Two new metal-organic frameworks based on 5-bromoisophthalic acid and 1,3-bi(4-pyridyl)propane: Hydrothermal syntheses, structures, and magnetic properties

Article abstract of DOI:10.1080/15533174.2011.613890

Two new complexes, [M((H₂O)(bpp)(Brip)]_n (M = Co ^II (1) and Ni^II (2), bpp = 1,3-bi(4-pyridyl)propane, H₂Brip = 5-bromoisophthalic acid), have been synthesized through hydrothermal reaction. They were characterized by elemental analysis, IR spectra, thermal analysis, magnetic properties, and X-ray single-crystal diffraction. The two complexes belong to monoclinic system, C2/c space group. The adjacent Co^II or Ni^II ions are bridged by Brip to form an alternate 1D chain. Such 1D chains are further connected by bpp to generate a twofold interpenetrating diamondoid 3D network. Variable-temperature magnetic susceptibility measurements indicate the occurrence of weak ferromagnetic interactions between the Co^II (1) and Ni^II (2) ions, respectively. Copyright Taylor & Francis Group, LLC.

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Two New Metal-Organic Frameworks Based on 5-
Bromoisophthalic Acid and 1,3-bi(4-pyridyl)propane:
Hydrothermal Syntheses, Structures, and Magnetic
Properties
Min-Le Han a , Hai-Xia Wu a , Ke-Yan Zhao a & Zu-Qiang Zhang a
a College of Chemistry and Chemical Engineering, Luoyang Normal University , Luoyang , P.
R. China
Accepted author version posted online: 14 Mar 2012.Published online: 01 May 2012.
To cite this article: Min-Le Han , Hai-Xia Wu , Ke-Yan Zhao & Zu-Qiang Zhang (2012) Two New Metal-Organic Frameworks
Based on 5-Bromoisophthalic Acid and 1,3-bi(4-pyridyl)propane: Hydrothermal Syntheses, Structures, and Magnetic
Properties, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:4, 590-595, DOI:
10.1080/15533174.2011.613890
To link to this article: http://dx.doi.org/10.1080/15533174.2011.613890
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:590–595, 2012
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.613890
Two New Metal-Organic Frameworks Based on
5-Bromoisophthalic Acid and 1,3-bi(4-pyridyl)propane:
Hydrothermal Syntheses, Structures, and Magnetic
Properties
Min-Le Han, Hai-Xia Wu, Ke-Yan Zhao, and Zu-Qiang Zhang
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, P. R. China
blocks, as they can promote helical or looped structural pat-
Two new complexes, [M((H2O)(bpp)(Brip)]n (M = CoII (1)
and Ni II (2), bpp = 1,3-bi(4-pyridyl)propane, H2Brip = 5-
bromoisophthalic acid), have been synthesized through hydrother-
mal reaction. They were characterized by elemental analysis, IR
spectra, thermal analysis, magnetic properties, and X-ray single-
crystal diffraction. The two complexes belong to monoclinic system,
C2/c space group. The adjacent CoII or Ni II ions are bridged by
Brip to form an alternate 1D chain. Such 1D chains are further con-
nected by bpp to generate a twofold interpenetrating diamondoid
3D network. Variable-temperature magnetic susceptibility mea-
surements indicate the occurrence of weak ferromagnetic interac-
tions between the CoII (1) and NiII (2) ions, respectively.
terns, through which other organic linkers can penetrate.
Among N-donors, 1,3-bi(4-pyridyl)propane, as a flexible
dipyridyl ligand, has four different conformations, TT, TG, GG,
and GG’[24] (the definition of TT, TG, GG, and GG’ is designed
to display quite different N-to-N distance of bpp ligands). It
can be used to construct interpenetrating nets.[24,25–31] In this
work, we will describe the synthesis, structural characteriza-
tion, and magnetic properties of two 3D twofold interpenetrat-
ing coordination frameworks, [Co(H2O)(bpp)(Brip)]n (1) and
[Ni(H2O)(bpp)(Brip)]n (2).
Keywords 1, 3-bi(4-pyridyl)propane, 5-bromoisophthalic acid, crys-
EXPERIMENTAL
tal structure, magnetic properties
Materials and Physical Measurement
All chemicals purchased were of reagent grade and used
without further purification. All the products were highly sta-
ble in air at ambient conditions. Elemental analyses (C, H, and
N) were performed on a Flash 2000 organic elemental ana-
lyzer (Thermo Scientific, Madison, WI, USA). The crystal de-
termination was performed on a Bruker SMART APEX II CCD
diffractometer (Madison, WI, USA) equipped with graphite-
monochromatized Mo Kα radiation (λ = 0.71073 Å). Thermal
analyses were performed on a SII EXStar6000 (SII Nano Tech-
nology Inc., Japan) TG/DTA6300 analyzer heated from 30 to
INTRODUCTION
Recently, the design and construction of metal-organic
frameworks (MOFs) is of great interest in the fields of crys-
tal engineering. Major reasons for this interest stem from their
intriguing variety of topologies and structural diversity, such
as helixes and diamondoid nets and because of their potential
applications as functional materials, such as gas storage, catal-
ysis, fluorescent, magnetism, ion exchange, and sensor technol-
ogy.[1–11] Interpenetrating nets are a longstanding fascination for
chemists, and many interesting structures have been constructed
895◦C under nitrogen. The infrared spectra (4000∼600 cm−1
)
and well discussed in several comprehensive reviews.[12–23]
common strategy in the design of interpenetrating networks
is the use of polycarboxylates and flexible N-donor building
A
were recorded on a NICOLET 6700 FT-IR spectrometer (Madi-
son, WI, USA). Variable-temperature magnetic measurement
were performed on the Quantum Design (Madison, WI, USA)
SQUID MPMS XL-7 instruments in a magnetic field of 2000
Oe in the temperature of 2∼300 K.
Syntheses of Complexes 1 and 2
Received 6 August 2011; accepted 9 August 2011.
The authors gratefully acknowledge the support of the Natu-
ral Science Foundation of Henan Province Educational Committee
(12B150019) and the Youth Foundation of Luoyang Normal Univer-
sity (2011-QNJJ-003).
Address correspondence to Min-Le Han, College of Chemistry and
Chemical Engineering, Luoyang Normal University, Longman Road,
No. 71, Luoyang 471022, P. R. China. E-mail: minle han@163.com
Complex 1 was synthesized by hydrothermal method in
a 25 mL Teflon-lined autoclave by heating a mixture of 5-
bromoisophthalic acid (24.5 mg, 0.1 mmol), bpp (19.8 mg, 0.1
mmol), Co(OAc)2•4H2O (24 mg, 0.1 mmol), and KOH (11.2
mg, 0.2 mmol) in 15 mL water at 433 K for three days. And
then slowly cooled down to room temperature. Red block single
590

COORDINATED CHEMISTRY
591
TABLE 1
Crystal data and structure refinement for 1 and 2
crystals of 1 were obtained. Anal. Calcd. for C21H19BrCoN2 O5
(%): C, 48.67; H, 3.70; N, 5.41. Found: C, 48.71; H, 3.65; N,
5.38. I.R. data (cm−1): 1614s, 1575 m, 1543 m, 1380s, 1358s,
773s, 733s, 716s.
Complex
1
2
2 was synthesized in a similar way to that described for 1,
except that Co(OAc)2•4H2O was replaced by Ni(OAc)2•4H2O.
Green block crystals of 2 were obtained. Anal. Calcd. for
C21H19BrN2NiO5 (%): C, 48.69; H, 3.70; N, 5.41. Found: C,
48.64; H, 3.67; N, 5.44. IR data (cm−1): 1614s, 1538 m, 1447
m, 1423 m, 1358s, 1223 m, 820 m, 769s, 734s, 718s.
Empirical formula
Molecular weight
Crystal system
Space group
a (Å)
C21H19BrN2CoO5 C21H19BrN2NiO5
518.22
518.00
Monoclinic
C2/c
Monoclinic
C2/c
14.279(12)
18.573(16)
16.228(14)
99.777(10)
4261(6)
8
14.602(5)
17.978(6)
16.997(6)
106.590(5)
4276(3)
8
b (Å)
c (Å)
Single-Crystal X-Ray Diffraction
B (◦)
The crystallographic data collections for complexes 1 and
2 were carried out on a Bruker Smart Apex II CCD diffrac-
tometer with a graphite monochromated Mo Kα radiation (λ =
0.71073 Å) by using ϕ/ω scan technique at room temperature.
The empirical absorption corrections were applied. The struc-
tures were solved by direct methods using the SHELXS-97[32]
program and refined by full-matrix least-squares on F2 using the
SHELXL-97[33] program. All of the non-hydrogen atoms were
refined anisotropically. The hydrogen atoms of the ligands were
placed in the geometrically calculated positions. The crystal-
lographic data and structure refinement of complexes 1 and 2
are summarized in Table 1. Selected bond lengths (Å) and bond
angles (◦) as well as the hydrogen bond distances and angles are
presented in Tables 2 and 3, respectively.
V (Å3)
Z
T (K)
296(2)
294(2)
Dcalc (g•cm−3
)
1.623
1.609
µ (mm−1
F(000)
)
2.728
2.811
2088
2096
Max./min.
0.5219/0.4334
0.6943/0.5898
transmission
θ range (◦)
2.35–25.50
2.27–25.50
15853
Reflections collected 14242
Independent
reflections (Rint)
Restraint/parameters 0/271
3945(Rint
0.0284)
=
3964(Rint
0.0805)
0/271
=
Goodness-of-fit
0.973
1.017
(GOF) on F2
R1, wR2 [I > 2σ(I)] 0.0319, 0.0573
0.0482, 0.1099
0.1065, 0.1451
0.693/–0.723
RESULTS AND DISCUSSION
R1, wR2 [all data]
Largest diff. peak
and hole (e •Å−3
ꢀ
0.0516, 0.0643
0.490/–0.506
Description of Crystal Structures
Figure 1 shows a perspective view of the title complexes
with atomic numbering scheme. Complexes 1 and 2 crystal-
lize in the same monoclinic space group C2/c, and the crystal
structure analysis revealed that they have the same structure.
Thus, only the structure of 1 is described here. The asymmet-
)
ꢀ
ꢀ
ꢀ
R = [ || F0 | – | Fc || /
| F0 | ], RW
=
[ | F02 –Fc2 | 2/
(|
W
W
Fw|2) 2]1/2
ric unit of 1 contains one CoII center, one Brip dianion, and ometry. The six-coordinated atoms come from two cis-nitrogen
one bpp ligand, as well as one coordinated water molecule. atoms of two bpp ligands, three carboxylate oxygen atoms of two
Both of the carboxylate groups of the acid are deprotonated. Brip ligands, and one water molecule. The water oxygen atom
The CoII ion is six-coordinated with a distorted octahedral ge- (O5) and a pyridyl nitrogen (N2B) atom of bpp are axial of the
FIG. 1. Molecular structure of the title complexes. H atoms are omitted for clarity.

592
M.-L. HAN ET AL.
TABLE 2
Selected bond lengths (Å) and angles (◦) for complexes 1 and 2
1
Co1-O4#1
Co1-O5
2.028(2)
2.131(3)
93.72(11)
90.00(8)
95.38(9)
116.41(9)
89.18(8)
Co1-N1
Co1-N2#2
2.120(2)
2.165(3)
83.21(8)
90.86(8)
172.25(8)
149.52(8)
89.00(8)
Co1-O2
Co1-O1
2.177(3)
2.252(2)
175.39(8)
90.59(10)
95.20(8)
90.33(8)
59.16(8)
O4#1-Co1-N1
N1-Co1-O5
N1-Co1-N2#2
O4#1-Co1-O2
O5-Co1-O2
O4#1-Co1-O5
O4#1-Co1-N2#2
O5-Co1-N2#2
N1-Co1-O2
N2#2-Co1-O2
O4#1-Co1-O1
N1-Co1-O1
O5-Co1-O1
N2#2-Co1-O1
O2-Co1-O1
2
Ni1-O1
Ni1-N1
2.030(4)
2.073(4)
Ni1-O5
Ni1-O4#3
2.066(4)
2.092(4)
Ni1-N2#4
Ni1-O3#3
2.113(5)
2.296(4)
O1-Ni1-O5
O5-Ni1-N1
O5-Ni1-O4#3
O1-Ni1-N2#4
N1-Ni1-N2#4
88.19(16)
92.31(16)
89.41(15)
90.82(17)
95.00(18)
O1-Ni1-N1
O1-Ni1-O4#3
N1-Ni1-O4#3
O5-Ni1-N2#4
O4#3-Ni1-N2#4
91.85(17)
174.78(16)
92.87(17)
172.65(16)
90.97(16)
O1-Ni1-O3#3
O5-Ni1-O3#3
N1-Ni1-O3#3
O4#1-Ni1-O3#3
N2#2-Ni1-O3#3
115.25(15)
86.63(14)
152.80(16)
59.96(14)
87.21(16)
Symmetry codes: 1: #1: x, –y + 1, z – 1/2; #2: x + 1/2, –y + 3/2, z + 1/2; 2: #3: x, –y + 1, z – 1/2; #4: x – 1/2, –y + 1/2, z – 1/2.
TABLE 3
Distance (Å) and angles (◦) of hydrogen bonding for complexes 1 and 2
D-H. . .A
d(D-H)
d(H. . .A)
d(D. . .A)
∠D-H. . .A
Complex 1
O(5)-H(1W). . .O(2)#5
O(5)-H(2W). . .O(3)#6
Complex 2
0.82
0.84
2.11
1.85
2.832(3)
2.676(3)
145.6
168.0
O(5)-H(2W). . .O(3)#7
O(5)-H(1W). . .O(2)#8
0.83
0.82
1.99
1.91
2.750(5)
2.703(6)
152.1
161.5
Symmetry codes: 1: #5: –x, –y + 1, –z + 2; #6: –x, y, –z + 5/2; 2: #7: –x + 2, y, –z + 1/2; #8: –x + 2, –y + 1, –z.
distorted octahedral coordination sphere of M, with an O5-M-
N2B angle of 172.25(8)◦ for 1 and 172.65(16)◦ for 2. The Co-N
bond lengths are 2.120(2) and 2.165(3) Å and the Co-O ones
are in the range of 2.028(2)–2.252(2) Å. The Ni-N bond lengths
are 2.073(4) and 2.113(5) Å and the Ni-O ones are in the range
of 2.030(4)–2.296(4) Å. Each Brip ligand acts as a µ2-bridge
linking two M ions, in which one carboxylate group adopts
a monodentate mode while another adopts a chelating mode
FIG. 2. Polyhedral view of 1D chains of complexes 1 and 2.

COORDINATED CHEMISTRY
593
coordinating to one M ion. And the bpp ligands with a GG’
Thermal Analysis
conformation providing a N-to-N separation with the distance
of 8.543 Å link the adjacent M ions. Based on the previous
connection, the adjacent M ions are bridged by Brip to form
an alternating 1D chain (Figure 2). Such 1D chains are further
connected through bpp ligands to generate a 3D network with
diamondoid topology with the Schla¨fli symbol of (62. 62. 62. 62.
62. 62.) (Figure 3). The large distances between the metal ions
result in large cavities within the network, and thus one identical
framework fill this space to generate a twofold interpenetrating
network (Figure 3). Hydrogen bonds between the coordinated
water molecules and the carboxylate groups of the Brip ligands
further stabilize the structure (Table 3).
To investigate thermal stabilities of 1 and 2, we studied them
by TGA in Figure 4. The experiments were performed on sam-
ples consisting of numerous single crystals of 1 and 2 under N2
atmosphere with a heating rate of 10◦C•min−1. For complex 1,
weight loss begins at 235◦C, and coordinated water molecules
are lost from 235◦C to 270◦C (calcd. 3.5%, obsd. 3.3%) and
then a rapid weight loss was detected, which is attributed to the
decomposition of complex 1. For complex 2, the first weight
loss of 3.6% between 127◦C and 174◦C indicates the loss of
coordinated water molecules (calcd. 3.5%) and the residue re-
mains unchanged until about 310◦C, and then a rapid weight
loss was detected, which is attributed to the decomposition of
complex 2.
Magnetic Properties
The magnetic susceptibilities, χM, of 1 and 2 were measured
in the 2–300 K temperature range at 2,000 G, and shown as
χMT and χM versus T plots in Figure 5. For complex 1, the
experimental χMT value at 300 K is 2.93 cm3 K mol−1, which
is greater larger than that expected for the spin-only one for a
high-spin cobalt ion (1.87 cm3·mol−1·K with g = 2.0), but is
close to the value of 3.37 cm3·mol−1·K expected when the spin
momentum and the orbit momentum exist independently (µLS
= [L(L + 1) + 4S(S + 1)]1/2, L = 3, S = 3/2). This is due
to the occurrence of an unquenched orbital contribution typi-
4
cal of the T1g ground state in six-coordinated cobalt(II) com-
plexes. Upon cooling, the value continuously increases reaching
a maximum value of 3.33 cm3·mol−1·K at 76 K, and then de-
creases upon further cooling. The χMT values increase with
the decrease of the temperature, typical of the presence of in-
tradimeric ferromagnetic interaction, and the decrease of χMT
may be attributed to intermolecular antiferromagnetic interac-
tion and/or the zero-field splitting term of the Co(II) ion.[34] The
FIG. 3. (a) Polyhedral view of 3D network of complexes 1 and 2. (b) Topology
of complexes 1 and 2.
FIG. 4. The TGA curves for complexes 1 and 2.

594
M.-L. HAN ET AL.
1.65 K, and R = 2.572 × 10−4, the positive θ value supports the
presence of overall ferromagnetic interactions.
CONCLUSIONS
In summary, two new complexes, [M((H2O)(bpp)(Brip)]n
(M = CoII (1) and Ni II (2), bpp = 1,3-bi(4-pyridyl)propane,
H2Brip = 5-bromoisophthalic acid), have been synthesized and
characterized. The two complexes have twofold interpenetrat-
ing diamondoid 3D networks. Variable-temperature magnetic
susceptibility measurements indicate the occurrence of weak
ferromagnetic interactions between the CoII (1) and NiII (2)
ions, respectively.
SUPPLEMENTARY MATERIALS
The atomic coordinates and other parameters of structure
1 and 2 have been deposited with the Cambridge Crystallo-
graphic Data Centre (nos. 824627 and 824628, respectively;
deposit@ccdc.cain-ac.uk or http://www.ccdc.ac.uk).
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Graphic Abstract-Pictogram:
Title: Syntheses, Structures, and Magnetic Properties
of Two New Metal-Organic Frameworks Based on 5-
bromoisophthalic acid and 1,3-bi(4-pyridyl)propane
Two new complexes, [M((H2O)(bpp)(Brip)]n (M = CoII
(1) and Ni II (2), bpp = 1,3-bi(4-pyridyl)propane, H2Brip =
5-bromoisophthalic acid), have been synthesized through hy-
drothermal reaction. Complexes 1 and 2 have the same struc-
ture. The adjacent metal ions are bridged by Brip to form an
alternate 1D chain. Such 1D chains are further connected by
Cd(II) coordination polymers based on bromoisophthalic acids and various bpp to generate a twofold interpenetrating diamondoid 3D net-
dipyridyl-type coligands. Cryst. Growth Des. 2011, 11, 175–184.
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work. Moreover, thermal stabilities and magnetic properties of
complexes 1 and 2 have also been investigated.
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