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MATERIALS
VOLUME 6, NUMBER 9
SEPTEMBER 1994
0 Copyright 1994 by the American Chemical Society
Communications Hydrothermal Synthesis and Structural Characterization of the T w o New Vanadium Arsenates H2NC4HsNH2[(VrVO)2(HAs04)2(HzAsO4)21 and
Green plates of the 1-D material HzNC4HsNH2prepared in 86% yield by the reaction of VC14:piperazine:As205:H20 in the mole ratios of 1:3:5:84 a t 150 “C for 72 hours. Comparison of the measured X-ray powder pattern of 1 H ~ N C H ~ C H ~ N H S ~ ~ ( H A ~ O ~ ) ~ ( H ~ Ato ~the O ~pattern ) I * calculated H Z O from the coordinates of the single-crystal study show that 1 is formed as a pure Robert C. Haushalter,*Ja Zhanwen Wan lb single-phase material. Single-crystal X-ray diffraction studies of 1 revealed novel [(VIvO)2(HAsO4)2(H204)2l2Linda M. Meyer,la Sandee S. Dhingra,e Mark E. Thompson,*JCa n Jon Zubieta*Jd chains and piperazine dicatiorm6 A projection of the unit cell contents down [OOlI is shown in Figure 1. The NEC Research Institute, 4 Independence Way VO6 octahedra are bridged by HAsO4 and HAsO4, the Princeton, New Jersey 08540 hydrogen atoms of which were located on the later difference Fourier maps but were kept fixed during Received February 8, 1994 refinement. The chains are hydrogen bonded into Revised Manuscript Received May 30,1994 sheets, via-0-H-0-As hydrogen bonds (in the range from 2.573 to 2.777 A),that lie in planes which are While layered and three-dimensional (3-D) metal parallel to the (101) plane. The H-bonded V-As-0 oxides are very common, examples of discrete 1-D sheets are interleaved by the organic dications, the NH2 transition metal oxides are quite rare. Known examples groups of which are also H bonded to some of the 0 of these 1-D polymers are provided by the phosphates atoms of the chains. The backbone of these chains are Mo(OH)~PO and ~ ~VO(HP04).4H2O3while Na+ bridged strings are found in ( P P ~ ~ ) ~ [ ( H ~ O ) ~ N ~ M O ~ Ocomposed I ~ ( H P of ~ ~VO6 ) - octahedra sharing opposite corners generating strings running parallel to the crystal(H2P04)31.4 The 1-D metal oxide (Et4N)2[Mo408lographic [OOlI direction as shown in Figure 2a. The (P04)u2(H1.5P04)21’2H20,5 which contains chains com-V-0-V-0infinite chain has short V-0 vanadyl posed of metal-metal bonded Mo408 “cubes” bridged contacts of 1.627(4) A alternating with longer V-0 together by (PO4)uz groups into 1-D chains, displays a distances of 2.248(4) A. The short V=O bonds trans to unique type of chirality. We report here the hydrotherlonger V-0 contacts (i.e., the V atoms displaced toward mal synthesis of the 1-D V4+ polymer H2NC4H8one of the vertices along the 4-fold axis of the octaheNH2[(VN0)2(HAs04)2(HzAs04)21(1) and the V3+ chain compound H3NCH2CH2NH3[V111(H04)2(H2As04)1.H20 dron) is typical of V4f. The 4 f oxidation state is confirmed by valence sum calculation^.^ Corner sharing (2) which represent the first examples of 1-D vanadium 1-D chains of VO6 octahedra are also found in the 3-D arsenate polymers with organic cations. materials N a V 0 A ~ 0 4and ~ NH4VOP049 which have [(VNO)2(~~04)2(H2As04)21 (1) were
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(1).(a) NEC Research Institute. (b) Syracuse and Princeton Universities. (c) Princeton University. (d) Syracuse University. (2) Kierkegaard, P. Acta Chem. Scand. 1958,12, 1701. (3) Leonowicz, M.E.;Johnson, J. W.; Brody, J. F.; Shannon, A. F.; Newsam, J. M. J.Solid State Chem. 1985,56, 370. (4) Haushalter, R. C.; Lai, F. W. I n o g . Chem. 1989,28, 2904. (5) Mundi, L. A.;Haushalter, R. C. J.Am. Chem. SOC.1991, 113, 6340.
0897-4756/94/2806-1463$04.50/0
(6) Crystal data for 1: orthorhombic, s ace group Pbca with a = 14.567(1), b = 17.495(1), and c = 7.277(1) V = 1854.5(4) A3, 2 = 8 and Dcale= 2.807 g ~ m - ~R(R,) . = 0.029(0.036) for 136 variables and 2084 observed data with I > 301. (7) Brown, I. D.;Wu, K. K. A,cta Crystallogr. 1976,B32, 1957. (8) Haddad, A,; Jouini, T.; Piffard, Y. Eur. J. Solid State Chem. 1992,29, 57.
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0 1994 American Chemical Society
1464 Chem. Mater., Vol. 6, No. 9,1994
Communications
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Figure 1. Projection of the structure of 1 down the LOO11 direction with the interlamellar organic cations omitted for clarity. The individual 1-D chains are H-bonded into sheets via the HxAs04groups.
0
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c-+
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Figure 3. Projection of the structure of 2 down the [lOOl direction showing the pendant arsenate groups H-bonded to the other chains, the HzO and to the ethylenediammonium cations. chains of isolated VO6 octahedra (Figure 2b) with two {HAsOd}and one (HAs04} per vanadium octahedron, but with no covalent intrachain -V-0-Vinteractions. The two extra free vertices in the octahedra of 2 as compared to 1 are compensated by two vertices from an additional (AsOl} tetrahedron. Unlike the distorted octahedra ofV4+found in 1, the octahedra in 2 are quite b regular and the V-0 bonds all lie in the range of 2.000(4)-2.017(4) A indicative of V3+. This oxidation state is confirmed by valence sum calculations. The high quality of the diffraction data allowed the resolution of the H atoms on the {AsOl} tetrahedra, two of which were found on 0 1 and 0 2 terminally bound to As1 while one each were found on 0 1 1 on As2 and 0 1 0 on As3 respectively. Whereas arsenate 1 has its chains hydroJ J J J gen bonded into sheets with the organic cations between Figure 2. ( a )Polyhedral representation of the chain of edge the layers, the chains in arsenate 2 are in an arrangesharingV4+octahedra and (AsO,}tetrahedra in 1. (b)Similar ment more reminiscent of the close packing of cylinders view of the Vi octahedra and (AsOa) groups in 2. (Figure 3). Also shown in Figure 3 is the water molecule that is hydrogen bonded to the arsenate tetrahedra from chains sharing trans vertices and alternating cis-trans three different chains. The chains are also H-bonded vertices, respectively. In contrast to the very darkly to the -NH3' groups of the ethylenediammonium colored NaVOPOl and NH4VOP04, arsenate 1 is transcations. Chains structurally similar to those found in parent and green. 2 were recently reported in the vanadium phosphate Using VzO3 as the V source and ethylenediamine as Sr?lV(POa)?(HIPOa)l.ll _. ._ -. the organic template has allowed the isolation of H3In summary, the results reported here show that it NCHZCHZNH~[V(HA~O~)~(H (2). ~A a~ 1-D ~ ~va) ~ . His~ possible ~ to prepare by means of hydrothermal synnadium arsenate polymer with V(III)O6 octahedra. The thesis a new type of 1-D inorganic oxide based on VOs reaction ofVz03:HCl:ethylenediamine:AszOs:HzOin the octahedra and As04 tetrahedra. The solid-state strucmole ratios of 1:1618:13:222at 150 "C for 72 h gives a tures of both materials are strongly influenced by the 45% yield of green needles of 2. Single-crystal X-ray hydrogen bonding of the pendant H,As04 groups to one diffraction shows'" that compound 2, like arsenate 1, another and to the polar organic cationic templates. also has VOs octahedra bridged into 1-D chains via Acknowledgment. The work at Syracuse Univer{HAsOl} and (H&04} groups. The main difference sity was supported by NSF Grant CHE 9119910, between the two polymers is that arsenate 2 contains Supplementary Material Available: Additional experimental crystallographic details (12 pages); observed and ( 9 ) Haushalter, R. C.; Chen, Q.;Soghomanian, V.: Zubieta, J.; calculated structure factors (15pages). Ordering information WConnor, C. J. J . Solid Sfole Chem., in press. is given on any current masthead page. (10) Crystal data f o r 2 monoclinic, spacegmupP2~withn = 4.714-
-
(21, b = 16.072(1),and e = 8.687(1)A,/j = 90.56(2)",V = 666.50)A3, Z = 2. R K I = O.OZl(0.029) for 189 variables and 1917 observed data with I > 3 d
(11) SrzlV(P0ddH~POdI:Lii, K.-H.: Lee, T X . ; Liu, S.-N., Wang,
S.-L. J . Chem. Soe., Dalton Trans. 1993, 1051.
