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The structural phases observed in LiKSO_4 crystals due to thermotropic transitions have been studied for more than a century. Nowadays many different phases are referenced, but some of the results are still controversial. Structural studies by single-crystal X-ray diffraction from room temperature to 803 K are presented here. Phase II (708  \lt T  \lt 943 K) is extensively discussed on the basis of ordered and disordered models, using harmonic and anharmonic atomic displacements, and considering a twinned crystal composed of three orthorhombic domains. Analyses of the same phase at different temperatures determine the best structure model.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100003219/ca0003sup1.cif
Contains datablocks global, 573K, 723K, 803K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003219/ca0003573Ksup2.hkl
Contains datablock 573K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003219/ca0003723Ksup3.hkl
Contains datablock 723K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768100003219/ca0003803Ksup4.hkl
Contains datablock 803K

Computing details top

(573K) top
Crystal data top
LiO4SKF(000) = 140
Mr = 142.1Dx = 2.328 Mg m3
Hexagonal, P63Mo Kα radiation, λ = 0.71073 Å
a = 5.202 (1) ŵ = 1.69 mm1
c = 8.647 (2) ÅT = 573 K
V = 202.65 (9) Å3Hexagonal, colourless
Z = 20.20 × 0.20 × 0.10 mm
Data collection top
Image-Plate
diffractometer
Rint = 0.029
Oscillating scansθmax = 30.2°, θmin = 4.5°
2231 measured reflectionsh = 77
396 independent reflectionsk = 77
363 reflections with I > 3σ(I)l = 1212
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/[σ2(F) + 0.0001F2]
R[F2 > 2σ(F2)] = 0.020(Δ/σ)max = 0.001
wR(F2) = 0.026Δρmax = 0.18 e Å3
S = 2.24Δρmin = 0.19 e Å3
394 reflectionsExtinction correction: B-C type 1 Lorentzian isotropic
41 parametersExtinction coefficient: 1.4 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
K0003.71 (2)0.999999
Li0.3333330.6666670.311 (2)3.1 (1)0.999999
S0.3333330.6666670.70785 (9)2.04 (1)0.999999
O10.3333330.6666670.5411 (8)6.62 (8)0.999999
O20.3589 (7)0.4211 (6)0.7615 (6)5.07 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.0484 (2)0.0484 (2)0.0443 (3)0.0242 (1)00
Li0.033 (1)0.033 (1)0.051 (4)0.0166 (6)00
S0.0254 (2)0.0254 (2)0.0265 (2)0.0127 (1)00
O10.111 (2)0.111 (2)0.0304 (8)0.0553 (8)00
O20.0590 (8)0.0447 (7)0.0982 (9)0.0328 (6)0.0014 (8)0.0190 (8)
Bond lengths (Å) top
K—Lii3.419 (7)Li—O1ii3.804 (9)
K—Liii3.419 (7)Li—O1iii3.804 (9)
K—Liiii3.419 (7)Li—O1xv3.804 (9)
K—Siv3.9245 (5)Li—O2ii1.920 (5)
K—Sv3.9245 (5)Li—O2xv3.423 (3)
K—Svi3.9245 (5)Li—O2xvi3.423 (4)
K—Si3.5001 (4)Li—O2x1.920 (5)
K—Sii3.5001 (4)Li—O2xiv3.423 (5)
K—Siii3.5001 (4)Li—O2xvii1.920 (6)
K—O1i3.0243 (8)S—O11.442 (7)
K—O1ii3.0243 (8)S—O21.426 (4)
K—O1iii3.0243 (8)S—O2xviii3.888 (4)
K—O2iv3.795 (3)S—O2xix3.888 (3)
K—O2vi2.907 (4)S—O2xx1.426 (3)
K—O2i3.906 (4)S—O2xxi1.426 (5)
K—O2ii3.051 (5)S—O2xxii3.888 (5)
K—O2vii2.907 (4)O1—O22.335 (7)
K—O2viii3.795 (4)O1—O2ii3.057 (7)
K—O2ix3.051 (4)O1—O2xx2.335 (7)
K—O2x3.906 (4)O1—O2x3.057 (7)
K—O2xi2.907 (5)O1—O2xxi2.335 (8)
K—O2xii3.795 (4)O1—O2xvii3.057 (7)
K—O2xiii3.906 (4)O2—O2xix3.547 (4)
K—O2xiv3.051 (4)O2—O2xxiii3.242 (6)
Li—S3.43 (1)O2—O2xx2.336 (5)
Li—Sii3.133 (4)O2—O2xxiv3.547 (4)
Li—Siii3.133 (4)O2—O2xxi2.336 (6)
Li—Sxv3.133 (4)O2—O2xxii3.242 (5)
Li—O11.99 (2)
Symmetry codes: (i) xy, x1, z1/2; (ii) xy, x, z1/2; (iii) xy+1, x, z1/2; (iv) x1, y1, z1; (v) x, y1, z1; (vi) x, y, z1; (vii) y, xy, z1; (viii) y+1, xy, z1; (ix) x, y, z1/2; (x) x+1, y+1, z1/2; (xi) x+y, x, z1; (xii) x+y, x+1, z1; (xiii) y1, x+y, z1/2; (xiv) y, x+y, z1/2; (xv) xy+1, x+1, z1/2; (xvi) x, y+1, z1/2; (xvii) y, x+y+1, z1/2; (xviii) x, y+1, z; (xix) y, xy, z; (xx) y+1, xy+1, z; (xxi) x+y, x+1, z; (xxii) x+y+1, x+1, z; (xxiii) y+1, xy, z; (xxiv) x+y, x, z.
(723K) top
Crystal data top
LiO4SKF(000) = 280
Mr = 142.1Dx = 2.261 Mg m3
Orthorhombic, PmcnMo Kα radiation, λ = 0.71073 Å
a = 5.264 (4) ŵ = 1.64 mm1
b = 9.148 (3) ÅT = 723 K
c = 8.666 (4) ÅHexagoal, colorless
V = 417.3 (4) Å30.20 × 0.20 × 0.10 mm
Z = 4
Data collection top
Image-Plate
diffractometer
Rint = 0.063
Oscillating scansθmax = 30.5°, θmin = 3.2°
13569 measured reflectionsh = 77
2380 independent reflectionsk = 1212
986 reflections with I > 3σ(I)l = 1212
Refinement top
Refinement on F60 parameters
R[F2 > 2σ(F2)] = 0.055Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
wR(F2) = 0.063(Δ/σ)max = 0.001
S = 3.55Δρmax = 0.18 e Å3
1066 reflectionsΔρmin = 0.14 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
K0.250.2050 (1)0.99706 (8)0.1039 (3)
Li0.750.0779 (4)0.6603 (5)0.072 (1)
S0.7500 (7)0.4048 (1)0.78394 (9)0.0766 (4)
O10.670 (2)0.400 (1)0.9370 (5)0.273 (5)0.5
O21.000 (1)0.442 (1)0.7481 (8)0.165 (3)0.5
O30.598 (2)0.498 (1)0.723 (2)0.281 (7)0.5
O40.842 (1)0.2692 (6)0.7347 (7)0.187 (5)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.1066 (7)0.1157 (6)0.0895 (5)000.0054 (4)
Li0.059 (2)0.067 (3)0.090 (3)000.002 (2)
S0.0751 (8)0.0800 (8)0.0747 (5)0.034 (2)0.019 (2)0.0025 (6)
O10.27 (1)0.45 (1)0.092 (2)0.162 (8)0.098 (5)0.049 (4)
O20.022 (3)0.235 (8)0.236 (7)0.031 (3)0.023 (2)0.080 (5)
O30.120 (6)0.280 (9)0.44 (2)0.011 (6)0.019 (7)0.26 (1)
O40.133 (6)0.103 (3)0.32 (1)0.006 (3)0.018 (3)0.084 (4)
Bond lengths (Å) top
K—Lii3.939 (4)Li—O3xiv3.93 (1)
K—Liii3.588 (3)Li—O3vi2.21 (1)
K—Liiii3.588 (3)Li—O3xv3.65 (1)
K—Liiv3.674 (4)Li—O3vii3.65 (1)
K—Sv3.705 (3)Li—O3xvi2.21 (1)
K—S3.692 (3)Li—O3xvii3.93 (1)
K—Sii3.764 (3)Li—O3xi3.97 (1)
K—Siii3.751 (3)Li—O41.927 (7)
K—Svi3.670 (1)Li—O4xiv3.973 (8)
K—Svii3.670 (1)Li—O4xv3.664 (7)
K—Sviii3.751 (3)Li—O4vii3.664 (7)
K—Six3.764 (3)Li—O4xvii3.973 (8)
K—Sx3.692 (3)Li—O4xi1.927 (7)
K—Sxi3.705 (3)S—Sxi0.018 (5)
K—O1v3.572 (9)S—O11.389 (5)
K—O12.888 (9)S—O1xii3.728 (8)
K—O1xii3.685 (9)S—O1xviii3.739 (8)
K—O1xiii3.685 (9)S—O1xi1.395 (5)
K—O1x2.888 (9)S—O2v3.964 (8)
K—O1xi3.572 (9)S—O21.405 (8)
K—O2v3.331 (8)S—O2xi1.388 (8)
K—O2ii2.877 (8)S—O2xix3.983 (8)
K—O2vi3.468 (8)S—O31.28 (1)
K—O2vii3.468 (8)S—O3xi1.29 (1)
K—O2ix2.877 (8)S—O41.401 (6)
K—O2xi3.331 (8)S—O4xx3.975 (6)
K—O3xii3.73 (1)S—O4xxi3.965 (6)
K—O3iii3.26 (1)S—O4xi1.395 (6)
K—O3vi2.81 (1)O1—O1xii2.79 (1)
K—O3vii2.81 (1)O1—O1xiii3.39 (1)
K—O3viii3.26 (1)O1—O1xviii3.39 (1)
K—O3xiii3.73 (1)O1—O1xi0.84 (1)
K—O4v3.183 (7)O1—O2v3.91 (1)
K—O43.901 (7)O1—O22.42 (1)
K—O4ii2.986 (7)O1—O2xxii3.54 (1)
K—O4iii3.741 (7)O1—O2xiii3.21 (1)
K—O4viii3.741 (7)O1—O2xi1.907 (9)
K—O4ix2.986 (7)O1—O32.09 (1)
K—O4x3.901 (7)O1—O3xii3.39 (1)
K—O4xi3.183 (7)O1—O3xviii3.82 (1)
Li—S3.177 (4)O1—O3xi2.39 (1)
Li—Sxiv3.265 (4)O1—O42.305 (9)
Li—Svi3.102 (4)O1—O4iii3.140 (9)
Li—Sxv3.117 (4)O1—O4ix3.008 (9)
Li—Svii3.117 (4)O1—O4xi2.122 (9)
Li—Sxvi3.102 (4)O2—O2xi2.64 (1)
Li—Sxvii3.265 (4)O2—O2xix2.63 (1)
Li—Sxi3.177 (4)O2—O32.19 (1)
Li—O13.820 (9)O2—O3xxiii3.19 (1)
Li—O1xiv1.990 (6)O2—O3xi0.76 (1)
Li—O1vi2.874 (9)O2—O41.79 (1)
Li—O1xv3.561 (9)O2—O4xx3.11 (1)
Li—O1vii3.561 (9)O2—O4xxiv3.49 (1)
Li—O1xvi2.874 (9)O2—O4xi2.40 (1)
Li—O1xvii1.990 (6)O2—O4xix3.81 (1)
Li—O1xi3.820 (9)O3—O3x3.66 (2)
Li—O23.66 (1)O3—O3xi1.60 (2)
Li—O2xiv3.811 (8)O3—O42.46 (1)
Li—O2xv1.974 (9)O3—O4iv3.41 (1)
Li—O2vii1.974 (9)O3—O4xx3.87 (1)
Li—O2xvii3.811 (8)O3—O4xxi2.84 (1)
Li—O2xi3.66 (1)O3—O4xi2.12 (1)
Li—O33.97 (1)O4—O4xi0.97 (1)
Symmetry codes: (i) x+1, y, z+2; (ii) x1, y+1/2, z+1/2; (iii) x, y+1/2, z+1/2; (iv) x+1, y+1/2, z+3/2; (v) x1, y, z; (vi) x+1, y1/2, z+3/2; (vii) x1/2, y1/2, z+3/2; (viii) x+1/2, y+1/2, z+1/2; (ix) x+3/2, y+1/2, z+1/2; (x) x+1/2, y, z; (xi) x+3/2, y, z; (xii) x+1, y+1, z+2; (xiii) x1/2, y+1, z+2; (xiv) x, y+1/2, z1/2; (xv) x+2, y1/2, z+3/2; (xvi) x+1/2, y1/2, z+3/2; (xvii) x+3/2, y+1/2, z1/2; (xviii) x+1/2, y+1, z+2; (xix) x+5/2, y, z; (xx) x+2, y+1/2, z+3/2; (xxi) x1/2, y+1/2, z+3/2; (xxii) x+2, y+1, z+2; (xxiii) x+1, y, z; (xxiv) x+1/2, y+1/2, z+3/2.
(803K) top
Crystal data top
LiO4SKZ = 4
Mr = 142.1F(000) = 280
Orthorhombic, PmcnMo Kα radiation, λ = 0.71073 Å
a = 5.270 (2) ŵ = 1.62 mm1
b = 9.193 (2) ÅT = 803 K
c = 8.751 (2) ÅHexagoal, colorless
V = 424.0 (2) Å30.20 × 0.20 × 0.10 mm
Data collection top
Image-Plate
diffractometer
Rint = 0.077
Oscillating scansθmax = 30.5°, θmin = 3.2°
10251 measured reflectionsh = 77
4752 independent reflectionsk = 1212
1433 reflections with I > 3σ(I)l = 1212
Refinement top
Refinement on F60 parameters
R[F2 > 2σ(F2)] = 0.059Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
wR(F2) = 0.065(Δ/σ)max = 0.0003
S = 2.95Δρmax = 0.93 e Å3
1095 reflectionsΔρmin = 1.03 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
K0.250.2070 (1)0.9972 (1)0.1209 (5)
Li0.750.0776 (5)0.6599 (5)0.069 (2)
S0.7500 (9)0.4059 (2)0.7809 (1)0.0845 (5)
O10.655 (2)0.401 (1)0.9316 (6)0.276 (6)0.5
O20.994 (2)0.443 (1)0.7488 (9)0.196 (5)0.5
O30.612 (3)0.489 (2)0.707 (2)0.40 (1)0.5
O40.847 (2)0.2717 (7)0.7350 (9)0.204 (6)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.1236 (9)0.1365 (9)0.1027 (6)000.0052 (6)
Li0.067 (3)0.059 (3)0.083 (3)000.008 (3)
S0.078 (1)0.089 (1)0.0864 (7)0.036 (2)0.019 (2)0.0049 (8)
O10.25 (1)0.48 (1)0.106 (3)0.151 (9)0.088 (5)0.055 (6)
O20.018 (3)0.28 (1)0.285 (9)0.054 (4)0.027 (3)0.077 (7)
O30.16 (1)0.40 (2)0.63 (3)0.059 (8)0.06 (1)0.41 (2)
O40.152 (7)0.090 (4)0.37 (2)0.007 (3)0.038 (5)0.074 (4)
Bond lengths (Å) top
K—Lii3.981 (5)Li—O2xi3.68 (1)
K—Liii3.591 (3)Li—O33.88 (2)
K—Liiii3.591 (3)Li—O3vi2.38 (2)
K—Liiv3.674 (5)Li—O3xv3.65 (1)
K—Sv3.718 (4)Li—O3vii3.65 (1)
K—S3.731 (4)Li—O3xvi2.38 (2)
K—Sii3.760 (4)Li—O3xi3.88 (2)
K—Siii3.773 (4)Li—O41.969 (8)
K—Svi3.685 (2)Li—O4xv3.642 (8)
K—Svii3.685 (2)Li—O4vii3.642 (8)
K—Sviii3.773 (4)Li—O4xi1.969 (8)
K—Six3.760 (4)S—Sxi0.018 (7)
K—Sx3.731 (4)S—O11.415 (7)
K—Sxi3.718 (4)S—O1xii3.753 (9)
K—O1v3.65 (1)S—O1xviii3.743 (9)
K—O12.84 (1)S—O1xi1.408 (7)
K—O1xii3.69 (1)S—O21.354 (9)
K—O1xiii3.69 (1)S—O2xi1.371 (9)
K—O1x2.84 (1)S—O2xix3.997 (9)
K—O1xi3.65 (1)S—O31.24 (2)
K—O2v3.355 (9)S—O3xi1.23 (2)
K—O2ii2.928 (9)S—O41.391 (7)
K—O2vi3.49 (1)S—O4xx3.976 (7)
K—O2vii3.49 (1)S—O4xxi3.985 (7)
K—O2ix2.928 (9)S—O4xi1.397 (7)
K—O2xi3.355 (9)O1—O1xii2.73 (1)
K—O3xii3.88 (2)O1—O1xiii3.42 (1)
K—O3iii3.20 (2)O1—O1xviii3.42 (1)
K—O3vi2.78 (2)O1—O1xi1.00 (1)
K—O3vii2.78 (2)O1—O2v3.85 (1)
K—O3viii3.20 (2)O1—O22.43 (1)
K—O3xiii3.88 (2)O1—O2xxii3.64 (1)
K—O4v3.183 (8)O1—O2xiii3.25 (1)
K—O43.938 (9)O1—O2xi1.83 (1)
K—O4ii2.981 (8)O1—O32.14 (2)
K—O4iii3.777 (9)O1—O3xii3.60 (2)
K—O4viii3.777 (9)O1—O3xi2.45 (2)
K—O4ix2.981 (8)O1—O42.32 (1)
K—O4x3.938 (9)O1—O4iii3.25 (1)
K—O4xi3.183 (8)O1—O4ix3.09 (1)
Li—S3.199 (5)O1—O4xi2.09 (1)
Li—Sxiv3.321 (5)O2—O2xi2.58 (1)
Li—Svi3.122 (5)O2—O2xix2.69 (1)
Li—Sxv3.107 (5)O2—O32.09 (2)
Li—Svii3.107 (5)O2—O3xxiii3.30 (2)
Li—Sxvi3.122 (5)O2—O3xi0.79 (2)
Li—Sxvii3.321 (5)O2—O41.76 (1)
Li—Sxi3.199 (5)O2—O4xx3.14 (1)
Li—O13.84 (1)O2—O4xxiv3.55 (1)
Li—O1xiv2.069 (7)O2—O4xi2.39 (1)
Li—O1vi2.80 (1)O2—O4xix3.81 (1)
Li—O1xv3.62 (1)O3—O3xxv3.82 (3)
Li—O1vii3.62 (1)O3—O3x3.81 (2)
Li—O1xvi2.80 (1)O3—O3xi1.46 (2)
Li—O1xvii2.069 (7)O3—O42.36 (2)
Li—O1xi3.84 (1)O3—O4iv3.58 (2)
Li—O23.68 (1)O3—O4xx3.89 (2)
Li—O2xiv3.826 (9)O3—O4xxi2.99 (2)
Li—O2xv1.99 (1)O3—O4xi2.03 (2)
Li—O2vii1.99 (1)O4—O4xi1.02 (1)
Li—O2xvii3.826 (9)
Symmetry codes: (i) x+1, y, z+2; (ii) x1, y+1/2, z+1/2; (iii) x, y+1/2, z+1/2; (iv) x+1, y+1/2, z+3/2; (v) x1, y, z; (vi) x+1, y1/2, z+3/2; (vii) x1/2, y1/2, z+3/2; (viii) x+1/2, y+1/2, z+1/2; (ix) x+3/2, y+1/2, z+1/2; (x) x+1/2, y, z; (xi) x+3/2, y, z; (xii) x+1, y+1, z+2; (xiii) x1/2, y+1, z+2; (xiv) x, y+1/2, z1/2; (xv) x+2, y1/2, z+3/2; (xvi) x+1/2, y1/2, z+3/2; (xvii) x+3/2, y+1/2, z1/2; (xviii) x+1/2, y+1, z+2; (xix) x+5/2, y, z; (xx) x+2, y+1/2, z+3/2; (xxi) x1/2, y+1/2, z+3/2; (xxii) x+2, y+1, z+2; (xxiii) x+1, y, z; (xxiv) x+1/2, y+1/2, z+3/2; (xxv) x+1, y+1, z+1.
 

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