SU-62: Synthesis and Structure Investigation of a ... - ACS Publications

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SU-62: Synthesis and Structure Investigation of a Germanate with a Novel Three-Dimensional Net and Interconnected 10- and 14-Ring Channels A. Ken Inge, Maxim V. Peskov, Junliang Sun, and Xiaodong Zou* Berzelii Center EXSELENT on Porous Materials and Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden S Supporting Information *

ABSTRACT: A novel 3D open-framework germanate, |N 2 C 4 H 1 4 | 4 [Ge20O41(OH)6]·3H2O (SU-62), was prepared from hydrothermal synthesis using 1,4-diaminobutane as the organic structure directing agent (SDA). The crystal structure was solved by single crystal X-ray diffraction. The framework is built from Ge10(O,OH)27 (Ge10) secondary building units and exhibits an irregular three-dimensional channel system encircled by 10- and 14-rings. The framework of SU-62 has an underlying topology that follows a novel fivecoordinated svh-5-I41/amd net, while the pores follow the tsi net. The thermal behavior of SU-62 was studied by thermogravimetric (TG) analysis and in situ Xray diffraction (XRPD). Crystallographic data: orthorhombic, space group Fdd2, unit cell parameters a = 15.297(3) Å, b = 53.58(1) Å, c = 14.422(3) Å, V = 11821(4) Å3, Z = 8.

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INTRODUCTION Porous materials such as zeolites are of significant importance as selective catalysts in the petrochemical industry and are of commercial interest as water softeners due to their ability to selectively host guest molecules in their pores and channels.1 The framework element type affects the physical and chemical properties of porous materials. Germanium oxide based frameworks are of particular interest for their ability to form structures with large pores (>12 ring), and they have the potential to host large-sized or a large volume of guest molecules in comparison to aluminosilicates.2 Unlike silicates which are built of tetrahedral units, open-framework germanates can be constituted from tetrahedral, trigonalbipyramidal, square pyramidal, and octahedral building units, reflecting the ability of germanium to be in four-, five-, and six-coordinated forms. The average Ge−O bond length (1.76 Å) is notably longer than the average Si−O bond (1.61 Å), tolerating smaller Ge−O−Ge angles (130°) compared to Si− O−Si (145°).3 These small bond angles are necessary for the formation of certain building units, such as 3-rings, that have been hypothesized to allow the formation of open-frameworks with low framework density.4 Most open-framework germanates are constructed from a few types of clusters consisting of 7−10 polyhedra.5 These large cluster building units provide unique possibilities to fabricate frameworks with extra large pores and low framework density. The germanate system shows an excellent example of scale chemistry;6 that is, for a given topology, structures built from larger building units lead to larger pores. Two of the most common secondary building units (SBUs) containing mixed polyhedra are Ge7(O,OH,F)19 (Ge7) and Ge10(O,OH)27 (Ge10). While controlling the formation of specific clusters © 2011 American Chemical Society

can be a difficult task, we found that the concentration of hydrofluoric acid (HF) has a strong influence on the formation of the cluster type in germanate-based materials.7 A high HF concentration often results in the formation of Ge7 clusters.8 All reported frameworks containing Ge10 SBUs involve either no hydrofluoric acid or low HF concentrations in the synthesis.2a,9 These include SU-M2a and SU-61 synthesized 9e from germanium oxide (GeO2 ), 2-methyl-1,5-pentanediamine (MPMD), and water; both contain Ge10 SBUs. The Ge10 SBUs in SU-M follow the gyroidal (G) surface, forming mesoporous gyroidal channels with 30-ring pore windows. SU61 contains 26-ring channels arranged in a hexagonal manner. SU-M and SU-61 can be considered as the crystalline analogues of the mesoporous silica MCM-48 and MCM-41, respectively.10 A study of the connectivity of Ge7 and Ge10 SBUs in known germanates and their framework topologies has recently been reported.11 We were interested in studying the roles of different organic structure directing agents (SDAs) in the formation of different germanate frameworks. When we substituted the MPMD in the synthesis of SU-M by 1,4-diaminobutane (DAB), a novel germanate |N2C4H14|4[Ge20O41(OH)6]·3H2O, denoted as SU62, was discovered. Similar to SU-M, SU-62 was built by Ge10 SBUs and has a three-dimensional (3D) open-framework with a 3D channel system involving intersecting 10- and 14-ring channels. Received: September 7, 2011 Revised: November 30, 2011 Published: December 2, 2011 369

dx.doi.org/10.1021/cg201482n | Cryst. Growth Des. 2012, 12, 369−375

Crystal Growth & Design

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EXPERIMENTAL SECTION

Table 1. Crystal Data and Details of the Structure Determination for SU-62

Synthesis. SU-62 was prepared under hydrothermal conditions from a mixture of germanium dioxide, 1,4-diaminobutane (DAB), and distilled water. A powder sample of SU-62 with crystal dimensions up to 5 μm was prepared from a mixture of GeO2 (300 mg), DAB (4.00 mL), and distilled water (2.70 mL) with a molar ratio of 1:13.9:52.3, respectively. The mixture was heated under autogenous pressure at 180 °C in a 22 mL Teflon-lined autoclave for 4 days. The powder was rinsed in distilled water and dried at room temperature overnight. The product was recovered with a yield of 170 mg (respectively, 45.2%) based on GeO2. The purity of the product was confirmed by X-ray powder diffraction (XRPD), as the experimental XRPD pattern agrees well with the simulated pattern (Figure S1 of the Supporting Information). Square plate-crystals of SU-62 with crystal dimensions up to 22 × 37 × 37 μm3 suitable for single crystal X-ray diffraction were obtained together with another novel germanate phase SU-7512 using a more diluted batch with GeO2 (300 mg), DAB (3.48 mL), and distilled water (5.40 mL) with a molar ratio of 1:12.1:104.5, respectively, at 160 °C for 4 days. The crystals were rinsed in distilled water and dried at room temperature overnight. The crystalline product was recovered with a yield of 110 mg. Crystal Structure Determination. Single crystal X-ray diffraction data of SU-62 were collected from a square plate-crystal at 100 K on a MarCCD detector using synchrotron radiation (λ = 0.9077 Å) at the Beamline I911:5, Max Lab, Sweden. Data reduction and numerical absorption correction were applied with TwinSolve.13 The structure was solved by direct methods with SHELXS97.14 All non-hydrogen atoms were refined with anisotropic atomic displacement parameters using a full-matrix least-squares technique on F2 with SHELXL97.14 Restraints and constraints were applied on anisotropic displacement parameters of framework atoms in similar environments. All guest species, including two symmetry-independent H2DAB2+ cations and two water molecules, could be located. One of the H2DAB2+ cations had significantly larger atomic displacement parameters than the other (Figure S2 of the Supporting Information). An attempt to introduce two-site disorders to describe the H2DAB2+ cation with large atomic displacement parameters was not successful. A riding model was used to constrain the coordinates of hydrogen atoms bonded to the atoms of the H2DAB2+ cations. The atomic displacement parameters of hydrogen atoms were set to 1.2 times those of the bonded carbon atom or 1.5 times those of the bonded nitrogen atom. Hydrogen atoms belonging to terminal Ge−OH groups were found in the Fourier difference map, and their bond lengths were restrained. The hydrogen atoms of the water molecules were manually placed at appropriate positions along the hydrogen-bond vectors. Crystal data and details of structure determination are given in Table 1. Topology Study. The underlying topology of the framework and connectivity of the cavities in SU-62 were analyzed using the TOPOS package.15 The pore and channel systems were studied by a tiling approach.16 Characterization. X-ray powder diffraction (XRPD) and in situ XRPD were performed on a PANalytical X’Pert PRO MRD equipped with an Anton-Parr XRK900 reaction chamber using Cu Kα radiation (λ = 1.5418 Å) and variable slits. For the in situ study, the sample was heated in vacuum with a heating rate of 7 °C·min−1 up to 450 °C. XRPD patterns were recorded every 50 °C. The temperature was equilibrated for 2 min prior to each measurement. Thermogravimetric (TG) analysis was performed on a Perkin-Elmer TGA7 under nitrogen atmosphere. The sample of SU-62 was placed in a platinum crucible and heated from 20 to 800 °C with a heating rate of 5 °C·min−1. Elemental analysis of C, H, and N was performed on a Fisons Instruments 1108 at Santiago de Compostela University, Spain, giving the C, H, N contents in SU-62: 7.07, 2.53, and 4.09 wt %, respectively (calculated 7.32, 2.61, and 4.27 wt %). The C/H/N molar ratio was deduced to be 4.04:17.22:2 (calculated 4:17:2). The chemical composition obtained from CHN analysis agreed with that determined from the structure refinement by single crystal X-ray diffraction.

identification code empirical formula formula weight temperature wavelength crystal system space group unit cell dimensions

volume Z density (calculated) absorption coefficient F(000) crystal size θ range for data collection index ranges reflections collected independent reflections completeness to θmax absorption correction max. and min transmission refinement method data/restraints/parameters goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data) Flack parameter largest diff peak and hole

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SU-62 |N2C4H14|4[Ge20O41(OH)6]·3H2O 2618.54 100 K 0.9077 Å orthorhombic Fdd2 (No. 43) a = 15.297(3) Å b = 53.58(1) Å c = 14.422(3) Å 11821(4) Å3 8 2.943 g/cm3 19.054 mm−1 10032 0.022 × 0.037 × 0.037 mm3 3.74−32.95° −18 ≤ h ≤ 18, −63 ≤ k ≤ 64, −17 ≤ l ≤ 17 32695 5275 [R(int) = 0.0640] 98.9% to θ = 32.95° empirical 0.5769 and 1 full-matrix least-squares on F2 5275/13/358 1.082 R1 = 0.0267, wR2 = 0.0632 R1 = 0.0275, wR2 = 0.0634 −0.007(8) 1.237 and −0.788 e/Å3

RESULTS AND DISCUSSION SU-62 crystallizes in an orthorhombic space group Fdd2. The framework structure is built from a unique Ge10(O,OH)27 SBU, which consists of four edge-sharing GeO6 octahedra (Ge4O16 unit) and six GeO4 tetrahedra (Figure 1a, b and Figure S2 of the Supporting Information). There are a total of 16 symmetryrelated SBUs in the unit cell. Each tetrameric Ge4O16 unit connects to five other tetramers; three of the connections are through pairs of tetrahedra, and the remaining two connections are via single tetrahedra (Figure 1c). Four of the six GeO4 tetrahedra (Ge6, Ge7, Ge8, and Ge9) in each Ge10 SBU are connected to four other Ge10 SBUs. Two other GeO4 tetrahedra (Ge5 and Ge10) are not involved in bridging, with one of their four oxygen atoms being a terminal hydroxyl group. There are a total of three terminal hydroxyl groups (bonded to Ge5, Ge8, and Ge10, respectively) in each Ge10 SBU, and the atomic displacement parameters for the terminal oxygen atoms are larger than those for other oxygen atoms. SU-62 has a 3D framework structure formed by corrugated layers stacked along the b-axis (Figure 1d and e). There are four such layers within each unit cell (Figure 2a, d, and g). Each layer has a thickness of 13.3 Å. Within the layer in Figure 1d, each Ge4O16 unit is connected to two Ge4O16 units via a single GeO4 tetrahedron along [101] and to two other Ge4O16 units through a pair of tetrahedra along [101̅]. The upper Ge10 SBUs in each layer are oriented in the same way, while those that are below (shown in faded colors) are related to the upper Ge10 SBUs by a diamond glide plane perpendicular to the b-axis. The layer in Figure 1d is corrugated in the [101̅] direction, resulting 370



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Figure 1. Ge10(O, OH)27 (Ge10) secondary building unit (SBU) in SU-62 shown in (a) polyhedral representation and (b) thermal ellipsoid representation (90% probability). The GeO6 octahedra (Ge1−Ge4) are shown in red and GeO4 tetrahedra (Ge5−Ge10) in green. (c) Connectivity of the Ge10 SBU in SU-62. Each Ge10 SBU is connected to five other Ge10 SBUs. (d and e) Two adjacent building layers perpendicular to the b-axis, each with a thickness of 13.3 Å. The two layers are related by a 2-fold axis along the c-axis.

hydrogen-bonding between the framework and the H2DAB2+ cations/water molecules as well as that between the Ge10 SBUs (Figure 3 and Figure S3). Within each 10-ring channel, one water molecule Ow1 and one nitrogen atom N3 are hydrogenbonded (N3−H···Ow1 = 3.124(3) Å) to each other. The N3− H···Ow1 pair are further hydrogen-bonded to four Ge10 SBUs that construct the 10-ring (Figure 3a). On the other hand, all the guest species (two water molecules and two H2DAB2+ cations) are involved in hydrogen-bonding in the 14-ring channel. Nitrogen atoms (N1 and N2′) from two symmetryrelated H2DAB2+ cations are found in the 14-rings, each hydrogen-bonded to three Ge10 SBUs. The nitrogen atoms (N1 and N2) from a single H2DAB2+ cation are found in two separate perpendicular 14-ring channels. One water molecule (Ow2) is located between two parallel 14-rings in the same channel and strongly hydrogen-bonded to two H2DAB2+ cations (N4−H···Ow2 = 2.839(3) Å) and six framework oxygen atoms from two Ge10 SBUs in separate 14-rings (Figure 3b and Figure S3c). The other H2DAB2+ cation with N3 and N4 also forms hydrogen-bonds across two parallel 14-rings, with each nitrogen hydrogen-bonded to two SBUs (Figure S3 and Table S1). Intercluster hydrogen-bonding is observed, with each Ge10 SBU hydrogen-bonded to two other Ge10 SBUs

in 10-ring channels in the [101] direction. The layer in Figure 1e is corrugated in the [101] direction, resulting in 10-ring channels in the [101̅] direction. The layers are connected by vertex-sharing of the GeO4 tetrahedra, one from each layer to form a 3D framework (Figure 2a, d, and g). The 3D framework has 10-ring and 14-ring channels running in parallel along [101̅], as shown in Figure 2g. The 10-rings are within each layer as defined by four Ge10 SBUs. The 14-rings are between the layers as defined by five Ge10 SBUs: two from one layer and the other three from an adjacent layer. Similar 10-ring and 14-ring channels are also present in the [101] direction. In addition, there are zigzag channels along the b-axis, which can be visualized using the topology approach, as discussed later. Unlike many other reported germanates where guest species could not be found by the structure refinement due to disorder, all guest species in the as-synthesized SU-62 could be located crystallographically (Figure S2 of the Supporting Information). There are two symmetry-independent H2DAB2+ cations to balance the charge of the framework. There are two symmetryindependent water molecules: one of them is at a special position. The arrangement of Ge10 SBUs in SU-62 is evidently influenced by various modes of hydrogen-bonding, as shown in Figure 3 and Figure S3, and listed in Table S1. This includes 371



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Figure 2. Various representations of the SU-62 framework viewed along (a−c) [100], (d−f) [001], and (g−i) [101̅]. (a, d, g) Polyhedral representation. (b, e, h) Underlying topology of SU-62 with each node representing a Ge10 SBU, which is identified as a distorted svh-5-I41/amd net. (c, f, i) The ideal svh-5-I41/amd net with its natural tiling shown in blue.

The SU-62 framework follows a novel topology of a fivecoordinated net derived from the svh net (Figure 2b, e, and h). Despite the orthorhombic lattice of the crystal, the ideal net follows a tetragonal symmetry (Figure 2c, f, and i). The uninodal svh-5-I41/amd net has three unique edges and is described by a uniform natural tiling consisting of only one type of tile. To the best of our knowledge, SU-62 is the first example where structural units adopt the svh-5-I41/amd topology. The svh-5-I41/amd net belongs to the group of uninodal graphs that are derived from RCSR topologies.17 It was generated by lowering the coordination number of the vertex in the seven-

across the shortest diameter of the 14-ring (Figure S3f). Two protonated GeO3(OH) tetrahedra per cluster behave as hydrogen-bond donors. The hydrogen-bonds between the Ge10 SBUs are relatively shorter (O···O distances 2.778(6) and 2.878(6) Å) compared to those involving guest species (on average 3.01 Å). Therefore, the 14-ring is virtually separated along the shortest diameter into two voids of 4.89 × 7.38 Å and 5.33 × 7.41 Å as given by the O···O distances. The O···O distances across the 10-ring, owing to their regular shape, are larger (5.34 × 8.84 Å) compared to those for the 14-ring. 372



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Figure 4. Relationship between the svh and svh-5-I41/amd nets. (a) Seven-coordinated svh net. The edges to be removed to generate the five-coordinated svh-5-I41/amd net are drawn in yellow. (b) The svh net and its natural tiling with two types of tiles. (c) The svh-5-I41/ amd net as found in SU-62 with its natural tiling. The transformation of the svh net to the svh-5-I41/amd net is achieved by removing the yellow edges in part a. Each cube in part b merges with two neighboring trigonal-prisms to form a single tile shown in part c.

Figure 3. Hydrogen-bonding within (a) the 10-ring channel and (b) the 14-ring channel viewed along [101̅]. In the 10-ring channel in part a, each water molecule is hydrogen-bonded to one H2DAB2+ cation; they together hold four Ge10 SBUs that form the 10-ring. Two water− H2DAB2+ pairs are shown in part a, with one below and one above the 10-ring. In the 14-ring channel in part b, N1 and N2 atoms form hydrogen-bonds within the 14-ring while Ow2, N3, and N4 are located either above or below the ring, hydrogen-bonded across two 14-rings in the channel.

SU-62 and a fcz net for SU-M.2a The chemical formulas of SU62 and SU-M are similar, |H2DAB|4[Ge20O41(OH)6]·3H2O and |H2MPMD|4[Ge20O41(OH)6]·xH2O, respectively. The synthesis conditions of SU-62 and SU-M are also similar, with GeO2, water, and a diamine as the only reagents and with a heating temperature of 160 °C. SU-62 contains a large cavity with the face symbol [320·44·104·144] encircled by four 10-ring windows and four 14-ring windows (Figure 5a). As a result of the irregular shape of the cavity, it is not easy to visualize the channels and their connectivity. To describe voids in a more systematic manner, we have examined the topology formed by the stacking of the cavities. Besides the relative positions of the cavities, the size of their windows is another criterion defining the structure of channels. The topology of voids of the framework is fully characterized by a net where every node symbolizes a cavity, and an edge corresponds to a window that is big enough to allow the migration of small molecules between the cavities. Thus, in the structure SU-62, only those edges that connect cavities through 10- or 14-ring windows were established. The resulting net that describes the topology of the channels is recognized as the uninodal tsi net,21 where eight edges (channels) meet in one vertex (the center of a cavity), as illustrated in Figure 5b. The topology of the voids in SU-62 clearly shows that the channel system is three-dimensional.

coordinated svh net (Figure 4a). Such a transition can be conveniently described through the evolution of empty space depicted by the natural tiling. The svh net is reproduced by the set of two kinds of tiles, cubes and trigonal-prisms, which correspond to the framework cavities (Figure 4b). In order to obtain the five-coordinated svh-5-I41/amd net topology, two out of seven edges per vertex are removed (Figure 4c). The final tiles are produced by uniting three adjacent tiles, including a cube and two trigonal-prisms, into a single new tile (Figures 2c, f, i and 4c.). A systematic study of the occurrence of the nets produced by Blatov17 has not yet been conducted, and currently only a few other examples are known.18−20 It is worth mentioning that the Ge10 SBUs in SU-62 are closely related to those found in SU-M.2a The SBUs in SU-62 and SU-M are similar; both contain an apical GeO3(OH) tetrahedron connecting to three tetrahedra in the SBUs. The Ge10 SBUs share vertices, and each connects to five other Ge10 SBUs in both structures. However, as shown in Figure S4 of the Supporting Information, the connectivity of each SBU to the neighboring SBUs is different, which results in different topologies for the two frameworks; a svh-5-I41/amd net for 373



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and aid in visual and mathematical inspection of the structure. This is particularly useful in structures with nonlinear channels, as in SU-62.

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ASSOCIATED CONTENT * Supporting Information Crystallographic information file (CIF) for SU-62, experimental and calculated XRPD patterns, thermal ellipsoid plot, hydrogen-bonding figures, comparison between the Ge10 SBUs in SU-M and SU-62, thermogravimetric plot, in situ XRPD patterns of SU-62, and the hydrogen-bond distances. This material is available free of charge via the Internet at http:// pubs.acs.org. S

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Figure 5. (a) Accessible cavity of the SU-62 net with face symbol [320·44·104·144], identifying the size of the face forming rings. (b) Connectivity of cavities in SU-62 shown in blue with the tsi net. Nodes of the channel net correspond to the centers of the cavities.

AUTHOR INFORMATION Corresponding Author *Telephone: +46 8 16 23 89. Fax: +46 8 15 21 87. E-mail: [email protected]. Web site: http://www.mmk.su.se/∼zou.

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Note that the derived topological map of voids describes the connectivity of channels and does not include information regarding trajectory. The topological description of channel systems inside a crystalline solid follows the concept of “dual” chemistry,22 where two nonintersecting topological subspaces describing the solid net and channels individually are considered as interpenetrating nets and provide a simple method of describing void systems within complex porous architectures. TG analysis was performed to determine the temperatures at which the guest molecules, water and H2DAB2+, leave the channels (Figure S5 of the Supporting Information). The first weight loss of 3.2 wt % was observed between 40 and 160 °C and was attributed to the loss of water molecules in the crystal structure (calculated 2.8 wt %). The weight loss (14.0 wt %) occurring from 160 to 750 °C corresponds to the loss of the DAB molecules (calculated 13.8 wt %). In situ XRPD was performed on SU-62 to determine the thermal stability of the framework (Figure S6 of the Supporting Information). The structure was stable up to at least 200 °C and retained its rigidity upon the removal of water. After the removal of water (200 °C), many of the high angle reflections lost intensity. Low angle peaks with 2θ < 13° were still present until 400 °C. The crystalline structure collapsed completely after 400 °C due to removal of the organic template as confirmed by TGA.

ACKNOWLEDGMENTS This project is supported by the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA) through the Berzelii Center EXSELENT and the GöranGustafsson Foundation. M.V.P. was supported by a postdoctoral grant from the Wenner-Gren Foundation.

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REFERENCES

(1) (a) Cheetham, A. K.; Ferey, G.; Loiseau, T. Angew. Chem., Int. Ed. 1999, 38, 3268−3292. (b) Č ejka, J., van Bekkum, H., Corma, A., Schüth, F., Eds. Introduction to Zeolite Science and Practice, 3rd ed.; Studies in Surface Science and Catalysis; Elsevier: Amsterdam, 2007; p 168. (c) Corma, A. J. Catal. 2003, 216, 298−312. (d) Sun, J.; Bonneau, C.; Cantín, Á .; Corma, A.; Díaz-Cabañas, M. J.; Moliner, M.; Zhang, D.; Li, M.; Zou, X. Nature 2009, 458, 1154−1157. (e) Davis, M. E. Nature 2002, 417, 813−821. (f) Schüth, F.; Schmidt, W. Adv. Mater. 2002, 14, 629−638. (2) (a) Zou, X. D.; Conradsson, T.; Klingstedt, M.; Dadachov, M. S.; O’Keeffe, M. Nature 2005, 437, 716−719. (b) Ren, X.; Li, Y.; Pan, Q.; Yu, J.; Xu, R.; Xu, Y. J. Am. Chem. Soc. 2011, 131, 14128. (3) O’Keeffe, M.; Yaghi, O. M. Chem.Eur. J. 1999, 5, 2796−2801. (4) Brunner, G.; Meier, W. Nature 1989, 337, 146−147. (5) Lin, Z.-E.; Yang, G.-Y. Eur. J. Inorg. Chem. 2010, 2895−2902. (6) Férey, G. J. Solid State Chem. 2000, 152, 37−48. (7) Guo, B.; Inge, A. K.; Bonneau, C.; Sun, J.; Christensen, K. E.; Yuan, Z.; Zou, X. Inorg. Chem. 2011, 50, 201−207. (8) (a) Zhang, H.-X.; Zhang, J.; Zheng, S.-T.; Yang, G.-Y. Inorg. Chem. 2003, 42, 6595−6597. (b) Plévert, J.; Gentz, T. M.; Groy, T. L.; O’Keeffe, M.; Yaghi, O. M. Chem. Mater. 2003, 15, 714−718. (c) Shi, L.; Bonneau, C.; Li, Y.; Sun, J.; Yue, H.; Zou, X. Cryst. Growth Des. 2008, 8, 3695−3699. (d) Pan, Q.; Li, J.; Ren, X.; Wang, Z.; Li, G.; Yu, J.; Xu, R. Chem. Mater. 2008, 20, 370−372. (e) Pan, Q.; Li, J.; Christensen, K. E.; Bonneau, C.; Ren, X.; Shi, L.; Sun, J.; Zou, X.; Li, G.; Yu, J.; Xu, R. Angew. Chem., Int. Ed. 2008, 47, 7868−7871. (f) Li, H.; Eddaoudi, M.; Richardson, D. A.; Yaghi, O. M. J. Am. Chem. Soc. 1998, 120, 8567−8568. (g) Plévert, J.; Gentz, T. M.; Laine, A.; Li, H.; Young, V. G.; Yaghi, O. M.; O’Keeffe, M. J. Am. Chem. Soc. 2001, 123, 12706−12707. (h) Tang, L.; Dadachov, M. S.; Zou, X. Chem. Mater. 2005, 17, 2530−2536. (i) Beitone, L.; Loiseau, T.; Férey, G. Inorg. Chem. 2002, 41, 3962−3966. (j) Villaescusa, L. A.; Wheatley, P. S.; Morris, R. E.; Lightfoot, P. Dalton Trans. 2004, 820−824. (k) Su, J.; Wang, Y.; Wang, Z.; Liao, F.; Lin, J. Inorg. Chem. 2010, 49, 9765− 9769. (9) (a) Medina, M. E.; Gutiérrez-Puebla, E.; Monge, M. A.; Snejko, N. Chem. Commun. 2004, 2868−2869. (b) Lorgouilloux, Y.; Paillaud, J.-L.; Caullet, P.; Bats, N. Solid State Sci. 2008, 10, 12−19. (c) Xu, Y.; You, W. Inorg. Chem. 2006, 45, 7705−7708. (d) Fleet, M. E. Acta

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CONCLUSIONS We have synthesized a new 3D open-framework germanate containing intersecting 10- and 14-ring channels built of Ge10 SBUs. The framework was held by extensive hydrogen-bonding with the guest water and H2DAB2+ cations in the channels. While bridging the gap between synthesis conditions and openframework structures remains a challenging task, the study of the host−guest interactions in complete crystal structures will help design novel porous architectures. The Ge10 SBU, in particular, appears promising for the development of tailored open-frameworks, as it is capable of forming a large number of open-frameworks from relatively dense structures, such as SU62, to very open frameworks, such as SU-M. The complex framework structure and channel system in SU-62 were greatly simplified by careful analysis of the underlying topology. The topological analyses of the framework and channels described here provide alternative descriptions of the framework and pores, and they are generally applicable to porous structures 374



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Crystallogr. 1990, C46, 1202−1204. (e) Christensen, K. E.; Bonneau, C.; Gustafsson, M.; Shi, L.; Sun, J.; Grins, J.; Jansson, K.; Sbille, I.; Su, B.-L.; Zou, X. J. Am. Chem. Soc. 2008, 130, 3758−3759. (f) Bonneau, C.; Sun, J. L.; Sanchez-Smith, R.; Guo, B.; Zhang, D.; Inge, A. K.; Edén, M.; Zou, X. D. Inorg. Chem. 2009, 48, 9962−9964. (10) Beck, J.; Vartuli, J.; Roth, W.; Leonowicz, M.; Kresge, C.; Schmitt, K.; Chu, C.; Olson, D.; Sheppard, E.; McCullen, S.; Higgins, J. ; Schlenker, J. J. Am. Chem. Soc. 1992, 114, 10834−10843. (11) Peskov, M. V.; Zou, X. J. Phys. Chem. 2011, C115, 7729−7739. (12) Huang, S.; Inge, A. K.; Yang, S.; Peskov, M. V.; Christensen, K. E.; Zou, X. D.; Sun, J. Manuscript in preparation. (13) Rigaku/MSC. TwinSolve; Rigaku/MSC: The Woodlands, TX, USA, 2002. (14) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112−122. (15) Blatov, V. A. Int. Union Crystallogr., Comput. Commun. Newsl. 2006, 4−38. (16) Blatov, V. A.; Delgado-Friedrichs, O.; O’Keeffe, M.; Proserpio, D. M. Acta Crystallogr. 2007, A63, 418−425. (17) Blatov, V. A. Acta Crystallogr. 2007, A63, 329−343. (18) Gándara, F.; de Andrés, A.; Gómez-Lor, B.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Proserpio, D. M.; Snejko, N. Cryst. Growth Des. 2008, 8, 378−380. (19) Jiang, X.-J.; Du, M.; Sun, Y.; Guo, J.-H.; Li, J.-S. J. Solid State Chem. 2009, 182, 3211−3214. (20) Weng, H.-S.; Lin, J.-D.; Long, X.-F.; Li, Z.-H.; Lin, P.; Du, S.-W. J. Solid State Chem. 2009, 182, 1408−1416. (21) O’Keefee, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. Acc. Chem. Res. 2008, 41, 1782−1789. (22) Blatov, V. A.; Shevchenko, A. P. Acta Crystallogr. 2003, A59, 34−44.

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SU-62: Synthesis and Structure Investigation of a ... - ACS Publications

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