Barium manganese(II) selenostannate(IV), BaMnSnSe4

Assoud, A.; Kuropatwa, B.A.; Kleinke, H.

doi:10.1107/S1600536811047283

inorganic compounds

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Volume 67| Part 12| December 2011| Page i72

https://doi.org/10.1107/S1600536811047283

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Barium manganese(II) selenostannate(IV), BaMnSnSe₄

Abdeljalil Assoud,^a Bryan A. Kuropatwa ^a and Holger Kleinke ^a ^*

^aDepartment of Chemistry, Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1
^*Correspondence e-mail: kleinke@uwaterloo.ca

(Received 17 October 2011; accepted 8 November 2011; online 16 November 2011)

The title compound, BaMnSnSe₄, was obtained by reaction of the elements at 1123 K in an evacuated silica tube. It adopts the BaCdSnS₄ structure type, which is a variant of the SrIn₂Se₄ structure type. Its structure consists of distorted edge-sharing tetrahedra, alternating with Mn and Sn atoms as central atom. These [MnSnSe₆] units display corner sharing, forming stacked infinite layers in the ac plane. The three different Ba²⁺ atoms are located between the [MnSnSe₆] layers, two on twofold rotation axes, and exhibit distorted square-antiprismatic coordinations.

Related literature

For the synthesis and structures of quaternary sulfides A^IIM^IIB^IVS₄ (A^II = Ba, M^II = Zn, Cd, Hg, Mn, B^IV = Ge, Sn), see: Teske (1980a ,b ,c ,d ). For the SrIn₂Se₄ structure type, see: Eisenmann & Hofmann (1991 ) and for the BaCdSnS₄ structure type, see: Assoud et al. (2004 ).

Experimental

Crystal data

BaMnSnSe₄
M_r = 626.81
Orthorhombic, F d d 2
a = 22.3143 (10) Å
b = 22.7057 (11) Å
c = 13.4523 (6) Å
V = 6815.8 (5) Å³
Z = 32
Mo Kα radiation
μ = 25.93 mm⁻¹
T = 298 K
0.17 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.67, T_max = 0.97
18387 measured reflections
6703 independent reflections
4800 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.13
6703 reflections
129 parameters
1 restraint
Δρ_max = 1.95 e Å⁻³
Δρ_min = −1.64 e Å⁻³
Absolute structure: Flack (1983 ), 2823 Friedel pairs
Flack parameter: 0.044 (12)

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811047283/ru2017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047283/ru2017Isup2.hkl

checkCIF report

Comment top

A number of quaternary sulfides A^IIM^IIB^IVS₄ (A^II = Ba, M^II = Zn, Cd, Hg, Mn, B^IV = Ge, Sn) were synthesized and reported in 1980 (Teske, 1980a,b,c,d). They adopt the BaCdSnS₄ structure type and crystallize in the space group Fdd2, with the exception of BaHgSnS₄, which adopts the Pnn2 group with the same structural motifs. These structures are variants of the SrIn₂Se₄ type (Fddd) (Eisenmann et al., 1991) through the loss of the inversion centre due to the presence of two different M^II and B^IV centering cations. Here we report the synthesis and the crystal structure of the first selenide-based compound of this family, denoted BaMnSnSe₄.

One dark red block-like single-crystal of BaMnSnSe₄ was chosen under an optical microscope for study via single-crystal X-ray diffraction. The diffraction data were measured with the use of graphite-monochromated Mo—Kα radiation on a BRUKER Smart APEX CCD diffractometer. Data were collected by scans of 0.3° in two groups of 606 frames at φ = 0° and 90°. The exposure times per frame were 40 s. The data were corrected for Lorentz and polarization effects. Absorption corrections were based on fitting a function to the empirical transmission surface as sampled by multiple equivalent measurements using SADABS.

The unit cell refinement gave an orthorhombic F-centered cell with a = 22.3143 (10) Å, b = 22.7057 (11) Å, c = 13.4523 (6) Å, V = 6815.8 (5) Å³. The structure refinement was performed using the SrSn₂Se₄ model, producing satisfying residual factors. The Ba atoms replaced Sr atoms, the tetravalent Sn3 and Sn4 atoms remained in the same Wyckoff positions and the divalent Sn1 and Sn2 of SrSn₂Se₄ were reassigned as Mn1 and Mn2, while the Se positions were retained.

The new selenide, BaMnSnSe₄ crystallizes in the BaCdSnS₄ structure type, which - as previously mentioned - is a variant of the SrIn₂Se₄ structure type (Eisenmann et al., 1991). We present just a short summary of the principal features of the structure since it has since been described elsewhere (Assoud et al., 2004; Eisenmann et al., 1991; Teske, 1980a,b,c,d). Fig. 1 shows a unit cell projection along the c-axis.

In this structure, there are four crystallographically independent metal atom sites, namely Mn1, Mn2, Sn3 and Sn4, which are each tetrahedrally coordinated by Se atoms. The tetrahedra are severely distorted, with Se—Mn—Se and Se—Sn—Se angles between 96° and 126°. The Mn—Se and Sn—Se bonds vary from 2.50 Å to 2.61 Å and 2.49 Å to 2.54 Å, respectively. Similar distortions were observed in the case of the mixed valent selenostannate SrSn₂Se₄, in SrMgSnSe₄, (Assoud et al., 2004) and in BaMSnS₄ (M = Mn, Zn, Cd, Hg) (Teske, 1980a,b,c,d), with Se—Sn—Se bond angles ranging from 94° to 129°. The tetrahedra in BaMnSnSe₄ are interconnected by sharing edges between the MnSe₄ and SnSe₄ units. These [MnSnSe₆] units then share corners with four identical units (two per tetrahedron) forming an infinite two-dimensional layer in the ac plane. The Ba atoms are in a square antiprismatic coordination, with Ba—Se bonds between 3.33 Å and 3.39 Å, occupying the space between the [MnSnSe₆] layers. A single MnSnSe₄^2- layer is displayed in Fig. 2.

Related literature top

For the synthesis and structures of quaternary sulfides A^IIM^IIB^IVS₄ (A^II = Ba, M^II = Zn, Cd, Hg, Mn, B^IV = Ge, Sn), see: Teske (1980a,b,c,d). For the the SrIn₂Se₄ structure type, see: Eisenmann et al. (1991) and for the BaCdSnS₄ structure type, see: Assoud et al. (2004).

Experimental top

The elements were acquired either in large blocks (Ba, 99.95% nominal purity, ALFA AESAR) or in powder form (Sn, 99.8%, -325 mesh, ALFA AESAR; Se, 99.5%, -100 mesh, Aldrich; Mn, 99.9%, -100 mesh, Aldrich). Because of the air sensitive nature of barium, all elements were handled in an argon-filled glove box. The elements were loaded in a silica tube (in 1:1:1:4 ratio), which was evacuated and sealed under dynamic vacuum, then placed into a temperature controlled resistance furnace. The silica tube was heated to 850°C within 24 h, kept at 850°C for a period of 4 days, and then cooled to 200°C within 8 days. Thereafter, the furnace was turned off. The samples looked homogeneous, comprising mostly microcrystalline red powder.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of BaMnSnSe₄ in a projection along the c axis. Black: Ba; green: Mn; blue: Sn; red: Se.
	Fig. 2. A single MnSnSe₄^2- layer of the structure of BaMnSnSe₄. Green: Mn; blue: Sn; red: Se.

Barium manganese(II) selenostannate(IV) top

Crystal data top

BaMnSnSe₄	D_x = 4.887 Mg m⁻³
M_r = 626.81	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 1000 reflections
a = 22.3143 (10) Å	θ = 2.0–35°
b = 22.7057 (11) Å	µ = 25.93 mm⁻¹
c = 13.4523 (6) Å	T = 298 K
V = 6815.8 (5) Å³	Block, red
Z = 32	0.17 × 0.13 × 0.07 mm
F(000) = 8544

Data collection top

Bruker SMART APEX CCD diffractometer	6703 independent reflections
Radiation source: fine-focus sealed tube	4800 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 35.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −35→35
T_min = 0.67, T_max = 0.97	k = −32→36
18387 measured reflections	l = −21→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0177P)² + 37.4914P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.028	(Δ/σ)_max = 0.001
wR(F²) = 0.072	Δρ_max = 1.95 e Å⁻³
S = 1.13	Δρ_min = −1.64 e Å⁻³
6703 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
129 parameters	Extinction coefficient: 0.0000363 (16)
1 restraint	Absolute structure: Flack (1983), 2823 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.044 (12)

Crystal data top

BaMnSnSe₄	V = 6815.8 (5) Å³
M_r = 626.81	Z = 32
Orthorhombic, Fdd2	Mo Kα radiation
a = 22.3143 (10) Å	µ = 25.93 mm⁻¹
b = 22.7057 (11) Å	T = 298 K
c = 13.4523 (6) Å	0.17 × 0.13 × 0.07 mm

Data collection top

Bruker SMART APEX CCD diffractometer	6703 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4800 reflections with I > 2σ(I)
T_min = 0.67, T_max = 0.97	R_int = 0.031
18387 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0177P)² + 37.4914P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.072	Δρ_max = 1.95 e Å⁻³
S = 1.13	Δρ_min = −1.64 e Å⁻³
6703 reflections	Absolute structure: Flack (1983), 2823 Friedel pairs
129 parameters	Absolute structure parameter: 0.044 (12)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 2σ(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
Ba1	0.5000	0.0000	0.51434 (7)	0.01461 (15)
Ba2	0.2500	0.2500	0.76741 (7)	0.01464 (14)
Ba3	0.498642 (19)	0.252102 (14)	0.51495 (6)	0.01478 (13)
Mn1	0.42578 (5)	0.12560 (6)	0.80278 (9)	0.0199 (2)
Mn2	0.38807 (5)	0.12366 (6)	0.26964 (9)	0.0198 (2)
Sn3	0.36418 (2)	0.12530 (3)	0.51561 (4)	0.01241 (9)
Sn4	0.56889 (2)	0.12516 (3)	0.22465 (4)	0.01295 (9)
Se1	0.45804 (3)	0.12557 (5)	0.62286 (5)	0.01312 (14)
Se2	0.37358 (3)	0.03939 (4)	0.89544 (8)	0.01486 (19)
Se3	0.37316 (3)	0.21127 (4)	0.89774 (8)	0.0156 (2)
Se4	0.28052 (3)	0.12657 (5)	0.63900 (6)	0.01672 (14)
Se5	0.46781 (3)	0.12444 (5)	0.13819 (6)	0.01467 (15)
Se6	0.37314 (4)	0.20988 (4)	0.39409 (7)	0.0160 (2)
Se7	0.37225 (4)	0.03902 (4)	0.39730 (7)	0.01519 (19)
Se8	0.54326 (3)	0.12649 (5)	0.40527 (6)	0.01468 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.0128 (3)	0.0114 (3)	0.0196 (4)	0.0003 (3)	0.000	0.000
Ba2	0.0142 (3)	0.0128 (3)	0.0169 (4)	0.0001 (3)	0.000	0.000
Ba3	0.0134 (2)	0.0122 (2)	0.0188 (4)	−0.0004 (2)	0.00082 (10)	−0.00034 (18)
Mn1	0.0209 (5)	0.0239 (6)	0.0148 (6)	−0.0002 (5)	0.0049 (4)	0.0000 (5)
Mn2	0.0183 (4)	0.0271 (6)	0.0141 (6)	−0.0004 (5)	0.0029 (4)	0.0001 (6)
Sn3	0.01249 (14)	0.0135 (2)	0.0113 (2)	0.00023 (18)	0.00052 (16)	0.0000 (2)
Sn4	0.01337 (17)	0.0137 (2)	0.0118 (2)	0.00020 (16)	0.00104 (15)	0.00006 (19)
Se1	0.0133 (2)	0.0150 (4)	0.0111 (4)	0.0002 (3)	0.0004 (2)	0.0001 (4)
Se2	0.0131 (4)	0.0128 (5)	0.0187 (5)	0.0012 (2)	−0.0017 (4)	−0.0018 (3)
Se3	0.0142 (4)	0.0134 (5)	0.0192 (5)	−0.0018 (2)	−0.0021 (4)	0.0019 (3)
Se4	0.0161 (3)	0.0176 (3)	0.0164 (4)	−0.0001 (3)	0.0056 (3)	0.0003 (4)
Se5	0.0129 (3)	0.0175 (4)	0.0136 (4)	−0.0002 (3)	0.0017 (2)	0.0000 (4)
Se6	0.0183 (5)	0.0133 (5)	0.0165 (5)	−0.0007 (3)	−0.0050 (4)	0.0024 (3)
Se7	0.0166 (4)	0.0129 (5)	0.0160 (5)	0.0007 (3)	−0.0039 (4)	−0.0021 (3)
Se8	0.0172 (2)	0.0150 (3)	0.0119 (3)	0.0007 (3)	0.0025 (2)	−0.0003 (4)

Geometric parameters (Å, º) top

Ba1—Se1ⁱ	3.3373 (11)	Mn1—Se3	2.6067 (17)
Ba1—Se1	3.3373 (11)	Mn1—Se4ⁱⁱ	2.6097 (13)
Ba1—Se8ⁱ	3.3664 (11)	Mn2—Se5	2.5086 (14)
Ba1—Se8	3.3664 (11)	Mn2—Se6	2.5974 (18)
Ba1—Se7	3.3748 (9)	Mn2—Se7	2.6014 (17)
Ba1—Se7ⁱ	3.3748 (9)	Mn2—Se8^vii	2.6160 (14)
Ba1—Se6ⁱⁱ	3.3804 (10)	Sn3—Se4	2.4982 (8)
Ba1—Se6ⁱⁱⁱ	3.3804 (10)	Sn3—Se6	2.5299 (12)
Ba2—Se5^iv	3.3375 (12)	Sn3—Se7	2.5304 (11)
Ba2—Se5^v	3.3375 (12)	Sn3—Se1	2.5431 (8)
Ba2—Se4	3.3619 (12)	Sn4—Se8	2.4963 (10)
Ba2—Se4^vi	3.3620 (12)	Sn4—Se3^xi	2.5276 (11)
Ba2—Se3^vi	3.3764 (10)	Sn4—Se2^xi	2.5277 (11)
Ba2—Se3	3.3765 (10)	Sn4—Se5	2.5377 (7)
Ba2—Se2^vii	3.3838 (9)	Se2—Sn4^v	2.5276 (11)
Ba2—Se2^viii	3.3838 (9)	Se2—Ba3ⁱⁱⁱ	3.3520 (10)
Ba3—Se5^ix	3.3417 (12)	Se2—Ba2ⁱⁱ	3.3838 (9)
Ba3—Se1	3.3440 (11)	Se3—Sn4^v	2.5275 (11)
Ba3—Se2^viii	3.3521 (10)	Se3—Ba3^ix	3.3705 (10)
Ba3—Se4^viii	3.3587 (12)	Se4—Mn1^vii	2.6097 (13)
Ba3—Se8	3.3619 (11)	Se4—Ba3ⁱⁱⁱ	3.3586 (12)
Ba3—Se3^x	3.3706 (10)	Se5—Ba2^xi	3.3375 (12)
Ba3—Se6	3.3772 (10)	Se5—Ba3^x	3.3416 (12)
Ba3—Se7ⁱⁱ	3.4132 (10)	Se6—Ba1^vii	3.3804 (10)
Mn1—Se1	2.5251 (15)	Se7—Ba3^vii	3.4133 (10)
Mn1—Se2	2.5965 (17)	Se8—Mn2ⁱⁱ	2.6160 (14)

Se1ⁱ—Ba1—Se1	128.12 (4)	Se1—Ba3—Se7ⁱⁱ	75.97 (2)
Se1ⁱ—Ba1—Se8ⁱ	62.758 (16)	Se2^viii—Ba3—Se7ⁱⁱ	116.97 (3)
Se1—Ba1—Se8ⁱ	147.042 (13)	Se4^viii—Ba3—Se7ⁱⁱ	130.54 (2)
Se1ⁱ—Ba1—Se8	147.044 (13)	Se8—Ba3—Se7ⁱⁱ	75.97 (2)
Se1—Ba1—Se8	62.757 (16)	Se3^x—Ba3—Se7ⁱⁱ	68.02 (3)
Se8ⁱ—Ba1—Se8	128.32 (4)	Se6—Ba3—Se7ⁱⁱ	147.523 (18)
Se1ⁱ—Ba1—Se7	131.71 (2)	Se1—Mn1—Se2	126.01 (6)
Se1—Ba1—Se7	75.09 (2)	Se1—Mn1—Se3	126.75 (7)
Se8ⁱ—Ba1—Se7	77.20 (2)	Se2—Mn1—Se3	97.19 (5)
Se8—Ba1—Se7	79.33 (2)	Se1—Mn1—Se4ⁱⁱ	99.83 (4)
Se1ⁱ—Ba1—Se7ⁱ	75.10 (2)	Se2—Mn1—Se4ⁱⁱ	100.04 (5)
Se1—Ba1—Se7ⁱ	131.71 (2)	Se3—Mn1—Se4ⁱⁱ	101.51 (5)
Se8ⁱ—Ba1—Se7ⁱ	79.33 (2)	Se5—Mn2—Se6	122.69 (6)
Se8—Ba1—Se7ⁱ	77.20 (2)	Se5—Mn2—Se7	124.52 (6)
Se7—Ba1—Se7ⁱ	124.38 (4)	Se6—Mn2—Se7	96.54 (5)
Se1ⁱ—Ba1—Se6ⁱⁱ	77.07 (2)	Se5—Mn2—Se8^vii	99.15 (5)
Se1—Ba1—Se6ⁱⁱ	76.82 (2)	Se6—Mn2—Se8^vii	106.04 (5)
Se8ⁱ—Ba1—Se6ⁱⁱ	133.47 (2)	Se7—Mn2—Se8^vii	106.12 (5)
Se8—Ba1—Se6ⁱⁱ	76.24 (2)	Se4—Sn3—Se6	118.66 (4)
Se7—Ba1—Se6ⁱⁱ	148.952 (15)	Se4—Sn3—Se7	118.69 (4)
Se7ⁱ—Ba1—Se6ⁱⁱ	67.98 (2)	Se6—Sn3—Se7	100.12 (4)
Se1ⁱ—Ba1—Se6ⁱⁱⁱ	76.82 (2)	Se4—Sn3—Se1	103.79 (3)
Se1—Ba1—Se6ⁱⁱⁱ	77.07 (2)	Se6—Sn3—Se1	107.44 (4)
Se8ⁱ—Ba1—Se6ⁱⁱⁱ	76.24 (2)	Se7—Sn3—Se1	107.46 (3)
Se8—Ba1—Se6ⁱⁱⁱ	133.47 (2)	Se8—Sn4—Se3^xi	121.17 (4)
Se7—Ba1—Se6ⁱⁱⁱ	67.98 (2)	Se8—Sn4—Se2^xi	120.77 (4)
Se7ⁱ—Ba1—Se6ⁱⁱⁱ	148.952 (15)	Se3^xi—Sn4—Se2^xi	101.07 (3)
Se6ⁱⁱ—Ba1—Se6ⁱⁱⁱ	117.82 (4)	Se8—Sn4—Se5	104.04 (3)
Se5^iv—Ba2—Se5^v	121.73 (4)	Se3^xi—Sn4—Se5	103.49 (4)
Se5^iv—Ba2—Se4	155.821 (13)	Se2^xi—Sn4—Se5	103.94 (4)
Se5^v—Ba2—Se4	65.669 (17)	Mn1—Se1—Sn3	108.00 (4)
Se5^iv—Ba2—Se4^vi	65.669 (17)	Mn1—Se1—Ba1	119.97 (5)
Se5^v—Ba2—Se4^vi	155.821 (13)	Sn3—Se1—Ba1	88.90 (3)
Se4—Ba2—Se4^vi	118.17 (4)	Mn1—Se1—Ba3	119.55 (5)
Se5^iv—Ba2—Se3^vi	72.66 (2)	Sn3—Se1—Ba3	88.79 (3)
Se5^v—Ba2—Se3^vi	78.02 (3)	Ba1—Se1—Ba3	117.91 (3)
Se4—Ba2—Se3^vi	130.45 (2)	Sn4^v—Se2—Mn1	80.81 (4)
Se4^vi—Ba2—Se3^vi	83.38 (2)	Sn4^v—Se2—Ba3ⁱⁱⁱ	91.25 (3)
Se5^iv—Ba2—Se3	78.03 (3)	Mn1—Se2—Ba3ⁱⁱⁱ	107.70 (4)
Se5^v—Ba2—Se3	72.66 (2)	Sn4^v—Se2—Ba2ⁱⁱ	113.64 (4)
Se4—Ba2—Se3	83.38 (2)	Mn1—Se2—Ba2ⁱⁱ	93.33 (3)
Se4^vi—Ba2—Se3	130.45 (2)	Ba3ⁱⁱⁱ—Se2—Ba2ⁱⁱ	149.93 (3)
Se3^vi—Ba2—Se3	117.43 (4)	Sn4^v—Se3—Mn1	80.62 (4)
Se5^iv—Ba2—Se2^vii	129.74 (2)	Sn4^v—Se3—Ba3^ix	114.00 (4)
Se5^v—Ba2—Se2^vii	80.38 (2)	Mn1—Se3—Ba3^ix	91.78 (3)
Se4—Ba2—Se2^vii	72.51 (2)	Sn4^v—Se3—Ba2	91.42 (3)
Se4^vi—Ba2—Se2^vii	78.60 (2)	Mn1—Se3—Ba2	107.85 (4)
Se3^vi—Ba2—Se2^vii	69.03 (2)	Ba3^ix—Se3—Ba2	150.40 (3)
Se3—Ba2—Se2^vii	149.488 (14)	Sn3—Se4—Mn1^vii	111.94 (4)
Se5^iv—Ba2—Se2^viii	80.38 (2)	Sn3—Se4—Ba3ⁱⁱⁱ	118.05 (4)
Se5^v—Ba2—Se2^viii	129.74 (2)	Mn1^vii—Se4—Ba3ⁱⁱⁱ	92.00 (4)
Se4—Ba2—Se2^viii	78.60 (2)	Sn3—Se4—Ba2	120.16 (4)
Se4^vi—Ba2—Se2^viii	72.51 (2)	Mn1^vii—Se4—Ba2	93.59 (4)
Se3^vi—Ba2—Se2^viii	149.489 (15)	Ba3ⁱⁱⁱ—Se4—Ba2	113.76 (3)
Se3—Ba2—Se2^viii	69.03 (2)	Mn2—Se5—Sn4	107.90 (4)
Se2^vii—Ba2—Se2^viii	121.99 (4)	Mn2—Se5—Ba2^xi	119.33 (5)
Se5^ix—Ba3—Se1	124.48 (3)	Sn4—Se5—Ba2^xi	92.14 (3)
Se5^ix—Ba3—Se2^viii	73.18 (2)	Mn2—Se5—Ba3^x	120.96 (5)
Se1—Ba3—Se2^viii	76.66 (2)	Sn4—Se5—Ba3^x	91.31 (3)
Se5^ix—Ba3—Se4^viii	65.659 (18)	Ba2^xi—Se5—Ba3^x	114.86 (3)
Se1—Ba3—Se4^viii	152.79 (2)	Sn3—Se6—Mn2	81.63 (4)
Se2^viii—Ba3—Se4^viii	83.91 (2)	Sn3—Se6—Ba3	88.28 (3)
Se5^ix—Ba3—Se8	149.66 (2)	Mn2—Se6—Ba3	114.70 (4)
Se1—Ba3—Se8	62.735 (17)	Sn3—Se6—Ba1^vii	118.29 (3)
Se2^viii—Ba3—Se8	133.24 (2)	Mn2—Se6—Ba1^vii	88.54 (4)
Se4^viii—Ba3—Se8	123.35 (3)	Ba3—Se6—Ba1^vii	147.80 (3)
Se5^ix—Ba3—Se3^x	80.50 (2)	Sn3—Se7—Mn2	81.55 (4)
Se1—Ba3—Se3^x	130.17 (2)	Sn3—Se7—Ba1	88.28 (3)
Se2^viii—Ba3—Se3^x	150.829 (18)	Mn2—Se7—Ba1	112.79 (4)
Se4^viii—Ba3—Se3^x	73.79 (2)	Sn3—Se7—Ba3^vii	118.84 (3)
Se8—Ba3—Se3^x	75.68 (2)	Mn2—Se7—Ba3^vii	88.13 (4)
Se5^ix—Ba3—Se6	131.51 (2)	Ba1—Se7—Ba3^vii	148.66 (3)
Se1—Ba3—Se6	74.95 (2)	Sn4—Se8—Mn2ⁱⁱ	112.78 (4)
Se2^viii—Ba3—Se6	69.46 (3)	Sn4—Se8—Ba3	120.35 (4)
Se4^viii—Ba3—Se6	80.52 (2)	Mn2ⁱⁱ—Se8—Ba3	89.00 (4)
Se8—Ba3—Se6	78.08 (2)	Sn4—Se8—Ba1	118.66 (4)
Se3^x—Ba3—Se6	123.27 (4)	Mn2ⁱⁱ—Se8—Ba1	88.53 (4)
Se5^ix—Ba3—Se7ⁱⁱ	77.86 (2)	Ba3—Se8—Ba1	116.59 (3)

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

Experimental details

Crystal data
Chemical formula	BaMnSnSe₄
M_r	626.81
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	298
a, b, c (Å)	22.3143 (10), 22.7057 (11), 13.4523 (6)
V (Å³)	6815.8 (5)
Z	32
Radiation type	Mo Kα
µ (mm⁻¹)	25.93
Crystal size (mm)	0.17 × 0.13 × 0.07

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.67, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	18387, 6703, 4800
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.13
No. of reflections	6703
No. of parameters	129
No. of restraints	1
	w = 1/[σ²(F_o²) + (0.0177P)² + 37.4914P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.95, −1.64
Absolute structure	Flack (1983), 2823 Friedel pairs
Absolute structure parameter	0.044 (12)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Acknowledgements

Financial support from the Natural Sciences and Engineering Research Council of Canada is gratefully acknowledged.

References

Assoud, A., Soheilnia, N. & Kleinke, H. (2004). Chem. Mater. 16, 2215–2221. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2000). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Eisenmann, B. & Hofmann, A. (1991). Z. Kristallogr. 197, 167–168. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Teske, C. L. (1980a). Z. Anorg. Allg. Chem. 460, 163–168. CrossRef CAS Web of Science Google Scholar
Teske, C. L. (1980b). Z. Anorg. Allg. Chem. 468, 27–34. CrossRef CAS Google Scholar
Teske, C. L. (1980c). Z. Naturforsch. Teil B, 35, 7–11. Google Scholar
Teske, C. L. (1980d). Z. Naturforsch. Teil B, 35, 509–510. Google Scholar