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

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ISSN: 2056-9890

Tripraseodymium penta­iron(III) dodeca­oxide, Pr3Fe5O12: a synchrotron radiation study

aGraduate School of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Japan, and bHokkaido University of Education HAKODATE, Yahata-cho, Hakodate-shi, Japan
*Correspondence e-mail: tkomori@katch.ne.jp

(Received 14 September 2009; accepted 21 September 2009; online 3 October 2009)

The title compound, penta­iron tripraseodymium dodeca­oxide (PrIG), has an iron garnet structure. There are two Fe site symmetries. One of the Fe atoms is coordinated by six O atoms, forming a slightly distorted octa­hedron, and has [\overline{3}] site symmetry. The other Fe atom is coordinated by four O atoms, forming a slightly distorted tetra­hedron, and has [\overline{4}] site symmetry. FeO6 octa­hedra and FeO4 tetra­hedra are linked together by corners. The Pr atom is coordinated by eight O atoms, forming a distorted dodeca­hedron, and has 222 site symmetry. The O atoms occupy the general positions.

Related literature

The title compound is isotypic with the Ia[\overline{3}]d form of Y3Fe5O12 (YIG). For related structures, see: Bonnet et al. (1975[Bonnet, M., Delapalme, A., Fuess, H. & Thomas, M. (1975). Acta Cryst. B31, 2233-2240.]). For details of the crystal growth from low-temperature liquid-phase epitaxy, see: Fratello et al. (1986[Fratello, V. J., Brandle, C. D., Slusky, S. E. G., Valentino, A. J., Norelli, M. P. & Wolfe, R. (1986). Cryst. Growth, 75, 281-283.]). For the extinction correction, see: Becker & Coppens (1975[Becker, P. J. & Coppens, P. (1975). Acta Cryst. A31, 417-425.]). X-ray intensities were measured avoiding multiple diffraction, see: Takenaka et al. (2008[Takenaka, Y., Sakakura, T., Tanaka, K. & Kishimoto, S. (2008). Acta Cryst. A64, C566.]).

Experimental

Crystal data
  • Pr3Fe5O12

  • Mr = 893.98

  • Cubic, [I a \overline 3d ]

  • a = 12.6302 (3) Å

  • V = 2014.79 (8) Å3

  • Z = 8

  • Synchrotron radiation

  • λ = 0.67171 Å

  • μ = 17.41 mm−1

  • T = 298 K

  • 0.035 mm (radius)

Data collection
  • Rigaku AFC four-circle diffractometer

  • Absorption correction: for a sphere [transmission coefficients for spheres tabulated in International Tables C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation; Yamauchi et al., 1965[Yamauchi, J., Moriguchi, S. & Ichimatsu, S. (1965). Numerical Calculation Method for Computer. Tokyo: Baifūkan.])] Tmin = 0.413, Tmax = 0.441

  • 9351 measured reflections

  • 1728 independent reflections

  • 1728 reflections with F > 3σ(F)

  • Rint = 0.016

Refinement
  • R[F2 > 2σ(F2)] = 0.019

  • wR(F2) = 0.021

  • S = 1.06

  • 9351 reflections

  • 17 parameters

  • Δρmax = 2.52 e Å−3

  • Δρmin = −3.16 e Å−3

Table 1
Selected geometric parameters (Å, °)

Pr1—O1 2.42410 (10)
Pr1—O1i 2.54010 (10)
Fe1—O1 2.03220 (10)
Fe2—O1ii 1.87450 (10)
O1—Fe1—O1i 85.87 (1)
O1ii—Fe2—O1iii 114.39 (1)
O1ii—Fe2—O1iv 100.02 (1)
Symmetry codes: (i) z, x, y; (ii) [x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]; (iii) [-x+{\script{1\over 4}}, z-{\script{1\over 4}}, y+{\script{1\over 4}}]; (iv) [x+{\script{1\over 2}}, -y, z].

Data collection: AFC-5, specially designed for PF-BL14A (Rigaku, 1984[Rigaku (1984). AFC-5. Rigaku Corporation, Tokyo, Japan.]) and IUANGLE (Tanaka et al., 1994[Tanaka, K., Kumazawa, S., Tsubokawa, M., Maruno, S. & Shirotani, I. (1994). Acta Cryst. A50, 246-252.]); cell refinement: RSLC-3 UNICS system (Sakurai & Kobayashi, 1979[Sakurai, T. & Kobayashi, K. (1979). Rep. Inst. Phys. Chem. Res. 55, 69-77.]); data reduction: RDEDIT (Tanaka, 2008[Tanaka, K. (2008). RDEDIT. Unpublished.]); program(s) used to solve structure: QNTAO (Tanaka et al., 2008[Tanaka, K., Makita, R., Funahashi, S., Komori, T. & Zaw Win, (2008). Acta Cryst. A64, 437-449.]); program(s) used to refine structure: QNTAO; molecular graphics: ATOMS for Windows (Dowty, 2000[Dowty, E. (2000). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA.]); software used to prepare material for publication: RDEDIT.

Supporting information


Comment top

The title compound, Pr3Fe5O12 (PrIG), was difficult to be grown. It was grown by the low-temperature-liquid-phase epitaxy for the first time by Fratello et al. (1986). Though the crystal structure was assumed as iron-garnet-type structure by lattice constant and extinction rule, the complete structure was not determined. In this paper, we determine the O atom position and the complete structure by the full matrix least-squares program QNTAO. Since the R-factor is small and the residual density has no significant peaks where no atoms exists, the structure was finally determined to be iron-garnet structure. It is isotypic with the Ia3d form of Y3Fe5O12 (YIG). (Bonnet et al., 1975). The Pr atom is coordinated by eight oxygen atoms. It forms a distorted dodecahedron. There are two Fe site symmetries. One of the Fe atom is coordinated by six oxygen atoms. It forms a slitely distorted octahedron. The other Fe atom is coordinated by four oxygen atoms. It forms a slightly distorted tetrahedron. FeO6 octahedron and FeO4 tetrahedron are linked together by corners. The structure of PrIG is drawn in Fig.1. And displacement ellipsoids of PrO8 is drawn in Fig.2.

Related literature top

The title compound is isotypic with the Ia3d form of Y3Fe5O12 (YIG). For related structures, see : Bonnet et al. (1975). For details of the crystal growth from low-temperature liquid-phase epitaxy, see: Fratello et al. (1986).

For related literature, see: Becker & Coppens (1975); Takenaka et al. (2008).

Experimental top

Single crystals of praseodymium iron garnet were prepared by low temperature liquid phase epitaxy on Sm3(ScGa)5O12 seeds with lattice parameters near the projected values for PrIG.

Refinement top

X-ray intensities were measured avoiding multiple diffraction. (Takenaka et al., 2008).

Structure description top

The title compound, Pr3Fe5O12 (PrIG), was difficult to be grown. It was grown by the low-temperature-liquid-phase epitaxy for the first time by Fratello et al. (1986). Though the crystal structure was assumed as iron-garnet-type structure by lattice constant and extinction rule, the complete structure was not determined. In this paper, we determine the O atom position and the complete structure by the full matrix least-squares program QNTAO. Since the R-factor is small and the residual density has no significant peaks where no atoms exists, the structure was finally determined to be iron-garnet structure. It is isotypic with the Ia3d form of Y3Fe5O12 (YIG). (Bonnet et al., 1975). The Pr atom is coordinated by eight oxygen atoms. It forms a distorted dodecahedron. There are two Fe site symmetries. One of the Fe atom is coordinated by six oxygen atoms. It forms a slitely distorted octahedron. The other Fe atom is coordinated by four oxygen atoms. It forms a slightly distorted tetrahedron. FeO6 octahedron and FeO4 tetrahedron are linked together by corners. The structure of PrIG is drawn in Fig.1. And displacement ellipsoids of PrO8 is drawn in Fig.2.

The title compound is isotypic with the Ia3d form of Y3Fe5O12 (YIG). For related structures, see : Bonnet et al. (1975). For details of the crystal growth from low-temperature liquid-phase epitaxy, see: Fratello et al. (1986).

For related literature, see: Becker & Coppens (1975); Takenaka et al. (2008).

Computing details top

Data collection: AFC-5, specially designed for PF-BL14A (Rigaku, 1984) and IUANGLE (Tanaka et al., 1994).; cell refinement: RSLC-3 UNICS system (Sakurai & Kobayashi, 1979); data reduction: RDEDIT (Tanaka, 2008); program(s) used to solve structure: QNTAO (Tanaka et al., 2008); program(s) used to refine structure: QNTAO (Tanaka et al., 2008); molecular graphics: ATOMS for Windows (Dowty, 2000); software used to prepare material for publication: RDEDIT (Tanaka, 2008).

Figures top
[Figure 1] Fig. 1. The structure of Pr3Fe5O12. Small red and large green spheres represent O and Pr atoms, respectively. Purple octahedron and blue tetrahedron represent FeO6 and FeO4 units, respectively.
[Figure 2] Fig. 2. View of PrO8 with displacement ellipsoids at the 90% probability level. Green and red ellipsoids represent Pr and O atoms, in Fig.1.
Pentairon tripraseodymium dodecaoxide top
Crystal data top
Pr3Fe5O12Dx = 5.894 Mg m3
Mr = 893.98Synchrotron radiation, λ = 0.67171 Å
Cubic, Ia3dCell parameters from 9 reflections
Hall symbol: -I 4bd 2c 3θ = 17.5–52.3°
a = 12.6302 (3) ŵ = 17.41 mm1
V = 2014.79 (8) Å3T = 298 K
Z = 8Sphere, black
F(000) = 32240.04 mm (radius)
Data collection top
Rigaku AFC four-circle
diffractometer
1728 independent reflections
Si 111 monochromator1728 reflections with F > 3σ(F)
Detector resolution: 1.25 × 1.25° pixels mm-1Rint = 0.016
ω/2θ scansθmax = 68.3°, θmin = 3.7°
Absorption correction: for a sphere
[Transmission coefficients for spheres tabulated in International Tables C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation (Yamauchi et al., 1965)]
h = 934
Tmin = 0.413, Tmax = 0.441k = 932
9351 measured reflectionsl = 934
Refinement top
Refinement on FPrimary atom site location: isomorphous structure methods
Least-squares matrix: fullWeighting scheme based on measured s.u.'s
R[F2 > 2σ(F2)] = 0.019(Δ/σ)max = 0.003
wR(F2) = 0.021Δρmax = 2.52 e Å3
S = 1.06Δρmin = 3.16 e Å3
9351 reflectionsExtinction correction: B–C type 1 Gaussian isotropic (Becker & Coppens, 1975)
17 parametersExtinction coefficient: 0.255 (5)
Crystal data top
Pr3Fe5O12Z = 8
Mr = 893.98Synchrotron radiation, λ = 0.67171 Å
Cubic, Ia3dµ = 17.41 mm1
a = 12.6302 (3) ÅT = 298 K
V = 2014.79 (8) Å30.04 mm (radius)
Data collection top
Rigaku AFC four-circle
diffractometer
1728 independent reflections
Absorption correction: for a sphere
[Transmission coefficients for spheres tabulated in International Tables C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation (Yamauchi et al., 1965)]
1728 reflections with F > 3σ(F)
Tmin = 0.413, Tmax = 0.441Rint = 0.016
9351 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.01917 parameters
wR(F2) = 0.021Δρmax = 2.52 e Å3
S = 1.06Δρmin = 3.16 e Å3
9351 reflections
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pr10.1250000.0000000.2500000.00531 (1)
Fe10.0000000.0000000.0000000.00512 (1)
Fe20.3750000.0000000.2500000.00533 (1)
O10.029622 (2)0.052553 (2)0.149166 (2)0.00711 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pr10.00406 (2)0.00594 (2)0.00594 (2)000.00111 (1)
Fe10.00512 (2)0.00512 (2)0.00512 (2)0.00023 (1)0.00023 (1)0.00023 (1)
Fe20.00411 (3)0.00594 (2)0.00594 (2)000
O10.00718 (8)0.00829 (8)0.00587 (7)0.00004 (6)0.00080 (6)0.00038 (6)
Geometric parameters (Å, º) top
Pr1—O12.4241 (1)Fe1—O1i2.0322 (1)
Pr1—O1i2.5401 (1)Fe1—O1viii2.0322 (1)
Pr1—O1ii2.4241 (1)Fe1—O1ix2.0322 (1)
Pr1—O1iii2.5401 (1)Fe1—O1x2.0322 (1)
Pr1—O1iv2.4241 (1)Fe1—O1xi2.0322 (1)
Pr1—O1v2.5401 (1)Fe2—O1xii1.8745 (1)
Pr1—O1vi2.4241 (1)Fe2—O1iv1.8745 (1)
Pr1—O1vii2.5401 (1)Fe2—O1xiii1.8745 (1)
Fe1—O12.0322 (1)Fe2—O1vi1.8745 (1)
O1—Pr1—O1i67.75 (1)O1—Fe1—O1viii85.87 (1)
O1—Pr1—O1ii72.66 (1)O1—Fe1—O1ix180.00
O1—Pr1—O1iii124.91 (1)O1—Fe1—O1x94.13 (1)
O1—Pr1—O1iv111.18 (1)O1—Fe1—O1xi94.13 (1)
O1—Pr1—O1v73.25 (1)O1xii—Fe2—O1vi114.39 (1)
O1—Pr1—O1vi159.51 (1)O1xii—Fe2—O1iv114.39 (1)
O1—Pr1—O1vii95.43 (1)O1xii—Fe2—O1xiii100.02 (1)
O1—Fe1—O1i85.87 (1)
Symmetry codes: (i) z, x, y; (ii) x, y, z+1/2; (iii) z, x, y+1/2; (iv) x+1/4, z+1/4, y+1/4; (v) z+1/4, y+1/4, x+1/4; (vi) x+1/4, z1/4, y+1/4; (vii) z+1/4, y1/4, x+1/4; (viii) y, z, x; (ix) x, y, z; (x) z, x, y; (xi) y, z, x; (xii) x+1/2, y, z+1/2; (xiii) x+1/2, y, z.

Experimental details

Crystal data
Chemical formulaPr3Fe5O12
Mr893.98
Crystal system, space groupCubic, Ia3d
Temperature (K)298
a (Å)12.6302 (3)
V3)2014.79 (8)
Z8
Radiation typeSynchrotron, λ = 0.67171 Å
µ (mm1)17.41
Crystal size (mm)0.04 (radius)
Data collection
DiffractometerRigaku AFC four-circle
Absorption correctionFor a sphere
[Transmission coefficients for spheres tabulated in International Tables C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation (Yamauchi et al., 1965)]
Tmin, Tmax0.413, 0.441
No. of measured, independent and
observed [F > 3σ(F)] reflections
9351, 1728, 1728
Rint0.016
(sin θ/λ)max1)1.383
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.021, 1.06
No. of reflections9351
No. of parameters17
No. of restraints?
Δρmax, Δρmin (e Å3)2.52, 3.16

Computer programs: AFC-5, specially designed for PF-BL14A (Rigaku, 1984) and IUANGLE (Tanaka et al., 1994)., RSLC-3 UNICS system (Sakurai & Kobayashi, 1979), RDEDIT (Tanaka, 2008), QNTAO (Tanaka et al., 2008), ATOMS for Windows (Dowty, 2000).

Selected geometric parameters (Å, º) top
Pr1—O12.4241 (1)Fe1—O12.0322 (1)
Pr1—O1i2.5401 (1)Fe2—O1ii1.8745 (1)
O1—Fe1—O1i85.87 (1)O1ii—Fe2—O1iv100.02 (1)
O1ii—Fe2—O1iii114.39 (1)
Symmetry codes: (i) z, x, y; (ii) x+1/2, y, z+1/2; (iii) x+1/4, z1/4, y+1/4; (iv) x+1/2, y, z.
 

Acknowledgements

The authors thank Dr V. J. Fratello for supplying the crystals.

References

First citationBecker, P. J. & Coppens, P. (1975). Acta Cryst. A31, 417–425.  CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationBonnet, M., Delapalme, A., Fuess, H. & Thomas, M. (1975). Acta Cryst. B31, 2233–2240.  CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationDowty, E. (2000). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA.  Google Scholar
First citationFratello, V. J., Brandle, C. D., Slusky, S. E. G., Valentino, A. J., Norelli, M. P. & Wolfe, R. (1986). Cryst. Growth, 75, 281–283.  CrossRef CAS Web of Science Google Scholar
First citationRigaku (1984). AFC-5. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSakurai, T. & Kobayashi, K. (1979). Rep. Inst. Phys. Chem. Res. 55, 69–77.  Google Scholar
First citationTakenaka, Y., Sakakura, T., Tanaka, K. & Kishimoto, S. (2008). Acta Cryst. A64, C566.  CrossRef IUCr Journals Google Scholar
First citationTanaka, K. (2008). RDEDIT. Unpublished.  Google Scholar
First citationTanaka, K., Kumazawa, S., Tsubokawa, M., Maruno, S. & Shirotani, I. (1994). Acta Cryst. A50, 246–252.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationTanaka, K., Makita, R., Funahashi, S., Komori, T. & Zaw Win, (2008). Acta Cryst. A64, 437–449.  Google Scholar
First citationYamauchi, J., Moriguchi, S. & Ichimatsu, S. (1965). Numerical Calculation Method for Computer. Tokyo: Baifūkan.  Google Scholar

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