PH Dependent Synthesis of Two Manganese Compounds based on 5-(2-Pyrimidyl)tetrazole-1-acetic Acid

Article abstract of DOI:10.1002/zaac.201500134

Reactions of Hpymtza [Hpymtza = 5-(2-pyrimidyl)tetrazole-1-acetic acid] with MnCl₂·4H₂O under different pH conditions, afforded the complexes [Mn(pymtza)₂(H₂O)₄] (1) and [Mn₂(pymtza)₂Cl₂(EtOH)]·H₂O (2). The compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compound 1 shows a mononuclear structure, whereas complex 2 has a 1D chain structure. In compound 1, the pymtza ligand only acts in a monodentate manner to coordinate to one central Mn^II atom by one carboxylate atom, In 2, pymtza acts as tetradentate ligand to connect three Mn^II ions. Compounds 1 and 2 display 3D networks by hydrogen bonding interactions. Furthermore, the luminescence properties of Hpymtza as well as compounds 1 and 2 were investigated at room temperature in the solid state.

Full text of DOI:10.1002/zaac.201500134

Journal of Inorganic and General Chemistry
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ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
DOI: 10.1002/zaac.201500134
pH Dependent Synthesis of Two Manganese Compounds based on
5-(2-Pyrimidyl)tetrazole-1-acetic Acid
Xiu Yun Li,[a] Ping Zhang,[a] He Tian,[a] Da Liang Zhu,[a] Fei Fei Zhang,[a]
Qiao Yun Li,[a] Gao Wen Yang,[a] Bo Wei,*[a] and Jian Hua Zou*[a]
Keywords: pH value; Manganese; 5-(2-Pyrimidyl)tetrazole-1-acetic acid; Crystal structure; Luminescence
Abstract. Reactions of Hpymtza [Hpymtza = 5-(2-pyrimidyl)tetrazole- pymtza ligand only acts in a monodentate manner to coordinate to
1-acetic acid] with MnCl2·4H2O under different pH conditions,
one central MnII atom by one carboxylate atom, In 2, pymtza acts as
afforded the complexes [Mn(pymtza)2(H2O)4] (1)
and tetradentate ligand to connect three MnII ions. Compounds 1 and 2
[Mn2(pymtza)2Cl2(EtOH)]·H2O (2). The compounds were structurally display 3D networks by hydrogen bonding interactions. Furthermore,
characterized by elemental analysis, IR spectroscopy and single-crystal the luminescence properties of Hpymtza as well as compounds 1 and
X-ray diffraction. Compound 1 shows a mononuclear structure,
whereas complex 2 has a 1D chain structure. In compound 1, the
2 were investigated at room temperature in the solid state.
related connection modes, therefore it is particularly important
in the formation of the resulting structures.[17–19]
1 Introduction
Over the past decade, coordination compounds based on
tetrazole-carboxylate ligands have attracted intense attention
from chemists, due to their fascinating structural topologies
and potential applications as functional materials in the fields
of chemistry.[1–9] Numerous tetrazole-carboxylate ligands such
as tetrazolate-5-acetic acid, tetrazolate-5-formic acid, tetrazole-
1-acetic acid, 5-(2-pyridyl) tetrazole-2-acetic acid have already
been studied, and a number of their complexes have been re-
ported.[10–13] The selection of these ligand arises from several
considerations as follows: Tetrazole-carboxylate ligands in-
cludes both nitrogen atoms and carboxylate oxygen atoms are
very likely to display a variety of coordination modes; the
abundant nitrogen and oxygen atoms can participate in
hydrogen bonds, stabilizing the supramolecular assembly.
However, it would still be a challenge for a long time to design
and construct coordination compounds with desired topologies
and properties, because many factors can affect the formation
of the targeted molecules, such as ligand-to-metal ratio, solvent
system, pH value, and temperature etc.[14–16] As is well known,
the pH value of the reaction system can affect not only the
coordination ability of the multicarboxylate ligand but also the
Taking all the observations into consideration, in this work,
5-(2-pyrimidyl)tetrazole-1-acetic acid was chosen to react with
MnCl2·4H2O. Notably, [Mn(pyrtza)Cl], which is derived from
5-(2-pyrimidyl)tetrazole-2-acetic aicd (Hpyrtza, Scheme 1),
the isomer of 5-(2-pyrimidyl)tetrazole-1-acetic aicd (Hpymtza,
Scheme 1), has been reported earlier.[4] The different position
of the carboxylate group of the tetrazole ring is likely to have
a great impact on the coordination modes of such ligands, thus
leading to structure variation. By reaction of Hpymtza and
MnCl2·4H2O at low pH value, [Mn(pymtza)2(H2O)4] (1) was
constructed under solvothermal conditions, whereas at a higher
pH value, [Mn2(pymtza)2Cl2(EtOH)]·H2O (2) was obtained.
Herein, the structures and the luminescence properties of these
compounds are discussed in detail.
Scheme 1. Structures of Hpymtza and Hpyrtza.
* Dr. B. Wei
Fax: +86-512-52251842
E-Mail: weibo@cslg.cn
2 Experimental Section
* Dr. J. H. Zou
Fax: +86-512-52251842
E-Mail: zoujh93@126.com
2.1 Materials and Instrumentation
[a] Department of Chemistry and Material Engineering
Jiangsu Laboratory of Advanced Functional Materials
Changshu Institute of Technology
Changshu, 215500, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201500134 or from the au-
thor.
General chemicals were commercially available reagents of analytical
grade and used without further purification. IR spectra were recorded
with a Thermo NICOLET-380 instrument as KBr disks (4000–400 cm–1).
Photoluminescent analyses were performed with an F-4600 fluores-
cence spectrometer. Single crystal X-ray diffraction was carried out
Z. Anorg. Allg. Chem. 2015, 641, (11), 1948–1952
1948
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with a Rigaku SCXmini-CCD diffractometer. The 1H NMR spectro-
scopic measurement was performed with a Bruker DPX300 instru-
Table 1. Selected crystallographic data and structure refinement for 1
and 2.
ment. The elemental analysis was performed with a PE-2400 instru-
ment.
1
2
Empirical formula
Formula mass
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C14H18MnN12O8
537.34
monoclinic
P21/c
5.2653(11)
10.953(2)
19.147(5)
C16H18Cl2Mn2N12O6
655.20
triclinic
2.2 Synthesis of Hpymtza
¯
P1
8.9624(18)
8.9998(18)
17.720(4)
100.16(3)
96.70(3)
104.51(3)
1342.5(5)
2
291(2)
1.621
1.195
14102
5-(2-Pyrimidyl)tetrazole (Hpymtz) was prepared by a [2+3] cycload-
dition reaction, involving a treatment of 2-cyanopyrimidyl with NaN3
in toluene in the presence of triethylammonium chloride. A mixture of
chloroacetic acid (4.73 g, 0.05 mol), Hpymtz (7.40 g, 0.05 mol), and
potassium hydroxide (5.61 g, 0.10 mol) in ethanol (100 mL) were re-
fluxed for 24 h at 90 °C. After cooling to room temperature, the pre-
cipitate was filtered off, washed with 2ϫ30 mL of ethanol, and dis-
solved in distilled water (30 mL). The pH of the solution was adjusted
to 2 with concentrated HCl (12 mol·L–1), giving 5-(2-pyrimidyl)tetraz-
ole-1-acetic acid (Hpymtza) as a powder. Yield: 51% (based on
Hpymtz). C7H6N6O2: calcd. C 40.8; H 2.9; N 40.8%; found: C 40.5;
H 3.0; N 40.9%. IR (KBr): ν˜ = 3494 (w), 1634 (s), 1581 (s), 1533
(m), 1395 (s), 1352 (m), 1277 (w), 1043 (s), 1031 (w), 1010 (m), 994
(m), 825 (m) cm–1. 1H NMR (400 MHz, in D2O): δ = 11.96 (1H),
7.66(1H), 8.95(2H), 5.20 (2H) ppm.
103.72(3)
γ /°
V /Å3
1072.7(4)
2
291(2)
1.664
Z
T /K
Dcalcd. /g·cm–3
μ /mm–1
0.687
Reflections collected
Unique reflections (Rint
No. observations
[I Ͼ2.00 σ (I)]
No. variables
Ra), wRb)
10772
2454 (0.1031)
1567
)
6135 (0.0459)
4258
154
349
0.0716, 0.1227
1.074
0.341
0.0523, 0.1016
1.046
0.557
GOFc)
Δ/ρmax /e·Å–3
Δ/ρmin /e·Å–3
–0.389
–0.424
2.3 Synthesis of [Mn(pymtza)2(H2O)4] (1)
2
2 2
2 2
a) R = Σ||Fo|–|Fc|/Σ|Fo|. b) Rw = {Σw(Fo –Fc ) /Σw(Fo ) }1/2. c) GOF
Hpymtza (0.0412 g, 0.2 mmol) was dissolved in a mixture of distilled
water (2 mL) and ethanol (3 mL), and the pH value of the solution
was adjusted to 4 with KOH (0.2 mol·L–1). MnCl2·4H2O (0.0197 g,
0.1 mmoL) was added to this solution. The mixture was sealed in a
25 mL Teflon-lined stainless steel container, which was heated at
120 °C for 48 h and finally cooled to room temperature. Colorless
2
2 2
= {Σ[w((Fo –Fc ) )/(n-p)}1/2, where n = number of reflections and p =
total numbers of parameters refined.
Table 2. Selected bond lengths /Å and angles /° for 1 and 2.
[Mn(pymtza)2(H2O)4] (1)
crystals of
1 .
were obtained. Yield: 44% based on Mn2+
C14H18MnN12O8: calcd. C 31.29; H 3.38; N 31.28%; found: C 31.51;
H 3.35; N 31.08%. IR (KBr): ν˜ = 3432 (s), 1651 (s), 1617 (s),1578
(s), 1437 (s), 1414 (s), 1325 (m), 1304 (w), 1270 (w), 1061 (w), 823
(s), 739 (s), 708 (m), 684 (m), 640 (m), 593 (m) cm–1.
Mn(1)–O(3)
Mn(1)–O(4)
2.1563
Mn(1)–O(1)
2.213(3)
2.226(2)
91.65(7)
92.59(6)
87.41(6)
90.27(9)
180.00
O(3A)–Mn(1)–O(1)
O(3)–Mn(1)–O(4)
O(3A)–Mn(1)–O(4)
O(1)–Mn(1)–O(4)
O(3A)–Mn(1)–O(3)
O(3)–Mn(1)–O(1)
O(1A)–Mn(1)–O(1)
O(1A)–Mn(1)–O(4)
O(4A)–Mn(1)–O(4)
88.35(7)
180.00(13)
89.73(9)
180.00
2.4 Synthesis of [Mn2(pymtza)2Cl2(EtOH)]·H2O (2)
[Mn2(pymtza)2Cl2(EtOH)]·H2O (2)
An identical procedure to that of 1 was followed to prepare 2 except
that the pH value of the solution was adjusted to 6 with KOH
(0.2 mol·L–1). Colorless crystals of 2 were obtained. Yield: 48% based
on Mn. C16H18Cl2Mn2N12O6: calcd. C 29.33; H 2.77; N 25.65%;
found: C 29.11; H 2.75; N 25.85%. IR (KBr): ν˜ = 3425 (s), 1654 (s),
1618 (s), 1579 (s), 1481 (w), 1435 (m), 1409 (s), 1322 (w), 1307 (w),
1270 (w), 824 (s), 743 (m), 707 (m), 680 (m), 641 (m), 592 (m)
cm–1.
Mn(1)–O(2A)
Mn(1)–N(7)
Mn(1)–Cl(2)
Mn(2)–O(4B)
Mn(2)–O(5)
Mn(2)–N(5)
2.131(2)
2.343(3)
2.4525(13)
2.105(2)
2.219(2)
2.373(3)
Mn(1)–O(3B)
Mn(1)–N(11)
Mn(1)–Cl(1)
Mn(2)–O(1A)
Mn(2)–N(1)
2.159(3)
2.393(3);
2.5285(12)
2.141(3)
2.319(3)
Mn(2)–Cl(1)
O(2A)–Mn(1)–N(7)
2.4713(11)
154.21(10)
O(2A)–Mn(1)–O(3B) 88.30(11)
O(3B)–Mn(1)–N(7) 85.94(10)
O(2A)–Mn(1)–N(11) 84.20(10)
N(7)–Mn(1)–N(11) 70.08(10)
O(3B)–Mn(1)–Cl(2) 171.53(7)
N(11)–Mn(1)–Cl(2) 91.50(8)
O(3B)–Mn(1)–Cl(1) 92.45(8)
O(3B)–Mn(1)–N(11) 81.00(10)
O(2A)–Mn(1)–Cl(2) 94.88(9)
2.5 X-ray Data Collection and Structure Determinations
N(7)–Mn(1)–Cl(2)
87.82(8)
O(2A)–Mn(1)–Cl(1) 104.46(7)
Suitable single crystals of complexes 1 and 2 were mounted on a Ri-
gaku SCXmini-CCD diffractometer equipped with a graphite-mono-
chromated Mo-Kα radiation (λ = 0.71073 Å) at 291 K. All absorption
corrections were performed using the CrystalClear programs. The crys-
tal structures of 1 and 2 were solved by direct methods and refined on
F2 by full-matrix least-squares using anisotropic displacement param-
eters for all non-hydrogen atoms.[20] For 1 and 2, important crystal
data and collection and refinement parameters are summarized in
Table 1, and selected bond lengths and angles are given in Table 2.
Hydrogen-bonding parameters are given in Table S1 (Supporting In-
formation).
N(7)–Mn(1)–Cl(1)
Cl(2)–Mn(1)–Cl(1)
O(4B)–Mn(2)–O(5)
O(4B)–Mn(2)–N(1)
O(5)–Mn(2)–N(1)
O(1A)–Mn(2)–N(5)
N(1)–Mn(2)– N(5)
100.89(7)
94.34(5)
N(11)–Mn(1)–Cl(1)
O(4B)–Mn(2)–O(1)
O(1A)–Mn(2)–O(5)
O(1A)–Mn(2)–N(1)
O(4B)–Mn(2)–N(5)
O(5)–Mn(2)–N(5)
169.08(8)
93.51(11)
168.41(9)
87.35(10)
88.85(10)
83.72(11)
91.34(11)
159.72(10)
84.48(10)
85.85(10)
70.99(10)
O(4B)–Mn(2)–Cl(1) 99.72(7)
O(1A)–Mn(2)–Cl(1) 99.37(8)
N(1)–Mn(2)–Cl(1) 100.13(7)
O(5)–Mn(2)–Cl(1)
N(5)–Mn(2)–Cl(1)
90.17(8)
169.62(8)
Symmetry code: For 1 A: –x, 1–y, 1–z; For 2. A: –x, –y, 1–z. B:
–x, –y, –z.
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Crystallographic data (excluding structure factors) for the structures in
ring [O(4)–H(4A)···N(3), 2.933(4) Å/139°], between the coor-
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-893413 (1) and CCDC-893414 (2)
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk)
dinated water and the oxygen atom of the carboxylate group
[O(4)–H(4B)···O(1), 2.772(4) Å/164°], and between the C–H
group of the carboxylate group and the oxygen atom of the
carboxylate group [C(2)–H(2A)···O(2), 3.479(5) Å/170°], gen-
erating a 3D supramolecular network (Table S1, Figure S1,
Supporting Information).
Supporting Information (see footnote on the first page of this article):
Depictions of the packing of compounds 1 and 2.
3 Results and Discussion
3.1 General Characterizations of 1 and 2
In this investigation, we have selected Hpymtza and MnII to
construct metal coordination architectures in order to explore
whether or not the pH value will have an effect on the forma-
tion of such compounds and the structure variation caused by
the different positions of the carboxylate group. Compound 1,
with mononuclear structure, was obtained when the pH value
was 4, whereas complex 2, which has a 1D chain structure,
was synthesized at a pH value of 6. Compounds 1 and 2 are
stable towards oxygen and moisture. The elemental analyses
show that the components of these complexes are in accord-
ance with the results of the structural analysis. IR spectra of
the products show typical bands (1304–1604 cm–1) of the tet-
razolyl and pyrimidyl groups. The band at 3432 cm–1 for com-
pound 1 is attributed to the O–H stretching vibration of coordi-
nated water, and the band at 3425 cm–1 for compound 2 is
attributed to the O–H stretching vibration of both guest water
and coordinated ethanol. The structures of 1 and 2 are con-
firmed by X-ray crystallography.
Figure 1. Coordination environment of the MnII atoms in compound
1.
3.3 Crystal Structure of [Mn2(pymtza)2Cl2(EtOH)]·H2O (2)
Compound 2 crystallizes in the triclinic lattice space
¯
group P1 and the asymmetric unit contains one
[Mn2(pymtza)2Cl2(EtOH)]·H2O molecule. Two crystallograph-
ically independent MnII atoms [Mn(1) and Mn(2)] are ob-
served. As shown in Figure 2, both central MnII(1) or MnII(2)
atoms are surrounded by six atoms, forming a distorted octahe-
dral coordination arrangement, respectively. The Mn(1) atom
is coordinated by two O(O2B, O3A) atoms from two pymtza
ligands, and two N(N7, N11) atoms from one pymtza ligand
and two Cl anions. The Mn(2) atom is coordinated by two
O(O1B, O4A) atoms from two pymtza ligands, and two nitro-
gen (N1, N5) atoms from one pymtza ligand, and one chloride
anion and one oxygen(O5) atom from one ethanol molecule.
Compared to compound 1, in which pymtza adopts a mono-
dentate mode, neighboring MnII atoms are doubly bridged by
two carboxylate groups from two pymtza ligands in a
μ1,3-COO bridging mode and one chloride ligand in a μ1,1-Cl
bridging mode with the Mn(1)···Mn(2) distance of 3.6890 Å,
forming a one-dimensional structure stretching along the c axis
with the Mn···Mn···Mn bite angle of 154.953°. Each pymtza
ligand acts as a tetradentate ligand to connect three MnII by
3.2 Crystal Structure of [Mn(pymtza)2(H2O)4] (1)
X-ray diffraction demonstrates that compound 1 crystallizes
in monoclinic lattice space group P21/n and the asymmetric
unit contains half of the [Mn(pymtza)2(H2O)4] molecule. As
shown in Figure 1, the MnII ion lies on an inversion center and
is six-coordinate by two oxygen (O1, O1A) atoms from the
carboxylate group of two pymtza ligands and four oxygen (O3,
O3A, O4, O4A) atoms from four water molecules, forming a
distorted MnO6 octahedral arrangement. The Mn–O distances
[2.1563–2.226(2) Å] are similar to those of previously reported
MnII complexes.[21] Compared to the previously reported 2D
complex [Mn(pztza)2(H2O)2],[9] in which the pztza ligand acts
as a bidentate ligand bridging coordination mode by the pyraz-
inyl ring and the oxygen of the carboxylate group, the pymtza
anion in 1 acts as a monodentate ligand to connect one MnII
ion by one carboxylate oxygen atom, resulting in a mononu-
clear structure. Adjacent [Mn(pymtza)2(H2O)4] molecules are
linked together through five kinds of hydrogen bonding inter-
actions between the coordinated water and the nitrogen atom
of the tetrazole ring [O(3)–H(3A)···N(4), 2.8211 Å/142°], be-
tween the coordinated water and the oxygen atom of the carb-
oxylate group [O(3)–H(3B)···O(2), 2.7070 Å/145°], between
Figure 2. 1D chain structure extending along the c axis of compound
the coordinated water and the nitrogen atom of the tetrazole 2, showing the coordination environment of MnII.
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two nitrogen atoms from the tetrazole and the pyrimidine to
link the same MnII atom and two oxygen atoms from the same
carboxylate group to connect two MnII atoms, whereas
[Mn(pyrtza)Cl] contains neither ethanol nor water mol-
ecules.[4] The pyrtza ligand adopts a tetradentate coordination
mode to connect to three MnII ions, showing a 2D network.
Adjacent one-dimensional chains are held together through
four kinds of hydrogen bonding interactions between the eth-
anol and the solvent water [O(5)–H(5A)···O(6), 2.720(4) Å/
173(4)°], between the guest water and the Cl atom [O(6)–
H(6B)···Cl(2), 3.116(3) Å/164°], between the C–H group of the
carboxylate group and the Cl atom [C(9)–H(9A)···Cl(2),
3.675(4) Å/163°], and between the C–H group of the pyrimid-
ine and the nitrogen atom from tetrazole [C(14)–H(14)···N(8),
3.234(5) Å/126°], to generate a three-dimensional network
structure (Table S1, Figure S2, Supporting Information).
Figure 4. TG curves of compounds 1 and 2.
and 2 were carried out under nitrogen atmosphere (Figure 4).
From the TG curves, Complexes 1 and 2 are stable up to
230 °C and 275 °C, respectively, and above the temperature,
the decomposition of the complexes start. For complexes 1 and
2 the remaining weight of 16.50%, 26.27% corresponds to the
final product MnO2 (calcd. 16.18%, 900 °C; 26.53%, 900 °C,
respectively).
3.4 Luminescence Properties and Thermogravimetric
Analyses (TGA)
The luminescence properties of 1 and 2 and the free ligand
were investigated at room temperature in the solid state. As is
shown in Figure 3, the free ligand Hpymtza exhibits emission
with maximum intensity at 442 nm and upon excitation at
375 nm. Compound 2 exhibits fluorescent emission bands at
460 nm with λex = 375 nm. This luminescence could be tenta-
tively assigned to the intraligand luminescence, because sim-
ilar emission was also observed for the free ligand Hpymtza
(442 nm). Generally speaking, the intraligand wavelength is
determined by the energy gap between the π and π* molecular
orbitals of the free ligand, which is related to the extent of π
conjugation.[9] Complex 1 does not exhibit detectable emis-
sion, and this can be explained by the fact that this complex
contains manganese, whose low d-d transition quenches lumi-
nescence, which is similar to that of [Mn(pztza)2(4,4Ј-
bipy)(H2O)2]·2H2O.[7] To characterize the compounds in terms
of thermal stability, thermal gravimetric analysis (TGA) of 1
4 Conclusions
Different positions of the carboxylate group of the tetrazole
ring have a substantial effect on the crystal structures of com-
plexes like those investigated in this paper. The luminescence
of compound 2 shows intraligand emission. The experimental
results show that the pH value and the position of the carboxyl-
ate group have a significant influence on the structures. Further
exploration of other metal ions compounds with Hpymtza is
underway.
Acknowledgements
The authors acknowledge financial support from the Natural Science
Foundation of Jiangsu Province (Grant No. BK2012210), the Natural
Science Foundation of the Jiangsu Higher Education Institutions of
China (Grant No. 10KJB430001) and the Opening Fund of Jiangsu
Key Laboratory of Advanced Functional Materials (Grant No.
12KFJJ010).
References
[1] A. Rodrıguez-Dieguez, A. Salinas-Castillo, A. Sironi, J. M. Seco,
E. Colacio, CrystEngComm 2010, 12, 1876–1879.
[2] R. D. Antonio, J. M. Antonio, C. Joan, R. José, C. L. Duane, C.
Enrique, Dalton Trans. 2009, 6335–6344.
[3] L. Ma, G. Peng, J. B. Cai, H. Deng, M. Zeller, Z. Anorg. Allg.
Chem. 2011, 637, 755–758.
[4] J. H. Zou, D. Y. Chen, G. W. Yang, Q. Y. Li, J. Yang, L. Shen,
RSC Adv. 2015, 5, 27887–27890.
[5] M. F. Wua, F. K. Zheng, G. Xu, A. Q. Wu, Y. Li, H. F. Chen, S. P.
Guo, F. Chen, Z. F. Liu, G. C. Guo, J. S. Huang, Inorg. Chem.
Commun. 2010, 13, 250–253.
Figure 3. Emission spectra of compound 2 and Hpymtza at room tem-
perature in the solid state.
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[6] M. F. Wu, M. S. Wang, S. P. Guo, F. K. Zheng, H. F. Chen, X. M. [14] M. Fujita, M. Tominaga, A. Hori, B. Therrien, Acc. Chem. Res.
2005, 38, 369.
Jiang, G. N. Liu, G. C. Guo, J. S. Huang, Cryst. Growth Des.
[15] E. Menozzi, M. Busi, C. Massera, F. Ugozzoli, D. Zuccaccia, A.
Macchioni, E. Dalcanale, J. Org. Chem. 2006, 71, 2617.
[16] Q. Y. Li, G. W. Yang, L. Shen, M. H. He, W. Shen, K. Gu, J. N.
Jin, Z. Anorg. Allg. Chem. 2012, 638, 826–831.
[17] Q. Yu, X. Q. Zhang, H. D. Bian, H. Liang, B. Zhao, S. P. Yan,
D. Z. Liao, Cryst. Growth Des. 2008, 8, 1143.
[18] Q. Y. Li, M. H. He, Z. D. Shen, G. W. Yang, Z. Y. Yuan, Inorg.
Chem. Commun. 2012, 15, 218.
[19] J. H. Zou, H. Wu, D. L. Zhu, H. E. Tian, P. Zhang, L. Y. Zhao,
Z. W. Ruan, J. Xie, Q. Y. Li, G. W. Yang, J. Coord. Chem. 2014,
3444, 3453.
[20] G. M. Sheldrick, SHELXS-97 and SHELXL-97, Programs for the
Solution and Refinement of Crystal Structures, University of
Göttingen, Göttingen, Germany, 1997.
[21] Q. Y. Li, H. Tian, X. Y. Li, J. H. Zou, G. D. Mei, L. J. Qiu, B.
Wei, G. W. Yang, RSC Adv. 2015, 5, 43741–43749.
2011, 11, 373.
[7] D. L. Zhu, H. Tian, F. F. Li, J. Xie, P. Zhang, J. H. Zou, L. Y.
Zhao, F. F. Zhang, G. W. Yang, Q. Y. Li, J. Inorg. Organomet.
Polym. 2014, 24, 1103–1109.
[8] F. Wu, Z. F. Liu, S. H. Wang, J. Chen, G. Xu, F. K. Zheng, G. C.
Guo, J. S. Huang, CrystEngComm 2011, 13, 6386.
[9] J. Yang, L. Shen, G. W. Yang, Q. Y. Li, W. Shen, J. N. Jin, J. J.
Zhao, J. Dai, J. Solid State Chem. 2012, 186, 124–133.
[10] Z. J. Zhang, S. C. Xiang, Q. Zheng, X. T. Rao, J. U. Mondal,
H. D. Arman, G. D. Qian, B. L. Chen, Cryst. Growth Des. 2010,
10, 2372.
[11] Q. Y. Chen, Y. Li, F. K. Zheng, W. Q. Zou, M. F. Wu, G. C. Guo,
A. Q. Wu, J. S. Huang, Inorg. Chem. Commun. 2008, 11, 969–
971.
[12] X. Q. Zhang, Q. Yu, H. D. Bian, X. G. Bao, H. J. Liang, Coord.
Chem. Rev. 2009, 6, 2108.
[13] Q. Y. Li, G. W. Yang, X. Y. Tang, Y. S. Ma, F. Zhou, W. Liu, J.
Received: March 7, 2015
Chen, H. Zhou, Inorg. Chem. Commun. 2010, 13, 254.
Published Online: July 22, 2015
Z. Anorg. Allg. Chem. 2015, 1948–1952
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