Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014246/br6028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014246/br6028Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Ru-Ru) = 0.002 Å
- R factor = 0.030
- wR factor = 0.045
- Data-to-parameter ratio = 10.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
GOODF_01 Alert C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 2.510
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was crystallized from a solid-state reaction between a 1:10 mixture of Ru and Sn. The mixture was heated in an evacuated quartz ampoule at 973 K for 24 h and let to cool to room temperature over a period of approximately 1 h. Small crystals of the title compound were found in a matrix of Sn. The excess Sn was removed by treatment with NaOH aqueous solution, 2 mol dm-3.
The maximum residual electron density was located at (0.1229, 0, 0.1229), 1.59 Å from Sn2, and the minimum residual density was located at (0, 0, 0), 2.61 Å from Sn2. None of these residual densities were interpreted as anything other than artefacts, perhaps occurring due to the high symmetry of these positions. The lattice parameter from the single-crystal experiment were checked by powder diffraction methods with a Guinier-Hägg camera using Si as internal standard for the 2θ scale giving a value of the unit-cell edge a = 9.3533 (4) Å, well in accordance with the value estimated from the IPDS measurements.
Data collection: EXPOSE in IPDS (Stoe & Cie, 1997); cell refinement: CELL in IPDS; data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996).
Ru3Sn7 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 1134.04 | Cell parameters from 984 reflections |
Cubic, Im3m | θ = 1.6–26.0° |
a = 9.3532 (19) Å | µ = 26.25 mm−1 |
V = 818.2 (3) Å3 | T = 293 K |
Z = 4 | Prism, dark grey |
F(000) = 1928 | 0.12 × 0.11 × 0.10 mm |
Dx = 9.206 Mg m−3 |
STOE IPDS diffractometer | 102 independent reflections |
Radiation source: fine-focus sealed tube | 97 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 6.0 pixels mm-1 | θmax = 25.9°, θmin = 3.1° |
area detector scans | h = −11→11 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | k = −11→9 |
Tmin = 0.045, Tmax = 0.083 | l = −11→7 |
1394 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)] = 0.030 | w = 1/[σ2(Fo2) + (0.010P)2 where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.045 | (Δ/σ)max < 0.001 |
S = 2.51 | Δρmax = 0.83 e Å−3 |
102 reflections | Δρmin = −2.17 e Å−3 |
10 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0022 (2) |
Ru3Sn7 | Z = 4 |
Mr = 1134.04 | Mo Kα radiation |
Cubic, Im3m | µ = 26.25 mm−1 |
a = 9.3532 (19) Å | T = 293 K |
V = 818.2 (3) Å3 | 0.12 × 0.11 × 0.10 mm |
STOE IPDS diffractometer | 102 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | 97 reflections with I > 2σ(I) |
Tmin = 0.045, Tmax = 0.083 | Rint = 0.042 |
1394 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 10 parameters |
wR(F2) = 0.045 | 0 restraints |
S = 2.51 | Δρmax = 0.83 e Å−3 |
102 reflections | Δρmin = −2.17 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 | ||
Ru | 0.34513 (15) | 0.0000 | 0.0000 | 0.0067 (4) | |
Sn1 | 0.2500 | 0.0000 | 0.5000 | 0.0094 (4) | |
Sn2 | 0.16110 (6) | 0.16110 (6) | 0.16110 (6) | 0.0086 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru | 0.0058 (7) | 0.0072 (5) | 0.0072 (5) | 0.000 | 0.000 | 0.000 |
Sn1 | 0.0066 (7) | 0.0108 (5) | 0.0108 (5) | 0.000 | 0.000 | 0.000 |
Sn2 | 0.0086 (4) | 0.0086 (4) | 0.0086 (4) | 0.0006 (2) | 0.0006 (2) | 0.0006 (2) |
Ru—Sn2i | 2.7393 (11) | Sn1—Rux | 2.7506 (9) |
Ru—Sn2 | 2.7393 (11) | Sn1—Ruxi | 2.7506 (9) |
Ru—Sn2ii | 2.7393 (11) | Sn1—Ruxii | 2.7506 (9) |
Ru—Sn2iii | 2.7393 (11) | Sn2—Rux | 2.7393 (11) |
Ru—Sn1iv | 2.7506 (9) | Sn2—Ruiv | 2.7393 (11) |
Ru—Sn1v | 2.7506 (9) | Sn2—Sn2xiii | 2.8804 (19) |
Ru—Sn1vi | 2.7506 (9) | Sn2—Sn2ii | 3.0136 (12) |
Ru—Sn1vii | 2.7506 (9) | Sn2—Sn2iii | 3.0136 (12) |
Ru—Ruviii | 2.897 (3) | Sn2—Sn2xiv | 3.0136 (12) |
Sn1—Ruix | 2.7506 (9) | ||
Sn2i—Ru—Sn2 | 102.14 (5) | Sn1iv—Ru—Ruviii | 58.22 (2) |
Sn2i—Ru—Sn2ii | 66.74 (3) | Sn1v—Ru—Ruviii | 58.22 (2) |
Sn2—Ru—Sn2ii | 66.74 (3) | Sn1vi—Ru—Ruviii | 58.22 (2) |
Sn2i—Ru—Sn2iii | 66.74 (3) | Sn1vii—Ru—Ruviii | 58.22 (2) |
Sn2—Ru—Sn2iii | 66.74 (3) | Ruix—Sn1—Rux | 136.27 (3) |
Sn2ii—Ru—Sn2iii | 102.14 (5) | Ruix—Sn1—Ruxi | 63.56 (5) |
Sn2i—Ru—Sn1iv | 142.990 (9) | Rux—Sn1—Ruxi | 136.27 (3) |
Sn2—Ru—Sn1iv | 82.142 (15) | Ruix—Sn1—Ruxii | 136.27 (3) |
Sn2ii—Ru—Sn1iv | 142.990 (9) | Rux—Sn1—Ruxii | 63.56 (5) |
Sn2iii—Ru—Sn1iv | 82.143 (15) | Ruxi—Sn1—Ruxii | 136.27 (3) |
Sn2i—Ru—Sn1v | 142.990 (9) | Rux—Sn2—Ruiv | 112.87 (2) |
Sn2—Ru—Sn1v | 82.142 (15) | Rux—Sn2—Ru | 112.87 (2) |
Sn2ii—Ru—Sn1v | 82.143 (15) | Ruiv—Sn2—Ru | 112.87 (2) |
Sn2iii—Ru—Sn1v | 142.990 (9) | Rux—Sn2—Sn2xiii | 105.81 (2) |
Sn1iv—Ru—Sn1v | 73.90 (2) | Ruiv—Sn2—Sn2xiii | 105.81 (2) |
Sn2i—Ru—Sn1vi | 82.143 (15) | Ru—Sn2—Sn2xiii | 105.81 (2) |
Sn2—Ru—Sn1vi | 142.990 (9) | Rux—Sn2—Sn2ii | 56.628 (13) |
Sn2ii—Ru—Sn1vi | 142.990 (9) | Ruiv—Sn2—Sn2ii | 128.93 (2) |
Sn2iii—Ru—Sn1vi | 82.143 (15) | Ru—Sn2—Sn2ii | 56.628 (13) |
Sn1iv—Ru—Sn1vi | 73.90 (2) | Sn2xiii—Sn2—Sn2ii | 125.3 |
Sn1v—Ru—Sn1vi | 116.44 (5) | Rux—Sn2—Sn2iii | 128.93 (2) |
Sn2i—Ru—Sn1vii | 82.143 (15) | Ruiv—Sn2—Sn2iii | 56.628 (13) |
Sn2—Ru—Sn1vii | 142.990 (9) | Ru—Sn2—Sn2iii | 56.628 (13) |
Sn2ii—Ru—Sn1vii | 82.143 (15) | Sn2xiii—Sn2—Sn2iii | 125.3 |
Sn2iii—Ru—Sn1vii | 142.990 (9) | Sn2ii—Sn2—Sn2iii | 90.0 |
Sn1iv—Ru—Sn1vii | 116.44 (5) | Rux—Sn2—Sn2xiv | 56.628 (13) |
Sn1v—Ru—Sn1vii | 73.90 (2) | Ruiv—Sn2—Sn2xiv | 56.628 (13) |
Sn1vi—Ru—Sn1vii | 73.90 (2) | Ru—Sn2—Sn2xiv | 128.93 (2) |
Sn2i—Ru—Ruviii | 128.93 (2) | Sn2xiii—Sn2—Sn2xiv | 125.3 |
Sn2—Ru—Ruviii | 128.93 (2) | Sn2ii—Sn2—Sn2xiv | 90.0 |
Sn2ii—Ru—Ruviii | 128.93 (2) | Sn2iii—Sn2—Sn2xiv | 90.0 |
Sn2iii—Ru—Ruviii | 128.93 (2) |
Symmetry codes: (i) x, −y, −z; (ii) x, −y, z; (iii) x, y, −z; (iv) z, x, y; (v) −y+1/2, −z+1/2, −x+1/2; (vi) y+1/2, z−1/2, x−1/2; (vii) −z+1, −x, −y; (viii) −x+1, −y, −z; (ix) −z+1/2, −x+1/2, −y+1/2; (x) y, z, x; (xi) z+1/2, x−1/2, y+1/2; (xii) −y, −z, −x+1; (xiii) −x+1/2, −y+1/2, −z+1/2; (xiv) −x, y, z. |
Experimental details
Crystal data | |
Chemical formula | Ru3Sn7 |
Mr | 1134.04 |
Crystal system, space group | Cubic, Im3m |
Temperature (K) | 293 |
a (Å) | 9.3532 (19) |
V (Å3) | 818.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 26.25 |
Crystal size (mm) | 0.12 × 0.11 × 0.10 |
Data collection | |
Diffractometer | STOE IPDS diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1997) |
Tmin, Tmax | 0.045, 0.083 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1394, 102, 97 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.614 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.045, 2.51 |
No. of reflections | 102 |
No. of parameters | 10 |
Δρmax, Δρmin (e Å−3) | 0.83, −2.17 |
Computer programs: EXPOSE in IPDS (Stoe & Cie, 1997), CELL in IPDS, X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996).
Ru—Sn2 | 2.7393 (11) | Sn2—Sn2iii | 2.8804 (19) |
Ru—Sn1i | 2.7506 (9) | Sn2—Sn2iv | 3.0136 (12) |
Ru—Ruii | 2.897 (3) |
Symmetry codes: (i) z, x, y; (ii) −x+1, −y, −z; (iii) −x+1/2, −y+1/2, −z+1/2; (iv) x, −y, z. |
The title compound was synthesized as part of a reinvestigation of the Ru–Sn binary system. Earlier reports (Nial, 1947) of this compound were based on visually estimated intensities from powder data and only approximate structural parameters were determined. Ru3Sn7 is an example of an electron-rich compound (Häusserman et al., 1998) in the Ru/Sn system. The structure is built of square-face-sharing dimers of square antiprisms of Ru–Sn polyhedra (Fig. 1). These barrel-like dimers are, in turn, connected via edges of the outer square faces, occupied by Sn1, to each other giving one of the two component networks. The quadratic faces of six barrels make up an empty cube at the corner of the unit cell. The two equivalent interpenetrating frameworks (Fig. 2) are related by the I-centering condition and are connected to each other with the corner-shared Sn2 atom. The valence electron concentration (VEC) of the title compound is 52 electrons per formula unit. Several isomorphous T3E7 compounds (T is a transition metal and E is an electron-rich main group element) are known with VEC ranging from 51 to 55. The improved accuracy of parameters of the structural model may imply slight changes to the interpretation of the bonding situation in similar compounds. Doping of the title compound, both with neighbouring transition metals and electron-rich main group elements will be attempted in future experiments in order to elucidate the possibilities for affecting electronic properties.