Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105043076/fa1155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105043076/fa1155Isup2.hkl |
Cs[(Zr6C)Cl15] is conventionally prepared from appropriate mixtures of CsCl, ZrCl4, elemental Zr and Al4C3, which are enclosed in welded niobium (or tantalum) ampoules, which in turn are sealed in evacuated silica ampoules. Reactions are carried out by heating the enclosed ampoules at 1123 K for two to three weeks. The air- and moisture-sensitive compound was obtained as dark red crystals.
During structure refinement, it quickly became obvious that the Cs cation is distributed on several disordered positions. As in the CsK[(Zr6B)Cl15] structure (Ziebarth & Corbett, 1987) the Wyckoff sites 4k, 2f and 2c are involved. Unconstrained refinements of all five positions (two sites split into two positions) including variations of the occupational factors indicated the site 2f to be fully occupied, which accounts for one-half of a Cs atom per formula unit. The refinement of this atom was carried out using a split position (Cs1 and Cs2), with the sum of the site occupation factors being fixed to full occupation (occupation factors are given in the deposited CIF). Using a restrained occupation for atoms Cs3, Cs4 and Cs5, the total Cs content per formula unit refines to Cs1.00 (7)[(Zr6C)Cl15]. The two independent interstitial C atoms were refined isotropically. All the other atoms were refined using anisotropic displacement parameters.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998 or? 2001); software used to prepare material for publication: SHELXL97.
Cs[Zr6CCl15] | F(000) = 2224 |
Mr = 1223.99 | Dx = 3.274 Mg m−3 |
Orthorhombic, Pmma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2a 2a | Cell parameters from 42 reflections |
a = 18.513 (2) Å | θ = 2.9–19.9° |
b = 13.916 (1) Å | µ = 5.47 mm−1 |
c = 9.6383 (7) Å | T = 293 K |
V = 2483.1 (4) Å3 | Irregular block, dark red |
Z = 4 | 0.52 × 0.43 × 0.40 mm |
Siemens P4 diffractometer | 2627 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 28.0°, θmin = 2.1° |
ω scans | h = −1→24 |
Absorption correction: ψ scan (Farrugia, 1999) | k = −18→1 |
Tmin = 0.047, Tmax = 0.112 | l = −12→1 |
4087 measured reflections | 2 standard reflections every 98 reflections |
3223 independent reflections | intensity decay: 0.0% |
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)] = 0.046 | w = 1/[σ2(Fo2) + (0.0687P)2 + 15.1304P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.128 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 2.00 e Å−3 |
3223 reflections | Δρmin = −1.62 e Å−3 |
141 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00071 (11) |
Cs[Zr6CCl15] | V = 2483.1 (4) Å3 |
Mr = 1223.99 | Z = 4 |
Orthorhombic, Pmma | Mo Kα radiation |
a = 18.513 (2) Å | µ = 5.47 mm−1 |
b = 13.916 (1) Å | T = 293 K |
c = 9.6383 (7) Å | 0.52 × 0.43 × 0.40 mm |
Siemens P4 diffractometer | 2627 reflections with I > 2σ(I) |
Absorption correction: ψ scan (Farrugia, 1999) | Rint = 0.033 |
Tmin = 0.047, Tmax = 0.112 | 2 standard reflections every 98 reflections |
4087 measured reflections | intensity decay: 0.0% |
3223 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0687P)2 + 15.1304P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | Δρmax = 2.00 e Å−3 |
3223 reflections | Δρmin = −1.62 e Å−3 |
141 parameters |
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 | Occ. (<1) | |
Cs1 | 0.2500 | 0.5000 | 1.034 (1) | 0.060 (2) | 0.66 (7) |
Cs2 | 0.2500 | 0.5000 | 1.071 (5) | 0.044 (5) | 0.34 (7) |
Cs3 | 0.2500 | 0.2513 (5) | 0.6600 (7) | 0.025 (1) | 0.08 |
Cs4 | 0.012 (1) | 0.0000 | 0.534 (4) | 0.06 (2) | 0.27 (3) |
Cs5 | −0.037 (2) | 0.0000 | 0.405 (4) | 0.038 (3) | 0.15 (3) |
Zr1 | 0.47113 (3) | 0.38426 (4) | 0.34092 (6) | 0.0168 (2) | |
Zr2 | 0.61535 (4) | 0.5000 | 0.42067 (9) | 0.0164 (2) | |
Zr3 | 0.33744 (3) | 0.11620 (4) | 0.14316 (6) | 0.0161 (2) | |
Zr4 | 0.2500 | 0.0000 | 0.3755 (1) | 0.0142 (2) | |
Zr5 | 0.2500 | 0.0000 | 0.9088 (1) | 0.0168 (2) | |
Cl1 | 0.43813 (9) | 0.2512 (1) | 0.1532 (2) | 0.0289 (4) | |
Cl2 | 0.2500 | 0.0000 | 0.6421 (3) | 0.0415 (9) | |
Cl3 | 0.7500 | 0.5000 | 0.3207 (3) | 0.0257 (6) | |
Cl4 | 0.5000 | 0.2457 (2) | 0.5000 | 0.0262 (5) | |
Cl5 | 0.4367 (1) | 0.5000 | 0.1488 (2) | 0.0252 (4) | |
Cl6 | 0.59655 (8) | 0.3724 (1) | 0.2367 (2) | 0.0268 (3) | |
Cl7 | 0.34025 (7) | 0.3748 (1) | 0.4114 (2) | 0.0243 (3) | |
Cl8 | 0.2500 | 0.2560 (2) | 0.1398 (3) | 0.0254 (5) | |
Cl9 | 0.4426 (1) | 0.0000 | 0.1452 (3) | 0.0309 (5) | |
Cl10 | 0.34499 (8) | 0.1276 (1) | 0.40434 (16) | 0.0244 (3) | |
Cl11 | 0.15255 (9) | 0.1271 (1) | 0.8832 (2) | 0.0283 (3) | |
C1 | 0.5000 | 0.5000 | 0.5000 | 0.009 (2)* | |
C2 | 0.2500 | 0.0000 | 0.140 (1) | 0.011 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs1 | 0.076 (5) | 0.054 (4) | 0.049 (3) | 0.000 | 0.000 | 0.000 |
Cs2 | 0.033 (3) | 0.020 (3) | 0.079 (11) | 0.000 | 0.000 | 0.000 |
Cs3 | 0.023 (3) | 0.023 (3) | 0.030 (4) | 0.000 | 0.000 | 0.003 (3) |
Cs4 | 0.06 (2) | 0.0191 (12) | 0.09 (3) | 0.000 | 0.06 (2) | 0.000 |
Cs5 | 0.033 (6) | 0.036 (4) | 0.045 (8) | 0.000 | 0.029 (5) | 0.000 |
Zr1 | 0.0102 (3) | 0.0169 (3) | 0.0232 (3) | −0.00108 (18) | −0.00091 (19) | −0.0020 (2) |
Zr2 | 0.0084 (3) | 0.0176 (4) | 0.0233 (4) | 0.000 | 0.0003 (3) | 0.000 |
Zr3 | 0.0134 (3) | 0.0166 (3) | 0.0182 (3) | −0.00228 (19) | 0.00087 (19) | −0.0001 (2) |
Zr4 | 0.0132 (5) | 0.0168 (5) | 0.0127 (5) | 0.000 | 0.000 | 0.000 |
Zr5 | 0.0194 (5) | 0.0183 (5) | 0.0129 (5) | 0.000 | 0.000 | 0.000 |
Cl1 | 0.0268 (7) | 0.0291 (8) | 0.0310 (9) | −0.0142 (6) | 0.0072 (6) | −0.0090 (6) |
Cl2 | 0.063 (2) | 0.050 (2) | 0.0120 (14) | 0.000 | 0.000 | 0.000 |
Cl3 | 0.0089 (11) | 0.0362 (17) | 0.0318 (16) | 0.000 | 0.000 | 0.000 |
Cl4 | 0.0233 (10) | 0.0182 (10) | 0.0370 (12) | 0.000 | 0.0060 (8) | 0.000 |
Cl5 | 0.0233 (10) | 0.0281 (11) | 0.0242 (10) | 0.000 | −0.0058 (8) | 0.000 |
Cl6 | 0.0155 (6) | 0.0300 (8) | 0.0348 (8) | −0.0015 (5) | 0.0038 (6) | −0.0114 (7) |
Cl7 | 0.0112 (5) | 0.0267 (7) | 0.0350 (8) | −0.0049 (5) | 0.0005 (5) | −0.0082 (6) |
Cl8 | 0.0224 (9) | 0.0169 (9) | 0.0370 (12) | 0.000 | 0.000 | 0.0002 (9) |
Cl9 | 0.0128 (9) | 0.0265 (11) | 0.0534 (15) | 0.000 | 0.0057 (9) | 0.000 |
Cl10 | 0.0255 (7) | 0.0262 (7) | 0.0215 (7) | −0.0083 (6) | −0.0039 (5) | −0.0022 (6) |
Cl11 | 0.0326 (8) | 0.0298 (8) | 0.0225 (7) | 0.0109 (6) | −0.0068 (6) | 0.0026 (6) |
Zr—C(average) | 2.278 (2) | Zr3—Cl1 | 2.6486 (16) |
Zr—Zr(average) | 3.221 (1) | Zr4—Cl10 | 2.5146 (14) |
Zr—Cla(average) | 2.643 (2) | Zr4—Cl2 | 2.569 (3) |
Zr—Cli(average) | 2.527 (2) | Zr5—Cl11iv | 2.5388 (15) |
Zr1—Zr1i | 3.221 (1) | Zr5—Cl2 | 2.571 (3) |
Zr1—Zr1ii | 3.248 (1) | Cs1—Cl3iii | 3.415 (13) |
Zr1—Zr2iii | 3.2307 (9) | Cs1—Cl8ix | 3.547 (4) |
Zr1—Zr2 | 3.2115 (9) | Cs1—Cl5vii | 3.630 (5) |
Zr3—Zr3iv | 3.234 (1) | Cs2—Cl8ix | 3.461 (10) |
Zr3—Zr3v | 3.237 (1) | Cs2—Cl5vii | 3.537 (11) |
Zr3—Zr4 | 3.2014 (9) | Cs2—Cl3iii | 3.77 (5) |
Zr3—Zr5vi | 3.215 (1) | Cs2—Cl7x | 4.08 (4) |
Zr1—C1 | 2.2871 (6) | Cs3—Cl11v | 3.297 (6) |
Zr2—C1 | 2.2682 (7) | Cs3—Cl7 | 3.389 (6) |
Zr3—C2 | 2.2883 (6) | Cs3—Cl6ii | 3.449 (4) |
Zr4—C2 | 2.27 (1) | Cs3—Cl3iii | 3.466 (7) |
Zr5—C2vii | 2.23 (1) | Cs3—Cl10 | 3.483 (6) |
Zr1—Cl7 | 2.5197 (15) | Cs3—Cl2 | 3.502 (7) |
Zr1—Cl4 | 2.5206 (17) | Cs4—Cl9xi | 3.35 (3) |
Zr1—Cl5 | 2.5353 (18) | Cs4—Cl10v | 3.422 (10) |
Zr1—Cl6 | 2.5354 (15) | Cs4—Cl4xii | 3.442 (5) |
Zr1—Cl1 | 2.6602 (17) | Cs4—Cl10xiii | 3.616 (16) |
Zr2—Cl7iii | 2.5164 (16) | Cs4—Cl9xii | 3.84 (3) |
Zr2—Cl6 | 2.5339 (17) | Cs5—Cl9xii | 3.054 (19) |
Zr2—Cl3 | 2.6726 (14) | Cs5—Cl10xi | 3.362 (12) |
Zr3—Cl11viii | 2.5172 (17) | Cs5—Cl4xi | 3.605 (13) |
Zr3—Cl10 | 2.5262 (16) | Cs5—Cl11xiv | 3.93 (4) |
Zr3—Cl9 | 2.5306 (17) | Cs5—Cl2xiv | 3.97 (3) |
Zr3—Cl8 | 2.5306 (17) | Cs5—Cl10v | 3.97 (2) |
Zr2xv—Cl3—Zr2 | 137.7 (1) | Cl8ix—Cs1—Cl8vii | 146.5 (4) |
Zr1—Cl1—Zr3 | 132.84 (6) | Cl8ix—Cs2—Cl3iii | 101.1 (8) |
Zr4—Cl2—Zr5 | 180.0 | Cl8ix—Cs2—Cl5vii | 87.7 (3) |
Cl5—Zr1—Cl1 | 83.54 (5) | Cl8ix—Cs2—Cl7x | 54.9 (5) |
Cl5—Zr1—Cl6 | 88.99 (7) | Cl8ix—Cs2—Cl8vii | 157.8 (16) |
Cl5—Zr1—Zr1i | 50.56 (3) | Cl8—Zr3—Cl1 | 84.57 (5) |
Cl5—Zr1—Zr2 | 93.74 (5) | Cl8—Zr3—Zr3iv | 140.22 (3) |
C1—Zr1—Zr1ii | 44.767 (15) | Cl8—Zr3—Zr4 | 94.23 (5) |
C1—Zr1—Zr2iii | 44.593 (15) | Cl8—Zr3—Zr5vi | 93.18 (5) |
Cl1—Zr1—Zr1i | 134.10 (4) | Cl9xi—Cs4—Cl10v | 129.3 (11) |
Cl1—Zr1—Zr2 | 134.65 (4) | Cl9xi—Cs4—Cl4xii | 93.6 (4) |
C1—Zr1—Cl1 | 179.22 (5) | Cl9xi—Cs4—Cl9xii | 170.1 (11) |
C1—Zr1—Cl5 | 95.79 (4) | Cl9xi—Cs4—Zr4 | 131.7 (11) |
C1—Zr1—Cl6 | 95.60 (4) | Cl9xii—Cs5—Cl10xi | 145.1 (6) |
C1—Zr1—Cl7 | 94.64 (4) | Cl9xii—Cs5—Cl11xvi | 74.4 (7) |
Cl4—Zr1—Cl1 | 86.01 (5) | Cl9xii—Cs5—Cl2xiv | 118.3 (12) |
Cl4—Zr1—Cl5 | 169.55 (5) | Cl9xii—Cs5—Cl4xi | 95.7 (2) |
Cl4—Zr1—Cl6 | 89.82 (4) | Cl2xiv—Cs5—Cl10v | 152.7 (4) |
Cl4—Zr1—Zr1i | 139.89 (3) | Cl9—Zr3—Cl1 | 84.94 (5) |
Cl4—Zr1—Zr2 | 93.54 (3) | Cl9—Zr3—Cl8 | 169.49 (5) |
Cl6—Zr1—Cl1 | 83.99 (5) | Cl9—Zr3—Zr3v | 140.28 (3) |
Cl6—Zr1—Zr1i | 93.74 (4) | Cl9—Zr3—Zr4 | 93.47 (5) |
Cl6—Zr1—Zr2 | 50.67 (4) | Cl9—Zr3—Zr5vi | 94.10 (5) |
Cl6i—Zr2—Cl3 | 82.86 (6) | Cl10v—Cs3—Cl10 | 60.65 (13) |
Cl6—Zr2—Cl6i | 89.01 (8) | Cl10v—Cs3—Cl2 | 58.08 (12) |
Cl6—Zr2—Zr1 | 50.71 (4) | Cl10v—Cs3—Zr2iii | 123.91 (18) |
Cl3—Zr2—Zr1i | 133.56 (6) | Cl10—Cs3—Zr5 | 89.56 (14) |
C1—Zr2—Cl3 | 178.56 (8) | Cl10v—Cs4—Cl10xi | 117.8 (3) |
C1—Zr2—Cl6 | 96.12 (4) | Cl10v—Cs4—Cl4xii | 122.1 (3) |
C1—Zr2—Cl7iii | 95.20 (4) | Cl10xiii—Cs4—Cl9xii | 110.4 (10) |
C1—Zr2—Zr1 | 45.410 (16) | Cl10xiii—Cs4—Zr4 | 149.6 (2) |
C2—Zr3—Cl1 | 178.7 (3) | Cl10xi—Cs5—Cl10v | 110.3 (6) |
C2—Zr3—Cl10 | 95.6 (3) | Cl10xi—Cs5—Cl11xiv | 105.7 (8) |
C2—Zr3—Cl11viii | 94.6 (3) | Cl10xiii—Cs5—Cl4xi | 119.1 (5) |
C2—Zr3—Cl8 | 95.19 (4) | Cl10—Zr3—Cl1 | 83.13 (5) |
C2—Zr3—Cl9 | 95.32 (4) | Cl10—Zr3—Cl8 | 90.00 (7) |
C2—Zr3—Zr3v | 44.977 (15) | Cl10—Zr3—Cl9 | 89.41 (7) |
C2—Zr3—Zr4 | 45.2 (3) | Cl10—Zr3—Zr3v | 93.17 (4) |
C2—Zr3—Zr5vi | 43.8 (3) | Cl10—Zr3—Zr4 | 50.41 (4) |
C2—Zr4—Cl10 | 96.35 (4) | Cl10—Zr3—Zr5vi | 139.43 (4) |
C2—Zr4—Cs3 | 128.10 (9) | Cl10—Zr4—Cl10xii | 167.30 (9) |
C2—Zr4—Zr3xii | 45.618 (17) | Cl10—Zr4—Cl2 | 83.65 (4) |
C2vii—Zr5—Cl11iv | 95.57 (4) | Cl10—Zr4—Zr3xii | 141.97 (5) |
C2vii—Zr5—Cs3 | 124.43 (10) | Cl11v—Cs3—Cl10v | 118.6 (2) |
C2vii—Zr5—Zr3vii | 45.364 (17) | Cl11v—Cs3—Cl11 | 66.36 (14) |
Cl1—Zr3—Zr3v | 134.73 (4) | Cl11v—Cs3—Cl2 | 60.57 (12) |
Cl1—Zr3—Zr4 | 133.54 (4) | Cl11v—Cs3—Cl3iii | 119.24 (19) |
Cl1—Zr3—Zr5vi | 137.44 (4) | Cl11v—Cs3—Cl6xi | 121.2 (2) |
Cl2—Zr4—Zr3 | 134.382 (17) | Cl11v—Cs3—Cl7 | 117.21 (4) |
Cl2—Zr5—Zr3vii | 134.636 (17) | Cl11v—Cs3—Zr2iii | 102.76 (8) |
Cl3iii—Cs1—Cl5ix | 107.8 (2) | Cl11v—Cs3—Zr5 | 36.75 (8) |
Cl3iii—Cs1—Cl8ix | 106.8 (2) | Cl11xiv—Cs5—Cl10v | 133.4 (6) |
Cl3iii—Cs2—Cl7x | 143.7 (4) | Cl11xiv—Cs5—Cl11xvi | 53.5 (6) |
Cl3iii—Cs3—Cl10 | 122.11 (18) | Cl11xiv—Cs5—Cl2xiv | 51.5 (5) |
Cl3iii—Cs3—Cl2 | 179.8 (2) | Cl11viii—Zr3—Cl1 | 86.64 (5) |
Cl3iii—Cs3—Zr5 | 142.5 (2) | Cl11viii—Zr3—Cl10 | 169.76 (5) |
Cl4xi—Cs4—Cl10xiii | 116.6 (6) | Cl11viii—Zr3—Cl8 | 89.30 (7) |
Cl4xii—Cs4—Cl4xi | 166.9 (14) | Cl11viii—Zr3—Cl9 | 89.42 (8) |
Cl4xii—Cs4—Cl9xii | 85.5 (6) | Cl11viii—Zr3—Zr3iv | 93.46 (4) |
Cl4xi—Cs5—Cl10v | 53.6 (3) | Cl11viii—Zr3—Zr5vi | 50.81 (4) |
Cl4xii—Cs5—Cl11xvi | 135.2 (9) | Cl11iv—Zr5—Cl11v | 168.85 (9) |
Cl4xii—Cs5—Cl2xiv | 102.6 (4) | Cl11iv—Zr5—Cl2 | 84.43 (4) |
Cl4xi—Cs5—Cl4xii | 143.1 (13) | Cl11iv—Zr5—Cs3 | 121.32 (7) |
Cl5vii—Cs1—Cl5ix | 144.4 (4) | Zr1ii—Cl4—Zr1 | 80.21 (7) |
Cl5vii—Cs2—Cl3iii | 102.3 (8) | Zr1i—Cl5—Cs1vi | 117.57 (15) |
Cl5vii—Cs2—Cl5ix | 155.4 (16) | Zr1i—Cl5—Zr1 | 78.88 (7) |
Cl5vii—Cs2—Cl7ix | 103.2 (10) | Zr1i—Zr1—Zr1ii | 90.0 |
Cl6ii—Cs3—Cl10v | 149.48 (18) | Zr1i—Zr1—Zr2iii | 60.097 (12) |
Cl6ii—Cs3—Cl2 | 120.13 (12) | Zr1—Zr2—Zr1i | 60.20 (2) |
Cl6ii—Cs3—Cl3iii | 59.79 (11) | Zr2—C1—Zr1ii | 90.34 (2) |
Cl6ii—Cs3—Cl6xi | 110.9 (2) | Zr2—Cl6—Zr1 | 78.62 (5) |
Cl7x—Cs2—Cl7ix | 48.4 (5) | Zr2iii—Cl7—Zr1 | 79.81 (4) |
Cl7—Cs3—Cl10 | 60.09 (10) | Zr2—Zr1—Zr1i | 59.899 (12) |
Cl7—Cs3—Cl2 | 118.12 (19) | Zr2—Zr1—Zr1ii | 60.02 (2) |
Cl7—Cs3—Cl3iii | 62.08 (12) | Zr2—Zr1—Zr2iii | 89.52 (2) |
Cl7—Cs3—Cl6xi | 111.25 (18) | Zr3xii—C2—Zr3 | 178.3 (5) |
Cl7—Cs3—Cl7v | 59.07 (13) | Zr3xvii—Cl11—Zr5 | 78.98 (5) |
Cl7—Zr1—Cl1 | 85.76 (5) | Zr3v—Cl8—Zr3 | 79.53 (7) |
Cl7—Zr1—Cl4 | 90.00 (4) | Zr3iv—Cl9—Zr3 | 79.43 (6) |
Cl7—Zr1—Cl5 | 89.33 (7) | Zr3iv—Zr3—Zr3v | 90.0 |
Cl7—Zr1—Cl6 | 169.74 (6) | Zr3xii—Zr4—Zr3iv | 60.75 (3) |
Cl7—Zr1—Zr1i | 93.00 (4) | Zr3vii—Zr5—Zr3xviii | 60.39 (3) |
Cl7—Zr1—Zr2 | 139.57 (4) | Zr4—C2—Zr3xii | 89.2 (3) |
Cl7iii—Zr2—Cl3 | 85.83 (6) | Zr4—Cl10—Zr3 | 78.85 (5) |
Cl7iii—Zr2—Cl6 | 168.65 (6) | Zr4—Zr3—Zr3iv | 59.662 (13) |
Cl7iii—Zr2—Cl7ii | 87.64 (8) | Zr4—Zr3—Zr5vi | 89.02 (2) |
Cl7iii—Zr2—Zr1 | 140.61 (4) | Zr5vi—C2—Zr3xii | 90.8 (3) |
Cl10xi—Cs5—Cl2xiv | 54.3 (3) | Zr5vi—Zr3—Zr3iv | 59.807 (13) |
Cl8ix—Cs1—Cl5vii | 84.94 (11) |
Symmetry codes: (i) x, −y+1, z; (ii) −x+1, y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, −y, z; (v) −x+1/2, y, z; (vi) x, y, z−1; (vii) x, y, z+1; (viii) −x+1/2, y, z−1; (ix) −x+1/2, −y+1, z+1; (x) x, −y+1, z+1; (xi) x−1/2, y, −z+1; (xii) −x+1/2, −y, z; (xiii) x−1/2, −y, −z+1; (xiv) −x, −y, −z+1; (xv) −x+3/2, −y+1, z; (xvi) −x, y, −z+1; (xvii) −x+1/2, y, z+1; (xviii) x, −y, z+1. |
Experimental details
Crystal data | |
Chemical formula | Cs[Zr6CCl15] |
Mr | 1223.99 |
Crystal system, space group | Orthorhombic, Pmma |
Temperature (K) | 293 |
a, b, c (Å) | 18.513 (2), 13.916 (1), 9.6383 (7) |
V (Å3) | 2483.1 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.47 |
Crystal size (mm) | 0.52 × 0.43 × 0.40 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (Farrugia, 1999) |
Tmin, Tmax | 0.047, 0.112 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4087, 3223, 2627 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.128, 1.08 |
No. of reflections | 3223 |
No. of parameters | 141 |
w = 1/[σ2(Fo2) + (0.0687P)2 + 15.1304P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.00, −1.62 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998 or? 2001), SHELXL97.
Zr—C(average) | 2.278 (2) | Zr—Cla(average) | 2.643 (2) |
Zr—Zr(average) | 3.221 (1) | Zr—Cli(average) | 2.527 (2) |
Zr2i—Cl3—Zr2 | 137.7 (1) | Zr4—Cl2—Zr5 | 180.0 |
Zr1—Cl1—Zr3 | 132.84 (6) |
Symmetry code: (i) −x+3/2, −y+1, z. |
In the present paper, we describe the structure of the cluster compound Cs[(Zr6C)Cl15], which was prepared using Al4C3 as carbon source and reactor grade (extreme low Hf content) Zr powder and ZrCl4 [for reviews on Zr cluster chemistry see Corbett (1992, 1995, 1996, 2000)]. Being a member of the K[(Zr6C)Cl15] structure type (Ziebarth & Corbett, 1987), this compound crystallizes in the orthorhombic space group Pmma. This structure type is based on two symmetry-independent anionic cluster units, [(Zr6C)Cl12iCl6/2a]− [where `inner' and `outer' ligands are denoted by i and a, respectively (Schäfer & von Schnering, 1964)] (Fig. 1), sharing the outer ligands with neighboring units, forming two different types of cluster chains. One linear chain runs along the c axis, where all cluster units are connected by linear chlorine bridges, and the other type is built up of bent chlorine bridges [Zr2—Cl3a—Zr2 = 137.7 (1)°] forming a zigzag chain of clusters along the a axis (Fig. 2). Additional bent chlorine bridges [Zr1—Cl1a—Zr3 = 132.84 (6)°] interconnect the two groups of chains leading to a three-dimensional cluster network. Within the cluster network the Cs cations are distributed on serveral sites. The title compound is structurally comparable to the boron-centered zirconium cluster compound CsK[(Zr6B)Cl15], in which the potassium site is fully occupied and the caesium cation is distributed on two sites (Ziebarth & Corbett, 1987). Contrary to CsK[(Zr6B)Cl15] the cation distribution within the cluster network in the title phase is different. Apparently the size of the cavities plays an important role. Whereas in CsK[(Zr6B)Cl15] the Wyckhoff site 4k is completely occupied by potassium, in Cs[(Zr6C)Cl15] the occupation is rather small (0.08). This site is surrounded by 10 Cl atoms with Cs3—Cl distances as short as 3.297 (6) Å, compared with the sum of the ionic (Shannon) radii of Cs and Cl of 3.55 Å (Shannon, 1976). Therefore, we can assume that this site is too small to accommodate more than marginal numbers of Cs cations.
The two remaining cation sites are filled with caesium ions as in CsK[(Zr6B)Cl15]. For both sites the Cs atoms had to be refined on split positions (Cs1/Cs2 and Cs4/Cs5). Both sites have longer distances to the surrounding Cl atoms [3.42 (1) and 3.46 (1) Å, respectively]; therefore, size restrictions are much less pronounced. The Cs4/Cs5 site is especially interesting, because the Cs atoms are disordered along a channel running down the [001] direction (Fig. 3). This might be understood as a structural hint for the possibility that this phase could be an acceptable ionic conductor. Conductivity measurements are being planned.
The coordination polyhedron of Cs3 can be described as an irregular twofold capped tetragonal prism, whereas the other two coordination environments are rather irregular. The coordination environment of each Zr atom consists of a tetragonal pyramidal arrangement of Cl atoms, a square arrangement of Zr atoms and one additional C atom.