Trineodymium(III) penta­iron(III) dodeca­oxide, Nd3Fe5O12

Komori, T.; Sakakura, T.; Takenaka, Y.; Tanaka, K.; Okuda, T.

doi:10.1107/S1600536809036794

inorganic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page i72

doi:10.1107/S1600536809036794

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Trineodymium(III) pentairon(III) dodecaoxide, Nd₃Fe₅O₁₂

Takashi Komori,^a ^* Terutoshi Sakakura,^a Yasuyuki Takenaka,^b Kiyoaki Tanaka ^a and Takashi Okuda ^a

^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 3 September 2009; accepted 11 September 2009; online 26 September 2009)

The title compound, Nd₃Fe₅O₁₂ (NdIG), has an iron garnet structure. One of the Fe atoms is coordinated by six O atoms in a slightly distorted octahedral geometry and has $[\overline{3}]$ site symmetry. The other Fe atom is coordinated by four O atoms in a slightly distorted tetrahedral geometry and has $[\overline{4}]$ site symmetry. The FeO₆ octahedron and FeO₄ tetrahedron are linked together by corners. The Nd atom is coordinated by eight O atoms in a distorted dodecahedral geometry and has 222 site symmetry. The O atoms occupy general positions.

Related literature

The title compound is isotypic with the Ia $[\overline{3}]$ d form of Y₃Fe₅O₁₂ (YIG), see: Bonnet et al. (1975 ). For crystal growth from low-temperature liquid-phase epitaxy, see: Fratello et al. (1986 ). X-ray intensities were measured avoiding multiple diffraction, see: Takenaka et al. (2008 ). For details of the full-matrix least-squares program QNTAO, see: Tanaka et al. (2008 ). For the anisotropic extinction refinement, see: Becker & Coppens (1975 ).

Experimental

Crystal data

Nd₃Fe₅O₁₂
M_r = 903.97
Cubic, $[I a \overline 3d ]$
a = 12.6128 (2) Å
V = 2006.48 (6) Å³
Z = 8
Synchrotron radiation
λ = 0.67171 Å
μ = 18.30 mm⁻¹
T = 298 K
0.025 mm (radius)

Data collection

Rigaku AFC four-circle diffractometer
Absorption correction: spherical [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 )] T_min = 0.502, T_max = 0.527
6653 measured reflections
1159 independent reflections
1159 reflections with F > 3σ(F)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.018
S = 1.42
6653 reflections
23 parameters
Δρ_max = 1.61 e Å⁻³
Δρ_min = −1.75 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Nd1—O1	2.41820 (10)
Nd1—O1ⁱ	2.52960 (10)
Fe1—O1	2.03300 (10)
Fe2—O1ⁱⁱ	1.87550 (10)

O1—Fe1—O1ⁱ	85.59 (1)
O1ⁱⁱ—Fe2—O1ⁱⁱⁱ	114.47 (1)
O1ⁱⁱ—Fe2—O1^iv	99.87 (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 Corporation, 1984 ) and IUANGLE (Tanaka et al., 1994 ).; cell refinement: RSLC-3 (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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809036794/br2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809036794/br2118Isup2.hkl

checkCIF report

Comment top

The title compound, Nd₃Fe₅O₁₂ (NdIG), 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 Nd 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 with site symmetry 3. It forms a slightly distorted octahedron. The other Fe atom is coordinated by four oxygen atoms, site symmetry 4. It forms a slightly distorted tetrahedron. FeO₆ octahedron and FeO₄ tetrahedron are linked together by corners. The structure of NdIG is drawn in Fig.1. And displacement ellipsoids of NdO₈ is drawn in Fig.2.

Related literature top

The title compound is isotypic with the Ia3d form of Y₃Fe₅O₁₂ (YIG), see: Bonnet et al. (1975). For crystal growth from low-temperature liquid-phase epitaxy, see: Fratello et al. (1986). X-ray intensities were measured avoiding multiple diffraction, see: Takenaka et al. (2008). For details of the full-matrix least-squares program QNTAO, see: Tanaka et al. (2008). For the anisotropic extinction refinement, see: Becker & Coppens (1975).

Experimental top

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

Computing details top

Data collection: AFC-5, specially designed for PF-BL14A (Rigaku Corporation, 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

	Fig. 1. The structure of Nd₃Fe₅O₁₂. Small red and large green spheres represent O and Nd atoms, respectively. Purple octahedron and blue tetrahedron represent FeO₆ and FeO₄ units, respectively.
	Fig. 2. View of NdO₈ with displacement ellipsoids at the 90% probability level. Green and red ellipsoids represent Nd and O atoms, in Fig.1.

Trineodymium(III) pentairon(III) dodecaoxide top

Crystal data top

Nd₃Fe₅O₁₂	D_x = 5.985 Mg m⁻³
M_r = 903.97	Synchrotron radiation, λ = 0.67171 Å
Cubic, Ia3d	Cell parameters from 24 reflections
Hall symbol: -I 4bd 2c 3	θ = 35.7–42.4°
a = 12.6128 (2) Å	µ = 18.30 mm⁻¹
V = 2006.48 (6) Å³	T = 298 K
Z = 8	Sphere, black
F(000) = 3248	0.03 mm (radius)

Data collection top

Rigaku AFC four-circle diffractometer	1159 independent reflections
Si 111 monochromator	1159 reflections with F > 3σ(F)
Detector resolution: 1.25×1.25 degrees pixels mm^-1	R_int = 0.017
ω/2θ scans	θ_max = 53.9°, θ_min = 3.7°
Absorption correction: for a sphere Transmission coefficients for spheres tabulated in International Tables C (1992\bbr00), Table 6.3.3.3, were interpolated with Lagrange's method (four point interpolation; Yamauchi et al., 1965).	h = −8→30
T_min = 0.502, T_max = 0.527	k = −8→30
6653 measured reflections	l = −8→30

Refinement top

Refinement on F	Primary atom site location: isomorphous structure methods
Least-squares matrix: full	Weighting scheme based on measured s.u.'s
R[F² > 2σ(F²)] = 0.016	(Δ/σ)_max = 0.003
wR(F²) = 0.018	Δρ_max = 1.61 e Å⁻³
S = 1.42	Δρ_min = −1.75 e Å⁻³
6653 reflections	Extinction correction: (B-C type 1 Gaussian anisotropic; Becker & Coppens (1975)
23 parameters	Extinction coefficient: 0.308 (5)

Crystal data top

Nd₃Fe₅O₁₂	Z = 8
M_r = 903.97	Synchrotron radiation, λ = 0.67171 Å
Cubic, Ia3d	µ = 18.30 mm⁻¹
a = 12.6128 (2) Å	T = 298 K
V = 2006.48 (6) Å³	0.03 mm (radius)

Data collection top

Rigaku AFC four-circle diffractometer	1159 independent reflections
Absorption correction: for a sphere Transmission coefficients for spheres tabulated in International Tables C (1992\bbr00), Table 6.3.3.3, were interpolated with Lagrange's method (four point interpolation; Yamauchi et al., 1965).	1159 reflections with F > 3σ(F)
T_min = 0.502, T_max = 0.527	R_int = 0.017
6653 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	23 parameters
wR(F²) = 0.018	Δρ_max = 1.61 e Å⁻³
S = 1.42	Δρ_min = −1.75 e Å⁻³
6653 reflections

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

	x	y	z	U_iso*/U_eq
Nd1	0.125000	0.000000	0.250000	0.00557 (1)
Fe1	0.000000	0.000000	0.000000	0.00501 (1)
Fe2	0.375000	0.000000	0.250000	0.00564 (1)
O1	−0.029295 (2)	0.053092 (2)	0.149342 (2)	0.00762 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.00421 (1)	0.00525 (1)	0.00525 (1)	0	0	0.00121 (1)
Fe1	0.00501 (2)	0.00501 (2)	0.00501 (2)	−0.00024 (2)	−0.00024 (2)	−0.00024 (2)
Fe2	0.00442 (3)	0.00625 (2)	0.00625 (2)	0	0	0
O1	0.00791 (8)	0.00880 (9)	0.00614 (7)	−0.00027 (7)	0.00102 (6)	0.00041 (7)

Geometric parameters (Å, º) top

Nd1—O1	2.4182 (1)	Fe1—O1ⁱ	2.0330 (1)
Nd1—O1ⁱ	2.5296 (1)	Fe1—O1^viii	2.0330 (1)
Nd1—O1ⁱⁱ	2.4182 (1)	Fe1—O1^ix	2.0330 (1)
Nd1—O1ⁱⁱⁱ	2.5296 (1)	Fe1—O1^x	2.0330 (1)
Nd1—O1^iv	2.4182 (1)	Fe1—O1^xi	2.0330 (1)
Nd1—O1^v	2.5296 (1)	Fe2—O1^xii	1.8755 (1)
Nd1—O1^vi	2.4182 (1)	Fe2—O1^iv	1.8755 (1)
Nd1—O1^vii	2.5296 (1)	Fe2—O1^xiii	1.8755 (1)
Fe1—O1	2.0330 (1)	Fe2—O1^vi	1.8755 (1)

O1—Nd1—O1ⁱ	67.83 (1)	O1—Fe1—O1^viii	85.59 (1)
O1—Nd1—O1ⁱⁱ	72.82 (1)	O1—Fe1—O1^ix	180.00
O1—Nd1—O1ⁱⁱⁱ	124.94 (1)	O1—Fe1—O1^x	94.41 (1)
O1—Nd1—O1^iv	110.91 (1)	O1—Fe1—O1^xi	94.41 (1)
O1—Nd1—O1^v	72.97 (1)	O1^xii—Fe2—O1^vi	114.47 (1)
O1—Nd1—O1^vi	159.79 (1)	O1^xii—Fe2—O1^iv	114.47 (1)
O1—Nd1—O1^vii	95.60 (1)	O1^xii—Fe2—O1^xiii	99.87 (1)
O1—Fe1—O1ⁱ	85.59 (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, z−1/4, y+1/4; (vii) −z+1/4, y−1/4, 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 formula	Nd₃Fe₅O₁₂
M_r	903.97
Crystal system, space group	Cubic, Ia3d
Temperature (K)	298
a (Å)	12.6128 (2)
V (Å³)	2006.48 (6)
Z	8
Radiation type	Synchrotron, λ = 0.67171 Å
µ (mm⁻¹)	18.30
Crystal size (mm)	0.03 (radius)

Data collection
Diffractometer	Rigaku AFC four-circle diffractometer
Absorption correction	For a sphere Transmission coefficients for spheres tabulated in International Tables C (1992\bbr00), Table 6.3.3.3, were interpolated with Lagrange's method (four point interpolation; Yamauchi et al., 1965).
T_min, T_max	0.502, 0.527
No. of measured, independent and observed [F > 3σ(F)] reflections	6653, 1159, 1159
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	1.202

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.018, 1.42
No. of reflections	6653
No. of parameters	23
No. of restraints	?
Δρ_max, Δρ_min (e Å⁻³)	1.61, −1.75

Computer programs: AFC-5, specially designed for PF-BL14A (Rigaku Corporation, 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

Nd1—O1	2.4182 (1)	Fe1—O1	2.0330 (1)
Nd1—O1ⁱ	2.5296 (1)	Fe2—O1ⁱⁱ	1.8755 (1)

O1—Fe1—O1ⁱ	85.59 (1)	O1ⁱⁱ—Fe2—O1^iv	99.87 (1)
O1ⁱⁱ—Fe2—O1ⁱⁱⁱ	114.47 (1)

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

Acknowledgements

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

References

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