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One of the purposes of this work is to provide a crystallographic review of group 1 and thallium rare-earth ternary sulfides M+Ln3+S2. We have therefore determined crystal structures of KLaS2, KPrS2, KEuS2, KGdS2, KLuS2, KYS2, RbYS2, which belong to the α-NaFeO2 structural family (R \bar 3 m), as well as NaLaS2, which is derived from the disordered NaCl structural type (Fm \bar 3 m). The determined structures were compared with known members of the group 1 as well as thallium(I) rare-earth sulfides by the standard tools of crystal-chemical analysis such as comparison of bond-valences, analysis of interatomic distances and comparison of the unit-cell parameters. The results indicate why the cubic structural type is limited to Li+ and Na+ members of the series only. The analysis has also revealed frequent problems in the reported crystal structures, especially in the determination of the K+ compounds, probably due to severe absorption and different accuracy and sensitivity of various instruments. Intense diffuse scattering has been discovered in NaLaS2, which will be the subject of further investigation. The newly determined as well as already known structures are summarized, together with critical comments about possible errors in the previous structure determinations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520613034574/bp5060sup1.cif
Contains datablocks global, I, II, III, IV, V, VI, VII, VIII

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060IIsup3.hkl
Contains datablock II

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060IIIsup4.hkl
Contains datablock III

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060IVsup5.hkl
Contains datablock IV

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060Vsup6.hkl
Contains datablock V

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060VIsup7.hkl
Contains datablock VI

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060VIIsup8.hkl
Contains datablock VII

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Structure factor file (CIF format) https://doi.org/10.1107/S2052520613034574/bp5060VIIIsup9.hkl
Contains datablock VIII

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Extra tables

CCDC references: 978623; 978624; 978625; 978626; 978627; 978628; 978629; 978630

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

The text is given in the hard-copy of the article.

Computing details top

For all compounds, data collection: CrysAlis PRO (Agilent Technologies, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et. al., 2006); molecular graphics: DIAMOND 3.0 (Brandenburg, K. - Crystal Impact, GbR, Bonn, Germany, 2010).; software used to prepare material for publication: JANA2006 (Petříček et. al., 2006).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
[Figure 10]
[Figure 11]
[Figure 12]
[Figure 13]
[Figure 14]
[Figure 15]
[Figure 16]
[Figure 17]
[Figure 18]
(I) Potassium Lanthanum sulfide top
Crystal data top
KLaS2Dx = 3.490 Mg m3
Mr = 242.1Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 607 reflections
Hall symbol: -R 3 2"θ = 5.6–28.8°
a = 4.2651 (4) ŵ = 10.87 mm1
c = 21.929 (3) ÅT = 300 K
V = 345.47 (7) Å3Plate, colourless
Z = 30.16 × 0.11 × 0.04 mm
F(000) = 324
Data collection top
Xcalibur, Gemini ultra
diffractometer
226 independent reflections
Radiation source: Enhance (Mo) X-ray Source224 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 10.3784 pixels mm-1θmax = 29.0°, θmin = 5.6°
ω scansh = 54
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 45
Tmin = 0.377, Tmax = 0.646l = 2827
909 measured reflections
Refinement top
Refinement on F20 restraints
R[F2 > 2σ(F2)] = 0.0280 constraints
wR(F2) = 0.073Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 2.03(Δ/σ)max = 0.010
226 reflectionsΔρmax = 2.50 e Å3
9 parametersΔρmin = 1.72 e Å3
Crystal data top
KLaS2Z = 3
Mr = 242.1Mo Kα radiation
Trigonal, R3mµ = 10.87 mm1
a = 4.2651 (4) ÅT = 300 K
c = 21.929 (3) Å0.16 × 0.11 × 0.04 mm
V = 345.47 (7) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
226 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
224 reflections with I > 3σ(I)
Tmin = 0.377, Tmax = 0.646Rint = 0.046
909 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0289 parameters
wR(F2) = 0.0730 restraints
S = 2.03Δρmax = 2.50 e Å3
226 reflectionsΔρmin = 1.72 e Å3
Special details top

Refinement. The refinement has been carried out under assumption of presence of obverse-reverse twinning with the refined domain-state proportions 0.547 (3)/0.453 (3).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1000.23718 (11)0.0117 (7)
La10.3333330.6666670.1666670.0108 (3)
K10000.0204 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0113 (8)0.0113 (8)0.0126 (12)0.0057 (4)00
La10.0077 (3)0.0077 (3)0.0169 (5)0.00386 (17)00
K10.0211 (11)0.0211 (11)0.0190 (17)0.0105 (5)00
Geometric parameters (Å, º) top
S1—S1i3.953 (3)S1—La12.9076 (15)
S1—S1ii3.953 (3)S1—K1vi3.2420 (17)
S1—S1iii3.953 (3)S1—K1vii3.2420 (17)
S1—La1iv2.9076 (15)S1—K1viii3.2420 (17)
S1—La1v2.9076 (14)
S1i—S1—S1ii65.30 (5)K1vi—S1—K1vii82.26 (5)
S1i—S1—S1iii65.30 (5)K1vi—S1—K1viii82.26 (5)
S1i—S1—La1iv47.18 (3)K1vii—S1—K1viii82.26 (5)
S1i—S1—La1v47.18 (3)S1—La1—S1ix94.35 (4)
S1i—S1—La196.41 (7)S1—La1—S1x94.35 (4)
S1i—S1—K1vi92.04 (3)S1—La1—S1ii85.65 (4)
S1i—S1—K1vii138.194 (17)S1—La1—S1iii85.65 (4)
S1i—S1—K1viii138.194 (17)S1—La1—S1xi180.0 (5)
S1ii—S1—S1iii65.30 (5)S1ix—La1—S1x94.35 (4)
S1ii—S1—La1iv47.18 (3)S1ix—La1—S1ii85.65 (4)
S1ii—S1—La1v96.41 (7)S1ix—La1—S1iii180.0 (5)
S1ii—S1—La147.18 (3)S1ix—La1—S1xi85.65 (4)
S1ii—S1—K1vi138.194 (17)S1x—La1—S1ii180.0 (5)
S1ii—S1—K1vii92.04 (3)S1x—La1—S1iii85.65 (4)
S1ii—S1—K1viii138.194 (17)S1x—La1—S1xi85.65 (4)
S1iii—S1—La1iv96.41 (7)S1ii—La1—S1iii94.35 (4)
S1iii—S1—La1v47.18 (3)S1ii—La1—S1xi94.35 (4)
S1iii—S1—La147.18 (3)S1iii—La1—S1xi94.35 (4)
S1iii—S1—K1vi138.194 (17)S1xii—K1—S1xiii82.26 (4)
S1iii—S1—K1vii138.194 (17)S1xii—K1—S1xiv82.26 (4)
S1iii—S1—K1viii92.04 (3)S1xii—K1—S1i97.74 (4)
La1iv—S1—La1v94.35 (6)S1xii—K1—S1ii97.74 (4)
La1iv—S1—La194.35 (6)S1xii—K1—S1iii180.0 (5)
La1iv—S1—K1vi91.389 (13)S1xiii—K1—S1xiv82.26 (4)
La1iv—S1—K1vii91.389 (12)S1xiii—K1—S1i97.74 (4)
La1iv—S1—K1viii171.55 (8)S1xiii—K1—S1ii180.0 (5)
La1v—S1—La194.35 (6)S1xiii—K1—S1iii97.74 (4)
La1v—S1—K1vi91.389 (12)S1xiv—K1—S1i180.0 (5)
La1v—S1—K1vii171.55 (8)S1xiv—K1—S1ii97.74 (4)
La1v—S1—K1viii91.389 (12)S1xiv—K1—S1iii97.74 (4)
La1—S1—K1vi171.55 (8)S1i—K1—S1ii82.26 (4)
La1—S1—K1vii91.389 (12)S1i—K1—S1iii82.26 (4)
La1—S1—K1viii91.389 (13)S1ii—K1—S1iii82.26 (4)
Symmetry codes: (i) y1/3, x2/3, z+1/3; (ii) y1/3, x+1/3, z+1/3; (iii) y+2/3, x+1/3, z+1/3; (iv) x1, y1, z; (v) x, y1, z; (vi) x1/3, y2/3, z+1/3; (vii) x1/3, y+1/3, z+1/3; (viii) x+2/3, y+1/3, z+1/3; (ix) x, y+1, z; (x) x+1, y+1, z; (xi) y+2/3, x+4/3, z+1/3; (xii) x2/3, y1/3, z1/3; (xiii) x+1/3, y1/3, z1/3; (xiv) x+1/3, y+2/3, z1/3.
(II) Potassium praseodym sulfide top
Crystal data top
KPrS2Dx = 3.648 Mg m3
Mr = 244.1Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 1542 reflections
Hall symbol: -R 3 2"θ = 5.6–32.5°
a = 4.1925 (3) ŵ = 12.62 mm1
c = 21.8920 (14) ÅT = 302 K
V = 333.24 (4) Å3Plate, yellow
Z = 30.52 × 0.21 × 0.07 mm
F(000) = 330
Data collection top
Xcalibur, Gemini ultra
diffractometer
306 independent reflections
Radiation source: Enhance (Mo) X-ray Source264 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 10.3784 pixels mm-1θmax = 32.7°, θmin = 5.6°
ω scansh = 66
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 66
Tmin = 0.098, Tmax = 0.454l = 3133
3338 measured reflections
Refinement top
Refinement on F20 constraints
R[F2 > 2σ(F2)] = 0.016Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.056(Δ/σ)max = 0.012
S = 1.78Δρmax = 0.21 e Å3
306 reflectionsΔρmin = 0.36 e Å3
10 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 520 (50)
Crystal data top
KPrS2Z = 3
Mr = 244.1Mo Kα radiation
Trigonal, R3mµ = 12.62 mm1
a = 4.1925 (3) ÅT = 302 K
c = 21.8920 (14) Å0.52 × 0.21 × 0.07 mm
V = 333.24 (4) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
306 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
264 reflections with I > 3σ(I)
Tmin = 0.098, Tmax = 0.454Rint = 0.027
3338 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.01610 parameters
wR(F2) = 0.0560 restraints
S = 1.78Δρmax = 0.21 e Å3
306 reflectionsΔρmin = 0.36 e Å3
Special details top

Refinement. The refinement has been carried out under assumption of presence of obverse-reverse twinning with the refined domain-state proportions 0.99868 (4)/0.00131 (4).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pr10.3333330.6666670.1666670.00875 (15)
K10000.0169 (4)
S2000.23618 (7)0.0105 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pr10.00712 (19)0.00712 (19)0.0120 (2)0.00356 (9)00
K10.0179 (5)0.0179 (5)0.0149 (7)0.0089 (2)00
S20.0098 (3)0.0098 (3)0.0120 (5)0.00491 (17)00
Bond lengths (Å) top
Pr1—S22.8592 (9)K1—S2viii3.2222 (10)
Pr1—S2i2.8592 (8)K1—S2ix3.2222 (10)
Pr1—S2ii2.8592 (9)K1—S2iii3.2222 (10)
Pr1—S2iii2.8592 (9)K1—S2iv3.2222 (10)
Pr1—S2iv2.8592 (8)S2—S2ix3.8887 (16)
Pr1—S2v2.8592 (9)S2—S2iii3.8887 (16)
K1—S2vi3.2222 (10)S2—S2iv3.8887 (16)
K1—S2vii3.2222 (10)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) y1/3, x+1/3, z+1/3; (iv) y+2/3, x+1/3, z+1/3; (v) y+2/3, x+4/3, z+1/3; (vi) x2/3, y1/3, z1/3; (vii) x+1/3, y1/3, z1/3; (viii) x+1/3, y+2/3, z1/3; (ix) y1/3, x2/3, z+1/3.
(III) Potassium europium sulfide top
Crystal data top
EuKS2Dx = 4.004 Mg m3
Mr = 255.2Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 1662 reflections
Hall symbol: -R 3 2"θ = 5.6–32.4°
a = 4.0981 (3) ŵ = 16.56 mm1
c = 21.8212 (15) ÅT = 302 K
V = 317.38 (4) Å3Plate, brown
Z = 30.27 × 0.14 × 0.12 mm
F(000) = 342
Data collection top
Xcalibur, Gemini ultra
diffractometer
177 independent reflections
Radiation source: Enhance (Mo) X-ray Source177 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 10.3784 pixels mm-1θmax = 32.4°, θmin = 5.6°
ω scansh = 55
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 66
Tmin = 0.049, Tmax = 0.220l = 3232
1970 measured reflections
Refinement top
Refinement on F20 constraints
R[F2 > 2σ(F2)] = 0.010Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.025(Δ/σ)max = 0.001
S = 0.90Δρmax = 0.44 e Å3
177 reflectionsΔρmin = 0.38 e Å3
9 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 142 (17)
Crystal data top
EuKS2Z = 3
Mr = 255.2Mo Kα radiation
Trigonal, R3mµ = 16.56 mm1
a = 4.0981 (3) ÅT = 302 K
c = 21.8212 (15) Å0.27 × 0.14 × 0.12 mm
V = 317.38 (4) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
177 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
177 reflections with I > 3σ(I)
Tmin = 0.049, Tmax = 0.220Rint = 0.030
1970 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0109 parameters
wR(F2) = 0.0250 restraints
S = 0.90Δρmax = 0.44 e Å3
177 reflectionsΔρmin = 0.38 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Eu10.3333330.6666670.1666670.00867 (9)
K10000.0134 (3)
S2000.23536 (4)0.0111 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Eu10.00749 (12)0.00749 (12)0.01104 (14)0.00375 (6)00
K10.0145 (3)0.0145 (3)0.0113 (4)0.00724 (16)00
S20.0108 (3)0.0108 (3)0.0119 (3)0.00539 (13)00
Geometric parameters (Å, º) top
Eu1—S22.8009 (7)K1—S2viii3.1889 (8)
Eu1—S2i2.8009 (5)K1—S2ix3.1889 (8)
Eu1—S2ii2.8009 (7)K1—S2iii3.1889 (7)
Eu1—S2iii2.8009 (7)K1—S2iv3.1889 (8)
Eu1—S2iv2.8009 (5)S2—S2ix3.8191 (11)
Eu1—S2v2.8009 (7)S2—S2iii3.8191 (11)
K1—S2vi3.1889 (8)S2—S2iv3.8191 (11)
K1—S2vii3.1889 (7)
S2—Eu1—S2i94.037 (16)Eu1x—S2—K1xiii92.602 (6)
S2—Eu1—S2ii94.037 (17)Eu1x—S2—K1xiv170.25 (3)
S2—Eu1—S2iii85.964 (17)Eu1x—S2—S2ix47.018 (11)
S2—Eu1—S2iv85.963 (16)Eu1x—S2—S2iii47.018 (12)
S2—Eu1—S2v180Eu1x—S2—S2iv95.93 (3)
S2i—Eu1—S2ii94.037 (16)Eu1xi—S2—Eu194.04 (2)
S2i—Eu1—S2iii85.964 (16)Eu1xi—S2—K1xii92.602 (6)
S2i—Eu1—S2iv180Eu1xi—S2—K1xiii170.25 (3)
S2i—Eu1—S2v85.964 (16)Eu1xi—S2—K1xiv92.602 (6)
S2ii—Eu1—S2iii180Eu1xi—S2—S2ix47.018 (12)
S2ii—Eu1—S2iv85.963 (16)Eu1xi—S2—S2iii95.93 (3)
S2ii—Eu1—S2v85.964 (17)Eu1xi—S2—S2iv47.018 (12)
S2iii—Eu1—S2iv94.036 (16)Eu1—S2—K1xii170.25 (3)
S2iii—Eu1—S2v94.036 (17)Eu1—S2—K1xiii92.602 (6)
S2iv—Eu1—S2v94.036 (16)Eu1—S2—K1xiv92.602 (8)
S2vi—K1—S2vii79.967 (14)Eu1—S2—S2ix95.93 (3)
S2vi—K1—S2viii79.967 (15)Eu1—S2—S2iii47.018 (12)
S2vi—K1—S2ix100.033 (15)Eu1—S2—S2iv47.018 (11)
S2vi—K1—S2iii100.033 (14)K1xii—S2—K1xiii79.97 (2)
S2vi—K1—S2iv180K1xii—S2—K1xiv79.97 (2)
S2vii—K1—S2viii79.967 (14)K1xii—S2—S2ix93.819 (12)
S2vii—K1—S2ix100.033 (14)K1xii—S2—S2iii139.122 (7)
S2vii—K1—S2iii180K1xii—S2—S2iv139.122 (6)
S2vii—K1—S2iv100.033 (14)K1xiii—S2—K1xiv79.97 (2)
S2viii—K1—S2ix180K1xiii—S2—S2ix139.122 (7)
S2viii—K1—S2iii100.033 (14)K1xiii—S2—S2iii93.819 (10)
S2viii—K1—S2iv100.033 (15)K1xiii—S2—S2iv139.122 (7)
S2ix—K1—S2iii79.967 (14)K1xiv—S2—S2ix139.122 (6)
S2ix—K1—S2iv79.967 (15)K1xiv—S2—S2iii139.122 (7)
S2iii—K1—S2iv79.967 (14)K1xiv—S2—S2iv93.819 (12)
Eu1x—S2—Eu1xi94.04 (2)S2ix—S2—S2iii64.895 (18)
Eu1x—S2—Eu194.04 (2)S2ix—S2—S2iv64.895 (18)
Eu1x—S2—K1xii92.602 (8)S2iii—S2—S2iv64.895 (18)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) y1/3, x+1/3, z+1/3; (iv) y+2/3, x+1/3, z+1/3; (v) y+2/3, x+4/3, z+1/3; (vi) x2/3, y1/3, z1/3; (vii) x+1/3, y1/3, z1/3; (viii) x+1/3, y+2/3, z1/3; (ix) y1/3, x2/3, z+1/3; (x) x1, y1, z; (xi) x, y1, z; (xii) x1/3, y2/3, z+1/3; (xiii) x1/3, y+1/3, z+1/3; (xiv) x+2/3, y+1/3, z+1/3.
(IV) Potassium gadolinium sulfide top
Crystal data top
GdKS2Dx = 4.126 Mg m3
Mr = 260.5Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 1335 reflections
Hall symbol: -R 3 -2"θ = 5.6–29.0°
a = 4.0715 (7) ŵ = 17.57 mm1
c = 21.901 (4) ÅT = 303 K
V = 314.41 (10) Å3Plate, colourless
Z = 30.66 × 0.38 × 0.04 mm
F(000) = 345
Data collection top
Xcalibur, Gemini ultra
diffractometer
221 independent reflections
Radiation source: Enhance (Mo) X-ray Source216 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.058
Detector resolution: 10.3784 pixels mm-1θmax = 29.2°, θmin = 5.6°
ω scansh = 55
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 55
Tmin = 0.016, Tmax = 0.497l = 2927
2426 measured reflections
Refinement top
Refinement on F20 restraints
R[F2 > 2σ(F2)] = 0.0350 constraints
wR(F2) = 0.093Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 2.88(Δ/σ)max = 0.029
221 reflectionsΔρmax = 1.08 e Å3
9 parametersΔρmin = 0.76 e Å3
Crystal data top
GdKS2Z = 3
Mr = 260.5Mo Kα radiation
Trigonal, R3mµ = 17.57 mm1
a = 4.0715 (7) ÅT = 303 K
c = 21.901 (4) Å0.66 × 0.38 × 0.04 mm
V = 314.41 (10) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
221 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
216 reflections with I > 3σ(I)
Tmin = 0.016, Tmax = 0.497Rint = 0.058
2426 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0359 parameters
wR(F2) = 0.0930 restraints
S = 2.88Δρmax = 1.08 e Å3
221 reflectionsΔρmin = 0.76 e Å3
Special details top

Refinement. The refinement has been carried out under assumption of presence of obverse-reverse twinning with the refined domain-state proportions 0.9639 (7)/0.0361 (7).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1000.23501 (17)0.0098 (8)
Gd10.3333330.6666670.1666670.0079 (3)
K10000.0159 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0090 (10)0.0090 (10)0.0113 (15)0.0045 (5)00
Gd10.0060 (4)0.0060 (4)0.0117 (5)0.0030 (2)00
K10.0169 (14)0.0169 (14)0.014 (2)0.0085 (7)00
Geometric parameters (Å, º) top
S1—S1i3.806 (4)S1—Gd12.787 (2)
S1—S1ii3.806 (4)S1—K1vi3.188 (3)
S1—S1iii3.806 (4)S1—K1vii3.188 (3)
S1—Gd1iv2.787 (2)S1—K1viii3.188 (3)
S1—Gd1v2.787 (2)
S1i—S1—S1ii64.67 (7)K1vi—S1—K1vii79.37 (7)
S1i—S1—S1iii64.67 (7)K1vi—S1—K1viii79.37 (7)
S1i—S1—Gd1iv46.93 (4)K1vii—S1—K1viii79.37 (7)
S1i—S1—Gd1v46.93 (4)S1—Gd1—S1ix93.86 (6)
S1i—S1—Gd195.65 (10)S1—Gd1—S1x93.86 (6)
S1i—S1—K1vi94.35 (4)S1—Gd1—S1ii86.14 (6)
S1i—S1—K1vii139.37 (2)S1—Gd1—S1iii86.14 (6)
S1i—S1—K1viii139.37 (2)S1—Gd1—S1xi180.0 (5)
S1ii—S1—S1iii64.67 (7)S1ix—Gd1—S1x93.86 (6)
S1ii—S1—Gd1iv46.93 (4)S1ix—Gd1—S1ii86.14 (6)
S1ii—S1—Gd1v95.65 (10)S1ix—Gd1—S1iii180.0 (5)
S1ii—S1—Gd146.93 (4)S1ix—Gd1—S1xi86.14 (6)
S1ii—S1—K1vi139.37 (2)S1x—Gd1—S1ii180.0 (5)
S1ii—S1—K1vii94.35 (4)S1x—Gd1—S1iii86.14 (6)
S1ii—S1—K1viii139.37 (2)S1x—Gd1—S1xi86.14 (6)
S1iii—S1—Gd1iv95.65 (10)S1ii—Gd1—S1iii93.86 (6)
S1iii—S1—Gd1v46.93 (4)S1ii—Gd1—S1xi93.86 (6)
S1iii—S1—Gd146.93 (4)S1iii—Gd1—S1xi93.86 (6)
S1iii—S1—K1vi139.37 (2)S1xii—K1—S1xiii79.37 (5)
S1iii—S1—K1vii139.37 (2)S1xii—K1—S1xiv79.37 (5)
S1iii—S1—K1viii94.35 (4)S1xii—K1—S1i100.63 (5)
Gd1iv—S1—Gd1v93.86 (9)S1xii—K1—S1ii100.63 (5)
Gd1iv—S1—Gd193.86 (9)S1xii—K1—S1iii180.0 (5)
Gd1iv—S1—K1vi92.97 (2)S1xiii—K1—S1xiv79.37 (5)
Gd1iv—S1—K1vii92.97 (2)S1xiii—K1—S1i100.63 (5)
Gd1iv—S1—K1viii170.00 (11)S1xiii—K1—S1ii180.0 (5)
Gd1v—S1—Gd193.86 (9)S1xiii—K1—S1iii100.63 (5)
Gd1v—S1—K1vi92.97 (2)S1xiv—K1—S1i180.0 (5)
Gd1v—S1—K1vii170.00 (11)S1xiv—K1—S1ii100.63 (5)
Gd1v—S1—K1viii92.97 (2)S1xiv—K1—S1iii100.63 (5)
Gd1—S1—K1vi170.00 (11)S1i—K1—S1ii79.37 (5)
Gd1—S1—K1vii92.97 (2)S1i—K1—S1iii79.37 (5)
Gd1—S1—K1viii92.97 (2)S1ii—K1—S1iii79.37 (5)
Symmetry codes: (i) y1/3, x2/3, z+1/3; (ii) y1/3, x+1/3, z+1/3; (iii) y+2/3, x+1/3, z+1/3; (iv) x1, y1, z; (v) x, y1, z; (vi) x1/3, y2/3, z+1/3; (vii) x1/3, y+1/3, z+1/3; (viii) x+2/3, y+1/3, z+1/3; (ix) x, y+1, z; (x) x+1, y+1, z; (xi) y+2/3, x+4/3, z+1/3; (xii) x2/3, y1/3, z1/3; (xiii) x+1/3, y1/3, z1/3; (xiv) x+1/3, y+2/3, z1/3.
(V) Potassium lutetium sulfide top
Crystal data top
KLuS2Dx = 4.690 Mg m3
Mr = 278.2Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 797 reflections
Hall symbol: -R 3 2"θ = 5.6–29.0°
a = 3.9490 (4) ŵ = 26.93 mm1
c = 21.871 (3) ÅT = 301 K
V = 295.37 (6) Å3Plate, yellow
Z = 30.29 × 0.21 × 0.08 mm
F(000) = 366
Data collection top
Xcalibur, Gemini ultra
diffractometer
126 independent reflections
Radiation source: Enhance (Mo) X-ray Source126 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.061
ω scansθmax = 29.1°, θmin = 5.6°
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
h = 55
Tmin = 0.049, Tmax = 0.223k = 54
981 measured reflectionsl = 2828
Refinement top
Refinement on F20 restraints
R[F2 > 2σ(F2)] = 0.0240 constraints
wR(F2) = 0.056Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 1.85(Δ/σ)max = 0.002
126 reflectionsΔρmax = 2.01 e Å3
8 parametersΔρmin = 1.42 e Å3
Crystal data top
KLuS2Z = 3
Mr = 278.2Mo Kα radiation
Trigonal, R3mµ = 26.93 mm1
a = 3.9490 (4) ÅT = 301 K
c = 21.871 (3) Å0.29 × 0.21 × 0.08 mm
V = 295.37 (6) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
126 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
126 reflections with I > 3σ(I)
Tmin = 0.049, Tmax = 0.223Rint = 0.061
981 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0248 parameters
wR(F2) = 0.0560 restraints
S = 1.85Δρmax = 2.01 e Å3
126 reflectionsΔρmin = 1.42 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Lu10.3333330.6666670.1666670.0116 (3)
K10000.0174 (11)
S1000.23369 (15)0.0111 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Lu10.0090 (3)0.0090 (3)0.0169 (4)0.00450 (17)00
K10.0177 (13)0.0177 (13)0.0169 (18)0.0089 (7)00
S10.0090 (9)0.0090 (9)0.0151 (14)0.0045 (5)00
(VI) top
Crystal data top
KS2YDx = 3.121 Mg m3
Mr = 192.1Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 411 reflections
Hall symbol: -R 3 2"θ = 5.6–28.9°
a = 4.0216 (5) ŵ = 16.07 mm1
c = 21.884 (4) ÅT = 293 K
V = 306.52 (8) Å3Plate, colourless
Z = 30.18 × 0.11 × 0.06 mm
F(000) = 270
Data collection top
Xcalibur, Gemini ultra
diffractometer
125 independent reflections
Radiation source: Enhance (Mo) X-ray Source121 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 10.3784 pixels mm-1θmax = 29.3°, θmin = 5.6°
ω scansh = 54
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 43
Tmin = 0.229, Tmax = 0.477l = 2828
512 measured reflections
Refinement top
Refinement on F20 constraints
R[F2 > 2σ(F2)] = 0.020Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.050(Δ/σ)max = 0.001
S = 1.45Δρmax = 0.43 e Å3
125 reflectionsΔρmin = 0.69 e Å3
9 parametersExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 680 (60)
Crystal data top
KS2YZ = 3
Mr = 192.1Mo Kα radiation
Trigonal, R3mµ = 16.07 mm1
a = 4.0216 (5) ÅT = 293 K
c = 21.884 (4) Å0.18 × 0.11 × 0.06 mm
V = 306.52 (8) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
125 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
121 reflections with I > 3σ(I)
Tmin = 0.229, Tmax = 0.477Rint = 0.023
512 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0209 parameters
wR(F2) = 0.0500 restraints
S = 1.45Δρmax = 0.43 e Å3
125 reflectionsΔρmin = 0.69 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Y10.3333330.6666670.1666670.0079 (3)
K10000.0182 (6)
S1000.23444 (8)0.0124 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Y10.0076 (4)0.0076 (4)0.0086 (5)0.00381 (19)00
K10.0202 (7)0.0202 (7)0.0142 (11)0.0101 (3)00
S10.0130 (5)0.0130 (5)0.0111 (9)0.0065 (3)00
Geometric parameters (Å, º) top
Y1—S12.7552 (12)K1—S1ix3.1740 (14)
Y1—S1i2.7552 (10)K1—S1iii3.1740 (13)
Y1—S1ii2.7552 (12)K1—S1iv3.1740 (14)
Y1—S1iii2.7552 (12)S1—Y1x2.7552 (12)
Y1—S1iv2.7552 (10)S1—Y1xi2.7552 (10)
Y1—S1v2.7552 (12)S1—Y12.7552 (12)
K1—S1vi3.1740 (14)S1—K1xii3.1740 (14)
K1—S1vii3.1740 (13)S1—K1xiii3.1740 (13)
K1—S1viii3.1740 (14)S1—K1xiv3.1740 (14)
S1—Y1—S1i93.74 (3)S1viii—K1—S1iv101.38 (3)
S1—Y1—S1ii93.74 (3)S1ix—K1—S1iii78.62 (3)
S1—Y1—S1iii86.26 (3)S1ix—K1—S1iv78.62 (3)
S1—Y1—S1iv86.26 (3)S1iii—K1—S1iv78.62 (3)
S1—Y1—S1v180.0 (5)Y1x—S1—Y1xi93.74 (4)
S1i—Y1—S1ii93.74 (3)Y1x—S1—Y193.74 (4)
S1i—Y1—S1iii86.26 (3)Y1x—S1—K1xii93.371 (15)
S1i—Y1—S1iv180.0 (5)Y1x—S1—K1xiii93.371 (13)
S1i—Y1—S1v86.26 (3)Y1x—S1—K1xiv169.58 (5)
S1ii—Y1—S1iii180.0 (5)Y1x—S1—S1ix46.87 (2)
S1ii—Y1—S1iv86.26 (3)Y1x—S1—S1iii46.87 (2)
S1ii—Y1—S1v86.26 (3)Y1x—S1—S1iv95.48 (5)
S1iii—Y1—S1iv93.74 (3)Y1xi—S1—Y193.74 (4)
S1iii—Y1—S1v93.74 (3)Y1xi—S1—K1xii93.371 (13)
S1iv—Y1—S1v93.74 (3)Y1xi—S1—K1xiii169.58 (5)
S1vi—K1—S1vii78.62 (3)Y1xi—S1—K1xiv93.371 (13)
S1vi—K1—S1viii78.62 (3)Y1—S1—K1xii169.58 (5)
S1vi—K1—S1ix101.38 (3)Y1—S1—K1xiii93.371 (13)
S1vi—K1—S1iii101.38 (3)Y1—S1—K1xiv93.371 (15)
S1vi—K1—S1iv180.0 (5)K1xii—S1—K1xiii78.62 (4)
S1vii—K1—S1viii78.62 (3)K1xii—S1—K1xiv78.62 (4)
S1vii—K1—S1ix101.38 (3)K1xii—S1—S1ix94.94 (2)
S1vii—K1—S1iii180.0 (5)K1xii—S1—S1iii139.672 (13)
S1vii—K1—S1iv101.38 (3)K1xii—S1—S1iv139.672 (11)
S1viii—K1—S1ix180.0 (5)K1xiii—S1—K1xiv78.62 (4)
S1viii—K1—S1iii101.38 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) y1/3, x+1/3, z+1/3; (iv) y+2/3, x+1/3, z+1/3; (v) y+2/3, x+4/3, z+1/3; (vi) x2/3, y1/3, z1/3; (vii) x+1/3, y1/3, z1/3; (viii) x+1/3, y+2/3, z1/3; (ix) y1/3, x2/3, z+1/3; (x) x1, y1, z; (xi) x, y1, z; (xii) x1/3, y2/3, z+1/3; (xiii) x1/3, y+1/3, z+1/3; (xiv) x+2/3, y+1/3, z+1/3.
(VII) Rubidium yttrium sulfide top
Crystal data top
RbYS2Dx = 3.673 Mg m3
Mr = 238.49Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 1155 reflections
Hall symbol: -R 3 2"θ = 5.4–29.0°
a = 4.0444 (3) ŵ = 25.48 mm1
c = 22.8267 (16) ÅT = 302 K
V = 323.36 (4) Å3Plate, colourless
Z = 30.45 × 0.31 × 0.04 mm
F(000) = 324
Data collection top
Xcalibur, Gemini ultra
diffractometer
140 independent reflections
Radiation source: Enhance (Mo) X-ray Source131 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 10.3784 pixels mm-1θmax = 29.1°, θmin = 5.4°
ω–scansh = 55
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 55
Tmin = 0.018, Tmax = 0.512l = 3030
1568 measured reflections
Refinement top
Refinement on F20 restraints
R[F2 > 2σ(F2)] = 0.0350 constraints
wR(F2) = 0.098Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 2.98(Δ/σ)max = 0.004
140 reflectionsΔρmax = 1.64 e Å3
8 parametersΔρmin = 2.42 e Å3
Crystal data top
RbYS2Z = 3
Mr = 238.49Mo Kα radiation
Trigonal, R3mµ = 25.48 mm1
a = 4.0444 (3) ÅT = 302 K
c = 22.8267 (16) Å0.45 × 0.31 × 0.04 mm
V = 323.36 (4) Å3
Data collection top
Xcalibur, Gemini ultra
diffractometer
140 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
131 reflections with I > 3σ(I)
Tmin = 0.018, Tmax = 0.512Rint = 0.059
1568 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0358 parameters
wR(F2) = 0.0980 restraints
S = 2.98Δρmax = 1.64 e Å3
140 reflectionsΔρmin = 2.42 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Y10.3333330.6666670.1666670.0047 (5)
Rb10000.0156 (6)
S1010.23090 (15)0.0135 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Y10.0043 (6)0.0043 (6)0.0055 (8)0.0021 (3)00
Rb10.0167 (7)0.0167 (7)0.0133 (9)0.0084 (3)00
S10.0137 (9)0.0137 (9)0.0131 (15)0.0069 (5)00
(VIII) Sodium lanthanum sulfide top
Crystal data top
LaNaS2Dx = 3.697 Mg m3
Mr = 226Mo Kα radiation, λ = 0.7107 Å
Cubic, Fm3mCell parameters from 706 reflections
Hall symbol: -F 4 2 3θ = 6.0–27.7°
a = 5.8766 (7) ŵ = 11.41 mm1
V = 202.94 (4) Å3T = 301 K
Z = 2Prisma, colourless
F(000) = 2000.26 × 0.07 × 0.05 mm
Data collection top
Xcalibur, Gemini ultra
diffractometer
25 independent reflections
Radiation source: Enhance (Mo) X-ray Source25 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.053
Detector resolution: 10.3784 pixels mm-1θmax = 27.7°, θmin = 6.0°
ω scansh = 77
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
k = 77
Tmin = 0.152, Tmax = 0.509l = 77
738 measured reflections
Refinement top
Refinement on F21 constraint
R[F2 > 2σ(F2)] = 0.012Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.028(Δ/σ)max = 0.0003
S = 1.48Δρmax = 0.15 e Å3
25 reflectionsΔρmin = 0.27 e Å3
4 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 3800 (300)
Crystal data top
LaNaS2Z = 2
Mr = 226Mo Kα radiation
Cubic, Fm3mµ = 11.41 mm1
a = 5.8766 (7) ÅT = 301 K
V = 202.94 (4) Å30.26 × 0.07 × 0.05 mm
Data collection top
Xcalibur, Gemini ultra
diffractometer
25 independent reflections
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
25 reflections with I > 3σ(I)
Tmin = 0.152, Tmax = 0.509Rint = 0.053
738 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0124 parameters
wR(F2) = 0.0280 restraints
S = 1.48Δρmax = 0.15 e Å3
25 reflectionsΔρmin = 0.27 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
La10000.0139 (3)0.5
Na10000.0139 (3)0.5
S10.50.50.50.0148 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La10.0139 (6)0.0139 (6)0.0139 (6)000
Na10.0139 (6)0.0139 (6)0.0139 (6)000
S10.0148 (7)0.0148 (7)0.0148 (7)000
Geometric parameters (Å, º) top
La1—Na10Na1—S1i2.9383 (7)
La1—S1i2.9383 (7)Na1—S1ii2.9383 (7)
La1—S1ii2.9383 (7)Na1—S1iii2.9383 (7)
La1—S1iii2.9383 (7)Na1—S1iv2.9383 (7)
La1—S1iv2.9383 (7)Na1—S1v2.9383 (7)
La1—S1v2.9383 (7)Na1—S1vi2.9383 (7)
La1—S1vi2.9383 (7)
Na1—La1—S1i0La1viii—S1—Na1vii180
Na1—La1—S1ii0La1viii—S1—Na1viii0
Na1—La1—S1iii0La1viii—S1—Na1ix90
Na1—La1—S1iv0La1viii—S1—Na1x90
Na1—La1—S1v0La1viii—S1—Na1xi90
Na1—La1—S1vi0La1viii—S1—Na1xii90
S1i—La1—S1ii180La1ix—S1—La1x180
S1i—La1—S1iii90La1ix—S1—La1xi90
S1i—La1—S1iv90La1ix—S1—La1xii90
S1i—La1—S1v90La1ix—S1—Na1vii90
S1i—La1—S1vi90La1ix—S1—Na1viii90
S1ii—La1—S1iii90La1ix—S1—Na1ix0
S1ii—La1—S1iv90La1ix—S1—Na1x180
S1ii—La1—S1v90La1ix—S1—Na1xi90
S1ii—La1—S1vi90La1ix—S1—Na1xii90
S1iii—La1—S1iv180La1x—S1—La1xi90
S1iii—La1—S1v90La1x—S1—La1xii90
S1iii—La1—S1vi90La1x—S1—Na1vii90
S1iv—La1—S1v90La1x—S1—Na1viii90
S1iv—La1—S1vi90La1x—S1—Na1ix180
S1v—La1—S1vi180La1x—S1—Na1x0
S1i—Na1—S1ii180La1x—S1—Na1xi90
S1i—Na1—S1iii90La1x—S1—Na1xii90
S1i—Na1—S1iv90La1xi—S1—La1xii180
S1i—Na1—S1v90La1xi—S1—Na1vii90
S1i—Na1—S1vi90La1xi—S1—Na1viii90
S1ii—Na1—S1iii90La1xi—S1—Na1ix90
S1ii—Na1—S1iv90La1xi—S1—Na1x90
S1ii—Na1—S1v90La1xi—S1—Na1xi0
S1ii—Na1—S1vi90La1xi—S1—Na1xii180
S1iii—Na1—S1iv180La1xii—S1—Na1vii90
S1iii—Na1—S1v90La1xii—S1—Na1viii90
S1iii—Na1—S1vi90La1xii—S1—Na1ix90
S1iv—Na1—S1v90La1xii—S1—Na1x90
S1iv—Na1—S1vi90La1xii—S1—Na1xi180
S1v—Na1—S1vi180La1xii—S1—Na1xii0
La1vii—S1—La1viii180Na1vii—S1—Na1viii180
La1vii—S1—La1ix90Na1vii—S1—Na1ix90
La1vii—S1—La1x90Na1vii—S1—Na1x90
La1vii—S1—La1xi90Na1vii—S1—Na1xi90
La1vii—S1—La1xii90Na1vii—S1—Na1xii90
La1vii—S1—Na1vii0Na1viii—S1—Na1ix90
La1vii—S1—Na1viii180Na1viii—S1—Na1x90
La1vii—S1—Na1ix90Na1viii—S1—Na1xi90
La1vii—S1—Na1x90Na1viii—S1—Na1xii90
La1vii—S1—Na1xi90Na1ix—S1—Na1x180
La1vii—S1—Na1xii90Na1ix—S1—Na1xi90
La1viii—S1—La1ix90Na1ix—S1—Na1xii90
La1viii—S1—La1x90Na1x—S1—Na1xi90
La1viii—S1—La1xi90Na1x—S1—Na1xii90
La1viii—S1—La1xii90Na1xi—S1—Na1xii180
Symmetry codes: (i) x1, y1/2, z1/2; (ii) x, y1/2, z1/2; (iii) x1/2, y1, z1/2; (iv) x1/2, y, z1/2; (v) x1/2, y1/2, z1; (vi) x1/2, y1/2, z; (vii) x, y+1/2, z+1/2; (viii) x+1, y+1/2, z+1/2; (ix) x+1/2, y, z+1/2; (x) x+1/2, y+1, z+1/2; (xi) x+1/2, y+1/2, z; (xii) x+1/2, y+1/2, z+1.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaKLaS2KPrS2EuKS2GdKS2
Mr242.1244.1255.2260.5
Crystal system, space groupTrigonal, R3mTrigonal, R3mTrigonal, R3mTrigonal, R3m
Temperature (K)300302302303
a, b, c (Å)4.2651 (4), 4.2651 (4), 21.929 (3)4.1925 (3), 4.1925 (3), 21.8920 (14)4.0981 (3), 4.0981 (3), 21.8212 (15)4.0715 (7), 4.0715 (7), 21.901 (4)
α, β, γ (°)90, 90, 12090, 90, 12090, 90, 12090, 90, 120
V3)345.47 (7)333.24 (4)317.38 (4)314.41 (10)
Z3333
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)10.8712.6216.5617.57
Crystal size (mm)0.16 × 0.11 × 0.040.52 × 0.21 × 0.070.27 × 0.14 × 0.120.66 × 0.38 × 0.04
Data collection
DiffractometerXcalibur, Gemini ultra
diffractometer
Xcalibur, Gemini ultra
diffractometer
Xcalibur, Gemini ultra
diffractometer
Xcalibur, Gemini ultra
diffractometer
Absorption correctionAnalytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Tmin, Tmax0.377, 0.6460.098, 0.4540.049, 0.2200.016, 0.497
No. of measured, independent and
observed [I > 3σ(I)] reflections
909, 226, 224 3338, 306, 264 1970, 177, 177 2426, 221, 216
Rint0.0460.0270.0300.058
(sin θ/λ)max1)0.6820.7600.7540.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.073, 2.03 0.016, 0.056, 1.78 0.010, 0.025, 0.90 0.035, 0.093, 2.88
No. of reflections226306177221
No. of parameters91099
Δρmax, Δρmin (e Å3)2.50, 1.720.21, 0.360.44, 0.381.08, 0.76


(V)(VI)(VII)(VIII)
Crystal data
Chemical formulaKLuS2KS2YRbYS2LaNaS2
Mr278.2192.1238.49226
Crystal system, space groupTrigonal, R3mTrigonal, R3mTrigonal, R3mCubic, Fm3m
Temperature (K)301293302301
a, b, c (Å)3.9490 (4), 3.9490 (4), 21.871 (3)4.0216 (5), 4.0216 (5), 21.884 (4)4.0444 (3), 4.0444 (3), 22.8267 (16)5.8766 (7), 5.8766 (7), 5.8766 (7)
α, β, γ (°)90, 90, 12090, 90, 12090, 90, 12090, 90, 90
V3)295.37 (6)306.52 (8)323.36 (4)202.94 (4)
Z3332
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)26.9316.0725.4811.41
Crystal size (mm)0.29 × 0.21 × 0.080.18 × 0.11 × 0.060.45 × 0.31 × 0.040.26 × 0.07 × 0.05
Data collection
DiffractometerXcalibur, Gemini ultra
diffractometer
Xcalibur, Gemini ultra
diffractometer
Xcalibur, Gemini ultra
diffractometer
Xcalibur, Gemini ultra
diffractometer
Absorption correctionAnalytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Analytical
CrysAlis PRO, Agilent Technologies (2012), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (1995).
Tmin, Tmax0.049, 0.2230.229, 0.4770.018, 0.5120.152, 0.509
No. of measured, independent and
observed [I > 3σ(I)] reflections
981, 126, 126 512, 125, 121 1568, 140, 131 738, 25, 25
Rint0.0610.0230.0590.053
(sin θ/λ)max1)0.6840.6890.6830.654
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.056, 1.85 0.020, 0.050, 1.45 0.035, 0.098, 2.98 0.012, 0.028, 1.48
No. of reflections12612514025
No. of parameters8984
Δρmax, Δρmin (e Å3)2.01, 1.420.43, 0.691.64, 2.420.15, 0.27

Computer programs: CrysAlis PRO (Agilent Technologies, 2012), CrysAlis PRO, Superflip (Palatinus & Chapuis, 2007), JANA2006 (Petříček et. al., 2006), DIAMOND 3.0 (Brandenburg, K. - Crystal Impact, GbR, Bonn, Germany, 2010)..

Selected bond lengths (Å) for (II) top
Pr1—S22.8592 (9)K1—S2viii3.2222 (10)
Pr1—S2i2.8592 (8)K1—S2ix3.2222 (10)
Pr1—S2ii2.8592 (9)K1—S2iii3.2222 (10)
Pr1—S2iii2.8592 (9)K1—S2iv3.2222 (10)
Pr1—S2iv2.8592 (8)S2—S2ix3.8887 (16)
Pr1—S2v2.8592 (9)S2—S2iii3.8887 (16)
K1—S2vi3.2222 (10)S2—S2iv3.8887 (16)
K1—S2vii3.2222 (10)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) y1/3, x+1/3, z+1/3; (iv) y+2/3, x+1/3, z+1/3; (v) y+2/3, x+4/3, z+1/3; (vi) x2/3, y1/3, z1/3; (vii) x+1/3, y1/3, z1/3; (viii) x+1/3, y+2/3, z1/3; (ix) y1/3, x2/3, z+1/3.
Selected geometric parameters (Å, º) for (III) top
Eu1—S22.8009 (7)K1—S2viii3.1889 (8)
Eu1—S2i2.8009 (5)K1—S2ix3.1889 (8)
Eu1—S2ii2.8009 (7)K1—S2iii3.1889 (7)
Eu1—S2iii2.8009 (7)K1—S2iv3.1889 (8)
Eu1—S2iv2.8009 (5)S2—S2ix3.8191 (11)
Eu1—S2v2.8009 (7)S2—S2iii3.8191 (11)
K1—S2vi3.1889 (8)S2—S2iv3.8191 (11)
K1—S2vii3.1889 (7)
S2—Eu1—S2i94.037 (16)Eu1x—S2—K1xiii92.602 (6)
S2—Eu1—S2ii94.037 (17)Eu1x—S2—K1xiv170.25 (3)
S2—Eu1—S2iii85.964 (17)Eu1x—S2—S2ix47.018 (11)
S2—Eu1—S2iv85.963 (16)Eu1x—S2—S2iii47.018 (12)
S2—Eu1—S2v180Eu1x—S2—S2iv95.93 (3)
S2i—Eu1—S2ii94.037 (16)Eu1xi—S2—Eu194.04 (2)
S2i—Eu1—S2iii85.964 (16)Eu1xi—S2—K1xii92.602 (6)
S2i—Eu1—S2iv180Eu1xi—S2—K1xiii170.25 (3)
S2i—Eu1—S2v85.964 (16)Eu1xi—S2—K1xiv92.602 (6)
S2ii—Eu1—S2iii180Eu1xi—S2—S2ix47.018 (12)
S2ii—Eu1—S2iv85.963 (16)Eu1xi—S2—S2iii95.93 (3)
S2ii—Eu1—S2v85.964 (17)Eu1xi—S2—S2iv47.018 (12)
S2iii—Eu1—S2iv94.036 (16)Eu1—S2—K1xii170.25 (3)
S2iii—Eu1—S2v94.036 (17)Eu1—S2—K1xiii92.602 (6)
S2iv—Eu1—S2v94.036 (16)Eu1—S2—K1xiv92.602 (8)
S2vi—K1—S2vii79.967 (14)Eu1—S2—S2ix95.93 (3)
S2vi—K1—S2viii79.967 (15)Eu1—S2—S2iii47.018 (12)
S2vi—K1—S2ix100.033 (15)Eu1—S2—S2iv47.018 (11)
S2vi—K1—S2iii100.033 (14)K1xii—S2—K1xiii79.97 (2)
S2vi—K1—S2iv180K1xii—S2—K1xiv79.97 (2)
S2vii—K1—S2viii79.967 (14)K1xii—S2—S2ix93.819 (12)
S2vii—K1—S2ix100.033 (14)K1xii—S2—S2iii139.122 (7)
S2vii—K1—S2iii180K1xii—S2—S2iv139.122 (6)
S2vii—K1—S2iv100.033 (14)K1xiii—S2—K1xiv79.97 (2)
S2viii—K1—S2ix180K1xiii—S2—S2ix139.122 (7)
S2viii—K1—S2iii100.033 (14)K1xiii—S2—S2iii93.819 (10)
S2viii—K1—S2iv100.033 (15)K1xiii—S2—S2iv139.122 (7)
S2ix—K1—S2iii79.967 (14)K1xiv—S2—S2ix139.122 (6)
S2ix—K1—S2iv79.967 (15)K1xiv—S2—S2iii139.122 (7)
S2iii—K1—S2iv79.967 (14)K1xiv—S2—S2iv93.819 (12)
Eu1x—S2—Eu1xi94.04 (2)S2ix—S2—S2iii64.895 (18)
Eu1x—S2—Eu194.04 (2)S2ix—S2—S2iv64.895 (18)
Eu1x—S2—K1xii92.602 (8)S2iii—S2—S2iv64.895 (18)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) y1/3, x+1/3, z+1/3; (iv) y+2/3, x+1/3, z+1/3; (v) y+2/3, x+4/3, z+1/3; (vi) x2/3, y1/3, z1/3; (vii) x+1/3, y1/3, z1/3; (viii) x+1/3, y+2/3, z1/3; (ix) y1/3, x2/3, z+1/3; (x) x1, y1, z; (xi) x, y1, z; (xii) x1/3, y2/3, z+1/3; (xiii) x1/3, y+1/3, z+1/3; (xiv) x+2/3, y+1/3, z+1/3.
Selected geometric parameters (Å, º) for (VIII) top
La1—Na10Na1—S1i2.9383 (7)
La1—S1i2.9383 (7)Na1—S1ii2.9383 (7)
La1—S1ii2.9383 (7)Na1—S1iii2.9383 (7)
La1—S1iii2.9383 (7)Na1—S1iv2.9383 (7)
La1—S1iv2.9383 (7)Na1—S1v2.9383 (7)
La1—S1v2.9383 (7)Na1—S1vi2.9383 (7)
La1—S1vi2.9383 (7)
Na1—La1—S1i0La1viii—S1—Na1vii180
Na1—La1—S1ii0La1viii—S1—Na1viii0
Na1—La1—S1iii0La1viii—S1—Na1ix90
Na1—La1—S1iv0La1viii—S1—Na1x90
Na1—La1—S1v0La1viii—S1—Na1xi90
Na1—La1—S1vi0La1viii—S1—Na1xii90
S1i—La1—S1ii180La1ix—S1—La1x180
S1i—La1—S1iii90La1ix—S1—La1xi90
S1i—La1—S1iv90La1ix—S1—La1xii90
S1i—La1—S1v90La1ix—S1—Na1vii90
S1i—La1—S1vi90La1ix—S1—Na1viii90
S1ii—La1—S1iii90La1ix—S1—Na1ix0
S1ii—La1—S1iv90La1ix—S1—Na1x180
S1ii—La1—S1v90La1ix—S1—Na1xi90
S1ii—La1—S1vi90La1ix—S1—Na1xii90
S1iii—La1—S1iv180La1x—S1—La1xi90
S1iii—La1—S1v90La1x—S1—La1xii90
S1iii—La1—S1vi90La1x—S1—Na1vii90
S1iv—La1—S1v90La1x—S1—Na1viii90
S1iv—La1—S1vi90La1x—S1—Na1ix180
S1v—La1—S1vi180La1x—S1—Na1x0
S1i—Na1—S1ii180La1x—S1—Na1xi90
S1i—Na1—S1iii90La1x—S1—Na1xii90
S1i—Na1—S1iv90La1xi—S1—La1xii180
S1i—Na1—S1v90La1xi—S1—Na1vii90
S1i—Na1—S1vi90La1xi—S1—Na1viii90
S1ii—Na1—S1iii90La1xi—S1—Na1ix90
S1ii—Na1—S1iv90La1xi—S1—Na1x90
S1ii—Na1—S1v90La1xi—S1—Na1xi0
S1ii—Na1—S1vi90La1xi—S1—Na1xii180
S1iii—Na1—S1iv180La1xii—S1—Na1vii90
S1iii—Na1—S1v90La1xii—S1—Na1viii90
S1iii—Na1—S1vi90La1xii—S1—Na1ix90
S1iv—Na1—S1v90La1xii—S1—Na1x90
S1iv—Na1—S1vi90La1xii—S1—Na1xi180
S1v—Na1—S1vi180La1xii—S1—Na1xii0
La1vii—S1—La1viii180Na1vii—S1—Na1viii180
La1vii—S1—La1ix90Na1vii—S1—Na1ix90
La1vii—S1—La1x90Na1vii—S1—Na1x90
La1vii—S1—La1xi90Na1vii—S1—Na1xi90
La1vii—S1—La1xii90Na1vii—S1—Na1xii90
La1vii—S1—Na1vii0Na1viii—S1—Na1ix90
La1vii—S1—Na1viii180Na1viii—S1—Na1x90
La1vii—S1—Na1ix90Na1viii—S1—Na1xi90
La1vii—S1—Na1x90Na1viii—S1—Na1xii90
La1vii—S1—Na1xi90Na1ix—S1—Na1x180
La1vii—S1—Na1xii90Na1ix—S1—Na1xi90
La1viii—S1—La1ix90Na1ix—S1—Na1xii90
La1viii—S1—La1x90Na1x—S1—Na1xi90
La1viii—S1—La1xi90Na1x—S1—Na1xii90
La1viii—S1—La1xii90Na1xi—S1—Na1xii180
Symmetry codes: (i) x1, y1/2, z1/2; (ii) x, y1/2, z1/2; (iii) x1/2, y1, z1/2; (iv) x1/2, y, z1/2; (v) x1/2, y1/2, z1; (vi) x1/2, y1/2, z; (vii) x, y+1/2, z+1/2; (viii) x+1, y+1/2, z+1/2; (ix) x+1/2, y, z+1/2; (x) x+1/2, y+1, z+1/2; (xi) x+1/2, y+1/2, z; (xii) x+1/2, y+1/2, z+1.
 

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