J O U R N A L O F C H E M I S T R Y Materials Synthesis and structure of a 2-D aluminophosphate Al3P4O16·3CH3CH2CH2NH3 N. Togashi,a J. Yu,*a,b,c S. Zheng,c K. Sugiyama,d K. Hiraga,d O. Terasaki,*a,b W. Yan,c S. Qiuc and R. Xuc aDepartment of Physics, Graduate School of Science and CIR, Tohoku University, Sendai 980–8578, Japan bCREST, Japan Science and Technology Corporation (JST), Japan cKey Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130023, P.R. China dInstitute for Materials Research, Tohoku University, Sendai 980–8577, Japan Received 13th July 1998, Accepted 25th September 1998 Using n-propylamine as a template, a new two-dimensional aluminophosphate Al3P4O16·3CH3CH2CH2NH3, 1 [space group P21/n (no. 14), a=11.310(1) A° , b=14.854(1) A° , c=14.796(1) A° , b=93.64(1)°, Z=4] is synthesised in an alcoholic system and the structure is solved using single-crystal X-ray diVraction data.The structure consists of tetrahedral AlO4 and PO3(LO) which are linked alternatively to form macroanionic layers parallel to the (1019) plane. The organic cations (C3H7NH3+) are located in the interlayer regions and are connected to the oxgens of the layers by hydrogen bonding.The 2-D nets of compound 1 are constructed from 4.6.8-nets which resemble the 2-D nets (4.6.8)1(6.8.8)1 in microporous AlPO4-21.under autogeneous pressure. The resulting product was filtered Introduction oV and dried in air at 70 °C. Following the discovery of microporous aluminophosphates Powder X-ray diVraction (XRD) patterns were obtained on (AlPO4-n) whose formation is promoted by the presence of a Philips PW3050 X-ray diVractometer using Cu-Ka radiation organic templates,1–3 a number of low-dimensional materials, (l=1.5418 A° ).The powder X-ray diVraction pattern of comi. e., one-dimensional (1-D) chains and 2-D layers, have been pound 1 shows good agreement with the simulated one based successfully synthesized in non-aqueous systems.4 These mate- on single-crystal XRD structure analysis, establishing that the rials exhibit diverse stoichiometries with Al/P ratios lower product is a single phase.than unity, in contrast to 3-D aluminophosphates with an Al/P ratio of 1/1 (except for JDF-20: [Al5P6O24H]2-5 and Single-crystal X-ray diVraction analysis AlPO-HDA: [Al4P5O20H]2- 6).Among the 2-D layer compounds, three diVerent stoichiometries have been observed, A colourless plate-like crystal of dimensions i.e., Al3P4O163-,7–14 Al2P3O123-,15,16 and AlP2O83-.14,17,18 In 0.16×0.80×0.03 mm was selected and mounted on a thin the case of Al3P4O163- compounds, except for Al3P4O16- glass capillary using cyanoacrylate adhesive. The intensity data 2C3N2H5,14 all the anionic inorganic layers are constructed were measured on a Rigaku R-AXIS IV imaging-plate detector from tetrahedral AlO4 and PO3(LO) alternately linked to form using graphite-monochromated Mo-Ka radiation (l= 4.6-,7,8 4.6.8-,9–11 and 4.6.12-nets.12,13 The topologies of these 0.710 69 A° ) generated by a rotating anode X-ray tube. Details 2-D nets show a resemblance to some of the three-connected of data collection are listed in Table 1.The lattice constants 2-D nets in 3-D microporous compounds. For example, the were determined by a least-squares procedure applied to the 4.6.12-nets resemble the 2-D nets in AlPO4-5.19 Here we report measurement of 25 well centered reflections (2h range a new 2-D aluminophosphate with 4.6.8-nets. The 4.6.8-nets 24.2–31.8°, Mo-Ka) on a Rigaku AFC7R diVractometer. resemble the 2-D nets in 3-D AlPO4-2119,20 that can be The structure was solved by direct methods using the structurally directed by the same template, n-propylamine, as program SIR9222 and refined by the least-squares program for the title compound.SHELXL97.23 In the final cycles of each refinement, nonhydrogen atoms except for C atoms were refined with anisotropic thermal parameters. Some C atoms have large thermal motions because the organic cations are located in large spaces Synthesis Compound 1 was synthesised solvothermally in a reaction Table 1 Summary of data collection details for Al3P4O16· mixture of 1.0 Al(OPri)352.4 H3PO455.0 CH3CH2CH2NH2550 3CH3CH2CH2NH3 butan-2-ol at 180 °C for 9 days.AlPO4-21 was prepared Resolution range/A° 14.80–0.76 hydrothermally in a reaction mixture of 1.0 Al(OPri)351.0 Total measured reflections 19 097 H3PO45(0.5–1.0) CH3CH2CH2NH25100 H2O at 180–220 °C Unique reflections 5228 for 9–12 days.2,21 The synthesis procedure is identical for both Possible reflections 6053 compounds, except for the solvent. Aluminium triisopropoxide Completeness(%) 86.3 was first dispersed into weighed amounts of butan-2-ol or Rmerge=.|I -Ii|/. Ii (%) 6.22 H2O.Phosphoric acid (85%) was then added dropwise and Oscillation angle per exposure 4.8 Total oscillation range 144.3 the mixture was stirred continuously. Finally, n-propylamine Camera length/mm 100 was added to the mixture with further stirring to form a Exposure time per frame/min 30 homogeneous gel.The reaction mixture was placed in a Teflon- Overlapped angle/° 0.3 lined stainless steel autoclave and heated at 180 °C for 9 days J. Mater. Chem., 1998, 8, 2827–2830 2827Table 2 Crystal data and structure refinement for Al3P4O16· Table 3 Atomic coordinates (×104) and equivalent isotropic displacement parameters (A° 2×103) of compound 1 3CH3CH2CH2NH3 Compound Al3P4O16·3CH3CH2CH2NH3 Atom x y z Ueq a Empirical formula C9H30Al3N3O16P4 Formula weight 641.18 P(1) 9162(2) -2406(2) 4392(2) 12(1) P(2) 8774(2) -2608(2) 1286(2) 12(1) Temperature/K 293(2) Wavelength/A° 0.71069 P(3) 5862(3) -923(1) 2402(2) 12(1) P(4) 5867(3) -4068(1) 2643(2) 13(1) Crystal system Monoclinic Space group P21/n Al(1) 8668(3) -1113(2) 2742(2) 12(1) Al(2) 5963(2) -2578(2) 1122(2) 10(1) Unit cell dimensions a/A° 11.310(1) Al(3) 8662(3) -3897(2) 2955(2) 11(1) O(1) 10252(5) -2327(3) 5057(4) 18(2) b/A° 14.854(1) c/A° 14.796(1) O(2) 9231(7) -1612(4) 3740(5) 18(2) O(3) 8025(5) -2393(4) 4853(5) 26(2) b/° 93.64(1) Volume/A° 3 2480.7(4) O(4) 9317(7) -3276(4) 3844(5) 22(2) O(5) 4555(5) -2315(4) 5514(4) 21(2) Z 4 Dc/g cm-3 1.717 O(6) 8964(7) -3402(4) 1928(5) 22(2) O(7) 9072(7) -1738(4) 1812(5) 22(2) Absorption coeYcient/mm-1 0.488 F(000) 1328 O(8) 7470(5) -2567(4) 955(4) 23(2) O(9) 9223(7) -4979(4) 3004(5) 23(2) Crystal size/mm 0.160×0.080×0.030 h range for data collection/° 2.20–27.44 O(10) 5550(7) -1584(4) 1623(5) 23(2) O(11) 5069(8) -1021(4) 3160(5) 29(2) Index ranges 0h14, 0k17, -19l18 Independent reflections (I>0) 2620 O(12) 7144(7) -1088(4) 2754(5) 24(2) O(13) 7155(7) -3907(4) 3013(5) 25(2) No.obs. data [I>2s(I )] 1948 Adsorption correction — O(14) 5617(7) -3476(4) 1813(5) 20(2) O(15) 5028(7) -3884(4) 3362(5) 26(2) Refinement method Full-matrix least-squares on F2 No. of parameters refined 263 O(16) 9237(7) -44(3) 2679(5) 21(2) N(11) 6318(8) -1079(4) 4822(6) 30(2) Goodness-of-fit on F2 0.934 Final R indices [I>2s(I )] R1=0.0668, wR2=0.1146 C(12) 6479(13) -104(8) 5088(11) 68(4) C(13) 7722(15) 215(9) 4953(11) 75(5) R indices (all data) R1=0.1111, wR2=0.1266 Largest diV.peak and hole/e A° -3 0.655, -0.467 C(14) 8457(16) -118(9) 5699(12) 89(6) N(21) 6232(8) -3625(4) 5093(6) 24(2) C(22) 6347(12) -4429(6) 5686(9) 50(3) C(23) 7080(15) -5193(9) 5186(12) 80(5) between the layers and while one end of the cation is connected C(24) 8339(18) -4990(11) 5361(15) 117(7) by hydrogen bonds to the oxygens of the layers (as will be N(31) 3674(6) -2415(5) 3694(5) 27(2) discussed in the next section) the other end is free.The C(32) 2351(11) -2337(8) 3488(9) 61(4) hydrogen atoms were geometrically placed. The isotropic C(33) 2098(16) -2536(12) 2448(13) 120(6) thermal parameters of all the hydrogen atoms were constrained C(34) 2160(3) -3517(14) 2280(2) 275(18) to be equal. A summary of the crystallographic data is given aUeq is defined as one third of the trace of the orthogonalized Uij tensor.in Table 2. Full crystallographic details, excluding structure factors, have been deposited at the Cambridge Crystallographic Data of these capped-6-MRs along [101] and [010], respectively, to Centre (CCDC).See Information for Authors, J. Mater. form the 4.6.8-nets. It should be noted that the eight- Chem., 1998, Issue 1. Any request to the CCDC for this membered-rings (8-MRs) possess both circular and elliptical material should quote the full literature citation and the shapes, as is the case in [Al3P4O16]3-[NH3(CH2)5NH3]2+- reference number 1145/126.[C5H10NH2]+,10 in which the distortion of the 8-MRs was thought to be due to the diVerential templating eVect of the Results and discussion two organic cations in the structure. However, in compound 1, only one template species exists in the structure. The factors The atomic coordinates, and selected bond lengths and bond causing the distortion of 8-MRs are worth considering.angles of compound 1 are given in Table 3 and 4, respectively. The organic ammonium cations (CH3CH2CH2NH3+) reside The Al3P4O163- anionic layers are constructed from alterin the interlayer regions between the inorganic layers, and the nating tetrahedral Al and P units [Fig. 1(a)] and the labeling layers are stacked in AAAA sequence along the c-axis (Fig. 2). scheme is shown in Fig. 1(b). There are three crystallograph- There are extensive H-bonding networks between the organic ically distinct Al sites. Each aluminium atom is coordinated ammonium cations and the framework oxygens. The H- to four phosphate groups. The AlKO bond lengths and bonding information is summarised in Table 5. Each RNH3+ OKAlKO bond angles are in the range 1.711(9)–1.746(7) A° supplies three H atoms to form H-bonds with three diVerent and 106.0(3)–111.3(3)°, which are typical for aluminophosterminal oxygens attached to the phosphate groups.The O(5) phates.7–18 All the four crystallographically distinct P atoms atom attached to the capped phosphate P(2) group accepts share three oxygens with adjacent Al atoms and the PKO bond three H atoms from three crystallographically distinct organic lengths are in the range 1.522 (6)–1.543(8) A° .The fourth PKO ammonium cations, whereas other terminal oxygens accept bond lengths for each P atom are P(1)KO(3) 1.493(6) A° , two H atoms from two crystallographically distinct templates P(2)KO(5) 1.492(6) A° , P(3)KO(11) 1.488(8) A° and to form H-bonds. P(4)KO(15) 1.496(8) A° , which are the shortest among the 4.6.8-nets have been observed in several 2-D aluminophos- others.These distances suggest that each crystallographically phates, such as [Al3P4O16]3-[NH3(CH2)5NH3]2+- distinct P atom possesses one PLO group.7–18 [C5H10NH2]+ 2,10 [Al3P4O16]3-[NH3(CH2)2NH3]2+- The inorganic layer consists of a series of capped six- [OH(CH2)2OH2]+[OH(CH2)2(OH)] 39 and [Al3P4O16]3-· membered-rings (capped-6-MRs)† [Fig. 1(a)]. All the tetra- 3[CH3CH2NH3]2+.23 However, all 2-D structures with 4.6.8- hedral P(2) atoms cap the 6-MRs with the terminal oxygens nets possess the same topology, which is schematically shown protruding into the interlayer region above or below the sheet. in Fig. 3(a). The direction of the PLO in the capped phosphate The layer is constructed from corner sharing and edge sharing groups is opposite to that of the other three PLO in the 6- MR.It is found that there are two typical stacking sequences †n-MR represents a loop, where n is the number of T(Al or P)-atoms or O-atoms forming the loop. of the inorganic layers, i.e., AAAA (e.g. compound 210) and 2828 J. Mater. Chem., 1998, 8, 2827–2830Table 4 Selected bond lengths (A° ) and angles (°) of compound 1 P(1)KO(3) 1.493(6) P(1)KO(2) 1.530(6) P(1)KO(1) 1.532(6) P(1)KO(4) 1.542(6) P(2)KO(5)a 1.492(6) P(2)KO(6) 1.521(6) P(2)KO(8) 1.525(6) P(2)KO(7) 1.534(6) P(3)KO(11) 1.487(8) P(3)KO(9)b 1.527(6) P(3)KO(12) 1.528(8) P(3)KO(10) 1.538(7) P(4)KO(15) 1.496(8) P(4)KO(14) 1.522(7) P(4)KO(16)c 1.528(6) P(4)KO(13) 1.541(8) Al(1)KO(16) 1.718(6) Al(1)KO(12) 1.725(9) Al(1)KO(2) 1.736(7) Al(1)KO(7) 1.745(7) Al(2)KO(10) 1.728(6) Al(2)KO(1)d 1.728(6) Al(2)KO(8) 1.738(6) Al(2)KO(14) 1.740(7) Al(3)KO(13) 1.713(9) Al(3)KO(9) 1.727(6) Al(3)KO(4) 1.734(7) Al(3)KO(6) 1.742(7) N(11)KC(12) 1.51(1) C(12)KC(13) 1.51(2) C(13)KC(14) 1.43(2) N(21)KC(22) 1.48(1) C(22)KC(23) 1.61(2) C(23)KC(24) 1.46(2) N(31)KC(32) 1.51(1) C(32)KC(33) 1.57(2) C(33)KC(34) 1.48(2) O(3)KP(1)KO(2) 111.0(4) O(3)KP(1)KO(1) 112.8(4) O(2)KP(1)KO(1) 106.0(4) O(3)KP(1)KO(4) 112.4(4) O(2)KP(1)KO(4) 107.6(3) O(1)KP(1)KO(4) 106.7(4) O(5)aKP(2)KO(6) 110.5(4) O(5)aKP(2)KO(8) 111.4(4) O(6)KP(2)KO(8) 109.1(4) O(5)aKP(2)KO(7) 109.3(4) O(6)KP(2)KO(7) 108.6(3) O(8)KP(2)KO(7) 107.9(4) O(11)KP(3)KO(9)b 111.1(4) O(11)KP(3)KO(12) 109.4(5) O(9)bKP(3)KO(12) 108.4(4) O(11)KP(3)KO(10) 112.5(4) O(9)bKP(3)KO(10) 106.6(4) O(12)KP(3)KO(10) 108.7(4) O(15)KP(4)KO(14) 112.0(4) O(15)KP(4)KO(16)c 110.8(4) O(14)KP(4)KO(16)c 106.9(4) O(15)KP(4)KO(13) 110.2(4) O(14)KP(4)KO(13) 108.7(4) O(16)cKP(4)KO(13) 108.1(4) O(16)KAl(1)KO(12) 111.0(4) O(16)KAl(1)KO(2) 108.8(4) O(12)KAl(1)KO(2) 108.3(4) O(16)KAl(1)KO(7) 109.4(4) O(12)KAl(1)KO(7) 109.4(4) O(2)KAl(1)KO(7) 110.1(4) O(10)KAl(2)KO(1)d 109.7(3) O(10)KAl(2)KO(8) 110.3(4) O(1)dKAl(2)KO(8) 105.9(3) O(10)KAl(2)KO(14) 109.0(3) O(1)dKAl(2)KO(14) 111.3(3) O(8)KAl(2)KO(14) 110.5(4) O(13)KAl(3)KO(9) 110.7(4) O(13)KAl(3)KO(4) 110.2(4) O(9)KAl(3)KO(4) 109.0(3) O(13)KAl(3)KO(6) 107.3(4) O(9)KAl(3)KO(6) 109.8(4) O(4)KAl(3)KO(6) 109.8(4) P(1)KO(1)KAl(2)e 152.6(4) P(1)KO(2)KAl(1) 146.6(5) P(1)KO(4)KAl(3) 142.0(5) P(2)KO(6)KAl(3) 147.6(5) P(2)KO(7)KAl(1) 141.9(5) P(2)KO(8)KAl(2) 153.0(4) P(3)cKO(9)KAl(3) 145.5(5) P(3)KO(10)KAl(2) 144.2(5) P(3)KO(12)KAl(1) 157.9(5) P(4)KO(13)KAl(3) 154.7(5) Fig. 1 (a) The inorganic sheet parallel to the (1019) plane and P(4)KO(14)KAl(2) 151.6(5) P(4)bKO(16)KAl(1) 150.7(5) (b) capped-6-MR showing the labeling scheme. C(13)KC(12)KN(11) 111.(1) C(14)KC(13)KC(12) 107.(1) N(21)KC(22)KC(23) 109.(1) C(24)KC(23)KC(22) 107.(1) N(31)KC(32)KC(33) 107.(1) C(34)KC(33)KC(32) 110.(2) Symmetry transformations used to generate equivalent atoms: ax+1/2, -y-1/2, z-1/2 b-x+3/2, y+1/2, -z+1/2; c-x+3/2, y-1/2, -z+1/2; dx-1/2, -y-1/2, z-1/2; ex+1/2, -y-1/2, z+1/2; fx-1/2, -y-1/2, z+1/2.ABAB (e.g. compound 39). Taking account of the 8-MR shape, two types of configurations are observed. In the case of compound 1 and 2 mentioned above, the inorganic layers contain two types of 8-MR systems with both circular and elliptical shape, whereas all the other layers contain regular elliptical 8-MRs.It is worth mentioning that the 4.6.8-nets in the 2-D aluminophosphates resemble the (4.6.8)1(6.8.8)1 2-D net (node 401) in 3-D microporous AlPO4-21 as shown in Fig. 3(b) (its 3-D structure can be represented by the addition of up–down linkages to the 2-D nets).19 An obvious diVerence of the 2-D nets in 2-D layer compounds from that in 3-D AlPO4-21 lies Fig. 2 View of the stacking of the layers with the interlamellar organic in the presence of capped phosphate groups in the 6-MRs . It cations; H-bondings are indicated by dashed lines.can be seen that if the capped phosphate groups are removed from the 6-MRs in the 2-D layer network, all the tetrahedral Al and P become three-connected, like the 2-D net in AlPO4-21. non-aqueous systems favour the formation of low-dimensional materials. It should be noted that most of the low-dimensional Interestingly, the 3-D microporous AlPO4-21 can be synthesized in an aqueous system using the same template, n- materials were synthesized in non-aqueous systems.The existence of triply, doubly, or singly-bridging phosphate groups propylamine, as for compound 1. However, compound 1 can only be prepared in non-aqueous systems. It is known that with terminal oxygens (PLO /or PKOH) in the low-dimensional J. Mater. Chem., 1998, 8, 2827–2830 2829Table 5 Hydrogen-bonding distances (A° ) present in Al3P4O16· structure consists of alternately linked tetrahedral AlO4 and 3CH3CH2CH2NH3 PO3(LO) to give Al3P4O163- stoichiometry.The 2-D inorganic nets are constructed from 4.6.8-nets which resemble the Distance NKH,O (4.6.8)1(6.8.8)1 2-D nets in 3-D microporous AlPO4-21, which can be also synthesized using the same template (n-propyl- N11KH113,O3 2.74 (1) N11KH111,O11 2.76 (1) amine) but in aqueous systems.Further investigation of the N11KH112,O5 2.94 (1) formation mechanism in diVerent solvent systems might prove N21KH212,O5 2.81 (1) to be a valuable contribution towards achieving a rational N21KH213,O15 2.85 (1) design of target materials. N21KH211,O3 2.77 (1) N31KH312,O5 2.82 (1) N31KH313,O11 2.75 (1) Acknowledgments N31KH311,O15 2.73 (1) We are grateful to CREST (Japan Science and Technology Corporation), NNSF (China) and the Key Lab of ISPC (China) for their support.References 1 S. T. Wilson, B. M. 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Giacovazzo, A. Guagliardi, The utilization of a non-aqueous synthesis technique has M. C. Burla, G. Polidori and M. Camalli, J. Appl. Crystallogr., greatly extended the aluminophosphate family upon continu- 1994, 27, 453. 23 SHELXL97, G. M. Sheldrick, Program for the Refinement of ing synthesis of a number of low-dimensional materials. A Crystal Structure, University of Go� ttingen, Germany, 1997. new compound Al3P4O16·3CH3CH2CH2NH3 was prepared in an alcoholic system in the presence of n-propylamine. Its Paper 8/05423A 2830 J. Mater. Chem., 1998, 8, 2827–28