Constructing two MnII coordination polymers with 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene and different dicarboxylate ligands: Syntheses, crystal structures, and luminescent properties

Article abstract of DOI:10.1002/zaac.201300623

Two new coordination polymers, [Mn(tda)(bimb)_0.5]_n (1) and [Mn(obb)(bimb)]_n (2) [H₂tda = 2,5- thiophenedicarboxylic acid, H₂obb = 4,4′-oxybis(benzoic acid) and bimb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene], were hydrothermally synthesized by reactions of Mn^II salt with a rigid ligand 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene and dicarboxylate ligands. Complex 1 exhibits an unusual binodal (3,7)-connected three-dimensional (3D) architecture with point symbol (4⁴.6¹⁷).(6³). Complex 2 is a three-dimensional structure with pcu topology. Furthermore, the luminescent properties of complexes 1 and 2 are investigated. Copyright

Full text of DOI:10.1002/zaac.201300623

ARTICLE
DOI: 10.1002/zaac.201300623
Constructing Two MnII Coordination Polymers with 1,4-Bis(1-imidazol-yl)-
2,5-dimethyl Benzene and Different Dicarboxylate Ligands: Syntheses,
Crystal Structures, and Luminescent Properties
Liping Xu*[a] and Xiaoming Wang[a]
Keywords: Crystal structure; Manganese; Hydrothermal synthesis
Abstract. Two new coordination polymers, [Mn(tda)(bimb)0.5 n
and [Mn(obb)(bimb)]n (2) [H2tda = 2,5-thiophenedicarboxylic acid,
H2obb = 4,4Ј-oxybis(benzoic acid) and bimb = 1,4-bis(1-imidazol-yl)-
]
(1) benzene and dicarboxylate ligands. Complex 1 exhibits an unusual bi-
nodal (3,7)-connected three-dimensional (3D) architecture with point
symbol (44.617).(63). Complex 2 is a three-dimensional structure with
2,5-dimethyl benzene], were hydrothermally synthesized by reactions pcu topology. Furthermore, the luminescent properties of complexes 1
of MnII salt with a rigid ligand 1,4-bis(1-imidazol-yl)-2,5-dimethyl
and 2 are investigated.
dination polymers [Mn(tda)(bimb)0.5 n (1) and [Mn (obb)
(bimb)]n (2). Furthermore, the luminescent properties of com-
plexes 1 and 2 are investigated at room temperature.
]
Introduction
The construction of new coordination polymers (CPs) has
aroused intense interests in the last decade not only for their
intriguing structures and variety of topological net, but also for
their potential applications as functional materials in the areas
of magnetism, gad adsorption, catalysis, luminescence and so
Results and Discussion
on.[1–12] In order to construct new CPs, much effort has been Structural Description
devoted on the design and modification of the organic ligands
to control the architectures of CPs because the geometries of
[Mn(tda) (bimb)0.5]n (1)
organic ligands have a great effect on the structural frame-
works of CPs.[13,14] For the self-assembly processes of CPs,
the mixed-ligand strategy of multicarboxylate and N-donor li-
gands has been certified an effective method for construction
of the new frameworks, which can result in greater tenability
of structural frameworks than single ligands.[15–21] Among N-
donor bridging ligands, imidazole-containing ligands have
been widely employed to construct CPs due to their flexible
and diverse coordination modes, which can lead to form versa-
tile topologies. Up to now, a large number of CPs are con-
structed by flexible imidazole-containing ligands.[22–25] The
CPs constructed by rigid bidentate 1,4-bis(1-imidazol-yl)-2,5-
dimethyl benzene are scarcely reported.[26,27] In the bimb li-
gand, the two imidazole rings can rotate around the central
phenyl ring with the result that a variety of intriguing struc-
tures would be obtained.
Single crystal X-ray analysis reveals that complex 1 crys-
tallized in the monoclinic space group P21. Crystal structure
analysis reveals that the asymmetric unit of 1 consists of two
central MnII atoms. As shown in Figure 1, the Mn1 ion adopts
a distorted octahedral arrangement, which is ligated by three
carboxylate oxygen atoms and one nitrogen atoms composing
the equatorial plane, and one oxygen atom and one nitrogen
Considering the above mentioned, we employed the mixed-
ligand strategy of the rigid imidazole-containing ligand (bimb)
and different carboxylate ligands to synthesize two MnII coor-
* L. Xu
E-Mail: zjkyangxm@163.com
[a] Department of Chemistry Engineering
Zibo Vocational Institute
Shandong 255314, China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300623 or from the au-
thor.
Figure 1. Coordination environment of the MnII ion in complex 1.
Hydrogen atoms are omitted for clarity.
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Z. Anorg. Allg. Chem. 2014, 640, (8-9), 1680–1683

MnII Coordination Polymers with 1,4-Bis(1-imidazol-yl)-2,5-dimethyl Benzene
atom at the apical positions with the O8–Mn1–N1 angle of
172.60(8)°. The central Mn2 atom is five-coordinated by five
carboxylate atoms with a distorted square-pyramidal arrange-
ment.
The Mn–O bond lengths vary from 2.024(2) Å and
2.265(2) Å. Mn–N bond lengths are 2.214(2) Å and
2.244(2) Å. In 1, the carboxylate ligands adopt chelating/bridg-
ing and bis(bridging-bidentate) coordination modes. Two inde-
pendent central MnII atoms are bridged together by three carb-
oxylate groups to form a dinuclear unit with the Mn–Mn dis-
tance of 3.586 Å. The manganese(II) cations are bridged by
the carboxylate groups to form a rod-like chain. These chains
as infinite rod-shaped secondary building units are further
interlinked by the carboxylate ligands to produce a three-
dimensional network with a large widow (approximate
11.440ϫ18.946 Å based on the Mn1···Mn1 distance) (Fig-
ure 2). The bimb ligands lie in the large widows and connect
the Mn2 ions (Figure 3). From the view point of topology, the
final 3D structure can be represented as a (3,7)-connected net
with (44.617).(63) by reducing the dinuclear MnII unit and
BDC2– ligand as 7-connected and 3-connected nodes (Fig-
ure 4).
Figure 4. (3,7)-connected topology for complex 1.
[Mn(obb) (bimb)]n (2)
When H2tda was replaced by H2obb, a structurally different
complex 2 was obtained. Single crystal X-ray analysis reveals
that complex 2 belongs to the triclinic system with space group
II
¯
P1 and with a pcu topological net. Each Mn ion is six-coordi-
nate with an octahedral arrangement completed by four carb-
oxylate oxygen atoms [Mn–O, ranging from 2.1072(16) Å to
2.3200(17) Å] and two nitrogen atoms [Mn(1)–N(1) = 2.264 Å
and Mn(1)–N(3) = 2.223(2) Å] (Figure 5). The four carboxyl-
ate oxygen atoms comprise the equatorial plane and two nitro-
gen atoms occupy the axial positions. In 2, the carboxylate
groups adopt the μ2-η1:η1 and μ1-η1:η1 coordination modes.
The μ2-η1:η1 carboxylate ligands connect the MnII ions to a
one-dimensional chain based on the dinuclear MnII unit with
Mn–Mn distances of 4.849 Å along the a axis (Figure 6).
Furthermore, the 1D chains are connected by bimb ligands to
form a 3D structure. If the dinuclear MnII ion and the organic
ligands can be viewed as nodes and linkers, the 3D structure
can be simplified as a pcu topological net (Figure 7).
Figure 2. Left: 3D MnII-carboxylate framework; right: the chain
formed from the SBUs with two corner-sharing Mn polyhedra.
Figure 3. Final 3D framework constructed by Mn-carboxylate-bimb
system.
Figure 5. Coordination environment of the MnII ion in complex 1.
Hydrogen atoms are omitted for clarity.
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www.zaac.wiley-vch.de
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L. Xu, X. Wang
ARTICLE
Figure 6. 1D chain constructed by carboxylate ligands and MnII ions.
Figure 8. Luminescent emission spectra for complexes 1 and 2 in the
solid state at room temperature.
Conclusions
We obtained two new MnII coordination polymers based on
dicarboxylate and imidazole-containing ligands. Complex 1
shows a (3,7)-connected topological net, whereas complex 2
features a pcu topological net. The complexes 1 and 2 show
emissions at room temperature.
Figure 7. 3D pcu topological net for complex 2.
Experimental Section
General Materials and Methods: All reagents and solvents employed
were commercially available and used as received. C, H, and N analy-
ses were carried out with a Perkin-Elmer 240C elemental analyzer. FT-
IR spectra were recorded with a Bruker Equinox 55 FT-IR spectrome-
Luminescent Properties
The simulated and experimental X-ray powder pattern is
shown in Figure S1 (Supporting Information). All the peaks
presented in the measured curves approximately match the ter as a dry KBr pellet in the 400–4000 cm–1 range. Solid-state fluores-
cence spectra were recorded with a Hitachi F-4600 equipped with a
xenon lamp and a quartz carrier at room temperature. Topological
analysis were performed and confirmed by the Topos program.[33,34]
simulated curves generated from single-crystal diffraction data,
which confirms the phase purity of the as-synthesized product.
In the solid state, the complexes 1 and 2 show photolumi-
nescence at room temperature. Complexes 1 and 2 exhibit
Synthesis of [Mn(tda)(bimb)0.5]n(1): A mixture of MnCl2·4H2O
(0.099 g, 0.5 mmol), H2tda (0.086 g, 0.5 mmol), bimb (0.105 g,
0.5 mmol), NaOH (0.04 g, 1 mmol) and deionized water (15 mL) was
heated at 140 °C for 72 h, and afterwards cooled to room temperature.
emission at ca. 395 nm (λex = 334 nm) and 409 nm (λex
=
338 nm) at room temperature (Figure 8). To understand the na-
ture of the emission bands, we analyzed the photolumines-
cence properties of carboxylate and bimb ligands. The carb- The brown block crystals were obtained and washed with alcohol for
several times (Yield: 41% based on Mn). C13H9MnN2O4: calcd. C
45.36; H 2.64; N 8.14; S 9.32%; found: C 45.38; H 2.63; N 8.15%.
IR (KBr): ν˜ = 1622 (m), 1537 (m), 1423 (s), 1347 (m), 1230 (s), 1017
(m), 914 (m), 876 (m), 778 (m), 647 (m) cm–1.
oxylate ligands have not obvious emission bands and the bimb
ligand shows emission at 421 nm.[28] As well known, MnII ion
is not an excellent metal source for photoluminescence,
whereas complexes 1 and 2 exhibit obvious emission spectra,
which indicates that the photoluminescence properties are
closely related with the ligand structure. The emissions of
complexes 1 and 2 are different from those of the free organic
Synthesis of [Mn(obb)(bimb)]n (2): Complex 2 was obtained by a
similar method as described for 1 by using of H2obb (0.129 g,
0.5 mmol) instead of H2tda. The yellow crystals of 2 (54% based on
ligands, which might be assigned to the intraligand emission Mn) were obtained in pure phase, washed with water and ethanol, and
excited state.[29,30] Several factors might serve for the emis-
dried at room temperature. C28H22MnN4O5: calcd. C 61.21; H 4.04; N
10.20%; found: C 61.23; H 4.05; N 10.22%. IR (KBr): ν˜ = 1604 (m),
1517 (m), 1447 (m), 1330 (m), 1241 (m), 1131 (m), 907 (m), 833 (m),
771 (m), 630 (m) cm–1.
sions, such as a change in the highest occupied and lowest
unoccupied molecular orbital energy levels of deprotonated di-
carboxylate anions and neutral ligands coordinating to central
metal atoms, a charge-transfer transition between ligands and
X-ray Crystallography: Single crystal X-ray diffraction analyses of
metal atoms, and a joint contribution of the intraligands or
charge-transfer transitions between the coordinated ligands and
central metal atoms.[31,32]
complexes 1 and 2 were carried out with a Bruker SMART APEX II
CCD diffractometer equipped with a graphite monochromated Mo-Kα
radiation (λ = 0.71073 Å) by using a ω-scan mode. Empirical absorp-
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© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 1680–1683

MnII Coordination Polymers with 1,4-Bis(1-imidazol-yl)-2,5-dimethyl Benzene
Table 1. Crystallographic data and structure refinement summary for [4] R. L. Jeffrey, M. Y. Omar, Chem. Soc. Rev. 2009, 38, 1213.
complexes 1 and 2.
[5] C. Y. Su, A. M. Goforth, M. D. Smith, P. J. Pellechia, H. C.
Zur Loye, J. Am. Chem. Soc. 2004, 126, 3576.
[6] J. F. Song, R. S. Zhou, J. Zhang, C. L. Pan, Z. Anorg. Allg. Chem.
2012, 638, 201.
[7] J. B. Lin, J. P. Zhang, X. M. Chen, J. Am. Chem. Soc. 2010, 132,
6654.
[8] G. Q. Kong, C. D. Wu, Inorg. Chem. Commun. 2009, 12, 731.
[9] G. E. Fryxell, Inorg. Chem. Commun. 2006, 9, 1141.
[10] A. D. Wang, F. K. Hu, Z. C. Ke, C. Fang, W. Wei, Synth. React.
Inorg. Met.-Org. Nano-Metal Chem.2013, 43, 1146.
[11] J. H. Cui, L. F. Huang, Z. Z. Lu, Y. Z. Li, Z. J. Guo, H. G. Zheng,
CrystEngComm 2010, 14, 2809.
[12] Y. M. Song, F. Luo, M. B. Luo, Z. W. Liao, G. M. Sun, X. Z.
Tian, Y. Zhu, Z. J. Yuan, S. J. Liu, W. Y. Xu, X. F. Feng, Chem.
Commun. 2012, 48, 1006.
[13] F. Guo, F. Wang, H. Yang, X. L. Zhang, J. Zhang, Inorg. Chem.
2012, 51, 9677.
[14] G. P. Yang, Y. Y. Wang, W. H. Zhang, A. Y. Fu, R. T. Liu, E. K.
Lermontova, Q. Z. Shi, CrystEngComm 2010, 12, 1509.
[15] L. F. Ma, L. Y. Wang, J. L. Hu, Y. Y. Wang, G. P. Yang, Cryst.
Growth Des. 2009, 9, 5334.
[16] J. S. Hu, X. Q. Yao, M. D. Zhang, L. Qin, Y. Z. Li, Z. J. Guo,
H. G. Zheng, Z. L. Xue, Cryst. Growth Des. 2012, 12, 3426.
[17] K. K. Bisht, E. Suresh, Cryst. Growth Des. 2013, 13, 664.
[18] A. Demessence, A. Mesbah, M. Francois, G. Rogez, P. Rabu, Eur.
J. Inorg. Chem. 2009, 2009, 3713.
[19] A. Demessence, G. Rogez, R. Welter, P. Rabu, Inorg. Chem. 2007,
46, 3423.
[20] Y. Q. Cheng, H. P. Xiao, X. H. Li, J. G. Wang, A. Morsali, Z.
Anorg. Allg. Chem. 2007, 633, 1140.
1
2
Empirical formula
Formula weight
Crystal system
Space group
C13H9MnN2O4S
344.22
monoclinic
P21
C28H22MnN4O5
549.44
triclinic
¯
P1
Unit cell dimensions
a /Å
b /Å
c /Å
α /°
8.762(4)
17.118(3)
9.854(7)
90
108.920(5)
90
8.536(5)
11.402(7)
15.099(9)
91.470(8)
101.496(7)
111.362(7)
1333.3(11)
2
β /°
γ /°
Volume /Å3
Z
1398.1(11)
2
Calculated density /mg·m–3 1.635
1.369
4642
Independent reflections
[I Ͼ 2σ(I)]
F(000)
θ range for data collection 2.380–27.551
Limiting indices
4222
696
566
1.38–27.51
–10 Յ h Յ 11
–12 Յ k Յ 14
–19 Յ l Յ 19
1.032
R1 = 0.0412
wR2 = 0.1061
R1 = 0.0599
wR2 = 0.1158
–11 Յ h Յ 11
–22 Յ k Յ 11
–12 Յ l Յ 12
1.086
R1 = 0.0238
wR2 = 0.0645
R1 = 0.0252
wR2 = 0.0656
Goodness-of-fit on F2
a)
b)
R1 ,wR2 [I Ͼ 2σ(I)]
a)
b)
R1 ,wR2 (all data)
2
a) R = Σ(||Fo|–|Fc||)/Σ|Fo|. b) wR = [Σw(|Fo|2–|Fc|2)2/Σw(Fo )]1/2
.
[21] Q. Chen, P. C. Guo, S. P. Zhao, J. L. Liu, X. M. Ren, Crys-
tEngComm 2013, 15, 1264.
[22] S. Yuan, H. Wang, D. X. Wang, H. F. Lu, S. Y. Feng, D. Sun,
CrystEngComm 2013, 15,7792.
[23] D. Sun, M. Z. Xu, S. S. Liu, S. Yuan, H. F. Lu, S. Y. Feng, D. F.
Sun, Dalton Trans. 2013,42, 12324.
[24] S. S. Chen, J. Fan, T. Okamura, M. S. Chen, Z. Su, W. Y. Sun, N.
Ueyama, Cryst. Growth Des. 2010, 10, 812.
[25] Z. Su, J. Fan, T. Okamura, M. S. Chen, S. S. Chen, W. Y. Sun, N.
Ueyama, Cryst. Growth Des. 2010, 10, 1911.
[26] F. Guo, B. Y. Zhu, G. L. Xu, M. M. Zhang, X. L. Zhang, J. Zhang,
J. Solid State Chem. 2013, 199, 42.
[27] F. Guo, B. Y. Zhu, M. L. Liu, X. L. Zhang, J. Zhang, J. P. Zhao,
CrystEngComm 2013, 15,6191.
tion correction was applied using the SADABS programs.[35] All the
structures were solved by direct methods and refined by full-matrix
least-squares methods on F2 using the program SHELXTL 97.[36] All
non-hydrogen atoms were refined anisotropically. The hydrogen atoms
were located by geometrically calculations, and their positions and
thermal parameters were fixed during the structure refinement. The
crystallographic data and experimental details of structural analyses
for coordination polymers are summarized in Table 1. Selected bond
lengths and bond angles are listed in Table S1 (Supporting Infor-
mation).
[28] G. L. Xu, F. Guo, Inorg. Chem. Commun. 2013, 16,27,146.
[29] L. Y. Zhang, G. F. Liu, S. L. Zheng, B. H. Ye, X. M. Zhang, X. M.
Chen, Eur. J. Inorg. Chem. 2003, 16, 2965.
[30] Z. Y. Fu, X. T. Wu, J. C. Dai, S. M. Hu, W. X. Du, H. H. Zhang,
R. Q. Sun, Eur. J. Inorg. Chem. 2002, 10, 2730.
[31] J. H. Qin, L. F. Ma, Y. Hu, L. Y. Wang, CrystEngComm 2012, 14,
2891.
[32] F. Guo, F. Wang, H. Yang, X. L. Zhang, J. Zhang, Inorg. Chem.
2012, 51, 9677.
[33] V. A. Blatov, IUCr Compcomm. Newsletter 2006, 7, 4.
[34] V. A. Blatov, M. O’Keeffe, D. M. Proserpio, CrystEngComm
2010, 12, 44, see also: http://www.topos.ssu.Samara.ru.
[35] SAINT Software Reference Manual; Bruker AXS, Madison, WI,
USA, 1998.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-975329 and CCDC-975330 (Fax: +44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Supporting Information (see footnote on the first page of this article):
Additional plots of the structures of 1 and 2; XRPD patterns of 1
and 2.
[36] G. M. Sheldrick, SHELXTL NT, version 5.1; Program for Solution
and Refinement of Crystal Structures, University of Göttingen,
Göttingen, Germany, 1997.
References
[1] A. D. Sean, K. H. George, J. Am. Chem. Soc. 2007, 129, 12114.
[2] Z. J. Zhang, L. P. Zhang, L. Wojtas, P. Nugent, M. Eddaoudi,
M. J. Zaworotko, J. Am. Chem. Soc. 2012, 134, 924.
Received: December 5, 2013
[3] A. H. Corma, Chem. Rev. 2010, 110, 4606.
Published Online: February 19, 2014
Z. Anorg. Allg. Chem. 2014, 1680–1683
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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