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The crystal structures of the complex sulfides SrLnCuS3 (Ln = Sm, Gd, Er and Lu) have been determined and refined using powder X-ray diffraction. The crystals are found to be ortho­rhom­bic, with the structure type changing con­secutively in the order BaLaCuS3 → Eu2CuS3 → KZrCuS3 as the Ln3+ ionic radius decreases in the order La/Pr → Sm/Gd → Er/Lu. Variations of the structure parameters along the series of compounds studied are analyzed, and an effect caused by crystallochemical contraction on the stabilization of the respective structure types is demonstrated.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619004984/lg3238sup1.cif
Contains datablocks global, SrErCuS3, SrGdCuS3, SrLuCuS3, SrSmCuS3

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S2053229619004984/lg3238SrErCuS3sup2.rtv
Contains datablock SrErCuS3

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S2053229619004984/lg3238SrGdCuS3sup3.rtv
Contains datablock SrGdCuS3

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S2053229619004984/lg3238SrLuCuS3sup4.rtv
Contains datablock SrLuCuS3

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S2053229619004984/lg3238SrSmCuS3sup5.rtv
Contains datablock SrSmCuS3

CCDC references: 1909592; 1909591; 1909590; 1909589

Computing details top

For all structures, program(s) used to refine structure: Powder diffraction, Derivative Difference Method (DDM) (Solovyov, 2004).

Strontium erbium copper trisulfide (SrErCuS3) top
Crystal data top
SrErCuS3V = 513.99 (1) Å3
Mr = 414.54Z = 4
Orthorhombic, CmcmDx = 5.359 Mg m3
Hall symbol: -C 2C 2Cu Kα radiation
a = 3.92672 (5) ÅT = 298 K
b = 12.9632 (2) Åyellow
c = 10.0974 (1) Å
Data collection top
PANalytical X'Pert PRO
diffractometer
2θmin = 10.007°, 2θmax = 139.996°, 2θstep = 0.013°
Refinement top
Least-squares matrix: fullR(F) = 0.026
Rwp = 0.05722 parameters
Rexp = 0.0160 restraints
RBragg = 0.031(Δ/σ)max = 0.004
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Er0.000000.000000.000000.0118 (10)
Sr0.000000.74764 (12)0.250000.0176 (11)
Cu0.000000.47116 (17)0.250000.0176 (12)
S10.000000.3642 (2)0.0658 (3)0.0169 (12)
S20.000000.0755 (3)0.250000.0114 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Er0.0066 (11)0.0122 (11)0.0167 (12)0.00000.00000.0010 (6)
Sr0.0127 (14)0.0138 (13)0.0265 (15)0.00000.00000.0000
Cu0.022 (2)0.0153 (18)0.0155 (18)0.00000.00000.0000
S10.023 (2)0.0055 (19)0.023 (2)0.00000.00000.0028 (16)
S20.013 (3)0.010 (3)0.012 (2)0.00000.00000.0000
Geometric parameters (Å, º) top
Er—S1i2.7194 (19)Sr—S2ii2.972 (3)
Er—S22.7074 (13)Cu—S12.320 (3)
Sr—S1ii3.098 (2)Cu—S2ii2.384 (2)
S1i—Er—S1iii92.44 (8)S1ii—Sr—S2ii86.99 (5)
S1i—Er—S1iv87.56 (8)S1ii—Sr—S2vi141.70 (6)
S1i—Er—S290.36 (8)S2ii—Sr—S2vi82.68 (10)
S1i—Er—S2v89.64 (8)S1—Cu—S1ix106.59 (16)
S1ii—Sr—S1vi78.65 (7)S1—Cu—S2ii109.82 (5)
S1ii—Sr—S1vii73.80 (10)S2ii—Cu—S2vi110.87 (16)
S1ii—Sr—S1viii121.62 (11)
Symmetry codes: (i) x1/2, y1/2, z; (ii) x1/2, y+1/2, z; (iii) x+1/2, y1/2, z; (iv) x1/2, y+1/2, z; (v) x, y, z1/2; (vi) x+1/2, y+1/2, z; (vii) x1/2, y+1/2, z+1/2; (viii) x+1/2, y+1/2, z+1/2; (ix) x, y, z+1/2.
Strontium gadolinium copper trisulfide (SrGdCuS3) top
Crystal data top
SrGdCuS3V = 529.62 (2) Å3
Mr = 404.54Z = 4
Orthorhombic, PnmaDx = 5.075 Mg m3
Hall symbol: -P 2AC 2NCu Kα radiation
a = 10.3288 (2) ÅT = 298 K
b = 3.96271 (7) Åyellow
c = 12.9397 (2) Å
Data collection top
PANalytical X'Pert PRO
diffractometer
2θmin = 10.007°, 2θmax = 139.996°, 2θstep = 0.013°
Refinement top
Least-squares matrix: fullR(F) = 0.022
Rwp = 0.04436 parameters
Rexp = 0.0160 restraints
RBragg = 0.025(Δ/σ)max = 0.021
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Gd0.01504 (11)0.250000.74014 (7)0.0111 (9)
Sr0.77629 (16)0.250000.00231 (11)0.0141 (10)
Cu0.2346 (2)0.250000.22237 (17)0.0193 (12)
S10.0521 (4)0.250000.1178 (2)0.0101 (15)
S20.4085 (4)0.250000.1067 (3)0.0077 (15)
S30.2612 (4)0.250000.8273 (3)0.0099 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Gd0.0104 (13)0.0092 (12)0.0139 (11)0.00000.0003 (6)0.0000
Sr0.0221 (18)0.0099 (14)0.0102 (13)0.00000.0005 (10)0.0000
Cu0.014 (2)0.019 (2)0.026 (2)0.00000.0017 (15)0.0000
S10.012 (3)0.017 (6)0.002 (3)0.00000.001 (2)0.0000
S20.014 (3)0.005 (5)0.004 (3)0.00000.001 (2)0.0000
S30.012 (3)0.004 (3)0.015 (3)0.00000.003 (3)0.0000
Geometric parameters (Å, º) top
Gd—S1i2.791 (2)Sr—S2v3.092 (3)
Gd—S2ii2.745 (3)Sr—S3vi2.990 (3)
Gd—S32.781 (4)Cu—S12.320 (4)
Gd—S3iii2.763 (4)Cu—S22.339 (5)
Sr—S1iv3.217 (4)Cu—S3vii2.402 (2)
Sr—S1v3.079 (3)
S1i—Gd—S1viii90.47 (9)S1v—Sr—S2v73.32 (9)
S1i—Gd—S2ii88.49 (7)S1v—Sr—S2x122.53 (9)
S1i—Gd—S2ix177.11 (12)S1v—Sr—S3vi91.16 (7)
S1i—Gd—S387.72 (10)S1v—Sr—S3xi150.83 (12)
S1i—Gd—S3iii88.40 (10)S2v—Sr—S2x79.72 (10)
S2ii—Gd—S2ix92.42 (11)S2v—Sr—S3vi80.31 (8)
S2ii—Gd—S389.55 (10)S2v—Sr—S3xi132.93 (12)
S2ii—Gd—S3iii94.26 (10)S3vi—Sr—S3xi83.01 (9)
S3—Gd—S3iii174.49 (7)S1—Cu—S2104.50 (15)
S1iv—Sr—S1v74.01 (8)S1—Cu—S3vii110.14 (12)
S1iv—Sr—S2v139.34 (6)S2—Cu—S3vii110.35 (12)
S1iv—Sr—S3vi76.83 (9)S3vii—Cu—S3xii111.15 (16)
S1v—Sr—S1x80.10 (9)
Symmetry codes: (i) x, y1/2, z+1; (ii) x+1/2, y, z+1/2; (iii) x1/2, y+1/2, z+3/2; (iv) x+1, y, z; (v) x+1, y1/2, z; (vi) x+1, y1/2, z+1; (vii) x+1/2, y, z1/2; (viii) x, y+1/2, z+1; (ix) x+1/2, y+1, z+1/2; (x) x+1, y+1/2, z; (xi) x+1, y+1/2, z+1; (xii) x+1/2, y+1, z1/2.
Strontium lutetium copper trisulfide (SrLuCuS3) top
Crystal data top
SrLuCuS3V = 507.54 (1) Å3
Mr = 422.31Z = 4
Orthorhombic, CmcmDx = 5.529 Mg m3
Hall symbol: -C 2C 2Cu Kα radiation
a = 3.91105 (4) ÅT = 298 K
b = 12.9504 (1) Åpurple
c = 10.0206 (1) Å
Data collection top
PANalytical X'Pert PRO
diffractometer
2θmin = 10.007°, 2θmax = 139.996°, 2θstep = 0.013°
Refinement top
Least-squares matrix: fullR(F) = 0.013
Rwp = 0.05322 parameters
Rexp = 0.0150 restraints
RBragg = 0.027(Δ/σ)max = 0.010
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Lu0.000000.000000.000000.0081 (8)
Sr0.000000.74784 (9)0.250000.0097 (8)
Cu0.000000.47066 (13)0.250000.0097 (9)
S10.000000.36458 (17)0.0637 (4)0.0064 (8)
S20.000000.0758 (3)0.250000.0059 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Lu0.0062 (10)0.0096 (8)0.0086 (11)0.00000.00000.0010 (4)
Sr0.0033 (10)0.0073 (10)0.0183 (16)0.00000.00000.0000
Cu0.0154 (15)0.0091 (13)0.0048 (17)0.00000.00000.0000
S10.0045 (15)0.0072 (13)0.0074 (12)0.00000.00000.0029 (11)
S20.007 (2)0.0052 (19)0.006 (2)0.00000.00000.0000
Geometric parameters (Å, º) top
Lu—S1i2.7030 (17)Sr—S2ii2.965 (3)
Lu—S22.6905 (13)Cu—S12.318 (3)
Sr—S1ii3.098 (3)Cu—S2ii2.383 (2)
S1i—Lu—S1iii92.68 (7)S1ii—Sr—S2ii87.16 (5)
S1i—Lu—S1iv87.32 (7)S1ii—Sr—S2vi141.55 (6)
S1i—Lu—S290.97 (9)S2ii—Sr—S2vi82.54 (10)
S1i—Lu—S2v89.03 (9)S1—Cu—S1ix107.31 (15)
S1ii—Sr—S1vi78.29 (7)S1—Cu—S2ii109.79 (5)
S1ii—Sr—S1vii74.14 (11)S2ii—Cu—S2vi110.32 (16)
S1ii—Sr—S1viii121.57 (9)
Symmetry codes: (i) x1/2, y1/2, z; (ii) x1/2, y+1/2, z; (iii) x+1/2, y1/2, z; (iv) x1/2, y+1/2, z; (v) x, y, z1/2; (vi) x+1/2, y+1/2, z; (vii) x1/2, y+1/2, z+1/2; (viii) x+1/2, y+1/2, z+1/2; (ix) x, y, z+1/2.
Strontium samarium copper trisulfide (SrSmCuS3) top
Crystal data top
SrSmCuS3V = 537.63 (2) Å3
Mr = 397.74Z = 4
Orthorhombic, PnmaDx = 4.916 Mg m3
Hall symbol: -P 2AC 2NCu Kα radiation
a = 10.4285 (2) ÅT = 298 K
b = 3.98640 (7) Åyellow
c = 12.9325 (2) Å
Data collection top
PANalytical X'Pert PRO
diffractometer
2θmin = 10.007°, 2θmax = 139.996°, 2θstep = 0.013°
Refinement top
Least-squares matrix: fullR(F) = 0.021
Rwp = 0.04936 parameters
Rexp = 0.0190 restraints
RBragg = 0.029(Δ/σ)max = 0.003
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sm0.01587 (10)0.250000.73736 (7)0.0093 (12)
Sr0.78116 (18)0.250000.00217 (11)0.0089 (12)
Cu0.2342 (2)0.250000.22281 (18)0.0159 (14)
S10.0504 (4)0.250000.1190 (3)0.0082 (17)
S20.4031 (5)0.250000.1040 (3)0.0105 (17)
S30.2606 (4)0.250000.8264 (3)0.0096 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sm0.0096 (16)0.0081 (16)0.0102 (13)0.00000.0005 (6)0.0000
Sr0.0117 (17)0.0073 (17)0.0076 (14)0.00000.0001 (8)0.0000
Cu0.0075 (19)0.019 (2)0.021 (2)0.00000.0014 (16)0.0000
S10.009 (4)0.005 (5)0.011 (3)0.00000.006 (2)0.0000
S20.010 (3)0.019 (5)0.003 (3)0.00000.000 (2)0.0000
S30.002 (3)0.016 (3)0.012 (3)0.00000.001 (2)0.0000
Geometric parameters (Å, º) top
Sm—S1i2.811 (3)Sr—S2v3.090 (4)
Sm—S2ii2.768 (3)Sr—S3vi3.013 (3)
Sm—S32.800 (4)Cu—S12.340 (5)
Sm—S3iii2.787 (5)Cu—S22.337 (5)
Sr—S1iv3.188 (5)Cu—S3vii2.402 (2)
Sr—S1v3.085 (3)
S1i—Sm—S1viii90.33 (11)S1v—Sr—S2v73.24 (11)
S1i—Sm—S2ii88.63 (8)S1v—Sr—S2x123.04 (10)
S1i—Sm—S2ix175.91 (13)S1v—Sr—S3vi91.64 (8)
S1i—Sm—S387.26 (10)S1v—Sr—S3xi152.08 (13)
S1i—Sm—S3iii87.75 (10)S2v—Sr—S2x80.33 (12)
S2ii—Sm—S2ix92.12 (12)S2v—Sr—S3vi79.07 (9)
S2ii—Sm—S388.75 (12)S2v—Sr—S3xi131.60 (13)
S2ii—Sm—S3iii96.15 (12)S3vi—Sr—S3xi82.85 (10)
S3—Sm—S3iii172.92 (7)S1—Cu—S2103.90 (17)
S1iv—Sr—S1v74.89 (10)S1—Cu—S3vii109.79 (13)
S1iv—Sr—S2v139.29 (7)S2—Cu—S3vii110.46 (13)
S1iv—Sr—S3vi77.20 (10)S3vii—Cu—S3xii112.13 (17)
S1v—Sr—S1x80.50 (10)
Symmetry codes: (i) x, y1/2, z+1; (ii) x+1/2, y, z+1/2; (iii) x1/2, y+1/2, z+3/2; (iv) x+1, y, z; (v) x+1, y1/2, z; (vi) x+1, y1/2, z+1; (vii) x+1/2, y, z1/2; (viii) x, y+1/2, z+1; (ix) x+1/2, y+1, z+1/2; (x) x+1, y+1/2, z; (xi) x+1, y+1/2, z+1; (xii) x+1/2, y+1, z1/2.
Experimental details top
SrErCuS3SrGdCuS3SrLuCuS3SrSmCuS3
Crystal data
Chemical formulaCuErS3SrCuGdS3SrCuLuS3SrCuS3SmSr
Mr414.54404.54422.31397.74
Crystal system, space groupOrthorhombic, CmcmOrthorhombic, PnmaOrthorhombic, CmcmOrthorhombic, Pnma
Temperature (K)298298298298
a, b, c (Å)3.92672 (5), 12.9632 (2), 10.0974 (1)10.3288 (2), 3.96271 (7), 12.9397 (2)3.91105 (4), 12.9504 (1), 10.0206 (1)10.4285 (2), 3.98640 (7), 12.9325 (2)
V3)513.99 (1)529.62 (2)507.54 (1)537.63 (2)
Z4444
Radiation typeCu Kα, λ = 1.5418 ÅCu Kα, λ = 1.5418 ÅCu Kα, λ = 1.5418 ÅCu Kα, λ = 1.5418 Å
Specimen shape, size (mm)Cylinder, 25 × 25Cylinder, 25 × 25Cylinder, 25 × 25Cylinder, 25 × 25
Data collection
DiffractometerPANalytical X'Pert PROPANalytical X'Pert PROPANalytical X'Pert PROPANalytical X'Pert PRO
Specimen mountingFlat plateFlat plateFlat plateFlat plate
Data collection modeReflectionReflectionReflectionReflection
Scan methodStepStepStepStep
2θmin values (°) 2θmax values (°) 2θstep values (°)10.01 140.00 0.01310.01 140.00 0.01310.01 140.00 0.01310.01 140.00 0.013
Time/step (sec)1.51.51.51.5
Refinement
Rp0.0440.0370.0420.032
Rwp0.0570.0440.0530.049
Rexp0.0160.0160.0150.019
RBragg0.0310.0250.0270.029
R(F)0.0260.0220.0130.021
χ213.1557.63211.6546.627
No. of parameters22362236
Computer programs: DDM (Solovyov, 2004)
Interatomic distances (d) and their average values in SrLnCuS3 structures (Ln = La, Pr, Sm, Gd, Er and Lu) top
Bondd (Å)Bondd (Å)Bondd (Å)
SrLCuS3a
<La—S>2.966 (1)b<Sr—S>3.058 (2)b<Cu—S>2.353 (2)b
2.96 (5)c3.05 (5)c2.35 (1)c
SrPrCuS3a
<Pr—S>2.924 (2)b<Sr—S>3.056 (2)b<Cu—S>2.343 (2)b
2.92 (5)c3.05 (6)c2.34 (2)c
SrSmCuS3
Sm—S12.811 (3) (×2)Sr—S13.188 (5) (×1)Cu—S12.340 (5) (×1)
Sm—S22.768 (3) (×2)Sr—S13.085 (3) (×2)Cu—S22.337 (5) (×1)
Sm—S32.800 (4) (×1)Sr—S23.090 (4) (×2)Cu—S32.402 (2) (×2)
Sm—S32.787 (5) (×1)Sr—S33.013 (3) (×2)
<Sm—S>2.792 (2)b<Sr—S>3.080 (2)b<Cu—S>2.372 (2)b
2.79 (2)c3.08 (6)c2.37 (4)c
SrGdCuS3
Gd—S12.791 (2) (×2)Sr—S13.217 (4) (×1)Cu—S12.320 (4) (×1)
Gd—S22.745 (3) (×2)Sr—S13.079 (3) (×2)Cu—S22.339 (5) (×1)
Gd—S32.781 (4) (×1)Sr—S23.092 (3) (×2)Cu—S32.402 (2) (×2)
Gd—S32.763 (4) (×1)Sr—S32.990 (3) (×2)
<Gd—S>2.769 (2)b<Sr—S>3.077 (2)b<Cu—S>2.366 (2)b
2.77 (2)c3.08 (8)c2.37 (4)c
SrErCuS3
Er—S12.719 (2) (×4)Sr—S13.098 (2) (×4)Cu—S12.320 (3) (×2)
Er—S22.707 (1) (×2)Sr—S22.972 (3) (×2)Cu—S22.384 (2) (×2)
<Er—S>2.715 (1)b<Sr—S>3.056 (2)b<Cu—S>2.352 (2)b
2.72 (1)c3.06 (7)c2.35 (4)c
SrLuCuS3
Lu—S12.703 (2) (×4)Sr—S13.098 (3) (×4)Cu—S12.318 (3) (×2)
Lu—S22.691 (1) (×2)Sr—S22.965 (3) (×2)Cu—S22.383 (2) (×2)
<Lu—S>2.699 (1)b<Sr—S>3.054 (2)b<Cu—S>2.350 (2)b
2.699 (6)c3.05 (7)c2.35 (4)c
Notes: (a) data for SrLCuS3 and SrPrCuS3 are from Ruseikina et al. (2014); (b) experimental error (DDM; Solovyov, 2004); (c) regular variations of distances due to the polyhedron distortion (Bell, 2001).
 

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