A new microporous hydrogen-bonding framework constructed from 1-(4-hydroxyphenyl)-5-thioacetatetetrazole

Article abstract of DOI:10.1007/s10870-010-9821-8

The new complex with flexible heterocyclic carboxylate ligand, [Ba(HL ^-)₂ (H)₂O)₃] H)₂O (H)₂L = 1-(4- Hydroxyphenyl)-5-thioacetatetetrazole), were synthesized and structurally determined by

Full text of DOI:10.1007/s10870-010-9821-8

J Chem Crystallogr (2011) 41:587–590
DOI 10.1007/s10870-010-9821-8
COMMUNICATION
A New Microporous Hydrogen-Bonding Framework Constructed
from 1-(4-Hydroxyphenyl)-5-Thioacetatetetrazole
•
Xiao-Yong Zheng Cai-Hong Zhan
•
•
Shu-Guang Zhang Yun-Long Feng
Received: 23 October 2008 / Accepted: 20 May 2010 / Published online: 10 June 2010
Ó Springer Science+Business Media, LLC 2010
Abstract The new complex with flexible heterocyclic
carboxylate ligand, [Ba(HL-)2(H2O)3]ÁH2O (H2L = 1-(4-
Hydroxyphenyl)-5-thioacetatetetrazole), were synthesized
and structurally determined by X-ray diffraction analysis.
The complex belongs to the monoclinic system, space
group C2/c. The center Ba(II) is nine-coordinated by six
carboxylate oxygen atoms from four HL-ligands and three
water molecules in a distorted monocapped square trans-
prism geometry. The ligand serves as a bridge to link two
adjacent Ba(II) atoms into a chain structure which are
further assembled into the final three-dimensional supra-
molecular architecture with microporous open channel via
hydrogen bonds.
explored and summarized [18]. One of the important fea-
tures for the construction of hydrogen-bond supramolecular
porous framework is to obtain the possible connections.
On the basis of 1-(4-Hydroxyphenyl)-5-mercaptotetrazole
[19], we successfully designed a new carboxylate ligand,
1-(4-Hydroxyphenyl)-5-thioacetatetetrazole (H2L), which
possesses one phenolic hydroxy group and one flexible
thioacetate group (Scheme 1). This new ligand has the
characteristic coordination chemistry of seven coordinated
sites. In addition, it should be noted that H2L acts not only
as a hydrogen-bond acceptor but also as a hydrogen-bond
donor, depending on the deprotonated carboxyl group and
phenolic hydroxy group. Herein we report the synthesis
and characterization of a new microporous complex con-
structed from H2L ligand.
Keywords 1-(4-Hydroxyphenyl)-5-thioacetatetetrazole Á
Hydrogen bond Á Crystal structure
Experiment
Introduction
Materials and Measurements
More attentions have been paid to metal-organic frame-
works (MOFs) because of their intriguing topological
networks and wide potential applications in catalysis, chi-
rality, luminescence, magnetism, sensors, nonlinear optics
and porosity [1–16]. Recently, the use of hydrogen-bond to
construct supramolecular frameworks with large porosity
has become an appealing field due to their potential
applications as zeolite-like solids in catalysis [17]. A series
of hydrogen-bond porous molecular frameworks have been
1-(4-Hydroxyphenyl)-5-mercaptotetrazole was purchased
from the Meryer Company. 1-(4-Hydroxyphenyl)-5-thioac-
etatetetrazole (H2L) was synthesized from 1-(4-Hydroxy-
phenyl)-5-mercaptotetrazole via nucleophilic substitution
reaction [20]. FT-IR spectra (KBr pellets) were taken on a
FT-IR 170SX (Nicolet) spectrometer. Elementary analysis
was performed on a EuroEA3000 element analyzer. And the
crystal data collection was carried out on a Bruker APEX II
diffractometer.
Synthesis of [Ba(HL-)2(H2O)3]ÁH2O
X.-Y. Zheng Á C.-H. Zhan Á S.-G. Zhang Á Y.-L. Feng (&)
Zhejiang Key Laboratory for Reactive Chemistry on Solid
Surfaces, Institute of Physical Chemistry, Zhejiang Normal
University, Jinhua 321004, Zhejiang, People’s Republic of China
e-mail: sky37@zjnu.edu.cn
H2L (0.061 g, 0.5 mmol) and Ba(CH3COO)2Á3H2O (0.155 g,
0.5 mmol) were added into 15 mL of water and stirred for 2 h
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J Chem Crystallogr (2011) 41:587–590
SCH2COOH
Table 1 Crystal data and structure refinement for the title complex
Empirical formula
C18H21BaN8O10S2
HO
N
N
N
Formula weight
Crystal system
Space group
710.89
Monoclinic
C2/c
N
Scheme 1 Structure of H2L ligand
Unit cell dimensions
´
˚
a (A)
28.4486(5)
10.4208(2)
9.2501(1)
96.839(1)
2722.75(8)
4
´
˚
b (A)
under 60 °C. Then it was cooled to the room temperature. The
deposit was filtrated and crystals were obtained from the fil-
trate after 2 days. Anal. Calc. for C18H21BaN8O10S2: C,
30.41; H, 2.98; N, 15.76; S, 9.02%. Found: C, 30.44; H, 2.96;
N, 15.70; S, 9.32%. IR (KBr, cm-1): m(C-S) 600, ms(OCO-)
1400, mas(OCO-) 1570.
´
˚
c (A)
b (°)
´
3
˚
V (A )
Z
Dc/(Mg m-3
Absorption coefficient (mm-1
)
1.734
)
1.677
Crystal Structure Determination
F(000)
1412
Crystal size (mm)
h range/(°)
Reflections collected/Independent
reflections
0.309 9 0.143 9 0.059
2.08–27.36
10451/3046
The crystal data was collected at room temperature on a
Bruker Apex II CCD diffractometer with a graphite
˚
monochromator and Mo-Ka (k = 0.71073 A) radiation.
The data intensity was corrected by Lorentz-polarization
factor and empirical absorption on the SADABS program.
The structure was solved by direct methods and refined by
the full-matrix least-squares on the F2 technique, employ-
ing the Siemens SHELXS-97 [21] and SHELXL-97 [22]
program package. Except the hydrogen atoms on carbon
atoms were added theoretically, the remained hydrogen
atoms were located in successive difference Fourier syn-
theses. Crystal data and summary of data collection for the
title complex is shown in Table 1, the selected bond dis-
tances and angles are listed in Table 2, and hydrogen bonds
are displayed in Table 3.
Observed reflections [I [ 2a(I)]/Rint
Parameters
Goodness-of-fit on F2
2527/0.0314
182
1.090
R, wR [I [ 2a(I)]
R, wR (all data)
0.0336, 0.0866
0.0441, 0.0920
0.625, -0.431
3
Residual electron densities (e/A )
˚
carboxylate of HL- acts as a bridge atom to connect two
adjacent Ba(II) atoms forming a 1D chain structure with
´
˚
the BaÁÁÁBa of 4.6370 A (Fig. 2). It should be noted that the
carboxylate group coordinate in an asymmetric mode
´
˚
forming a short Ba–O bond (2.820(2) A) and a long Ba–O
´
˚
bond (2.946(2) A). The two planes, O1#1–Ba1–O2#1 and
Results and Discussion
O1–Ba1–O2, are not on a plane and the dihedral angle is
39.764(1)°, while the atoms of O2, Ba1, O2#3 and Ba1#3
display an almost coplanar configuration with a mean
Single-crystal X-ray diffraction analysis revealed that the
title complex belongs to the monoclinic system, space
group C2/c. As shown in Fig. 1, the center Ba(II) is nine-
coordinated by six carboxylate oxygen atoms from four
HL- ligands and three water molecules in a distorted
monocapped square antiprism coordination geometry.
Atoms of O2, O2w, O2#2, O1w and O2#1, O1#1, O2#3,
O1w#1 (symmetry codes: #1 -x ? 1,-y ? 1,-z ? 1; #2
x,-y ? 1,z - 1/2; #3 -x ? 1,y,-z ? 1/2) form the upper
and lower least-square planes with mean deviations of
´
˚
deviation to the least square plane of -0.296 A.
An interesting aspect of the structure concerns the non-
coordination of the nitrogen atoms of tetrazole ring. These
nitrogen atoms are directed away from the Ba atom. Fur-
thermore, the nitrogen atoms do not make close intermo-
lecular contacts to Ba in the crystal lattice, which maybe
due to the presence of the aromatic group precluding close
contacts with neighbouring Ba centre [23].
´
˚
-0.144 and 0.206 A, respectively, and the dihedral angle
In the structure, hydrogen-bonding interactions play an
important role in the synthesis of supramolecular archi-
tecture. There are persistent intermolecular hydrogen-
bonds which extend the 1-D chain structure into a 3-D
supramolecular framework, as shown in Fig. 3. O3 atom of
phenolic hydroxyl acts as both hydrogen-bond donor and
between the two planes is 8.64° and the two planes are
rotated by 53.55°. O1 atom caps the upper plane and
because of the force of repulsion from the four oxygen
atoms upon the upper plane, the Ba–O1 length bond of
´
˚
2.946(2) A is longer than the other Ba–O bond lengths
´
´
˚
which range from 2.707(2) to 2.820(2) A. O2 atom from
˚
acceptor, with the OÁÁÁO separation of 2.656(4) A for
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J Chem Crystallogr (2011) 41:587–590
589
´
˚
Table 2 Selected bond lengths (A) and bond angles (°)
Ba(1)–O(1W)
2.793(3)
2.744(6)
143.09(7)
72.69(7)
Ba(1)–O(2)
2.820(2)
2.946(2)
73.32(9)
70.86(6)
Ba(1)–C(8)
3.244(3)
Ba(1)–O(2W)
Ba(1)–O(1)
O(1W)–Ba(1)–O(2W)
O(1W)–Ba(1)–O(2)
O(2W)–Ba(1)–O(2)
O(1W)–Ba(1)–O(1)
O(2W)–Ba(1)–O(1)
O(2)–Ba(1)–O(1)
75.05(9)
44.79(7)
˚
Table 3 Hydrogen-bonding Geometry (A, °)
D–HÁÁÁA
d(D–H) d(HÁÁÁA) d(DÁÁÁA) \(DHA)
O(1W)–H(1WA)ÁÁÁO(3)#5
0.81
2.19
2.20
1.84
2.26
2.988(4) 169.0
2.985(8) 165.9
2.656(4) 166.2
2.985(8) 142.6
O(1W)–H(1WB)ÁÁÁO(3W)#1 0.80
O(3)–H(3)ÁÁÁO(1)#6
O(3W)–H(3WA)ÁÁÁO(1W)#1 0.85
0.83
Symmetry codes: #1 -x ? 1,-y ? 1,-z ? 1; #5 -x ? 1/2,y ? 1/
2,-z ? 1/2; #6 -x ? 1/2,-y ? 1/2,-z
Fig. 3 A view along the c axis of the 2-D layer structure in the title
complex
four Ba(II) ions (Fig. 3), in which metals locate on the
vertexs and ligands occupy the edges of a rhombic grid.
Notably, the rhombic unit as a secondary building block is
further assembled into a 2-D grid-like network structure
paralleling the ab plane which can be considered as a
network of (4,4), and furthermore the 2-D layers expand
into 3-D supramolecular architecture with rectangular
Fig. 1 Ball-and-stick representation of the title complex (symmetry
codes, #1 -x ? 1,-y ? 1,-z ? 1; #2 x,-y ? 1,z - 1/2; #3 -
x ? 1,y,-z ? 1/2; #4 -x ? 1,-y ? 1,-z)
˚
windows (7.00 9 8.01 A). The lattice water molecules are
located in these windows (Fig. 4).
Taking the structural feature of the title complex into
account in view point of topology for clarity, as depicted in
Fig. 5, the purple pillars stand for metal 1-D chains, the
blue ones mean ligands, and the green ones represent
hydrogen-bonding. It shows clearly that the ligands like
ladders and the hydrogen-bondings link the ladders to form
the 3-D framework. It should be noted that the hydrogen-
bonds appear alternately left and right sides along metal 1-
D chains.
Fig. 2 1-D chain structure viewed along the b axis in the title
complex
´
˚
O3ÁÁÁO1#6 (-x ? 1/2,-y ? 1/2,-z), 2.988(4) A for
O1wÁÁÁO3#5 (-x ? 1/2,y ? 1/2,-z ? 1/2).
From c axis direction, adjacent metals are linked by
ligands of different directions and hydrogen bonds to form
˚
a rhombic unit with side length 15.149(3) A containing
Fig. 4 The 3-D packing structure with rectangular microporous.
Lattice water molecules were omitted for clarity
´
123

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J Chem Crystallogr (2011) 41:587–590
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