HBTC2- ligand connects four metal ions
[three Cd(II) and one Cu(II)] with carboxylate groups, adopting m1-
0
1
1
1
2
1
h : h monodentate, m1-h : h -chelating, and m2-h : h -bridging
coordination modes, as shown in Scheme 1f and Fig. 4b.
In the view of topology, the Cd(II) ions and HBTC2- ligands
both are 4-connected nodes. Therefore, the whole structure can
be defined as uni-nodal (4,4)-connected 3D micropore framework
with Schla¨fli symbols (42.63.8), which is a typical sra structure
(Fig. 4c). Such a structure has also been referred by to Smith as
an ABW tetrahedral net in a Li–ABW zeolite and as a SrAl2 net
by O’Keeffe and Hyde.18
Fig. 3 (a) Portion of the crystal structure of 5 showing coordinate
environments of Cd(II) and Ni(II) ions; all H atoms are omitted for
clarity. (b) The polyhedral view of the self-assembly 2D sheet constructed
by BTC3-, HBTC2- and the center Cd(II) atoms; the green polyhedrons
represent Cd(II) atoms; NiL ligands were removed for clarity. (c) The
topological representation of the 2D sheet; the green and orange sticks
represent Cd(II) atoms and 1,3,5-benzenetricarboxylate, respectively.
Magnetic Properties
The magnetization measurements for the complexes 1 and 4 have
been carried out under 2 kOe. The value cM T = 9.36 cm3 mol-1
K
at 300 K for powder sample 1 is larger than the spin-only value
of 7.50 cm3 mol-1 K expected for the uncoupled CoII4 tetranuclear
system (Fig. 5). This indicates an important contribution from the
orbital momentum typical for the high-spin octahedral CoII with
4T1g ground state. On lowering the temperature, cM T decreases
capped-octahedral geometry. The Cd(1)–O bond lengths range
˚
from 2.2448(18) to 2.6283(19) A. Two adjacent cadmium(II) ions
are connected by two carboxylates from two different HBTC2-,
5534 | Dalton Trans., 2011, 40, 5528–5537
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3kT cCo
gCo
=
N b2S(S +1)
7l(3−A )2 12(2 + A )2
2l(11−2A )
45kT
176(A + 2)2
2
⎡
⎢
⎢
⎣
⎤
⎥
⎥
⎦
F =
+
+
+
1
5kT
25A
27A
2
20(A + 2)2
27A
⎡
⎢
⎢
⎣
⎤
⎥
⎥
⎦
⎛
⎞
⎟
⎠
⎛
⎜
⎜
⎞
−4Al
−5Al
2kT
l(A +5)
⎟
⎟
⎜
exp
⎜
+
−
exp
⎟
⎟
⎟
⎟
⎟
⎜
⎜
⎝
⎝
⎠
kT
9kT
⎡
⎢
⎣
⎤
⎞
−4Al
⎛
⎜
⎜
⎞
⎟
⎛
⎜
⎜
l
kT
−5Al
2kT
⎟
⎢
⎥
⎟
F =
3+ 2exp
+ exp
⎟
2
⎟
⎟
⎟
⎥
⎟
⎜
⎝
⎜
⎝
⎠
⎠
kT
⎦
(3)
Where J1 and J2 are the exchange integrals between the Co(II)
and Co(II) ions. A is the ligand field parameter, and l is the spin–
orbit coupling parameter. The least-squares fit to the experimental
data was found with J1 = -3.58 cm-1, J2 = -0.031 cm-1, gTd = 2.00
(fixed), A = 1.49 and l = -170 cm- (fixed), and the agreement
factor defined as R = R(cM)Cal - (cM)obsd]2 / R[(cM)obsd]2 is 3.52 ¥
10-6. The points below 20 K can not be reproduced with this
model. The magnetic behaviors below 20 K may be attributed to
the intralayer and/or interlayer magnetic interactions. The weak
antiferromagnetic interaction presumably originates from the high
Co–O–Co angles of 122.9◦ or 95.98◦, which differ considerably
from 90◦.20
Fig. 5 cM (O) versus T and cMT (ꢀ) versus T plots for the complex 1.
continuously and reaches 0.74 cm3 mol-1 K at 2 K. The shape of the
cM T vs. T curve suggests an overall antiferromagnetic behavior.
On the basis of the crystal structure of 1, NiII ion is diamagnetic
in the NiL subunit, so the magnetic interactions between the
cobalt and nickel ions can be neglected. Meanwhile, the magnetic
interactions between the adjacent tetranuclear units [Co4(m3-OH)2]
can also be neglected, because of the larger separation of Co ◊ ◊ ◊ Co
˚
(about 9.62 A). Thus, the coupling topology deduces from the
For complex 4, the cM T value is equal to 3.45 cm3 mol-1 K at
300 K, which is higher than the spin-only value (3.00 cm3 mol-1
crystal structure has to be considered as the Co4 tetranuclear
units shown in Scheme 2, and the contribution of the spin–orbit
coupling of Co(II) ion is considered according to van Vleck’s
equation.19 The magnetic analysis was carried out by using the
spin Hamiltonian:
K) expected for the uncoupled NiII trinuclear system (Fig. 6).
3
Upon cooling, cM T increases from 300 K to 17 K, and reaches a
maxima of 3.64 cm3 mol-1 K at 17 K. Below 17 K, cM T decreases
quickly to 0.61 cm3 mol-1 K at 2 K. This feature is characteristic
of a noticeable intramolecular ferromagnetic interaction together
with the effect of the zero-field splitting and/or intermolecular
interaction.
ˆ
ˆ ˆ
ˆ ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ ˆ
H = -2J1(S1S2 + S2S1A + S1AS2A + S2AS1) -2J2(S1S1A)+ gb
(1)
ˆ
HZSZ
Scheme 2 The model of magnetic interaction for 1.
The magnetic susceptibility of the tetranuclear complex can be
calculated from eqn 2.
S(S +1)(2S +1)exp(−E(S,S11A )/ kT )
∑
N b2g2
12kT
S
ctetra
=
(2S +1)exp(−E(S,S11A )/ kT )
(2)
∑
Fig. 6 cM-1(O) versus T and cMT (ꢀ) versus T plots for the complex 4.
S
Complex 4 is actually a 1D NiII entity formed by pentanuclear
units [Ni3(BTC)2(NiL)2(H2O)4] linked by the BTC3-, but NiII ion is
diamagnetic in the NiL subunit. Thus, in a first approach the mag-
netic analysis was carried out by using the theoretical expression
of the magnetic susceptibility deduced from the spin Hamiltonian
g = gTd + gCo (T )
Where, part of the orbital angular momentum of Co(II) ion is
reflected in the temperature dependence of the gCo factor (eqn 3).19
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ˆ
ˆ ˆ
ˆ ˆ
the 1D double chains of 4, the (3,6)-connected 2D nets of 1–3,
the (3,4,3)-connected 2D nets of 5, and the (4,4)-connected 3D
sra-type framework of 6. To some extent, this work will enrich the
field of coordination polymers. Further exploration of macrocyclic
oxamide and polycarboxylate-bridged heterometallic materials
combining multi-dimensional frameworks and interesting physical
properties is currently under way in our laboratory.
H = -2J(S1S2 + S2S3). So far as magnetic interactions between the
adjacent trinuclear NiII units are concerned, the molecular field
3
approximation was used cM = ctri/[1 - ctri(2zj¢/Ng2b )]. Where
2
J is the intramolecular exchange integral between nickel(II) ions,
and zj¢ stands for the intermolecular exchange integral of the NiII
3
units. The best-fit parameters obtained were J = 2.69 cm-1, gNi
=
2.12, zj¢ = -0.38 cm-1, and the agreement factor defined as R =
R(cM )Cal - (cM )obsd]2 / R[(cM )obsd]2 is 1.26 ¥ 10-2. The point below
6 K can not be fitted (Fig. S7†). With this hypothesis for fitting,
the zj¢ parameter is overestimated, because the logical D parameter
(zero-field splitting) was not considered.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (No. 20771083, No. 20901059, No. 21001081,
21043004, 90922032 and No. 20771081) and National Basic
Research Program of China, 978 Program, 2007CB815305.
Thus, a more realistic second approach for the magnetic
ˆ
analysis was carried out by using the spin Hamiltonian: H =
2
ˆ ˆ
ˆ ˆ
ˆ
-2J(S1S2 + S2S3) + D[SZ - S(S+1)/3]dS,S
= 3. So far as
magnetic interactions between the adjacent trinuclear NiII units
3
are concerned, the molecular field approximation was used:
cM = ctri/[1 - ctri(2zj¢/Ng2b )]. Where D is a zero-field splitting
2
Notes and references
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gNi = 2.12 (fixed), D = 2.33 cm-1, zj¢ = -0.038 cm-1 and the
2
agreement factor defined as R = R(cM )Cal - (cM )obsd]2 / R[(cM)obsd
]
is 2.65 ¥ 10-5. For complex 4, the second approach reproduces
more satisfactorily the magnetic data in the whole temperature
range (Fig. 6). However, this approach does not improve the fit
because the inter-trinuclear magnetic coupling and D are very
closely related and their independent contribution can not be
easily accounted for.21 Thus, the fitted results only indicate that,
besides the intra-trinuclear coupling, the zero-field splitting and
inter-trinuclear coupling are present.
The weak ferromagnetic coupling observed for complex 4 can
be rationalized by the geometry parameters considerations. The
interaction is predicted to be ferromagnetic for Ni–O–Ni angles
lower than 93.5◦, while the magnetic coupling is antiferromagnetic
for greater values.22 For complex 4, the bond angles of Ni–O–
Ni are 126.23◦ which usually give antiferromagnetic coupling.
However, according to R. Mukherjee et al., when the bridging
ligands are dissimilar, the ferromagnetic interaction between Ni(II)
ions would result from the counter-complementary effect of the
dissimilar bridges.23 Another possible reason for the ferromagnetic
interaction between the Ni(II) ions is the dihedral angles. For
4, the two dissimilar bridges (H2O, COO-) destroy the planar
structure of the two magnetic orbitals of the Ni(II) ions, and
this distortion reduced the overlap integral that exists between
the magnetic orbitals, resulting in a relatively small ferromagnetic
coupling constant.
Conclusions
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One homometallic and five heterometallic coordination poly-
mers were synthesized with macrocyclic oxamide and 1,3,5-
benzenetricarboxylate co-ligands under solvothermal reaction
conditions. This research reveals that (i) the coexistence of
macrocyclic oxamide and polycarboxylate bridged-ligands have
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