Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014137/mg6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014137/mg6013Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-Si) = 0.002 Å
- R factor = 0.023
- wR factor = 0.047
- Data-to-parameter ratio = 24.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.120
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Dysprosium metal chips (StremChem, 99.9%), sulfur powder (Aldrich, 99.98%), silicon powder (Merck, >99%), and bromine (Riedel-de Haën, >99%) were added in a quartz glass tube in a ratio of 1:3.28:1.06:~0.3. The ampoule was evacuated, sealed, and heated for 10 d in a temperature gradient of 1273 to 1073 K. After the tube was cooled, a few air-stable green crystals were obtained.
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.
Dy4(SiS4)3 | F(000) = 1992 |
Mr = 1118.99 | Dx = 4.341 Mg m−3 |
Monoclinic, P21/n | Melting point: not measured K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.813 (2) Å | Cell parameters from 7997 reflections |
b = 10.9387 (18) Å | θ = 2.5–28.1° |
c = 16.360 (4) Å | µ = 18.91 mm−1 |
β = 102.86 (3)° | T = 293 K |
V = 1712.1 (6) Å3 | Plate, green |
Z = 4 | 0.22 × 0.10 × 0.02 mm |
STOE IPDS diffractometer | 4184 independent reflections |
Radiation source: fine-focus sealed tube | 3327 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.120 |
Detector resolution: 60 pixels mm-1 | θmax = 28.2°, θmin = 2.2° |
240 exposures, Δ ϕ 1.2 ° scans | h = −12→13 |
Absorption correction: gaussian (X-RED; Stoe & Cie, 1998) | k = −14→14 |
Tmin = 0.117, Tmax = 0.685 | l = −21→21 |
29396 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)] = 0.023 | w = 1/[σ2(Fo2)] |
wR(F2) = 0.047 | (Δ/σ)max = 0.001 |
S = 0.87 | Δρmax = 1.29 e Å−3 |
4184 reflections | Δρmin = −1.42 e Å−3 |
173 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00081 (4) |
Dy4(SiS4)3 | V = 1712.1 (6) Å3 |
Mr = 1118.99 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.813 (2) Å | µ = 18.91 mm−1 |
b = 10.9387 (18) Å | T = 293 K |
c = 16.360 (4) Å | 0.22 × 0.10 × 0.02 mm |
β = 102.86 (3)° |
STOE IPDS diffractometer | 4184 independent reflections |
Absorption correction: gaussian (X-RED; Stoe & Cie, 1998) | 3327 reflections with I > 2σ(I) |
Tmin = 0.117, Tmax = 0.685 | Rint = 0.120 |
29396 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 173 parameters |
wR(F2) = 0.047 | 0 restraints |
S = 0.87 | Δρmax = 1.29 e Å−3 |
4184 reflections | Δρmin = −1.42 e Å−3 |
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 | ||
Dy1 | 0.61037 (2) | 0.98387 (3) | 0.124986 (17) | 0.01090 (7) | |
Dy2 | 0.87638 (2) | 0.65205 (3) | 0.059681 (16) | 0.01025 (7) | |
Dy3 | 0.53109 (2) | 0.37677 (3) | 0.131055 (17) | 0.01181 (7) | |
Dy4 | 0.32137 (2) | 0.76108 (3) | 0.288987 (17) | 0.01307 (7) | |
S1 | 0.50347 (11) | 0.77960 (14) | 0.18937 (9) | 0.0130 (3) | |
S2 | 0.41939 (11) | 0.15310 (14) | 0.18410 (8) | 0.0113 (3) | |
S3 | 0.74682 (11) | 0.21352 (14) | 0.13550 (9) | 0.0115 (3) | |
S4 | 0.84701 (11) | 0.83727 (13) | 0.18728 (8) | 0.0099 (3) | |
S5 | 0.61230 (11) | 0.75951 (13) | 0.01329 (9) | 0.0110 (3) | |
S6 | 0.91010 (11) | 0.84639 (14) | 0.94613 (9) | 0.0137 (3) | |
S7 | 0.04205 (11) | 0.43674 (14) | 0.09416 (9) | 0.0123 (3) | |
S8 | 0.34970 (11) | 0.48068 (14) | 0.22872 (9) | 0.0141 (3) | |
S9 | 0.66502 (11) | 0.47329 (14) | 0.97688 (9) | 0.0130 (3) | |
S10 | 0.15065 (11) | 0.73252 (13) | 0.12650 (9) | 0.0115 (3) | |
S11 | 0.65770 (11) | 0.05886 (14) | 0.97265 (9) | 0.0121 (3) | |
S12 | 0.75600 (11) | 0.54329 (13) | 0.18751 (9) | 0.0115 (3) | |
Si1 | 0.22185 (12) | 0.55471 (15) | 0.11744 (10) | 0.0103 (3) | |
Si2 | 0.70047 (12) | 0.88347 (15) | 0.93948 (10) | 0.0103 (3) | |
Si3 | 0.70889 (12) | 0.71649 (15) | 0.23333 (10) | 0.0096 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Dy1 | 0.01038 (10) | 0.00939 (14) | 0.01267 (13) | 0.00096 (8) | 0.00202 (8) | 0.00137 (11) |
Dy2 | 0.00816 (10) | 0.01019 (14) | 0.01199 (13) | 0.00129 (8) | 0.00136 (8) | 0.00045 (11) |
Dy3 | 0.00955 (10) | 0.01044 (15) | 0.01395 (14) | 0.00056 (8) | −0.00058 (8) | −0.00045 (11) |
Dy4 | 0.01157 (10) | 0.01701 (16) | 0.01117 (13) | −0.00360 (9) | 0.00366 (8) | −0.00137 (12) |
S1 | 0.0081 (5) | 0.0163 (8) | 0.0150 (7) | 0.0013 (4) | 0.0034 (4) | 0.0045 (6) |
S2 | 0.0089 (5) | 0.0139 (8) | 0.0106 (6) | 0.0006 (4) | 0.0007 (4) | −0.0014 (6) |
S3 | 0.0125 (5) | 0.0119 (8) | 0.0103 (6) | 0.0002 (5) | 0.0025 (4) | −0.0012 (6) |
S4 | 0.0081 (4) | 0.0095 (7) | 0.0117 (6) | 0.0004 (4) | 0.0014 (4) | −0.0007 (6) |
S5 | 0.0104 (5) | 0.0107 (7) | 0.0118 (7) | 0.0005 (4) | 0.0021 (4) | 0.0012 (6) |
S6 | 0.0096 (5) | 0.0148 (8) | 0.0161 (7) | 0.0016 (5) | 0.0013 (4) | 0.0013 (6) |
S7 | 0.0118 (5) | 0.0096 (7) | 0.0146 (7) | 0.0009 (5) | 0.0014 (4) | 0.0022 (6) |
S8 | 0.0124 (5) | 0.0154 (8) | 0.0129 (7) | 0.0035 (5) | −0.0008 (4) | 0.0027 (6) |
S9 | 0.0124 (5) | 0.0138 (8) | 0.0131 (7) | 0.0027 (5) | 0.0035 (4) | −0.0008 (6) |
S10 | 0.0093 (5) | 0.0096 (7) | 0.0141 (7) | 0.0015 (4) | −0.0005 (4) | −0.0011 (6) |
S11 | 0.0132 (5) | 0.0100 (7) | 0.0129 (7) | 0.0003 (5) | 0.0026 (4) | −0.0012 (6) |
S12 | 0.0120 (5) | 0.0089 (7) | 0.0138 (7) | −0.0015 (4) | 0.0030 (4) | −0.0013 (6) |
Si1 | 0.0105 (5) | 0.0095 (8) | 0.0100 (7) | 0.0016 (5) | 0.0006 (5) | −0.0005 (7) |
Si2 | 0.0097 (5) | 0.0108 (8) | 0.0098 (7) | 0.0016 (5) | 0.0008 (5) | −0.0007 (7) |
Si3 | 0.0086 (5) | 0.0099 (8) | 0.0101 (7) | 0.0003 (5) | 0.0016 (5) | 0.0015 (7) |
Dy1—S11i | 2.7597 (15) | Dy3—S4viii | 2.9780 (16) |
Dy1—S1 | 2.7740 (15) | Dy3—S9vi | 3.2680 (15) |
Dy1—S11ii | 2.7962 (14) | Dy4—S1 | 2.6809 (14) |
Dy1—S4 | 2.8194 (13) | Dy4—S2ix | 2.7629 (13) |
Dy1—S3iii | 2.8338 (15) | Dy4—S6x | 2.7844 (16) |
Dy1—S2iii | 2.9464 (14) | Dy4—S10 | 2.8263 (16) |
Dy1—S5 | 3.0625 (15) | Dy4—S7ix | 2.8289 (15) |
Dy1—S12iv | 3.1243 (16) | Dy4—S8ix | 2.9079 (16) |
Dy2—S5 | 2.7924 (13) | Dy4—S8 | 3.2526 (17) |
Dy2—S10v | 2.8114 (13) | Si1—S7 | 2.1504 (19) |
Dy2—S7v | 2.8460 (15) | Si1—S8 | 2.128 (2) |
Dy2—S12 | 2.8783 (15) | Si1—S9ii | 2.114 (2) |
Dy2—S6vi | 2.8903 (16) | Si1—S10 | 2.083 (2) |
Dy2—S9vi | 2.9512 (15) | Si2—S2ii | 2.138 (2) |
Dy2—S4 | 2.9688 (15) | Si2—S5xi | 2.124 (2) |
Dy2—S7vii | 2.9691 (16) | Si2—S6 | 2.0757 (17) |
Dy3—S3 | 2.7580 (14) | Si2—S11iii | 2.062 (2) |
Dy3—S9ii | 2.8281 (15) | Si3—S1 | 2.1003 (17) |
Dy3—S12 | 2.8520 (13) | Si3—S3iv | 2.093 (2) |
Dy3—S8 | 2.8774 (15) | Si3—S4 | 2.1458 (19) |
Dy3—S5vii | 2.8809 (15) | Si3—S12 | 2.126 (2) |
Dy3—S2 | 2.8921 (15) | ||
S11i—Dy1—S1 | 137.41 (4) | S1—Dy4—S8ix | 108.98 (4) |
S11i—Dy1—S11ii | 81.94 (4) | S2ix—Dy4—S8ix | 82.75 (4) |
S1—Dy1—S11ii | 72.25 (4) | S6x—Dy4—S8ix | 119.71 (4) |
S11i—Dy1—S4 | 101.82 (4) | S10—Dy4—S8ix | 77.85 (4) |
S1—Dy1—S4 | 75.83 (4) | S7ix—Dy4—S8ix | 71.48 (4) |
S11ii—Dy1—S4 | 134.89 (4) | S1—Dy4—S8 | 76.90 (4) |
S11i—Dy1—S3iii | 67.61 (4) | S2ix—Dy4—S8 | 77.23 (4) |
S1—Dy1—S3iii | 154.76 (4) | S6x—Dy4—S8 | 81.46 (4) |
S11ii—Dy1—S3iii | 123.68 (4) | S10—Dy4—S8 | 71.54 (4) |
S4—Dy1—S3iii | 98.18 (4) | S7ix—Dy4—S8 | 141.80 (4) |
S11i—Dy1—S2iii | 110.91 (4) | S8ix—Dy4—S8 | 146.638 (19) |
S1—Dy1—S2iii | 93.41 (4) | S1—Dy4—Si2x | 150.89 (4) |
S11ii—Dy1—S2iii | 72.92 (4) | S2ix—Dy4—Si2x | 39.42 (4) |
S4—Dy1—S2iii | 140.50 (4) | S6x—Dy4—Si2x | 38.09 (3) |
S3iii—Dy1—S2iii | 75.50 (4) | S10—Dy4—Si2x | 113.92 (4) |
S11i—Dy1—S5 | 71.01 (4) | S7ix—Dy4—Si2x | 90.91 (4) |
S1—Dy1—S5 | 68.54 (4) | S8ix—Dy4—Si2x | 99.89 (4) |
S11ii—Dy1—S5 | 69.83 (4) | S8—Dy4—Si2x | 81.15 (4) |
S4—Dy1—S5 | 69.26 (4) | Si3—S1—Dy4 | 119.07 (7) |
S3iii—Dy1—S5 | 132.92 (4) | Si3—S1—Dy1 | 88.83 (6) |
S2iii—Dy1—S5 | 142.02 (3) | Dy4—S1—Dy1 | 130.64 (6) |
S11i—Dy1—S12iv | 134.97 (4) | Si2ii—S2—Dy4xiii | 85.46 (5) |
S1—Dy1—S12iv | 84.62 (4) | Si2ii—S2—Dy3 | 92.29 (7) |
S11ii—Dy1—S12iv | 137.01 (4) | Dy4xiii—S2—Dy3 | 94.64 (5) |
S4—Dy1—S12iv | 68.38 (4) | Si2ii—S2—Dy1xiv | 80.11 (6) |
S3iii—Dy1—S12iv | 70.52 (4) | Dy4xiii—S2—Dy1xiv | 161.77 (5) |
S2iii—Dy1—S12iv | 72.88 (4) | Dy3—S2—Dy1xiv | 96.99 (4) |
S5—Dy1—S12iv | 134.07 (4) | Si3viii—S3—Dy3 | 90.00 (6) |
S11i—Dy1—Si2xii | 84.89 (4) | Si3viii—S3—Dy1xiv | 93.64 (7) |
S1—Dy1—Si2xii | 94.25 (4) | Dy3—S3—Dy1xiv | 102.88 (4) |
S11ii—Dy1—Si2xii | 38.10 (4) | Si3—S4—Dy1 | 86.75 (5) |
S4—Dy1—Si2xii | 170.05 (4) | Si3—S4—Dy2 | 89.68 (6) |
S3iii—Dy1—Si2xii | 91.15 (4) | Dy1—S4—Dy2 | 109.58 (5) |
S2iii—Dy1—Si2xii | 39.24 (4) | Si3—S4—Dy3iv | 83.32 (6) |
S5—Dy1—Si2xii | 106.69 (4) | Dy1—S4—Dy3iv | 113.19 (5) |
S12iv—Dy1—Si2xii | 112.02 (4) | Dy2—S4—Dy3iv | 136.10 (5) |
S5—Dy2—S10v | 136.39 (4) | Si2vi—S5—Dy2 | 87.28 (5) |
S5—Dy2—S7v | 148.96 (4) | Si2vi—S5—Dy3vii | 92.91 (6) |
S10v—Dy2—S7v | 74.15 (4) | Dy2—S5—Dy3vii | 105.03 (5) |
S5—Dy2—S12 | 82.26 (4) | Si2vi—S5—Dy1 | 83.40 (7) |
S10v—Dy2—S12 | 111.05 (4) | Dy2—S5—Dy1 | 107.69 (4) |
S7v—Dy2—S12 | 79.79 (4) | Dy3vii—S5—Dy1 | 146.83 (4) |
S5—Dy2—S6vi | 75.39 (4) | Si2—S6—Dy4xv | 86.08 (6) |
S10v—Dy2—S6vi | 77.46 (4) | Si2—S6—Dy2xi | 85.61 (6) |
S7v—Dy2—S6vi | 126.44 (4) | Dy4xv—S6—Dy2xi | 103.06 (5) |
S12—Dy2—S6vi | 153.54 (4) | Si1—S7—Dy4xiii | 92.37 (6) |
S5—Dy2—S9vi | 68.86 (4) | Si1—S7—Dy2xvi | 87.05 (7) |
S10v—Dy2—S9vi | 154.17 (4) | Dy4xiii—S7—Dy2xvi | 149.30 (6) |
S7v—Dy2—S9vi | 81.65 (4) | Si1—S7—Dy2vii | 88.91 (6) |
S12—Dy2—S9vi | 72.51 (4) | Dy4xiii—S7—Dy2vii | 100.03 (4) |
S6vi—Dy2—S9vi | 111.20 (4) | Dy2xvi—S7—Dy2vii | 110.65 (5) |
S5—Dy2—S4 | 70.99 (4) | Si1—S8—Dy3 | 89.72 (6) |
S10v—Dy2—S4 | 75.36 (4) | Si1—S8—Dy4xiii | 90.68 (6) |
S7v—Dy2—S4 | 124.47 (4) | Dy3—S8—Dy4xiii | 91.90 (5) |
S12—Dy2—S4 | 69.60 (4) | Si1—S8—Dy4 | 80.01 (6) |
S6vi—Dy2—S4 | 89.59 (4) | Dy3—S8—Dy4 | 130.24 (5) |
S9vi—Dy2—S4 | 127.35 (4) | Dy4xiii—S8—Dy4 | 136.28 (4) |
S5—Dy2—S7vii | 108.44 (4) | Si1ii—S9—Dy3ii | 91.33 (6) |
S10v—Dy2—S7vii | 90.95 (4) | Si1ii—S9—Dy2xi | 90.08 (6) |
S7v—Dy2—S7vii | 69.35 (5) | Dy3ii—S9—Dy2xi | 102.32 (5) |
S12—Dy2—S7vii | 135.43 (4) | Si1ii—S9—Dy3xi | 152.03 (8) |
S6vi—Dy2—S7vii | 66.71 (4) | Dy3ii—S9—Dy3xi | 109.55 (4) |
S9vi—Dy2—S7vii | 71.86 (4) | Dy2xi—S9—Dy3xi | 102.83 (4) |
S4—Dy2—S7vii | 154.96 (4) | Si1—S10—Dy2xvi | 89.27 (6) |
S3—Dy3—S9ii | 143.47 (4) | Si1—S10—Dy4 | 91.85 (6) |
S3—Dy3—S12 | 82.58 (4) | Dy2xvi—S10—Dy4 | 135.73 (5) |
S9ii—Dy3—S12 | 101.64 (4) | Si2xiv—S11—Dy1xvii | 92.65 (7) |
S3—Dy3—S8 | 143.82 (4) | Si2xiv—S11—Dy1ii | 85.12 (6) |
S9ii—Dy3—S8 | 72.46 (4) | Dy1xvii—S11—Dy1ii | 98.06 (4) |
S12—Dy3—S8 | 95.60 (4) | Si3—S12—Dy3 | 118.04 (6) |
S3—Dy3—S5vii | 85.33 (4) | Si3—S12—Dy2 | 92.55 (7) |
S9ii—Dy3—S5vii | 69.39 (4) | Dy3—S12—Dy2 | 116.22 (5) |
S12—Dy3—S5vii | 142.89 (4) | Si3—S12—Dy1viii | 85.18 (6) |
S8—Dy3—S5vii | 114.20 (4) | Dy3—S12—Dy1viii | 108.09 (5) |
S3—Dy3—S2 | 77.54 (4) | Dy2—S12—Dy1viii | 130.46 (4) |
S9ii—Dy3—S2 | 115.30 (4) | S10—Si1—S9ii | 115.23 (9) |
S12—Dy3—S2 | 139.53 (4) | S10—Si1—S8 | 115.95 (9) |
S8—Dy3—S2 | 81.08 (4) | S9ii—Si1—S8 | 105.30 (8) |
S5vii—Dy3—S2 | 70.10 (4) | S10—Si1—S7 | 107.33 (7) |
S3—Dy3—S4viii | 75.19 (4) | S9ii—Si1—S7 | 109.10 (9) |
S9ii—Dy3—S4viii | 140.68 (4) | S8—Si1—S7 | 103.14 (9) |
S12—Dy3—S4viii | 70.09 (4) | S11iii—Si2—S6 | 115.18 (9) |
S8—Dy3—S4viii | 70.35 (4) | S11iii—Si2—S5xi | 108.17 (8) |
S5vii—Dy3—S4viii | 139.23 (4) | S6—Si2—S5xi | 111.71 (9) |
S2—Dy3—S4viii | 70.89 (4) | S11iii—Si2—S2ii | 108.75 (8) |
S3—Dy3—S9vi | 77.96 (4) | S6—Si2—S2ii | 110.06 (9) |
S9ii—Dy3—S9vi | 70.45 (4) | S5xi—Si2—S2ii | 102.13 (8) |
S12—Dy3—S9vi | 68.19 (4) | S11iii—Si2—Dy1xii | 56.78 (5) |
S8—Dy3—S9vi | 134.89 (4) | S6—Si2—Dy1xii | 158.27 (8) |
S5vii—Dy3—S9vi | 75.02 (4) | S5xi—Si2—Dy1xii | 89.88 (5) |
S2—Dy3—S9vi | 138.53 (4) | S2ii—Si2—Dy1xii | 60.65 (5) |
S4viii—Dy3—S9vi | 132.53 (3) | S11iii—Si2—Dy4xv | 139.20 (8) |
S1—Dy4—S2ix | 146.99 (5) | S6—Si2—Dy4xv | 55.84 (6) |
S1—Dy4—S6x | 118.65 (4) | S5xi—Si2—Dy4xv | 111.81 (7) |
S2ix—Dy4—S6x | 77.00 (4) | S2ii—Si2—Dy4xv | 55.13 (5) |
S1—Dy4—S10 | 76.84 (4) | Dy1xii—Si2—Dy4xv | 114.92 (5) |
S2ix—Dy4—S10 | 75.75 (4) | S3iv—Si3—S1 | 108.70 (8) |
S6x—Dy4—S10 | 145.07 (4) | S3iv—Si3—S12 | 109.63 (9) |
S1—Dy4—S7ix | 94.58 (4) | S1—Si3—S12 | 116.08 (9) |
S2ix—Dy4—S7ix | 118.42 (4) | S3iv—Si3—S4 | 111.49 (8) |
S6x—Dy4—S7ix | 70.07 (5) | S1—Si3—S4 | 108.09 (9) |
S10—Dy4—S7ix | 143.43 (4) | S12—Si3—S4 | 102.77 (8) |
Symmetry codes: (i) x, y+1, z−1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+3/2, y+1/2, −z+1/2; (v) x+1, y, z; (vi) x, y, z−1; (vii) −x+1, −y+1, −z; (viii) −x+3/2, y−1/2, −z+1/2; (ix) −x+1/2, y+1/2, −z+1/2; (x) x−1/2, −y+3/2, z−1/2; (xi) x, y, z+1; (xii) −x+1, −y+2, −z+1; (xiii) −x+1/2, y−1/2, −z+1/2; (xiv) x, y−1, z; (xv) x+1/2, −y+3/2, z+1/2; (xvi) x−1, y, z; (xvii) x, y−1, z+1. |
Experimental details
Crystal data | |
Chemical formula | Dy4(SiS4)3 |
Mr | 1118.99 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.813 (2), 10.9387 (18), 16.360 (4) |
β (°) | 102.86 (3) |
V (Å3) | 1712.1 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 18.91 |
Crystal size (mm) | 0.22 × 0.10 × 0.02 |
Data collection | |
Diffractometer | STOE IPDS diffractometer |
Absorption correction | Gaussian (X-RED; Stoe & Cie, 1998) |
Tmin, Tmax | 0.117, 0.685 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29396, 4184, 3327 |
Rint | 0.120 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.047, 0.87 |
No. of reflections | 4184 |
No. of parameters | 173 |
Δρmax, Δρmin (e Å−3) | 1.29, −1.42 |
Computer programs: IPDS Software (Stoe & Cie, 1998), IPDS Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXL97.
Dy1—S11i | 2.7597 (15) | Dy3—S4viii | 2.9780 (16) |
Dy1—S1 | 2.7740 (15) | Dy3—S9vi | 3.2680 (15) |
Dy1—S11ii | 2.7962 (14) | Dy4—S1 | 2.6809 (14) |
Dy1—S4 | 2.8194 (13) | Dy4—S2ix | 2.7629 (13) |
Dy1—S3iii | 2.8338 (15) | Dy4—S6x | 2.7844 (16) |
Dy1—S2iii | 2.9464 (14) | Dy4—S10 | 2.8263 (16) |
Dy1—S5 | 3.0625 (15) | Dy4—S7ix | 2.8289 (15) |
Dy1—S12iv | 3.1243 (16) | Dy4—S8ix | 2.9079 (16) |
Dy2—S5 | 2.7924 (13) | Dy4—S8 | 3.2526 (17) |
Dy2—S10v | 2.8114 (13) | Si1—S7 | 2.1504 (19) |
Dy2—S7v | 2.8460 (15) | Si1—S8 | 2.128 (2) |
Dy2—S12 | 2.8783 (15) | Si1—S9ii | 2.114 (2) |
Dy2—S6vi | 2.8903 (16) | Si1—S10 | 2.083 (2) |
Dy2—S9vi | 2.9512 (15) | Si2—S2ii | 2.138 (2) |
Dy2—S4 | 2.9688 (15) | Si2—S5xi | 2.124 (2) |
Dy2—S7vii | 2.9691 (16) | Si2—S6 | 2.0757 (17) |
Dy3—S3 | 2.7580 (14) | Si2—S11iii | 2.062 (2) |
Dy3—S9ii | 2.8281 (15) | Si3—S1 | 2.1003 (17) |
Dy3—S12 | 2.8520 (13) | Si3—S3iv | 2.093 (2) |
Dy3—S8 | 2.8774 (15) | Si3—S4 | 2.1458 (19) |
Dy3—S5vii | 2.8809 (15) | Si3—S12 | 2.126 (2) |
Dy3—S2 | 2.8921 (15) |
Symmetry codes: (i) x, y+1, z−1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+3/2, y+1/2, −z+1/2; (v) x+1, y, z; (vi) x, y, z−1; (vii) −x+1, −y+1, −z; (viii) −x+3/2, y−1/2, −z+1/2; (ix) −x+1/2, y+1/2, −z+1/2; (x) x−1/2, −y+3/2, z−1/2; (xi) x, y, z+1. |
Only a few thiosilicate compounds with lanthanide ions are known: Ln2SiS5 (Ln = La—Nd) with unknown structure (Michelet et al., 1970), Ln6Si2.5S14 (Ln = Gd—Dy, Y) (Michelet & Flahaut, 1969; Perez & Duale, 1969), trigonal Ln4Si3S12 (Ln = Ce—Sm, Gd) (Perez & Duale, 1969), and more recently Eu2SiS4 (Johrendt & Pocha, 2001). In all the reported structures, isolated SiS4 tetrahedra are a dominant feature, one exception being the second Si position in Ln6Si2.5S14, which is coordinated by six sulfides in the shape of a slightly distorted octahedron. Also known are lanthanide thiogermanates, such as La4(GeS4)3 (Mazurier & Etienne, 1974) containing isolated GeS4 groups. The formation of corner-sharing tetrahedra resulting in Si2O76− anions, commonly seen in lanthanide oxosilicates, is up to now unknown for the lanthanide thiosilicates.
We recently reported the structure of a new lanthanide thiosilicate Tb4(SiS4)3 (Hatscher & Urland, 2002) and present here the homologous dysprosium compound. The isolated (SiS4)4− tetrahedra (Fig. 1) are slightly distorted and contain Si—S distances between 2.062 (2) and 2.150 (2) Å, in agreement with those reported for SiS2 (Buessem et al., 1935). La4(GeS4)3 has a similar formula but the arrangement of tetrahedra differs (Mazurier & Etienne, 1974). There is no known lanthanide oxosilicate analogue.
The Dy1, Dy2 and Dy3 ions are each coordinated by eight sulfide ions. Two Dy1S8 polyhedra share edges to form dimers. The same basic motif can be found for Dy2 and Dy3. Dy4 is surrounded by only seven sulfide ions and forms infinite chains along [010] by sharing two opposite corners with other Dy4S7 building blocks. The dimers of Dy1, Dy2, and Dy3 form a three-dimensional network consisting of alternating building blocks, which results in a channel structure that is filled by the one-dimensional chain of Dy4 (Fig. 2).