Synthesis, crystal structure, and thermal stability of 1D coordination polymer [Zn(BDOA)(Py)2(H2O)] n

Article abstract of DOI:10.1134/S1070328413020103

A new coordination polymer, [Zn(BDOA)(Py)₂(H₂O)] _n (I) (BDOA = benzene-1,4-dioxylacetate, Py = pyridine), has been prepared via self-assembly of benzene-1,4-dioxylacetate with zinc nitrate under mild conditions and characterized by IR spectra, elemental analysis and X-ray diffraction single-crystal analysis. The complex crystallizes in the monoclinic system, space group C2/c with a = 15.5751(9), b = 6.0898(4), c = 21.7133(13) A, V = 1991.9(2) A³, β = 104.719(1), Z = 4. The zinc atoms are bridged by BDOA ligand, forming a one-dimensional chain along the z axis. A two-dimensional layer structure is formed by the intermolecular hydrogen bonds. The thermal decomposition profile of the complex is reported as well.

Full text of DOI:10.1134/S1070328413020103

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 2, pp. 225–228. © Pleiades Publishing, Ltd., 2013.
Synthesis, Crystal Structure, and Thermal Stability of 1D
1
Coordination Polymer [Zn(BDOA)(Py)2(H2O)]n
L. J. Li*, X. X. Hua, G. Y. Wang, Y. Y. Huang, L. Z. Wang, C. Tian, and J. L. Du*
Key Laboratory of Medicinal Chemistry and Molecular Diagnosis, Hebei University, Baoding, 071002 P.R. China
*eꢀmail: llj@hbu.edu.cn; dujl@hbu.edu.cn
Received August 11, 2011
Abstract—A new coordination polymer, [Zn(BDOA)(Py)2(H2O)]n (
tate, Py = pyridine), has been prepared via selfꢀassembly of benzeneꢀ1,4ꢀdioxylacetate with zinc nitrate
under mild conditions and characterized by IR spectra, elemental analysis and Xꢀray diffraction singleꢀcrysꢀ
tal analysis. The complex crystallizes in the monoclinic system, space group 2/ with = 15.5751(9),
6.0898(4), = 21.7133(13) Å, = 104.719(1) = 4. The zinc atoms are bridged by BDOA
= 1991.9(2) Å3,
ligand, forming a oneꢀdimensional chain along the axis. A twoꢀdimensional layer structure is formed by the
I) (BDOA = benzeneꢀ1,4ꢀdioxylaceꢀ
C
c
a
b =
c
V
β
°
, Z
z
intermolecular hydrogen bonds. The thermal decomposition profile of the complex is reported as well.
DOI: 10.1134/S1070328413020103
1
INTRODUCTION
on a Heraeus CHNꢀOꢀRAPID elemental analyzer.
TG analysis were recorded with a NETZSCH TGꢀ209
microanalyzer under nitrogen atmosphere at a heating
Metal organic frameworks (MOFs) have attracted a
great deal of recent interest not only for the potential
discovery of novel functional materials, which may
have applications in the areas including gas storage,
molecular sieves, ionꢀexchange, catalysis, magnetism,
and optoelectronics, but also for their intriguing variꢀ
ety of architectures and topologies, such as molecular
grids, bricks, herringbones, ladders, rings, boxes, diaꢀ
mondoids, and honeycombs [1–5]. Two kinds of these
ligands have been generally used in this field, either
flexible ligands, such as butanedioic and glutaric acids
and such analogous compounds [6–8], or rigid
ligands, such as benzenedicarboxylate, benzenetricarꢀ
boxylate, and so on [9, 10]. Although many ligands
with characteristics of both flexibility and rigidity have
been reported, here the ligands refer to those containꢀ
ing both a benzene ring and an aliphatic acid group,
rate of 10 C/min.
°
Synthesis of ligand BDOA. Hydroquinone 5.5 g
(0.05 mol) was dissolved in 50 mL 2 M NaOH (aq),
the mixture was heated to 70
25 mL 5 M monochloroacetic acid was added,
adjusted pH 11 with 4 M NaOH and heated to 120
°
C with stiring. Then
°
C
for 3 h (4 M NaOH was dropped in continuously to
keep pH 8), cooling to room temperature, acdic with
6 M HCl. The resulting white solid was filtered and
washed with water and ethanol and dried. The yield
1
was 6.057 g (53%); mp 250–251
(600 MHz; DMSO;
= 7.2 Hz, 4H), 13.019 (s., 2H).
°
C; H NMR
δ
, ppm): 4.703 (s., 4H), 6.985 (d,
J
For C10H10O6
reports of which are comparatively rare; these ligands anal. calcd., %:
C, 53.10;
C, 53.48;
H, 4.43.
H, 4.29.
are very important in the development of soꢀcalled
thirdꢀgeneration coordination polymers with dynamic
frameworks and striking functions. In this context, we
report the synthesis, characterization and thermal
studies of a new Zn(II) coordination polymer
[Zn(BDOA)(Py)2(H2O)]n(
zeneꢀ1,4ꢀdioxylacetate.
Found, %:
Synthesis of I. A solution of BDOA (0.03 mM),
NaOH (0.06 mM) in pyridine–H2O (1 : 1, 2.5 mL) was
carefully layered on the top of a solution of Zn(NO3)2
⋅
I), where BDOA = benꢀ
6H2O (0.03 mM) in DMF–H2O (1 : 1, 2.5 mL). The
yellow crystals suitable for Xꢀray diffraction were
obtained in a few weeks. The yield was 48%.
EXPERIMENTAL
For C20H20N2O7Zn
All reagents were commercially available and were
used without further purification. FTꢀIR spectra (KBr
pellets) were taken on a Nicolet 380 infrared specꢀ
trometer. Elemental analysis (CHN) were performed
anal. calcd., %: C, 51.57;
Found, %: C, 51.82;
H, 4.33;
H, 4.16;
N, 6.01.
N, 6.28.
Xꢀray crystallography. Single crystals of
for Xꢀray diffraction study were collected on a Bruker
I suitable
1
The article is published in the original.
225

226
LI et al.
Table 1. Crystallographic data and Xꢀray experiment details
for complex
nonꢀhydrogen atoms were located in successive differꢀ
ence Fourier syntheses and with the hydrogen atoms at
calculated position riding on the carbon atoms. Crysꢀ
tallographic data and experimental details for strucꢀ
ture analysis are summarized in Table 1. Bond lengths
and bond angles of the complex are listed in Table 2.
The atomic coordinates and other parameters of strucꢀ
ture have been deposited with the Cambridge Crystalꢀ
lographic Data Centre (no. 836460; deposit@
ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
I
Parameter
Formula weight
Value
465.75
296(2)
Temperature, K
Crystal system
Space group
Monoclinic
C2/c
a
, Å
, Å
, Å
15.5751(9)
6.0898(4)
21.7133(13)
1991.9(2)
1.553
b
c
RESULTS AND DISCUSSION
Volume, Å3
ρcalcd, mg/m3
Singelꢀcrystal Xꢀray structure analysis reveals that
the asmmetric unit of I contains one Zn(II) atom, one
Absorption coefficient, mm–1
1.279
BDOA ligand, two coordination pyridine molecules
and one coordination water molecule. Figure 1 shows
the view of the local coordination geometries around
the Zn(II) atom. The Zn(II) atom is fiveꢀcoordinated
in a distorted squareꢀpyramidal arrangement, with two
O atoms of different carboxylate groups and two
N atoms of two pyridine molecules in basal positions
and a water O atom at the apex. The distortion of the
regular squareꢀpyramidal geometry is due to the big
angle of the three coordination molecules;
F
(000)
Crystal size, mm
Range, deg
960
1.10
1.94–28.20
< 17, –8 <
–28 < < 21
6972
×
0.73
×
0.51
θ
Limited indice
–20 <
h
k < 7,
l
Reflections collected
Independent reflection
3774 (R
int = 0.0223)
99.9
Completeness to
Parameters
θ
= 28.20 , %
°
O(4)Zn(1)N(1) (and O(4)Zn(1)N(1
chelate angles 99.72(4) . The bisꢀmonodentate BDOA
A) have the same
273
°
Goodnessꢀofꢀfit on F 2
Final indices, ( > 2
indices, all data
Largest diff. peak and hole,
1.061
ligand has inversion symmetry and acts as bridge to
link the Zn(II) atoms to form an infinite zigzag chain
R
I
σ(
I
))
Å–3
R
R
1 = 0.0243, wR2 = 0.0605
1 = 0.0270, wR2 = 0.0619
0.229 and –0.284
along the
between two adjacent Zn(II) atoms in the same chain
is half the length of the axis.
z axis, as shown in Fig. 2. And the distance
R
e
z
It should be noted that the O–H…O hydrogen
bonds (Fig. 3), which are between the coordinated
water molecule and the free carboxylate O atoms, link
the zigzag chains into twoꢀdimensional layers. Simulꢀ
taneously, between the pyridyl rings there exist
SMART APEXꢀII CCD diffractometer equipped with
a graphite crystal and incident beam monochromator
using Mo
K
radiation (
λ
= 0.71073 Å) at room temꢀ
α
perature. Data processing was accomplished with the
supramolecular weak interactions
π
–
π
stacking
SAINT processing program. The structure was solved (Fig. 2). They are probably an important factor in the
by direct methods and refined on F2 by full matrix
leastꢀsquares analysis with SHELXTLꢀ97 [11]. The
supramolecular assembly and stabilization of the layer
[11].
C(7)
C(2A)
C(8)
C(1
O(2
N(1)
A)
C(6)
A
)
O(1A
)
x
C(9)
O(3
A
)
C(10)
O(2)
C(5)
C(4)
C(2B)
Zn(1)
O(4)
C(1
B
)
C(3
A
)
N(1A)
O(1B)
O(1)
C(1)
O(2B)
C(4A)
C(3)
C(5A)
C(2)
O(3)
y
Fig. 1. A segment of the polymeric structure of complex
with displacement ellipsoids drawn at the 30% probability
level.
I
Fig. 2. The crystal structure of complex
I, viewed down the
y axis. All H atoms have been omitted for clarity.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 2
2013

SYNTHESIS, CRYSTAL STRUCTURE, AND THERMAL STABILITY
227
Table 2. Bond lengths and bond angles of complex
Bond , Å
Zn(l)–O(4)
I
d
Bond
d, Å
2.0088(16)
2.0387(13)
2.1454(13)
1.332(2)
O(4)–H(4
A)
0.78
Zn(1)–O(1)
Zn(1)–N(1)
N(l)–C(6)
N(l)–C(10)
O(1)–C(1)
O(2)–C(1)
O(3)–C(3)
O(3)–C(2)
C(1)–C(2)
1.518(2)
1.382(2)
1.388(2)
1.390(2)
1.381(3)
1.369(3)
1.378(3)
1.373(3)
C(3)–C(5)#1
C(3)–C(4)
C(4)–C(5)
C(6)–C(7)
C(7)–C(8)
C(8)–(9)
1.340(2)
1.259(2)
1.226(2)
1.3748(19)
1.4162(19)
C(9)–C(10)
Angle
ω
, deg
Angle
ω
, deg
O(4)Zn(1)O(1)
O(1)Zn(1)O(1)#1
O(4)Zn(1)N(1)
O(1)Zn(1)N(1)
N(1)#1Zn(1)N(1)
C(6)N(1)C(10)
C(6)N(1)Zn()
C(10)N(1)Zn(1)
C(1)O(1)Zn(1)
C(3)O(3)C(2)
93.16(4)
173.68(8)
99.72(4)
O(1)C(1)C(2)
O(3)C(2)C(1)
O(3)C(3)C(5)#1
O(3)C(3)C(4)
C(5)#1C(3)C(4)
C(3)C(4)C(5)
C(3)#1C(5)C(4)
N(1)C(6)C(7)
C(8)C(7)C(6)
C(7)C(8)C(9)
C(10)C(9)C(8)
N(1)C(10)C(9)
113.96(15)
114.62(13)
115.39(14)
125.28(14)
119.30(15)
119.65(14)
121.05(15)
122.77(17)
119.62(18)
117.92(18)
119.49(18)
122.85(18)
87.83(5)
160.56(8)
117.32(15)
122.81(11)
119.87(12)
115.60(12)
117.71(12)
124
Zn(1)O(4)H(4
O(2)C(l)O(l)
A)
125.97(16)
120.07(15)
O(2)C(1)C(2)
#1
Note:
–x + 2, –y + 1, –z + 1.
IR analysis shows that peaks appearing at 1601 and the compounds. A further confirmation of this was
1502 cm–1 are attributed to the asymmetric vibrations
obtained from the single crystal Xꢀray structure of the
of carboxylated groups. The bands of 1445 and
1413 cm–1 should be assigned to the symmetric vibraꢀ
tions of carboxylated groups. The broad band at
3257 cm–1 belongs to the typical band of hydroxyl
group, confirming the presence of water molecule in
complex.
The thermogravimetric analyses (TGA) of the
complex was conducted under N2 atmosphere in the
temperature range of 25–800
°
C at a rate of 10°C/min
Lost weigth, %
100
80
60
40
20
0
0
100 200 300 400 500 600 700 800
Temperature,
°
C
Fig. 3. The twoꢀdimensional layer linked by intermolecuꢀ
Fig. 4. The thermogravimetric curves of complex
No. 2 2013
I.
lar hydrogen bonds.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39

228
Intensity
LI et al.
ACKNOWLEDGMENTS
This work was supported by grants of the Natural
Simulated
Science
Foundation
of
Hebei
Province
(nos. B2010000223, B2012201109) and Doctoral
Foundation of Hebei University (no. 2009ꢀ164).
Experimental
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calcd. 3.87%). Two pyridine molecules have lost
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33.98%). The BODA thermal decomposite in the
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°
°
°
°
suggested to be ZnO (obsd. 19.10%, calcd. 17.42%).
In order to confirm the phase purity of the bulk
materials, Xꢀray powder diffraction (XRPD) experiꢀ
ment has been carried out for complex
I. The XRPD
of determined by experiment is in a good agreement
I
with the simulated one of single crystal, which shows
that the bulk synthesized material has the same comꢀ
ponents and structure as those of single crystals
(Fig. 5).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 2
2013