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The title structures NaGdS2 (sodium gadolinium sulfide), NaLuS2 (sodium lutetium sulfide) and NaYS2 (sodium yttrium sulfide) were redetermined in order to improve the structural information available for the family of group 1 and thallium rare earth sulfides, which are isostructural with the rhombohedral α-NaFeO2 structure type. In particular, the present investigation has been directed at the rhombohedral sodium rare earth sulfides. The observed dependence of the fractional coordinate z(S2−) on the identity of the rare earth element in the newly determined structures is in agreement with the known structures of the potassium and rubidium analogues. Crystals of NaGdS2 and NaLuS2 display obverse–reverse twinning.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614009607/fa3334sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009607/fa3334Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009607/fa3334IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009607/fa3334IIIsup4.hkl
Contains datablock III

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614009607/fa3334sup5.pdf
Supplementary material

CCDC references: 1000029; 1000030; 1000031

Introduction top

This study was motivated by the potential use of the rhombohedral group 1 rare earth sulfides as X-ray and white LED luminophores (Verheijen et al., 1975). Optical properties were reported recently for several group 1 lanthanide ternary sulfides M+Ln3+S2, namely RbLaS2 doped with Ce, Pr, Sm, Eu and Tb (Havlák et al., 2011); RbLuS2 doped with Ce, Pr, Sm and Tb (Jarý et al., 2012); RbGdS2 doped with Ce and Pr (Jarý et al., 2013a); KLuS2 doped with Eu (Jarý et al., 2013b); KLnS2 doped with Pr, Sm, Tb and Tm (Ln = La, Gd, Lu) (Jarý, Havlák, Bárta, Mihóková & Nikl, 2014); and KLuS2 doped with Ce (Jarý, Havlák, Bárta, Mihóková, Pruša & Nikl, 2014). (The lanthanide elements are hereinafter denoted by Ln.)

Experimental top

Synthesis and crystallization top

The starting raw materials were Na2S (99.9%, Alfa Aesar), Gd2O3 (99.999%, Koch–Light Laboratories), Lu2O3 (99.999%, Fluka), Y2O3 (99.999%, Fluka) and CeO2 (99.95%, Koch–Light Laboratories). The gases used were Ar (99.999%, Linde) and H2S (99.5%, Linde). The chemical reactions were carried out in a monocrystalline sapphire tube (99.99% Al2O3, Crytur). The tube was placed in an electric resistance furnace equipped with heating/cooling rate regulation. The scheme of the set-up was outlined by Havlák et al. (2011). Either Ar or H2S gas was then connected to the reaction tube. The gases were taken directly from pressurized bottles using a three-way stopcock to switch between them. A mixture of Na2S and one of the rare earth (RE) oxides in the molar ratio 40:1 was the starting material for the Ce3+-doped compounds. (The rare earth oxides were doped with 0.05 mol% cerium in conjunction with the investigation of the title compounds as scintillation materials.) Ce doping was done by simple mixing and grinding of RE2O3 (RE = Gd, Lu and Y) and CeO2. Prior to the reaction itself, the reagents (Na2S and RE2O3:CeO2) were mixed and the mixture homogenized in an agate mortar. The mixture was placed in a corundum boat (99.7% Al2O3; Dengfeng Jinyu Thermoelectric Material Co.) and placed in a sapphire tube (inner volume 0.9 l). The mixture was then heated to 1323 K for NaLuS2 and NaYS2, and to 1373 K for NaGdS2, using the electric resistance furnace (heating rate 10 K min-1) under a flow of argon gas from a pressurized bottle (15 l h-1). After the desired temperature had been reached, the reaction mixture was annealed for 2 h under a flow of hydrogen sulfide (5 l h-1). Following annealing, the system was cooled under a flow of Ar (1 K min-1, 0.3 l h-1). Upon reaching room temperature, the corundum boat was removed from the tube furnace and the reaction products were purified by suspension and decantation – three times with distilled water and once with ethanol. Na2S was removed with water while the sodium rare earth sulfides were left behind. The yield was nearly 100%, with any loss attributed to imperfect product separation. The products were stored in small glass flasks under an Ar atmosphere and used for further analysis. Ternary sulfide NaRES2 is produced according to the following reaction scheme:

Na2S(l) + RE2O3(s) + 3 H2S(g) 2NaRES2(s) + 3H2O(g).

As the melting point of sodium sulfide (Alfa Aesar) is lower than 1323 K, the reaction occurred in the melt.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The structures were solved using SUPERFLIP (Palatinus & Chapuis, 2007) implemented in JANA2006 (Petříček et al., 2006). All of the samples were doped with 0.05 mol% of Ce, which was neglected during refinement. The crystals of NaGdS2 and NaLuS2 (at least those used for diffraction measurements) suffered obverse–reverse twinning, with domain fractions equal to 0.9243 (8):0.0757 (8) and 0.808 (2):0.192 (2), respectively. The twinning matrix relation was h2 = h1 + k1; k2 = -h1; l2 = l1. The Rint value was quite high (0.1092) in the case of NaYS2, which is probably a result of unusually high background.

Results and discussion top

We recently reported the structures of KLaS2, KPrS2, KEuS2, KGdS2, KLuS2, KYS2, RbYS2 and NaLaS2 (Fábry et al., 2014). With the exception of NaLaS2, all of these structures belong to the rhombohedral modification and are isostructural with the title compounds. The structure of NaLaS2 is cubic and is derived from the NaCl structure type, with Na+ and La3+ disordered at the cation position. Since crystals of NaLaS2 produce intense diffuse scattering, it is likely that the structure is more complicated than the simple model with a statistical distribution of Na+ and La3+ at the cation positions of the ideal NaCl structure (Fábry et al., 2014). Further work on this problem is in progress.

In contrast, the rhombohedral modification is characterized by the occurrence of either group 1 or thallium(1+) and rare earth cations at different sites in the structure. Fig. 1 shows a representative of this structural family, the title structure of NaGdS2. Both the cationic species and S2- anions are ordered in planes perpendicular to the c axis. Each S2- anion is surrounded by 3+3 cations in a trigonal anti­prismatic environment. The driving force for the segregation of the cationic species onto distinct ordered sites is the different size of the cations and the related bonding properties (Fábry et al., 2014).

Previous structure analyses of the sodium rare earth sulfides seem to present inconsistencies, as seen in Fig. 2, which presents z(S2-), i.e. the fractional coordinates of S2-, in group 1 and thallium rare earth sulfides. (The numerical data presented in Fig. 2 are collected in a table in the Supporting information.) As seen in Fig. 2, the fractional coordinates z(S2-) are improbably scattered for the rhombohedral sodium rare earth sulfides in contrast with what is seen for the rare earth sulfides of other alkali metals. The title structures were redetermined in order to improve the data for this series of compounds.

The present determinations are in agreement (Fig. 2) with the trends seen for KGdS2, KLuS2 and KYS2 (Fábry et al., 2014), and for RbGdS2 (Bronger et al., 1996), RbLuS2 (Bronger et al., 1996) and RbYS2 (Fábry et al., 2014).

However, there is a significant discrepancy between the determination of NaGdS2 by Sato et al. (1984) with z(S2-) = 0.241 and the present structure determination, with z(S2-) = 0.2433 (1).

The structure of NaYS2 was not determined reliably in a previous study, because the fractional coordinate z(S2-) was derived from the ionic radii as 0.24 (Brüesch & Schüler, 1971).

As for NaLuS2, two quite different structure determinations were reported by Tromme (1971) [z(S2-) = 0.231] and by Schleid & Lissner (1993) [z(S2-) = 0.24284 (9)]. The determination by Tromme (1971) is an evident outlier and therefore it has not been included in Fig. 2.

Fig. 2 also shows that potassium rare earth sulfides seem to have been dubiously determined in the inter­val from KDyS2 to KYbS2. KSmS2 also seems to have been dubiously determined.

In conclusion, the present work provides useful extra data on this series of compounds and highlights shortcomings in historic data sets. [Added text OK? If not, please supply an alternative conclusion to tie the paper together.]

Related literature top

For overall information about group 1 rare earth sulfides, see Fábry et al. (2014). For selected Li rare earth sulfides, see Ohtani et al. (1987). For selected Na rare earth sulfides, see Sato et al. (1984), Ballestracci & Bertaut (1964) and Schleid & Lissner (1993), and specifically for NaYS2, see Brüesch & Schüler (1971). For selected K rare earth sulfides, see Fábry et al. (2014), Plug & Verschoor (1976), Verheijen et al. (1975) and Ballestracci (1965). For selected Rb rare earth sulfides, see Bronger et al. (1996) and Fábry et al. (2014). For selected Cs rare earth sulfides, see Bronger et al. (1993). For selected Tl rare earth sulfides, see Tromme (1971) and Duczmal & Pawlak (1994). For information about the preparation and application of the structural family of rhombohedral group 1 rare earth sulfides as white LED luminophors, see Verheijen et al. (1975) and Havlák et al. (2011); Jarý et al. (2012, 2013a, 2013b; Jarý, Havlák, Bárta, Mihóková & Nikl, 2014; Jarý, Havlák, Bárta, Mihóková, Pruša & Nikl, 2014).

Computing details top

For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).

Figures top
Fig. 1. A view of the unit cell of NaGdS2, one of the isostructural title structures. The layer of atoms at z = 0 is composed of Na+ which are depicted as white spheres; the following layer is composed of S2- (yellow spheres) and the blue spheres in the subsequent layer represent Gd3+.

Fig. 2. Fractional coordinate z(S2-) in the group 1 and thallium rare earth sulfides. The figure is based on data compiled in a table in the Supporting information (Ln denotes a lathanide). All LiLnS2 (Ohtani et al., 1987); NaGdS2 (Sato et al., 1984); NaHoS2 and NaErS2 (Ballestracci & Bertaut, 1964); NaTmS2 (Schleid & Lissner, 1993); NaYbS2 and NaYS2 (this study); KLaS2 (Fábry et al., 2014); KCeS2 (Plug & Verschoor, 1976); KPrS2 (Fábry et al., 2014); KNdS2 (Verheijen et al., 1975); KSmS2 (Ballestracci, 1965); KEuS2 and KGdS2 (Fábry et al., 2014); KDyS2, KHoS2, KErS2 and KYbS2 (Ballestracci, 1965); KLuS2 and KYS2 (Fábry et al., 2014); all RbLnS2 (Bronger et al., 1996); RbYS2 (Fábry et al., 2014); all CsLnS2 (Bronger et al., 1993); all TlLnS2 (Duczmal & Pawlak, 1994).
(I) Sodium gadolinium sulfide top
Crystal data top
NaGdS2Dx = 4.388 Mg m3
Mr = 244.4Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 685 reflections
Hall symbol: -R 3 2"θ = 5.9–27.0°
a = 4.0138 (4) ŵ = 18.91 mm1
c = 19.878 (2) ÅT = 304 K
V = 277.34 (5) Å3Plate, pink
Z = 30.12 × 0.09 × 0.03 mm
F(000) = 321
Data collection top
Agilent Xcalibur Gemini ultra
diffractometer
164 independent reflections
Radiation source: X-ray tube161 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 5.1892 pixels mm-1θmax = 27.8°, θmin = 3.1°
ω scansh = 54
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
k = 44
Tmin = 0.213, Tmax = 0.561l = 1825
935 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) = 0.048(Δ/σ)max = 0.015
S = 1.35Δρmax = 0.73 e Å3
164 reflectionsΔρmin = 0.54 e Å3
10 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 140 (20)
Crystal data top
NaGdS2Z = 3
Mr = 244.4Mo Kα radiation
Trigonal, R3mµ = 18.91 mm1
a = 4.0138 (4) ÅT = 304 K
c = 19.878 (2) Å0.12 × 0.09 × 0.03 mm
V = 277.34 (5) Å3
Data collection top
Agilent Xcalibur Gemini ultra
diffractometer
164 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
161 reflections with I > 3σ(I)
Tmin = 0.213, Tmax = 0.561Rint = 0.031
935 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02010 parameters
wR(F2) = 0.0480 restraints
S = 1.35Δρmax = 0.73 e Å3
164 reflectionsΔρmin = 0.54 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 0.9243 (8)/0.0757 (8).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Na10000.0182 (16)
Gd10.3333330.6666670.1666670.0088 (3)
S1000.24332 (12)0.0100 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0183 (19)0.0183 (19)0.018 (3)0.0092 (10)00
Gd10.0074 (4)0.0074 (4)0.0116 (5)0.00369 (18)00
S10.0089 (7)0.0089 (7)0.0121 (12)0.0045 (4)00
Geometric parameters (Å, º) top
Gd1—S12.7734 (14)Na1—S1iv2.9278 (15)
Gd1—S1i2.7734 (13)S1—S1x4.0138 (12)
Gd1—S1ii2.7734 (14)S1—S1xi4.0138 (8)
Gd1—S1iii2.7734 (14)S1—S1xii4.0138 (8)
Gd1—S1iv2.7734 (13)S1—S1i4.0138 (8)
Gd1—S1v2.7734 (14)S1—S1xiii4.0138 (8)
Na1—S1vi2.9278 (15)S1—S1ii4.0138 (12)
Na1—S1vii2.9278 (15)S1—S1ix3.828 (3)
Na1—S1viii2.9278 (15)S1—S1iii3.828 (3)
Na1—S1ix2.9278 (15)S1—S1iv3.828 (3)
Na1—S1iii2.9278 (15)
S1vi—Na1—S1vii86.54 (4)Na1xv—S1—Na1xvi86.54 (5)
S1vi—Na1—S1viii86.54 (4)S1—Gd1—S1i92.71 (4)
S1vi—Na1—S1ix93.46 (4)S1—Gd1—S1ii92.71 (4)
S1vi—Na1—S1iii93.46 (4)S1—Gd1—S1iii87.29 (4)
S1vi—Na1—S1iv180.0 (5)S1—Gd1—S1iv87.29 (4)
S1vii—Na1—S1viii86.54 (4)S1—Gd1—S1v180.0 (5)
S1vii—Na1—S1ix93.46 (4)S1i—Gd1—S1ii92.71 (4)
S1vii—Na1—S1iii180.0 (5)S1i—Gd1—S1iii87.29 (4)
S1vii—Na1—S1iv93.46 (4)S1i—Gd1—S1iv180.0 (5)
S1viii—Na1—S1ix180.0 (5)S1i—Gd1—S1v87.29 (4)
S1viii—Na1—S1iii93.46 (4)S1ii—Gd1—S1iii180.0 (5)
S1viii—Na1—S1iv93.46 (4)S1ii—Gd1—S1iv87.29 (4)
S1ix—Na1—S1iii86.54 (4)S1ii—Gd1—S1v87.29 (4)
S1ix—Na1—S1iv86.54 (4)S1iii—Gd1—S1iv92.71 (4)
S1iii—Na1—S1iv86.54 (4)S1iii—Gd1—S1v92.71 (4)
Na1xiv—S1—Na1xv86.54 (5)S1iv—Gd1—S1v92.71 (4)
Na1xiv—S1—Na1xvi86.54 (5)
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) x1, y, z; (xii) x, y1, z; (xiii) x+1, y, z; (xiv) x1/3, y2/3, z+1/3; (xv) x1/3, y+1/3, z+1/3; (xvi) x+2/3, y+1/3, z+1/3.
(II) Sodium lutetium sulfide top
Crystal data top
NaLuS2Dx = 5.015 Mg m3
Mr = 262.1Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 673 reflections
Hall symbol: -R 3 2"θ = 6.1–28.8°
a = 3.8909 (4) ŵ = 29.49 mm1
c = 19.850 (3) ÅT = 300 K
V = 260.24 (6) Å3Plate, pink
Z = 30.12 × 0.11 × 0.04 mm
F(000) = 342
Data collection top
Agilent Xcalibur Gemini ultra
diffractometer
183 independent reflections
Radiation source: Enhance (Mo) X-ray source183 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.053
Detector resolution: 5.1892 pixels mm-1θmax = 29.4°, θmin = 3.1°
ω scansh = 54
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
k = 45
Tmin = 0.150, Tmax = 0.508l = 2624
947 measured reflections
Refinement top
Refinement on F20 constraints
R[F2 > 2σ(F2)] = 0.031Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2]
wR(F2) = 0.066(Δ/σ)max = 0.011
S = 1.83Δρmax = 2.05 e Å3
183 reflectionsΔρmin = 1.83 e Å3
10 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 90 (20)
Crystal data top
NaLuS2Z = 3
Mr = 262.1Mo Kα radiation
Trigonal, R3mµ = 29.49 mm1
a = 3.8909 (4) ÅT = 300 K
c = 19.850 (3) Å0.12 × 0.11 × 0.04 mm
V = 260.24 (6) Å3
Data collection top
Agilent Xcalibur Gemini ultra
diffractometer
183 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
183 reflections with I > 3σ(I)
Tmin = 0.150, Tmax = 0.508Rint = 0.053
947 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03110 parameters
wR(F2) = 0.0660 restraints
S = 1.83Δρmax = 2.05 e Å3
183 reflectionsΔρmin = 1.83 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 0.808 (2)/0.192 (2).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Lu10.3333330.6666670.1666670.0090 (3)
Na10000.017 (2)
S1010.24146 (17)0.0091 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Lu10.0061 (4)0.0061 (4)0.0148 (6)0.0030 (2)00
Na10.014 (3)0.014 (3)0.021 (5)0.0072 (13)00
S10.0078 (10)0.0078 (10)0.0117 (17)0.0039 (5)00
Geometric parameters (Å, º) top
Lu1—S1i2.693 (2)Na1—S1iv2.893 (2)
Lu1—S12.6927 (19)S1—S1x3.8909 (12)
Lu1—S1ii2.693 (2)S1—S1xi3.8909 (8)
Lu1—S1iii2.693 (2)S1—S1i3.8909 (8)
Lu1—S1iv2.6927 (19)S1—S1xii3.8909 (8)
Lu1—S1v2.693 (2)S1—S1ii3.8909 (8)
Na1—S1vi2.893 (2)S1—S1xiii3.8909 (12)
Na1—S1vii2.893 (2)S1—S1iii3.723 (4)
Na1—S1viii2.893 (2)S1—S1xiv3.723 (4)
Na1—S1ix2.893 (2)S1—S1v3.723 (4)
Na1—S1iii2.893 (2)
S1i—Lu1—S192.52 (6)Lu1xi—S1—S1x43.74 (4)
S1i—Lu1—S1ii92.52 (6)Lu1xi—S1—S1xi43.74 (4)
S1i—Lu1—S1iii87.48 (6)Lu1xi—S1—S1i90.00 (4)
S1i—Lu1—S1iv87.48 (6)Lu1xi—S1—S1xii90.00 (4)
S1i—Lu1—S1v180.0 (5)Lu1xi—S1—S1ii136.26 (9)
S1—Lu1—S1ii92.52 (6)Lu1xi—S1—S1xiii136.26 (9)
S1—Lu1—S1iii87.48 (6)Lu1xi—S1—S1iii46.26 (4)
S1—Lu1—S1iv180.0 (5)Lu1xi—S1—S1xiv46.26 (4)
S1—Lu1—S1v87.48 (6)Lu1xi—S1—S1v93.65 (10)
S1ii—Lu1—S1iii180.0 (5)Lu1—S1—Lu1xii92.52 (9)
S1ii—Lu1—S1iv87.48 (6)Lu1—S1—Na1xv91.356 (12)
S1ii—Lu1—S1v87.48 (6)Lu1—S1—Na1xvi174.39 (11)
S1iii—Lu1—S1iv92.52 (6)Lu1—S1—Na1xvii91.356 (12)
S1iii—Lu1—S1v92.52 (6)Lu1xii—S1—Na1xv174.39 (11)
S1iv—Lu1—S1v92.52 (6)Lu1xii—S1—Na1xvi91.356 (12)
Lu1xi—S1—Lu192.52 (9)Lu1xii—S1—Na1xvii91.356 (13)
Lu1xi—S1—Lu1xii92.52 (9)Na1xv—S1—Na1xvi84.50 (8)
Lu1xi—S1—Na1xv91.356 (13)Na1xv—S1—Na1xvii84.50 (8)
Lu1xi—S1—Na1xvi91.356 (12)Na1xvi—S1—Na1xvii84.50 (8)
Lu1xi—S1—Na1xvii174.39 (11)
Symmetry codes: (i) x, y1, z; (ii) x+1, y, z; (iii) y4/3, x+1/3, z+1/3; (iv) y1/3, x+1/3, z+1/3; (v) y1/3, x+4/3, z+1/3; (vi) x2/3, y4/3, z1/3; (vii) x+1/3, y4/3, z1/3; (viii) x+1/3, y1/3, z1/3; (ix) y4/3, x2/3, z+1/3; (x) x1, y1, z; (xi) x1, y, z; (xii) x, y+1, z; (xiii) x+1, y+1, z; (xiv) y4/3, x+4/3, z+1/3; (xv) x1/3, y+1/3, z+1/3; (xvi) x1/3, y+4/3, z+1/3; (xvii) x+2/3, y+4/3, z+1/3.
(III) Sodium yttrium sulfide top
Crystal data top
NaYS2Dx = 3.248 Mg m3
Mr = 176Mo Kα radiation, λ = 0.7107 Å
Trigonal, R3mCell parameters from 688 reflections
Hall symbol: -R 3 2"θ = 6.0–28.5°
a = 3.9604 (12) ŵ = 17.21 mm1
c = 19.867 (8) ÅT = 302 K
V = 269.9 (2) Å3Prism, colourless
Z = 30.12 × 0.07 × 0.06 mm
F(000) = 246
Data collection top
Agilent Xcalibur Gemini ultra
diffractometer
120 independent reflections
Radiation source: Enhance (Mo) X-ray source112 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.109
Detector resolution: 5.1892 pixels mm-1θmax = 29.5°, θmin = 3.1°
ω scansh = 55
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
k = 55
Tmin = 0.344, Tmax = 0.479l = 2525
1233 measured reflections
Refinement top
Refinement on F20 restraints
R[F2 > 2σ(F2)] = 0.0310 constraints
wR(F2) = 0.067Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2]
S = 1.78(Δ/σ)max = 0.002
120 reflectionsΔρmax = 0.93 e Å3
8 parametersΔρmin = 0.72 e Å3
Crystal data top
NaYS2Z = 3
Mr = 176Mo Kα radiation
Trigonal, R3mµ = 17.21 mm1
a = 3.9604 (12) ÅT = 302 K
c = 19.867 (8) Å0.12 × 0.07 × 0.06 mm
V = 269.9 (2) Å3
Data collection top
Agilent Xcalibur Gemini ultra
diffractometer
120 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
112 reflections with I > 3σ(I)
Tmin = 0.344, Tmax = 0.479Rint = 0.109
1233 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0318 parameters
wR(F2) = 0.0670 restraints
S = 1.78Δρmax = 0.93 e Å3
120 reflectionsΔρmin = 0.72 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Y10.3333330.6666670.1666670.0124 (4)
Na10000.0207 (14)
S1000.24260 (10)0.0125 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Y10.0088 (4)0.0088 (4)0.0196 (7)0.0044 (2)00
Na10.0181 (16)0.0181 (16)0.026 (3)0.0090 (8)00
S10.0095 (7)0.0095 (7)0.0183 (11)0.0048 (3)00
Geometric parameters (Å, º) top
Y1—S12.739 (2)Na1—S1iv2.912 (2)
Y1—S1i2.7393 (14)S1—S1x3.960 (4)
Y1—S1ii2.739 (2)S1—S1xi3.960 (2)
Y1—S1iii2.739 (2)S1—S1xii3.960 (2)
Y1—S1iv2.7393 (14)S1—S1i3.960 (2)
Y1—S1v2.739 (2)S1—S1xiii3.960 (2)
Na1—S1vi2.912 (2)S1—S1ii3.960 (4)
Na1—S1vii2.9117 (16)S1—S1ix3.786 (3)
Na1—S1viii2.912 (2)S1—S1iii3.786 (3)
Na1—S1ix2.912 (2)S1—S1iv3.786 (3)
Na1—S1iii2.9117 (16)
S1—Y1—S1i92.59 (4)S1vi—Na1—S1iii94.30 (4)
S1—Y1—S1ii92.59 (4)S1vi—Na1—S1iv180.0 (5)
S1—Y1—S1iii87.41 (4)S1vii—Na1—S1viii85.70 (4)
S1—Y1—S1iv87.41 (4)S1vii—Na1—S1ix94.30 (4)
S1—Y1—S1v180.0 (5)S1vii—Na1—S1iii180.0 (5)
S1i—Y1—S1ii92.59 (4)S1vii—Na1—S1iv94.30 (4)
S1i—Y1—S1iii87.41 (4)S1viii—Na1—S1ix180.0 (5)
S1i—Y1—S1iv180.0 (5)S1viii—Na1—S1iii94.30 (4)
S1i—Y1—S1v87.41 (4)S1viii—Na1—S1iv94.30 (4)
S1ii—Y1—S1iii180.0 (5)S1ix—Na1—S1iii85.70 (4)
S1ii—Y1—S1iv87.41 (4)S1ix—Na1—S1iv85.70 (4)
S1ii—Y1—S1v87.41 (4)S1iii—Na1—S1iv85.70 (4)
S1iii—Y1—S1iv92.59 (4)Y1x—S1—Y1xii92.59 (5)
S1iii—Y1—S1v92.59 (4)Y1x—S1—Y192.59 (5)
S1iv—Y1—S1v92.59 (4)Y1xii—S1—Y192.59 (5)
S1vi—Na1—S1vii85.70 (4)Na1xiv—S1—Na1xv85.70 (5)
S1vi—Na1—S1viii85.70 (4)Na1xiv—S1—Na1xvi85.70 (5)
S1vi—Na1—S1ix94.30 (4)Na1xv—S1—Na1xvi85.70 (5)
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) x1, y, z; (xii) x, y1, z; (xiii) x+1, y, z; (xiv) x1/3, y2/3, z+1/3; (xv) x1/3, y+1/3, z+1/3; (xvi) x+2/3, y+1/3, z+1/3.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaNaGdS2NaLuS2NaYS2
Mr244.4262.1176
Crystal system, space groupTrigonal, R3mTrigonal, R3mTrigonal, R3m
Temperature (K)304300302
a, c (Å)4.0138 (4), 19.878 (2)3.8909 (4), 19.850 (3)3.9604 (12), 19.867 (8)
V3)277.34 (5)260.24 (6)269.9 (2)
Z333
Radiation typeMo KαMo KαMo Kα
µ (mm1)18.9129.4917.21
Crystal size (mm)0.12 × 0.09 × 0.030.12 × 0.11 × 0.040.12 × 0.07 × 0.06
Data collection
DiffractometerAgilent Xcalibur Gemini ultra
diffractometer
Agilent Xcalibur Gemini ultra
diffractometer
Agilent Xcalibur Gemini ultra
diffractometer
Absorption correctionAnalytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
Analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
Analytical
[CrysAlis PRO (Agilent, 2012); analytical numeric absorption correction using a multifaceted crystal (Clark & Reid, 1995)]
Tmin, Tmax0.213, 0.5610.150, 0.5080.344, 0.479
No. of measured, independent and
observed [I > 3σ(I)] reflections
935, 164, 161 947, 183, 183 1233, 120, 112
Rint0.0310.0530.109
(sin θ/λ)max1)0.6560.6910.693
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.048, 1.35 0.031, 0.066, 1.83 0.031, 0.067, 1.78
No. of reflections164183120
No. of parameters10108
Δρmax, Δρmin (e Å3)0.73, 0.542.05, 1.830.93, 0.72

Computer programs: CrysAlis PRO (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005).

 

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