Filled skutterudite structure of europium ruthenium polyphosphide, EuRu4P12

Kagomiya, I.; Funahashi, S.; Sakakura, T.; Komori, T.; Tanaka, K.

doi:10.1107/S1600536810000589

inorganic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page i6

https://doi.org/10.1107/S1600536810000589

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Filled skutterudite structure of europium ruthenium polyphosphide, EuRu₄P₁₂

Isao Kagomiya,^a ^* Shiro Funahashi,^a Terutoshi Sakakura,^a Takashi Komori ^a and Kiyoaki Tanaka ^a

^aGraduate School of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Japan
^*Correspondence e-mail: kagomiya@nitech.ac.jp

(Received 11 December 2009; accepted 5 January 2010; online 13 January 2010)

The crystal structure of EuRu₄P₁₂ is isotypic with filled skutterudite structures of rare earth transition metal polyphosphides: RFe₄P₁₂ (R = Ce, Pr, Nd, Sm and Eu), RRu₄P₁₂ (R = La, Ce, Pr and Nd) and ROs₄P₁₂ (R = La, Ce, Pr and Nd). The Ru cation is coordinated by six P anions in a distorted octahedral manner. The partially occupied Eu position (site occupancy 0.97) is enclosed by a cage formed by the corner-shared framework of the eight RuP₆ octahedra.

Related literature

The title compound is isotypic with the Im $[\overline{3}]$ form of LaFe₄P₁₂, see: Jeitschko & Braun (1977 ). For the single-crystal preparation and magnetic and electrical properties of EuRu₄P₁₂, see: Sekine et al. (2000 ). For hyperfine interaction in EuRu₄P₁₂, see: Grandjean et al. (1983 ); Indoh et al. (2002 ). For the method used to avoid multiple diffraction, see: Takenaka et al. (2008 ).

Experimental

Crystal data

Eu_0.97Ru₄P₁₂
M_r = 923.37
Cubic, $[I m \overline 3]$
a = 8.04163 (10) Å
V = 520.04 (1) Å³
Z = 2
Mo Kα radiation
μ = 13.37 mm⁻¹
T = 100 K
0.04 mm (radius)

Data collection

MacScience M06XHF22 four-circle diffractometer
Absorption correction: for a sphere [transmission coefficients for spheres tabulated in International Tables Vol. C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation; Yamauchi et al., 1965 )] T_min = 0.486, T_max = 0.526
1564 measured reflections
769 independent reflections
625 reflections with F > 3σ(F)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.024
S = 1.54
1304 reflections
30 parameters
Δρ_max = 2.08 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Selected bond lengths (Å)

Eu1—P1	3.1112 (3)
Eu1—Ru1	3.4821 (1)
Ru1—P1	2.3558 (1)
P1—P1ⁱ	2.3061 (1)
P1—P1ⁱⁱ	3.0829 (1)
Symmetry codes: (i) -x, y, -z; (ii) $[-z+{\script{1\over 2}}, x+{\script{1\over 2}}, -y+{\script{1\over 2}}]$ .

Data collection: MXCSYS (MacScience, 1995 ) 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; molecular graphics: ATOMS for Windows (Dowty, 2000 ); software used to prepare material for publication: RDEDIT.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000589/br2130sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000589/br2130Isup2.hkl

checkCIF report

Related literature top

The title compound is isotypic with the Im3 form of LaFe₄P₁₂ (Jeitschko & Braun, 1977). For the single-crystal preparation and magnetic and electrical properties of LaRu₄P₁₂, see: Sekine et al. (2000). For hyperfine interaction in LaRu₄P₁₂, see: Grandjean et al. (1983); Indoh et al. (2002). For extinction correction method, see: Becker & Coppens (1975). For the method used to avoid multiple diffraction, see: Takenaka et al. (2008). [Please check added citations]

Structure description top

Computing details top

Data collection: MXCSYS (MacScience, 1995) 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

	Fig. 1. The structure of EuRu₄P₁₂ at 100 K. Small yellow and large red spheres, respectively, represent P and Eu atoms. Green distorted octahedron represent RuO₆ units.
	Fig. 2. Bonding of Ru₄ and P₁₂ around an Eu ion with displacement ellipsoids at the 90% probability level. Red, blue and yellow ellipsoids represent Eu, Ru and P atoms, in Fig. 1.

Europium ruthenium polyphosphide top

Crystal data top

Eu_0.97Ru₄P₁₂	D_x = 5.925 Mg m⁻³
M_r = 923.37	Mo Kα radiation, λ = 0.71073 Å
Cubic, Im3	Cell parameters from 37 reflections
Hall symbol: -I 2 2 3	θ = 36.0–37.7°
a = 8.04163 (10) Å	µ = 13.37 mm⁻¹
V = 520.04 (1) Å³	T = 100 K
Z = 2	Sphere, black
F(000) = 828.4	0.04 mm (radius)

Data collection top

MacScience M06XHF22 four-circle diffractometer	769 independent reflections
Radiation source: fine-focus rotating anode	625 reflections with F > 3σ(F)
Graphite monochromator	R_int = 0.016
Detector resolution: 1.25 x 1.25° pixels mm^-1	θ_max = 74.2°, θ_min = 3.6°
ω/2θ scans	h = −18→20
Absorption correction: for a sphere [transmission coefficients for spheres tabulated in International Tables Vol. C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation; Yamauchi et al., 1965)]	k = −21→21
T_min = 0.486, T_max = 0.526	l = −18→20
1564 measured reflections

Refinement top

Refinement on F	Weighting scheme based on measured s.u.'s
Least-squares matrix: full	(Δ/σ)_max = 0.018
R[F² > 2σ(F²)] = 0.020	Δρ_max = 2.08 e Å⁻³
wR(F²) = 0.024	Δρ_min = −1.14 e Å⁻³
S = 1.54	Extinction correction: B–C type 1 Gaussian isotropic (Becker & Coppens, 1975)
1304 reflections	Extinction coefficient: 0.068 (6)
30 parameters

Crystal data top

Eu_0.97Ru₄P₁₂	Z = 2
M_r = 923.37	Mo Kα radiation
Cubic, Im3	µ = 13.37 mm⁻¹
a = 8.04163 (10) Å	T = 100 K
V = 520.04 (1) Å³	0.04 mm (radius)

Data collection top

MacScience M06XHF22 four-circle diffractometer	769 independent reflections
Absorption correction: for a sphere [transmission coefficients for spheres tabulated in International Tables Vol. C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation; Yamauchi et al., 1965)]	625 reflections with F > 3σ(F)
T_min = 0.486, T_max = 0.526	R_int = 0.016
1564 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	30 parameters
wR(F²) = 0.024	Δρ_max = 2.08 e Å⁻³
S = 1.54	Δρ_min = −1.14 e Å⁻³
1304 reflections

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Eu1	0.000000	0.000000	0.000000	0.00270 (2)	0.970 (4)
Ru1	0.250000	0.250000	0.250000	0.001840 (15)
P1	0.000000	0.359329	0.143386	0.00283 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1	0.00271 (3)	0.00271 (3)	0.00271 (3)	0	0	0
Ru1	0.00185 (3)	0.00185 (3)	0.00185 (3)	0.000108 (17)	0.000108 (17)	0.000108 (17)
P1	0.00268 (10)	0.00301 (10)	0.00285 (10)	0	0	−0.00009 (7)

Geometric parameters (Å, º) top

Eu1—P1	3.1112 (3)	Ru1—P1ⁱ	2.3558 (1)
Eu1—Ru1	3.4821 (1)	P1—P1ⁱⁱ	2.3061 (1)
Ru1—P1	2.3558 (1)	P1—P1ⁱ	3.0829 (1)

Eu1—P1—Ru1	77.78	Ru1—P1—P1ⁱ	49.13
Eu1—P1—P1ⁱⁱ	68.25	P1—Ru1—P1ⁱ	81.74
Eu1—P1—P1ⁱ	109.77	P1ⁱⁱ—P1—P1ⁱ	89.59
Ru1—P1—P1ⁱⁱ	111.34

Symmetry codes: (i) −z+1/2, x+1/2, −y+1/2; (ii) −x, y, −z.

Experimental details

Crystal data
Chemical formula	Eu_0.97Ru₄P₁₂
M_r	923.37
Crystal system, space group	Cubic, Im3
Temperature (K)	100
a (Å)	8.04163 (10)
V (Å³)	520.04 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	13.37
Crystal size (mm)	0.04 (radius)

Data collection
Diffractometer	MacScience M06XHF22 four-circle
Absorption correction	For a sphere [transmission coefficients for spheres tabulated in International Tables Vol. C (1992), Table 6.3.3.3, were interpolated with Lagrange's method (four-point interpolation; Yamauchi et al., 1965)]
T_min, T_max	0.486, 0.526
No. of measured, independent and observed [F > 3σ(F)] reflections	1564, 769, 625
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	1.354

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.024, 1.54
No. of reflections	1304
No. of parameters	30
No. of restraints	?
Δρ_max, Δρ_min (e Å⁻³)	2.08, −1.14

Computer programs: MXCSYS (MacScience, 1995) 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 bond lengths (Å) top

Eu1—P1	3.1112 (3)	P1—P1ⁱ	2.3061 (1)
Eu1—Ru1	3.4821 (1)	P1—P1ⁱⁱ	3.0829 (1)
Ru1—P1	2.3558 (1)

Symmetry codes: (i) −x, y, −z; (ii) −z+1/2, x+1/2, −y+1/2.

Acknowledgements

Part of this study was supported by the International Training Programme (ITP) from the Japan Society for the Promotion of Science (JSPS).

References

Dowty, E. (2000). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Grandjean, F., Gerard, A., Hodges, J., Braun, D. J. & Jeitschko, W. (1983). Hyperfine Interact. 15–16, 765–765. CrossRef Web of Science Google Scholar
Indoh, K., Onodera, H., Sekine, C., Shirotani, I. & Yamaguchi, Y. (2002). J. Phys. Soc. Jpn, 71 (Suppl.), 243–245. Google Scholar
Jeitschko, W. & Braun, D. (1977). Acta Cryst. B33, 3401–3406. CrossRef CAS IUCr Journals Web of Science Google Scholar
MacScience (1995). MXCSYS. Bruker AXS Inc., Tsukuba, Ibaraki, Japan. Google Scholar
Sakurai, T. & Kobayashi, K. (1979). Rikagaku Kenkyusho Hokoku (Rep. Inst. Phys. Chem. Res.), 55, 69–77. Google Scholar
Sekine, C., Inoue, M., Inaba, T. & Shirotani, I. (2000). Physica B, 281–282, 308–310. Web of Science CrossRef Google Scholar
Takenaka, Y., Sakakura, T., Tanaka, K. & Kishimoto, S. (2008). Acta Cryst. A64, C566. CrossRef IUCr Journals Google Scholar
Tanaka, K. (2008). RDEDIT. Unpublished. Google Scholar
Tanaka, K., Kumazawa, S., Tsubokawa, M., Maruno, S. & Shirotani, I. (1994). Acta Cryst. A50, 246–252. CrossRef CAS Web of Science IUCr Journals Google Scholar
Tanaka, K., Makita, R., Funahashi, S., Komori, T. & Zaw Win (2008). Acta Cryst. A64, 437–449. Web of Science CrossRef IUCr Journals Google Scholar
Yamauchi, J., Moriguchi, S. & Ichimatsu, S. (1965). Numerical Calculation Method for Computer. Tokyo: Baifukan. Google Scholar