- Email: [email protected]
Hydrothermal synthesis and structural characterization of a three-dimensional organically-templated vanadium phosphate [H3NCH2CH2NH3][(VO)3(H2O)2(PO4)2(HPO4)]
ELSEVIER
Inorganica Chimica Acta 268 (1998) 257-261
Hydrothermal synthesis and structural characterization of a three-dimensional organically-templated vanadium phosphate [H3NCH2CH2NH3] [ (VO) 3(H20) 2(PO4) 2(HPO4) ] Yingjie Lu a Robert C. Haushalter a,., Jon Zubieta b NEC Research Institute, 4 Independence Way, Princeton, NJ 08540, USA b Department of Chemistry, Syracuse UniversiO', Syracuse, NY 13244, USA
Received 13 February 1997; revised 10 April 1997; accepted 19 May 1997
Abstract
The title compound [(H3NCHzCH2NH3)][(VO)3(H20)2(PO4)2(HPO4)] was synthesized from the hydrothemaal reaction of V2Os:V:H3PO4:HzNCHzCH2NH2:H20in the mole ratio of 1: 1:10:5:740. The compound crystallizes in the triclinic space group P1 with unit cell parameters a = 10.187( 1),b= 10.241( l),c = 8.2137(7) ,~, a = 90.398(8),/3= 95.930(9) and3, = 117.325(7) °, V= 755.7(1) ~k3,Z = 2, Dealt = 2.570 g cm 3, R = 0.032, Rw = 0.035. The data were collected by using ~-20 scan technique and the structure was solved by direct method. The structure consists of binuclear units of comer-sharing [ VO6] octahedra and square-pyramidal [ VOs ] units linked by phosphate tetrahedra, forming double extended polyhedral slabs in the ( 101 ) plane with these slabs connected by comer-sharing [HPO4] tetrahedra to form a corner-sharing three-dimensional cage structure about the diammonium cations. © 1998 Elsevier Science S.A. Keywords." Crystal structures; Vanadium complexes; Phosphate complexes
1. Introduction
The recent interest in the hydrothermal synthesis of organically templated vanadium oxide phosphates derives from the observation that vanadium phosphates can form open framework solids with cavity dimensions similar to those of the technologically important aluminosilicate zeolites [ 1-5], from the notable catalytic properties [6,7] and significant structural diversity of the vanadium phosphates [8-14], and from the challenge to 'design' solid state materials by exploiting the structure-directing influence of organic molecules [ 15,16]. In the specific case of vanadium phosphates, the introduction of organic templates in hydrothermal synthesis to direct the organization of the metastable materials has greatly expanded the structural chemistry. Our recent results have demonstrated that the use of the organoamine species diaminobicyclooctane (N(C2H4)3N, DABCO), piperazine (HNC4HsNH), dimethylamine ((CH3) 2NH), 1,3-diaminopropane ( H2N (CH2) 3NH2 ), and ethylenediamine (H2NCH2-
* Correspondingauthor. 0020-1693 / 98 / $19.00 © 1998 Elsevier Science S.A. All rights reserved p//S0020- 1693 (97) 05753-8
CH2NH2) have produced a wide variety of new materials
such as the supercage phase: [H2DABCO]KL35[VsO9(P04)2] .H20 [ 17]; layered materials: [H2N(C4Hs)2NH2] [ (VO)4(OH)4(P04)2] [ 18], [HN(CzH4) 3NH][ (VO)s(HPO4)3(PO4)4(OH)2] "2H20 [ 18], [HN(C2H4)3NH] [ (VO3)3(OH)z(PO4)2] [ 18], [H2NC4HsNH2] [ (VO)2(PO4)2] [19] and [HeNC4HsNH2] [ ( V O ) 3(PO4) 2(HP04) 2]" H20 [ 19 ] ; one-dimensional phases: [ (H2NCHzCH2N H 3 ) ( V O ) ( P 0 4 ) ] ]8] and [H3NCH2CH2NH 3] [ V ( O H ) (HPO4)2] "H20 [20]); a complex structure exhibiting chiral intertwined double helices: [ ( C H 3)2NH2]K4[ (VO)Io(H20)z(OH)4(P04)7] "H20 [21] ); very large ethylenediammonium-fined tunnels: ](H3NCH2CHzNH3)2][ (H3NCH2CH2NH2] [ V ( H 2 0 ) 2(VO) s ( O H ) a ( P O 4 ) a (HPO4)4] "2H20 [22] ; and three-dimensional frameworks: [H3N(CHz)3NH3] K(VO)3(PO4)3] [23], [H3N(CH2)3NH3] [(VO)3(OH)2(H20)2(P04)2] [24], arid [(H3NCH2CH 2NH3)4] [V(HzO)2(VO)6(OH)2(HPO4)3(DO4)5] • 3H20
[25]. We report here a new three-dimensional vanadium phosphate, [H3NCH2CH2NH3] [ (VO)3(H20)2(PO4)2(HPO4) ], with a unique cage structure and framework connectivity.
258
E Lu et al. / Inorganica Chimica Acta 268 (1998) 257-261
Table 1 Crystallographical data for [ (H3NCH2CH2NH3] [ (VO) 3(H20) 2(PO4) (HPO4) ] Empirical formula Color, habit Space group a (A) b (A) c (A,) ot (o) 13(o) y (°) V (~3) Z T (°C) A(Mo Ka) (A.) p~ (cm- i ) Dcal~(gcm -3) Scan type No. reflections measured No. observation (1> 3o-(1) ) No. variables Reflection/parameter ratio R
HIsN2C2017V3P3 green, prismatic Pi (No. 2) 10.187(1) 10.24l(1) 8.2137(7) 90.398(8) 95.930(9) 117.325(7) 755.7( 1) 2 20 + 1 0.71073 22.36 2.570 to--20 4673 4444 (Ri,,=0.034) 2789 11,43 0.032 0.035 1.54
Rw
Goodness of fit
2. Experimental 2.1. P r e p a r a t i o n o f (H3NCH2CH2NH3)][(VO)3(H20)2(PO4)2(HP04)]
The hydrothermal reaction of V20 5 (0.1091 g ) , V ( - 325 mesh, 0.0305 g), H3PO 4 (0.6 m l ) , H2NCH2CH2NH2 (0.2 m l ) , and H20 (8.0 ml) in the mole ratio 1:1:10:5:740 in a 23 ml acid digestion bomb at 200°C for 7 days yielded a mixture containing a green crystalline phase of the title compound. Crystals suitable for X-ray analysis were separated mechanically to give a yield of crystalline material of 2% based on vanadium. Attempts to improve the yield proved unsuccessful. However, a 2 - 5 % yield under the conditions reported was reproducible in all cases. 2.2. X - r a y c r y s t a l l o g r a p h i c s t u d i e s
All measurements were made on a Rigaku A F C 7 R diffractometer with graphite-monochromated M o K a radiation and a 18 k W RU300 rotating anode generator. The data were collected by using oy-2 0 scan technique. An empirical absorption correction was applied. The structure was solved by direct methods [ 26 ]. The non-hydrogen atoms were refined anisotropically. The hydrogen atoms were located from difference Fourier maps and included in the refinement with fixed positional and thermal parameters. Detailed crystallographic data are given in Table 1. Atomic positional parameters and isotropic temperature factors are presented in Table 2 and selected bond lengths are given in Table 3.
R = EIIF,,I - IFcll/EIF,,I. Rw= [Ew( IFol- IF,.I)2/EwFo2] ~/a
Table 2 Positional parameters and isotropictemperaturefactorsB~ Atom
x
y
z
Bcq
V(1) V(2) V(3) P(1) P(2) P(3) O(1) 0(2) 0(3) 0(4) 0(5) 0(6) 0(7) 0(8) 0(9) O(10) O(11) O(12) O(13) O(14) O(15) 0(16) O(17) N(I) N(2) C(1) C(2)
-0.01344(7) -0.48027(8) -0.21316(8) -0.2169(1) 0.1859(1) -0.7133(1) 0.1198(3) -0.6338(3) -0.1120(3) -0.3728(3) -0.1363(3) 0.0189(3) -0.2272(3) -0.7394(3) 0.1260(3) -0.3996(3) 0.1109(4) -0.1048(3) -0.6470(3) 0.1276(3) -0.3718(3) 0.1557(3) -0.3782(3) -0.4774(4) -0.1810(4) -0.3285(5) -0.4476(5)
0.21530(7) -0.21654(7) 0.14798(7) -0.1157(1) 0.5368(1) -0.1207(1) 0.4305(3) -0.2152(3) -0.0025(3) -0.2058(3) 0.2260(3) 0.1839(3) -0.0414(3) -0.0584(3) 0.4445(3) -0.2726(3) 0.1720(3) 0.2360(3) -0.3982(3) 0.6504(3) 0.1319(3) 0.2231(3) -0.0028(3) 0.2247(4) 0.4948(5) 0.4868(5) 0.3797(5)
0.35432(8) 0.15204(8) 0.69350(8) 0.4557(1) 0.2053(1) -0.0590(l) 0.3383(3) -0.0191(3) 0.3472(3) 0.3682(3) 0.1588(3) 0.8052(4) 0.6148(3) 0.0971(3) 0.0346(3) 0.0346(4) 0.1541(4) 0.4970(3) 0.2248(3) 0.2022(3) 0.6199(4) 0.4950(3) 0.1638(3) 0.3193(4) 0.3089(5) 0.2589(5) 0.3528(5)
0.58(1) 0.71(1) 0.72(1) 0.57(2) 0.63(2) 0.58(2) 0.91(5) 0.89(5) 0.77(5) 0.99(5) 1.06(6) 1.26(6) 0.90(5) 1.04(6) 1.07(6) 1.34(6) 1.49(6) 1.00(6) 0.91(5) 0.90(5) 1.44(6) 0.80(5) 0.96(5) 1.42(7) 1.96(8) 1.58(9) 1.51(9)
~Be~ = (8/3)7/2(U~l(aa*) 2 + U22(bb*) 2 .4- U33(cc*) 2 + 2Ui2aa*bb* cos y + 2U13aa* cos fl + 2U23bb*cc* cos a).
Table 3 Selected bond distances (,~) V(1)-O(1) V(I)-O(3) V(1)-O(5) V(I)-O(ll) V(1)-O(12) V(1)-O(19) V(2)-O(2) V(2)-O(4) V(2)-O(10) V(2)-O(20) V(2)-0(21) V(3)-O(6) V(3)-O(7) V(3)-O(8) V(3)-O(12) V(3)-O(14) V(3)-O(15) P(1)-O(3) P(I)-O(4) P(I)-O(7) P(1)-O(19) P(2)-O(I) P(2)-O(9) P(2)-O(14) P(2)~O(21) P(3)-O(2) P(3)-O(5) P(3)-O(8) P(3)-O(20)
2.003(3) 1.980(3) 1.967(3) 2.333(3) 1.639(3) 1.942(3) 1.997(3) 1.962(3) 1.589(3) 1.94l(3) 2.007(3) 2.305(3) 1.978(3) 1.955(3) 2.028(3) 1.981(3) 1.599(3)
1.534(3) 1.517(3) 1.544(3)
1.532(3) 1.525(3) 1.584(3) 1.529(3) •.506(3) 1.539(3) 1.548(3) 1.528(3) 1.519(3)
Y. Lu et al. /Inorganica
Chimica
3. Results and discussion The first ethylenediamine ternplated three-dimensional vanadium phosphate [ H3NCH2CH,NH,] 2[ H3NCH,CH,NH21 IV(H~O)~(VO)~(OH)4(P04)4(HP0,),I .2H20 was reported in 1993 [ 221 and shown to contain vanadium in both the + 3 and + 4 oxidation states. The structure is constructed from comer-sharing V( IV) square pyramids, V( III) octahedra, and [PO,] and [ HPO, ] tetrahedra. The layers of comer-sharing V(IV) square pyramids and [PO,] and [HPO,] tetrahedra which resemble those in VOPO, are connected through [V(lII) (H20)2] centers to form a three-dimensional framework. Two additional etbylenediammonium-ternplated three-dimensional structures in the V-P-O system, (H3NCH2CH2NH,),[V(H,0),( VO),(OH),(HPO,),(PO,),l .3H20 [25] and (H3NCH,CH,NH,) [ (VO),(PO,),(H,PO,)] [27], have been reported more recently. The phosphate ( H3NCH2CH2NH,),[V(H,O),(VO),(OH),(HPO,),(PO,),1-3H,Oisbuiltup from V( IV) square pyramids, comer-sharing V( IV) square pyramids, and [PO,] and [HPO,] tetrahedra which are linked into a three-dimensional structure by V( III) octahedra, whereas (H,NCH&H,NH,) [ (VO) 2( PO,) 2( H,PO,) ] is connected from a three-dimensional network of [V(IV)O,], [V(V)O,J, [PO,] and [H,PO,I polyhedra. Mixed oxidation states of vanadium seem to be a common feature in these three-dimensional vanadium phosphates. The title material, however, exhibits in a single oxidation state of vanadium V(IV) in a new three-dimensional ethylenediamine ternplated vanadium phosphate. There are also other structures containing V( IV) such as [ ( VO) ( P04) (H,N-
Fig. 1. The title compound
with the labeling
scheme
Acta
268 (1998)
257-261
259
CH2CH2NH3) ] [ 81 where the V( IV) is in an octahedral site, and [H2NC4HsNH21 [(VO),(PO,),(HPO,),J -H,O [ 191 where the vanadium exhibits octahedral and square-pyramidal coordination modes. The title compound with the labeling scheme is shown in Fig. 1. There are three crystallographically independentvanadium atoms, all of which are in the +4 oxidation state (see Tables 2 and 3). The + 4 oxidation state of vanadium in this structure has been confirmed by valence sum calculations. The octahedra1 coordination about V( 1) atom is defined by four phosphate oxygens, a vanadyl oxygen and one water molecule. The V( 3) atom is coordinated by three phosphate oxygens, one water molecule, a remote bridging oxo-group associated with V( 1) and one terminal oxygen (0( 15) ) with a distance of 1.599( 3) A. These two vanadium octahedra are corner-sharing to form a dimer with a V( 1 )-0( 12)-V( 3) angleof 145,6(2)“.TheV(3) toO( 12) distanceis2.208(3) A, while the V( 1) to 0( 12) distance is 1.639( 3) A, providing { V( IV)=O...V( IV) ) short and long bonds. These distances are comparable with those found in (H,NCH,CH,NH,)[V(OH)(HPO,),l .HzO 12117 [NH,1 [(VO)(V,O,)(AsO,) 2(HAsO,) ] [ 281, the one-dimensional chain [NH,] [ VOPO,] [ 29 I ) , the two-dimensional layered material [ H3NCH2CH2NH,] [ VOPO,] [ 301 and [ H,N( CH,CH,) 2NH,][(VO),(H,O),(PO,),(HPO,),] [31].TheV-Odistances in the dimer including two coordinating wateroxygens (O(6) andO(11)) rangefrom 1.942(3) to2.332(3) A. The V( 2) atom has a square-pyramidal configuration with theapical vanadyl oxygenO( 10) atadistanceof 1.589(3) A, and the four basal phosphate oxygens at distances ranging from 1.94 l(3) to 2.007( 3) A. There are three distinct phos-
displaying
50% probability
thermal
ellipsoids.
260
E Lu et al. / lnorganica
Chimica Acta 268 (1998) 257-261
phorus atoms in the structure. The P( 1 ) and P(3) atoms have their four oxygens bridging to each of the three unique vanadium sites. The P(2) atom uses three of the oxygens bridging to three vanadium atoms. The fourth oxygen atom is protonated with a P ( 2 ) - O ( 9 ) distance of 1.584(3) ,4,. Thus, the structural unit consists of an octahedral corner-sharing [ VOsO-VO5 ] dimer and a square-pyramidal [ VOs ] connected by two tetrahedral [PO4] and one tetrahedral [HPO4] through corner-sharing. Perspective views of the structure are shown in Figs. 2 and 3. The [VOs-O-VOs] dimer and isolated square-pyramidal [VOs] are corner-sharing with phosphate tetrahedra of P( 1) and P(3) along the a-axis (Fig. 2) and the c-axis (Fig. 3) These connections form double extended polyhedral layers in the (101) plane (Fig. 4). Finally the [HP(2)O4] tetrahedral units are then used to link the complex double extended polyhedra layers into a three-dimensional structure through corner-sharing with the [VOs-O-VOs] dimer and squarepyramidal [VOs] units along the b-axis (Figs. 2 and 3). The structure exhibits multipoint hydrogen bonding. The distances between the oxygen and nitrogen atoms range from 2.834 (4) to 2.997 (4) .~ and are comparable with those found in (H3NCH2CH2NH3)4[V(H20)2(VO)6(OH)2(HPO4) 3(PO4) 5] "3H20 [ 25 ] and suggestive of significant hydrogen bonding interactions. The ethylenediammonium cations are inserted between the [HPO4] tetrahedra in the [100] direction (Fig. 3) and between the extended double polyhedra layers. A perspective
Fig. 2. A perspectiveview of the structure along the c-axis.
Fig. 4. The extended doublepolyhedralayer in the ( 101) plane.
Fig. 5. The cation locations in the structure. view of the location of the cations in the structure is shown in Fig. 5. The protonated (H3NCH2CH2NH3)2 + units are in close proximity to the anionic framework and the [-NH3 + ] moieties protrude into the V - P - O networks. Thus, the cations are encapsulated in cage-like frameworks. The cage is defined by a ring of eight tetrahedra, four octahedra and four square pyramids connected through corner-sharing of the polyhedra. The cages are then linked into extended frameworks by sharing [P(1)O4] tetrahedra. This unique three-dimensional network is the first example of an ethylenediammonium encapsulating cage structure in the vanadium phosphate system. Other ethylenediammonium templated three-dimensional structures in the V - P - O system [22,25,27] display open channel environments for the cations rather than the encapsulating cage structures adopted by the title compound. The synthesis of this compound is very condition dependent. Numerous interacting reaction parameters such as time, temperature, mole ratio of reactants, pH, concentration, and nature of the template are crucial to the formation of the final product. While several three- and one-dimensional ethylenediammonium templated vanadium phosphates have been synthesized, the goal of designing a given material is still a great challenge, we have used ethylenediamine for the synthesis of a new two-dimensional layered vanadium phosphate [30] which will be reported shortly.
Acknowledgements Fig. 3. The structure of (H3NCH2CH~NH3)[(VO)3(H20)2(PO4)2(HPO4)] viewed down the a-axis.
The work at Syracuse University was supported by NSF grant CHE-9617242.
Y. Lu et al. / lnorganica Chimica Acta 268 (1998) 257-261
References [ 1] M.L. Occelli and H.E. Robson, Zeolite Synthesis, American Chemical Society, Washington, DC, 1989. [2] D.W. Breck, Zeolite Molecule Sieves, Krieger, Malabar, FL, 1974. [3] D.E.W. Vaughan, in P.A. Jacobs and R.A. van Santen (eds.), Zeolites: Facts, Figures, Future, Elsevier, Amsterdam, 1989, pp. 95-116. [4] W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types, Butterworth, London, 1987. [5 ] R.M. Barfer, Hydrothermal Chemistry of Zeolites, Academic Press, New York, 1982. [6] G. Centi, F. Trifiro, J.R. Ebner and V.M. Franchetti, Chem. Rev., 88 (1988) 55. [7] B.L. Hodnett, Catal. Rev. Sci. Eng., 27 (1985) 373. [8] M.I. Khan, R.C. Haushalter, C.J. O'Connor, C. Tao and J. Zubieta, Chem. Mater., 7 (1995) 593. [9] See, for example, E. Droncova and K.-H. Lii, Inorg. Chem., 32 (1993) 4368, and Refs. therein. [ 10] A. Leclaire, J. Chardon, A. Grandin, M.M. Borel and B. Raveau, J. Solid State Chem., 108 (1994) 291, and Refs. therein. [ 11] J.T. Vaughey, W.T.A. Harrison and A.J. Jacobson, J. Solid State Chem., 110 (1994) 305. [12] C. Beltran-porter, A. Beltran-porter, P. Amoros, R. Ibanez, E. Martinez, A. LeBail, G. Ferey and G. Villenueve, Eur. J. Solid State Inorg. Chem., 28 ( 1991 ) 131, and Refs. therein. [ 13] P. Amoros and A. LeBail, J. Solid State Chem., 97 (1992) 183, and Refs. therein. [ 14] R.C. Haushalter, Z. Wang, M.E. Thompson, J. Zubieta and C.J. O'Connor, Inorg. Chem., 32 (1993) 3700. [ 15] P. Behrens, Angew. Chem., Int. Ed. Engl., 35 (1996) 515.
261
[ 16] M.E. Davis, CHEMTECH, (1994) 22. [ 17] M.I. Khan, L.M. Meyer, R.C. Haushalter, A.L. Schweitzer, J. Zubieta and J.L. Dye, Chem. Mater., 8 (1996) 43. [ 18] V. Soghomonian. Q. Chen, R.C. Haushalter, C.J. O'Connor, C. Tao and J. Zubieta, Inorg. Chem., 34 (1995) 3509. [ 19] V. Soghomonian, R.C. Haushalter, Q. Chen and J. Zubieta, Inorg. Chem., 33 (1994) 1700. [ 20] Y. Zhang, A. Clearfield and R.C. Hanshalter, unpublished result. [21] V. Soghomonian, Q. Chen, R.C. Haushalter, J. Zubieta and C.J. O'Connor, Science, 259 (1993) 1596. [22] V. Soghomonian, Q. Chert, R.C. Haushalter and J. Zubieta, Angew. Chem., Int. Ed. Engl., 32 (1993) 610. [23] V. Soghomonian, Q. Chen, R.C. Hanshalter and J. Zubieta, Chem. Mater., 5 (1993) 1595. [ 24] V. Soghomonian, Q. Chen, R.C. Haushalter, J. Zubieta, CJ. O'Connor and Y.-S. Lee, Chem. Mater., 5 (1993) 1690. [25] Y. Zhang, A. Clearfield and R.C. Haushalter, Chem. Mater., 7 (1995) 1221. [26] TeXsan: Texray structural analysis package, Molecular Structure Corporation, The Woodlands, TX, 1992. [27] W.T.A. Harrison, K. Hsu and A.J. Jacobson, Chem. Mater., 7 (1995) 2004. [28] R.C. Haushalter, L. Meyer, S. Dhingra, M.E. Thompson, Z. Wang and J. Zubieta, Inorg. Chim. Acta, 218 (1994) 59. [29] CJ. O'Connor, V. Soghomonian, R.C. Haushalter, Z. Wang and J. Zubieta, J. Appl. Phys., 75 (1994) 5859. [ 30] Y.-J. Lu, R.C. Hanshalter and J. Zubieta, unpublished result. [31] V. Soghomonian, R.C. Hanshalter, J. Zubieta and C.J. O'Connor, Inorg. Chem., 35 (1996) 2826.
Inorganica Chimica Acta 268 (1998) 257-261
Hydrothermal synthesis and structural characterization of a three-dimensional organically-templated vanadium phosphate [H3NCH2CH2NH3] [ (VO) 3(H20) 2(PO4) 2(HPO4) ] Yingjie Lu a Robert C. Haushalter a,., Jon Zubieta b NEC Research Institute, 4 Independence Way, Princeton, NJ 08540, USA b Department of Chemistry, Syracuse UniversiO', Syracuse, NY 13244, USA
Received 13 February 1997; revised 10 April 1997; accepted 19 May 1997
Abstract
The title compound [(H3NCHzCH2NH3)][(VO)3(H20)2(PO4)2(HPO4)] was synthesized from the hydrothemaal reaction of V2Os:V:H3PO4:HzNCHzCH2NH2:H20in the mole ratio of 1: 1:10:5:740. The compound crystallizes in the triclinic space group P1 with unit cell parameters a = 10.187( 1),b= 10.241( l),c = 8.2137(7) ,~, a = 90.398(8),/3= 95.930(9) and3, = 117.325(7) °, V= 755.7(1) ~k3,Z = 2, Dealt = 2.570 g cm 3, R = 0.032, Rw = 0.035. The data were collected by using ~-20 scan technique and the structure was solved by direct method. The structure consists of binuclear units of comer-sharing [ VO6] octahedra and square-pyramidal [ VOs ] units linked by phosphate tetrahedra, forming double extended polyhedral slabs in the ( 101 ) plane with these slabs connected by comer-sharing [HPO4] tetrahedra to form a corner-sharing three-dimensional cage structure about the diammonium cations. © 1998 Elsevier Science S.A. Keywords." Crystal structures; Vanadium complexes; Phosphate complexes
1. Introduction
The recent interest in the hydrothermal synthesis of organically templated vanadium oxide phosphates derives from the observation that vanadium phosphates can form open framework solids with cavity dimensions similar to those of the technologically important aluminosilicate zeolites [ 1-5], from the notable catalytic properties [6,7] and significant structural diversity of the vanadium phosphates [8-14], and from the challenge to 'design' solid state materials by exploiting the structure-directing influence of organic molecules [ 15,16]. In the specific case of vanadium phosphates, the introduction of organic templates in hydrothermal synthesis to direct the organization of the metastable materials has greatly expanded the structural chemistry. Our recent results have demonstrated that the use of the organoamine species diaminobicyclooctane (N(C2H4)3N, DABCO), piperazine (HNC4HsNH), dimethylamine ((CH3) 2NH), 1,3-diaminopropane ( H2N (CH2) 3NH2 ), and ethylenediamine (H2NCH2-
* Correspondingauthor. 0020-1693 / 98 / $19.00 © 1998 Elsevier Science S.A. All rights reserved p//S0020- 1693 (97) 05753-8
CH2NH2) have produced a wide variety of new materials
such as the supercage phase: [H2DABCO]KL35[VsO9(P04)2] .H20 [ 17]; layered materials: [H2N(C4Hs)2NH2] [ (VO)4(OH)4(P04)2] [ 18], [HN(CzH4) 3NH][ (VO)s(HPO4)3(PO4)4(OH)2] "2H20 [ 18], [HN(C2H4)3NH] [ (VO3)3(OH)z(PO4)2] [ 18], [H2NC4HsNH2] [ (VO)2(PO4)2] [19] and [HeNC4HsNH2] [ ( V O ) 3(PO4) 2(HP04) 2]" H20 [ 19 ] ; one-dimensional phases: [ (H2NCHzCH2N H 3 ) ( V O ) ( P 0 4 ) ] ]8] and [H3NCH2CH2NH 3] [ V ( O H ) (HPO4)2] "H20 [20]); a complex structure exhibiting chiral intertwined double helices: [ ( C H 3)2NH2]K4[ (VO)Io(H20)z(OH)4(P04)7] "H20 [21] ); very large ethylenediammonium-fined tunnels: ](H3NCH2CHzNH3)2][ (H3NCH2CH2NH2] [ V ( H 2 0 ) 2(VO) s ( O H ) a ( P O 4 ) a (HPO4)4] "2H20 [22] ; and three-dimensional frameworks: [H3N(CHz)3NH3] K(VO)3(PO4)3] [23], [H3N(CH2)3NH3] [(VO)3(OH)2(H20)2(P04)2] [24], arid [(H3NCH2CH 2NH3)4] [V(HzO)2(VO)6(OH)2(HPO4)3(DO4)5] • 3H20
[25]. We report here a new three-dimensional vanadium phosphate, [H3NCH2CH2NH3] [ (VO)3(H20)2(PO4)2(HPO4) ], with a unique cage structure and framework connectivity.
258
E Lu et al. / Inorganica Chimica Acta 268 (1998) 257-261
Table 1 Crystallographical data for [ (H3NCH2CH2NH3] [ (VO) 3(H20) 2(PO4) (HPO4) ] Empirical formula Color, habit Space group a (A) b (A) c (A,) ot (o) 13(o) y (°) V (~3) Z T (°C) A(Mo Ka) (A.) p~ (cm- i ) Dcal~(gcm -3) Scan type No. reflections measured No. observation (1> 3o-(1) ) No. variables Reflection/parameter ratio R
HIsN2C2017V3P3 green, prismatic Pi (No. 2) 10.187(1) 10.24l(1) 8.2137(7) 90.398(8) 95.930(9) 117.325(7) 755.7( 1) 2 20 + 1 0.71073 22.36 2.570 to--20 4673 4444 (Ri,,=0.034) 2789 11,43 0.032 0.035 1.54
Rw
Goodness of fit
2. Experimental 2.1. P r e p a r a t i o n o f (H3NCH2CH2NH3)][(VO)3(H20)2(PO4)2(HP04)]
The hydrothermal reaction of V20 5 (0.1091 g ) , V ( - 325 mesh, 0.0305 g), H3PO 4 (0.6 m l ) , H2NCH2CH2NH2 (0.2 m l ) , and H20 (8.0 ml) in the mole ratio 1:1:10:5:740 in a 23 ml acid digestion bomb at 200°C for 7 days yielded a mixture containing a green crystalline phase of the title compound. Crystals suitable for X-ray analysis were separated mechanically to give a yield of crystalline material of 2% based on vanadium. Attempts to improve the yield proved unsuccessful. However, a 2 - 5 % yield under the conditions reported was reproducible in all cases. 2.2. X - r a y c r y s t a l l o g r a p h i c s t u d i e s
All measurements were made on a Rigaku A F C 7 R diffractometer with graphite-monochromated M o K a radiation and a 18 k W RU300 rotating anode generator. The data were collected by using oy-2 0 scan technique. An empirical absorption correction was applied. The structure was solved by direct methods [ 26 ]. The non-hydrogen atoms were refined anisotropically. The hydrogen atoms were located from difference Fourier maps and included in the refinement with fixed positional and thermal parameters. Detailed crystallographic data are given in Table 1. Atomic positional parameters and isotropic temperature factors are presented in Table 2 and selected bond lengths are given in Table 3.
R = EIIF,,I - IFcll/EIF,,I. Rw= [Ew( IFol- IF,.I)2/EwFo2] ~/a
Table 2 Positional parameters and isotropictemperaturefactorsB~ Atom
x
y
z
Bcq
V(1) V(2) V(3) P(1) P(2) P(3) O(1) 0(2) 0(3) 0(4) 0(5) 0(6) 0(7) 0(8) 0(9) O(10) O(11) O(12) O(13) O(14) O(15) 0(16) O(17) N(I) N(2) C(1) C(2)
-0.01344(7) -0.48027(8) -0.21316(8) -0.2169(1) 0.1859(1) -0.7133(1) 0.1198(3) -0.6338(3) -0.1120(3) -0.3728(3) -0.1363(3) 0.0189(3) -0.2272(3) -0.7394(3) 0.1260(3) -0.3996(3) 0.1109(4) -0.1048(3) -0.6470(3) 0.1276(3) -0.3718(3) 0.1557(3) -0.3782(3) -0.4774(4) -0.1810(4) -0.3285(5) -0.4476(5)
0.21530(7) -0.21654(7) 0.14798(7) -0.1157(1) 0.5368(1) -0.1207(1) 0.4305(3) -0.2152(3) -0.0025(3) -0.2058(3) 0.2260(3) 0.1839(3) -0.0414(3) -0.0584(3) 0.4445(3) -0.2726(3) 0.1720(3) 0.2360(3) -0.3982(3) 0.6504(3) 0.1319(3) 0.2231(3) -0.0028(3) 0.2247(4) 0.4948(5) 0.4868(5) 0.3797(5)
0.35432(8) 0.15204(8) 0.69350(8) 0.4557(1) 0.2053(1) -0.0590(l) 0.3383(3) -0.0191(3) 0.3472(3) 0.3682(3) 0.1588(3) 0.8052(4) 0.6148(3) 0.0971(3) 0.0346(3) 0.0346(4) 0.1541(4) 0.4970(3) 0.2248(3) 0.2022(3) 0.6199(4) 0.4950(3) 0.1638(3) 0.3193(4) 0.3089(5) 0.2589(5) 0.3528(5)
0.58(1) 0.71(1) 0.72(1) 0.57(2) 0.63(2) 0.58(2) 0.91(5) 0.89(5) 0.77(5) 0.99(5) 1.06(6) 1.26(6) 0.90(5) 1.04(6) 1.07(6) 1.34(6) 1.49(6) 1.00(6) 0.91(5) 0.90(5) 1.44(6) 0.80(5) 0.96(5) 1.42(7) 1.96(8) 1.58(9) 1.51(9)
~Be~ = (8/3)7/2(U~l(aa*) 2 + U22(bb*) 2 .4- U33(cc*) 2 + 2Ui2aa*bb* cos y + 2U13aa* cos fl + 2U23bb*cc* cos a).
Table 3 Selected bond distances (,~) V(1)-O(1) V(I)-O(3) V(1)-O(5) V(I)-O(ll) V(1)-O(12) V(1)-O(19) V(2)-O(2) V(2)-O(4) V(2)-O(10) V(2)-O(20) V(2)-0(21) V(3)-O(6) V(3)-O(7) V(3)-O(8) V(3)-O(12) V(3)-O(14) V(3)-O(15) P(1)-O(3) P(I)-O(4) P(I)-O(7) P(1)-O(19) P(2)-O(I) P(2)-O(9) P(2)-O(14) P(2)~O(21) P(3)-O(2) P(3)-O(5) P(3)-O(8) P(3)-O(20)
2.003(3) 1.980(3) 1.967(3) 2.333(3) 1.639(3) 1.942(3) 1.997(3) 1.962(3) 1.589(3) 1.94l(3) 2.007(3) 2.305(3) 1.978(3) 1.955(3) 2.028(3) 1.981(3) 1.599(3)
1.534(3) 1.517(3) 1.544(3)
1.532(3) 1.525(3) 1.584(3) 1.529(3) •.506(3) 1.539(3) 1.548(3) 1.528(3) 1.519(3)
Y. Lu et al. /Inorganica
Chimica
3. Results and discussion The first ethylenediamine ternplated three-dimensional vanadium phosphate [ H3NCH2CH,NH,] 2[ H3NCH,CH,NH21 IV(H~O)~(VO)~(OH)4(P04)4(HP0,),I .2H20 was reported in 1993 [ 221 and shown to contain vanadium in both the + 3 and + 4 oxidation states. The structure is constructed from comer-sharing V( IV) square pyramids, V( III) octahedra, and [PO,] and [ HPO, ] tetrahedra. The layers of comer-sharing V(IV) square pyramids and [PO,] and [HPO,] tetrahedra which resemble those in VOPO, are connected through [V(lII) (H20)2] centers to form a three-dimensional framework. Two additional etbylenediammonium-ternplated three-dimensional structures in the V-P-O system, (H3NCH2CH2NH,),[V(H,0),( VO),(OH),(HPO,),(PO,),l .3H20 [25] and (H3NCH,CH,NH,) [ (VO),(PO,),(H,PO,)] [27], have been reported more recently. The phosphate ( H3NCH2CH2NH,),[V(H,O),(VO),(OH),(HPO,),(PO,),1-3H,Oisbuiltup from V( IV) square pyramids, comer-sharing V( IV) square pyramids, and [PO,] and [HPO,] tetrahedra which are linked into a three-dimensional structure by V( III) octahedra, whereas (H,NCH&H,NH,) [ (VO) 2( PO,) 2( H,PO,) ] is connected from a three-dimensional network of [V(IV)O,], [V(V)O,J, [PO,] and [H,PO,I polyhedra. Mixed oxidation states of vanadium seem to be a common feature in these three-dimensional vanadium phosphates. The title material, however, exhibits in a single oxidation state of vanadium V(IV) in a new three-dimensional ethylenediamine ternplated vanadium phosphate. There are also other structures containing V( IV) such as [ ( VO) ( P04) (H,N-
Fig. 1. The title compound
with the labeling
scheme
Acta
268 (1998)
257-261
259
CH2CH2NH3) ] [ 81 where the V( IV) is in an octahedral site, and [H2NC4HsNH21 [(VO),(PO,),(HPO,),J -H,O [ 191 where the vanadium exhibits octahedral and square-pyramidal coordination modes. The title compound with the labeling scheme is shown in Fig. 1. There are three crystallographically independentvanadium atoms, all of which are in the +4 oxidation state (see Tables 2 and 3). The + 4 oxidation state of vanadium in this structure has been confirmed by valence sum calculations. The octahedra1 coordination about V( 1) atom is defined by four phosphate oxygens, a vanadyl oxygen and one water molecule. The V( 3) atom is coordinated by three phosphate oxygens, one water molecule, a remote bridging oxo-group associated with V( 1) and one terminal oxygen (0( 15) ) with a distance of 1.599( 3) A. These two vanadium octahedra are corner-sharing to form a dimer with a V( 1 )-0( 12)-V( 3) angleof 145,6(2)“.TheV(3) toO( 12) distanceis2.208(3) A, while the V( 1) to 0( 12) distance is 1.639( 3) A, providing { V( IV)=O...V( IV) ) short and long bonds. These distances are comparable with those found in (H,NCH,CH,NH,)[V(OH)(HPO,),l .HzO 12117 [NH,1 [(VO)(V,O,)(AsO,) 2(HAsO,) ] [ 281, the one-dimensional chain [NH,] [ VOPO,] [ 29 I ) , the two-dimensional layered material [ H3NCH2CH2NH,] [ VOPO,] [ 301 and [ H,N( CH,CH,) 2NH,][(VO),(H,O),(PO,),(HPO,),] [31].TheV-Odistances in the dimer including two coordinating wateroxygens (O(6) andO(11)) rangefrom 1.942(3) to2.332(3) A. The V( 2) atom has a square-pyramidal configuration with theapical vanadyl oxygenO( 10) atadistanceof 1.589(3) A, and the four basal phosphate oxygens at distances ranging from 1.94 l(3) to 2.007( 3) A. There are three distinct phos-
displaying
50% probability
thermal
ellipsoids.
260
E Lu et al. / lnorganica
Chimica Acta 268 (1998) 257-261
phorus atoms in the structure. The P( 1 ) and P(3) atoms have their four oxygens bridging to each of the three unique vanadium sites. The P(2) atom uses three of the oxygens bridging to three vanadium atoms. The fourth oxygen atom is protonated with a P ( 2 ) - O ( 9 ) distance of 1.584(3) ,4,. Thus, the structural unit consists of an octahedral corner-sharing [ VOsO-VO5 ] dimer and a square-pyramidal [ VOs ] connected by two tetrahedral [PO4] and one tetrahedral [HPO4] through corner-sharing. Perspective views of the structure are shown in Figs. 2 and 3. The [VOs-O-VOs] dimer and isolated square-pyramidal [VOs] are corner-sharing with phosphate tetrahedra of P( 1) and P(3) along the a-axis (Fig. 2) and the c-axis (Fig. 3) These connections form double extended polyhedral layers in the (101) plane (Fig. 4). Finally the [HP(2)O4] tetrahedral units are then used to link the complex double extended polyhedra layers into a three-dimensional structure through corner-sharing with the [VOs-O-VOs] dimer and squarepyramidal [VOs] units along the b-axis (Figs. 2 and 3). The structure exhibits multipoint hydrogen bonding. The distances between the oxygen and nitrogen atoms range from 2.834 (4) to 2.997 (4) .~ and are comparable with those found in (H3NCH2CH2NH3)4[V(H20)2(VO)6(OH)2(HPO4) 3(PO4) 5] "3H20 [ 25 ] and suggestive of significant hydrogen bonding interactions. The ethylenediammonium cations are inserted between the [HPO4] tetrahedra in the [100] direction (Fig. 3) and between the extended double polyhedra layers. A perspective
Fig. 2. A perspectiveview of the structure along the c-axis.
Fig. 4. The extended doublepolyhedralayer in the ( 101) plane.
Fig. 5. The cation locations in the structure. view of the location of the cations in the structure is shown in Fig. 5. The protonated (H3NCH2CH2NH3)2 + units are in close proximity to the anionic framework and the [-NH3 + ] moieties protrude into the V - P - O networks. Thus, the cations are encapsulated in cage-like frameworks. The cage is defined by a ring of eight tetrahedra, four octahedra and four square pyramids connected through corner-sharing of the polyhedra. The cages are then linked into extended frameworks by sharing [P(1)O4] tetrahedra. This unique three-dimensional network is the first example of an ethylenediammonium encapsulating cage structure in the vanadium phosphate system. Other ethylenediammonium templated three-dimensional structures in the V - P - O system [22,25,27] display open channel environments for the cations rather than the encapsulating cage structures adopted by the title compound. The synthesis of this compound is very condition dependent. Numerous interacting reaction parameters such as time, temperature, mole ratio of reactants, pH, concentration, and nature of the template are crucial to the formation of the final product. While several three- and one-dimensional ethylenediammonium templated vanadium phosphates have been synthesized, the goal of designing a given material is still a great challenge, we have used ethylenediamine for the synthesis of a new two-dimensional layered vanadium phosphate [30] which will be reported shortly.
Acknowledgements Fig. 3. The structure of (H3NCH2CH~NH3)[(VO)3(H20)2(PO4)2(HPO4)] viewed down the a-axis.
The work at Syracuse University was supported by NSF grant CHE-9617242.
Y. Lu et al. / lnorganica Chimica Acta 268 (1998) 257-261
References [ 1] M.L. Occelli and H.E. Robson, Zeolite Synthesis, American Chemical Society, Washington, DC, 1989. [2] D.W. Breck, Zeolite Molecule Sieves, Krieger, Malabar, FL, 1974. [3] D.E.W. Vaughan, in P.A. Jacobs and R.A. van Santen (eds.), Zeolites: Facts, Figures, Future, Elsevier, Amsterdam, 1989, pp. 95-116. [4] W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types, Butterworth, London, 1987. [5 ] R.M. Barfer, Hydrothermal Chemistry of Zeolites, Academic Press, New York, 1982. [6] G. Centi, F. Trifiro, J.R. Ebner and V.M. Franchetti, Chem. Rev., 88 (1988) 55. [7] B.L. Hodnett, Catal. Rev. Sci. Eng., 27 (1985) 373. [8] M.I. Khan, R.C. Haushalter, C.J. O'Connor, C. Tao and J. Zubieta, Chem. Mater., 7 (1995) 593. [9] See, for example, E. Droncova and K.-H. Lii, Inorg. Chem., 32 (1993) 4368, and Refs. therein. [ 10] A. Leclaire, J. Chardon, A. Grandin, M.M. Borel and B. Raveau, J. Solid State Chem., 108 (1994) 291, and Refs. therein. [ 11] J.T. Vaughey, W.T.A. Harrison and A.J. Jacobson, J. Solid State Chem., 110 (1994) 305. [12] C. Beltran-porter, A. Beltran-porter, P. Amoros, R. Ibanez, E. Martinez, A. LeBail, G. Ferey and G. Villenueve, Eur. J. Solid State Inorg. Chem., 28 ( 1991 ) 131, and Refs. therein. [ 13] P. Amoros and A. LeBail, J. Solid State Chem., 97 (1992) 183, and Refs. therein. [ 14] R.C. Haushalter, Z. Wang, M.E. Thompson, J. Zubieta and C.J. O'Connor, Inorg. Chem., 32 (1993) 3700. [ 15] P. Behrens, Angew. Chem., Int. Ed. Engl., 35 (1996) 515.
261
[ 16] M.E. Davis, CHEMTECH, (1994) 22. [ 17] M.I. Khan, L.M. Meyer, R.C. Haushalter, A.L. Schweitzer, J. Zubieta and J.L. Dye, Chem. Mater., 8 (1996) 43. [ 18] V. Soghomonian. Q. Chen, R.C. Haushalter, C.J. O'Connor, C. Tao and J. Zubieta, Inorg. Chem., 34 (1995) 3509. [ 19] V. Soghomonian, R.C. Haushalter, Q. Chen and J. Zubieta, Inorg. Chem., 33 (1994) 1700. [ 20] Y. Zhang, A. Clearfield and R.C. Hanshalter, unpublished result. [21] V. Soghomonian, Q. Chen, R.C. Haushalter, J. Zubieta and C.J. O'Connor, Science, 259 (1993) 1596. [22] V. Soghomonian, Q. Chert, R.C. Haushalter and J. Zubieta, Angew. Chem., Int. Ed. Engl., 32 (1993) 610. [23] V. Soghomonian, Q. Chen, R.C. Hanshalter and J. Zubieta, Chem. Mater., 5 (1993) 1595. [ 24] V. Soghomonian, Q. Chen, R.C. Haushalter, J. Zubieta, CJ. O'Connor and Y.-S. Lee, Chem. Mater., 5 (1993) 1690. [25] Y. Zhang, A. Clearfield and R.C. Haushalter, Chem. Mater., 7 (1995) 1221. [26] TeXsan: Texray structural analysis package, Molecular Structure Corporation, The Woodlands, TX, 1992. [27] W.T.A. Harrison, K. Hsu and A.J. Jacobson, Chem. Mater., 7 (1995) 2004. [28] R.C. Haushalter, L. Meyer, S. Dhingra, M.E. Thompson, Z. Wang and J. Zubieta, Inorg. Chim. Acta, 218 (1994) 59. [29] CJ. O'Connor, V. Soghomonian, R.C. Haushalter, Z. Wang and J. Zubieta, J. Appl. Phys., 75 (1994) 5859. [ 30] Y.-J. Lu, R.C. Hanshalter and J. Zubieta, unpublished result. [31] V. Soghomonian, R.C. Hanshalter, J. Zubieta and C.J. O'Connor, Inorg. Chem., 35 (1996) 2826.