inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

An ortho­rhom­bic polymorph of cerium(III) ultraphosphate, CeP5O14

aDepartment of Material Science and Engineering, Yunnan University, Kunming, Yunnan 650091, People's Republic of China, and bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China
*Correspondence e-mail: jzhu@ynu.edu.cn

(Received 10 September 2008; accepted 12 October 2008; online 15 October 2008)

Cerium(III) ultraphosphate, CeP5O14, was synthesized by a high-temperature solution reaction between CeO2 and NH4H2PO4 in a Ce–P molar ratio of 1:12. Colourless crystals of the ortho­rhom­bic polymorph were obtained by cooling the melt of the mixture. The structure contains (P5O14)3− anionic ribbons linked by distorted CeO8 polyhedra.

Related literature

For applications of rare-earth ultraphosphates, see: Cole et al. (2000[Cole, J. M., Lees, M. R., Howard, J. A. K., Newport, R. J., Saunders, G. A. & Schönherr, E. (2000). J. Solid State Chem. 150, 377-382.]); Katrusiak & Kaczmarek (1995[Katrusiak, A. & Kaczmarek, F. (1995). Cryst. Res. Technol. 30, 501-507.]); Kobayashi et al. (1976[Kobayashi, T., Sawada, T., Ikeo, H., Muto, K. & Kai, J. (1976). J. Phys. Soc. Jpn, 40, 595-596.]); Schulz et al. (1974[Schulz, H., Thiemann, K. H. & Fenner, J. (1974). Mater. Res. Bull. 9, 1525-1530.]). For a discussion of structure types in this chemical system, see: Averbuch-Pouchot & Durif (1992[Averbuch-Pouchot, M. T. & Durif, A. (1992). Z. Kristallogr. 201, 69-92.]). For the triclinic polymorph of CeP5O14, see: Rzaigui et al. (1984[Rzaigui, M., Kbir Ariguib, N., Averbuch-Pouchot, M. T. & Durif, A. (1984). J. Solid State Chem. 52, 61-65.]).

Experimental

Crystal data
  • CeP5O14

  • Mr = 518.97

  • Orthorhombic, P m n a

  • a = 13.1252 (12) Å

  • b = 8.7991 (9) Å

  • c = 9.0741 (9) Å

  • V = 1047.97 (18) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 5.19 mm−1

  • T = 293 (2) K

  • 0.08 × 0.08 × 0.05 mm

Data collection
  • Rigaku Mercury CCD diffractometer

  • Absorption correction: multi-scan (CrystalClear; Molecular Structure Corporation & Rigaku, 2001[Molecular Structure Corporation & Rigaku (2001). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.663, Tmax = 0.771

  • 7608 measured reflections

  • 1262 independent reflections

  • 1212 reflections with I > 2σ(I)

  • Rint = 0.072

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.094

  • S = 1.00

  • 1262 reflections

  • 99 parameters

  • Δρmax = 1.70 e Å−3

  • Δρmin = −1.08 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001[Molecular Structure Corporation & Rigaku (2001). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Rare-earth ultraphosphates, LnP5O14 (Ln = rare-earth element), have attracted wide interest because of their potential applications in the laser domain (Schulz et al., 1974; Kobayashi et al., 1976; Katrusiak & Kaczmarek, 1995; Cole et al., 2000). These compounds can be generally classified into four structure types: monoclinic (P21/a), monoclinic (C2/c), orthorhombic (Pnma), and triclinic (P1) (Averbuch-Pouchot & Durif, 1992). In this chemical system, many of the compounds are isotypic, and some are polymorphic. However, many polymorphs of ultraphosphates LnP5O14 have not been realised to date. Herein, we present the synthesis and crystal structure of an orthorhombic polymorph of CeP5O14.

In the structure (Figs. 1 and 2), the Ce3+ cation plays an important bridging role, connecting neighbouring (P5O14)3- anionic ribbons. The CeO8 polyhedron is corner-sharing with eight PO4 tetrahedra, with the Ce—O bond distances ranging from 2.436 (5) to 2.534 (8) Å. The shortest Ce—Ce distance is 5.2271 (9) Å. The (P5O14)3- anionic ribbon may be described as two PO4 infinite chains linked by P(2)O4 tetrahedra, as shown in Fig. 3. P(1)O4, P(3)O4, and P(4)O4 tetrahedra are corner-shared to form screwed infinite chains along the b axis. P(2)O4 tetrahedra are corner-shared with two surrounding PO4 infinite chains along the a axis. Thus, a (P5O14)3- anionic ribbon is observed parallel to b.

Related literature top

For applications of rare-earth ultraphosphates, see: Cole et al. (2000); Katrusiak & Kaczmarek (1995); Kobayashi et al. (1976); Schulz et al. (1974). For a discussion of structure types in this chemical system, see: Averbuch-Pouchot & Durif (1992). For the triclinic polymorph of CeP5O14, see: Rzaigui et al. (1984).

Experimental top

The title compound was prepared by a high-temperature solution reaction, using analytical reagent CeO2 and NH4H2PO4 in a molar ratio corresponding to Ce/P = 1:12. Starting mixtures were finely ground in an agate mortar to ensure optimal homogeneity and reactivity, then placed in a platinum crucible and heated at 373 K for 4 h. Afterwards, the mixtures were reground and heated to 973 K for 24 h. Finally, the temperature was cooled to 773 K at a rate of 2 K/h and air-quenched to room temperature. A few colourless, block-shaped crystals were obtained from the melt of the mixture.

Refinement top

The position of the Ce atom was obtained using direct methods, and the remaining atoms were located in succesive difference Fourier syntheses. The chemical composition of the single crystal was confirmed by energy-dispersive X-ray (EDX) analysis, and no impurity elements were detected.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Asymmetric unit with displacement ellipsoids shown at 50% probability.
[Figure 2] Fig. 2. Projection of the structure along the b axis. The tetrahedra represent PO4 groups and the gray circles represent Ce3+ cations.
[Figure 3] Fig. 3. (P5O14)3- anionic ribbon running parallel to the b axis.
Cerium(III) ultraphosphate top
Crystal data top
CeP5O14F(000) = 980
Mr = 518.97Dx = 3.289 Mg m3
Orthorhombic, PmnaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2Cell parameters from 2047 reflections
a = 13.1252 (12) Åθ = 2.3–27.5°
b = 8.7991 (9) ŵ = 5.19 mm1
c = 9.0741 (9) ÅT = 293 K
V = 1047.97 (18) Å3Block, colourless
Z = 40.08 × 0.08 × 0.05 mm
Data collection top
Rigaku Mercury CCD
diffractometer
1262 independent reflections
Radiation source: fine-focus sealed tube1212 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.072
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(CrystalClear; Molecular Structure Corporation & Rigaku, 2001)
h = 1716
Tmin = 0.663, Tmax = 0.771k = 1111
7608 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048 w = 1/[σ2(Fo2) + 37.6801P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.094(Δ/σ)max = 0.001
S = 1.00Δρmax = 1.70 e Å3
1262 reflectionsΔρmin = 1.08 e Å3
99 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0114 (15)
Crystal data top
CeP5O14V = 1047.97 (18) Å3
Mr = 518.97Z = 4
Orthorhombic, PmnaMo Kα radiation
a = 13.1252 (12) ŵ = 5.19 mm1
b = 8.7991 (9) ÅT = 293 K
c = 9.0741 (9) Å0.08 × 0.08 × 0.05 mm
Data collection top
Rigaku Mercury CCD
diffractometer
1262 independent reflections
Absorption correction: multi-scan
(CrystalClear; Molecular Structure Corporation & Rigaku, 2001)
1212 reflections with I > 2σ(I)
Tmin = 0.663, Tmax = 0.771Rint = 0.072
7608 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.094 w = 1/[σ2(Fo2) + 37.6801P]
where P = (Fo2 + 2Fc2)/3
S = 1.00Δρmax = 1.70 e Å3
1262 reflectionsΔρmin = 1.08 e Å3
99 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ce0.50000.72337 (7)0.68985 (6)0.00797 (19)
P10.2936 (2)0.50000.50000.0113 (6)
P20.00000.3121 (3)0.7524 (3)0.0091 (5)
P30.3233 (2)0.00000.50000.0102 (5)
P40.16332 (14)0.2351 (2)0.54996 (19)0.0098 (4)
O10.1129 (4)0.2256 (7)0.4081 (6)0.0189 (12)
O20.3474 (4)0.5859 (7)0.6151 (6)0.0182 (12)
O30.2451 (5)0.1123 (8)0.5815 (6)0.0295 (16)
O40.00000.4655 (9)0.6859 (9)0.0155 (16)
O50.2151 (5)0.3901 (7)0.5849 (7)0.0307 (17)
O60.3778 (4)0.0799 (6)0.6175 (6)0.0165 (12)
O70.00000.2893 (10)0.9131 (8)0.0176 (17)
O80.0934 (4)0.2133 (6)0.6876 (6)0.0161 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ce0.0074 (3)0.0090 (3)0.0075 (3)0.0000.0000.0003 (2)
P10.0062 (11)0.0135 (13)0.0143 (13)0.0000.0000.0033 (11)
P20.0089 (12)0.0120 (13)0.0063 (11)0.0000.0000.0008 (10)
P30.0080 (11)0.0124 (13)0.0102 (12)0.0000.0000.0013 (10)
P40.0059 (8)0.0152 (10)0.0083 (8)0.0002 (7)0.0001 (6)0.0019 (7)
O10.021 (3)0.023 (3)0.013 (2)0.006 (3)0.008 (2)0.001 (2)
O20.014 (3)0.023 (3)0.018 (3)0.006 (2)0.003 (2)0.000 (2)
O30.029 (3)0.050 (4)0.010 (3)0.028 (3)0.001 (2)0.004 (3)
O40.019 (4)0.012 (4)0.016 (4)0.0000.0000.005 (3)
O50.034 (4)0.031 (4)0.027 (3)0.027 (3)0.019 (3)0.015 (3)
O60.016 (3)0.017 (3)0.016 (3)0.006 (2)0.002 (2)0.001 (2)
O70.021 (4)0.024 (4)0.008 (3)0.0000.0000.002 (3)
O80.017 (3)0.017 (3)0.014 (2)0.007 (2)0.005 (2)0.004 (2)
Geometric parameters (Å, º) top
Ce—O22.436 (5)P2—O8ix1.614 (5)
Ce—O2i2.436 (5)P2—O81.614 (5)
Ce—O6ii2.449 (5)P3—O6x1.464 (5)
Ce—O6iii2.449 (5)P3—O61.464 (5)
Ce—O7iv2.513 (7)P3—O3x1.606 (6)
Ce—O1v2.514 (5)P3—O31.606 (6)
Ce—O1vi2.514 (5)P4—O11.450 (5)
Ce—O4vii2.534 (8)P4—O31.549 (6)
P1—O21.470 (6)P4—O51.557 (6)
P1—O2viii1.470 (6)P4—O81.562 (5)
P1—O5viii1.609 (6)O1—Ceiv2.514 (5)
P1—O51.609 (6)O4—Cexi2.534 (7)
P2—O71.472 (8)O6—Cexii2.449 (5)
P2—O41.479 (8)O7—Cevi2.513 (7)
O2—Ce—O2i110.6 (3)O2viii—P1—O5viii106.0 (3)
O2—Ce—O6ii144.55 (18)O2—P1—O5106.0 (3)
O2i—Ce—O6ii74.82 (19)O2viii—P1—O5109.8 (3)
O2—Ce—O6iii74.82 (19)O5viii—P1—O5100.4 (6)
O2i—Ce—O6iii144.55 (18)O7—P2—O4121.9 (5)
O6ii—Ce—O6iii81.8 (3)O7—P2—O8ix106.7 (3)
O2—Ce—O7iv72.54 (17)O4—P2—O8ix110.1 (3)
O2i—Ce—O7iv72.54 (17)O7—P2—O8106.7 (3)
O6ii—Ce—O7iv76.3 (2)O4—P2—O8110.1 (3)
O6iii—Ce—O7iv76.3 (2)O8ix—P2—O898.9 (4)
O2—Ce—O1v142.43 (19)O6x—P3—O6121.5 (5)
O2i—Ce—O1v79.83 (19)O6x—P3—O3x105.8 (3)
O6ii—Ce—O1v72.48 (18)O6—P3—O3x110.6 (3)
O6iii—Ce—O1v118.08 (19)O6x—P3—O3110.6 (3)
O7iv—Ce—O1v142.65 (14)O6—P3—O3105.8 (3)
O2—Ce—O1vi79.83 (19)O3x—P3—O3100.5 (5)
O2i—Ce—O1vi142.43 (19)O1—P4—O3116.1 (3)
O6ii—Ce—O1vi118.08 (19)O1—P4—O5115.5 (4)
O6iii—Ce—O1vi72.48 (18)O3—P4—O5105.7 (4)
O7iv—Ce—O1vi142.65 (14)O1—P4—O8115.8 (3)
O1v—Ce—O1vi72.2 (3)O3—P4—O8100.0 (3)
O2—Ce—O4vii71.29 (16)O5—P4—O8101.6 (3)
O2i—Ce—O4vii71.29 (16)P4—O1—Ceiv163.4 (4)
O6ii—Ce—O4vii138.78 (13)P1—O2—Ce148.0 (4)
O6iii—Ce—O4vii138.78 (14)P4—O3—P3141.9 (4)
O7iv—Ce—O4vii113.9 (3)P2—O4—Cexi129.5 (5)
O1v—Ce—O4vii79.0 (2)P4—O5—P1135.1 (4)
O1vi—Ce—O4vii79.0 (2)P3—O6—Cexii148.7 (3)
O2—P1—O2viii122.6 (5)P2—O7—Cevi174.7 (6)
O2—P1—O5viii109.8 (3)P4—O8—P2132.2 (4)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z; (iii) x, y+1, z; (iv) x+1/2, y+1, z1/2; (v) x+1/2, y+1, z+1/2; (vi) x+1/2, y+1, z+1/2; (vii) x+1/2, y, z+3/2; (viii) x, y+1, z+1; (ix) x, y, z; (x) x, y, z+1; (xi) x1/2, y, z+3/2; (xii) x, y1, z.

Experimental details

Crystal data
Chemical formulaCeP5O14
Mr518.97
Crystal system, space groupOrthorhombic, Pmna
Temperature (K)293
a, b, c (Å)13.1252 (12), 8.7991 (9), 9.0741 (9)
V3)1047.97 (18)
Z4
Radiation typeMo Kα
µ (mm1)5.19
Crystal size (mm)0.08 × 0.08 × 0.05
Data collection
DiffractometerRigaku Mercury CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Molecular Structure Corporation & Rigaku, 2001)
Tmin, Tmax0.663, 0.771
No. of measured, independent and
observed [I > 2σ(I)] reflections
7608, 1262, 1212
Rint0.072
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.094, 1.00
No. of reflections1262
No. of parameters99
w = 1/[σ2(Fo2) + 37.6801P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.70, 1.08

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005).

 

Acknowledgements

This investigation was based on work supported by the Foundation of Yunnan University (Project No. 2007Q013B).

References

First citationAverbuch-Pouchot, M. T. & Durif, A. (1992). Z. Kristallogr. 201, 69–92.  CAS
First citationBrandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationCole, J. M., Lees, M. R., Howard, J. A. K., Newport, R. J., Saunders, G. A. & Schönherr, E. (2000). J. Solid State Chem. 150, 377–382.  Web of Science CrossRef CAS
First citationKatrusiak, A. & Kaczmarek, F. (1995). Cryst. Res. Technol. 30, 501–507.  CrossRef CAS Web of Science
First citationKobayashi, T., Sawada, T., Ikeo, H., Muto, K. & Kai, J. (1976). J. Phys. Soc. Jpn, 40, 595–596.  CrossRef CAS Web of Science
First citationMolecular Structure Corporation & Rigaku (2001). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
First citationRzaigui, M., Kbir Ariguib, N., Averbuch-Pouchot, M. T. & Durif, A. (1984). J. Solid State Chem. 52, 61–65.  CrossRef CAS Web of Science
First citationSchulz, H., Thiemann, K. H. & Fenner, J. (1974). Mater. Res. Bull. 9, 1525–1530.  CrossRef CAS Web of Science
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds