Acta Cryst. (2008). E64, i45 [ doi:10.1107/S1600536808016875 ]
Single crystals of lithium dysprosium polyphosphate, LiDy(PO3)4, were prepared by the flux method. The atomic arrangement is built up by infinite (PO3)n chains extending along the b axis. Dy3+ and Li+ cations alternate in the middle of four such chains, with Dy
Li distances of 3.54 (1) and 3.48 (1) Å. The DyO8 dodecahedra and LiO4 tetrahedra deviate significantly from the ideal geometry. Both Dy and Li occupy special positions (Wyckoff position 4e, site symmetry 2).
A mixture of Li2CO3 (2 g), Dy2O3 (0.5 g) and H3PO4 (85%, 17 ml), were mixed in a vitreous carbon crucible and preheated progressively to 473 K four 2 h. The temperature was then raised and kept at 600 K for 15 days. Colourless single crystals of LiDy(PO3)4 were isolated from the reaction mixture by washing with hot water.
The distances between dysprosium atoms and the highest peak and the deepest hole are respectively, 1.39 Å and 0.78 Å.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./fi2064fig1thm.gif)
| Fig. 1. : The asymmetric unit of LiDy(PO3)4 with anisotropic displacement parameters drawn at the 50% probability level.Symmetry code: (i)-x + 1, y, -z + 1.5. |
![[Figure 2]](./fi2064fig2thm.gif)
| Fig. 2. : Projection of the structure of LiDy(PO3)4 along the b axis. |
![[Figure 3]](./fi2064fig3thm.gif)
| Fig. 3. : The O-atom coordination around Dy and Li atoms showing the connection of DyO8 and LiO4 polyhedra. [Symmetry codes: (i)-x + 1, y, -z + 1.5; (ii)-x + 1, -y + 1, -z + 2; (iii)x, -y + 1, z - 1/2; (iv)x, y + 1, z; (v)-x + 1, y + 1, -z + 1.5. |
![[Figure 4]](./fi2064fig4thm.gif)
| Fig. 4. : Structural arrangement of LiDy(PO3)4 along the 1 0 1 direction. |
| LiDy(P1O3)4 | F000 = 900 |
| Mr = 485.32 | Dx = 3.646 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1631 reflections |
| a = 16.2690 (10) Å | θ = 0.7–27.9º |
| b = 7.0236 (3) Å | µ = 9.24 mm−1 |
| c = 9.5781 (8) Å | T = 295 (2) K |
| β = 126.106 (3)º | Block, colourless |
| V = 884.24 (10) Å3 | 0.10 × 0.09 × 0.08 mm |
| Z = 4 |
| Nonius KappaCCD diffractometer | 1021 independent reflections |
| Radiation source: fine-focus sealed tube | 858 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.080 |
| T = 295(2) K | θmax = 27.7º |
| φ & ω scans | θmin = 3.6º |
| Absorption correction: analytical (de Meulenaer & Tompa, 1965) | h = −21→20 |
| Tmin = 0.42, Tmax = 0.45 | k = −9→7 |
| 3313 measured reflections | l = −12→9 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0468P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.087 | (Δ/σ)max < 0.001 |
| S = 0.95 | Δρmax = 2.26 e Å−3 |
| 1021 reflections | Δρmin = −2.13 e Å−3 |
| 83 parameters | Extinction correction: none |
| LiDy(P1O3)4 | V = 884.24 (10) Å3 |
| Mr = 485.32 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 16.2690 (10) Å | µ = 9.24 mm−1 |
| b = 7.0236 (3) Å | T = 295 (2) K |
| c = 9.5781 (8) Å | 0.10 × 0.09 × 0.08 mm |
| β = 126.106 (3)º |
| Nonius KappaCCD diffractometer | 1021 independent reflections |
| Absorption correction: analytical (de Meulenaer & Tompa, 1965) | 858 reflections with I > 2σ(I) |
| Tmin = 0.42, Tmax = 0.45 | Rint = 0.080 |
| 3313 measured reflections |
| R[F2 > 2σ(F2)] = 0.038 | 83 parameters |
| wR(F2) = 0.087 | Δρmax = 2.26 e Å−3 |
| S = 0.95 | Δρmin = −2.13 e Å−3 |
| 1021 reflections |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Dy1 | 0.5000 | 0.79714 (6) | 0.7500 | 0.01295 (18) | |
| P1 | 0.36225 (14) | 0.5523 (2) | 0.8849 (2) | 0.0108 (4) | |
| P2 | 0.35333 (14) | 0.1513 (3) | 0.8039 (2) | 0.0124 (4) | |
| O1 | 0.3870 (4) | 0.7158 (6) | 0.8178 (7) | 0.0148 (11) | |
| O2 | 0.4353 (4) | 0.5025 (7) | 1.0727 (6) | 0.0142 (10) | |
| O3 | 0.2555 (4) | 0.5780 (7) | 0.8535 (7) | 0.0141 (11) | |
| O4 | 0.3421 (4) | 0.3778 (7) | 0.7655 (6) | 0.0169 (11) | |
| O5 | 0.4287 (4) | 0.0852 (7) | 0.7730 (7) | 0.0147 (10) | |
| O6 | 0.3726 (4) | 0.1159 (6) | 0.9727 (6) | 0.0180 (12) | |
| Li | 0.5000 | 0.292 (2) | 0.7500 | 0.012 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Dy1 | 0.0130 (3) | 0.0101 (3) | 0.0150 (3) | 0.000 | 0.0078 (2) | 0.000 |
| P1 | 0.0103 (9) | 0.0098 (9) | 0.0115 (9) | 0.0003 (6) | 0.0059 (8) | −0.0008 (6) |
| P2 | 0.0106 (10) | 0.0115 (9) | 0.0123 (9) | −0.0008 (7) | 0.0053 (8) | −0.0007 (7) |
| O1 | 0.016 (3) | 0.013 (3) | 0.014 (3) | −0.002 (2) | 0.008 (2) | 0.0012 (19) |
| O2 | 0.008 (3) | 0.014 (2) | 0.016 (3) | −0.0022 (19) | 0.004 (2) | 0.001 (2) |
| O3 | 0.007 (3) | 0.017 (3) | 0.018 (3) | 0.0056 (19) | 0.007 (2) | 0.006 (2) |
| O4 | 0.023 (3) | 0.012 (3) | 0.012 (2) | 0.004 (2) | 0.008 (2) | 0.0057 (19) |
| O5 | 0.015 (3) | 0.016 (2) | 0.020 (3) | 0.0014 (19) | 0.014 (2) | −0.0011 (19) |
| O6 | 0.027 (3) | 0.008 (2) | 0.019 (3) | −0.003 (2) | 0.013 (3) | −0.0008 (19) |
| Li | 0.015 (9) | 0.004 (8) | 0.023 (9) | 0.000 | 0.015 (8) | 0.000 |
| Dy1—O6i | 2.288 (5) | P2—O3vi | 1.589 (5) |
| Dy1—O6ii | 2.288 (5) | P2—O4 | 1.619 (5) |
| Dy1—O1 | 2.352 (5) | P2—Li | 2.896 (5) |
| Dy1—O1iii | 2.352 (5) | O2—Lii | 1.992 (11) |
| Dy1—O5iv | 2.406 (5) | O2—Dy1i | 2.513 (5) |
| Dy1—O5v | 2.406 (5) | O3—P2vii | 1.589 (5) |
| Dy1—O2ii | 2.513 (5) | O5—Li | 1.951 (11) |
| Dy1—O2i | 2.513 (5) | O5—Dy1viii | 2.406 (5) |
| Dy1—Liv | 3.476 (14) | O6—Dy1i | 2.288 (5) |
| Dy1—Li | 3.548 (14) | Li—O5iii | 1.951 (11) |
| P1—O1 | 1.483 (5) | Li—O2i | 1.992 (11) |
| P1—O2 | 1.500 (5) | Li—O2ii | 1.992 (11) |
| P1—O4 | 1.573 (5) | Li—P2iii | 2.896 (5) |
| P1—O3 | 1.589 (5) | Li—P1i | 3.035 (5) |
| P1—Lii | 3.035 (5) | Li—P1ii | 3.035 (5) |
| P2—O6 | 1.475 (5) | Li—Dy1viii | 3.476 (14) |
| P2—O5 | 1.495 (5) | ||
| O6i—Dy1—O6ii | 149.0 (2) | O3vi—P2—O4 | 100.9 (3) |
| O6i—Dy1—O1 | 93.73 (18) | O6—P2—Li | 126.0 (2) |
| O6ii—Dy1—O1 | 93.71 (19) | O3vi—P2—Li | 121.1 (2) |
| O6i—Dy1—O1iii | 93.71 (19) | O4—P2—Li | 67.6 (3) |
| O6ii—Dy1—O1iii | 93.73 (18) | P1—O1—Dy1 | 139.8 (3) |
| O1—Dy1—O1iii | 151.9 (2) | P1—O2—Lii | 120.0 (4) |
| O6i—Dy1—O5iv | 74.10 (17) | P1—O2—Dy1i | 136.6 (3) |
| O6ii—Dy1—O5iv | 79.93 (18) | Lii—O2—Dy1i | 103.3 (3) |
| O1—Dy1—O5iv | 136.63 (17) | P1—O3—P2vii | 134.3 (4) |
| O1iii—Dy1—O5iv | 71.43 (16) | P1—O4—P2 | 130.8 (3) |
| O6i—Dy1—O5v | 79.93 (18) | P2—O5—Li | 113.7 (4) |
| O6ii—Dy1—O5v | 74.10 (17) | P2—O5—Dy1viii | 140.9 (3) |
| O1—Dy1—O5v | 71.43 (16) | Li—O5—Dy1viii | 105.4 (3) |
| O1iii—Dy1—O5v | 136.63 (17) | P2—O6—Dy1i | 133.6 (3) |
| O5iv—Dy1—O5v | 65.5 (2) | O5—Li—O5iii | 83.7 (6) |
| O6i—Dy1—O2ii | 137.74 (17) | O5—Li—O2i | 119.6 (2) |
| O6ii—Dy1—O2ii | 72.95 (15) | O5iii—Li—O2i | 125.8 (2) |
| O1—Dy1—O2ii | 84.22 (17) | O5—Li—O2ii | 125.8 (2) |
| O1iii—Dy1—O2ii | 72.18 (16) | O5iii—Li—O2ii | 119.6 (2) |
| O5iv—Dy1—O2ii | 132.43 (17) | O2i—Li—O2ii | 87.2 (6) |
| O5v—Dy1—O2ii | 137.20 (17) | O5—Li—P2 | 28.19 (15) |
| O6i—Dy1—O2i | 72.95 (15) | O5iii—Li—P2 | 111.9 (5) |
| O6ii—Dy1—O2i | 137.74 (17) | O2i—Li—P2 | 99.89 (18) |
| O1—Dy1—O2i | 72.18 (16) | O2ii—Li—P2 | 108.8 (2) |
| O1iii—Dy1—O2i | 84.22 (17) | O5—Li—P2iii | 111.9 (5) |
| O5iv—Dy1—O2i | 137.20 (17) | O5iii—Li—P2iii | 28.19 (15) |
| O5v—Dy1—O2i | 132.43 (17) | O2i—Li—P2iii | 108.8 (2) |
| O2ii—Dy1—O2i | 66.2 (2) | O2ii—Li—P2iii | 99.89 (18) |
| O6i—Dy1—Liv | 74.52 (12) | P2—Li—P2iii | 140.1 (5) |
| O6ii—Dy1—Liv | 74.52 (12) | O5—Li—P1i | 102.86 (18) |
| O1—Dy1—Liv | 104.06 (11) | O5iii—Li—P1i | 108.3 (2) |
| O1iii—Dy1—Liv | 104.06 (11) | O2i—Li—P1i | 25.34 (15) |
| O5iv—Dy1—Liv | 32.77 (12) | O2ii—Li—P1i | 112.5 (5) |
| O5v—Dy1—Liv | 32.77 (12) | P2—Li—P1i | 92.53 (5) |
| O2ii—Dy1—Liv | 146.88 (11) | P2iii—Li—P1i | 101.64 (5) |
| O2i—Dy1—Liv | 146.88 (11) | O5—Li—P1ii | 108.3 (2) |
| O6i—Dy1—Li | 105.48 (12) | O5iii—Li—P1ii | 102.86 (18) |
| O6ii—Dy1—Li | 105.48 (12) | O2i—Li—P1ii | 112.5 (5) |
| O1—Dy1—Li | 75.94 (11) | O2ii—Li—P1ii | 25.34 (15) |
| O1iii—Dy1—Li | 75.94 (11) | P2—Li—P1ii | 101.64 (5) |
| O5iv—Dy1—Li | 147.23 (12) | P2iii—Li—P1ii | 92.53 (5) |
| O5v—Dy1—Li | 147.23 (12) | P1i—Li—P1ii | 137.8 (5) |
| O2ii—Dy1—Li | 33.12 (11) | O5—Li—Dy1viii | 41.9 (3) |
| O2i—Dy1—Li | 33.12 (11) | O5iii—Li—Dy1viii | 41.9 (3) |
| Liv—Dy1—Li | 180.000 (5) | O2i—Li—Dy1viii | 136.4 (3) |
| O1—P1—O2 | 118.3 (3) | O2ii—Li—Dy1viii | 136.4 (3) |
| O1—P1—O4 | 106.4 (3) | P2—Li—Dy1viii | 70.0 (3) |
| O2—P1—O4 | 111.6 (3) | P2iii—Li—Dy1viii | 70.0 (3) |
| O1—P1—O3 | 112.1 (3) | P1i—Li—Dy1viii | 111.1 (2) |
| O2—P1—O3 | 105.0 (3) | P1ii—Li—Dy1viii | 111.1 (2) |
| O4—P1—O3 | 102.4 (3) | O5—Li—Dy1 | 138.1 (3) |
| O1—P1—Lii | 90.9 (3) | O5iii—Li—Dy1 | 138.1 (3) |
| O4—P1—Lii | 144.5 (3) | O2i—Li—Dy1 | 43.6 (3) |
| O3—P1—Lii | 99.2 (2) | O2ii—Li—Dy1 | 43.6 (3) |
| O6—P2—O5 | 119.7 (3) | P2—Li—Dy1 | 110.0 (3) |
| O6—P2—O3vi | 112.5 (3) | P2iii—Li—Dy1 | 110.0 (3) |
| O5—P2—O3vi | 107.3 (3) | P1i—Li—Dy1 | 68.9 (2) |
| O6—P2—O4 | 109.7 (3) | P1ii—Li—Dy1 | 68.9 (2) |
| O5—P2—O4 | 104.9 (3) | Dy1viii—Li—Dy1 | 180.0 |
| Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1, z−1/2; (iii) −x+1, y, −z+3/2; (iv) −x+1, y+1, −z+3/2; (v) x, y+1, z; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x+1/2, y+1/2, −z+3/2; (viii) x, y−1, z. |
This work was supported by the Ministry of Higher Education, Scientific Research and Technology of Tunisia.
Averbuch-Pouchot, M. T. & Bagieu Beucher, M. (1987). Z. Anorg. Allg. Chem. 552, 171–180.
Ben Zarkouna, E. & Driss, A. (2004). Acta Cryst. E60, i102–i104.
Ben Zarkouna, E., Férid, M. & Driss, A. (2005). Mater. Res. Bull. 40, 198–1992.
Ben Zarkouna, E., Horchani-Naifer, K., Férid, M. & Driss, A. (2007). Acta Cryst. E63, i1–i2.
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Chehimi-Moumen, F. & Férid, M. (2007). Acta Cryst. E63, i129–i130.
Durif, A. (1995). Crystal Chemistry of condensed phosphates. New York: Plenum Press.
Ettis, H., Naili, H. & Mhiri, T. (2006). J. Solid State Chem. 179, 3107–3113.
Férid, M. (2006). Etude des propriétés cristallochimiques et physiques de phosphates condensés de terres rares. Paris: Publibook.
Hashimoto, N., Takada, Y., Sato, K. & Ibuki, S. (1991). J. Lumin. 48–49, 893–897.
Hong, H. Y. P. (1975). Mater. Res. Bull. 10, 635–640.
Horchani, K., Gâcon, J. C., Férid, M., Trabelsi-Ayadi, M., Krachni, G. K. & Liu, G. K. (2003). Opt. Mater. 24, 169–174.
Koizumi, H. (1976). Acta Cryst. B32, 266–268.
Liu, J.-C. & Li, D.-Y. (1983). Acta Phys. Sinica, 32, 786–790.
Meulenaer, J. de & Tompa, H. (1965). Acta Cryst. 19, 1014–1018.
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Yamada, T., Otsuka, K. & Nakano, J. (1974). J. Appl. Phys. 45, 5096–5097.
Condensed phosphates of rare earth and monovalent cations of general formula MILn(PO3)4 have attracted large interest in the literature of the last three decades due to their possible application as phosphors and laser materials (Yamada et al., 1974; Hashimoto et al., 1991; Horchani et al., 2003).
In order to enrich the chemistry of this compound family, we have successfully synthesized single crystals of lithium dysprosium polyphosphate and investigated its crystal structure.
Structural studies reported for lithium lanthanide polyphosphates LiLn(PO3)4, Ln = Nd (Hong, 1975, Koizumi, 1976), Er (Liu et al., 1983, Ben Zarkouna et al., 2005),Yb (Ben Zarkouna et al., 2004), Gd (Ettis et al., 2006), Tb (Ben Zarkouna et al., 2007), showed that all these compounds crystallize in space group C2/c and have similar unit-cell parameters. However, it was reported that the lithium atom is located in the (4a) site in LiNd(PO3)4 (Hong, 1975) and LiEr(PO3)4 (Liu et al., 1983) and in the (4 e) site in the remaining structures. LiDy(PO3)4 is found to be isotypic with the latter group LiLn(PO3)4 previously reported. The corresponding asymmetric unit (Fig. 1) is formed by dysprosium and lithium atoms, both located in the (4 e) site, and two PO4 tetrahedra with all atoms in general positions.
These tetrahedra share common corners yielding infinite chains, of four tetrahedra period, extending along the 21 screw axes in the b direction. Four such chains cross the unit cell (Fig. 2).
The polyphosphate chains display two type of distances, P—O terminal ranging from 1.475 (5) to 1.500 (5)Å and P—O bridging, noticeably longer, ranging from 1.573 (5) to 1.619 (5) Å. These distances are comparable with those reported for other condensed phosphates (Durif, 1995; Averbuch-Pouchot & Bagieu Beucher, 1987; Chehimi-Moumen & Férid, 2007; Férid, 2006, Ben Zarkouna et al., 2007).
Dy3+ and Li+ cations lie alternatingly on the two-fold axis in the middle of four polyphosphate chains, with Dy—Li distances of 3.55 (1) and 3.48 (1) Å. They are coordinated by eight and four external oxygen atoms, respectively. The resulting DyO8 dodecahedra and LiO4 tetrahedra are considerably distorted (Figure 3). The Dy—O and Li—O distances range from 2.288 (5) to 2.513 (5)Å and 1.95 (1) to 1.99 (1)Å respectively. The DyO8 dodecahedra share corners and edges with neighbouring LiO4 (Fig. 3) and PO4 tetrahedra building a three dimensional network (Fig. 4). It can be noted that, in the present arrangement, the DyO8 dodecahedra are isolated from each other, the shortest Dy—Dy distance is 5.563 (5) Å.