Fine tuning of the coordination environments and magnetic properties of first row transition metal ions with 5-methylisophthalate and 2,2′-bipyridine/phenanthroline

Article abstract of DOI:10.1016/j.poly.2012.10.052

Twelve coordination compounds of Mn²⁺, Fe²⁺, Co ²⁺, Ni²⁺, Cu²⁺ and Zn²⁺, with mixed organic ligands 5-methylisophthalic acid, 2,2′-bipyridine or phenanthroline, have been hydrothermally synthesised and characterised. The magnetic properties of the Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ compounds have been investigated. Structure analysis shows that the assemblies with a bridging ligand possessing a smaller methyl group (compared to the tert-butyl group) afford coordination compounds containing multinuclear metal centres and structures of higher dimension. The result shows that the structures and properties of the metal-organic materials can be finely tuned by the substituent on the organic bridging ligands.

Full text of DOI:10.1016/j.poly.2012.10.052

Polyhedron 50 (2013) 219–228
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Fine tuning of the coordination environments and magnetic properties of first
row transition metal ions with 5-methylisophthalate and 2,20-bipyridine/
phenanthroline
⇑
⇑
Xi-Ling Deng, Shi-Yao Yang , Rui-Fang Jin, Jun Tao , Chao-Qing Wu, Ze-Lan Li, La-Sheng Long,
Rong-Bin Huang, Lan-Sun Zheng
State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
a r t i c l e i n f o
a b s t r a c t
Twelve coordination compounds of Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+, with mixed organic ligands
5-methylisophthalic acid, 2,20-bipyridine or phenanthroline, have been hydrothermally synthesised
and characterised. The magnetic properties of the Mn2+, Co2+, Ni2+ and Cu2+ compounds have been inves-
tigated. Structure analysis shows that the assemblies with a bridging ligand possessing a smaller methyl
group (compared to the tert-butyl group) afford coordination compounds containing multinuclear metal
centres and structures of higher dimension. The result shows that the structures and properties of the
metal–organic materials can be finely tuned by the substituent on the organic bridging ligands.
Ó 2012 Elsevier Ltd. All rights reserved.
Article history:
Received 9 August 2012
Accepted 29 October 2012
Available online 19 November 2012
Keywords:
Crystal engineering
Hydrothermal synthesis
Crystal structure
Magnetic properties
1. Introduction
metal centres for discrete coordination compounds or low dimen-
sional coordination polymers. We predicted that when ligands
The metal centres of coordination compounds are extremely
important in designing the structures and properties of metal–
organic materials [1–10], because the coordination environments
of metal ions determine the distances and interactions between
the metal ions [11–14]. For example, the structures of the metal
clusters, whether monomer, dimer, trimer or infinite 1D, 2D and
3D structures, are very important in the understanding of the mag-
netic properties of cobalt MOFs [15].
with less coordination hindrance are applied in the assembly,
structures with multinuclear metal centres and higher dimensions
will be obtained [53]. Here we report the fine tuning of the coordi-
nation environments of first row transition metal ions with
5-methylisophthalate as a bridging ligand and 2,20-bipyridine or
phenanthroline as coligands (Scheme 1), in 12 coordination
compounds 1–12 (Table 1). The magnetic properties of 1, 3, 4, 5,
6, 7 and 8 have also been investigated.
Since organic ligands are easily modified, one straightforward
approach is the use of organic ligands with different substituents
to adjust the coordination environments of the metal ions. A large
number of coordination compounds containing first row transition
metal ions (Mn, Fe, Co, Ni and Cu) and 5-substituted isophthalic
acids, e.g. isophthalic acid, (H2ip) [16–39], 5-tert-butylisophthalic
acid (H2tbip) [40–43] and other analogues [44,45], have been
reported recently. A few reports on 5-methylisophthalic acid
(H2mip) [46,47] have been reported, correspondingly. In our previ-
ous works we found that the coordination steric effect plays a deci-
sive role in determining the forms of the metal centres and the
structures of the products [48–52]. Accordingly, when a bridging
ligand with significant steric hindrance, i.e. 5-tert-butylisophthalic
acid (H2tbip), was applied in the assembly, small metal ions tend to
connect to fewer bridging ligands and thus act as mononuclear
2. Experiment
2.1. Materials and instrumentation
All reagents and solvents were of analytical reagent grade, and
were used without further purification. The concentration of the
NaOH solution was determined by auto-potential titration analysis
with a Mettler Toledo DL50 Titrator. Infrared spectra were re-
corded on a Nicolet AVATAR FT-IR 330 spectrometer as KBr pellets
in the frequency range 4000–400 cmꢀ1. The elemental analyses (C,
H, N) were measured on a Vario EL III analyzer. X-ray powder dif-
fractions were measured on a Panalytical X-Pert pro diffractometer
with Cu K
a radiation. DSC-TGA data were recorded on a TA SDT
Q600 thermal analyzer in N2 with a 10 °C/min heating rate, in
the temperature range 30–800 °C. X-ray powder diffraction plots,
IR spectra and photoluminescent measurement of the compounds
are displayed in the Supporting information.
⇑
Corresponding authors. Fax: +86 592 2183047.
E-mail addresses: syyang@xmu.edu.cn (S.-Y. Yang), taojun@xmu.edu.cn (J. Tao).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.10.052

220
X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
Scheme 1. Ligands used in our work.
Table 1
Coordination compounds synthesised in this work.
mip
bpy
Mn2+
Fe2+
Co2+
Ni2+
Cu2+
Zn2+
{[Mn6(bpy)4(mip)6]
ꢁ3.5H2O}n
{[Co3(bpy)2(mip)3]ꢁ2H2O}n
3
{[Ni(bpy)(H2O)
[Cu3(bpy)2(Hmip)2(mip)2]n
[Cu3(bpy)2(mip)2(OH)2]n
7
[Zn2(bpy)2(H2O)
(mip)2]n 11
1
(mip)]ꢁH2O}n
{[Ni3(mip)3(phen)2] [Cu3(Hmip)2(mip)2(phen)2]n
ꢁ3.8 H2O}n [Cu(Hmip)2(phen)] 10
5
8
phen
[Fe(phen)3]ꢁ(H0.5mip)
[Co(mip)(H2O)(phen)]n
4
9
[Zn4(mip)4
(phen)4]n 12
ꢁ(H1.5mip)ꢁ(H2mip)ꢁ4.5H2O 2
6
2.2. Syntheses
2.2.1. General procedure
(KBr, cmꢀ1): 3419(s), 3060(w), 1621(vs), 1580, 1547, 1428, 1384,
1343(vs), 728(s).
Under vigorous magnetic stirring, 5-methylisophthalic acid
(H2mip, 0.090 g, 0.50 mmol) was suspended in 10 ml water, an
accurate amount of 1.0 mmol (if not mentioned specially) NaOH
was slowly added, and then the (hydrated) chloride salt of
manganese, iron, cobalt, nickel, copper or zinc was added. Finally,
2,20-bipyridine (bpy, 0.078 g, 0.50 mmol) or 1,10-phenanthroline
(phen, 0.100 g, 0.50 mmol) was added. The mixture was trans-
ferred into a 20 ml Teflon-lined vessel, heated to 120–200 °C at
the rate of 5 °C/h, and kept at that temperature for 3 days, then
slowly cooled down to room temperature at the rate of 5 °C/h.
Crystals were obtained by filtration, washed with water and dried
in air. The purity of products was verified by powder X-ray diffrac-
tion measurement.
2.2.1.5. Synthesis of {[Ni(bpy)(H2O)(mip)]ꢁH2O}n (5). NiCl2ꢁ6H2O
(0.118 g, 0.50 mmol) was used in the synthesis, and the reaction
temperature was 150 °C. Green crystals were obtained (0.153 g,
yield 73 % based on NiCl2ꢁ6H2O). Elemental Anal. Calc. for C38H34N4-
Ni2O11: C, 54.33; H, 4.08; N, 6.67. Found: C, 55.35; H, 4.06; N 6.74%.
FTIR (KBr, cmꢀ1): 3369(s), 1622(s), 1444(s), 1332(s), 762(s), 728.
2.2.1.6. Synthesis of {[Ni3(mip)3(phen)2]ꢁ3.8H2O}n (6). NiCl2ꢁ6H2O
(0.118 g, 0.50 mmol) was used in the synthesis, and the reaction
temperature was 200 °C. Light green crystals were obtained
(0.069 g, yield 37% based on NiCl2ꢁ6H2O). Elemental Anal. Calc.
for C51H41.60N4Ni3O15.8: C, 53.76; H, 3.68; N, 4.92. Found: C,
54.06; H, 4.00; N, 5.11%. FTIR (KBr, cmꢀ1): 3438(s), 3070(w),
2920(w), 1620(s), 1585(s), 1420(s), 1375(vs), 773, 727(s).
2.2.1.1. Synthesis of {[Mn6(bpy)4(mip)6]ꢁ3.5H2O}n (1). MnCl2ꢁ4H2O
(0.099 g, 0.50 mmol) was used in the synthesis, and the reaction
temperature was 150 °C. Yellow crystals were obtained (0.127 g,
yield 61% based on MnCl2ꢁ4H2O). Elemental Anal. Calc. for
2.2.1.7. Synthesis of [Cu3(bpy)2(Hmip)2(mip)2]n (7). CuCl2ꢁ2H2O
(0.085 g, 0.50 mmol) and 0.5 mmol NaOH were used in the synthe-
sis, and the reaction temperature was 150 °C. Blue block crystals
were obtained (0.100 g, yield 50% based on CuCl2ꢁ2H2O). Elemental
Anal. Calc. for C56H42Cu3N4O16: C, 55.24; H, 3.48; N, 4.60. Found: C,
55.15; H, 3.46; N, 4.35%. FTIR (KBr, cmꢀ1): 3442, 3070(w), 2920(w),
1666, 1615(s), 1569(s), 1372(s), 773(s), 718.
C
94H75Mn6N8O27.5: C, 54.07; H, 3.60; N, 5.37. Found: C, 53.63; H,
3.82; N, 5.26%. FTIR (KBr, cmꢀ1): 3431(s), 1614, 1575, 1408,
1369(s), 769, 723.
2.2.1.2. Synthesis of [Fe(phen)3]ꢁ(H0.5mip)ꢁ(H1.5mip)ꢁ(H2mip)ꢁ4.5H2O
(2). FeCl2ꢁ4H2O (0.099 g, 0.50 mmol) was used in the synthesis,
and the reaction temperature was 120 °C. Red block crystals were
obtained (0.085 g, yield 61% based on FeCl2ꢁ4H2O). Elemental Anal.
Calc. for C63H55FeN6O16.5: C, 62.23; H, 4.56; N, 6.91. Found: C,
62.10; H, 4.87; N, 6.68%. FTIR (KBr, cmꢀ1): 3423(vs), 2920(w),
1686(s), 1603, 1425(s), 1277, 1222, 846, 724.
2.2.1.8. Synthesis of {[Cu3(bpy)2(mip)2(OH)2]ꢁH2O}n (8). CuCl2ꢁ2H2O
(0.085 g, 0.50 mmol) and 1 mmol NaOH were used in the synthesis,
and the reaction temperature was 150 °C. Dark blue block crystals
were obtained (0.033 g, yield 22% based on CuCl2ꢁ2H2O). Elemental
Anal. Calc. for C38H30Cu3N4O10: C, 51.09; H, 3.38; N, 6.27. Found: C,
50.42; H, 3.58; N, 6.14%. FTIR (KBr, cmꢀ1): 3422(w), 3040(w), 1619,
1559, 1434(w), 1339(s), 1030(w), 775, 730(w).
2.2.1.3. Synthesis of {[Co3(bpy)2(mip)3]ꢁ2H2O}n (3). CoCl2ꢁ6H2O
(0.119 g, 0.50 mmol) was used in the synthesis, and the reaction
temperature was 200 °C. Dark red crystals were obtained
(0.068 g, yield 39% based on CoCl2ꢁ6H2O). Elemental Anal. Calc.
for C47H38Co3N4O14: C, 53.27; H, 3.61; N, 5.29. Found: C, 52.71;
H, 3.75; N, 5.12%. FTIR (KBr, cmꢀ1): 3446, 3070, 2920, 1616(s),
1566(s), 1443(s), 1371(s), 770(s), 720(s).
2.2.1.9. Synthesis of [Cu3(Hmip)2(mip)2(phen)2]n (9). CuCl2ꢁ2H2O
(0.085 g, 0.50 mmol) and 0.5 mmol NaOH were used in the synthe-
sis, and the reaction temperature was 150 °C. Blue block crystals
were obtained (0.108 g, yield 51% based on CuCl2ꢁ2H2O). Powder
X-ray diffraction measurement showed that the product was not
pure. Efforts to get a pure phase of the product were not successful.
2.2.1.10. Synthesis of [Cu(Hmip)2(phen)] (10). Blue block crystals of
the compound were separated and collected in the synthesis (Sec-
tion 2.2.1.9) (0.036 g, yield 12% based on CuCl2ꢁ2H2O). Elemental
Anal. Calc. for C30H22CuN2O8: C, 59.85; H, 3.68; N, 4.65. Found: C,
59.18; H, 3.84; N, 4.53%. FTIR (KBr, cmꢀ1): 3437, 3120, 1713(s),
1610, 1543(s), 1415(s), 1178, 723.
2.2.1.4. Synthesis of [Co(mip)(H2O)(phen)]n (4). CoCl2ꢁ6H2O (0.119 g,
0.50 mmol) was used in the synthesis, and the reaction tempera-
ture was 180 °C. Dark red crystals were obtained (0.062 g, yield
28% based on CoCl2ꢁ6H2O). Elemental Anal. Calc. for C21H16CoN2O5:
C, 57.94; H, 3.70; N, 6.44. Found: C, 57.52; H, 3.62; N, 6.31%. FTIR

X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
221
2.2.1.11. Synthesis of [Zn2(bpy)2(H2O)(mip)2]n (11). ZnCl2 (0.068 g,
0.50 mmol) was used in the synthesis, and the reaction tempera-
ture was 200 °C. Colorless block crystals were obtained (0.123 g,
yield 33% based on ZuCl2). Powder X-ray diffraction measurement
showed that the product was not pure. Efforts to get a pure phase
of the product were not successful.
direct method or Patterson method using SHELXS-97 and refined
by full-matrix least-squares techniques using SHELXL-97. The H
atoms on ligands were positioned geometrically and were allowed
to ride on the C atoms in the subsequent refinement (aromatic
C–H = 0.93 Å, U(H) = 1.2 Ueq(C), methyl C–H = 0.95 Å, U(H) = 1.5 Ueq
(C)). The water H-atoms were located and refined with O–
H = 0.85 Å, U(H) = 1.5 Ueq(O) restraints. The water H-atoms were
set to proper positions so that more hydrogen bonds could be
formed. Occupancy factors for the H atoms in 2 were determined
according to charge balance and electron density residuals. Crystal
data for the 12 compounds are listed in Table 2.
2.2.1.12. Synthesis of [Zn4(mip)4(phen)4]n (12). ZnCl2 (0.068 g,
0.50 mmol) was used in the synthesis, and the reaction temperature
was 200 °C. Colorless block crystals were obtained (0.172 g, yield
81% based on ZnCl2). Elemental Anal. Calc. for C84H56N8O16Zn4: C,
59.52; H, 3.33; N, 6.61. Found: C, 59.11; H, 3.97; N, 6.48%. FTIR
(KBr, cmꢀ1): 3439(vs), 3060, 2910, 1622(s), 1579, 1425, 1384,
1352, 725(w).
2.4. Magnetic measurements
2.3. X-ray crystallography
Magnetic measurements were performed on a Quantum Design
MPMS-XL SQUID magnetometer operating in the temperature
range 2–300 K with a dc magnetic field up to 7 T. No pure phase
of 9 was obtained, and 10 was a discrete coordination compound
with mononuclear Cu2+, therefore their magnetic properties were
not investigated.
Data were collected on a Bruker-APEX CCD diffractometer
equipped with a graphite-monochromated Mo Ka radiation source
(k = 0.71073 Å). Absorption corrections were performed with the
SADABS program (Bruker, 2002). The structures were solved by the
Table 2
Crystal data for the 12 compounds.
1
2
3
4
5
6
Empirical formula
Moiety formula
C
94H75Mn6N8O27.5
C63H55FeN6O16.5
C47H38Co3N4O14
{[Co3(bpy)2(mip)3]ꢁ
C21H16CoN2O5
[Co(mip)(H2O)
(phen)]n
435.29
173(2)
C19H17N2NiO5.5
{[Ni(bpy)(H2O)
(mip)]ꢁH2O}n
420.06
C51H41.6N4Ni3O15.8
{[Ni3(mip)3(phen)2]ꢁ
3.8H2O}n
1139.41
173(2)
{[Mn6(bpy)4(mip)6]ꢁ [Fe(phen)3]ꢁ(H0.5mip)ꢁ
3.5H2O}n
2086.26
299(2)
(H1.5mip)ꢁ(H2mip)ꢁ4.5H2O 2H2O}n
Formula weight
T (K)
1215.98
173(2)
1059.60
299(2)
173(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
triclinic
P1
triclinic
P1
triclinic
P1
triclinic
P1
triclinic
P1
triclinic
P1
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
9.8064(4)
14.1070(6)
17.7991(7)
74.497(1)
85.240(1)
70.980(1)
2243.16(16)
1, 1.544
0.905
13.1812(6)
15.3279(7)
16.1465(8)
110.516(1)
100.594(1)
108.165(1)
2741.1(2)
2, 1.473
0.358
9.7077(5)
13.8542(7)
17.3724(9)
77.689(1)
88.098(1)
70.716(1)
2152.90(19)
2, 1.635
1.220
8.2424(5)
9.8018(5)
13.0866(7)
70.271(1)
86.450(1)
67.053(1)
913.49(9)
2, 1.583
0.977
9.1258(4)
9.5473(4)
11.7644(5)
85.291(1)
69.763(1)
65.111(1)
869.97(6)
2, 1.604
1.153
9.4704(4)
14.6546(7)
19.3856(9)
109.822(1)
90.184(1)
108.004(1)
2389.48(19)
2, 1.584
1.248
a
(°)
b (°)
c
(°)
V (Å3)
Z, Dcalc (g cmꢀ3
l
)
(mmꢀ1
)
F(000)
1065
1266
1082
446
434
1172
Rint
0.0361
0.0279
0.0352
0.0267
0.0209
0.0483
S
0.995
1.049
1.055
1.043
1.036
1.019
R1 [I > 2
r
(I)]
0.0506
0.0517
0.0562
0.0426
0.0305
0.0529
wR2 (all data)
(e Aꢀ3
CCDC No.
0.1584
0.1485
0.1423
0.1092
0.0827
0.1250
D
q
)
0.743/ꢀ0.536
0.492/ꢀ0.383
0.712/ꢀ0.528
0.613/ꢀ0.309
0.450/ꢀ0.255
0.731/ꢀ0.469
870216
870217
870218
870219
870220
870221
7
8
9
10
11
12
Empirical formula
Moiety formula
C
56H42Cu3N4O16
C38H30Cu3N4O10
C60H42Cu3N4O16
C30H22CuN2O8
C38H30N4O9Zn2
C84H56N8O16Zn4
[Cu3(bpy)2(Hmip)2 [Cu3(bpy)2(mip)2(OH)2]n [Cu3(Hmip)2(mip)2(phen)2]n [Cu(Hmip)2(phen)] [Zn2(bpy)2(H2O)(mip)2]n [Zn4(mip)4(phen)4]n
(mip)2]n
Formula weight
T (K)
Crystal system
Space group
a (Å)
1217.56
173(2)
893.28
173(2)
1265.60
297(2)
602.04
173(2)
monoclinic
C2/c
9.405(2)
15.603(3)
17.309(3)
90
94.029(3)
90
817.40
173(2)
triclinic
1694.85
173(2)
monoclinic
C2/c
37.8339(17)
21.0751(10)
17.8468(8)
90
101.727(1)
90
triclinic
monoclinic
P21/c
9.7952(4)
17.3004(7)
14.9976(4)
90
138.927(1)
90
1669.82(11)
2, 1.777
1.964
triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
10.1241(5)
11.1747(5)
11.8998(5)
81.934(1)
65.219(1)
84.761(1)
1209.42(10)
1, 1.672
1.390
8.4538(4)
13.0424(6)
13.1171(6)
111.201(1)
97.688(1)
103.576(1)
1271.98(15)
1, 1.652
1.325
8.6409(4)
11.9867(5)
16.5066(7)
89.304(1)
89.792(1)
73.497(1)
1639.13(12)
2, 1.656
1.531
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
2533.8(7)
4, 1.578
0.922
13933.2(11)
8, 1.616
1.442
Z, Dcalc (g cmꢀ3
l
)
(mmꢀ1
)
F(000)
621
906
645
1236
836
6912
Rint
S
0.0222
1.042
0.0360
1.009
0.0300
1.015
0.0299
1.064
0.0289
1.044
0.0430
1.033
R1 [I > 2
r
(I)]
0.0341
0.0937
0.0394
0.1071
0.0432
0.1162
0.0395
0.1009
0.617/ꢀ0.800
884191
0.0385
0.1030
0.0443
0.1177
wR2 (all data)
(e Aꢀ3
CCDC No.
D
q
)
0.483/ꢀ0.305
0.760/ꢀ0.689
1.582/ꢀ0.305
0.625/ꢀ0.392
0.757/ꢀ0.415
870222
884190
870223
870224
870225

222
X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
In compound 1, each Mn3 metal centre contains three
3. Results and discussion
3.1. Structure descriptions
edge-sharing polyhedra: one octahedron between two pentagonal
bipyramids, as in [Mn3(tbip)3(bpy)2]n [53] (Fig. 1, I and II). The
coordination bond distances for the two metal centres are
different, being longer in type II. (2.268, 2.164 Å in type I; 2.357,
2.180 Å in type II)
3.1.1. The structures of 1, 3 and 6
As predicted in our previous report [53], when a ligand with less
coordination hindrance (mip relative to tbip) is applied in the
assembly of coordination compounds, it is expected that structures
with multinuclear metal centres and higher dimensions are
obtained. The structures of the three compounds, even the Ni ana-
logue (6), are formed with trinuclear metal centres connected by
mip bridging ligands (Fig. 1). In the trinuclear metal centre, the
three metal ions are arranged in a straight line by six carboxyls
from six mip bridging ligands. The metal ion in the middle is coor-
dinated by six oxygen atoms from six carboxyls, and the metal ions
at either of the two ends are coordinated by four to five oxygen
atoms from three carboxyls, in addition to two nitrogen atoms
from chelating ligand bpy or phen ligands. The mip ligand can
In 3, as Co2+ is smaller than Mn2+, the coordination number of
Co2+ is smaller, and there are two types of Co3 metal centres, types
I and III (three corner-sharing octahedra). The coordination bond
distances for the two metal centres are 2.186 and 2.086 Å in
type I, and 2.166 and 2.108 Å in type III. In the tbip analogue,
{[Co3(bpy)2(tbip)3Co(bpy)(tbip)]ꢁ5H2O}n, in which the coordination
hindrance is larger, there are trinuclear Co3 and mononuclear Co
mixed metal centres [53].
Both of the two metal centres in 6 belong to type III, the coor-
dination bond distances are slightly different, with 2.091 and
2.044 Å for one Ni3 centre, and 2.076 and 2.030 Å for the other.
The average coordination numbers and the average coordination
bond lengths for the three compounds are Mn 6.7, 2.265 Å, Co
6.3, 2.150 Å and Ni 6, 2.072 Å, correspondingly. The decrease in
distinguish the tiny difference in the radii of Mn2+ Co2+ and Ni2+
and results in the formation of three types of trinuclear metal
centres (Fig. 1).
,
Fig. 1. Coordination modes of trinuclear metal centres in 1 (I, II), 3 (I, III) and 6 (III). Hydrogen atoms and guest water molecules have been omitted for clarity.
Fig. 2. The 2D structure of 1 in the (011) plane (hydrogen atoms and water molecules are omitted). The structures of 3 and 6 are the same.

X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
223
the coordination numbers of the metal ions verifies the effect of
the ionic radius.
The mip ligands adopt three kinds of coordination modes: syn–
syn, syn–anti (with l2-oxygen) and anti-anti (with l2-oxygen). The
trinuclear metal centres are bridged by six mip ligands to form a
(3,6) net. Their 2D structure motifs are quite similar to that in
[Mn3(tbip)3(bpy)2]n, reported recently by us (Fig. 2) [53]. All the
three compounds contain some lattice water molecules in their
crystal structures.
3.1.2. The structure of 2
This compound is similar to [Fe(phen)3]ꢁ2Htbipꢁ3.5H2O [53],
containing tri-phen coordinated low-spin Fe2+ ions (average Fe–N
bonds 1.973 Å), partly deprotonated mip anions, H2mip and lattice
water molecules (Fig. 3). Hydrogen bonds are formed between
carboxyl groups (2.470(3) Å 170(6)°, 2.5057(19) Å 169.7°, 2.4805
(19) Å 175.7°), carboxyl groups and water molecules (2.549(2) Å
167.3°, 2.779(2) Å 172(3)°, 2.803(2) Å 170(3)°), and water mole-
cules (2.732(2) Å 165(3)°).
3.1.3. The structures of 4 and 5
In the structures of 4 and 5, each metal ion is coordinated by
two nitrogen atoms from bpy or phen, one oxygen atom from a
Fig. 3. Crystal structure of 2. Hydrogen bonds are shown in dashed red lines, and C–
H hydrogen atoms have been omitted for clarity. (Colour online.)
Fig. 4. Crystal structures of 4 (left) and 5 (right).
Fig. 5. Coordination modes of trinuclear Cu3 centres (left) and 2D structure (right) of 7. Intramolecular hydrogen bonds are shown in dashed red lines, and C–H hydrogen
atoms have been omitted for clarity. (Colour online.)

224
X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
The structure of 8 is a chain constructed by Cu3 metal centres
joined by pairs of mip2ꢀ ligands. (Fig. 6) In the metal centre, every
two Cu2+ ions are bridged by one
2-hydroxyl and one oxygen
l
atom from a carboxyl group of mip2ꢀ. Cu2 in the middle is further
chelated by two carboxyls from two trans mip ligands. Cu1 at the
end is further coordinated by two oxygen atoms from bpy and
two oxygen atoms from two cis mip ligands. The coordination
mode for mip is (bidentate (syn–anti) + monoatomic bridge) and
monodentate. Each Cu3 centre is linked to other two adjacent ones
along the a axis by pairs of mip ligands.
3.1.5. The structures of 9 and 10
The Cu3 metal centre in 9, attached to two Hmipꢀ and four
mip2ꢀ ligands, is different from those discussed above in Sections
3.1.1 and 3.1.4 (Fig. 7). The protonated carboxyl group of Hmipꢀ
is not involved in coordination, and the deprotonated carboxyl
group coordinates to two Cu ions in chelating and monoatomic
bridge manners. The Cu3 metal centres are connected to each other
in a line by pairs of trans mip2ꢀ bridging ligands in syn–syn biden-
tate and monoatomic bridging modes to form a chain running
along the a axis (Fig. 7, right).
Fig. 6. Coordination modes of the trinuclear Cu3 centre in the 1D structure of 8.
Intramolecular hydrogen bonds are shown in dashed red lines. (Colour online.)
10 is a discrete coordination compound, with a Cu2+ ion coordi-
nated by four oxygen atoms from two trans Hmipꢀ ligands in a che-
lating mode and two nitrogen atoms from one phen (Fig. 8).
Hydrogen bonds are formed between –COOH and –COOꢀ (2.605
(2) Å, 153.6°).
water molecule and three oxygen atoms from two mip ligands
(Fig. 4). The mip ligand adopts chelating and monodentate
coordination modes. The two mip bridging ligands attached to
one metal ion are in a cis arrangement and the three oxygen atoms
from them are in mer positions. The metal ions are bridged by mip
ligands to form the chain structures of the two coordination poly-
mers along the [1–10] direction. The straight chain structures are
the same as that in {[Zn(phen)(tbip)(H2O)]ꢁH2O}n [53].
3.1.6. The structure of 11
There are two crystallographically independent zinc ions in 11,
and each one is coordinated by two oxygen atoms from bpy, one
water molecule and two (Zn1) or three (Zn2) oxygen atoms from
mip. The coordination modes of the two mip ligands are bismonod-
entate and chelating-monodentate. Every two zinc ions are bridged
3.1.4. The structures of 7 and 8
by one l2-H2O molecule to form a Zn2 metal centre as two corner-
The structure of 7 contains three edge-sharing octahedra
formed by two crystallographically independent Cu2+ ions (Fig. 5
left). Cu1 in the middle is coordinated by six oxygen atoms from
two trans mip ligands and two trans Hmip ligands. Cu2 is coordi-
nated by two nitrogen atoms from bpy and four oxygen atoms
from two cis mip ligands and two trans Hmip ligands. The bridging
mip ligand adopts monodentate and (chelating + monoatomic
bridge) coordination modes, and Hmip adopts bidentate (syn–anti)
and monodentate modes. The Cu3 metal centre is connected to four
other metal centres by eight bridging ligands (four Hmipꢀ along
the a axis and four mip2ꢀ along the b axis) to form a (4,4) net
parallel to the ab plane (Fig. 5 right).
sharing polyhedra. The metal centres are further connected to each
other by two pairs of mip2ꢀ bridging ligands in a cis arrangement
to form a chain running along the c axis (Fig. 9).
3.1.7. The structure of 12
There are four crystallographically independent zinc ions in the
structure of 12, forming two Zn2 metal centres. In each metal cen-
tre, one Zn2+ is in an octahedral environment, whilst the other one
is in a square pyramidal environment. The coordination modes for
one pair of mip ligands are bridging (syn–syn) and monodentate,
and for the other, bridging (syn–syn) and chelating. The motif of
Fig. 7. Coordination modes of the trinuclear Cu3 centres (left) and chain structure (right) of 9. C–H hydrogen atoms have been omitted for clarity.

X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
225
magnetic exchange interaction in the linear trinuclear Mn2+ unit
is given by H = ꢀ2J(S2S1 + S2S3) (S1 = S2 = S3 = 5/2, J is the exchange
constant between the adjacent Mn2+ ions, and it is assumed to be 0
between the terminal manganese ions). The
vMT versus T relation
of the two Mn3 units obeys the following equation [54]:
vM
¼
v
t=ð1 ꢀ vtð2zJ0=Ng2b2ÞÞ
vt ¼ 2ðN2g b2=2kTÞðA=BÞ
A ¼ 35 þ 84 expð5xÞ þ 35 expðꢀ2xÞ þ 10 expðꢀ7xÞ
þ 165 expð10xÞ þ 84 expðxÞ þ 35 expðꢀ6xÞ
þ 10 expðꢀ11xÞ þ expðꢀ14xÞ þ 286 expð15xÞ
þ 165 expð4xÞ þ 84 expðꢀ5xÞ þ 35 expðꢀ12xÞ
þ 10 expðꢀ17xÞ þ expðꢀ20xÞ þ 455 expð20xÞ
þ 286 expð7xÞ þ 165 expðꢀ4xÞ þ 84 expðꢀ13xÞ
þ 35 expðꢀ20xÞ þ 10 expðꢀ25xÞ þ 680 expð25xÞ
þ 455 expð10xÞ þ 286 expðꢀ3xÞ þ 165 expðꢀ14xÞ
þ 84 expðꢀ23xÞ þ 35 expðꢀ30xÞ
B ¼ 6 þ 8 expð5xÞ þ 6 expðꢀ2xÞ þ 4 expðꢀ7xÞ þ 10 expð10xÞ
þ 8 expðxÞ þ 6 expðꢀ6xÞ þ 4 expðꢀ11xÞ þ 2 expðꢀ14xÞ
þ 12 expð15xÞ þ 10 expð4xÞ þ 8 expðꢀ5xÞ þ 6 expðꢀ12xÞ
þ 4 expðꢀ17xÞ þ 2 expðꢀ20xÞ þ 14 expð20xÞ þ 12 expð7xÞ
þ 10 expðꢀ4xÞ þ 8 expðꢀ13xÞ þ 6 expðꢀ20xÞ þ 4 expðꢀ25xÞ
þ 16 expð25xÞ þ 14 expð10xÞ þ 12 expðꢀ3xÞ þ 10 expðꢀ14xÞ
þ 8 expðꢀ23xÞ þ 6 expðꢀ30xÞ
Fig. 8. Structure of 10. Intermolecular hydrogen bonds are shown in dashed red
lines. (Colour online.)
the structure is a double stranded chain running along the c axis
formed by Zn2 units bridged by pairs of mip ligands (Fig. 10), same
as the reported structures assembled with the isophthalate ana-
logue ligands [16–39].
where x = J/(kT)
3.2. Magnetic properties
The best-fit parameters are: J = ꢀ1.35(1) cmꢀ1
, zJ = 0.0025
(9) cmꢀ1
,
g = 2.02(1). The field-dependent magnetisation
Magnetic measurements for 1 and 3–8 were performed on pow-
(Fig. S27a, inset) also confirms the antiferromagnetic properties
and the saturated value at 7 T nearly corresponds to the theoretical
one (NgSTNb = 10 Nb).
dered samples in the temperature range 2-300 K. The
and M versus H plots are displayed in Figs. S27 and S28, and vM
versus T plots are shown in Figs. S27–S35.
v
MT versus T
ꢀ1
The
vMT value for 3 (Fig. S27b) at room temperature is
The
v
MT value for 1 (Fig. S27a) at room temperature is
8.68 cm3 K molꢀ1, which is significantly higher than the spin-only
value (5.625 cm3 K molꢀ1) expected for three uncoupled high-spin
Co2+ ions and indicates unquenched orbital angular momentum
25.17 cm3 K molꢀ1, which is slightly smaller than the expected va-
lue (6 ꢂ 4.375 = 26.25 cm3 K molꢀ1) expected for six uncoupled
high-spin Mn2+ ions (Si = 5/2, gi = 2). As the temperature decreases
contributions. As the temperature decreases from 300 K, the
vMT
from 300 K, the
v
MT value decreases gradually to a value of
value decreases monotonously and attains a value of 4.38 cm3 -
K molꢀ1 at 2 K, which is smaller than the value (3 ꢂ 1.73 = 5.19
cm3 K molꢀ1) expected for three uncoupled Co2+ ions with effective
spin (Seff = 1/2, g = 4.3). Thus the overall profile can be attributed to
both spin–orbital coupling and intracluster antiferromagnetic
interactions (C = 3.53 cm3 molꢀ1 K and h = ꢀ1.41 K).
8.87 cm3 K molꢀ1 at about 2 K, which indicates that the three
Mn2+ ions within both of the two Mn3 clusters antiferromagneti-
cally interact with each other (C = 6.17 cm3 molꢀ1
K
and
h = ꢀ0.442 K according to Curie–Weiss Law, STtrimer + STtrimer = 5/
2 + 5/2). The Heisenberg spin Hamiltonian model for the isotropic
Fig. 9. Double stranded chain structure in 11. Intramolecular hydrogen bonds are shown in dashed red lines. (Colour online.)

226
X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
The best fit parameters are found as J = ꢀ2.8(1) cmꢀ1
,
D = ꢀ5.5(2) cmꢀ1, zJ = ꢀ0.6(1) cmꢀ1, g = 2.31(1). It is revealed that
the nature of the magnetic interactions between the Ni2+ ions
clearly depends on the Ni–O–Ni bridging angle, an increase of
the Ni–O–Ni bridge angle and hence Niꢁ ꢁ ꢁNi distance simulta-
neously strengthens the antiferromagnetic coupling and weakens
the ferromagnetic coupling, and the ferromagnetic crossover point
for the Ni–O–Ni bridge angle is 97° [56–58]. For complex 6, the Ni–
O–Ni bond angles are 91.39°, 98.36° and 104.72° in either of the
two Ni3 units, consistent with antiferromagnetic exchanges
(C = 4.11 cm3 molꢀ1 K and h = ꢀ0.364 K).
The value of
v ,
MT for 7 (Fig. S28c) at 300 K is 1.27 cm3 K molꢀ1
which is close to that expected for three uncoupled Cu2+ ions
(1.125 cm3 K molꢀ1 per Cu3 unit with S = 1/2, g = 2.00). On cooling
the temperature, the
vMT value increases to reach a maximum of
2.03 cm3 K molꢀ1 at 2.6 K and then decrease to 1.81 at 2 K, which
is indicative of ferromagnetic coupling between the adjacent Cu2+
ions in the trinuclear species (C = 0.595 cm3 molꢀ1
K
and
h = 36.2 K). The decrease of the
vMT value below 2.6 K is most likely
due to intercluster antiferromagnetic interactions. The
vMT versus
T relation of the Cu3 unit is:
Fig. 10. Crystal structure of the double stranded chain of 12 along the c axis.
vM ¼ ðN2b2=4kTÞðA=BÞ þ Na
g
The structure of 4 is a uniform chain, with Co2+ ions separated
by mip ligands, the same as that of [Co(tbip)(phen)(H2O)]nꢁH2O
[53], so their magnetic properties are expected to be similar. The
A ¼ 1 þ expð2J=kTÞ þ 10 expð3J=kTÞ
B ¼ 1 þ expð2J=kTÞ þ 2 expð3J=kTÞ
Na ¼ 12 ꢂ 10ꢀ6 cm3 molꢀ1
v
MT value for 4 Fig. S27c) at room temperature is 2.99 cm3 K
molꢀ1, which is higher than the expected value (1.875 cm3 -
K molꢀ1) for a spin-only Co2+ ion, thus showing a significant orbital
angular momentum contribution. As the temperature decreases,
The best fit gives the parameters J = 5.2(4) cmꢀ1
,
zJ = ꢀ0.17(1) cmꢀ1, g = 2.13(1). The \Cu–O–Cu angles in Cu3 are
91.35° and 102.48°, one is smaller and the other is larger than
97°, the limiting value for ferromagnetic coupling in the trinuclear
Cu2+ centre [59–66].
the v
MT value slowly decreases to 1.90 cm3 K molꢀ1 at 2 K, indicat-
ing antiferromagentic interactions as well as spin–orbital coupling.
However, an inclined plateau at 6–10 K implies that the antiferro-
magnetic interaction between the Co2+ ions may be canted.
Field-dependent magnetic susceptibilities between 2 and 50 K
(Fig. S27d) further revealed the canted antiferromagnetic interac-
tions (C = 2.55 cm3 molꢀ1 K and h = ꢀ1.49 K).
The value of v ,
MT for 8 (Fig. S28d) at 300 K is 0.68 cm3 K molꢀ1
which is smaller than the expected one for three uncoupled Cu2+
ions (1.125 cm3 K molꢀ1 per Cu3 unit with S = 1/2, g = 2.00). On
cooling the temperature, the
vMT value decreases rapidly to reach
a minimum of 0.46 cm3 K molꢀ1 at 90 K and then slightly rises to a
maximum (0.49 cm3 K molꢀ1) at 46 K, followed by a further de-
crease to 0.46 cm3 K molꢀ1 at 2 K. This behavior is indicative of
antiferromagnetic coupling between the adjacent Cu2+ ions in the
trinuclear species, which results in spin ground state ST = 1/2
(C = 0.751 cm3 molꢀ1 K and h = ꢀ95.7 K). In the Cu3 metal centre,
The
v ,
MT value for 5 (Fig. S28a) at 300 K is 1.25 cm3 K molꢀ1
which is slightly larger than the spin-only value of 1.00 cm3 -
K molꢀ1 for a paramagnetic Ni2+ ion. (S = 1, g = 2.00). On tempera-
ture lowering, the
vMT values decrease slowly until 13.7 K and
then decrease dramatically to 0.57 cm3 K molꢀ1, which suggests
that there exist very weak antiferromagnetic interactions between
every two Cu2+ ions are bridged by one
l2-hydroxyl (with strong
the Ni2+ ions and the sharp decrease of the
vMT value at low
Cu–O bonds 1.9064(17), 1.9215(18) Å, and large \Cu–O–Cu
127.1(1)° > 97°) and one oxygen atom from the carboxyl group of
mip2ꢀ (with long and weak Cu–O bonds 2.568(3), 2.835(2) Å, and
small \Cu–O–Cu 78.57(5)° < 97°). The antiferromagnetic coupling
within the Cu3 unit is consistent with the structural feature. The
peak at 46 K, which appears every time under different measure-
ments, may be caused by the interaction between the Cu3 units,
not by oxygen.
temperature may be due to
a zero-field splitting effect
(C = 2.56 cm3 molꢀ1 K and h = ꢀ0.276 K).
The
v ,
MT value for 6 (Fig. S28b) at 300 K is 4.06 cm3 K molꢀ1
which is larger than the spin-only value of 3.00 cm3 K molꢀ1for a
non-interacting Ni3 unit (S = 1, g = 2.00). On lowering the tempera-
ture, the
vMT value decreases gradually and below c.a. 10 K
decreases rapidly to 1.73 cm3 K molꢀ1 at 2 K. This profile suggests
antiferromagnetic interactions between the Ni2+ ions and also a
zero-field splitting effect. A theoretical treatment for the magnetic
properties of complex 6 can be described by the following equation
[55]:
3.3. Thermal properties
DSC-TGA plots for all the compounds are shown in Figs. S36–
S47. For 1, there is a tiny gradual weight loss (0.7%) before
400 °C (H2O = 0.9%), indicating the loss of part of the guest water
molecules before the measurement (3.5H2O = 3.0%). There is a
sharp weight loss at the range 400–459 °C (30.7%), indicating the
loss of four bpy ligands (30.3%). There is a weight loss (35.8%) clo-
sely following the last one, indicating the incomplete decomposi-
tion of Mn(mip) (ꢀ42.0%). For 2, the weight loss from 60 to
100 °C is caused by the release of two water molecules (2.9%,
2H2O = 3.0%). Then the compound undergoes four continuous
weight losses from 227 to 800 °C. For 3, there is a gradual weight
vM ¼ ðN2b2=2kTÞðA=BÞ þ Na
g
A ¼ 8 þ 18 expðꢀ5yÞ þ 2 expð3yÞ þ 10 expðꢀ6xÞ
þ 2 expðꢀ10xÞ þ 10 expðꢀ2xÞ þ 2 expðꢀ6xÞ þ 2 expðꢀ4xÞ
B ¼ 2 þ 2 expðꢀ5yÞ þ 2 expðꢀ3yÞ þ expðꢀ4yÞ þ 5 expðꢀ6xÞ
þ 3 expðꢀ10xÞ þ 5 expðꢀ2xÞ þ 3 expðꢀ6xÞ
þ expðꢀ8xÞ þ 3 expðꢀ4xÞ
where x = J/kT, y = D/kT, N = 120 ꢂ 10ꢀ6 cm3 molꢀ1
.
a

X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
[4] J.J. Perry IV, J.A. Perman, M.J. Zaworotko, Chem. Soc. Rev. 38 (2009) 1400.
227
loss (1.4%) before 340 °C corresponding to the loss of one water
molecule (H2O = 1.7%). From 340 to c.a. 500 °C, there is a rapid
weight loss indicating the decomposition of the compound. For 4,
the weight loss (4.0%) at 87–119 °C corresponds to the loss of
coordinate water (H2O 4.1%). A series of weight losses above
324 °C correspond to the decomposition of the compound. For 5,
the weight loss (7.8%) at 106–320 °C corresponds to the loss of
one guest water and one coordinate water molecule (2H2O 8.6%).
From c.a. 320 to 800 °C the compound undergoes incomplete
decomposition. For 6, a 1.2% weight loss occurs before 320 °C
which is caused by the loss of one water molecule (H2O, 1.6%), indi-
cating the loss of part of the guest water molecules before the mea-
surement. A series of weight losses after that corresponds to the
decomposition of the compound. The TGA–DSC plots for 7–10 are
quite similar, with one acute weight loss step occurring in the tem-
perature range 250–350 °C for each compound, corresponding to
one sharp DSC peak at about 291 °C for 7, 296 °C for 8, 286 °C for
9 and 257 °C for 10. The weight percentages for all the residues
at 800 °C are higher than that calculate for CuO, indicating that
the decompositions are not complete. For 11, a weight loss (2.3%)
occurs at 115-141 °C, corresponding to the coordinate water
(H2O = 2.20%), then the compound undergoes decomposition from
206 °C continuously to 800 °C. For 12, the compound undergoes
decomposition from 325 °C continuously to 800 °C. Thermal
analyses of the coordination polymers containing trinuclear metal
centres show that the skeletons collapse at lower temperature as
the atomic number increases: 1 (Mn3) 441 °C, 3 (Co3) 429 °C, 6
(Ni3) 339 °C, 7–9 (Cu3) ꢃ290 °C.
[5] Z. Wang, G. Chen, K. Ding, Chem. Rev. 109 (2009) 322.
[6] J.-R. Li, R.J. Kuppler, H.-C. Zhou, Chem. Soc. Rev. 38 (2009) 1477.
[7] J.Y. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Chem. Soc.
Rev. 38 (2009) 1450.
[8] G. Férey, J. Chem. Soc., Dalton Trans. (2009) 4400.
[9] A.U. Czaja, N. Trukhan, U. Müller, Chem. Soc. Rev. 38 (2009) 1284.
[10] M.D. Allendorf, C.A. Bauer, R.K. Bhakta, R.J.T. Houk, Chem. Soc. Rev. 38 (2009)
1330.
[11] K.-Z. Shao, Y.-H. Zhao, Y.-Q. Lan, X.-L. Wang, Z.-M. Su, R.-S. Wang,
CrystEngComm 13 (2011) 889.
[12] S. Bordiga, F. Bonino, K.P. Lillerudb, C. Lamberti, Chem. Soc. Rev. 39 (2010)
4885.
[13] D.J. Tranchemontagne, J.L. Mendoza-Cortés, M. O’Keeffe, O.M. Yaghi, Chem.
Soc. Rev. 38 (2009) 1257.
[14] M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. O’Keeffe, O.M. Yaghi,
Acc. Chem. Res. 34 (2001) 319.
[15] M. Kurmoo, Chem. Soc. Rev. 38 (2009) 1353. and references therein.
[16] J.-P. Zhang, Y.-Y. Lin, X.-C. Huang, X.-M. Chen, Eur. J. Inorg. Chem. (2006) 3407.
[17] A.L. Pochodylo, R.L. LaDuca, Z. Anorg. Allg. Chem. 636 (2010) 2568.
[18] L.-Y. Zhang, M.-H. Zeng, X.-Z. Sun, Z. Shi, S.-H. Feng, X.-M. Chen, J. Mol. Struct.
697 (2004) 181.
[19] C.-B. Ma, C.-N. Chen, Q.-T. Liu, F. Chen, D.-Z. Liao, L.-C. Li, L.-C. Sun, Eur. J. Inorg.
Chem. 16 (2004) 3316.
[20] C.-B. Ma, C.-N. Chen, Q.-T. Liu, D.-Z. Liao, L.-C. Li, Eur. J. Inorg. Chem. 11 (2008)
1865.
[21] Y.-F. Deng, D.-Z. Kuang, M.-S. Chen, Y.-L. Feng, Y.-F. Kuang, Y.-L. Peng, Chin. J.
Inorg. Chem. 22 (2006) 551.
[22] D.-W. Liu, L. Zhang, S.-Y. Niu, L. Li, Z.-F. Shi, J. Jin, Y.-X. Chi, Chin. J. Inorg. Chem.
25 (2009) 2175.
[23] Q. Zhang, B.-H. Ye, C.-X. Ren, X.-M. Chen, Z. Anorg. Allg. Chem. 629 (2003)
2053.
[24] Z.-B. Han, Y.-K. He, C.-H. Ge, J. Ribas, L. Xu, J. Chem. Soc., Dalton Trans. 28
(2007) 3020.
[25] X.-M. Chen, G.-F. Liu, Chem. Eur. J. 8 (2002) 4811.
[26] L. Gao, G.-H. Li, M.-H. Bi, Y.-W. Hu, X.-M. Liu, Z. Shi, S.-H. Feng, Chem. J. Chin.
Univ. 30 (2009) 1691.
[27] Y.-F. Zhou, W.-J. Lin, Y.-G. Huang, M.-C. Hong, Acta Crystallogr., Sect. E 61
(2005) m177.
4. Conclusion
[28] Y.-F. Zhou, Y.-J. Zhao, D.-F. Sun, J.-B. Weng, R. Cao, M.-C. Hong, Polyhedron 22
(2003) 1231.
In the hydrothermal syntheses with Mn2+, Fe2+, Co2+, Ni2+, Cu2+
and Zn2+, and the mixed organic ligands 5-R-isophalic acids, 2,20-
bipyridine (bpy) or phenanthroline (phen), when a bridging ligand
(H2mip) with a moderately small substituent, i.e. methyl, is applied
in the assembly, the metal ions Mn2+, Co2+, Ni2+ and Cu2+, of differ-
ent radii, can form multinuclear metal centres. Furthermore, the
metal centres display subtle differences, therefore the coordination
environments of the metal ions and the interactions between them
can be finely tuned. The substituent on the organic bridging ligand
can be used as a regulator to adjust the structures and properties of
metal–organic materials.
[29] L.-Y. Zhang, G.-F. Liu, S.-L. Zheng, B.-H. Ye, X.-M. Zhang, X.-M. Chen, Eur. J.
Inorg. Chem. 16 (2003) 2965.
[30] J.-J. Nie, L.-J. Liu, Y. Luo, D.-J. Xu, J. Coord. Chem. 53 (2001) 365.
[31] W.-H. Bi, D.-F. Sun, R. Cao, X. Li, Q. Shi, Chin. J. Chem. 22 (2004) 271.
[32] Y. Hou, E.-H. Shen, S.-T. Wang, E.-B. Wang, D.-R. Xiao, Y.-G. Li, L. Xu, C.-W. Hu,
Inorg. Chem. Commun. 6 (2003) 1347.
[33] Y.-F. Zhou, Q. Shi, D.-Q. Yuan, Y.-Q. Xu, M.-C. Hong, Chin. J. Struct. Chem. 24
(2005) 503.
[34] C.-B. Li, L.-J. Zhang, Y.-H. Sun, Y. Li, T.-G. Wang, J.-Q. Xu, Chem. J. Chin. Univ. 24
(2003) 1366.
[35] Y.-Z. Zheng, Y.-B. Zhang, M.-L. Tong, W. Xue, X.-M. Chen, J. Chem. Soc., Dalton
Trans. 8 (2009) 1396.
[36] Y. An, X.-F. Li, L.-H. Dong, Y.-S. Yin, Acta Crystallogr., Sect. E 64 (2008) m1574.
[37] Y.-C. Cui, X.-M. Li, C.-B. Li, Q.-W. Wang, B. Liu, G.-F. Li, Chin. J. Struct. Chem. 24
(2005) 1411.
[38] Y.-G. Sun, X.-F. Gu, E.-J. Gao, L. Ren, D.-S. Zhang, J. Xu, Chin. J. Struct. Chem. 26
(2007) 157.
Acknowledgement
[39] J.-P. Zhang, Y.-Y. Lin, X.-C. Huang, X.-M. Chen, Eur. J. Inorg. Chem. 17 (2006) 3407.
[40] C.-B. Tian, Z.-Z. He, Z.-H. Li, P. Lin, S.-W. Du, CrystEngComm 13 (2011) 3080.
[41] Z.-X. Du, L.-Y. Wang, H.-W. Hou, Z. Anorg. Allg. Chem. 635 (2009) 1659.
[42] Y.-T. Fan, B. Li, L.-F. Ma, L.-Y. Wang, Chin. J. Struct. Chem. 28 (2009) 1061.
[43] X.-L. Li, M.-L. Huang, Acta Crystallogr., Sect. E 64 (2008) m1501.
[44] A.M. Pochodylo, R.L. LaDuca, Inorg. Chim. Acta 371 (2011) 7178.
[45] Z.M. Wilseck, C.M. Gandolfo, R.L. LaDuca, Inorg. Chim. Acta 363 (2010) 3865.
[46] Q.-B. Bo, H.-Y. Wang, D.-Q. Wang, Z.-W. Zhang, J.-L. Miao, G.-X. Sun, Inorg.
Chem. 50 (2011) 10163.
We thank the NNSFC (Grant Nos. 21071117, 21021061) and
NFFTBS (No. J1030415) for supporting the research.
Appendix A. Supplementary material
CCDC 870216–870225, 884190, 884191 contain the supple-
mentary crystallographic data for compounds 1–7, 9, 11, 12, 8
and 10, respectively. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.poly.2012.10.052.
[47] Z.-L. Yu, J.-L. Hu, Acta Crystallogr., Sect. E 64 (2008) m1522.
[48] H.-M. Li, S.-Y. Yang, J.-W. Wang, L.-S. Long, R.-B. Huang, L.-S. Zheng, Polyhedron
29 (2010) 2851.
[49] D.-S. Zhou, F.-K. Wang, S.-Y. Yang, Z.-X. Xie, R.-B. Huang, CrystEngComm 11
(2009) 2548.
[50] S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, S.W. Ng, Inorg. Chim. Acta 358
(2005) 1882.
[51] S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, Chem. Commun. (2002) 472.
[52] S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, Main Group Metal Chem. 2
(2002) 329.
[53] R.-F. Jin, S.-Y. Yang, H.-M. Li, L.-S. Long, R.-B. Huang, L.-S. Zheng,
CrystEngComm 14 (2012) 1301.
[54] X.-J. Wang, J.-L. Yin, J. Chen, Y.-L. Feng, J. Inorg. Chem. (Wuji Huaxue Xuebao) 2
(2011) 367.
[55] J.-W. Lu, C.-Y. Chen, M.-C. Kao, C.-M. Cheng, H.-H. Wei, J. Mol. Struct. 936
(2009) 228.
[56] K.K. Nanda, R. Das, K. Venkatsubramanian, K. Nag, Proc. Indian Acad. Sci.
(Chem. Sci.) 106 (1994) 673.
References
[1] Y. Pang, D. Tian, X.-F. Zhu, Y.-H. Luo, X. Zheng, H. Zhang, CrystEngComm 13
(2011) 5142.
[2] Y. Liu, W. Xuan, Y. Cui, Adv. Mater. 22 (2010) 4112.
[3] W. Zhang, H.-Y. Ye, R.-G. Xiong, Coord. Chem. Rev. 253 (2009) 2980.

228
X.-L. Deng et al. / Polyhedron 50 (2013) 219–228
[57] K.K. Nanda, A.W. Addison, N. Paterson, E. Sinn, L.K. Thompson, U. Sakaguchi,
Inorg. Chem. 37 (1998) 1028.
[62] L.K. Thompson, S.K. Mandal, S.S. Tandon, J.N. Bridson, M.K. Park, Inorg. Chem.
35 (1996) 3117.
[58] P.D.W. Boyd, R.L. Martin, G. Schwarzenbach, Aust. J. Chem. 41 (1988) 1449. and
references cited therein.
[63] E.V. Rybak-Akimova, D.H. Busch, P.K. Kahol, N. Pinto, N.W. Alcock, H.J. Clase,
Inorg. Chem. 36 (1997) 510.
[59] E. Ruiz, P. Alemany, S. Alvarez, J. Cano, J. Am. Chem. Soc. 119 (1997) 1297.
[60] V.H. Crawford, H.W. Richardson, J.R. Wasson, D.J. Hodgson, W.E. Hatfield,
Inorg. Chem. 15 (1976) 2107.
[61] D. Black, A.J. Blake, K.P. Dancey, A. Harrison, M. McPartlin, S. Parsons, P.A.
Tasker, G. Whittaker, M. Schröder, J. Chem. Soc., Dalton Trans. (1998) 3953.
[64] C. Biswas, M.G.B. Drew, A. Figuerola, S. Gómez-Coca, E. Ruiz, V. Tangoulis, A.
Ghosh, Inorg. Chim. Acta 363 (2010) 846.
[65] A.J. Blake, J.P. Danks, A. Harrison, S. Parsons, P. Schooler, G. Whittaker, M.
Schröder, J. Chem. Soc., Dalton Trans. (1998) 2335.
[66] A.J. Blake, J.P. Danks, I.A. Fallis, A. Harrison, W.-S. Li, S. Parsons, S.A. Ross, G.
Whittaker, M. Schröder, J. Chem. Soc., Dalton Trans. (1998) 3969.