R-Ferrite-type barium cobalt stannate, BaCo2Sn4O11

Yamane, H.; Ono, T.; Yamada, T.

doi:10.1107/S1600536808030572

inorganic compounds

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Volume 64| Part 10| October 2008| Page i71

doi:10.1107/S1600536808030572

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R-Ferrite-type barium cobalt stannate, BaCo₂Sn₄O₁₁

Hisanori Yamane,^a ^* Takeshi Ono ^b and Takahiro Yamada ^a

^aInstitute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aobaku, Sendai 980-8577, Japan, and ^bCenter for Interdisciplinary Research, Tohoku University, Aramaki Aza-Aoba, Aobaku, Sendai 980-8578, Japan
^*Correspondence e-mail: yamane@tagen.tohoku.ac.jp

(Received 10 September 2008; accepted 23 September 2008; online 27 September 2008)

BaCo₂Sn₄O₁₁ is isotypic with R-ferrite, BaTi₂Fe₄O₁₁. The Co atoms fully occupy trigonal–bipyramidal sites ( $[\overline 6 m2]$ ) and are disordered with Sn atoms in octahedral sites (.2/m symmetry), as represented in the formula BaCoSn₂(Co_0.34Sn_0.66)₄O₁₁. Ba atoms are situated in a 12-fold coordinated site ( $[\=6m2]$ symmetry).

Related literature

For reports on R-ferrite structures, BaTi₂Fe₄O₁₁, see: Haberey & Velicescu (1974 ); Obradors et al. (1983 ); Cadée & Ijdo (1984 ); Sosnowska et al. (1996 ). For reports on R-ferrite structure with other compositions, see: Cadée & Ijdo (1984); Kanke et al. (1992 ); Martínez et al. (1993 ); Foo et al. (2006 ). Sosnowska et al. (1996). For Ba₃SnCo₁₀O₂₀, another phase in the Ba–Co–Sn–O system, see: Sonne & Müller-Buschbaum (1993 ).

Experimental

Crystal data

BaCo₂Sn₄O₁₁
M_r = 905.96
Hexagonal, P 6₃ /m m c
a = 6.0880 (2) Å
c = 14.1049 (6) Å
V = 452.74 (3) Å³
Z = 2
Mo Kα radiation
μ = 18.76 mm⁻¹
T = 293 (2) K
0.06 × 0.04 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.524, T_max = 0.801
3945 measured reflections
230 independent reflections
215 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.041
S = 1.13
230 reflections
28 parameters
1 restraint
Δρ_max = 0.73 e Å⁻³
Δρ_min = −1.81 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ba1—O1	2.918 (3)
Ba1—O2	3.051 (6)
Sn1—O3	2.068 (3)
Sn2—O1	2.040 (3)
Sn2—O2	2.127 (3)
Co2—O2	1.969 (4)
Co2—O3	2.437 (6)

O3—Sn1—O3^iv	180
O3—Sn1—O1^v	94.67 (11)
O3^iv—Sn1—O1^v	85.33 (11)
O1ⁱⁱ—Sn2—O1	101.38 (11)
O1ⁱⁱ—Sn2—O2	163.32 (12)
O1—Sn2—O2	89.07 (8)
O2^v—Co2—O2ⁱⁱⁱ	120
O2^v—Co2—O3	90
O3—Co2—O3ⁱ	180
Symmetry codes: (i) $[x, y, -z+{\script{1\over 2}}]$ ; (ii) -y, x-y, z; (iii) -x+y+1, -x+1, z; (iv) -x+1, -y, -z; (v) -y+1, x-y, z.

Data collection: PROCESS-AUTO (Rigaku/MSC, 2005 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: VESTA (Momma & Izumi, 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030572/mg2057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030572/mg2057Isup2.hkl

checkCIF report

Comment top

BaTi₂Fe₄O₁₁ crystallizes in a six-layer hexagonal structure (R-type, space group P6₃/mmc) (Haberey & Velicescu, 1974; Obradors et al., 1983; Cadée & Ijdo, 1984; Sosnowska et al., 1996) that is adopted by many multinary iron oxides and transition metal oxides exhibiting complex magnetic behavior (Cadée & Ijdo, 1984; Kanke et al., 1992; Martínez et al., 1993; Foo et al., 2006). BaCo₂Sn₄O₁₁ has been indicated to be the end member in a solid solution series BaFe_4-2xSn₂₊_xCo_xO₁₁, where the distribution of Fe, Co, and Sn cations was determined by combined powder X-ray and neutron diffraction (Martínez et al., 1993). However, no crystallographic information (cell parameters and atomic positions) was reported except for the Co and Sn site occupancies in BaCo₂Sn₄O₁₁. The present paper reports the detailed structure of BaCo₂Sn₄O₁₁ determined by single-crystal X-ray diffraction.

The structure of BaCo₂Sn₄O₁₁ can be described in terms of cation-centered oxygen polyhedra (Fig. 1). The disorder within the octahedral 6g site (occupancies of 0.664 (7) Sn1 and 0.336 (7) Co1) agrees with results reported by Martínez et al. (1993) (0.7 Sn1 and 0.3 Co1). These Sn1/Co1-centered octahedra share edges to form layers perpendicular to the c axis. Located between these layers are pillars of two face-sharing Sn2-centered octahedra stacked along the c axis. The trigonal bipyramidal 2d site is occupied exclusively by Co2 atoms and exhibits a displacement ellipsoid elongated along the c direction (Fig. 2). Ba atoms are situated in a 12-fold coordination site (2c).

Related literature top

For R-ferrite structures, see: Haberey & Velicescu (1974); Obradors et al. (1983). For BaTi₂Fe₄O₁₁, see: Cadée & Ijdo (1984); Sosnowska et al. (1996). For Ba₃SnCo₁₀O₂₀, another phase in the Ba–Co–Sn–O system, see: Sonne & Müller-Buschbaum (1993). For further related literature, see: Martínez et al. (1993); Kanke et al. (1992); Foo et al. (2006). [Please check re-arranged text]

Experimental top

A mixture of BaCO₃ (99.99%, Wako Pure Chemical Ind.), Co₃O₄ (99.95%, Kanto Chemical Co. Inc.), and SnO₂ (99.9%, Rare Metallic Co. Ltd.) powders in a molar ratio of Ba:Co:Sn = 1:2:4 was ground together and pressed into a pellet. The pellet was placed on a platinum plate and heated in air for 1 h at 1473 K or 1823 K in an electric furnace. The pellet was melted at 1823 K and green transparent single crystals of BaCo₂Sn₄O₁₁ were obtained. The chemical analysis of the polycrystalline single phase BaCo₂Sn₄O₁₁ prepared at 1473 K was carried out by inductively coupled plasma (ICP) emission spectrometry for Ba, Co and Sn, and by the He carrier melting-infrared absorption method (TC-436, LECO) for O. The results of the chemical analysis (Ba 14.9 (5), Co 13.8 (5), Sn 52.9 (8), and O 19.1 (8) wt%) agreed with the ideal contents (Ba 15.2, Co 13.4, Sn 51.9, O 19.5 wt%).

The magnetic susceptibility of BaCo₂Sn₄O₁₁ was measured with a superconducting quantum interference device (SQUID) magnetometer (Quantum Design, MPMS XL) from 5 to 400 K under a magnetic field of 5 kOe. The polycrystalline sample followed the Curie–Weiss law above the Neel temperature (T_N). The T_N of 7 K, the Weiss temperature (Θ) of -42 K, and the magnetic moment (µ_eff) of 4.7 µ_B per Co measured for the sample were consistent with the values reported by Martínez et al. (1993) (T_N = 9 K, Θ = -44 K, µ_eff = 4.4 µ_B).

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2005); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2005); data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: VESTA (Momma & Izumi, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Structure of BaCo₂Sn₄O₁₁ in terms of cation-centered oxygen polyhedra.
	Fig. 2. The O-atom coordination around the cation sites of BaCo₂Sn₄O₁₁ (symmetry codes as in Table 1). Displacement ellipsoids are drawn at the 99% probability level.

barium cobalt stannate top

Crystal data top

BaCo₂Sn₄O₁₁	D_x = 6.646 Mg m⁻³
M_r = 905.96	Mo Kα radiation, λ = 0.71075 Å
Hexagonal, P6₃/mmc	Cell parameters from 3536 reflections
Hall symbol: -P 6c 2c	θ = 7.7–54.7°
a = 6.0880 (2) Å	µ = 18.76 mm⁻¹
c = 14.1049 (6) Å	T = 293 K
V = 452.74 (3) Å³	Block, green
Z = 2	0.06 × 0.04 × 0.03 mm
F(000) = 796

Data collection top

Rigaku R-AXIS RAPID diffractometer	230 independent reflections
Radiation source: fine-focus sealed tube	215 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.9°
ω scans	h = −7→7
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −7→7
T_min = 0.524, T_max = 0.801	l = −18→18
3945 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	w = 1/[σ²(F_o²) + 0.8941P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.041	(Δ/σ)_max < 0.001
S = 1.13	Δρ_max = 0.73 e Å⁻³
230 reflections	Δρ_min = −1.81 e Å⁻³
28 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0041 (4)

Crystal data top

BaCo₂Sn₄O₁₁	Z = 2
M_r = 905.96	Mo Kα radiation
Hexagonal, P6₃/mmc	µ = 18.76 mm⁻¹
a = 6.0880 (2) Å	T = 293 K
c = 14.1049 (6) Å	0.06 × 0.04 × 0.03 mm
V = 452.74 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	230 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	215 reflections with I > 2σ(I)
T_min = 0.524, T_max = 0.801	R_int = 0.072
3945 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	28 parameters
wR(F²) = 0.041	1 restraint
S = 1.13	Δρ_max = 0.73 e Å⁻³
230 reflections	Δρ_min = −1.81 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba1	0.3333	0.6667	0.2500	0.0147 (2)
Sn1	0.5000	0.0000	0.0000	0.0112 (3)	0.664 (7)
Co1	0.5000	0.0000	0.0000	0.0112 (3)	0.336 (7)
Sn2	0.0000	0.0000	0.14643 (4)	0.0096 (2)
Co2	0.6667	0.3333	0.2500	0.0203 (4)
O1	0.1728 (3)	0.3456 (5)	0.0815 (2)	0.0118 (7)
O2	0.2933 (8)	0.1466 (4)	0.2500	0.0129 (10)
O3	0.6667	0.3333	0.0772 (4)	0.0136 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.0169 (3)	0.0169 (3)	0.0103 (4)	0.00844 (15)	0.000	0.000
Sn1	0.0139 (4)	0.0110 (4)	0.0076 (4)	0.0055 (2)	0.00013 (10)	0.0003 (2)
Co1	0.0139 (4)	0.0110 (4)	0.0076 (4)	0.0055 (2)	0.00013 (10)	0.0003 (2)
Sn2	0.0113 (3)	0.0113 (3)	0.0062 (3)	0.00563 (14)	0.000	0.000
Co2	0.0086 (5)	0.0086 (5)	0.0436 (13)	0.0043 (3)	0.000	0.000
O1	0.0139 (12)	0.0132 (17)	0.0080 (17)	0.0066 (8)	0.0015 (6)	0.0030 (13)
O2	0.010 (2)	0.0174 (18)	0.009 (2)	0.0051 (11)	0.000	0.000
O3	0.0159 (18)	0.0159 (18)	0.009 (3)	0.0080 (9)	0.000	0.000

Geometric parameters (Å, º) top

Ba1—O1ⁱ	2.918 (3)	Sn2—O2^xii	2.127 (3)
Ba1—O1ⁱⁱ	2.918 (3)	Sn2—Sn2^v	2.9217 (11)
Ba1—O1ⁱⁱⁱ	2.918 (3)	Sn2—O3^xvi	3.6479 (15)
Ba1—O1	2.918 (3)	Sn2—O3^xvii	3.6479 (15)
Ba1—O1^iv	2.918 (3)	Sn2—O3	3.6479 (15)
Ba1—O1^v	2.918 (3)	Sn2—Ba1^xviii	3.8064 (2)
Ba1—O2ⁱⁱ	3.051 (6)	Sn2—Co2^xvi	3.8064 (2)
Ba1—O2^vi	3.051 (6)	Co2—O2^x	1.969 (4)
Ba1—O2^vii	3.051 (6)	Co2—O2^viii	1.969 (4)
Ba1—O2^iv	3.051 (6)	Co2—O2	1.969 (4)
Ba1—O2	3.051 (6)	Co2—O3	2.437 (6)
Ba1—O2^viii	3.051 (6)	Co2—O3^v	2.437 (6)
Sn1—O3	2.068 (3)	Co2—Ba1^xix	3.5149 (1)
Sn1—O3^ix	2.068 (3)	O1—Co1^viii	2.074 (2)
Sn1—O1^x	2.074 (2)	O1—Sn1^viii	2.074 (2)
Sn1—O1^xi	2.074 (2)	O1—Co1^vi	2.074 (2)
Sn1—O1^xii	2.074 (2)	O1—Sn1^vi	2.074 (2)
Sn1—O1^xiii	2.074 (2)	O1—O3^xx	2.806 (5)
Sn1—Sn1^x	3.0440 (1)	O1—O3	3.045 (2)
Sn1—Sn1^xiv	3.0440 (1)	O1—O3^xvi	3.045 (2)
Sn1—Co1^x	3.0440 (1)	O1—Co2^xvi	3.8627 (19)
Sn1—Co1^xiv	3.0440 (1)	O2—Sn2^v	2.127 (3)
Sn1—Sn1^xv	3.0440 (1)	O2—Ba1^xviii	3.052 (3)
Sn1—Co1^xv	3.0440 (1)	O2—O3^v	3.133 (5)
Sn2—O1^vi	2.040 (3)	O2—O3	3.133 (5)
Sn2—O1	2.040 (3)	O3—Co1^x	2.068 (3)
Sn2—O1^xii	2.040 (3)	O3—Sn1^x	2.068 (3)
Sn2—O2	2.127 (3)	O3—Co1^viii	2.068 (3)
Sn2—O2^vi	2.127 (3)	O3—Sn1^viii	2.068 (3)

O1ⁱ—Ba1—O1ⁱⁱ	109.09 (11)	O2—Sn2—Sn2^v	46.63 (8)
O1ⁱ—Ba1—O1ⁱⁱⁱ	60.31 (9)	O2^vi—Sn2—Sn2^v	46.63 (8)
O1ⁱⁱ—Ba1—O1ⁱⁱⁱ	146.28 (5)	O2^xii—Sn2—Sn2^v	46.63 (8)
O1ⁱ—Ba1—O1	146.28 (5)	O1^vi—Sn2—O3^xvi	56.59 (3)
O1ⁱⁱ—Ba1—O1	60.31 (9)	O1—Sn2—O3^xvi	56.59 (3)
O1ⁱⁱⁱ—Ba1—O1	146.28 (5)	O1^xii—Sn2—O3^xvi	137.79 (12)
O1ⁱ—Ba1—O1^iv	146.28 (5)	O2—Sn2—O3^xvi	122.27 (6)
O1ⁱⁱ—Ba1—O1^iv	60.31 (9)	O2^vi—Sn2—O3^xvi	58.89 (11)
O1ⁱⁱⁱ—Ba1—O1^iv	109.09 (12)	O2^xii—Sn2—O3^xvi	122.27 (6)
O1—Ba1—O1^iv	60.31 (9)	Sn2^v—Sn2—O3^xvi	105.52 (8)
O1ⁱ—Ba1—O1^v	60.31 (9)	O1^vi—Sn2—O3^xvii	56.59 (3)
O1ⁱⁱ—Ba1—O1^v	146.28 (5)	O1—Sn2—O3^xvii	137.79 (12)
O1ⁱⁱⁱ—Ba1—O1^v	60.31 (9)	O1^xii—Sn2—O3^xvii	56.59 (3)
O1—Ba1—O1^v	109.09 (11)	O2—Sn2—O3^xvii	122.27 (6)
O1^iv—Ba1—O1^v	146.28 (5)	O2^vi—Sn2—O3^xvii	122.27 (6)
O1ⁱ—Ba1—O2ⁱⁱ	58.59 (5)	O2^xii—Sn2—O3^xvii	58.89 (11)
O1ⁱⁱ—Ba1—O2ⁱⁱ	58.59 (5)	Sn2^v—Sn2—O3^xvii	105.52 (8)
O1ⁱⁱⁱ—Ba1—O2ⁱⁱ	118.76 (5)	O3^xvi—Sn2—O3^xvii	113.12 (7)
O1—Ba1—O2ⁱⁱ	92.30 (4)	O1^vi—Sn2—O3	137.79 (12)
O1^iv—Ba1—O2ⁱⁱ	118.76 (5)	O1—Sn2—O3	56.59 (3)
O1^v—Ba1—O2ⁱⁱ	92.30 (5)	O1^xii—Sn2—O3	56.59 (3)
O1ⁱ—Ba1—O2^vi	92.30 (4)	O2—Sn2—O3	58.89 (11)
O1ⁱⁱ—Ba1—O2^vi	92.30 (4)	O2^vi—Sn2—O3	122.27 (6)
O1ⁱⁱⁱ—Ba1—O2^vi	118.76 (5)	O2^xii—Sn2—O3	122.27 (6)
O1—Ba1—O2^vi	58.59 (5)	Sn2^v—Sn2—O3	105.52 (8)
O1^iv—Ba1—O2^vi	118.76 (5)	O3^xvi—Sn2—O3	113.12 (7)
O1^v—Ba1—O2^vi	58.59 (5)	O3^xvii—Sn2—O3	113.12 (7)
O2ⁱⁱ—Ba1—O2^vi	67.94 (15)	O1^vi—Sn2—Ba1^xviii	125.796 (15)
O1ⁱ—Ba1—O2^vii	58.59 (5)	O1—Sn2—Ba1^xviii	125.796 (15)
O1ⁱⁱ—Ba1—O2^vii	58.59 (5)	O1^xii—Sn2—Ba1^xviii	49.26 (9)
O1ⁱⁱⁱ—Ba1—O2^vii	92.30 (4)	O2—Sn2—Ba1^xviii	53.189 (6)
O1—Ba1—O2^vii	118.76 (5)	O2^vi—Sn2—Ba1^xviii	114.06 (8)
O1^iv—Ba1—O2^vii	92.30 (4)	O2^xii—Sn2—Ba1^xviii	53.189 (6)
O1^v—Ba1—O2^vii	118.76 (5)	Sn2^v—Sn2—Ba1^xviii	67.432 (8)
O2ⁱⁱ—Ba1—O2^vii	52.06 (15)	O3^xvi—Sn2—Ba1^xviii	172.95 (8)
O2^vi—Ba1—O2^vii	120.000 (1)	O3^xvii—Sn2—Ba1^xviii	69.99 (4)
O1ⁱ—Ba1—O2^iv	92.30 (4)	O3—Sn2—Ba1^xviii	69.99 (4)
O1ⁱⁱ—Ba1—O2^iv	92.30 (4)	O1^vi—Sn2—Co2^xvi	76.11 (5)
O1ⁱⁱⁱ—Ba1—O2^iv	58.59 (5)	O1—Sn2—Co2^xvi	76.11 (5)
O1—Ba1—O2^iv	118.76 (5)	O1^xii—Sn2—Co2^xvi	175.88 (9)
O1^iv—Ba1—O2^iv	58.59 (5)	O2—Sn2—Co2^xvi	94.13 (5)
O1^v—Ba1—O2^iv	118.76 (5)	O2^vi—Sn2—Co2^xvi	20.80 (8)
O2ⁱⁱ—Ba1—O2^iv	120.0	O2^xii—Sn2—Co2^xvi	94.13 (5)
O2^vi—Ba1—O2^iv	172.06 (15)	Sn2^v—Sn2—Co2^xvi	67.432 (8)
O2^vii—Ba1—O2^iv	67.94 (15)	O3^xvi—Sn2—Co2^xvi	38.09 (8)
O1ⁱ—Ba1—O2	118.76 (5)	O3^xvii—Sn2—Co2^xvi	123.20 (2)
O1ⁱⁱ—Ba1—O2	118.76 (5)	O3—Sn2—Co2^xvi	123.20 (2)
O1ⁱⁱⁱ—Ba1—O2	92.30 (4)	Ba1^xviii—Sn2—Co2^xvi	134.863 (15)
O1—Ba1—O2	58.59 (5)	O2^x—Co2—O2^viii	120.000 (1)
O1^iv—Ba1—O2	92.30 (4)	O2^x—Co2—O2	120.0
O1^v—Ba1—O2	58.59 (5)	O2^viii—Co2—O2	120.0
O2ⁱⁱ—Ba1—O2	120.0	O2^x—Co2—O3	90.0
O2^vi—Ba1—O2	52.06 (15)	O2^viii—Co2—O3	90.000 (1)
O2^vii—Ba1—O2	172.06 (15)	O2—Co2—O3	90.0
O2^iv—Ba1—O2	120.0	O2^x—Co2—O3^v	90.0
O1ⁱ—Ba1—O2^viii	118.76 (5)	O2^viii—Co2—O3^v	90.0
O1ⁱⁱ—Ba1—O2^viii	118.76 (5)	O2—Co2—O3^v	90.0
O1ⁱⁱⁱ—Ba1—O2^viii	58.59 (5)	O3—Co2—O3^v	180.0
O1—Ba1—O2^viii	92.30 (4)	O2^x—Co2—Ba1^xix	60.0
O1^iv—Ba1—O2^viii	58.59 (5)	O2^viii—Co2—Ba1^xix	60.0
O1^v—Ba1—O2^viii	92.30 (4)	O2—Co2—Ba1^xix	180.0
O2ⁱⁱ—Ba1—O2^viii	172.06 (15)	O3—Co2—Ba1^xix	90.0
O2^vi—Ba1—O2^viii	120.0	O3^v—Co2—Ba1^xix	90.0
O2^vii—Ba1—O2^viii	120.0	Sn2—O1—Co1^viii	126.84 (8)
O2^iv—Ba1—O2^viii	52.06 (15)	Sn2—O1—Sn1^viii	126.84 (8)
O2—Ba1—O2^viii	67.94 (15)	Co1^viii—O1—Sn1^viii	0.0
O3—Sn1—O3^ix	180.0 (3)	Sn2—O1—Co1^vi	126.84 (8)
O3—Sn1—O1^x	94.67 (11)	Co1^viii—O1—Co1^vi	94.45 (12)
O3^ix—Sn1—O1^x	85.33 (11)	Sn1^viii—O1—Co1^vi	94.45 (12)
O3—Sn1—O1^xi	85.33 (11)	Sn2—O1—Sn1^vi	126.84 (8)
O3^ix—Sn1—O1^xi	94.67 (11)	Co1^viii—O1—Sn1^vi	94.45 (12)
O1^x—Sn1—O1^xi	180.00 (14)	Sn1^viii—O1—Sn1^vi	94.45 (12)
O3—Sn1—O1^xii	94.67 (11)	Co1^vi—O1—Sn1^vi	0.0
O3^ix—Sn1—O1^xii	85.33 (11)	Sn2—O1—O3^xx	153.78 (16)
O1^x—Sn1—O1^xii	89.97 (16)	Co1^viii—O1—O3^xx	47.25 (6)
O1^xi—Sn1—O1^xii	90.03 (16)	Sn1^viii—O1—O3^xx	47.25 (6)
O3—Sn1—O1^xiii	85.33 (11)	Co1^vi—O1—O3^xx	47.25 (6)
O3^ix—Sn1—O1^xiii	94.67 (11)	Sn1^vi—O1—O3^xx	47.25 (6)
O1^x—Sn1—O1^xiii	90.03 (16)	Sn2—O1—Ba1	98.77 (12)
O1^xi—Sn1—O1^xiii	89.97 (16)	Co1^viii—O1—Ba1	102.93 (9)
O1^xii—Sn1—O1^xiii	180.00 (14)	Sn1^viii—O1—Ba1	102.93 (9)
O3—Sn1—Sn1^x	42.60 (9)	Co1^vi—O1—Ba1	102.93 (9)
O3^ix—Sn1—Sn1^x	137.40 (9)	Sn1^vi—O1—Ba1	102.93 (9)
O1^x—Sn1—Sn1^x	91.55 (7)	O3^xx—O1—Ba1	107.45 (11)
O1^xi—Sn1—Sn1^x	88.45 (7)	Sn2—O1—O3	89.42 (7)
O1^xii—Sn1—Sn1^x	137.22 (6)	Co1^viii—O1—O3	42.59 (8)
O1^xiii—Sn1—Sn1^x	42.78 (6)	Sn1^viii—O1—O3	42.59 (8)
O3—Sn1—Sn1^xiv	137.40 (9)	Co1^vi—O1—O3	136.98 (15)
O3^ix—Sn1—Sn1^xiv	42.60 (9)	Sn1^vi—O1—O3	136.98 (15)
O1^x—Sn1—Sn1^xiv	88.45 (7)	O3^xx—O1—O3	89.84 (10)
O1^xi—Sn1—Sn1^xiv	91.55 (7)	Ba1—O1—O3	91.63 (10)
O1^xii—Sn1—Sn1^xiv	42.78 (6)	Sn2—O1—O3^xvi	89.42 (7)
O1^xiii—Sn1—Sn1^xiv	137.22 (6)	Co1^viii—O1—O3^xvi	136.98 (15)
Sn1^x—Sn1—Sn1^xiv	180.0	Sn1^viii—O1—O3^xvi	136.98 (15)
O3—Sn1—Co1^x	42.60 (9)	Co1^vi—O1—O3^xvi	42.59 (8)
O3^ix—Sn1—Co1^x	137.40 (9)	Sn1^vi—O1—O3^xvi	42.59 (8)
O1^x—Sn1—Co1^x	91.55 (7)	O3^xx—O1—O3^xvi	89.84 (10)
O1^xi—Sn1—Co1^x	88.45 (7)	Ba1—O1—O3^xvi	91.63 (10)
O1^xii—Sn1—Co1^x	137.22 (6)	O3—O1—O3^xvi	176.68 (18)
O1^xiii—Sn1—Co1^x	42.78 (6)	Sn2—O1—Co2	73.06 (6)
Sn1^x—Sn1—Co1^x	0.0	Co1^viii—O1—Co2	76.66 (3)
Sn1^xiv—Sn1—Co1^x	180.0	Sn1^viii—O1—Co2	76.66 (3)
O3—Sn1—Co1^xiv	137.40 (9)	Co1^vi—O1—Co2	157.83 (12)
O3^ix—Sn1—Co1^xiv	42.60 (9)	Sn1^vi—O1—Co2	157.83 (12)
O1^x—Sn1—Co1^xiv	88.45 (7)	O3^xx—O1—Co2	120.06 (6)
O1^xi—Sn1—Co1^xiv	91.55 (7)	Ba1—O1—Co2	60.56 (4)
O1^xii—Sn1—Co1^xiv	42.78 (6)	O3—O1—Co2	39.11 (11)
O1^xiii—Sn1—Co1^xiv	137.22 (6)	O3^xvi—O1—Co2	143.08 (14)
Sn1^x—Sn1—Co1^xiv	180.0	Sn2—O1—Co2^xvi	73.06 (6)
Sn1^xiv—Sn1—Co1^xiv	0.0	Co1^viii—O1—Co2^xvi	157.83 (12)
Co1^x—Sn1—Co1^xiv	180.0	Sn1^viii—O1—Co2^xvi	157.83 (12)
O3—Sn1—Sn1^xv	137.40 (9)	Co1^vi—O1—Co2^xvi	76.66 (3)
O3^ix—Sn1—Sn1^xv	42.60 (9)	Sn1^vi—O1—Co2^xvi	76.66 (3)
O1^x—Sn1—Sn1^xv	42.78 (6)	O3^xx—O1—Co2^xvi	120.06 (6)
O1^xi—Sn1—Sn1^xv	137.22 (6)	Ba1—O1—Co2^xvi	60.56 (4)
O1^xii—Sn1—Sn1^xv	88.45 (7)	O3—O1—Co2^xvi	143.08 (14)
O1^xiii—Sn1—Sn1^xv	91.55 (7)	O3^xvi—O1—Co2^xvi	39.11 (11)
Sn1^x—Sn1—Sn1^xv	120.0	Co2—O1—Co2^xvi	104.01 (7)
Sn1^xiv—Sn1—Sn1^xv	60.0	Co2—O2—Sn2	136.63 (8)
Co1^x—Sn1—Sn1^xv	120.0	Co2—O2—Sn2^v	136.63 (8)
Co1^xiv—Sn1—Sn1^xv	60.0	Sn2—O2—Sn2^v	86.75 (15)
O3—Sn1—Co1^xv	137.40 (9)	Co2—O2—Ba1^xviii	86.03 (8)
O3^ix—Sn1—Co1^xv	42.60 (9)	Sn2—O2—Ba1^xviii	92.88 (5)
O1^x—Sn1—Co1^xv	42.78 (6)	Sn2^v—O2—Ba1^xviii	92.88 (5)
O1^xi—Sn1—Co1^xv	137.22 (6)	Co2—O2—Ba1	86.03 (8)
O1^xii—Sn1—Co1^xv	88.45 (7)	Sn2—O2—Ba1	92.88 (5)
O1^xiii—Sn1—Co1^xv	91.55 (7)	Sn2^v—O2—Ba1	92.88 (5)
Sn1^x—Sn1—Co1^xv	120.0	Ba1^xviii—O2—Ba1	172.06 (15)
Sn1^xiv—Sn1—Co1^xv	60.0	Co2—O2—O3^v	51.07 (9)
Co1^x—Sn1—Co1^xv	120.0	Sn2—O2—O3^v	172.31 (15)
Co1^xiv—Sn1—Co1^xv	60.0	Sn2^v—O2—O3^v	85.56 (7)
Sn1^xv—Sn1—Co1^xv	0.0	Ba1^xviii—O2—O3^v	87.51 (5)
O1^vi—Sn2—O1	101.38 (11)	Ba1—O2—O3^v	87.51 (5)
O1^vi—Sn2—O1^xii	101.38 (11)	Co2—O2—O3	51.07 (9)
O1—Sn2—O1^xii	101.38 (11)	Sn2—O2—O3	85.56 (7)
O1^vi—Sn2—O2	163.32 (12)	Sn2^v—O2—O3	172.31 (15)
O1—Sn2—O2	89.07 (8)	Ba1^xviii—O2—O3	87.51 (5)
O1^xii—Sn2—O2	89.07 (8)	Ba1—O2—O3	87.51 (5)
O1^vi—Sn2—O2^vi	89.07 (8)	O3^v—O2—O3	102.13 (17)
O1—Sn2—O2^vi	89.07 (8)	Sn1—O3—Co1^x	94.80 (17)
O1^xii—Sn2—O2^vi	163.32 (12)	Sn1—O3—Sn1^x	94.80 (17)
O2—Sn2—O2^vi	78.03 (12)	Co1^x—O3—Sn1^x	0.0
O1^vi—Sn2—O2^xii	89.07 (8)	Sn1—O3—Co1^viii	94.80 (17)
O1—Sn2—O2^xii	163.32 (12)	Co1^x—O3—Co1^viii	94.80 (17)
O1^xii—Sn2—O2^xii	89.07 (8)	Sn1^x—O3—Co1^viii	94.80 (17)
O2—Sn2—O2^xii	78.03 (12)	Sn1—O3—Sn1^viii	94.80 (17)
O2^vi—Sn2—O2^xii	78.03 (12)	Co1^x—O3—Sn1^viii	94.80 (17)
O1^vi—Sn2—Sn2^v	116.69 (9)	Sn1^x—O3—Sn1^viii	94.80 (17)
O1—Sn2—Sn2^v	116.69 (9)	Co1^viii—O3—Sn1^viii	0.0
O1^xii—Sn2—Sn2^v	116.69 (9)

Symmetry codes: (i) −x+y, −x+1, −z+1/2; (ii) −x+y, −x+1, z; (iii) −y+1, x−y+1, −z+1/2; (iv) −y+1, x−y+1, z; (v) x, y, −z+1/2; (vi) −y, x−y, z; (vii) x, y+1, z; (viii) −x+y+1, −x+1, z; (ix) −x+1, −y, −z; (x) −y+1, x−y, z; (xi) y, −x+y, −z; (xii) −x+y, −x, z; (xiii) x−y+1, x, −z; (xiv) −y, x−y−1, z; (xv) −x+y+1, −x, z; (xvi) x−1, y, z; (xvii) x−1, y−1, z; (xviii) x, y−1, z; (xix) x+1, y, z; (xx) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	BaCo₂Sn₄O₁₁
M_r	905.96
Crystal system, space group	Hexagonal, P6₃/mmc
Temperature (K)	293
a, c (Å)	6.0880 (2), 14.1049 (6)
V (Å³)	452.74 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	18.76
Crystal size (mm)	0.06 × 0.04 × 0.03

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.524, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	3945, 230, 215
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.041, 1.13
No. of reflections	230
No. of parameters	28
No. of restraints	1
Δρ_max, Δρ_min (e Å⁻³)	0.73, −1.81

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2005), CrystalStructure (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), VESTA (Momma & Izumi, 2008).

Selected geometric parameters (Å, º) top

Ba1—O1ⁱ	2.918 (3)	Sn1—O1^xi	2.074 (2)
Ba1—O1ⁱⁱ	2.918 (3)	Sn1—O1^xii	2.074 (2)
Ba1—O1ⁱⁱⁱ	2.918 (3)	Sn1—O1^xiii	2.074 (2)
Ba1—O1	2.918 (3)	Sn2—O1^vi	2.040 (3)
Ba1—O1^iv	2.918 (3)	Sn2—O1	2.040 (3)
Ba1—O1^v	2.918 (3)	Sn2—O1^xii	2.040 (3)
Ba1—O2ⁱⁱ	3.051 (6)	Sn2—O2	2.127 (3)
Ba1—O2^vi	3.051 (6)	Sn2—O2^vi	2.127 (3)
Ba1—O2^vii	3.051 (6)	Sn2—O2^xii	2.127 (3)
Ba1—O2^iv	3.051 (6)	Sn2—Sn2^v	2.9217 (11)
Ba1—O2	3.051 (6)	Co2—O2^x	1.969 (4)
Ba1—O2^viii	3.051 (6)	Co2—O2^viii	1.969 (4)
Sn1—O3	2.068 (3)	Co2—O2	1.969 (4)
Sn1—O3^ix	2.068 (3)	Co2—O3	2.437 (6)
Sn1—O1^x	2.074 (2)	Co2—O3^v	2.437 (6)

O3—Sn1—O3^ix	180.0 (3)	O1—Sn2—O2	89.07 (8)
O3—Sn1—O1^x	94.67 (11)	O2^x—Co2—O2^viii	120.000 (1)
O3^ix—Sn1—O1^x	85.33 (11)	O2^x—Co2—O3	90.0
O1^vi—Sn2—O1	101.38 (11)	O3—Co2—O3^v	180.0
O1^vi—Sn2—O2	163.32 (12)

Acknowledgements

This work was supported in part by Special Coordination Funds from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

References

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