Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008431/bt6041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008431/bt6041Isup2.hkl |
The title compound was prepared from pure elements (Ce 0.98, Rh 0.999, Si 0.99999) by arc-melting under an argon atmosphere. The sample was annealed in double quartz ampoules at 973 K for 600 h and quenched in cool water. The single-crystal used for analysis was selected from the alloy obtained.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Fig. 1. The asymmetric unit of the title compound with the atom numbering. | |
Fig. 2. Projection onto XY plane (a) of Ce2Rh15Si7 unit cell and (b) of Ce4Pd29Si14 1/8 unit cell (X,Y,Z from 0 to 1/2). |
Ce2Rh15Si7 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 2020.52 | Cell parameters from 25 reflections |
Cubic, Pm3m | θ = 13.1–17.7° |
a = 8.818 (1) Å | µ = 24.57 mm−1 |
V = 685.66 (13) Å3 | T = 293 K |
Z = 2 | Prism, dark red |
F(000) = 1778 | 0.17 × 0.15 × 0.13 mm |
Dx = 9.787 Mg m−3 |
Enraf-Nonius CAD-4 diffractometer | 251 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.131 |
Graphite monochromator | θmax = 34.9°, θmin = 2.3° |
ω scans | h = 0→14 |
Absorption correction: multi-scan (Blessing, 1995) | k = 0→14 |
Tmin = 0.034, Tmax = 0.098 | l = 0→14 |
1756 measured reflections | 3 standard reflections every 120 min |
358 independent reflections | intensity decay: 2.5% |
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)] = 0.047 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.148 | (Δ/σ)max < 0.001 |
S = 0.86 | Δρmax = 4.22 e Å−3 |
358 reflections | Δρmin = −4.12 e Å−3 |
22 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0003 (2) |
Ce2Rh15Si7 | Z = 2 |
Mr = 2020.52 | Mo Kα radiation |
Cubic, Pm3m | µ = 24.57 mm−1 |
a = 8.818 (1) Å | T = 293 K |
V = 685.66 (13) Å3 | 0.17 × 0.15 × 0.13 mm |
Enraf-Nonius CAD-4 diffractometer | 251 reflections with I > 2σ(I) |
Absorption correction: multi-scan (Blessing, 1995) | Rint = 0.131 |
Tmin = 0.034, Tmax = 0.098 | 3 standard reflections every 120 min |
1756 measured reflections | intensity decay: 2.5% |
358 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 22 parameters |
wR(F2) = 0.148 | 0 restraints |
S = 0.86 | Δρmax = 4.22 e Å−3 |
358 reflections | Δρmin = −4.12 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 | ||
Ce1 | 0.5000 | 0.5000 | 0.5000 | 0.0135 (8) | |
Ce2 | 0.5000 | 0.0000 | 0.0000 | 0.0154 (6) | |
Rh3 | 0.2241 (3) | 0.0000 | 0.0000 | 0.0137 (5) | |
Rh4 | 0.26211 (14) | 0.26211 (14) | 0.5000 | 0.0127 (4) | |
Rh5 | 0.32339 (14) | 0.32339 (14) | 0.0000 | 0.0133 (4) | |
Si6 | 0.1345 (11) | 0.5000 | 0.5000 | 0.0147 (16) | |
Si7 | 0.2130 (6) | 0.2130 (6) | 0.2130 (6) | 0.0147 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.0135 (8) | 0.0135 (8) | 0.0135 (8) | 0.000 | 0.000 | 0.000 |
Ce2 | 0.0144 (11) | 0.0159 (8) | 0.0159 (8) | 0.000 | 0.000 | 0.000 |
Rh3 | 0.0119 (10) | 0.0146 (6) | 0.0146 (6) | 0.000 | 0.000 | 0.000 |
Rh4 | 0.0129 (5) | 0.0129 (5) | 0.0123 (7) | 0.0014 (5) | 0.000 | 0.000 |
Rh5 | 0.0140 (5) | 0.0140 (5) | 0.0119 (7) | −0.0022 (6) | 0.000 | 0.000 |
Si6 | 0.010 (3) | 0.017 (2) | 0.017 (2) | 0.000 | 0.000 | 0.000 |
Si7 | 0.0147 (13) | 0.0147 (13) | 0.0147 (13) | 0.0019 (16) | 0.0019 (16) | 0.0019 (16) |
Ce1—Rh4i | 2.9666 (18) | Rh4—Si6 | 2.380 (4) |
Ce1—Rh4 | 2.9666 (18) | Rh4—Si7 | 2.604 (7) |
Ce1—Rh4ii | 2.9666 (18) | Rh4—Si7xxiv | 2.604 (7) |
Ce1—Rh4iii | 2.9666 (18) | Rh4—Rh5v | 2.8389 (9) |
Ce1—Rh4iv | 2.9666 (18) | Rh4—Rh5xxv | 2.8389 (9) |
Ce1—Rh4v | 2.9666 (18) | Rh4—Rh5x | 2.8389 (9) |
Ce1—Rh4vi | 2.9666 (18) | Rh4—Rh5xxvi | 2.8389 (9) |
Ce1—Rh4vii | 2.9666 (18) | Rh4—Rh4vi | 2.9666 (18) |
Ce1—Rh4viii | 2.9666 (18) | Rh4—Rh4x | 2.9666 (18) |
Ce1—Rh4ix | 2.9666 (18) | Rh4—Rh4ii | 2.9666 (18) |
Ce1—Rh4x | 2.9666 (18) | Rh5—Si7xix | 2.3287 (10) |
Ce1—Rh4xi | 2.9666 (18) | Rh5—Si7 | 2.3287 (10) |
Ce2—Rh3xii | 2.433 (3) | Rh5—Si6v | 2.501 (5) |
Ce2—Rh3 | 2.433 (3) | Rh5—Si6xxvii | 2.501 (5) |
Ce2—Rh5xiii | 3.2492 (6) | Rh5—Rh4ii | 2.8389 (9) |
Ce2—Rh5vii | 3.2492 (6) | Rh5—Rh4v | 2.8389 (9) |
Ce2—Rh5xiv | 3.2492 (6) | Rh5—Rh4xxviii | 2.8389 (9) |
Ce2—Rh5xv | 3.2492 (6) | Rh5—Rh4xiv | 2.8389 (9) |
Ce2—Rh5 | 3.2492 (6) | Rh5—Rh3xxii | 2.9831 (18) |
Ce2—Rh5xvi | 3.2492 (6) | Rh5—Rh5xxix | 3.115 (2) |
Ce2—Rh5xii | 3.2492 (6) | Rh5—Rh5vii | 3.115 (2) |
Ce2—Rh5v | 3.2492 (6) | Si6—Si6xxx | 2.372 (19) |
Ce2—Rh4xvii | 3.2687 (18) | Si6—Rh4x | 2.380 (4) |
Ce2—Rh4ii | 3.2687 (18) | Si6—Rh4xi | 2.380 (4) |
Rh3—Si7xv | 2.658 (7) | Si6—Rh4v | 2.380 (4) |
Rh3—Si7 | 2.658 (7) | Si6—Rh5xxv | 2.501 (5) |
Rh3—Si7xviii | 2.658 (7) | Si6—Rh5i | 2.501 (5) |
Rh3—Si7xix | 2.658 (7) | Si6—Rh5xxvi | 2.501 (5) |
Rh3—Rh3xx | 2.794 (4) | Si6—Rh5ix | 2.501 (5) |
Rh3—Rh3xxi | 2.794 (4) | Si7—Rh5v | 2.3287 (10) |
Rh3—Rh3xxii | 2.794 (4) | Si7—Rh5xxv | 2.3287 (10) |
Rh3—Rh3v | 2.794 (4) | Si7—Rh4ii | 2.604 (7) |
Rh3—Rh5v | 2.9831 (18) | Si7—Rh4v | 2.604 (7) |
Rh3—Rh5 | 2.9831 (18) | Si7—Rh3v | 2.658 (7) |
Rh3—Rh5xv | 2.9831 (18) | Si7—Rh3xxii | 2.658 (7) |
Rh4—Si6xxiii | 2.380 (4) | ||
Rh4i—Ce1—Rh4 | 120.0 | Si7—Rh4—Rh5v | 50.44 (6) |
Rh4i—Ce1—Rh4ii | 180.0 | Si7xxiv—Rh4—Rh5v | 115.43 (9) |
Rh4—Ce1—Rh4ii | 60.0 | Si6xxiii—Rh4—Rh5xxv | 143.84 (8) |
Rh4i—Ce1—Rh4iii | 60.0 | Si6—Rh4—Rh5xxv | 56.46 (15) |
Rh4—Ce1—Rh4iii | 180.0 | Si7—Rh4—Rh5xxv | 50.44 (6) |
Rh4ii—Ce1—Rh4iii | 120.0 | Si7xxiv—Rh4—Rh5xxv | 115.43 (9) |
Rh4i—Ce1—Rh4iv | 60.0 | Rh5v—Rh4—Rh5xxv | 90.51 (7) |
Rh4—Ce1—Rh4iv | 120.0 | Si6xxiii—Rh4—Rh5x | 56.46 (15) |
Rh4ii—Ce1—Rh4iv | 120.0 | Si6—Rh4—Rh5x | 143.84 (8) |
Rh4iii—Ce1—Rh4iv | 60.0 | Si7—Rh4—Rh5x | 115.43 (9) |
Rh4i—Ce1—Rh4v | 120.0 | Si7xxiv—Rh4—Rh5x | 50.44 (6) |
Rh4—Ce1—Rh4v | 60.0 | Rh5v—Rh4—Rh5x | 66.54 (5) |
Rh4ii—Ce1—Rh4v | 60.0 | Rh5xxv—Rh4—Rh5x | 127.65 (7) |
Rh4iii—Ce1—Rh4v | 120.0 | Si6xxiii—Rh4—Rh5xxvi | 143.84 (8) |
Rh4iv—Ce1—Rh4v | 180.0 | Si6—Rh4—Rh5xxvi | 56.46 (15) |
Rh4i—Ce1—Rh4vi | 90.0 | Si7—Rh4—Rh5xxvi | 115.43 (9) |
Rh4—Ce1—Rh4vi | 60.0 | Si7xxiv—Rh4—Rh5xxvi | 50.44 (6) |
Rh4ii—Ce1—Rh4vi | 90.0 | Rh5v—Rh4—Rh5xxvi | 127.65 (7) |
Rh4iii—Ce1—Rh4vi | 120.0 | Rh5xxv—Rh4—Rh5xxvi | 66.54 (5) |
Rh4iv—Ce1—Rh4vi | 60.0 | Rh5x—Rh4—Rh5xxvi | 90.51 (7) |
Rh4v—Ce1—Rh4vi | 120.0 | Si6xxiii—Rh4—Rh4vi | 51.46 (9) |
Rh4i—Ce1—Rh4vii | 120.0 | Si6—Rh4—Rh4vi | 109.53 (13) |
Rh4—Ce1—Rh4vii | 90.0 | Si7—Rh4—Rh4vi | 143.60 (7) |
Rh4ii—Ce1—Rh4vii | 60.0 | Si7xxiv—Rh4—Rh4vi | 55.27 (10) |
Rh4iii—Ce1—Rh4vii | 90.0 | Rh5v—Rh4—Rh4vi | 104.67 (4) |
Rh4iv—Ce1—Rh4vii | 60.0 | Rh5xxv—Rh4—Rh4vi | 164.49 (3) |
Rh4v—Ce1—Rh4vii | 120.0 | Rh5x—Rh4—Rh4vi | 58.50 (3) |
Rh4vi—Ce1—Rh4vii | 60.0 | Rh5xxvi—Rh4—Rh4vi | 100.82 (2) |
Rh4i—Ce1—Rh4viii | 120.0 | Si6xxiii—Rh4—Ce1 | 73.2 (2) |
Rh4—Ce1—Rh4viii | 120.0 | Si6—Rh4—Ce1 | 73.2 (2) |
Rh4ii—Ce1—Rh4viii | 60.0 | Si7—Rh4—Ce1 | 103.60 (13) |
Rh4iii—Ce1—Rh4viii | 60.0 | Si7xxiv—Rh4—Ce1 | 103.60 (13) |
Rh4iv—Ce1—Rh4viii | 90.0 | Rh5v—Rh4—Ce1 | 116.17 (3) |
Rh4v—Ce1—Rh4viii | 90.0 | Rh5xxv—Rh4—Ce1 | 116.17 (3) |
Rh4vi—Ce1—Rh4viii | 120.0 | Rh5x—Rh4—Ce1 | 116.17 (3) |
Rh4vii—Ce1—Rh4viii | 60.0 | Rh5xxvi—Rh4—Ce1 | 116.17 (3) |
Rh4i—Ce1—Rh4ix | 90.0 | Rh4vi—Rh4—Ce1 | 60.0 |
Rh4—Ce1—Rh4ix | 120.0 | Si6xxiii—Rh4—Rh4x | 109.53 (13) |
Rh4ii—Ce1—Rh4ix | 90.0 | Si6—Rh4—Rh4x | 51.46 (9) |
Rh4iii—Ce1—Rh4ix | 60.0 | Si7—Rh4—Rh4x | 143.60 (7) |
Rh4iv—Ce1—Rh4ix | 120.0 | Si7xxiv—Rh4—Rh4x | 55.27 (10) |
Rh4v—Ce1—Rh4ix | 60.0 | Rh5v—Rh4—Rh4x | 164.49 (3) |
Rh4vi—Ce1—Rh4ix | 180.0 | Rh5xxv—Rh4—Rh4x | 104.67 (4) |
Rh4vii—Ce1—Rh4ix | 120.0 | Rh5x—Rh4—Rh4x | 100.82 (2) |
Rh4viii—Ce1—Rh4ix | 60.0 | Rh5xxvi—Rh4—Rh4x | 58.50 (3) |
Rh4i—Ce1—Rh4x | 60.0 | Rh4vi—Rh4—Rh4x | 60.0 |
Rh4—Ce1—Rh4x | 60.0 | Ce1—Rh4—Rh4x | 60.0 |
Rh4ii—Ce1—Rh4x | 120.0 | Si6xxiii—Rh4—Rh4ii | 51.46 (9) |
Rh4iii—Ce1—Rh4x | 120.0 | Si6—Rh4—Rh4ii | 109.53 (13) |
Rh4iv—Ce1—Rh4x | 90.0 | Si7—Rh4—Rh4ii | 55.27 (10) |
Rh4v—Ce1—Rh4x | 90.0 | Si7xxiv—Rh4—Rh4ii | 143.60 (7) |
Rh4vi—Ce1—Rh4x | 60.0 | Rh5v—Rh4—Rh4ii | 58.50 (3) |
Rh4vii—Ce1—Rh4x | 120.0 | Rh5xxv—Rh4—Rh4ii | 100.82 (2) |
Rh4viii—Ce1—Rh4x | 180.0 | Rh5x—Rh4—Rh4ii | 104.67 (4) |
Rh4ix—Ce1—Rh4x | 120.0 | Rh5xxvi—Rh4—Rh4ii | 164.49 (3) |
Rh4i—Ce1—Rh4xi | 60.0 | Rh4vi—Rh4—Rh4ii | 90.0 |
Rh4—Ce1—Rh4xi | 90.0 | Ce1—Rh4—Rh4ii | 60.0 |
Rh4ii—Ce1—Rh4xi | 120.0 | Rh4x—Rh4—Rh4ii | 120.0 |
Rh4iii—Ce1—Rh4xi | 90.0 | Si7xix—Rh5—Si7 | 107.5 (4) |
Rh4iv—Ce1—Rh4xi | 120.0 | Si7xix—Rh5—Si6v | 154.5 (3) |
Rh4v—Ce1—Rh4xi | 60.0 | Si7—Rh5—Si6v | 97.9 (3) |
Rh4vi—Ce1—Rh4xi | 120.0 | Si7xix—Rh5—Si6xxvii | 97.9 (3) |
Rh4vii—Ce1—Rh4xi | 180.0 | Si7—Rh5—Si6xxvii | 154.5 (3) |
Rh4viii—Ce1—Rh4xi | 120.0 | Si6v—Rh5—Si6xxvii | 56.6 (4) |
Rh4ix—Ce1—Rh4xi | 60.0 | Si7xix—Rh5—Rh4ii | 143.75 (11) |
Rh4x—Ce1—Rh4xi | 60.0 | Si7—Rh5—Rh4ii | 59.54 (17) |
Rh3xii—Ce2—Rh3 | 180.0 | Si6v—Rh5—Rh4ii | 52.48 (14) |
Rh3xii—Ce2—Rh5xiii | 61.36 (3) | Si6xxvii—Rh5—Rh4ii | 99.38 (17) |
Rh3—Ce2—Rh5xiii | 118.64 (3) | Si7xix—Rh5—Rh4v | 143.75 (11) |
Rh3xii—Ce2—Rh5vii | 61.36 (3) | Si7—Rh5—Rh4v | 59.54 (17) |
Rh3—Ce2—Rh5vii | 118.64 (3) | Si6v—Rh5—Rh4v | 52.48 (15) |
Rh5xiii—Ce2—Rh5vii | 76.72 (2) | Si6xxvii—Rh5—Rh4v | 99.38 (17) |
Rh3xii—Ce2—Rh5xiv | 118.64 (3) | Rh4ii—Rh5—Rh4v | 63.00 (6) |
Rh3—Ce2—Rh5xiv | 61.36 (3) | Si7xix—Rh5—Rh4xxviii | 59.54 (17) |
Rh5xiii—Ce2—Rh5xiv | 180.00 (6) | Si7—Rh5—Rh4xxviii | 143.75 (11) |
Rh5vii—Ce2—Rh5xiv | 103.28 (2) | Si6v—Rh5—Rh4xxviii | 99.38 (17) |
Rh3xii—Ce2—Rh5xv | 118.64 (3) | Si6xxvii—Rh5—Rh4xxviii | 52.48 (14) |
Rh3—Ce2—Rh5xv | 61.36 (3) | Rh4ii—Rh5—Rh4xxviii | 109.01 (5) |
Rh5xiii—Ce2—Rh5xv | 103.28 (2) | Rh4v—Rh5—Rh4xxviii | 150.65 (7) |
Rh5vii—Ce2—Rh5xv | 180.00 (6) | Si7xix—Rh5—Rh4xiv | 59.54 (17) |
Rh5xiv—Ce2—Rh5xv | 76.72 (2) | Si7—Rh5—Rh4xiv | 143.75 (11) |
Rh3xii—Ce2—Rh5 | 118.64 (3) | Si6v—Rh5—Rh4xiv | 99.38 (17) |
Rh3—Ce2—Rh5 | 61.36 (3) | Si6xxvii—Rh5—Rh4xiv | 52.48 (14) |
Rh5xiii—Ce2—Rh5 | 103.28 (2) | Rh4ii—Rh5—Rh4xiv | 150.65 (7) |
Rh5vii—Ce2—Rh5 | 57.28 (6) | Rh4v—Rh5—Rh4xiv | 109.01 (5) |
Rh5xiv—Ce2—Rh5 | 76.72 (2) | Rh4xxviii—Rh5—Rh4xiv | 63.00 (6) |
Rh5xv—Ce2—Rh5 | 122.72 (6) | Si7xix—Rh5—Rh3 | 58.51 (18) |
Rh3xii—Ce2—Rh5xvi | 61.36 (3) | Si7—Rh5—Rh3 | 58.51 (18) |
Rh3—Ce2—Rh5xvi | 118.64 (3) | Si6v—Rh5—Rh3 | 141.07 (13) |
Rh5xiii—Ce2—Rh5xvi | 122.72 (6) | Si6xxvii—Rh5—Rh3 | 141.07 (13) |
Rh5vii—Ce2—Rh5xvi | 76.72 (2) | Rh4ii—Rh5—Rh3 | 88.80 (4) |
Rh5xiv—Ce2—Rh5xvi | 57.28 (6) | Rh4v—Rh5—Rh3 | 117.94 (4) |
Rh5xv—Ce2—Rh5xvi | 103.28 (2) | Rh4xxviii—Rh5—Rh3 | 88.80 (4) |
Rh5—Ce2—Rh5xvi | 103.28 (2) | Rh4xiv—Rh5—Rh3 | 117.94 (4) |
Rh3xii—Ce2—Rh5xii | 61.36 (3) | Si7xix—Rh5—Rh3xxii | 58.51 (18) |
Rh3—Ce2—Rh5xii | 118.64 (3) | Si7—Rh5—Rh3xxii | 58.51 (18) |
Rh5xiii—Ce2—Rh5xii | 76.72 (2) | Si6v—Rh5—Rh3xxii | 141.07 (13) |
Rh5vii—Ce2—Rh5xii | 122.72 (6) | Si6xxvii—Rh5—Rh3xxii | 141.07 (13) |
Rh5xiv—Ce2—Rh5xii | 103.28 (2) | Rh4ii—Rh5—Rh3xxii | 117.94 (4) |
Rh5xv—Ce2—Rh5xii | 57.28 (6) | Rh4v—Rh5—Rh3xxii | 88.80 (4) |
Rh5—Ce2—Rh5xii | 180.00 (4) | Rh4xxviii—Rh5—Rh3xxii | 117.94 (4) |
Rh5xvi—Ce2—Rh5xii | 76.72 (2) | Rh4xiv—Rh5—Rh3xxii | 88.80 (4) |
Rh3xii—Ce2—Rh5v | 118.64 (3) | Rh3—Rh5—Rh3xxii | 55.86 (10) |
Rh3—Ce2—Rh5v | 61.36 (3) | Si7xix—Rh5—Rh5xxix | 114.71 (14) |
Rh5xiii—Ce2—Rh5v | 57.28 (6) | Si7—Rh5—Rh5xxix | 114.71 (14) |
Rh5vii—Ce2—Rh5v | 103.28 (2) | Si6v—Rh5—Rh5xxix | 51.50 (8) |
Rh5xiv—Ce2—Rh5v | 122.72 (6) | Si6xxvii—Rh5—Rh5xxix | 51.50 (8) |
Rh5xv—Ce2—Rh5v | 76.72 (2) | Rh4ii—Rh5—Rh5xxix | 100.97 (4) |
Rh5—Ce2—Rh5v | 76.72 (2) | Rh4v—Rh5—Rh5xxix | 56.73 (3) |
Rh5xvi—Ce2—Rh5v | 180.0 | Rh4xxviii—Rh5—Rh5xxix | 100.97 (4) |
Rh5xii—Ce2—Rh5v | 103.28 (2) | Rh4xiv—Rh5—Rh5xxix | 56.73 (3) |
Rh3xii—Ce2—Rh4xvii | 90.0 | Rh3—Rh5—Rh5xxix | 162.93 (5) |
Rh3—Ce2—Rh4xvii | 90.0 | Rh3xxii—Rh5—Rh5xxix | 107.07 (5) |
Rh5xiii—Ce2—Rh4xvii | 128.359 (12) | Si7xix—Rh5—Rh5vii | 114.71 (14) |
Rh5vii—Ce2—Rh4xvii | 128.359 (12) | Si7—Rh5—Rh5vii | 114.71 (14) |
Rh5xiv—Ce2—Rh4xvii | 51.641 (12) | Si6v—Rh5—Rh5vii | 51.50 (8) |
Rh5xv—Ce2—Rh4xvii | 51.641 (12) | Si6xxvii—Rh5—Rh5vii | 51.50 (8) |
Rh5—Ce2—Rh4xvii | 128.359 (12) | Rh4ii—Rh5—Rh5vii | 56.73 (3) |
Rh5xvi—Ce2—Rh4xvii | 51.641 (12) | Rh4v—Rh5—Rh5vii | 100.97 (4) |
Rh5xii—Ce2—Rh4xvii | 51.641 (12) | Rh4xxviii—Rh5—Rh5vii | 56.73 (3) |
Rh5v—Ce2—Rh4xvii | 128.359 (12) | Rh4xiv—Rh5—Rh5vii | 100.97 (4) |
Rh3xii—Ce2—Rh4ii | 90.0 | Rh3—Rh5—Rh5vii | 107.07 (5) |
Rh3—Ce2—Rh4ii | 90.0 | Rh3xxii—Rh5—Rh5vii | 162.93 (5) |
Rh5xiii—Ce2—Rh4ii | 51.641 (12) | Rh5xxix—Rh5—Rh5vii | 90.0 |
Rh5vii—Ce2—Rh4ii | 51.641 (12) | Si6xxx—Si6—Rh4x | 118.2 (2) |
Rh5xiv—Ce2—Rh4ii | 128.359 (12) | Si6xxx—Si6—Rh4xi | 118.2 (2) |
Rh5xv—Ce2—Rh4ii | 128.359 (12) | Rh4x—Si6—Rh4xi | 77.09 (17) |
Rh5—Ce2—Rh4ii | 51.641 (12) | Si6xxx—Si6—Rh4v | 118.2 (2) |
Rh5xvi—Ce2—Rh4ii | 128.359 (12) | Rh4x—Si6—Rh4v | 123.6 (4) |
Rh5xii—Ce2—Rh4ii | 128.359 (12) | Rh4xi—Si6—Rh4v | 77.09 (17) |
Rh5v—Ce2—Rh4ii | 51.641 (12) | Si6xxx—Si6—Rh4 | 118.2 (2) |
Rh4xvii—Ce2—Rh4ii | 180.00 (3) | Rh4x—Si6—Rh4 | 77.09 (17) |
Ce2—Rh3—Si7xv | 92.11 (13) | Rh4xi—Si6—Rh4 | 123.6 (4) |
Ce2—Rh3—Si7 | 92.11 (13) | Rh4v—Si6—Rh4 | 77.09 (17) |
Si7xv—Rh3—Si7 | 175.8 (3) | Si6xxx—Si6—Rh5xxv | 61.70 (19) |
Ce2—Rh3—Si7xviii | 92.11 (13) | Rh4x—Si6—Rh5xxv | 140.601 (9) |
Si7xv—Rh3—Si7xviii | 89.923 (10) | Rh4xi—Si6—Rh5xxv | 140.601 (9) |
Si7—Rh3—Si7xviii | 89.923 (10) | Rh4v—Si6—Rh5xxv | 71.06 (3) |
Ce2—Rh3—Si7xix | 92.11 (13) | Rh4—Si6—Rh5xxv | 71.06 (3) |
Si7xv—Rh3—Si7xix | 89.923 (10) | Si6xxx—Si6—Rh5i | 61.70 (19) |
Si7—Rh3—Si7xix | 89.923 (10) | Rh4x—Si6—Rh5i | 71.06 (3) |
Si7xviii—Rh3—Si7xix | 175.8 (3) | Rh4xi—Si6—Rh5i | 71.06 (3) |
Ce2—Rh3—Rh3xx | 135.0 | Rh4v—Si6—Rh5i | 140.601 (9) |
Si7xv—Rh3—Rh3xx | 58.29 (11) | Rh4—Si6—Rh5i | 140.601 (9) |
Si7—Rh3—Rh3xx | 118.27 (11) | Rh5xxv—Si6—Rh5i | 123.4 (4) |
Si7xviii—Rh3—Rh3xx | 58.29 (11) | Si6xxx—Si6—Rh5xxvi | 61.70 (19) |
Si7xix—Rh3—Rh3xx | 118.27 (11) | Rh4x—Si6—Rh5xxvi | 71.06 (3) |
Ce2—Rh3—Rh3xxi | 135.0 | Rh4xi—Si6—Rh5xxvi | 140.602 (9) |
Si7xv—Rh3—Rh3xxi | 58.29 (11) | Rh4v—Si6—Rh5xxvi | 140.601 (9) |
Si7—Rh3—Rh3xxi | 118.27 (11) | Rh4—Si6—Rh5xxvi | 71.06 (3) |
Si7xviii—Rh3—Rh3xxi | 118.27 (11) | Rh5xxv—Si6—Rh5xxvi | 77.01 (16) |
Si7xix—Rh3—Rh3xxi | 58.29 (11) | Rh5i—Si6—Rh5xxvi | 77.01 (16) |
Rh3xx—Rh3—Rh3xxi | 60.0 | Si6xxx—Si6—Rh5ix | 61.70 (19) |
Ce2—Rh3—Rh3xxii | 135.0 | Rh4x—Si6—Rh5ix | 140.602 (9) |
Si7xv—Rh3—Rh3xxii | 118.27 (11) | Rh4xi—Si6—Rh5ix | 71.06 (3) |
Si7—Rh3—Rh3xxii | 58.29 (11) | Rh4v—Si6—Rh5ix | 71.06 (3) |
Si7xviii—Rh3—Rh3xxii | 118.27 (11) | Rh4—Si6—Rh5ix | 140.601 (9) |
Si7xix—Rh3—Rh3xxii | 58.29 (11) | Rh5xxv—Si6—Rh5ix | 77.01 (16) |
Rh3xx—Rh3—Rh3xxii | 90.0 | Rh5i—Si6—Rh5ix | 77.01 (16) |
Rh3xxi—Rh3—Rh3xxii | 60.0 | Rh5xxvi—Si6—Rh5ix | 123.4 (4) |
Ce2—Rh3—Rh3v | 135.0 | Si6xxx—Si6—Ce1 | 180.0 |
Si7xv—Rh3—Rh3v | 118.27 (11) | Rh4x—Si6—Ce1 | 61.8 (2) |
Si7—Rh3—Rh3v | 58.29 (11) | Rh4xi—Si6—Ce1 | 61.8 (2) |
Si7xviii—Rh3—Rh3v | 58.29 (11) | Rh4v—Si6—Ce1 | 61.8 (2) |
Si7xix—Rh3—Rh3v | 118.27 (11) | Rh4—Si6—Ce1 | 61.8 (2) |
Rh3xx—Rh3—Rh3v | 60.0 | Rh5xxv—Si6—Ce1 | 118.30 (19) |
Rh3xxi—Rh3—Rh3v | 90.0 | Rh5i—Si6—Ce1 | 118.30 (19) |
Rh3xxii—Rh3—Rh3v | 60.0 | Rh5xxvi—Si6—Ce1 | 118.30 (19) |
Ce2—Rh3—Rh5v | 72.93 (5) | Rh5ix—Si6—Ce1 | 118.30 (19) |
Si7xv—Rh3—Rh5v | 133.34 (6) | Rh5v—Si7—Rh5xxv | 119.971 (12) |
Si7—Rh3—Rh5v | 48.34 (5) | Rh5v—Si7—Rh5 | 119.971 (12) |
Si7xviii—Rh3—Rh5v | 48.34 (5) | Rh5xxv—Si7—Rh5 | 119.971 (12) |
Si7xix—Rh3—Rh5v | 133.34 (6) | Rh5v—Si7—Rh4ii | 70.02 (12) |
Rh3xx—Rh3—Rh5v | 101.98 (4) | Rh5xxv—Si7—Rh4ii | 130.2 (3) |
Rh3xxi—Rh3—Rh5v | 152.07 (5) | Rh5—Si7—Rh4ii | 70.02 (12) |
Rh3xxii—Rh3—Rh5v | 101.98 (4) | Rh5v—Si7—Rh4v | 130.2 (3) |
Rh3v—Rh3—Rh5v | 62.07 (5) | Rh5xxv—Si7—Rh4v | 70.02 (12) |
Ce2—Rh3—Rh5 | 72.93 (5) | Rh5—Si7—Rh4v | 70.02 (12) |
Si7xv—Rh3—Rh5 | 133.34 (6) | Rh4ii—Si7—Rh4v | 69.5 (2) |
Si7—Rh3—Rh5 | 48.34 (5) | Rh5v—Si7—Rh4 | 70.02 (12) |
Si7xviii—Rh3—Rh5 | 133.34 (6) | Rh5xxv—Si7—Rh4 | 70.02 (12) |
Si7xix—Rh3—Rh5 | 48.34 (5) | Rh5—Si7—Rh4 | 130.2 (3) |
Rh3xx—Rh3—Rh5 | 152.07 (5) | Rh4ii—Si7—Rh4 | 69.5 (2) |
Rh3xxi—Rh3—Rh5 | 101.98 (4) | Rh4v—Si7—Rh4 | 69.5 (2) |
Rh3xxii—Rh3—Rh5 | 62.07 (5) | Rh5v—Si7—Rh3v | 73.15 (13) |
Rh3v—Rh3—Rh5 | 101.98 (4) | Rh5xxv—Si7—Rh3v | 73.15 (13) |
Rh5v—Rh3—Rh5 | 85.06 (3) | Rh5—Si7—Rh3v | 128.3 (3) |
Ce2—Rh3—Rh5xv | 72.93 (5) | Rh4ii—Si7—Rh3v | 142.96 (3) |
Si7xv—Rh3—Rh5xv | 48.34 (5) | Rh4v—Si7—Rh3v | 142.96 (3) |
Si7—Rh3—Rh5xv | 133.34 (6) | Rh4—Si7—Rh3v | 101.50 (7) |
Si7xviii—Rh3—Rh5xv | 48.34 (5) | Rh5v—Si7—Rh3xxii | 128.3 (3) |
Si7xix—Rh3—Rh5xv | 133.34 (6) | Rh5xxv—Si7—Rh3xxii | 73.15 (13) |
Rh3xx—Rh3—Rh5xv | 62.07 (5) | Rh5—Si7—Rh3xxii | 73.15 (13) |
Rh3xxi—Rh3—Rh5xv | 101.98 (4) | Rh4ii—Si7—Rh3xxii | 142.96 (3) |
Rh3xxii—Rh3—Rh5xv | 152.07 (5) | Rh4v—Si7—Rh3xxii | 101.50 (7) |
Rh3v—Rh3—Rh5xv | 101.98 (4) | Rh4—Si7—Rh3xxii | 142.96 (3) |
Rh5v—Rh3—Rh5xv | 85.06 (3) | Rh3v—Si7—Rh3xxii | 63.4 (2) |
Rh5—Rh3—Rh5xv | 145.86 (10) | Rh5v—Si7—Rh3 | 73.15 (13) |
Si6xxiii—Rh4—Si6 | 146.4 (4) | Rh5xxv—Si7—Rh3 | 128.3 (3) |
Si6xxiii—Rh4—Si7 | 93.90 (6) | Rh5—Si7—Rh3 | 73.15 (13) |
Si6—Rh4—Si7 | 93.90 (6) | Rh4ii—Si7—Rh3 | 101.50 (7) |
Si6xxiii—Rh4—Si7xxiv | 93.90 (6) | Rh4v—Si7—Rh3 | 142.96 (3) |
Si6—Rh4—Si7xxiv | 93.90 (6) | Rh4—Si7—Rh3 | 142.96 (3) |
Si7—Rh4—Si7xxiv | 152.8 (3) | Rh3v—Si7—Rh3 | 63.4 (2) |
Si6xxiii—Rh4—Rh5v | 56.46 (15) | Rh3xxii—Si7—Rh3 | 63.4 (2) |
Si6—Rh4—Rh5v | 143.84 (8) |
Symmetry codes: (i) z, −y+1, −x+1; (ii) −z+1, y, x; (iii) −x+1, −y+1, −z+1; (iv) −y+1, −z+1, −x+1; (v) y, z, x; (vi) −z+1, y, −x+1; (vii) −x+1, y, z; (viii) −y+1, −z+1, x; (ix) z, −y+1, x; (x) y, z, −x+1; (xi) x, −y+1, −z+1; (xii) −x+1, −y, −z; (xiii) −y+1, −z, x; (xiv) y, z, −x; (xv) x, −y, −z; (xvi) −y+1, −z, −x; (xvii) z, −y, −x; (xviii) x, −y, z; (xix) x, y, −z; (xx) y, −x, −z; (xxi) −y, −z, −x; (xxii) −y, x, z; (xxiii) −y+1, x, z; (xxiv) x, y, −z+1; (xxv) −z, y, x; (xxvi) −z, y, −x+1; (xxvii) −y+1, −z+1, −x; (xxviii) −z+1, y, −x; (xxix) x, −y+1, −z; (xxx) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | Ce2Rh15Si7 |
Mr | 2020.52 |
Crystal system, space group | Cubic, Pm3m |
Temperature (K) | 293 |
a (Å) | 8.818 (1) |
V (Å3) | 685.66 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 24.57 |
Crystal size (mm) | 0.17 × 0.15 × 0.13 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.034, 0.098 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1756, 358, 251 |
Rint | 0.131 |
(sin θ/λ)max (Å−1) | 0.806 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.148, 0.86 |
No. of reflections | 358 |
No. of parameters | 22 |
Δρmax, Δρmin (e Å−3) | 4.22, −4.12 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Intermetallic compounds consisting of Ce, Rh(Pd) and Si exibit many interesting physical properties, for example, magnetism, superconductivity, heavy-electron behavior and valence fluctuations (Buschow, 1993; Trovarelli et al., 1998; Gomez-Berisso et al., 1999). For this reason, we have been investigating ternary Ce–Rh–Si systems looking for new intermetallic compounds (Gribanov et al., 2000a,b; Tursina et al., 2001). Herein, we report the crystal structure of the new ternary compound, Ce2Rh15Si7, (I).
The coordination polyhedra of the Ce atoms are cubooctahedron Ce1 [Rh12] and distorted polyhedron with 14 Ce2 [Rh14] apexes. Coordination polyhedra of the Rh atoms are rather irregular polyhedra with 9 and 10 apexes: Rh3 [Ce1Rh4Si4], Rh4 [Ce2Rh4Si4] and Rh5 [Rh6Si4]. The Si atoms have slightly destorted polyhedra with 10 and 9 apexes: double-capped square antiprisms Si6 [Ce1Rh8Si1] and trigonal prisms with three additional atoms Si7 [Rh9]. All interatomic distances in (I) are typical for such compounds except two Ce2—Rh3 distances [2.432 (3) Å] which are significantly shorter than the sum of the metallic radii d(Ce—Rh) = 3.18 Å. This peculiarity of (I) makes the probability of the existence of isostructural compounds very low as any change in the composition must cause the changes in the crystal structure providing more appropriate Ce—Rh interatomic distances. This can be demonstrated through the comparison of the two crystal structures, (I) and the Ce4Pd29Si14, (II), crystal structure (Tursina et al., 2001), which may be considered as a derivative from the crystal structure of (I).
The Pd substitution for Rh causes negligible changes in the mutual positions of all atoms in the structure of (II) except two Pd atoms (Pd4 and Pd5), corresponding to the Rh3 atoms in structure (I). They change their positions considerably. However, the Pd4 atoms simply move aside of Ce2 atoms, d(Ce2—Pd4) = 2.903 (4) Å, while the Pd5 atoms pass into a new crystallographic position, d(Ce2—Pd5) = 3.339 (2) Å. These atoms shifts in structure (II) causes, firstly, the change of crystal structure [space group Fm3m, a = 18.010 (2) Å], secondly, the decrease in Pd percentage and in number of atoms per unit-cell volume. That is, the Dx falls from 9.787 Mg m-3 in (I) to 9.186 Mg m-3 in (II).