PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): i46.
Published online 2010 May 8. doi:  10.1107/S1600536810016363
PMCID: PMC2979408

Lutetium(III) cyclo­tetra­phosphate

Abstract

Single crystals of the title compound, tetra­lutetium(III) tris­(cyclo­tetra­phosphate), Lu4(P4O12)3, were obtained by solid-state reaction. The cubic structure is isotypic with its AlIII and ScIII analogues and is built up from four-membered (P4O12)4− phosphate ring anions (An external file that holds a picture, illustration, etc.
Object name is e-66-00i46-efi1.jpg symmetry), isolated from each other and further linked through isolated LuO6 octa­hedra (.3. symmetry) via corner sharing. Each LuO6 octa­hedron is linked to six (P4O12)4− rings, while each (P4O12)4− ring is linked to eight LuO6 octa­hedra.

Related literature

The title compound belongs to a structural type discovered a long time ago through the Al4(P4O12)3 member, the structure of which was first investigated by Hendricks & Wyckoff (1927 [triangle]) and then described by Pauling & Sherman (1937 [triangle]). Since then, five isotypic compounds have been characterized: Cr4(P4O12)3 (Rémy & Boullé, 1964 [triangle]); Ti4(P4O12)3 (Liebau & Williams, 1964 [triangle]); Fe4(P4O12)3 (d’Yvoire et al., 1962 [triangle]); Sc4(P4O12)3 (Bagieu-Beucher, 1976 [triangle]; Mezentseva et al., 1977 [triangle]; Bagieu-Beucher & Guitel, 1978 [triangle]; Smolin et al. 1978 [triangle]) and Yb4(P4O12)3 (Chudinova, 1979 [triangle]). For a review of the crystal chemistry of cyclo­tetra­phosphates, see: Durif (1995 [triangle]). For other polymorphs of composition Lu(PO3)3, see: Höppe & Sedlmaier (2007 [triangle]); Yuan et al. (2008 [triangle]); Bejaoui et al. (2008 [triangle]).

Experimental

Crystal data

  • Lu4(P4O12)3
  • M r = 1647.52
  • Cubic, An external file that holds a picture, illustration, etc.
Object name is e-66-00i46-efi2.jpg
  • a = 14.6920 (6) Å
  • V = 3171.3 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 13.08 mm−1
  • T = 296 K
  • 0.18 × 0.10 × 0.08 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.534, T max = 0.746
  • 3088 measured reflections
  • 717 independent reflections
  • 659 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.020
  • wR(F 2) = 0.038
  • S = 1.03
  • 717 reflections
  • 41 parameters
  • Δρmax = 0.90 e Å−3
  • Δρmin = −0.67 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 272 Friedel pairs
  • Flack parameter: 0.000 (15)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: CaRine (Boudias & Monceau, 1998 [triangle]) and ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810016363/wm2342sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016363/wm2342Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The title compound is the third polymorph of composition Lu(PO3)3 besides the monoclinic form described by Höppe & Sedlmaier (2007) and Yuan et al. (2008) and the trigonal form more recently reported by Bejaoui et al. (2008). The title compound is also the less dense polymorph with a calculated density of 3.451 Mg.m3 versus 3.587 Mg.m3 for the trigonal and 3.708 Mg.m3 for the monoclinic form and is probably the highest temperature form. This cyclotetraphosphate belongs to a structural type (cubic, with space group I43d) known since 1927 through the archetype Al4(P4O12)3 determined by Hendricks & Wyckoff (1927). Then Pauling & Sherman (1937) gave the first description of the structure and reported roughly estimated atomic coordinates deduced from geometrical considerations. Since this time only five members of this family, viz. Cr4III(P4O12)3 (Rémy & Boullé, 1964), Ti4III(P4O12)3 (Liebau & Williams, 1964), Fe4III(P4O12)3 (d'Yvoire et al., 1962), Sc4III(P4O12)3 (Bagieu-Beucher, 1976; Mezentseva et al.,1977 and Smolin et al., 1978) and Yb4III(P4O12)3 (Chudinova, 1979), have been identified. Corresponding unit cell parameters are listed in Durif (1995). Among these isotypic compounds only the structure of the Sc4(P4O12)3 cyclotetraphosphate has almost simultaneously been refined from single-crystal data by Bagieu-Beucher & Guittel (1978) and Smolin et al. (1978). Their refinements confirmed the description of Pauling & Sherman (1937) according to which all the crystallographically independent atoms except the AIII element (.3. symmetry) are in general positions. The structure is built of four-membered phosphate ring anions (P4O12)4- (Fig. 1), isolated from each other and further linked by LuO6 octahedra by sharing corners. Each LuO6 octahedron is linked to six (P4O12)4- rings (Fig. 2a) while each (P4O12)4- ring is linked to eight LuO6 octahedra (Fig. 2b) through oxygen atoms with shorter P—O distances (1.464 (4) and 1.481 (4) Å). The (P4O12)4- ring anions are located around the 12a Wyckoff positions of space group I43d and exhibit 4 symmetry. Comparison of the (P4O12)4- ring anions in both Sc4(P4O12)3 and Lu4(P4O12)3 structures shows these two ring anions being geometrically quite identical with alternating upward- and downward-pointing tetrahedra and P—O—P angles of 137.1° and 136.9 (2)°, respectively. The P—O distances in the PO4 groups are identical within their e.s.d.. The four bridging oxygen atoms of these ring anions are located at the apices of a flattened tetrahedron with characteristic angles of 148.22° and 94.30° for Sc and 147.95° and 94.37° for the Lu cyclotetraphosphate. The LuO6 octahedron is very slightly distorted along a threefold axis, resulting in two sets of Lu—O distances equal to 2.182 (3) and 2.185 (4) Å, respectively.

Experimental

Single crystals of the title compound were obtained by solid state reaction while attempting to synthesized a long chain polyphosphate by reacting Lu2O3 with (NH4)H2PO4 and Rb2CO3 in an alumina boat. A mixture of these reagents in the molar ratio 27 : 85.5 : 8.7 was used for the synthesis. The mixture was successively heated at 473 K for 24 hours, then at 573 K for 24 additional hours and finally at 813 K for 24 hours. Then the sample was cooled down to 683 K at the rate of 3 K h-1 and maintained at this temperature for 36 hours. Finally, the sample was cooled down to room temperature by shutting the muffle furnace off. Single crystals were extracted from the batch by washing with hot water and filtering. The crystals were dried at 353 K in an oven. A translucent octahedral crystal of the title compound was selected for the structure refinement.

Refinement

The highest residual peak in the final difference Fourier map was located 0.87 Å from atom Lu and the deepest hole was located 0.99 Å from atom Lu.

Figures

Fig. 1.
ORTEP-3 view of the four-membered phosphate (P4O12)4- ring anion. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) 1-z, 3/2-x, y ; (ii) 3/4+y, 5/4-x, 3/4-z ; (iii) 5/4-y, -3/4+x,3/4-z ; (iv) -1/4+x, 1/4-z, 3/4-y ; (v) ...
Fig. 2.
Partial view of the Lu4(P4O12)3 structure showing: (a) the connections between the LuO6 octahedron and the (P4O12)4- ring anions, (b) the connections between the (P4O12)4- ring anion and the LuO6 octahedra.

Crystal data

Lu4(P4O12)3Dx = 3.451 Mg m3
Mr = 1647.52Mo Kα radiation, λ = 0.71073 Å
Cubic, I43dCell parameters from 1548 reflections
Hall symbol: I -4bd 2c 3θ = 3.4–30.3°
a = 14.6920 (6) ŵ = 13.08 mm1
V = 3171.3 (2) Å3T = 296 K
Z = 4Truncated octahedron, colourless
F(000) = 30080.18 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer717 independent reflections
Radiation source: fine-focus sealed tube659 reflections with I > 2σ(I)
graphiteRint = 0.034
Detector resolution: 8.3333 pixels mm-1θmax = 30.4°, θmin = 3.9°
[var phi] and ω scansh = −16→11
Absorption correction: multi-scan (SADABS; Bruker, 2008)k = −6→20
Tmin = 0.534, Tmax = 0.746l = −19→9
3088 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020w = 1/[σ2(Fo2) + (0.0088P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.038(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.90 e Å3
717 reflectionsΔρmin = −0.67 e Å3
41 parametersAbsolute structure: Flack (1983), 272 Friedel pairs
0 restraintsFlack parameter: 0.000 (15)
0 constraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
Lu0.896610 (13)0.396610 (13)0.103390 (13)0.00602 (8)
P0.95737 (9)0.37294 (9)0.33447 (9)0.0077 (2)
O11.0613 (2)0.3432 (2)0.3430 (2)0.0128 (7)
O21.0325 (2)0.3642 (3)0.0522 (2)0.0188 (8)
O30.9295 (2)0.3498 (3)0.2404 (2)0.0142 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Lu0.00602 (8)0.00602 (8)0.00602 (8)0.00039 (8)−0.00039 (8)−0.00039 (8)
P0.0097 (5)0.0051 (6)0.0082 (6)0.0017 (5)−0.0008 (5)0.0015 (4)
O10.0113 (15)0.0146 (18)0.0123 (17)0.0007 (15)−0.0025 (14)0.0054 (17)
O20.0103 (17)0.024 (2)0.022 (2)0.0016 (18)0.0015 (16)−0.0014 (18)
O30.0202 (19)0.0141 (19)0.0084 (16)0.0012 (16)−0.0050 (15)0.0023 (16)

Geometric parameters (Å, °)

Lu—O3i2.182 (3)P—O2iii1.464 (4)
Lu—O3ii2.182 (3)P—O31.481 (4)
Lu—O32.182 (3)P—O1iv1.583 (3)
Lu—O2i2.185 (4)P—O11.594 (3)
Lu—O2ii2.185 (4)O1—Pv1.583 (3)
Lu—O22.185 (4)O2—Pvi1.464 (4)
O3i—Lu—O3ii89.06 (14)O3—Lu—O292.64 (13)
O3i—Lu—O389.06 (14)O2i—Lu—O287.72 (15)
O3ii—Lu—O389.06 (14)O2ii—Lu—O287.72 (15)
O3i—Lu—O2i92.64 (13)O2iii—P—O3118.0 (2)
O3ii—Lu—O2i178.26 (14)O2iii—P—O1iv107.3 (2)
O3—Lu—O2i90.59 (14)O3—P—O1iv111.5 (2)
O3i—Lu—O2ii90.59 (14)O2iii—P—O1109.2 (2)
O3ii—Lu—O2ii92.64 (13)O3—P—O1106.0 (2)
O3—Lu—O2ii178.26 (14)O1iv—P—O1103.9 (2)
O2i—Lu—O2ii87.72 (15)Pv—O1—P136.9 (2)
O3i—Lu—O2178.26 (14)Pvi—O2—Lu164.9 (2)
O3ii—Lu—O290.59 (14)P—O3—Lu148.2 (2)

Symmetry codes: (i) −z+1, x−1/2, −y+1/2; (ii) y+1/2, −z+1/2, −x+1; (iii) −z+1, −x+3/2, y; (iv) −y+5/4, x−3/4, −z+3/4; (v) y+3/4, −x+5/4, −z+3/4; (vi) −y+3/2, z, −x+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2342).

References

  • Bagieu-Beucher, M. (1976). J. Appl. Cryst.9, 368–369.
  • Bagieu-Beucher, M. & Guitel, J. C. (1978). Acta Cryst. B34, 1439–1442.
  • Bejaoui, A., Horchani-Naifer, K. & Férid, M. (2008). Acta Cryst. E64, i48. [PMC free article] [PubMed]
  • Boudias, C. & Monceau, D. (1998). CaRine CaRine Crystallography, DIVERGENT S.A., Compiègne, France.
  • Bruker (2008). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chudinova, N. N. (1979). Izv. Akad. Nauk SSSR Neorg. Mater 15, 833–837.
  • Durif, A. (1995). In Crystal Chemistry of Condensed Phosphates New York and London: Plenum Press.
  • d’Yvoire, F. (1962). Bull. Soc. Chim pp. 1237–1243.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Hendricks, S. B. & Wyckoff, R. W. G. (1927). Am. J. Sci 13, 491–496.
  • Höppe, H. A. & Sedlmaier, S. J. (2007). Inorg. Chem. 46, 3467–3474. [PubMed]
  • Liebau, F. & Williams, H. P. (1964). Angew. Chem 76, 303–304.
  • Mezentseva, L. P., Domanskii, A. I. & Bondar, I. A. (1977). Russ. J. Inorg. Chem 22, 43–45.
  • Pauling, L. & Sherman, J. S. (1937). Z. Kristallogr 96, 481–487.
  • Rémy, P. & Boullé, A. (1964). C. R. Acad. Sci 258, 927–929.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smolin, Y. I., Shepelev, Y. F., Domanskii, A. I. & Belov, N. V. (1978). Kristallografiya, 23, 187–188.
  • Yuan, J. L., Zhang, H., Zhao, J. T., Chen, H. H., Yang, X. X. & Zhang, G. B. (2008). Opt. Mater 30, 1369–1374.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography