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[(C4H12N)2][Zn3(HPO3)4] An Open-Framework Zinc Phosphite Containing Extra-Large 24-Ring Channels.

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Table 1: Examples for open-framework materials with 24-ring channels.[a]
[Ge14O29F4]ACHTUNGRE[H2dab]3ACHTUNGRE[dab]0.5� H2O (ASU-16)
[[email protected](OH)3]�NiL3 (FJ-1; L = en or enMe)
[5f ]
[a] btc = 1,3,5-benzenetricarboxylic acid; deta = diethylenetriamine;
dab = 1,4-diaminobutane; en = ethylenediamine; enMe = 1,2-diaminopropane.
Microporous Materials
DOI: 10.1002/anie.200504134
Zinc Phosphite Containing Extra-Large 24-Ring
Jing Liang, Jiyang Li, Jihong Yu,* Peng Chen,
Qianrong Fang, Fuxing Sun, and Ruren Xu
Microporous materials with open-framework structures are of
great importance due to their potential applications in
catalysis, separation, and ion-exchange processes.[1] The
discovery of the aluminophosphate molecular sieve VPI-5,
which contains 18-ring channels, in 1988[2] promoted the
search for new open-framework structures with increasing
pore sizes for use in catalysis and the separation of large
molecules.[3?5] A few open-framework structures with extralarge 24-ring windows have been described (Table 1). More
recently, Zou et al. reported a mesoporous germanium oxide
(SU-M) with the largest primitive cell and lowest framework
density of any inorganic material and channels that are
defined by 30-rings.[5i]
Several approaches toward the design and synthesis of
extra-large-pore materials have been explored in the past few
years.[6] One feasible method for the preparation of such
frameworks is based on the charge-density matching of host
and guest by the appropriate selection of framework elements
and organic structure-directing agents.[7] An alternative
strategy is to make interrupted open-frameworks with
[*] J. Liang, Dr. J. Li, Prof. J. Yu, P. Chen, Q. Fang, F. Sun, Prof. R. Xu
State Key Laboratory of Inorganic Synthesis and ACHTUNGREPreparative
College of Chemistry
Jilin University
Changchun 130012 (P.R. China)
Fax: (+ 86) 431-516-8608
E-mail: [email protected]
[**] This work was supported by the National Natural Science
Foundation of China.
Supporting Information for this article is available on the WWW
under or from the author.
terminal P OH and P=O groups, such as the 20-ring
gallophosphate cloverite[4a] and the 20-ring aluminophosphate
JDF-20.[4b] The replacement of tetrahedral phosphate groups
PO43 by pyramidal phosphite units HPO32 can reduce the
M-O-P connectivity and generate more-open interrupted
framework structures. Recently, metal phosphites with novel
open-framework structures and compositions have been
prepared by using various template molecules,[8] including
several vanadium hydrogenphosphites with 14-ring channels[9e] and zinc phosphites with 16-ring channels.[9a?d] Here,
we report the first metal phosphite, [(C4H12N)2]ACHTUNGRE[Zn3ACHTUNGRE(HPO3)4]
(denoted ZnHPO-CJ1; CJ stands for China Jilin University),
with extra-large 24-ring channels and a unique framework
ZnHPO-CJ1 was prepared by the hydrothermal reaction
of a mixture of ZnACHTUNGRE(OAc)2�H2O, n-butylamine, H3PO3, and
H2O in a 1:4.5:3:488 ratio at 180 8C for three days in a Teflonlined stainless-steel autoclave.
Single-crystal structural analysis revealed that ZnHPOCJ1 consists of a macroanionic [Zn3ACHTUNGRE(HPO3)4]2 framework
and n-butylammonium counterions, CH3ACHTUNGRE(CH2)3NH3+. Each
asymmetric unit contains two crystallographically distinct P
atoms and two crystallographically distinct Zn sites, with
Zn(2) located on a twofold axis (see Figure S1 in the
Supporting Information). Each P atom connects three O
atoms to nearby Zn atoms, leaving a terminal P H bond. All
Zn atoms are in tetrahedral environments. The P O and Zn
O bond lengths (P Oav. = 1.505, Zn Oav. = 1.956 A) are in
agreement with those observed in other zinc phosphites.[9] The
existence of P H bonds is confirmed by the characteristic
band of the phosphite anion (n?H P = 2399 cm 1) in the IR
spectrum (see Figure S2).
The open framework of ZnHPO-CJ1 is made up of strictly
alternating ZnO4 tetrahedra and HPO3 pseudo-pyramids,
which are arranged in parallel 24-ring and 8-ring channels
extending along the crystallographic c axis (Figure 1 a). The
approximate size of the 24-ring window is 11.0 B 11.0 A2,
which is comparable with those of the 24-ring channels in
NTHU-1[5c] (diameter 10.4 A) and FDU-4[5d] (12.65 A). Eight
CH3ACHTUNGRE(CH2)3NH3+ ions reside in each 24-ring window. The alkyl
groups of these cations extend into the hollow space of the 24ring channel and their NH3+ groups form H-bonds with the
framework oxygen atoms (Figure 1 b). The center space of the
channels between the organic cations is empty, as in ND-1,
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 2546 ?2548
Figure 1. a) The open-framework structure of ZnHPO-CJ1 viewed along
the [001] direction showing the extra-large 24-ring and the 8-ring
channels. The atoms O4?, O5?, O6?, and all H atoms have been
omitted for clarity; b) eight CH3ACHTUNGRE(CH2)3NH3+ ions reside in one 24-ring
pore. Hydrogen atoms have been omitted for clarity. Color code: Zn
green, P yellow, O red, N blue, C gray.
with a distance of about 2.6 A between the end carbon atoms
of two n-butylamine cations across the channels.
Figure 2 a shows the tetragonal array of four 8-ring
channels in the structure. These 8-ring channels with 6-ring
side pockets (Figure 2 b) are further connected by four
corner-sharing 4-ring chains (Figure 2 c) through Zn-O-P
linkages to form the 24-ring channels. Strikingly, the 8-ring
channels are hollow but do not contain encapsulated molecules. The pore size (ca. 3.4 B 3.4 A2) is typical for molecular
sieves containing eight-ring channels, such as ABW (3.4 B
3.8 A2), AFX (3.4 B 3.6 A2), PAU (3.6 B 3.6 A2), and RHO
(3.6 B 3.6 A2). The PH groups of the HP(1)O3 units point into
the 8-ring channels, which partially reduces the free volume
TG analysis (Figure S3) showed a weight loss of 24.02 %
between 160 and 395 8C, which is attributed to the decomposition of the n-butylammonium cations (calcd 22.35 %). An
XRD study showed that the structure collapses after heating
at 280 8C for 3 h, which suggests that the inorganic framework
structure is unstable upon removal of the organic molecules.
To the best of our knowledge, the largest pore opening
found in metal phosphites to date is 16-rings,[9] therefore
ZnHPO-CJ1 is the first metal phosphite with extra-large 24ring channels. Its framework density, 11.6 polyhedra per
1000 A3, is similar to the values of 12.1 for ND-1,[5a] 11.1 for
Angew. Chem. Int. Ed. 2006, 45, 2546 ?2548
Figure 2. a) The tetragonal array of four 8-ring channels; b) one 8-ring
channel with 6-ring side pockets; c) the corner-sharing 4-ring chain.
Color code: Zn green, P yellow, O red.
FDU-4,[5d] and 10.9 for NTHU-1.[5c] The structure of ZnHPOCJ1 provides useful information on the host?guest relationship in the formation of extra-large pores. As opposed to the
extra-large-pore high-silica zeolites UTD-1 and CIT-5, which
are templated by bulky organic cations with low charge
density, many metal phosphates and phosphites with extralarge pores have been prepared in the presence of relatively
small organic amines which yield ammonium ions with high
charge density. Examples include the 20-ring aluminophosphate JDF-20, templated by triethylamine,[4b] the 16-ring
gallophosphate ULM-5, templated by 1,6-hexACHTUNGREanediamine,[10]
the 16-ring gallophosphate ULM-16, templated by cyclopentylamine,[11] the 18-ring gallophosphate MIL-31, templated by NH2ACHTUNGRE(CH2)nNH2 (n = 9,10),[12] and the 24-ring zinc
phosphate ND-1, templated by 1,2-diaminocyclohexACHTUNGREane,[5a]
where several ammonium ions are included in one extralarge pore. This exemplifies the idea of a supramolecular
templating process being used for the preparation of mesoporous molecular sieves.[13]
Experimental Section
Synthesis and characterization: Typically, ZnACHTUNGRE(OAc)2�H2O (0.25 g)
was first dissolved in H2O (10 mL), and then n-butylamine (0.51 mL)
was added while stirring. Finally, H3PO3 (0.280 g) was added to the
above reaction mixture. A homogeneous reaction gel (pH 6) was
formed after stirring for 1 h, and this gel was sealed in a 15-mL Teflon-
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
lined stainless-steel autoclave and heated at 180 8C for three days
under static conditions. The colorless, rod-shaped single crystals
obtained were separated by sonication, washed with distilled water,
and then dried in the air.
X-ray powder diffraction (XRD) data were collected on a
Siemens D5005 diffractometer with CuKa radiation (l = 1.5418 A).
The experimental XRD pattern agreed well with the simulated one
generated on the basis of the single-crystal analysis (Figure S4). A
Perkin?Elmer TGA 7 unit was used for the thermogravimetric
analysis in air (heating rate 20 K min 1). ICP analysis was performed
with a Perkin?Elmer Optima 3300 DV ICP instrument (calcd (wt %):
Zn 29.52, P 18.65; found: Zn 28.95, P 18.03). Elemental analysis was
carried out with a Perkin?Elmer 2400 elemental analyzer (calcd
(wt %): C 14.46, H 4.25, N 4.22; found: C 14.65, H 3.89, N 4.33).
Structure determination: Structural analysis of a single crystal
(0.20 B 0.06 B 0.06 mm3) was performed with a Siemens SMART CCD
diffractometer using graphite-monochromated MoKa radiation (l =
0.71073 A). The data were collected at T = (20 2) 8C. Data processing was accomplished with the SAINT processing program.[14] The
structure was solved by direct methods and refined on F 2 by fullmatrix least-squares using SHELXTL97.[15] All Zn, P, and O atoms
were determined directly; C and N atoms were subsequently found in
the difference Fourier map. The H atoms of the HPO3 groups were
found in the final difference Fourier map, H atoms of the nbutylammonium cations were placed geometrically. The thermal
parameter of H(1) was fixed at 0.08. The O(4), O(5), and O(6) atoms
were disordered over two positions with an equal occupancy to the
O(4?), O(5?), and O(6?) atoms. P(1) is tetrahedrally coordinated either
to O(4), O(5), O(6?), and H1 or to O(4?), O(5?), O(6), and H1. Zn(1) is
tetrahedrally coordinated either to O(3), O(4), O(5?), and O(6) or to
O(3?), O(4?), O(5), and O(6?). All non-hydrogen atoms of the
inorganic framework were refined anisotropically.
Crystal data: C8H28N2O12P4Zn3, Mr = 664.32, tetragonal, space
group P4cc (no. 103), a = 16.4797(8), b = 16.4797(8), c = 8.8635(6) A,
V = 2407.2(2) A3, Z = 4, m = 3.283 mm 1, 1calcd = 1.833 g cm 3, 13 489
reflections measured, 2664 unique (Rint = 0.0688). The final wR2 (all
data) was 0.0727 and R1 was 0.0374. CCDC-290109 contains the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via
Received: November 21, 2005
Revised: January 25, 2006
Published online: March 17, 2006
Keywords: hydrothermal synthesis � materials science �
phosphites � template synthesis � zinc
[5] a) G. Yang, S. C. Sevov, J. Am. Chem. Soc. 1999, 121, 8389; b) J.
Zhu, X. Bu, P. Feng, G. D. Stucky, J. Am. Chem. Soc. 2000, 122,
11 563; c) C. H. Lin, S. L. Wang, K. H. Lii, J. Am. Chem. Soc.
2001, 123, 4649; d) Y. Zhou, H. Zhu, Z. Chen, M. Chen, Y. Xu,
H. Zhang, D. Zhao, Angew. Chem. 2001, 113, 2224; Angew.
Chem. Int. Ed. 2001, 40, 2166; e) J. PlLvert, T. M. Gentz, A.
Laine, H. Li, V. G. Young, O. M. Yaghi, M. OOKeeffe, J. Am.
Chem. Soc. 2001, 123, 12 706; f) N. Guillou, Q. Gao, M. NoguLs,
R. E. Morris, M. Hervieu, G. FLrey, A. K. Cheetham, C. R. Acad.
Sci. Paris Ser. IIc 1999, 2, 387; g) N. Guillou, Q. Gao, P. M.
Forster, J.-S. Chang, M. NoguLs, S.-E. Park, G. FLrey, A. K.
Cheetham, Angew. Chem. 2001, 113, 2913; Angew. Chem. Int.
Ed. 2001, 40, 2831; h) Z. Lin, J. Zhang, J. Zhao, S. Zheng, C. Pan,
G. Wang, G. Yang, Angew. Chem. 2005, 117, 7041; Angew. Chem.
Int. Ed. 2005, 44, 6881; i) X. Zou, T. Conradsson, M. Klingstedt,
M. S. Dadachov, M. OOKeeffe, Nature 2005, 437, 716.
[6] a) M. E. Davis, Chem. Eur. J. 1997, 3, 1745; b) T. E. Gier, G. D.
Stucky, Nature 1991, 349, 508; c) T. M. Nenoff, W. T. A. Harrison, T. E. Gier, G. D. Stucky, J. Am. Chem. Soc. 1991, 113, 378;
d) W. T. A. Harrison, T. E. Gier, K. L. Moran, J. M. Nicol, H.
Eckert, G. D. Stucky, Chem. Mater. 1991, 3, 27; e) D. E.
Akporiaye, Angew. Chem. 1998, 110, 2594; Angew. Chem. Int.
Ed. 1998, 37, 2456; f) K. J. Balkus, Jr., Progress in Inorganic
Chemistry, Vol. 50, Wiley, New York, 2001, p. 217.
[7] P. Feng, X. Bu, G. D. Stucky, Nature 1997, 388, 735.
[8] a) S. FernQndez, J. L. Mesa, J. L. Pizarro, L. Lezama, M. I.
Arriortua, T. Rojo, Angew. Chem. 2002, 114, 3835; Angew.
Chem. Int. Ed. 2002, 41, 3683; b) G. Bonavia, J. DeBord, R. C.
Haushalter, D. Rose, J. Zubieta, Chem. Mater. 1995, 7, 1995;
c) J. A. Rodgers, W. T. A. Harrison, Chem. Commun. 2000, 23,
2385; d) J. Liang, Y. Wang, J. Yu, Y. Li, R. Xu, Chem. Commun.
2003, 882.
[9] a) W. T. A. Harrison, J. Solid State Chem. 2001, 160, 4;
b) W. T. A. Harrison, M. L. F. Phillips, T. M. Nenoff, Int. J.
Inorg. Mater. 2001, 3, 1033; c) Z. Lin, J. Zhang, S. Zheng, G.
Yang, J. Mater. Chem. 2004, 14, 1652; d) W. Chen, N. Li, S. Xiang,
J. Solid State Chem. 2004, 177, 3229; e) R. K. Chiang, N. T.
Chuang, J. Solid State Chem. 2005, 178, 3040.
[10] T. Loiseau, G. FLrey, J. Solid State Chem. 1994, 111, 403.
[11] C. Sassoye, J. Marrot, T. Loiseau, G. FLrey, Chem. Mater. 2002,
14, 1340.
[12] C. Sassoye, T. Loiseau, F. Taulelle, G. FLrey, Chem. Commun.
2000, 943.
[13] H. O. Pastore, S. Coluccia, L. Marchese, Annu. Rev. Mater. Res.
2005, 35, 351.
[14] SMART and SAINT (software package), Siemens Analytical Xray Instruments Inc., Madison, WI, 1996.
[15] SHELXTL, version 5.1, Siemens Industrial Automation, Inc.,
Madison, WI, 1997.
[1] a) A. K. Cheetham, G. FLrey, T. Loiseau, Angew. Chem. 1999,
111, 3466; Angew. Chem. Int. Ed. 1999, 38, 3268, and references
therein; b) J. M. Thomas, R. Raja, G. Sankar, R. G. Bell, Acc.
Chem. Res. 2001, 34, 191; c) J. Yu, R. Xu, Acc. Chem. Res. 2003,
36, 481, and references therein; d) Ch. Baerlocher, W. M. Meier,
D. H. Olson, Atlas of Zeolite Framework Types 5th rev. ed.,
Elsevier, London, 2001; IZA Structure Commission website:
[2] M. E. Davis, C. Saldarriaga, C. Montes, J. M. Graces, C.
Crowder, Nature 1988, 331, 698.
[3] a) G. FLrey, A. K. Cheetham, Science 1999, 283, 1125; b) H. L.
Li, A. Laine, M. OOKeeffe, O. M. Yaghi, Science 1999, 283, 1145;
c) Q. Fang, G. Zhu, M. Xue, J. Sun, Y. Wei, S. Qiu, R. Xu, Angew.
Chem. 2005, 117, 3913; Angew. Chem. Int. Ed. 2005, 44, 3845.
[4] a) M. Estermann, L. B. McCusker, Ch. Baerlocher, A. Merrouche, H. Kessler, Nature 1991, 352, 320; b) Q. Huo, R. Xu, S. Li, Z.
Ma, J. M. Thomas, R. H. Jones, A. M. Chippindale, J. Chem. Soc.
Chem. Commun. 1992, 875.
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