Synthesis, crystal structure, and magnetic properties of a new manganese(II) complex based on 5-bromoisophthalate and 1,2-Bis(4-pyridyl)-ethane Ligands

Article abstract of DOI:10.1080/15533174.2011.591320

A new Mn(II) complex, [Mn(5-Br-ip)(bpa)]_n [5-Br-H₂ip = 5-bromoisophthalate; bpa = 1,2-bis(4-pyridyl)-ethane], has been prepared by hydrothermal reactions of Mn(II) salt and 5-bromoisophthalic acid with bpa and characterized by elemental analysis and single crystal X-ray analysis. The title complex belongs to the monoclinic system, P2/c space group, a = 10.2935(7) A, b = 13.7759(10) A, c = 17.0594(12) A,β = 103.9340(10)°, F(000) = 964. R₁ = 0.0586, wR₂ = 0.1716. Complex 1 consists of a two-dimensional (2D) network containing noncentrosymmetric dinuclear Mn units as nodes, and further extends into a three-dimensional (3D) supramolecular architecture via weak interlayer BrBr interactions. Moreover, the magnetic property of the title complex was investigated. Copyright Taylor &Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.591320

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:888–892, 2011
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.591320
Synthesis, Crystal Structure, and Magnetic Properties of a
New Manganese(II) Complex Based on
5-Bromoisophthalate and 1,2-Bis(4-pyridyl)-ethane Ligands
Jian-Hua Qin, Jian-Ge Wang, Ke-Yan Zhao, and Yue Hu
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, P. R. China
dination polymers in virtue of the robust and versatile coordina-
tion capability of carboxylate.[8–14] However, the related dicar-
boxylate ligands bearing noncoordinated electron-withdrawing
and electron-donating groups on the aromatic backbone have
received less attention at this stage. 5-Bromoisophthalate (5-
Br-H2ip), may serve as a suitable building block to construct
novel coordination polymers, due to the existence of a non-
coordinating electron-withdrawing Br group on the aromatic
backbone, which will have a profound impact on the electron
density of such a ligand and therefore different physical and
chemical properties.[15–18] Here we report the synthesis and crys-
tal structure of a new complex, [Mn(5-Br-ip)(bpa)]n. Moreover,
the magnetic property of this complex was investigated.
A new Mn(II) complex, [Mn(5-Br-ip)(bpa)]n [5-Br-H2ip = 5-
bromoisophthalate; bpa = 1,2-bis(4-pyridyl)-ethane], has been
prepared by hydrothermal reactions of Mn(II) salt and 5-
bromoisophthalic acid with bpa and characterized by elemental
analysis and single crystal x-ray analysis. The title complex be-
longs to the monoclinic system, P2/c space group, a = 10.2935(7)
Å, b = 13.7759(10) Å, c = 17.0594(12) Å, β = 103.9340(10)◦,
F(000) = 964. R1 = 0.0586, wR2 = 0.1716. Complex 1 consists of
a two-dimensional (2D) network containing noncentrosymmetric
dinuclear Mn units as nodes, and further extends into a three-
dimensional (3D) supramolecular architecture via weak interlayer
Br···Br interactions. Moreover, the magnetic property of the title
complex was investigated.
Keywords 5-bromoisophthalate, crystal structure, hydrothermal syn-
thesis, magnetic property
EXPERIMENTAL
Materials and Physical Measurements
INTRODUCTION
All reagents used in the syntheses were of analytical grade.
Elemental analyses for carbon, hydrogen and nitrogen were
performed on a Vario EL III elemental analyzer. The crystal
determination was performed on a Bruker Smart Apex II CCD
diffractometer equipped with graphite-monochromatized Mo-
Kα radiation (λ = 0.71073 Å). The magnetic measurement
was performed on the Quantum Design Squid MPMS XL-7
instrument in the temperature range of 2–300 K.
The construction of metal-organic frameworks (MOFs) has
become an exciting and expanding approach to novel materi-
als. The interest is stimulated not only by the MOFs’ structural
diversities but also by their extensive potential applications in
such areas as separation, molecular recognition, ion exchange,
gas sorption and storage, nonlinear optics, magnetics, and catal-
ysis.[1–7] In principle, the most effective approach for the con-
struction of MOFs is to rationally modify the building blocks
and to control the assembled motifs for required products via se-
lecting different organic ligands.[8,9] Among the various ligands,
isophthalic acid (H2isop) and its derivatives with special con-
formations, such as with a 120◦ angle between two carboxylic
groups, have been extensively used to prepare a variety of coor-
Synthesis of [Mn(5-Br-ip)(bpa)]n
This complex was prepared under hydrothermal condi-
tions. A mixture of 5-Br-H2ip (0.2 mmol), bpa (0.2 mmol),
Mn(OAc)2·4H2O (0.2 mmol), KOH (5.6 mg, 0.2 mmol), and
H2O (16 mL) was placed in a Teflon-lined stainless-steel vessel,
heated to 140◦C for 72 h, and then cooled to room temperature
over 36 h. Yellow block crystals of 1 were collected by filtra-
tion, washed with water, and dried in air. Anal.: Calcd. (%) for
C20H15BrMnN2O4: C, 49.82; H, 3.14; N, 5.81. Found (%):C,
49.85; H, 3.08; N, 5.85.
Received 14 January 2011; accepted 18 February 2011.
This work was supported by the Henan Tackle Key Problem of Sci-
ence and Technology (No. 112102310528 and 102102210246) and
the Foundation of Education Committee of Henan Province (No.
2011B150023).
Address correspondence to Jian-Hua Qin, College of Chemistry and
Chemical Engineering, Luoyang Normal University, Luoyang, 471022,
P. R. China. E-mail: jh q128105@126.com
Crystallographic Data Collection and Structure
Determination
Single crystal x-ray diffraction analysis of 1 was carried out
on a Bruker Smart Apex II CCD diffractometer equipped with
888

NEW MANGANESE(II) COMPLEX
889
TABLE 1
Crystallographic data
Empirical formula
Formula weight
Temperature (K)
Crystal system
C20H15BrMnN2O4
482.19
296(2)
Monoclinic
P2/c
Space group
Unit cell dimensions
a = 10.2935(7) Å
b = 13.7759(10) Å
c = 17.0594(12) Å
β = 103.9340(10)a˚
2347.9(3) Å3, 4
1.364
Volume, Z
Dc (kg m−3
F(000)
)
964
Crystal size (mm3)
0.21 × 0.18 × 0.15
θ range for data collection (a˚) 2.46–25.49
Reflections collected
Independent reflections
Final R indices (I > 2σ(I))
R indices (all data)
17566
4375R(int) = 0.0194
R = 0.0586, wR = 0.1716
R = 0.0676, wR = 0.1792
FIG. 1. A perspective drawing of the Mn(II) environment.
graphite-monochromated Mo Kα radiation (λ = 0.71073Å) by
using the ϕ/ω scan technique at room temperature. The structure
was solved by direct methods with SHELXS-97.[19] Empirical
absorption corrections were applied with the SADABS pro-
gram.[20] All nonhydrogen atoms were refined anisotropically.
The hydrogen atoms were assigned with common isotropic dis-
placement factors and included in the final refinement by use of
geometrical restrains. A full-matrix least-squares refinement on
F2 was carried out using SHELXL-97.[21] Table 1 shows crys-
tallographic crystal data of 1. Selected bond lengths and angles
are listed in Table 2.
nodes. As depicted in Figure 1, the asymmetric unit of 1 con-
tains one Mn(II) ion, one 5-Br-ip ligand, and one bpa lig-
and. Each octahedral Mn(II) ion is coordinated by four car-
boxylate oxygen atoms of three 5-Br-ip anions, located at the
basal equatorial plane, and a pair of pyridyl nitrogen atoms
of bpa from the axial positions with an N1–Mn(1)–N2A an-
gle of 171.8(3)◦. The Mn–O and Mn–N bond lengths are in
the range of 2.113(3)–2.347(3) and 2.200(7)–2.332(5) Å, re-
spectively, which are in the normal range expected for such
coordination bonds.[8,9] In this structure, the Mn···Mn distance
in the [Mn2(COO)2] dimeric unit is 4.347(1) Å. Each 5-Br-ip
anion serves as a tridentate ligand to link the Mn(II) centers to
generate a one-dimensional (1D) polymeric motif (Figure 2).
These 1D motifs are further connected by bpa ligands to form
a 2D layer (Figure 3), which extends into a three-dimensional
RESULTS AND DISCUSSION
Crystal Structure Description
[Mn(5-Br-ip)(bpa)]n.
The structure of 1 consists of a two-dimensional (2D) net- (3D) supramolecular architecture via weak interlayer Br···Br in-
work containing noncentrosymmetric dinuclea Mn units as teractions (Br···Br distance: 3.5123(7) Å). From the topological
TABLE 2
Selected bond lengths (Å) and bond angles (◦)
Mn(1)–O(2)#2
Mn(1)–O(1)
Mn(1)–O(3)#4
Mn(1)–O(4)#4
Mn(1)–N(1)
Mn(1)–N(2)#3
O(2)#2–Mn(1)–O(3)#4
O(2)#2–Mn(1)–N(1)
2.113 (3)
2.136 (3)
2.202 (3)
2.347 (3)
2.275 (4)
2.332 (5)
92.25 (12)
94.08 (14)
O(1)–Mn(1)–N(1)
85.91 (13)
92.65 (14)
91.9 (3)
92.25 (12)
94.08 (14)
85.91 (13)
92.65 (14)
91.9 (3)
O(3)#4–Mn(1)–N(1)
O(2)#2–Mn(1)–N(2)#3
O(2)#2–Mn(1)–O(3)#4
O(2)#2–Mn(1)–N(1)
O(1)–Mn(1)–N(1)
O(3)#4–Mn(1)–N(1)
O(2)#2–Mn(1)–N(2)#3
Symmetry transformations used to generate the equivalent atoms: #2, –x + 1, y, –z + 3/2; #3, x, y – 1, z; #4, x – 1, y, z.

890
J.-H. QIN ET AL.
FIG. 2. A view of the 1D chain structure.
view, if each Mn1 ion is considered as a five-connected node, of 1 were measured in the 2–300 K temperature range, and are
and 5-bromoisophthalic acid anion acts as a three-connected shown as χMT and χM versus T plots in Figure 5. The experi-
node, the structure of 1 can be considered as a (3,5)-connected mental χMT value of 1 at room temperature is 8.53 cm3 K mol−1
,
network with a Schla¨fli symbol of (42·6)(42·67·8) (Figure 4).
which is close to that expected for a non-interacting pair of S =
5/2 ions (8.75 cm3 K mol−1, S = 5/2) of the Mn(II). As temper-
ature is lowered to 2 K, the χMT values decrease, first slowly
Magnetic Property
From the magnetic point of view, complex 1 can be consid- and then rapidly. The behavior suggests that anti-ferromagnetic
ered as dinuclear, in which two Mn(II) ions are linked by two interactions are operative in 1.
carboxylate bridges, since coupling through 5-bromoisophthalic
In order to quantitatively evaluate these magnetic interac-
acid and bpa is almost negligible. The magnetic susceptibilities tions, for similar binuclear Mn(II) complexes, the following
FIG. 3. A view of the 2D layer structure.

NEW MANGANESE(II) COMPLEX
891
The least-squares analysis of magnetic susceptibilities data
led to J = −1.32 cm−1, g = 2.04, and R = 4.56×10−4 for
1. The J values suggest that weak anti-ferromagnetic interac-
tions between the neighboring Mn(II) ions are mediated through
carboxylate bridges.
CONCLUSIONS
In summary, we have prepared a new 5-bromoisophthalate
complex with Mn(II) salt with 1,2-bis(4-pyridyl)-ethane as the
ancillary ligand. Compound 1 is a 2D network containing non-
centrosymmetric dinuclear Mn units as nodes and further ex-
tends into a 3D supramolecular architecture via weak inter-
layer Br···Br interactions. The magnetic property of the complex
was also investigated. Further systematic studies for the design
and synthesis of such polymers with noncoordinated electron-
withdrawing and electron-donating groups are underway in our
laboratory.
SUPPLEMENTARY MATERIALS
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Centre,
CCDC number 780632. Copies of this information may be
FIG. 4. Schematic representation of the (3,5)-connected (42·6)(42·67·8) topol- obtained free of charge on application to CCDC, 12 Union
ogy.
Road, Cambridge CB2 1EZ, UK (deposit@ ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk).
[22]
ˆ
equation is induced from the Hamiltonian H = −JS1S2
:
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