The First Organically Templated Beryllium Phosphite [NH3(CH2)3NH3

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The First Organically Templated Beryllium Phosphite [NH3(CH2)3NH3]‚Be3 (HPO3)4: Hydrothermal Synthesis and X-ray Crystal Structure Wensheng Fu, Lei Wang, Zhan Shi, Guanghua Li, Xiaobo Chen, Zhimin Dai, Lei Yang, and Shouhua Feng*

CRYSTAL GROWTH & DESIGN 2004 VOL. 4, NO. 2 297-300

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People’s Republic of China Received July 3, 2003;

Revised Manuscript Received October 27, 2003

ABSTRACT: An organically templated beryllophosphite, [H3N(CH2)3NH3]‚[Be3(HPO3)4] 1, has been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction. It is the first beryllophosphite using organic amine as a structure-direction agent. Compound 1 crystallizes in a monoclinic system, space group P21/c with cell parameters: a ) 8.5983(15) Å, b ) 13.1561(19) Å, c ) 13.460(2) Å, β ) 92.470(5)°, and Z ) 4. The three-dimensional framework is built up from strictly alternating BeO4 tetrahedra and [HPO32-] pseudopyramid by sharing vertices. A new type of network containing 4-, 6-, 8-, 10-, 12-membered rings makes up the inorganic framework. The 1,3-diammonium propane template molecules are located in 8-membered ring windows. The compound was characterized by IR spectroscopy, inductively coupled plasma (ICP), and differential thermal and thermogravimetric analyses. Introduction Over the past several decades, a large number of open-framework metal phosphates have been synthesized for their potential applications in the fields of catalysis, biology, electrical conductivity, magnetism, and photochemistry.1-6 More recently, some of the vanadium phophites with piperazinium cations as structurally directing agents were synthesized by Zubieta et al.,7 and a great interest in the synthesis of new transition metal phosphites has been aroused. To date, the inorganic-organic hybrid phosphites containing V(III),8 Fe(III),8 Co(II),9 Mn(II),10,11 Zn(II),12-15 and Cr(III)16 have been extensively studied. However, only one of the organically templated main block metal phophites, [NH2(CH2)6NH2][Al(OH)(H(HPO3))2],17 was reported. It is well-known that the pyramidal hydrogen phosphite group [HPO32-] can link three adjacent cations via P-O-M (M ) metal) bonds and provides variety and novelty to the structures. Beryllium is a metal of the main block. From a structural point of view, beryllium is ideally suited as a building block for a new zeolite-like structure because its size is similar to that of Si4+ and it has a tendency to have tetrahedral coordination to an oxygen atom. A number of microporous beryllophosphates, such as ABW, ANA, CAN, EDI, FAU, LOS, RHO, BPH SOD, and WEI18-20 and some organically templated beryllophosphates21-23 have been prepared, but the beryllophosphites are less developed. We have recently reported the hydrothermal syntheses of the inorganic-organic hybrid phosphites.24-26 With an aim toward searching for novel organically templated phosphites, we conducted our study on the hydrothermal synthesis in berylliumphosphite-amine systems. * To whom correspondence should be addressed. Fax: +86-4315671974. E-mail: [email protected].

In this paper, we describe the synthesis and crystal structure of a novel organically templated beryllophosphite, [NH3(CH2)3NH3]‚Be3(HPO3)4 1, which has an open three-dimensional framework containing 4-, 6-, 8-, 10-, 12-membered rings and channels with 12-membered ring windows. It is the first organically templated beryllium phosphite. Experimental Section Synthesis. Caution! Use appropriate measures to avoid toxic BeO dust contamination. All syntheses were carried out in 23-mL Teflon-lined stainless steel vessels under autogenous pressure with a filling capacity of ∼15%. The elemental analysis was performed on a Perkin-Elmer 2400 element analyzer, and inductively coupled plasma (ICP) analysis was performed on a Perkin-Elmer optima 3300 DV ICP spectrometer. Infrared spectra were obtained on a Nicolet 5DX FT-IR instrument. A Perkin-Elmer DTA 1700 differential thermal analyzer and a Perkin-Elmer TGA 7 thermogravimetric analyzer were used to obtain DTA and TGA curves in air with a temperature increasing rate of 10 °C min-1. Synthesis of [H3N(CH2)3NH3]‚[Be3(HPO3)4] 1. The reactants BeO (0.025 g, 1 mmol), H3PO3 (0.410 g, 5 mmol), H3BO3 (0.305 g, 5 mmol), and 1,3-diammonium propane (0.2 mL, 2.35 mmol) were added to 2 mL (111 mmol) of distilled water. The solution pH values before and after the reaction were 2.2 and 4.6. The mixture was placed in 23-mL Teflon-lined stainless steel hydrothermal autoclaves with a filling capacity of ∼15% and heated at 160 °C for 120 h under autogenous pressure. The crystalline products were filtered, washed with deionized water, and dried at room temperature. The found data (wt %) are 6.45 for Be, 28.98 for P, 8.61 for C, 6.51 for N, and 3.78 for H, consistent with the caculated values of [H3N(CH2)3NH3]‚ [Be3(HPO3)4], Be: 6.39, P: 29.28, C: 8.52, N: 6.62, and H: 3.81. Determination of Crystal Structure. A suitable single crystal with dimensions 0.45 × 0.32 × 0.30 mm was selected for X-ray diffraction analysis. The intensity data were collected on a Siemens SMART CCD diffractometer with graphitemonochromated MoKR (λ ) 0.71073 Å) radiation at a temperature of 298 ( 2 K. A hemisphere of data was collected using a narrow-frame method with scan widths of 0.30° in ω and an

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Table 1. Crystal Data and Structure Refinement for [H3N(CH2)3NH3]‚[Be3(HPO3)4] empirical formula fw space group a, Å b, Å c, Å β, ° V, Å3 Z T, K λ (Mo KR), Å Fcalc, g cm-3 µ (Mo KR), mm-1 R1a, [I > 2σ(I)] wR2b, [I > 2σ(I)]

C3H16N2Be3P4O12 423.09 P21/c 8.5983(15) 13.1561(19) 13.460(2) 92.470(5) 1521.2(4) 4 293(2) 0.71073 1.847 0.559 0.0325 0.0960

exposure time of 30 s/frame. Data processing was accomplished with the SAINT processing program.27 The structure was solved by Direct Methods using the SHELXTL crystallographic software package.28 The beryllium and phosphorus atoms were first located, whereas the carbon, nitrogen, and oxygen atoms were found in the difference Fourier maps. The hydrogen atoms residing on the amine molecules and phosphorus were placed geometrically. A total of 7097 reflection intensities, of which 2183 were independent (Rint ) 0.0280), were collected within the range 2.17° < θ < 23.28° for the compound. The final cycle of refinement performed on F02 afforded residuals R ) 0.0325 and Rw ) 0.0960. Crystallographic data for this compound are listed in Table 1. Selected bond distances are summarized in Table 2.

Results and Discussion The IR spectra of the product phase exhibited the medium bands at 3005, 2900, and 1590 cm-1 due to the terminal NH3+ stretch, and the stretching vibrations of -CH2- groups at 2935 and 2892 cm-1. The bands at 2392 and 1045 cm-1 were attributed to the terminal P-H stretch and deformation. Absorption at 1151, 607, 523 cm-1 can be attributed to P-O vibration. The IR results showed clearly the vibrations from the [HPO32-] phosphite group and template molecule. The compound is a new organo-beryllophophite consisting of a three-dimensional network of vertex-linked BeO4 and [HPO32-] tetrahedra incorporating 1,3-diammonium propane cations into its pores. The asymmetric unit of 1 is presented in Figure 1. The asymmetric unit of the beryllophophite contains 24 non-hydrogen atoms, 19 of which belong to the “framework” (three Be, four P, and 12 O atoms) and five to the guest (three C and two N). The three beryllium atoms adopt tetrahedral coordination with typical geometrical parameters of dav(Be1-O) ) 1.615 (3) Å, dav (Be2-O) ) 1.625 (3) Å, dav(Be3-O) ) 1.627 (3) Å. The O-Be-O angles are in the range of 103.1-114.4° (av. O-Be(1)-O ) 109.33°, O-Be(2)-O ) 110.62°, O-Be(3)-O ) 109.45°). All these beryllium species bond to P atoms via Be-O-P links. As expected, the four distinct P atoms form the centers of pseudopyramid hydrogen phosphite groups with dav(P1-O) ) 1.517 Å, dav(P2O) ) 1.513 Å, dav(P3-O) ) 1.511 Å, dav(P4-O) ) 1.503 Å. The O-P-O bond angles are in the range 109.46114.11°, while the H-P-O angles range from 97.5° to 115.6°. The C-N and C-C geometrical parameters are in good agreement with those seen elsewhere. The structure of 1 is made up of strictly alternating BeO4 tetrahedra and [HPO32-] pseudopyramids via sharing vertices. The connectivity between these poly-

Fu et al. Table 2. Selected Bond Lengths (Å) and Angles (°) for [H3N(CH2)3NH3]‚[Be3(HPO3)4]a Be(1)-O(1) Be(1)-O(2) Be(1)-O(3) Be(1)-O(4) Be(3)-O(8) Be(3)-O(9)#3 Be(3)-O(10)#2 Be(3)-O(12)#2 P(2)-O(2) P(2)-O(6) P(2)-O(10) P(2)-H(2) P(4)-O(4)#4 P(4)-O(7)

1.627(5) 1.602(5) 1.612(4) 1.618(4) 1.628(4) 1.636(4) 1.622(4) 1.622(4) 1.513(2) 1.512(2) 1.514(2) 1.44(5) 1.509(2) 1.493(2)

O(2)-Be(1)-O(3) O(2)-Be(1)-O(4) O(3)-Be(1)-O(4) O(2)-Be(1)-O(1) O(3)-Be(1)-O(1) O(4)-Be(1)-O(1) O(10)#2-Be(3)-O(12)#2 O(10)#2-Be(3)-O(8) O(12)#2-Be(3)-O(8) O(10)#2-Be(3)-O(9)#3 O(12)#2-Be(3)-O(9)#3 O(8)-Be(3)-O(9)#3 O(6)-P(2)-O(2) O(6)-P(2)-O(10) O(2)-P(2)-O(10) O(6)-P(2)-H(2) O(2)-P(2)-H(2) O(10)-P(2)-H(2) O(7)-P(4)-O(8) O(7)-P(4)-O(4)#4 O(8)-P(4)-O(4)#4 O(7)-P(4)-H(4) O(8)-P(4)-H(4) O(4)#4-P(4)-H(4) P(4)-O(7)-Be(2) P(4)-O(8)-Be(3)

114.4(3) 110.6(3) 103.1(3) 113.7(3) 105.9(3) 108.4(3) 112.8(2) 105.2(2) 113.4(2) 111.0(2) 108.1(2) 106.3(2) 114.11(12) 110.67(12) 112.96(12) 107.1(18) 106.0(18) 105.3(18) 112.01(13) 111.10(14) 113.04(14) 106.0(19) 110 (2) 104 (2) 153.9(2) 141.8(2)

Be(2)-O(5) Be(2)-O(7) Be(2)-O(6) Be(2)-O(11)#1 P(1)-O(1) P(1)-O(5) P(1)-O(9) P(1)-H(1) P(3)-O(3) P(3)-O(11) P(3)-O(12) P(3)-H(3) P(4)-O(8) P(4)-H(4) O(7)-Be(2)-O(6) O(7)-Be(2)-O(11)#1 O(6)-Be(2)-O(11)#1 O(7)-Be(2)-O(5) O(6)-Be(2)-O(5) O(11)#1-Be(2)-O(5) O(5)-P(1)-O(9) O(5)-P(1)-O(1) O(9)-P(1)-O(1) O(5)-P(1)-H(1) O(9)-P(1)-H(1) O(1)-P(1)-H(1) O(3)-P(3)-O(12) O(3)-P(3)-O(11) O(12)-P(3)-O(11) O(3)-P(3)-H(3) O(12)-P(3)-H(3) O(11)-P(3)-H(3) P(1)-O(1)-Be(1) P(2)-O(2)-Be(1) P(3)-O(3)-Be(1) P(1)-O(9)-Be(3)#3 P(2)-O(6)-Be(2) P(2)-O(10)-Be(3)#6 P(3)-O(11)-Be(2)#7 P(3)-O(12)-Be(3)#6

1.640(4) 1.604(4) 1.619(4) 1.637(4) 1.518(2) 1.512(2) 1.517(2) 1.35(5) 1.499(2) 1.517(2) 1.517(2) 1.45(4) 1.508(2) 1.32(5) 107.0(2) 108.2(2) 112.1(2) 109.1(2) 110.9(2) 109.5(3) 111.14(13) 112.37(13) 110.30(13) 105.1(19) 107.6(19) 110.1(19) 112.58(13) 109.45(14) 109.89(13) 97.5(18) 115.6(17) 111.2(18) 137.8(2) 136.4(2) 142.0(2) 143.4(2) 139.1(2) 143.1 (2) 134.62(19) 140.2(2)

a #1 -x + 1, y - 1/2, -z + 1/2, #2 -x, y - 1/2, -z + 1/2, #3 x, -y, -z + 1, #4 x - 1, y, z, #5 x + 1, y, z, #6 - x, y + 1/2, -z + 1/2, #7 - x + 1, y + 1/2, -z + 1/2.

Figure 1. Asymmetric unit of 1 with thermal ellipsoids is shown at 50% probability.

hedra forms an infinite anionic three-dimensional network. The structure of 1 features a chain formed by a corner-sharing linkage of some 4,6-membered rings (Figure 2a). Each six-membered ring is capped by a [HPO32-] pseudopyramid. The four-membered ring is built from Be(1), Be(3), P(2), and P(3) tetrahedra, and the six-membered ring is built from Be(1), Be(2), Be(3), P(2), P(3), and P(4), whereas the capping moiety is built from P(1) tetrahedra, forming a four-membered ring (P(2), Be(1), P(1), Be(2)) and a six-membered ring (P(1), Be(1), P(4), Be(3), P(3), Be(2)). This type of chain is

First Organically Templated Beryllium Phosphite

Crystal Growth & Design, Vol. 4, No. 2, 2004 299

Figure 3. Polyhedral viewed down [100] of 1 showing the three-dimensional network of yellow (BeO4) and purple (HPO3) tetrahedral surrounding 12-membered channels occupied by the organic cations.

Figure 2. (a) The chain is composed of four six-membered rings, and each six-membered ring is capped by a [HPO32-] pseudopyramid. (b) The inorganic sheet built up by the linkages of the adjacent chains via Be-O-P linkages. Color code: Be, yellow; P, purple; O, red; H, white.

further connected to one another by the bridging oxygen atoms (P(1)-O(9)-Be(3) and P(4)-O(7)-Be(2)) and forms the three-dimensional structure, as shown in Figure 2b, with four 12-membered ring channels along [010]. The polyhedral connectivity along the [100] direction and [001] direction is shown in Figures 3 and 4, respectively. The 4-, 8-, 12-membered ring channels of the compound propagating along the [001] direction can be seen. Meanwhile, from Figure 4, it is obvious that there also exists 4-, 6-, 8-membered ring channels of the compound propagating along the [100] direction. Therefore, the structure can be considered to be built up from the network of those channels mentioned above. The structure directing organic amine molecules, wellordered, diprotonated 1,3-diammonium propane cations, sits in these channels and interacts with the framework through hydrogen bonds. The hydrogen bonds of the compound are listed in Table 3. TGA study was carried out from room temperature to 1000 °C, and it showed that the title compound has a relatively high thermal stability in air up to 325 °C. The 1,3-diammonium-propane groups were combusted in the range 340-470 °C with weight losses of 19.01% comparable with its calculated value, 18.91%. The DTA curve had a strong endothermic peak, which can be assigned to the loss of organoamine. Conclusions In summary, a open-framework beryllophosphite, [H3N(CH2)3NH3]‚[Be3(HPO3)4], was obtained by a hy-

Figure 4. Polyhedral viewed down [001] of 1 showing the three-dimensional network of yellow (BeO4) and purple (HPO3) tetrahedral surrounding eight-membered channels occupied by the organic cations. Table 3. Hydrogen Bonds Information for [H3N(CH2)3NH3]‚[Be3(HPO3)4]a D-H‚‚‚A N(1)-H(1A)‚‚‚O(9)#1 N(1)-H(1B)‚‚‚O(1) N(1)-H(1B)‚‚‚O(4) N(1)-H(1C)‚‚‚O(12)#2 N(1)-H(1C)‚‚‚O(11)#2 N(2)-H(2A)‚‚‚O(4)#2 N(2)-H(2A)‚‚‚O(7)#3 N(2)-H(2B)‚‚‚O(10)#3 N(2)-H(2C)‚‚‚O(11)#2

d (D-H) d (H‚‚‚A) d (D‚‚‚A) < (DHA) 0.89 0.89 0.89 0.89 0.89 0.89 0.89 0.89 0.89

1.99 2.17 2.29 2.09 2.51 2.35 2.66 2.12 2.29

2.878(4) 2.921(4) 2.944(4) 2.942(4) 3.060(3) 3.176(4) 3.268(4) 2.969(4) 3.083(4)

175.4 141.4 130.4 160.3 120.8 154.0 126.6 160.5 148.3

a #1 -x + 1, -y, -z + 1, #2 x, -y + 1/2, z + 1/2, #3 x + 1, -y + 1/2, z + 1/2.

drothermal method. It is the first organically templated beryllium phosphite, and possesses a totally different structure from those reported before. The title compound has a three-dimensional network containing 4-, 6-, 8-, and 12-membered ring windows. The basic unit of the framework was formed by capped four sixmembered rings; this kind of structure, which is capped by a [HPO32-] pseudopyramid, is seldom reported. This result shows that it is possible to prepare structural complex open-framework metal-phosphites possessing cavity size, limiting apertures, and framework densities rivaling those of the most open zeolites

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and aluminophosphates. At present, we are attempting to synthesize a wide variety of novel structure types with the aim of pursuing the diversity of the structures in the inorganic-organic hybrid materials family. Acknowledgment. We thank the National Natural Science Foundation of China (No. 20071013), the State Basic Research Project of China (G2000077507), and Foundation for “Chang-Jiang” scholarship by the Ministry of Education of China for support. Supporting Information Available: X-ray crystallographic files in CIF format for the structure determination of 1. This material is available free of charge via the Internet at http://pubs.acs.org.

References (1) Feng, S.; Xu, R. Acc. Chem. Res. 2001, 34, 239-247. (2) Shi, Z.; Feng, S.; Zhang, L.; Yang, G.; Hua, J. Chem. Mater. 2000, 12, 2930-2935. (3) Chui, S. S. Y.; Lo, S. M. F.; Charmant, J. P. H.; Orpen, A. G.; Willams, I. D. Science 1999, 283, 1148-1150. (4) Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D. Science 1999, 286, 945-947. (5) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460-1494. (6) Zaworotko, M. J. Angew. Chem., Int. Ed. 1998, 37, 12111213. (7) Bonavia, G.; Debord, J.; Haushalter, R. C.; Rose, D.; Zubieta, J. Chem. Mater. 1995, 7, 1995-1998. (8) Fernandez, S.; Pizarro, J. L.; Mesa, J. L.; Lezama, L.; Arriortua, M. I.; Olazcuaga, R.; Rojo, T. Chem. Mater. 2002, 14, 2300-2307. (9) Fernandez, S.; Pizarro, J. L.; Mesa, J. L.; Lezama, L.; Arriortua, M. I.; Rojo, T. Int. J. Inorg. Mater. 2001, 3, 331336.

Fu et al. (10) Fernandez, S.; Pizarro, J. L.; Mesa, J. L.; Lezama, L.; Arriortua, M. I.; Olazcuaga, R.; Rojo, T. Inorg. Chem. 2001, 40, 3476-3483. (11) Fernandez, S.; Mesa, J. L.; Pizarro, J. L.; Lezama, L.; Arriortua, M. I.; Olazcuaga, R.; Rojo, T. Chem. Mater. 2000, 12, 2092-2098. (12) Rodgers, J. A.; Harrison, W. T. A. Chem. Commun. 2000, 2385-2386. (13) Harrison, W. T. A.; Phillips, M. L. F.; Nenoff, T. M. Int. J. Inorg. Mater. 2001, 3, 1033-1038. (14) Harrison, W. T. A.; Phillips, M. L. F.; Nenoff, T. M. J. Chem. Soc., Dalton Trans. 2001, 2459-2461. (15) Harrison, W. T. A.; Phillips, M. L. F, Stanchfield, J.; Nenoff, T. M. Inorg Chem. 2001, 40, 895-899. (16) Fernandez, S.; Mesa, J. L.; Pizarro, J. L.; Lezama, L.; Arriortua, M. I.; Rojo, T. Angew. Chem., Int. Ed. 2002, 41, 3683-3685. (17) Li, N.; Xiang, S. J. Mater. Chem. 2002, 12, 1397-1400. (18) Feng, P.; Bu, X.; Stucky, G. D. Nature 1997, 388, 735-741. (19) Bu, X.; Gier, T. E.; Stucky, G. D. Microporous Mesoporous Mater. 1998, 26, 61-66. (20) Walter, F. Eur. J. Mineral. 1992, 4, 1275-1283. (21) Harrison, W. T. A. Int. J. Inorg. Mater. 2001, 3, 17-22. (22) Zhang, H.; Weng, L.; Zhou, Y.; Chen, Z.; Sun, J.; Zhao, D. J. Mater. Chem. 2002, 12, 658-662. (23) Zhang, H.; Chen, M.; Shi, Z.; Bu, X.; Zhou, Y.; Xu, X.; Zhao, D. Chem. Mater. 2001, 13, 2042-2048. (24) Shi, Z.; Li, G.; Feng, S. Inorg. Chem. 2003, 42, 2357. (25) Shi, Z.; Zhang, D.; Feng, S. J. Solid State Chem. 2003, 172, 464-470. (26) Dong, W.; Li, G.; Feng, S. Inorg. Chem. Commun. 2003, 6, 776-780. (27) SMART and SAINT Siemens Analytical X-ray Instruments, Inc.: Madison, WI, 1996. (28) SHELXTL, Version 5.1; Siemens Industrial Automation, Inc., 1997.

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