Two novel transition metal-organic frameworks based on 1,3,5- benzenetricarboxylate ligand: Syntheses, structures and thermal properties

Article abstract of DOI:10.1016/j.molstruc.2011.08.013

Two novel transition metal-organic frameworks, [Zn₆(OH) ₃(BTC)₃(H₂O)₃]7H₂O (1) and [Cd(BTC)(H₂O)][HIM] (2) (H₃BTC = 1,3,5- benzenetricarboxylic acid), have been synthe

Full text of DOI:10.1016/j.molstruc.2011.08.013

Journal of Molecular Structure 1004 (2011) 252–256
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Two novel transition metal–organic frameworks based on
1,3,5-benzenetricarboxylate ligand: Syntheses, structures and thermal properties
a
b
a,
Ying Fu a, Guobao Li a, , Fuhui Liao , Ming Xiong , Jianhua Lin
⇑
⇑
a Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications,
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China
b X-ray Laboratory, China University of Geoscience, Beijing 100083, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 6 July 2011
Received in revised form 4 August 2011
Accepted 4 August 2011
Available online 17 August 2011
Two novel transition metal–organic frameworks, [Zn6(OH)3(BTC)3(H2O)3]ꢀ7H2O (1) and [Cd(BTC)
(H2O)]ꢀ[HIM] (2) (H3BTC = 1,3,5-benzenetricarboxylic acid), have been synthesized under hydrothermal
conditions and characterized by single crystal and variable temperature powder X-ray diffraction
(VTPXRD), IR spectroscopy, elemental analyses, ICP measurements, and coupled TG–MS analyses. Com-
pound 1 crystallizes in the trigonal space group R3c, and could be described as a 3D porous network con-
sisting of (Zn2O8)n zigzag chains and bridging BTC ligands with 1D channels along c axis. Compound 2
crystallizes in the monoclinic space group P21/c, and exhibits a 2D framework made up of CdO6 octahedra
and BTC ligands parallel the bc plane. TG–MS and VTPXRD studies reveal that 1 is stable up to 320 °C
under air, and 2 stable up to 220 °C.
Keywords:
Metal–organic framework
1,3,5-Benzenetricarboxylic acid
d10 Transition metal
Hydrothermal synthesis
Structure
Ó 2011 Elsevier B.V. All rights reserved.
Thermal property
1. Introduction
structure. Following our recent interest in the systematic studies
on 1,3,5-benzenetricarboxylate coordinated with transition metals,
Metal–organic frameworks (MOFs) on the basis of self-assembly
of metal ions and multifunctional ligands have attracted much
attention for their enormous variety of interesting architectures
[1–5] and beneficial properties such as porosity, catalysis, magne-
tism, luminescence and nonlinear optics [6–14]. In the self-
assembly process, the construction of molecular architecture
depends on the judicious choice of the organic ligands and metal
centers [15–18]. Multicarboxylic ligands with suitable spacers,
such as 1,4-benzenedicarboxylic acid (H2BDC) [19–26], 1,3,5-
benzenetricarboxylic acid (H3BTC) [27–37] and 1,2,4,5-benzenetet-
racarboxylic acid (H4BTEC) [38–41], have been widely researched,
owing to the various coordination modes and structural features.
H3BTC has been extensively chosen to construct novel metal–or-
ganic frameworks in view of its following characteristics: (1) it
has three carboxylic ions for coordination, which exhibit different
coordination fashions to be favored to construct different frame-
works; (2) these carboxylate donor groups may be completely or
partially deprotonated to compensate for the charge and (3) the
carboxyl oxygen atoms are facilitating to form hydrogen bonds,
we have synthesized nine new structures, [Co(H2BTC)2(H2O)4],
[M3(BTC)(HCOO)4(H2O)]ꢀ [(CH3)2NH2]ꢀH2O (M = Mn, Co, Ni),
[Zn3Na2 (BTC)2(HCOO)2(H2O)8], [ZnNa(BTC)(H2O)2]ꢀH2O and
[Zn3Na(BTC)2(HCOO)(H2O)3]ꢀ2H2O,
[Cd3Na6(BTC)4(H2O)12]ꢀH2O
and [Cd3Na2(BTC)3(H2O)3]ꢀ[H2N(CH3)2 ]ꢀH2O [42–45]. As a sequel,
we report here two novel 3D and 2D metal–organic frameworks
based on d10 transition metal (Zn(II) or Cd(II)) with 1,3,5-benzene-
tricarboxylate ligands, [Zn6(OH)3 (BTC)3(H2O)3]ꢀ7H2O (1) and
[Cd(BTC)(H2O)]ꢀ[HIM] (2). The syntheses, crystal structures and
thermal properties of them have been discussed in detail.
2. Experimental
2.1. Materials and characterizations
All solvents and reagents for the syntheses were of analytical
grade and used as received from commercial sources without fur-
ther purification. Variable temperature powder X-ray diffraction
(VTPXRD) data of the studied samples were collected on a Bruker
and p–p stacking interactions are easy to form between aromatic
rings, which are good for stabilizing the whole supramolecular
D8 Discover diffractometer with Cu Ka radiation (k = 1.5418 Å) at
40 kV, 40 mAand a graphitemonochromator at the secondary beam.
The heating rate between two temperatures was 10 °C minꢁ1. Each
pattern was recorded after the corresponding temperature retained
600 s, within the 5–40° range (2h) with a step size of 0.02° and a
⇑
Corresponding authors. Tel.: +86 10 62750342; fax: +86 10 62753541(G.B. Li).
E-mail addresses: liguobao@pku.edu.cn (G.B. Li), jhlin@pku.edu.cn (J.H. Lin).
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.08.013

Y. Fu et al. / Journal of Molecular Structure 1004 (2011) 252–256
253
scanning rate of 10 s stepꢁ1. IR spectra were recorded on a Magna-IR
Table 1
750 FTIR spectrophotometer in the region 4000–650 cmꢁ1. Elemen-
tal analyses for C, H and N were carried out on an Elementar VarioEL
III microanalyzer. Thermo-gravimetric–mass spectrometric (TG–
MS) analyses were performed in air at a heating rate of 10 °C minꢁ1
from 50 to 800 °C, using a NETZSCH STA449C instrument.
Crystallographic and structural refinement parameters of 1 and 2.
1
2
Formula
Fw
Color, habit
Crystal dimensions (mm)
Temperature (K)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Zn6C27H32O31
1244.75
Colorless, needle
CdC12H10O7N2
406.62
Colorless, block
0.15 ꢂ 0.15 ꢂ 0.30 0.10 ꢂ 0.15 ꢂ 0.30
298
Trigonal
R3c
298
Monoclinic
P21/c
6.5160(13)
9.6687(19)
19.524(4)
96.23(3)
1222.8(4)
4
2.209
0.71073
1.829
Multi-scan
2.00, 32.50
2.2. Syntheses
30.159(4)
30.159(4)
6.9280(14)
90.00
5457.2(16)
6
2.273
0.71073
4.013
2.2.1. [Zn6(OH)3(BTC)3(H2O)3]ꢀ7H2O (1)
A mixture of ZnCl2 (2.0 mmol, 0.2725 g), H3BTC (1.0 mmol,
0.2101 g), NaOH (4 mmol, 0.1600 g) and distilled water (10.0 mL)
was placed in a 23 mL Teflon-lined stainless autoclave. The auto-
clave was sealed, heated at 170 °C for 5 days. After cooling to room
temperature, colorless crystals were filtered, washed with distilled
water and left to air-dry to give about 0.27 g of 1 (yield about 65%
based on H3BTC). Anal. Calcd for Zn6C27H32O31 (fw 1244.75): C
26.05, H 2.59. Found: C 26.36, H 2.21.
b (deg)
V (Å3)
Z
Dcalcd (g cmꢁ3
)
k (Mo K
a
)
) (Å)
l
(mmꢁ1
Absorption correction
Theta range for data collection
(deg)
Multi-scan
2.34, 33.49
F(0 0 0)
3732
1.004
800
1.008
GOF on F2
2.2.2. [Cd(BTC)(H2O)]ꢀ[HIM] (2)
Rint
0.0437
0.0219
2 was hydrothermally prepared from Cd(OAc)2ꢀ2H2O (1.0 mmol,
0.2665 g), H3BTC (1.0 mmol, 0.2101 g), IM (IM = imidazole) (1 mmol,
0.0681 g) and distilled water (10.0 mL). The mixture was sealed in the
23 mL Teflon-lined stainless autoclave and heated at 170 °C for
5 days, and then cooled to room temperature. The colorless crystal-
line products were filtered, washed with deionized water, and then
dried in air to give about 0.36 g of 2 (yield 88% based on H3BTC). Anal.
Calcd for CdC12H10O7N2 (fw 406.62): C 35.44, H 2.47, N 6.89. Found: C
35.43, H 2.48, N 6.90.
R1, wR2 [I > 2 (I)]
R1, wR2 (all data)
Largest diff. peak and hole (Åꢁ3
CCDC number
0.0519, 0.1281
0.0619, 0.1348
2.42, ꢁ0.79
823406
0.0340, 0.0989
0.0382, 0.1019
1.48, ꢁ1.12
829422
)
1680 to 1800 cmꢁ1 indicates the complete deprotonation of BTC li-
gands [52].
3.2. Crystal structure of [Zn6(OH)3(BTC)3(H2O)3]ꢀ7H2O (1)
2.3. Crystallographic studies
The single crystal X-ray diffraction analysis suggests compound
1 is in the trigonal space group R3c with the Flack parameter about
0.029(18), indicating that the absolute structure given by the struc-
ture refinement is likely correct. In the asymmetric unit of 1, there
are two crystallographic independent Zn(II) cations, one hydroxyl
group, one BTC ligand, one coordinated H2O and three solvated
water molecules (Fig. 1a). Each Zn(1) center exhibits a four coordi-
nated tetrahedron configuration composed by two carboxyl oxy-
gen atoms (O(2), O(4)) from two BTC ligands, and two oxygen
atoms (O(1) and O(1)i) from two hydroxyl groups. While, each
Zn(2) atom is six-coordinated with a distorted octahedron by four
BTC ligands (O(3), O(5), O(7) and O(8)), one hydroxyl group (O(1))
and a water molecule (O(6)). The lengths of Zn–O bonds are in the
range 1.959–2.280 Å (Table S1 in SI). Each BTC in 1 is completely
deprotonated, bridging two separate Zn(1) and four Zn(2) atoms
(Fig. S2a in SI). All of the three carboxyl groups adopt the bidentate
fashion: both the first and the second one connect one Zn(1) and
one Zn(2), and the third one links two Zn(2).
Suitable single crystals of 1 and 2 were carefully selected under
an optical microscope and glued to thin glass fibers with epoxy re-
sin. The intensity data were collected on a Bruker SMART X-ray dif-
fractometer, equipped with an APEX-CCD area detector and using
graphite-monochromatic Mo Ka (k = 0.71073 Å) radiation at room
temperature. The data absorption corrections were applied on the
basis of symmetry-equivalent reflections using the ABSCOR pro-
gram [46]. The structures were solved by the direct method and re-
fined on F2 with full-matrix least-squares methods using the
SHELXS-97 and SHELXL-97 programs, respectively [47,48]. All of
the non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were added in the riding model and refined isotropically
with O–H = 0.82 Å (H2O) or O–H = 0.98 Å (OH), C–H = 0.93 Å and
N–H = 0.86 Å. The crystallographic data and structural refinement
parameters are presented in Table 1, and the selected bond lengths
and angles are listed in Table S1 of the Supporting Information (SI).
As shown in Fig. 1b, Zn(1)O4 tetrahedra and Zn(2)O6 octahedra
link to each other through l3-O atoms of hydroxyl groups to form a
3. Results and discussion
zigzag chain of (Zn2O8)n along c axis. Such zigzag chains are con-
nected by the bridging BTC ligands parallel the ab plane to form
a 3D network with 1D channels of ca. 5.6 ꢂ 5.6 Å along c direction
(Fig. 1c). The guest water molecules occupy the void of the struc-
ture and interact with the framework through hydrogen bonds (Ta-
ble S2 in SI). The effective free volume of the dehydrated
framework was estimated by PLATON/SOLV to be 23.2% of the total
volume (1265.0 Å3 out of the 5457.2 Å3 unit cell volume). However,
N2 and H2 adsorption appeared to fail for dehydrated form of 1.
3.1. Infrared (IR) spectra
IR spectra of 1 and 2 (Fig. S1 in SI) confirm the presence of the
organic ligands used in the syntheses (through the characteristic
bands of aromatic and carboxylate groups). The broad absorption
bands of the asymmetric and symmetric stretching vibrations of
water (compounds 1 and 2) and imidazole (compound 2) appear
at 3700–2600 cmꢁ1 [49–51]. The bands at 1629–1544 cmꢁ1 and
1444–1357 cmꢁ1 correspond to the asymmetric and symmetric
stretching vibrations of the bound carboxylate groups (CO2M),
respectively [49–53]. The out-of-plane deformation vibrations of
the C–H groups in the benzene ring give absorption bands from
773 to 713 cmꢁ1 [50,51]. The absence of the absorption bands from
3.3. Crystal structure of [Cd(BTC)(H2O)]ꢀ[HIM] (2)
Crystallographic analysis reveals that compound 2 crystallizes
in the monoclinic space group P21/c. As illustrated in Fig. 2a, the

254
Y. Fu et al. / Journal of Molecular Structure 1004 (2011) 252–256
Fig. 1. Structural details of 1 drawn by Software Atoms 6.0 [54]. (a) Thermal ellipsoid plot (50%) drawing of the coordination environment of Zn(II) centers. Symmetry codes:
(i) ꢁy, ꢁx, z + 1/2; (ii) ꢁy, x ꢁ y, z; (iii) x, x ꢁ y, z + 1/2; (iv) ꢁx + y + 1/3, y + 2/3, z + 7/6; (v) ꢁx + y + 1/3, ꢁx + 2/3, z + 2/3. (b) Zigzag chain of (Zn2O8)n along the c axis. (c) 3D
framework viewed along the c axis. (Color codes: Zn(1), ciel; Zn(2), green; C, gray; O, red and yellow; Zn(1)O4 tetrahedra, ciel; Zn(2)O6 octahedra, green. The free water
molecules and hydrogen atoms are omitted for clarity.) (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)
Fig. 2. Structural details of 2 drawn by Software Atoms 6.0 [54]. (a) Thermal ellipsoid plot (50%) drawing of the coordination environment of Cd(II) ions. Symmetry codes: (i)
ꢁx, y + 1/2, ꢁz + 1/2; (ii) ꢁx, ꢁy, ꢁz. (b) The 2D layer parallel the bc plane. (c) 3D framework viewed along the b axis. (Color codes: Cd, ciel; C, gray; O, red; N, purple; Cd(1)O6
octahedra, ciel. The hydrogen atoms are omitted for clarity.) (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)
asymmetric unit of 2 contains one crystallographic unique Cd(II)
cation, one BTC ligand, one terminal water molecule and one imid-
azole cation. Each Cd(1) center shows six-coordinated fashions to
form distorted octahedra bound with five carboxyl oxygen atoms
(O(1), O(2), O(3), O(5) and O(6)) from four BTC ligands and one
oxygen atom (O(4)) from one terminal water. The distances of
the Cd–O bonds range from 2.217 to 2.558 Å (Table S1 in SI). Com-
pound 2 presents one type of completely deprotonated BTC con-
necting four Cd(1) atoms (see Fig. S2b in SI): the first carboxyl
group is of the chelating bidentate mode linking one Cd(1) atom,
the second one uses the bidentate fashion to connect with two
Cd(1) atoms, while the third one adopts the unidentate way to bind
with one Cd(1) atom.
Such BTC ligands link Cd(1)O6 octahedra to build up a 2D net-
work placed in the bc plane of the unit cell (Fig. 2b). The imidazole
cations reside in the void of the structure. The cooperative N–Hꢀ ꢀ ꢀO
and O–Hꢀ ꢀ ꢀO interactions connect with imidazole cations, coordi-
nated water molecules and carboxylate groups to form hydro-
gen-bonded network (Table S2 in SI), which establishes physical
connections between neighboring layers (Fig. 2c).
14.47 wt.%), without further weight loss up to 320 °C (Fig. 3a). The
second loss corresponded to the release of the organic part occurred
from 320 to 500 °C (Found 46.11 wt.%, Calc. 46.30 wt.%), leading to
ZnO as the residue (Found 39.88 wt.%, Calc. 39.22 wt.%). The TG anal-
ysis was confirmed by VTPXRD patterns (Fig. 3b). The ion currents of
m/z = 17 (HO+) and 18 (H2O+) appeared in above two steps, whereas
the MS peaks of ions with m/z = 28 (CO+) and 44 ðCO2þÞ were ob-
served in the second process (Fig. 3a).
The TG–MS analysis of compound 2 was demonstrated in
Fig. 3c. Compound 2 lost the coordinated water molecules in the
range of 100–220 °C (Found 4.79 wt.%, Calc. 4.43 wt.%). The ion
currents showed peaks at these temperature only for ions with
m/z = 17 and 18, which may be assigned to HO+ and H2O+, respec-
tively. And the destruction of the material occurred from 220 to
470 °C (Found 63.75 wt.%, Calc. 63.99 wt.%), founding HO+, H2O+,
CO+ and CO2+ (m/z = 17, 18, 28 and 44, respectively) by MS. The
VTPXRD studies (Fig. 3d) revealed the structure change of com-
pound 2 in the weight loss process. The diffraction pattern mea-
sured at 220 °C showed an apparent shift towards the lower
angle 2h of the peaks due to expansion of the framework with
the removal of coordinated water molecules. Interestingly, the
VTPXRD analysis exhibited that 2 undergone a distinct structural
transformation to form a new compound at 300 °C. And the result-
ing phase at the higher temperatures (above 500 °C) was CdO cor-
responding to the TG residue (Found 31.46 wt.%, Calc. 31.58 wt.%).
3.4. Thermal properties
The thermal stabilities of compound 1 and 2 were measured by
TG–MS and VTPXRD (shown in Fig. 3) in air, and related data
indicated that 1 and 2 were stable up to 320 °C and 220 °C,
respectively.
4. Conclusions
Thermal decomposition of compound 1 proceeded with two
distinct weight losses between 50 and 800 °C. The first weight loss
was attributed to the departure of all the water molecules in the
temperature range of 80–200 °C (Found 14.01 wt.%, Calc.
We have successfully combined d10 transition metal (Zn(II) or
Cd(II)) and the aromatic BTC ligands to afforded two novel
metal–organic frameworks through hydrothermal syntheses.

Y. Fu et al. / Journal of Molecular Structure 1004 (2011) 252–256
255
Fig. 3. (a) TG–MS curves for 1; (b) VTPXRD patterns for 1; (c) TG–MS curves for 2; (d) VTPXRD patterns for 2.
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Acknowledgment
This work is supported the National Key Basic Research Project
of China (Grant 2010CB833103).
Appendix A. Supplementary data
CCDC 823406 and 829422 contain the supplementary crystallo-
graphic data for 1 and 2. These data can be obtained free of charge
from the Cambridge Crystallographic Data Centre via http://
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at doi:
XXX. Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.molstruc.2011.08.013.
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