Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021694/br6070sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021694/br6070Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-Si) = 0.002 Å
- R factor = 0.020
- wR factor = 0.038
- Data-to-parameter ratio = 21.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.25 From the CIF: _reflns_number_total 2446 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2654 Completeness (_total/calc) 92.16% Alert C: < 95% complete RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.107
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Single crystals of the title compound were prepared from the elements. Samarium metal chips (StremChem, 99.9%), sulfur powder (Aldrich, 99.98%), silicon powder (Merck, >99%), and chlorine gas (Riedel-de Haën, >99%) were added in a quartz glass tube in a molar ratio of 1:2:0.3:~0.3. The ampoule was evacuated, sealed, and heated for 10 d in a two-zone furnace with its ends held at temperatures of 1273 and 1073 K. After cooling, a few air-stable orange crystals were obtained.
Tests in space groups with lower symmetry do not improve the residuals and lead to no improvement of the structural solution.
Data collection: IPDS Software (Stoe & Cie, 1998); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
Sm3ClS2(SiS4) | Dx = 4.620 Mg m−3 |
Mr = 706.95 | Melting point: not measured K |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 7998 reflections |
a = 12.300 (2) Å | θ = 5.1–56.1° |
b = 10.290 (2) Å | µ = 18.65 mm−1 |
c = 16.061 (3) Å | T = 293 K |
V = 2032.8 (7) Å3 | Slab, orange |
Z = 8 | 0.24 × 0.18 × 0.11 mm |
F(000) = 2504 |
Stoe IPDS diffractometer | 2446 independent reflections |
Radiation source: fine-focus sealed tube | 2041 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.107 |
Detector resolution: 60 pixels mm-1 | θmax = 28.3°, θmin = 2.5° |
240 exposures, Δ ϕ 1.2 ° scans | h = −16→16 |
Absorption correction: gaussian (X-RED; Stoe & Cie, 1998) | k = −13→13 |
Tmin = 0.03, Tmax = 0.13 | l = −21→21 |
32851 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.0111P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.038 | (Δ/σ)max = 0.001 |
S = 0.90 | Δρmax = 1.15 e Å−3 |
2446 reflections | Δρmin = −1.47 e Å−3 |
116 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00138 (3) |
Sm3ClS2(SiS4) | V = 2032.8 (7) Å3 |
Mr = 706.95 | Z = 8 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.300 (2) Å | µ = 18.65 mm−1 |
b = 10.290 (2) Å | T = 293 K |
c = 16.061 (3) Å | 0.24 × 0.18 × 0.11 mm |
Stoe IPDS diffractometer | 2446 independent reflections |
Absorption correction: gaussian (X-RED; Stoe & Cie, 1998) | 2041 reflections with I > 2σ(I) |
Tmin = 0.03, Tmax = 0.13 | Rint = 0.107 |
32851 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 116 parameters |
wR(F2) = 0.038 | 0 restraints |
S = 0.90 | Δρmax = 1.15 e Å−3 |
2446 reflections | Δρmin = −1.47 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Sm1 | 0.883659 (19) | 0.03529 (2) | 0.611482 (16) | 0.01023 (6) | |
Sm2 | 0.61418 (3) | 0.2500 | 0.62429 (2) | 0.00953 (8) | |
Sm3 | 0.37642 (3) | 0.2500 | 0.36265 (2) | 0.00903 (8) | |
Sm4 | 0.68727 (2) | 0.04288 (2) | 0.404352 (16) | 0.01294 (7) | |
Cl1 | 0.10394 (9) | 0.04629 (12) | 0.56010 (8) | 0.0173 (2) | |
Si1 | 0.88531 (14) | 0.7500 | 0.73933 (11) | 0.0085 (3) | |
Si2 | 0.83459 (14) | 0.2500 | 0.77794 (11) | 0.0085 (3) | |
S1 | 0.56346 (12) | 0.2500 | 0.45292 (10) | 0.0098 (3) | |
S2 | 0.37905 (13) | 0.2500 | 0.59584 (10) | 0.0131 (3) | |
S3 | 0.73771 (9) | 0.08870 (11) | 0.74619 (8) | 0.0106 (2) | |
S4 | 0.97444 (9) | 0.91899 (10) | 0.76918 (7) | 0.0103 (2) | |
S5 | 0.81591 (13) | 0.2500 | 0.52818 (11) | 0.0125 (3) | |
S6 | 0.26988 (12) | 0.2500 | 0.19945 (10) | 0.0106 (3) | |
S7 | 0.65556 (10) | 0.99036 (11) | 0.56796 (7) | 0.0116 (2) | |
S8 | 0.85757 (13) | 0.7500 | 0.61027 (10) | 0.0105 (3) | |
S9 | 0.98042 (12) | 0.2500 | 0.70888 (11) | 0.0109 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sm1 | 0.01080 (11) | 0.00982 (11) | 0.01006 (13) | 0.00027 (8) | −0.00025 (9) | −0.00076 (8) |
Sm2 | 0.00896 (14) | 0.01006 (15) | 0.00957 (17) | 0.000 | −0.00092 (13) | 0.000 |
Sm3 | 0.00788 (14) | 0.00833 (14) | 0.01088 (17) | 0.000 | −0.00027 (13) | 0.000 |
Sm4 | 0.01507 (12) | 0.01394 (11) | 0.00981 (13) | 0.00417 (9) | 0.00122 (10) | 0.00240 (9) |
Cl1 | 0.0112 (5) | 0.0275 (6) | 0.0131 (6) | 0.0022 (4) | 0.0004 (5) | −0.0048 (5) |
Si1 | 0.0085 (8) | 0.0087 (7) | 0.0084 (9) | 0.000 | −0.0013 (7) | 0.000 |
Si2 | 0.0085 (8) | 0.0091 (8) | 0.0079 (9) | 0.000 | −0.0015 (7) | 0.000 |
S1 | 0.0083 (7) | 0.0111 (7) | 0.0099 (8) | 0.000 | 0.0002 (6) | 0.000 |
S2 | 0.0119 (7) | 0.0181 (7) | 0.0092 (8) | 0.000 | 0.0017 (7) | 0.000 |
S3 | 0.0098 (5) | 0.0107 (5) | 0.0113 (6) | −0.0008 (4) | −0.0007 (4) | 0.0000 (4) |
S4 | 0.0100 (5) | 0.0092 (5) | 0.0117 (6) | −0.0008 (4) | −0.0018 (4) | 0.0002 (4) |
S5 | 0.0128 (7) | 0.0099 (7) | 0.0148 (9) | 0.000 | 0.0000 (7) | 0.000 |
S6 | 0.0096 (7) | 0.0125 (7) | 0.0096 (8) | 0.000 | −0.0003 (6) | 0.000 |
S7 | 0.0160 (5) | 0.0085 (5) | 0.0104 (6) | −0.0016 (4) | 0.0003 (5) | 0.0009 (4) |
S8 | 0.0134 (7) | 0.0099 (7) | 0.0082 (8) | 0.000 | −0.0009 (6) | 0.000 |
S9 | 0.0093 (7) | 0.0109 (7) | 0.0126 (8) | 0.000 | 0.0012 (6) | 0.000 |
Sm1—S5 | 2.7140 (11) | Cl1—Sm4ii | 2.7862 (12) |
Sm1—Cl1i | 2.8346 (12) | Cl1—Sm1xiii | 2.8346 (12) |
Sm1—S3 | 2.8646 (13) | Cl1—Sm1ii | 2.8847 (14) |
Sm1—Cl1ii | 2.8847 (14) | Si1—S8 | 2.101 (2) |
Sm1—S7iii | 2.9280 (13) | Si1—S4 | 2.1109 (15) |
Sm1—S8iii | 2.9532 (7) | Si1—S4iv | 2.1109 (15) |
Sm1—S9 | 2.9572 (12) | Si1—S6viii | 2.147 (2) |
Sm1—S4iii | 3.0156 (13) | Si2—S2xiv | 2.100 (2) |
Sm1—Sm2 | 3.9888 (6) | Si2—S3 | 2.1060 (16) |
Sm2—S1 | 2.8222 (18) | Si2—S3v | 2.1060 (15) |
Sm2—S7iii | 2.8663 (12) | Si2—S9 | 2.109 (2) |
Sm2—S7iv | 2.8663 (12) | S1—Sm4v | 2.7331 (10) |
Sm2—S5 | 2.9223 (17) | S2—Si2vi | 2.100 (2) |
Sm2—S2 | 2.9279 (17) | S2—Sm4ii | 3.1223 (8) |
Sm2—S3v | 2.9827 (12) | S2—Sm4xv | 3.1223 (8) |
Sm2—S3 | 2.9827 (12) | S3—Sm4xvi | 3.0228 (13) |
Sm2—S9vi | 3.1442 (18) | S4—Sm3xvii | 2.9398 (12) |
Sm2—Sm1v | 3.9888 (6) | S4—Sm4xvii | 2.9704 (12) |
Sm3—S1 | 2.7193 (16) | S4—Sm1xviii | 3.0156 (13) |
Sm3—S7vii | 2.7412 (12) | S5—Sm1v | 2.7140 (11) |
Sm3—S7viii | 2.7412 (12) | S5—Sm4v | 3.3168 (14) |
Sm3—S8viii | 2.9107 (16) | S6—Si1viii | 2.147 (2) |
Sm3—S6 | 2.9305 (17) | S6—Sm4xix | 2.8904 (12) |
Sm3—S4ix | 2.9398 (12) | S6—Sm4xx | 2.8904 (12) |
Sm3—S4x | 2.9398 (12) | S7—Sm4xviii | 2.7109 (13) |
Sm4—S7iii | 2.7109 (13) | S7—Sm3viii | 2.7412 (12) |
Sm4—S1 | 2.7331 (10) | S7—Sm2xviii | 2.8663 (12) |
Sm4—Cl1ii | 2.7862 (12) | S7—Sm1xviii | 2.9280 (13) |
Sm4—S6xi | 2.8904 (12) | S8—Sm3viii | 2.9107 (16) |
Sm4—S4x | 2.9704 (12) | S8—Sm1xviii | 2.9532 (6) |
Sm4—S3xii | 3.0228 (13) | S8—Sm1v | 2.9532 (7) |
Sm4—S2ii | 3.1223 (8) | S9—Sm1v | 2.9572 (12) |
Sm4—S5 | 3.3168 (14) | S9—Sm2xiv | 3.1442 (18) |
S5—Sm1—Cl1i | 96.74 (4) | S7iii—Sm4—S1 | 78.39 (4) |
S5—Sm1—S3 | 91.36 (4) | S7iii—Sm4—Cl1ii | 82.43 (4) |
Cl1i—Sm1—S3 | 144.22 (4) | S1—Sm4—Cl1ii | 135.39 (4) |
S5—Sm1—Cl1ii | 77.42 (4) | S7iii—Sm4—S6xi | 139.17 (4) |
Cl1i—Sm1—Cl1ii | 71.52 (4) | S1—Sm4—S6xi | 77.61 (4) |
S3—Sm1—Cl1ii | 144.14 (3) | Cl1ii—Sm4—S6xi | 92.12 (4) |
S5—Sm1—S7iii | 73.54 (4) | S7iii—Sm4—S4x | 129.67 (4) |
Cl1i—Sm1—S7iii | 148.50 (4) | S1—Sm4—S4x | 74.48 (4) |
S3—Sm1—S7iii | 67.05 (3) | Cl1ii—Sm4—S4x | 144.14 (4) |
Cl1ii—Sm1—S7iii | 77.10 (3) | S6xi—Sm4—S4x | 73.53 (4) |
S5—Sm1—S8iii | 140.59 (4) | S7iii—Sm4—S3xii | 140.28 (3) |
Cl1i—Sm1—S8iii | 98.14 (4) | S1—Sm4—S3xii | 139.40 (4) |
S3—Sm1—S8iii | 97.33 (4) | Cl1ii—Sm4—S3xii | 75.13 (3) |
Cl1ii—Sm1—S8iii | 73.15 (4) | S6xi—Sm4—S3xii | 74.83 (4) |
S7iii—Sm1—S8iii | 74.77 (4) | S4x—Sm4—S3xii | 69.48 (3) |
S5—Sm1—S9 | 77.06 (4) | S7iii—Sm4—S2ii | 76.76 (4) |
Cl1i—Sm1—S9 | 74.90 (4) | S1—Sm4—S2ii | 127.40 (4) |
S3—Sm1—S9 | 73.10 (4) | Cl1ii—Sm4—S2ii | 85.59 (4) |
Cl1ii—Sm1—S9 | 134.54 (4) | S6xi—Sm4—S2ii | 143.42 (4) |
S7iii—Sm1—S9 | 129.04 (4) | S4x—Sm4—S2ii | 87.24 (4) |
S8iii—Sm1—S9 | 142.18 (4) | S3xii—Sm4—S2ii | 69.30 (4) |
S5—Sm1—S4iii | 148.29 (4) | S7iii—Sm4—S5 | 67.39 (4) |
Cl1i—Sm1—S4iii | 84.63 (3) | S1—Sm4—S5 | 66.02 (4) |
S3—Sm1—S4iii | 70.96 (3) | Cl1ii—Sm4—S5 | 69.45 (3) |
Cl1ii—Sm1—S4iii | 131.86 (3) | S6xi—Sm4—S5 | 72.80 (4) |
S7iii—Sm1—S4iii | 119.51 (3) | S4x—Sm4—S5 | 132.28 (3) |
S8iii—Sm1—S4iii | 69.59 (4) | S3xii—Sm4—S5 | 130.24 (4) |
S9—Sm1—S4iii | 72.73 (3) | S2ii—Sm4—S5 | 138.20 (4) |
S5—Sm1—Sm2 | 47.11 (4) | Sm4ii—Cl1—Sm1xiii | 143.92 (5) |
Cl1i—Sm1—Sm2 | 141.92 (3) | Sm4ii—Cl1—Sm1ii | 92.93 (4) |
S3—Sm1—Sm2 | 48.24 (2) | Sm1xiii—Cl1—Sm1ii | 108.48 (4) |
Cl1ii—Sm1—Sm2 | 104.74 (2) | S8—Si1—S4 | 107.97 (7) |
S7iii—Sm1—Sm2 | 45.86 (2) | S8—Si1—S4iv | 107.97 (7) |
S8iii—Sm1—Sm2 | 117.43 (3) | S4—Si1—S4iv | 110.94 (10) |
S9—Sm1—Sm2 | 83.88 (3) | S8—Si1—S6viii | 107.90 (10) |
S4iii—Sm1—Sm2 | 118.96 (2) | S4—Si1—S6viii | 110.96 (7) |
S1—Sm2—S7iii | 74.42 (3) | S4iv—Si1—S6viii | 110.96 (7) |
S1—Sm2—S7iv | 74.42 (3) | S2xiv—Si2—S3 | 112.40 (7) |
S7iii—Sm2—S7iv | 137.53 (5) | S2xiv—Si2—S3v | 112.40 (7) |
S1—Sm2—S5 | 70.88 (5) | S3—Si2—S3v | 104.03 (10) |
S7iii—Sm2—S5 | 71.49 (3) | S2xiv—Si2—S9 | 106.64 (10) |
S7iv—Sm2—S5 | 71.49 (3) | S3—Si2—S9 | 110.73 (7) |
S1—Sm2—S2 | 68.25 (5) | S3v—Si2—S9 | 110.73 (7) |
S7iii—Sm2—S2 | 97.25 (3) | Sm3—S1—Sm4v | 108.62 (4) |
S7iv—Sm2—S2 | 97.25 (3) | Sm3—S1—Sm4 | 108.62 (4) |
S5—Sm2—S2 | 139.13 (5) | Sm4v—S1—Sm4 | 102.49 (5) |
S1—Sm2—S3v | 138.83 (3) | Sm3—S1—Sm2 | 134.99 (6) |
S7iii—Sm2—S3v | 129.45 (3) | Sm4v—S1—Sm2 | 98.93 (4) |
S7iv—Sm2—S3v | 66.30 (3) | Sm4—S1—Sm2 | 98.93 (4) |
S5—Sm2—S3v | 85.08 (4) | Si2vi—S2—Sm2 | 96.12 (8) |
S2—Sm2—S3v | 127.27 (3) | Si2vi—S2—Sm4ii | 86.15 (3) |
S1—Sm2—S3 | 138.83 (3) | Sm2—S2—Sm4ii | 104.97 (3) |
S7iii—Sm2—S3 | 66.30 (3) | Si2vi—S2—Sm4xv | 86.15 (3) |
S7iv—Sm2—S3 | 129.45 (3) | Sm2—S2—Sm4xv | 104.96 (3) |
S5—Sm2—S3 | 85.08 (4) | Sm4ii—S2—Sm4xv | 149.71 (6) |
S2—Sm2—S3 | 127.27 (3) | Si2—S3—Sm1 | 88.82 (6) |
S3v—Sm2—S3 | 67.63 (5) | Si2—S3—Sm2 | 90.49 (6) |
S1—Sm2—S9vi | 135.68 (4) | Sm1—S3—Sm2 | 86.00 (4) |
S7iii—Sm2—S9vi | 111.22 (2) | Si2—S3—Sm4xvi | 88.67 (6) |
S7iv—Sm2—S9vi | 111.22 (2) | Sm1—S3—Sm4xvi | 110.94 (4) |
S5—Sm2—S9vi | 153.44 (5) | Sm2—S3—Sm4xvi | 163.01 (5) |
S2—Sm2—S9vi | 67.43 (4) | Si1—S4—Sm3xvii | 87.29 (5) |
S3v—Sm2—S9vi | 72.97 (4) | Si1—S4—Sm4xvii | 85.82 (6) |
S3—Sm2—S9vi | 72.97 (4) | Sm3xvii—S4—Sm4xvii | 97.05 (4) |
S1—Sm2—Sm1v | 97.66 (3) | Si1—S4—Sm1xviii | 86.78 (6) |
S7iii—Sm2—Sm1v | 110.64 (3) | Sm3xvii—S4—Sm1xviii | 153.46 (4) |
S7iv—Sm2—Sm1v | 47.14 (2) | Sm4xvii—S4—Sm1xviii | 108.27 (4) |
S5—Sm2—Sm1v | 42.88 (2) | Sm1v—S5—Sm1 | 108.99 (6) |
S2—Sm2—Sm1v | 144.364 (13) | Sm1v—S5—Sm2 | 90.02 (4) |
S3v—Sm2—Sm1v | 45.76 (2) | Sm1—S5—Sm2 | 90.02 (4) |
S3—Sm2—Sm1v | 85.34 (3) | Sm1v—S5—Sm4 | 164.83 (5) |
S9vi—Sm2—Sm1v | 118.60 (2) | Sm1—S5—Sm4 | 85.350 (18) |
S1—Sm2—Sm1 | 97.66 (3) | Sm2—S5—Sm4 | 84.93 (4) |
S7iii—Sm2—Sm1 | 47.14 (2) | Sm1v—S5—Sm4v | 85.350 (18) |
S7iv—Sm2—Sm1 | 110.64 (3) | Sm1—S5—Sm4v | 164.83 (5) |
S5—Sm2—Sm1 | 42.88 (2) | Sm2—S5—Sm4v | 84.93 (4) |
S2—Sm2—Sm1 | 144.364 (13) | Sm4—S5—Sm4v | 79.97 (4) |
S3v—Sm2—Sm1 | 85.34 (3) | Si1viii—S6—Sm4xix | 87.23 (5) |
S3—Sm2—Sm1 | 45.76 (2) | Si1viii—S6—Sm4xx | 87.23 (5) |
S9vi—Sm2—Sm1 | 118.60 (2) | Sm4xix—S6—Sm4xx | 95.02 (5) |
Sm1v—Sm2—Sm1 | 67.272 (16) | Si1viii—S6—Sm3 | 89.31 (7) |
S1—Sm3—S7vii | 84.53 (3) | Sm4xix—S6—Sm3 | 132.31 (3) |
S1—Sm3—S7viii | 84.53 (3) | Sm4xx—S6—Sm3 | 132.31 (3) |
S7vii—Sm3—S7viii | 128.92 (5) | Sm4xviii—S7—Sm3viii | 126.48 (4) |
S1—Sm3—S8viii | 139.19 (5) | Sm4xviii—S7—Sm2xviii | 98.38 (4) |
S7vii—Sm3—S8viii | 78.31 (3) | Sm3viii—S7—Sm2xviii | 133.41 (5) |
S7viii—Sm3—S8viii | 78.31 (3) | Sm4xviii—S7—Sm1xviii | 93.56 (4) |
S1—Sm3—S6 | 148.78 (5) | Sm3viii—S7—Sm1xviii | 100.54 (4) |
S7vii—Sm3—S6 | 107.43 (3) | Sm2xviii—S7—Sm1xviii | 87.00 (3) |
S7viii—Sm3—S6 | 107.43 (3) | Si1—S8—Sm3viii | 90.76 (7) |
S8viii—Sm3—S6 | 72.03 (5) | Si1—S8—Sm1xviii | 88.62 (3) |
S1—Sm3—S4ix | 75.19 (4) | Sm3viii—S8—Sm1xviii | 96.11 (3) |
S7vii—Sm3—S4ix | 76.31 (3) | Si1—S8—Sm1v | 88.62 (3) |
S7viii—Sm3—S4ix | 146.19 (3) | Sm3viii—S8—Sm1v | 96.11 (3) |
S8viii—Sm3—S4ix | 133.89 (3) | Sm1xviii—S8—Sm1v | 167.50 (6) |
S6—Sm3—S4ix | 79.76 (4) | Si2—S9—Sm1 | 86.32 (5) |
S1—Sm3—S4x | 75.19 (4) | Si2—S9—Sm1v | 86.32 (5) |
S7vii—Sm3—S4x | 146.19 (3) | Sm1—S9—Sm1v | 96.69 (5) |
S7viii—Sm3—S4x | 76.31 (3) | Si2—S9—Sm2xiv | 89.82 (7) |
S8viii—Sm3—S4x | 133.89 (3) | Sm1—S9—Sm2xiv | 131.40 (3) |
S6—Sm3—S4x | 79.76 (4) | Sm1v—S9—Sm2xiv | 131.40 (3) |
S4ix—Sm3—S4x | 72.53 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) x, −y+3/2, z; (v) x, −y+1/2, z; (vi) x−1/2, y, −z+3/2; (vii) −x+1, y−1/2, −z+1; (viii) −x+1, −y+1, −z+1; (ix) −x+3/2, y−1/2, z−1/2; (x) −x+3/2, −y+1, z−1/2; (xi) x+1/2, y, −z+1/2; (xii) −x+3/2, −y, z−1/2; (xiii) x−1, y, z; (xiv) x+1/2, y, −z+3/2; (xv) −x+1, y+1/2, −z+1; (xvi) −x+3/2, −y, z+1/2; (xvii) −x+3/2, −y+1, z+1/2; (xviii) x, y+1, z; (xix) x−1/2, y, −z+1/2; (xx) x−1/2, −y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | Sm3ClS2(SiS4) |
Mr | 706.95 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 12.300 (2), 10.290 (2), 16.061 (3) |
V (Å3) | 2032.8 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 18.65 |
Crystal size (mm) | 0.24 × 0.18 × 0.11 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Gaussian (X-RED; Stoe & Cie, 1998) |
Tmin, Tmax | 0.03, 0.13 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32851, 2446, 2041 |
Rint | 0.107 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.038, 0.90 |
No. of reflections | 2446 |
No. of parameters | 116 |
Δρmax, Δρmin (e Å−3) | 1.15, −1.47 |
Computer programs: IPDS Software (Stoe & Cie, 1998), IPDS Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXL97.
Sm1—S5 | 2.7140 (11) | Sm3—S6 | 2.9305 (17) |
Sm1—Cl1i | 2.8346 (12) | Sm3—S4ix | 2.9398 (12) |
Sm1—S3 | 2.8646 (13) | Sm3—S4x | 2.9398 (12) |
Sm1—Cl1ii | 2.8847 (14) | Sm4—S7iii | 2.7109 (13) |
Sm1—S7iii | 2.9280 (13) | Sm4—S1 | 2.7331 (10) |
Sm1—S8iii | 2.9532 (7) | Sm4—Cl1ii | 2.7862 (12) |
Sm1—S9 | 2.9572 (12) | Sm4—S6xi | 2.8904 (12) |
Sm1—S4iii | 3.0156 (13) | Sm4—S4x | 2.9704 (12) |
Sm2—S1 | 2.8222 (18) | Sm4—S3xii | 3.0228 (13) |
Sm2—S7iii | 2.8663 (12) | Sm4—S2ii | 3.1223 (8) |
Sm2—S7iv | 2.8663 (12) | Sm4—S5 | 3.3168 (14) |
Sm2—S5 | 2.9223 (17) | Si1—S8 | 2.101 (2) |
Sm2—S2 | 2.9279 (17) | Si1—S4 | 2.1109 (15) |
Sm2—S3v | 2.9827 (12) | Si1—S4iv | 2.1109 (15) |
Sm2—S3 | 2.9827 (12) | Si1—S6viii | 2.147 (2) |
Sm2—S9vi | 3.1442 (18) | Si2—S2xiii | 2.100 (2) |
Sm3—S1 | 2.7193 (16) | Si2—S3 | 2.1060 (16) |
Sm3—S7vii | 2.7412 (12) | Si2—S3v | 2.1060 (15) |
Sm3—S7viii | 2.7412 (12) | Si2—S9 | 2.109 (2) |
Sm3—S8viii | 2.9107 (16) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) x, −y+3/2, z; (v) x, −y+1/2, z; (vi) x−1/2, y, −z+3/2; (vii) −x+1, y−1/2, −z+1; (viii) −x+1, −y+1, −z+1; (ix) −x+3/2, y−1/2, z−1/2; (x) −x+3/2, −y+1, z−1/2; (xi) x+1/2, y, −z+1/2; (xii) −x+3/2, −y, z−1/2; (xiii) x+1/2, y, −z+3/2. |
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The structures of compounds in the system of lanthanide, sulfide, silicon and halogen have been one of our focuses over the last two years. Up to now, the following homologue groups have been published: the lanthanide iodine thiosilicates Ln3I[SiS4]2 (Ln = La—Nd, Sm and Tb) (Gauthier et al., 1998a,b, Hatscher & Urland, 2001, 2002c), the lanthanide bromide thiosilicates Ln3Br[SiS4]2 (Ln = La—Nd, Sm and Gd) (Hatscher & Urland 2002a), and the lanthanide chloride thiosilicates Ln3Cl[SiS4]2 (Ln = La—Pr) (Hatscher & Urland, 2002b), all crystallizing in the monoclinic space group C2/c. These compounds are isotypic to the so called A-type of the lanthanide chloride oxosilicates, first discovered by Gravereau et al. (1988). With Nd3ClS2[SiS4] (Hatscher & Urland, 2002 d), a new compound in this system was published with no oxo analogue so far known. We now present the heavier homologue, viz. Sm3ClS2[SiS4].
Sm3ClS2[SiS4] crystallizes in the orthorhombic space group Pnma. The structure displays two independent crystallographic positions of Si, and four different Sm positions. The Si atoms are surrounded by four sulfide ions each, forming almost undistorted SiS4 tetrahedra which are isolated in the structure, as is usual for the lanthanide thiosilicates (Fig. 1). A common structural feature of the halogenide thiosilicates of the lanthanides is the formation of a chain of halogen atoms through the structure. Whereas in the homologues of the lanthanide chloride oxosilicates these tunnels are along the c axis, in the case of the title compound they are found along [010]. Similar to the Ln3X[SiS4]2 (X = Cl, Br and I), the X atom shows a coordination of three lanthanide atoms. However, in the lanthanide halide thiosilicates of the type Ln3X[SiS4]2, they form an isosceles triangle, whereas in the Ln3ClS2[SiS4] compounds a heavily distorted triangle is found. The Cl atoms are shifted out of the plane of the samarium ions. The weak fixation of the anion in the triangle of cations leads to the enlargement of the U22 displacement parameter along the direction of the chain. The Sm1, Sm2 and Sm4 ions are coordinated by eight anions, Sm3 by seven. The Sm1 surrounding polyhedron is made up by six sulfides and two chloride, and the one around Sm4 by seven sulfides and one chloride. The other ones only have sulfide ligands. The dominant connection motif are channels made up by Sm1 and Sm4 elements along [001]. These channels show alternating polyhedra of Sm1 and Sm4, each connected via edges (Fig. 2). In the space in the centre, double strings of corner-sharing Sm2 and Sm3-polyhedra can be found (Fig. 3).