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Doped barium lithium trifluoride has attracted attention as component for scintillators, luminescent materials and electrodes. With lithium and fluoride, it contains two possibly mobile species, which may account for its ionic conductivity. In this study, neutron diffraction on oxide-containing BaLiF3 single-crystals is performed at up to 636.2°C. Unfortunately, ion-migration pathways could not be mapped by modelling anharmonic ion displacement or by inspecting the scattering-length density that was reconstructed via maximum-entropy methods. However, analyses of the topology and bond-valence site energies derived from the high-temperature structure reveal that the anions can migrate roughly along the edges of the LiF6 coordination octahedra with an estimated migration barrier of ∼0.64 eV (if a vacancy permits), whereas the lithium ions are confined to their crystallographic positions. This finding is not only valid for the title compound but for ion migration in all perovskites with Goldschmidt tolerance factors near unity.

Supporting information

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Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520618014579/ra5041sup1.cif
Contains datablocks global, BaLiF3-rt, BaLiF3-412C, BaLiF3-555C, BaLiF3-636C, BaLiF3-XRD

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Portable Document Format (PDF) file https://doi.org/10.1107/S2052520618014579/ra5041sup2.pdf
Supplementary material

CCDC references: 434514; 434515; 434516; 434517

Computing details top

Data collection: NOMAD (Institut Laue-Langevin, 2016) for BaLiF3-rt, BaLiF3-412C, BaLiF3-555C, BaLiF3-636C; Bruker APEX2 (Bruker, 2012) for BaLiF3-XRD. Cell refinement: RAFD9 (Filhol, 1988) for BaLiF3-rt, BaLiF3-412C, BaLiF3-555C, BaLiF3-636C; Bruker SAINT (Bruker, 2012) for BaLiF3-XRD. Data reduction: RACER (Lehmann & Larsen, 1974; Wilkinson et al., 1988) for BaLiF3-rt, BaLiF3-412C, BaLiF3-555C, BaLiF3-636C; Bruker SAINT (Bruker, 2012) for BaLiF3-XRD. For all structures, program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: Jana2006 (Petříček et al., 2014); molecular graphics: VESTA (Momma & Izumi, 2011); software used to prepare material for publication: Jana2006 (Petříček et al., 2014).

barium lithium fluoride oxide (BaLiF3-rt) top
Crystal data top
BaLiF2.80O0.10Dx = 5.174 Mg m3
Mr = 199.1Neutron radiation, λ = 0.83860 Å
Cubic, Pm3mCell parameters from 126 reflections
Hall symbol: -P 4 2 3θ = 6.1–48.5°
a = 3.9978 (2) ŵ = 0.05 mm1
V = 63.89 (1) Å3T = 300 K
Z = 1Cube, colourless
F(000) = 19.5825.00 × 5.00 × 5.00 mm
Data collection top
D9 position-sensitive detector
diffractometer
82 independent reflections
Radiation source: nuclear reactor, ILL high-flux reactor, beam H381 reflections with I > 2σ(I)
Cu 220 monochromatorRint = 0.019
Detector resolution: 0.5 pixels mm-1θmax = 57.7°, θmin = 6.0°
ω and ω–2θ scansh = 48
Absorption correction: gaussian
Jana2006 (Petříček et al., 2014)
k = 48
Tmin = 0.975, Tmax = 0.978l = 08
364 measured reflections
Refinement top
Refinement on F22 constraints
Least-squares matrix: fullPrimary atom site location: iterative
R[F2 > 2σ(F2)] = 0.012Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0011048977I2)
wR(F2) = 0.046(Δ/σ)max < 0.001
S = 1.13Δρmax = 0.35 e Å3
82 reflectionsΔρmin = 0.25 e Å3
6 parametersExtinction correction: SHELXL-2017/1 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 6.6 (4)
Special details top

Refinement. Substitutionally disordered fluoride and oxide ions were constrained to have the same ADP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba10000.00734 (7)
Li10.50.50.50.01232 (11)
F10.50.500.01107 (7)0.9333
O10.50.500.01107 (7)0.0333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.00734 (12)0.00734 (12)0.00734 (12)000
Li10.0123 (2)0.0123 (2)0.0123 (2)000
F10.01255 (13)0.01255 (13)0.00811 (12)000
O10.01255 (13)0.01255 (13)0.00811 (12)000
Geometric parameters (Å, º) top
Ba1—O1i2.8269 (2)Li1—F11.9989 (2)
Ba1—O1ii2.8269 (2)Li1—F1xii1.9989 (2)
Ba1—O1iii2.8269 (2)Li1—F1vii1.9989 (2)
Ba1—O12.8269 (2)Li1—F1xiii1.9989 (2)
Ba1—O1iv2.8269 (2)Li1—F1xi1.9989 (2)
Ba1—O1v2.8269 (2)Li1—F1xiv1.9989 (2)
Ba1—O1vi2.8269 (2)Li1—O11.9989 (2)
Ba1—O1vii2.8269 (2)Li1—O1xii1.9989 (2)
Ba1—O1viii2.8269 (2)Li1—O1vii1.9989 (2)
Ba1—O1ix2.8269 (2)Li1—O1xiii1.9989 (2)
Ba1—O1x2.8269 (2)Li1—O1xi1.9989 (2)
Ba1—O1xi2.8269 (2)Li1—O1xiv1.9989 (2)
O1i—Ba1—O1ii90.000 (4)O1v—Ba1—O1ix60.000 (2)
O1i—Ba1—O1iii90.000 (4)O1v—Ba1—O1x120.000 (2)
O1i—Ba1—O1180O1v—Ba1—O1xi60.000 (2)
O1i—Ba1—O1iv60.000 (2)O1vi—Ba1—O1vii90.000 (4)
O1i—Ba1—O1v60.000 (2)O1vi—Ba1—O1viii60.000 (2)
O1i—Ba1—O1vi120.000 (2)O1vi—Ba1—O1ix120.000 (2)
O1i—Ba1—O1vii120.000 (2)O1vi—Ba1—O1x60.000 (2)
O1i—Ba1—O1viii60.000 (2)O1vi—Ba1—O1xi120.000 (2)
O1i—Ba1—O1ix60.000 (2)O1vii—Ba1—O1viii120.000 (2)
O1i—Ba1—O1x120.000 (2)O1vii—Ba1—O1ix60.000 (2)
O1i—Ba1—O1xi120.000 (2)O1vii—Ba1—O1x120.000 (2)
O1ii—Ba1—O1iii180O1vii—Ba1—O1xi60.000 (2)
O1ii—Ba1—O190.000 (4)O1viii—Ba1—O1ix90.000 (4)
O1ii—Ba1—O1iv120.000 (2)O1viii—Ba1—O1x90.000 (4)
O1ii—Ba1—O1v120.000 (2)O1viii—Ba1—O1xi180
O1ii—Ba1—O1vi60.000 (2)O1ix—Ba1—O1x180
O1ii—Ba1—O1vii60.000 (2)O1ix—Ba1—O1xi90.000 (4)
O1ii—Ba1—O1viii60.000 (2)O1x—Ba1—O1xi90.000 (4)
O1ii—Ba1—O1ix60.000 (2)F1—Li1—F1xii180
O1ii—Ba1—O1x120.000 (2)F1—Li1—F1vii90
O1ii—Ba1—O1xi120.000 (2)F1—Li1—F1xiii90
O1iii—Ba1—O190.000 (4)F1—Li1—F1xi90
O1iii—Ba1—O1iv60.000 (2)F1—Li1—F1xiv90
O1iii—Ba1—O1v60.000 (2)F1xii—Li1—F1vii90
O1iii—Ba1—O1vi120.000 (2)F1xii—Li1—F1xiii90
O1iii—Ba1—O1vii120.000 (2)F1xii—Li1—F1xi90
O1iii—Ba1—O1viii120.000 (2)F1xii—Li1—F1xiv90
O1iii—Ba1—O1ix120.000 (2)F1vii—Li1—F1xiii180
O1iii—Ba1—O1x60.000 (2)F1vii—Li1—F1xi90
O1iii—Ba1—O1xi60.000 (2)F1vii—Li1—F1xiv90
O1—Ba1—O1iv120.000 (2)F1xiii—Li1—F1xi90
O1—Ba1—O1v120.000 (2)F1xiii—Li1—F1xiv90
O1—Ba1—O1vi60.000 (2)F1xi—Li1—F1xiv180
O1—Ba1—O1vii60.000 (2)O1—Li1—O1xii180
O1—Ba1—O1viii120.000 (2)O1—Li1—O1vii90
O1—Ba1—O1ix120.000 (2)O1—Li1—O1xiii90
O1—Ba1—O1x60.000 (2)O1—Li1—O1xi90
O1—Ba1—O1xi60.000 (2)O1—Li1—O1xiv90
O1iv—Ba1—O1v90.000 (4)O1xii—Li1—O1vii90
O1iv—Ba1—O1vi90.000 (4)O1xii—Li1—O1xiii90
O1iv—Ba1—O1vii180O1xii—Li1—O1xi90
O1iv—Ba1—O1viii60.000 (2)O1xii—Li1—O1xiv90
O1iv—Ba1—O1ix120.000 (2)O1vii—Li1—O1xiii180
O1iv—Ba1—O1x60.000 (2)O1vii—Li1—O1xi90
O1iv—Ba1—O1xi120.000 (2)O1vii—Li1—O1xiv90
O1v—Ba1—O1vi180O1xiii—Li1—O1xi90
O1v—Ba1—O1vii90.000 (4)O1xiii—Li1—O1xiv90
O1v—Ba1—O1viii120.000 (2)O1xi—Li1—O1xiv180
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z; (iii) x, y1, z; (iv) z, x1, y1; (v) z, x1, y; (vi) z, x, y1; (vii) z, x, y; (viii) y1, z, x1; (ix) y1, z, x; (x) y, z, x1; (xi) y, z, x; (xii) x, y, z+1; (xiii) z+1, x, y; (xiv) y, z+1, x.
barium lithium fluoride oxide (BaLiF3-412C) top
Crystal data top
BaLiF2.80O0.10Dx = 5.011 Mg m3
Mr = 199.1Neutron radiation, λ = 0.83860 Å
Cubic, Pm3mCell parameters from 120 reflections
Hall symbol: -P 4 2 3θ = 6.0–48.5°
a = 4.0406 (2) ŵ = 0.05 mm1
V = 65.97 (1) Å3T = 685 K
Z = 1Cube, colourless
F(000) = 19.5825.00 × 5.00 × 5.00 mm
Data collection top
D9 position-sensitive detector
diffractometer
68 independent reflections
Radiation source: nuclear reactor, ILL high-flux reactor, beam H367 reflections with I > 2σ(I)
Cu 220 monochromatorRint = 0.020
Detector resolution: 0.5 pixels mm-1θmax = 49.7°, θmin = 6.0°
ω and ω–2θ scansh = 07
Absorption correction: gaussian
Jana2006 (Petříček et al., 2014)
k = 07
Tmin = 0.975, Tmax = 0.978l = 07
286 measured reflections
Refinement top
Refinement on F23 constraints
Least-squares matrix: fullPrimary atom site location: iterative
R[F2 > 2σ(F2)] = 0.011Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0013075456I2)
wR(F2) = 0.038(Δ/σ)max < 0.001
S = 0.85Δρmax = 0.13 e Å3
68 reflectionsΔρmin = 0.12 e Å3
7 parametersExtinction correction: SHELXL-2017/1 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 5.0 (3)
Special details top

Refinement. Substitutionally disordered fluoride and oxide ions were constrained to have the same ADP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba10000.01899 (9)
Li10.50.50.50.02730 (18)
F10.50.500.02823 (12)0.9333
O10.50.500.02823 (12)0.0333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.01899 (15)0.01899 (15)0.01899 (15)000
Li10.0273 (3)0.0273 (3)0.0273 (3)000
F10.0326 (2)0.0326 (2)0.01947 (17)000
O10.0326 (2)0.0326 (2)0.01947 (17)000
Geometric parameters (Å, º) top
Ba1—O1i2.8571 (2)Li1—F12.0203 (2)
Ba1—O1ii2.8571 (2)Li1—F1xii2.0203 (2)
Ba1—O1iii2.8571 (2)Li1—F1vii2.0203 (2)
Ba1—O12.8571 (2)Li1—F1xiii2.0203 (2)
Ba1—O1iv2.8571 (2)Li1—F1xi2.0203 (2)
Ba1—O1v2.8571 (2)Li1—F1xiv2.0203 (2)
Ba1—O1vi2.8571 (2)Li1—O12.0203 (2)
Ba1—O1vii2.8571 (2)Li1—O1xii2.0203 (2)
Ba1—O1viii2.8571 (2)Li1—O1vii2.0203 (2)
Ba1—O1ix2.8571 (2)Li1—O1xiii2.0203 (2)
Ba1—O1x2.8571 (2)Li1—O1xi2.0203 (2)
Ba1—O1xi2.8571 (2)Li1—O1xiv2.0203 (2)
O1i—Ba1—O1ii90.000 (4)F1—Li1—F1xii180
O1i—Ba1—O1iii90.000 (4)F1—Li1—F1vii90
O1i—Ba1—O1180F1—Li1—F1xiii90
O1i—Ba1—O1iv60.000 (2)F1—Li1—F1xi90
O1i—Ba1—O1v60.000 (2)F1—Li1—F1xiv90
O1i—Ba1—O1vi120.000 (2)F1—Li1—O10
O1i—Ba1—O1vii120.000 (2)F1—Li1—O1xii180
O1i—Ba1—O1viii60.000 (2)F1—Li1—O1vii90
O1i—Ba1—O1ix60.000 (2)F1—Li1—O1xiii90
O1i—Ba1—O1x120.000 (2)F1—Li1—O1xi90
O1i—Ba1—O1xi120.000 (2)F1—Li1—O1xiv90
O1ii—Ba1—O1iii180F1xii—Li1—F1vii90
O1ii—Ba1—O190.000 (4)F1xii—Li1—F1xiii90
O1ii—Ba1—O1iv120.000 (2)F1xii—Li1—F1xi90
O1ii—Ba1—O1v120.000 (2)F1xii—Li1—F1xiv90
O1ii—Ba1—O1vi60.000 (2)F1xii—Li1—O1180
O1ii—Ba1—O1vii60.000 (2)F1xii—Li1—O1xii0
O1ii—Ba1—O1viii60.000 (2)F1xii—Li1—O1vii90
O1ii—Ba1—O1ix60.000 (2)F1xii—Li1—O1xiii90
O1ii—Ba1—O1x120.000 (2)F1xii—Li1—O1xi90
O1ii—Ba1—O1xi120.000 (2)F1xii—Li1—O1xiv90
O1iii—Ba1—O190.000 (4)F1vii—Li1—F1xiii180
O1iii—Ba1—O1iv60.000 (2)F1vii—Li1—F1xi90
O1iii—Ba1—O1v60.000 (2)F1vii—Li1—F1xiv90
O1iii—Ba1—O1vi120.000 (2)F1vii—Li1—O190
O1iii—Ba1—O1vii120.000 (2)F1vii—Li1—O1xii90
O1iii—Ba1—O1viii120.000 (2)F1vii—Li1—O1vii0
O1iii—Ba1—O1ix120.000 (2)F1vii—Li1—O1xiii180
O1iii—Ba1—O1x60.000 (2)F1vii—Li1—O1xi90
O1iii—Ba1—O1xi60.000 (2)F1vii—Li1—O1xiv90
O1—Ba1—O1iv120.000 (2)F1xiii—Li1—F1xi90
O1—Ba1—O1v120.000 (2)F1xiii—Li1—F1xiv90
O1—Ba1—O1vi60.000 (2)F1xiii—Li1—O190
O1—Ba1—O1vii60.000 (2)F1xiii—Li1—O1xii90
O1—Ba1—O1viii120.000 (2)F1xiii—Li1—O1vii180
O1—Ba1—O1ix120.000 (2)F1xiii—Li1—O1xiii0
O1—Ba1—O1x60.000 (2)F1xiii—Li1—O1xi90
O1—Ba1—O1xi60.000 (2)F1xiii—Li1—O1xiv90
O1iv—Ba1—O1v90.000 (4)F1xi—Li1—F1xiv180
O1iv—Ba1—O1vi90.000 (4)F1xi—Li1—O190
O1iv—Ba1—O1vii180F1xi—Li1—O1xii90
O1iv—Ba1—O1viii60.000 (2)F1xi—Li1—O1vii90
O1iv—Ba1—O1ix120.000 (2)F1xi—Li1—O1xiii90
O1iv—Ba1—O1x60.000 (2)F1xi—Li1—O1xi0
O1iv—Ba1—O1xi120.000 (2)F1xi—Li1—O1xiv180
O1v—Ba1—O1vi180F1xiv—Li1—O190
O1v—Ba1—O1vii90.000 (4)F1xiv—Li1—O1xii90
O1v—Ba1—O1viii120.000 (2)F1xiv—Li1—O1vii90
O1v—Ba1—O1ix60.000 (2)F1xiv—Li1—O1xiii90
O1v—Ba1—O1x120.000 (2)F1xiv—Li1—O1xi180
O1v—Ba1—O1xi60.000 (2)F1xiv—Li1—O1xiv0
O1vi—Ba1—O1vii90.000 (4)O1—Li1—O1xii180
O1vi—Ba1—O1viii60.000 (2)O1—Li1—O1vii90
O1vi—Ba1—O1ix120.000 (2)O1—Li1—O1xiii90
O1vi—Ba1—O1x60.000 (2)O1—Li1—O1xi90
O1vi—Ba1—O1xi120.000 (2)O1—Li1—O1xiv90
O1vii—Ba1—O1viii120.000 (2)O1xii—Li1—O1vii90
O1vii—Ba1—O1ix60.000 (2)O1xii—Li1—O1xiii90
O1vii—Ba1—O1x120.000 (2)O1xii—Li1—O1xi90
O1vii—Ba1—O1xi60.000 (2)O1xii—Li1—O1xiv90
O1viii—Ba1—O1ix90.000 (4)O1vii—Li1—O1xiii180
O1viii—Ba1—O1x90.000 (4)O1vii—Li1—O1xi90
O1viii—Ba1—O1xi180O1vii—Li1—O1xiv90
O1ix—Ba1—O1x180O1xiii—Li1—O1xi90
O1ix—Ba1—O1xi90.000 (4)O1xiii—Li1—O1xiv90
O1x—Ba1—O1xi90.000 (4)O1xi—Li1—O1xiv180
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z; (iii) x, y1, z; (iv) z, x1, y1; (v) z, x1, y; (vi) z, x, y1; (vii) z, x, y; (viii) y1, z, x1; (ix) y1, z, x; (x) y, z, x1; (xi) y, z, x; (xii) x, y, z+1; (xiii) z+1, x, y; (xiv) y, z+1, x.
barium lithium fluoride oxide (BaLiF3-555C) top
Crystal data top
BaLiF2.80O0.10Dx = 4.947 Mg m3
Mr = 199.1Neutron radiation, λ = 0.83860 Å
Cubic, Pm3mCell parameters from 103 reflections
Hall symbol: -P 4 2 3θ = 6.0–43.3°
a = 4.0581 (3) ŵ = 0.05 mm1
V = 66.83 (2) Å3T = 827 K
Z = 1Cube, colourless
F(000) = 19.5825.00 × 5.00 × 5.00 mm
Data collection top
D9 position-sensitive detector
diffractometer
82 independent reflections
Radiation source: nuclear reactor, ILL high-flux reactor, beam H374 reflections with I > 2σ(I)
Cu 220 monochromatorRint = 0.023
Detector resolution: 0.5 pixels mm-1θmax = 56.4°, θmin = 5.9°
ω and ω–2θ scansh = 48
Absorption correction: gaussian
Jana2006 (Petříček et al., 2014)
k = 48
Tmin = 0.976, Tmax = 0.979l = 08
362 measured reflections
Refinement top
Refinement on F23 constraints
Least-squares matrix: fullPrimary atom site location: iterative
R[F2 > 2σ(F2)] = 0.015Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0015539365I2)
wR(F2) = 0.054(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.12 e Å3
82 reflectionsΔρmin = 0.20 e Å3
7 parametersExtinction correction: SHELXL-2017/1 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 5.3 (4)
Special details top

Refinement. Substitutionally disordered fluoride and oxide ions were constrained to have the same ADP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba10000.02452 (11)
Li10.50.50.50.0342 (2)
F10.50.500.03558 (15)0.9333
O10.50.500.03558 (15)0.0333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.02452 (19)0.02452 (19)0.02452 (19)000
Li10.0342 (4)0.0342 (4)0.0342 (4)000
F10.0413 (2)0.0413 (2)0.0242 (3)000
O10.0413 (2)0.0413 (2)0.0242 (3)000
Geometric parameters (Å, º) top
Ba1—O1i2.8695 (3)Ba1—O1ix2.8695 (3)
Ba1—O1ii2.8695 (3)Ba1—O1x2.8695 (3)
Ba1—O1iii2.8695 (3)Ba1—O1xi2.8695 (3)
Ba1—O12.8695 (3)Li1—O12.0291 (3)
Ba1—O1iv2.8695 (3)Li1—O1xii2.0291 (3)
Ba1—O1v2.8695 (3)Li1—O1vii2.0291 (3)
Ba1—O1vi2.8695 (3)Li1—O1xiii2.0291 (3)
Ba1—O1vii2.8695 (3)Li1—O1xi2.0291 (3)
Ba1—O1viii2.8695 (3)Li1—O1xiv2.0291 (3)
O1i—Ba1—O1ii90.000 (6)O1iv—Ba1—O1viii60.000 (3)
O1i—Ba1—O1iii90.000 (6)O1iv—Ba1—O1ix120.000 (3)
O1i—Ba1—O1180O1iv—Ba1—O1x60.000 (3)
O1i—Ba1—O1iv60.000 (3)O1iv—Ba1—O1xi120.000 (3)
O1i—Ba1—O1v60.000 (3)O1v—Ba1—O1vi180
O1i—Ba1—O1vi120.000 (3)O1v—Ba1—O1vii90.000 (6)
O1i—Ba1—O1vii120.000 (3)O1v—Ba1—O1viii120.000 (3)
O1i—Ba1—O1viii60.000 (3)O1v—Ba1—O1ix60.000 (3)
O1i—Ba1—O1ix60.000 (3)O1v—Ba1—O1x120.000 (3)
O1i—Ba1—O1x120.000 (3)O1v—Ba1—O1xi60.000 (3)
O1i—Ba1—O1xi120.000 (3)O1vi—Ba1—O1vii90.000 (6)
O1ii—Ba1—O1iii180O1vi—Ba1—O1viii60.000 (3)
O1ii—Ba1—O190.000 (6)O1vi—Ba1—O1ix120.000 (3)
O1ii—Ba1—O1iv120.000 (3)O1vi—Ba1—O1x60.000 (3)
O1ii—Ba1—O1v120.000 (3)O1vi—Ba1—O1xi120.000 (3)
O1ii—Ba1—O1vi60.000 (3)O1vii—Ba1—O1viii120.000 (3)
O1ii—Ba1—O1vii60.000 (3)O1vii—Ba1—O1ix60.000 (3)
O1ii—Ba1—O1viii60.000 (3)O1vii—Ba1—O1x120.000 (3)
O1ii—Ba1—O1ix60.000 (3)O1vii—Ba1—O1xi60.000 (3)
O1ii—Ba1—O1x120.000 (3)O1viii—Ba1—O1ix90.000 (6)
O1ii—Ba1—O1xi120.000 (3)O1viii—Ba1—O1x90.000 (6)
O1iii—Ba1—O190.000 (6)O1viii—Ba1—O1xi180
O1iii—Ba1—O1iv60.000 (3)O1ix—Ba1—O1x180
O1iii—Ba1—O1v60.000 (3)O1ix—Ba1—O1xi90.000 (6)
O1iii—Ba1—O1vi120.000 (3)O1x—Ba1—O1xi90.000 (6)
O1iii—Ba1—O1vii120.000 (3)O1—Li1—O1xii180
O1iii—Ba1—O1viii120.000 (3)O1—Li1—O1vii90
O1iii—Ba1—O1ix120.000 (3)O1—Li1—O1xiii90
O1iii—Ba1—O1x60.000 (3)O1—Li1—O1xi90
O1iii—Ba1—O1xi60.000 (3)O1—Li1—O1xiv90
O1—Ba1—O1iv120.000 (3)O1xii—Li1—O1vii90
O1—Ba1—O1v120.000 (3)O1xii—Li1—O1xiii90
O1—Ba1—O1vi60.000 (3)O1xii—Li1—O1xi90
O1—Ba1—O1vii60.000 (3)O1xii—Li1—O1xiv90
O1—Ba1—O1viii120.000 (3)O1vii—Li1—O1xiii180
O1—Ba1—O1ix120.000 (3)O1vii—Li1—O1xi90
O1—Ba1—O1x60.000 (3)O1vii—Li1—O1xiv90
O1—Ba1—O1xi60.000 (3)O1xiii—Li1—O1xi90
O1iv—Ba1—O1v90.000 (6)O1xiii—Li1—O1xiv90
O1iv—Ba1—O1vi90.000 (6)O1xi—Li1—O1xiv180
O1iv—Ba1—O1vii180
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z; (iii) x, y1, z; (iv) z, x1, y1; (v) z, x1, y; (vi) z, x, y1; (vii) z, x, y; (viii) y1, z, x1; (ix) y1, z, x; (x) y, z, x1; (xi) y, z, x; (xii) x, y, z+1; (xiii) z+1, x, y; (xiv) y, z+1, x.
barium lithium fluoride oxide (BaLiF3-636C) top
Crystal data top
BaLiF2.80O0.10Dx = 4.881 Mg m3
Mr = 199.1Neutron radiation, λ = 0.83860 Å
Cubic, Pm3mCell parameters from 628 reflections
Hall symbol: -P 4 2 3θ = 5.9–47.3°
a = 4.0763 (4) ÅT = 909 K
V = 67.73 (2) Å3Cube, colourless
Z = 15.00 × 5.00 × 5.00 mm
F(000) = 19.581
Data collection top
D9 position-sensitive detector
diffractometer
78 independent reflections
Radiation source: nuclear reactor, ILL high-flux reactor, beam H370 reflections with I > 2σ(I)
Cu 220 monochromatorRint = 0.021
Detector resolution: 0.5 pixels mm-1θmax = 56.0°, θmin = 5.9°
ω and ω–2θ scansh = 48
Absorption correction: gaussian
Jana2006 (Petříček et al., 2014)
k = 48
Tmin = 0.976, Tmax = 0.979l = 08
343 measured reflections
Refinement top
Refinement on F23 constraints
Least-squares matrix: fullPrimary atom site location: iterative
R[F2 > 2σ(F2)] = 0.011Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0010394176I2)
wR(F2) = 0.045(Δ/σ)max < 0.001
S = 0.98Δρmax = 0.08 e Å3
78 reflectionsΔρmin = 0.13 e Å3
7 parametersExtinction correction: SHELXL-2017/1 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 4.6 (3)
Special details top

Refinement. Substitutionally disordered fluoride and oxide ions were constrained to have the same ADP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba10000.02649 (10)
Li10.50.50.50.0368 (2)
F10.50.500.03918 (12)0.9333
O10.50.500.03918 (12)0.0333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.02649 (17)0.02649 (17)0.02649 (17)000
Li10.0368 (4)0.0368 (4)0.0368 (4)000
F10.0451 (2)0.0451 (2)0.02737 (19)000
O10.0451 (2)0.0451 (2)0.02737 (19)000
Geometric parameters (Å, º) top
Ba1—F1i2.8824 (4)Ba1—O1vi2.8824 (4)
Ba1—F1ii2.8824 (4)Ba1—O1vii2.8824 (4)
Ba1—F1iii2.8824 (4)Ba1—O1viii2.8824 (4)
Ba1—F12.8824 (4)Ba1—O1ix2.8824 (4)
Ba1—F1iv2.8824 (4)Ba1—O1x2.8824 (4)
Ba1—F1v2.8824 (4)Ba1—O1xi2.8824 (4)
Ba1—F1vi2.8824 (4)Li1—F12.0382 (4)
Ba1—F1vii2.8824 (4)Li1—F1xii2.0382 (4)
Ba1—F1viii2.8824 (4)Li1—F1vii2.0382 (4)
Ba1—F1ix2.8824 (4)Li1—F1xiii2.0382 (4)
Ba1—F1x2.8824 (4)Li1—F1xi2.0382 (4)
Ba1—F1xi2.8824 (4)Li1—F1xiv2.0382 (4)
Ba1—O1i2.8824 (4)Li1—O12.0382 (4)
Ba1—O1ii2.8824 (4)Li1—O1xii2.0382 (4)
Ba1—O1iii2.8824 (4)Li1—O1vii2.0382 (4)
Ba1—O12.8824 (4)Li1—O1xiii2.0382 (4)
Ba1—O1iv2.8824 (4)Li1—O1xi2.0382 (4)
Ba1—O1v2.8824 (4)Li1—O1xiv2.0382 (4)
F1i—Ba1—F1ii90.000 (8)O1ii—Ba1—O1vi60.000 (4)
F1i—Ba1—F1iii90.000 (8)O1ii—Ba1—O1vii60.000 (4)
F1i—Ba1—F1180O1ii—Ba1—O1viii60.000 (4)
F1i—Ba1—F1iv60.000 (4)O1ii—Ba1—O1ix60.000 (4)
F1i—Ba1—F1v60.000 (4)O1ii—Ba1—O1x120.000 (4)
F1i—Ba1—F1vi120.000 (4)O1ii—Ba1—O1xi120.000 (4)
F1i—Ba1—F1vii120.000 (4)O1iii—Ba1—O190.000 (8)
F1i—Ba1—F1viii60.000 (4)O1iii—Ba1—O1iv60.000 (4)
F1i—Ba1—F1ix60.000 (4)O1iii—Ba1—O1v60.000 (4)
F1i—Ba1—F1x120.000 (4)O1iii—Ba1—O1vi120.000 (4)
F1i—Ba1—F1xi120.000 (4)O1iii—Ba1—O1vii120.000 (4)
F1ii—Ba1—F1iii180O1iii—Ba1—O1viii120.000 (4)
F1ii—Ba1—F190.000 (8)O1iii—Ba1—O1ix120.000 (4)
F1ii—Ba1—F1iv120.000 (4)O1iii—Ba1—O1x60.000 (4)
F1ii—Ba1—F1v120.000 (4)O1iii—Ba1—O1xi60.000 (4)
F1ii—Ba1—F1vi60.000 (4)O1—Ba1—O1iv120.000 (4)
F1ii—Ba1—F1vii60.000 (4)O1—Ba1—O1v120.000 (4)
F1ii—Ba1—F1viii60.000 (4)O1—Ba1—O1vi60.000 (4)
F1ii—Ba1—F1ix60.000 (4)O1—Ba1—O1vii60.000 (4)
F1ii—Ba1—F1x120.000 (4)O1—Ba1—O1viii120.000 (4)
F1ii—Ba1—F1xi120.000 (4)O1—Ba1—O1ix120.000 (4)
F1iii—Ba1—F190.000 (8)O1—Ba1—O1x60.000 (4)
F1iii—Ba1—F1iv60.000 (4)O1—Ba1—O1xi60.000 (4)
F1iii—Ba1—F1v60.000 (4)O1iv—Ba1—O1v90.000 (8)
F1iii—Ba1—F1vi120.000 (4)O1iv—Ba1—O1vi90.000 (8)
F1iii—Ba1—F1vii120.000 (4)O1iv—Ba1—O1vii180
F1iii—Ba1—F1viii120.000 (4)O1iv—Ba1—O1viii60.000 (4)
F1iii—Ba1—F1ix120.000 (4)O1iv—Ba1—O1ix120.000 (4)
F1iii—Ba1—F1x60.000 (4)O1iv—Ba1—O1x60.000 (4)
F1iii—Ba1—F1xi60.000 (4)O1iv—Ba1—O1xi120.000 (4)
F1—Ba1—F1iv120.000 (4)O1v—Ba1—O1vi180
F1—Ba1—F1v120.000 (4)O1v—Ba1—O1vii90.000 (8)
F1—Ba1—F1vi60.000 (4)O1v—Ba1—O1viii120.000 (4)
F1—Ba1—F1vii60.000 (4)O1v—Ba1—O1ix60.000 (4)
F1—Ba1—F1viii120.000 (4)O1v—Ba1—O1x120.000 (4)
F1—Ba1—F1ix120.000 (4)O1v—Ba1—O1xi60.000 (4)
F1—Ba1—F1x60.000 (4)O1vi—Ba1—O1vii90.000 (8)
F1—Ba1—F1xi60.000 (4)O1vi—Ba1—O1viii60.000 (4)
F1iv—Ba1—F1v90.000 (8)O1vi—Ba1—O1ix120.000 (4)
F1iv—Ba1—F1vi90.000 (8)O1vi—Ba1—O1x60.000 (4)
F1iv—Ba1—F1vii180O1vi—Ba1—O1xi120.000 (4)
F1iv—Ba1—F1viii60.000 (4)O1vii—Ba1—O1viii120.000 (4)
F1iv—Ba1—F1ix120.000 (4)O1vii—Ba1—O1ix60.000 (4)
F1iv—Ba1—F1x60.000 (4)O1vii—Ba1—O1x120.000 (4)
F1iv—Ba1—F1xi120.000 (4)O1vii—Ba1—O1xi60.000 (4)
F1v—Ba1—F1vi180O1viii—Ba1—O1ix90.000 (8)
F1v—Ba1—F1vii90.000 (8)O1viii—Ba1—O1x90.000 (8)
F1v—Ba1—F1viii120.000 (4)O1viii—Ba1—O1xi180
F1v—Ba1—F1ix60.000 (4)O1ix—Ba1—O1x180
F1v—Ba1—F1x120.000 (4)O1ix—Ba1—O1xi90.000 (8)
F1v—Ba1—F1xi60.000 (4)O1x—Ba1—O1xi90.000 (8)
F1vi—Ba1—F1vii90.000 (8)F1—Li1—F1xii180
F1vi—Ba1—F1viii60.000 (4)F1—Li1—F1vii90
F1vi—Ba1—F1ix120.000 (4)F1—Li1—F1xiii90
F1vi—Ba1—F1x60.000 (4)F1—Li1—F1xi90
F1vi—Ba1—F1xi120.000 (4)F1—Li1—F1xiv90
F1vii—Ba1—F1viii120.000 (4)F1xii—Li1—F1vii90
F1vii—Ba1—F1ix60.000 (4)F1xii—Li1—F1xiii90
F1vii—Ba1—F1x120.000 (4)F1xii—Li1—F1xi90
F1vii—Ba1—F1xi60.000 (4)F1xii—Li1—F1xiv90
F1viii—Ba1—F1ix90.000 (8)F1vii—Li1—F1xiii180
F1viii—Ba1—F1x90.000 (8)F1vii—Li1—F1xi90
F1viii—Ba1—F1xi180F1vii—Li1—F1xiv90
F1ix—Ba1—F1x180F1xiii—Li1—F1xi90
F1ix—Ba1—F1xi90.000 (8)F1xiii—Li1—F1xiv90
F1x—Ba1—F1xi90.000 (8)F1xi—Li1—F1xiv180
O1i—Ba1—O1ii90.000 (8)O1—Li1—O1xii180
O1i—Ba1—O1iii90.000 (8)O1—Li1—O1vii90
O1i—Ba1—O1180O1—Li1—O1xiii90
O1i—Ba1—O1iv60.000 (4)O1—Li1—O1xi90
O1i—Ba1—O1v60.000 (4)O1—Li1—O1xiv90
O1i—Ba1—O1vi120.000 (4)O1xii—Li1—O1vii90
O1i—Ba1—O1vii120.000 (4)O1xii—Li1—O1xiii90
O1i—Ba1—O1viii60.000 (4)O1xii—Li1—O1xi90
O1i—Ba1—O1ix60.000 (4)O1xii—Li1—O1xiv90
O1i—Ba1—O1x120.000 (4)O1vii—Li1—O1xiii180
O1i—Ba1—O1xi120.000 (4)O1vii—Li1—O1xi90
O1ii—Ba1—O1iii180O1vii—Li1—O1xiv90
O1ii—Ba1—O190.000 (8)O1xiii—Li1—O1xi90
O1ii—Ba1—O1iv120.000 (4)O1xiii—Li1—O1xiv90
O1ii—Ba1—O1v120.000 (4)O1xi—Li1—O1xiv180
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z; (iii) x, y1, z; (iv) z, x1, y1; (v) z, x1, y; (vi) z, x, y1; (vii) z, x, y; (viii) y1, z, x1; (ix) y1, z, x; (x) y, z, x1; (xi) y, z, x; (xii) x, y, z+1; (xiii) z+1, x, y; (xiv) y, z+1, x.
barium lithium fluoride oxide (BaLiF3-XRD) top
Crystal data top
BaLiF2.80O0.10Dx = 5.177 Mg m3
Mr = 199.1Mo Kα radiation, λ = 0.71075 Å
Cubic, Pm3mCell parameters from 3487 reflections
Hall symbol: -P 4 2 3θ = 5.1–30.2°
a = 3.9970 (8) ŵ = 15.35 mm1
V = 63.86 (4) Å3T = 279 K
Z = 1Shard, colourless
F(000) = 850.33 × 0.21 × 0.10 mm
Data collection top
Bruker D8 VENTURE
diffractometer
34 independent reflections
Radiation source: X-ray tube34 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 7.376 pixels mm-1θmax = 30.2°, θmin = 5.1°
φ and ω scansh = 55
Absorption correction: numerical
SADABS 2014/5 (Bruker, 2001)
k = 55
Tmin = 0.020, Tmax = 0.089l = 55
2602 measured reflections
Refinement top
Refinement on F22 constraints
Least-squares matrix: fullPrimary atom site location: iterative
R[F2 > 2σ(F2)] = 0.010Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004177936I2)
wR(F2) = 0.023(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.73 e Å3
34 reflectionsΔρmin = 0.50 e Å3
6 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 5300 (500)
Special details top

Experimental. The following wavelength and cell were deduced by SADABS from the direction cosines etc. They are given here for emergency use only: CELL 0.71073 3.996 3.997 3.998 89.999 89.987 90.014

Refinement. Substitutionally disordered fluoride and oxide ions were constrained to have the same ADP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba10000.0076 (3)
F10.500.50.0124 (9)0.9333
O10.500.50.0124 (9)0.0333
Li10.50.50.50.012 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0076 (6)0.0076 (6)0.0076 (6)000
F10.0139 (13)0.0092 (19)0.0139 (13)000
O10.0139 (13)0.0092 (19)0.0139 (13)000
Li10.012 (4)0.012 (4)0.012 (4)000
Geometric parameters (Å, º) top
Ba1—O1i2.8263 (8)Li1—F11.9985 (8)
Ba1—O1ii2.8263 (8)Li1—F1xii1.9985 (8)
Ba1—O1iii2.8263 (8)Li1—F1vii1.9985 (8)
Ba1—O12.8263 (8)Li1—F1xiii1.9985 (8)
Ba1—O1iv2.8263 (8)Li1—F1xi1.9985 (8)
Ba1—O1v2.8263 (8)Li1—F1xiv1.9985 (8)
Ba1—O1vi2.8263 (8)Li1—O11.9985 (8)
Ba1—O1vii2.8263 (8)Li1—O1xii1.9985 (8)
Ba1—O1viii2.8263 (8)Li1—O1vii1.9985 (8)
Ba1—O1ix2.8263 (8)Li1—O1xiii1.9985 (8)
Ba1—O1x2.8263 (8)Li1—O1xi1.9985 (8)
Ba1—O1xi2.8263 (8)Li1—O1xiv1.9985 (8)
O1i—Ba1—O1ii90.000 (16)O1v—Ba1—O1ix120.000 (8)
O1i—Ba1—O1iii90.000 (16)O1v—Ba1—O1x60.000 (8)
O1i—Ba1—O1180O1v—Ba1—O1xi60.000 (8)
O1i—Ba1—O1iv60.000 (8)O1vi—Ba1—O1vii90.000 (16)
O1i—Ba1—O1v60.000 (8)O1vi—Ba1—O1viii60.000 (8)
O1i—Ba1—O1vi120.000 (8)O1vi—Ba1—O1ix60.000 (8)
O1i—Ba1—O1vii120.000 (8)O1vi—Ba1—O1x120.000 (8)
O1i—Ba1—O1viii60.000 (8)O1vi—Ba1—O1xi120.000 (8)
O1i—Ba1—O1ix120.000 (8)O1vii—Ba1—O1viii120.000 (8)
O1i—Ba1—O1x60.000 (8)O1vii—Ba1—O1ix120.000 (8)
O1i—Ba1—O1xi120.000 (8)O1vii—Ba1—O1x60.000 (8)
O1ii—Ba1—O1iii180O1vii—Ba1—O1xi60.000 (8)
O1ii—Ba1—O190.000 (16)O1viii—Ba1—O1ix90.000 (16)
O1ii—Ba1—O1iv60.000 (8)O1viii—Ba1—O1x90.000 (16)
O1ii—Ba1—O1v60.000 (8)O1viii—Ba1—O1xi180
O1ii—Ba1—O1vi120.000 (8)O1ix—Ba1—O1x180
O1ii—Ba1—O1vii120.000 (8)O1ix—Ba1—O1xi90.000 (16)
O1ii—Ba1—O1viii120.000 (8)O1x—Ba1—O1xi90.000 (16)
O1ii—Ba1—O1ix60.000 (8)F1—Li1—F1xii180
O1ii—Ba1—O1x120.000 (8)F1—Li1—F1vii90
O1ii—Ba1—O1xi60.000 (8)F1—Li1—F1xiii90
O1iii—Ba1—O190.000 (16)F1—Li1—F1xi90
O1iii—Ba1—O1iv120.000 (8)F1—Li1—F1xiv90
O1iii—Ba1—O1v120.000 (8)F1xii—Li1—F1vii90
O1iii—Ba1—O1vi60.000 (8)F1xii—Li1—F1xiii90
O1iii—Ba1—O1vii60.000 (8)F1xii—Li1—F1xi90
O1iii—Ba1—O1viii60.000 (8)F1xii—Li1—F1xiv90
O1iii—Ba1—O1ix120.000 (8)F1vii—Li1—F1xiii180
O1iii—Ba1—O1x60.000 (8)F1vii—Li1—F1xi90
O1iii—Ba1—O1xi120.000 (8)F1vii—Li1—F1xiv90
O1—Ba1—O1iv120.000 (8)F1xiii—Li1—F1xi90
O1—Ba1—O1v120.000 (8)F1xiii—Li1—F1xiv90
O1—Ba1—O1vi60.000 (8)F1xi—Li1—F1xiv180
O1—Ba1—O1vii60.000 (8)O1—Li1—O1xii180
O1—Ba1—O1viii120.000 (8)O1—Li1—O1vii90
O1—Ba1—O1ix60.000 (8)O1—Li1—O1xiii90
O1—Ba1—O1x120.000 (8)O1—Li1—O1xi90
O1—Ba1—O1xi60.000 (8)O1—Li1—O1xiv90
O1iv—Ba1—O1v90.000 (16)O1xii—Li1—O1vii90
O1iv—Ba1—O1vi90.000 (16)O1xii—Li1—O1xiii90
O1iv—Ba1—O1vii180O1xii—Li1—O1xi90
O1iv—Ba1—O1viii60.000 (8)O1xii—Li1—O1xiv90
O1iv—Ba1—O1ix60.000 (8)O1vii—Li1—O1xiii180
O1iv—Ba1—O1x120.000 (8)O1vii—Li1—O1xi90
O1iv—Ba1—O1xi120.000 (8)O1vii—Li1—O1xiv90
O1v—Ba1—O1vi180O1xiii—Li1—O1xi90
O1v—Ba1—O1vii90.000 (16)O1xiii—Li1—O1xiv90
O1v—Ba1—O1viii120.000 (8)O1xi—Li1—O1xiv180
Symmetry codes: (i) x1, y, z1; (ii) x1, y, z; (iii) x, y, z1; (iv) z1, x1, y; (v) z1, x, y; (vi) z, x1, y; (vii) z, x, y; (viii) y, z1, x1; (ix) y, z1, x; (x) y, z, x1; (xi) y, z, x; (xii) x, y+1, z; (xiii) z, x, y+1; (xiv) y+1, z, x.
 

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