Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702627X/bt2380sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702627X/bt2380Isup2.hkl |
CCDC reference: 654688
The reaction between the title compound and four equivalents of the lithium salt of an imidazoline-2-imine in hexane afforded the new polymorph of the ruthenium starting complex as unreacted material, dark red-brown crystals of which were obtained by re-crystallization from hexane solution at -35 °C.
Methyl hydrogen atoms were located in a difference synthesis; the methyl groups were idealized and refined as rigid groups allowed to rotate but not tip, with C—H 0.98 Å, H—C—H 109.5°. U(H) values were fixed at 1.2Ueq(C). The structure was refined as a racemic twin, with components 0.57, 0.43 (3). The twinning (Flack) parameter is based on 1573 Friedel pairs.
Fagan et al. (1990) reported two polymorphs of the title complex (I) [Cp*Ru(µ3-Cl)]4. At 201 K the crystal is triclinic with space group P1 (a = 11.281 (5), b = 11.354 (4), c = 18.846 (5) Å, α = 82.20 (2)°, β = 82.03 (3)°, γ = 65.45 (4) °; V = 2166.3 Å3) whereas at room temperature it adopts a monoclinic cell (a = 19.040; b = 12.240; c = 18.850 Å; β = 99.38°; V = 4334.2 Å3). Only the structure of the triclinic form was solved and refined; its Cambridge refcode (Allen, 2002) is JERTIJ.
Here we report the structure of a new, tetragonal polymorph of (I), which crystallizes in space group I4 (a = b = 12.0733 (8), c = 14.9611 (15) Å; V = 2180.8 (3) Å3). It is noteworthy that the new form has a significantly larger cell volume then the triclinic form despite the lower temperature. The tetrameric complex possesses imposed 4 symmetry (Fig. 1) and consists, as does the triclinic form, of a distorted cubic array of four Ru and Cl atoms, with angles at ruthenium ca 82° and angles at chlorine ca 97°. Each Ru atom in the complex adopts an 18-electron configuration in a pseudooctahedral environment. The C5Me5 ligand coordinates in η5 fashion to the Ru atom with a Cp* (centroid)—Ru distance of 1.727 Å, which is slightly longer than the average Cp*—Ru distance (1.720 Å) reported by Fagan et al. The C2—centroid vector eclipses the bond Ru···Cl (torsion angle 2.1°). The structure of the complex is closely similar to that of the triclinic form; a least-squares fit of the Ru4Cl4 core for one of the many possible atom permutations gave a r.m.s. deviation of 0.019 Å. In detail, the Ru—Cl bond lengths (av. 2.534 Å) are also slightly longer than in the triclinic form (av. 2.524 Å). The Ru···Ru distances are 3.8286 (4) to Ruii, 3.7920 (4) Å to Rui and Ruiii, cf. 3.776 (2)–3.821 Å (av. 3.797 Å) in the triclinic form. The thermal parameters of the Cp* rings are normal, but were high in the triclinic form; this and the above-mentioned bond lengthening effects (presumably attributable to reduced libration) may be a result of the lower measurement temperature of the current structure.
For related literature, see: Allen (2002); Fagan et al. (1990).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 30% probability levels. Symmetry operators are those of Table 1. |
[Ru4(C10H15)4Cl4] | Dx = 1.655 Mg m−3 |
Mr = 1086.96 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 5126 reflections |
a = 12.0733 (8) Å | θ = 2–30° |
c = 14.9611 (15) Å | µ = 1.63 mm−1 |
V = 2180.8 (3) Å3 | T = 133 K |
Z = 2 | Tablet, dark red |
F(000) = 1088 | 0.30 × 0.22 × 0.20 mm |
Bruker SMART 1000 CCD diffractometer | 3314 independent reflections |
Radiation source: fine-focus sealed tube | 3068 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 8.192 pixels mm-1 | θmax = 30.5°, θmin = 2.2° |
ω and φ scans | h = −16→17 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −16→17 |
Tmin = 0.530, Tmax = 0.736 | l = −21→21 |
13332 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0202P)2 + 1.4509P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.003 |
3314 reflections | Δρmax = 0.84 e Å−3 |
115 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1573 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.43 (3) |
[Ru4(C10H15)4Cl4] | Z = 2 |
Mr = 1086.96 | Mo Kα radiation |
Tetragonal, I4 | µ = 1.63 mm−1 |
a = 12.0733 (8) Å | T = 133 K |
c = 14.9611 (15) Å | 0.30 × 0.22 × 0.20 mm |
V = 2180.8 (3) Å3 |
Bruker SMART 1000 CCD diffractometer | 3314 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 3068 reflections with I > 2σ(I) |
Tmin = 0.530, Tmax = 0.736 | Rint = 0.034 |
13332 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.049 | Δρmax = 0.84 e Å−3 |
S = 1.07 | Δρmin = −0.33 e Å−3 |
3314 reflections | Absolute structure: Flack (1983), 1573 Friedel pairs |
115 parameters | Absolute structure parameter: 0.43 (3) |
0 restraints |
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 | 0.418223 (15) | 0.864161 (15) | 0.661262 (12) | 0.01407 (5) | |
C1 | 0.4531 (2) | 0.7131 (2) | 0.59544 (18) | 0.0208 (5) | |
C2 | 0.4159 (2) | 0.7947 (2) | 0.53127 (18) | 0.0231 (5) | |
C3 | 0.3056 (2) | 0.8280 (2) | 0.55638 (18) | 0.0223 (5) | |
C4 | 0.2743 (2) | 0.7683 (2) | 0.63523 (18) | 0.0220 (5) | |
C5 | 0.3659 (2) | 0.69705 (19) | 0.6597 (2) | 0.0205 (5) | |
C6 | 0.5628 (3) | 0.6547 (3) | 0.5945 (2) | 0.0344 (7) | |
H6A | 0.5772 | 0.6228 | 0.6535 | 0.041* | |
H6B | 0.6214 | 0.7077 | 0.5795 | 0.041* | |
H6C | 0.5613 | 0.5955 | 0.5496 | 0.041* | |
C7 | 0.4806 (3) | 0.8323 (3) | 0.4508 (2) | 0.0405 (8) | |
H7A | 0.4730 | 0.7775 | 0.4029 | 0.049* | |
H7B | 0.5589 | 0.8400 | 0.4669 | 0.049* | |
H7C | 0.4519 | 0.9039 | 0.4303 | 0.049* | |
C8 | 0.2339 (3) | 0.9097 (3) | 0.5071 (2) | 0.0447 (9) | |
H8A | 0.1893 | 0.8705 | 0.4624 | 0.054* | |
H8B | 0.2809 | 0.9645 | 0.4771 | 0.054* | |
H8C | 0.1849 | 0.9473 | 0.5495 | 0.054* | |
C9 | 0.1638 (2) | 0.7708 (3) | 0.6811 (2) | 0.0391 (8) | |
H9A | 0.1291 | 0.8433 | 0.6718 | 0.047* | |
H9B | 0.1739 | 0.7579 | 0.7452 | 0.047* | |
H9C | 0.1161 | 0.7128 | 0.6561 | 0.047* | |
C10 | 0.3684 (3) | 0.6195 (2) | 0.7381 (2) | 0.0333 (7) | |
H10A | 0.3344 | 0.5488 | 0.7212 | 0.040* | |
H10B | 0.3270 | 0.6521 | 0.7879 | 0.040* | |
H10C | 0.4453 | 0.6069 | 0.7564 | 0.040* | |
Cl | 0.38208 (4) | 1.06982 (5) | 0.67020 (3) | 0.01539 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru | 0.01418 (10) | 0.01413 (9) | 0.01390 (7) | −0.00059 (7) | −0.00012 (8) | −0.00179 (8) |
C1 | 0.0205 (13) | 0.0188 (13) | 0.0230 (13) | 0.0005 (10) | 0.0001 (10) | −0.0097 (10) |
C2 | 0.0288 (14) | 0.0238 (14) | 0.0166 (11) | −0.0085 (11) | 0.0025 (10) | −0.0060 (10) |
C3 | 0.0248 (14) | 0.0214 (13) | 0.0208 (12) | −0.0013 (10) | −0.0061 (10) | −0.0066 (10) |
C4 | 0.0173 (12) | 0.0229 (13) | 0.0258 (13) | −0.0043 (9) | 0.0012 (9) | −0.0082 (10) |
C5 | 0.0264 (12) | 0.0163 (11) | 0.0188 (11) | −0.0017 (8) | −0.0010 (11) | −0.0056 (11) |
C6 | 0.0236 (15) | 0.0338 (17) | 0.0459 (19) | 0.0055 (12) | −0.0031 (13) | −0.0193 (14) |
C7 | 0.060 (2) | 0.0366 (18) | 0.0250 (16) | −0.0154 (16) | 0.0137 (15) | −0.0080 (13) |
C8 | 0.052 (2) | 0.0400 (19) | 0.0420 (19) | 0.0067 (16) | −0.0282 (17) | −0.0007 (16) |
C9 | 0.0246 (15) | 0.0455 (19) | 0.047 (2) | −0.0093 (13) | 0.0071 (13) | −0.0194 (15) |
C10 | 0.054 (2) | 0.0184 (14) | 0.0277 (15) | −0.0075 (12) | −0.0030 (14) | 0.0014 (11) |
Cl | 0.0146 (2) | 0.0162 (2) | 0.0154 (2) | 0.00040 (17) | 0.0002 (2) | 0.0005 (2) |
Ru—C1 | 2.115 (3) | Cl—Ruiii | 2.5349 (6) |
Ru—C2 | 2.118 (3) | Cl—Ruii | 2.5428 (6) |
Ru—C3 | 2.122 (3) | C6—H6A | 0.9800 |
Ru—C4 | 2.124 (3) | C6—H6B | 0.9800 |
Ru—C5 | 2.114 (2) | C6—H6C | 0.9800 |
Ru—Cl | 2.5245 (6) | C7—H7A | 0.9800 |
Ru—Cli | 2.5350 (6) | C7—H7B | 0.9800 |
Ru—Clii | 2.5427 (6) | C7—H7C | 0.9800 |
C1—C5 | 1.439 (4) | C8—H8A | 0.9800 |
C1—C2 | 1.447 (4) | C8—H8B | 0.9800 |
C1—C6 | 1.500 (4) | C8—H8C | 0.9800 |
C2—C3 | 1.440 (4) | C9—H9A | 0.9800 |
C2—C7 | 1.504 (4) | C9—H9B | 0.9800 |
C3—C4 | 1.433 (4) | C9—H9C | 0.9800 |
C3—C8 | 1.506 (4) | C10—H10A | 0.9800 |
C4—C5 | 1.448 (4) | C10—H10B | 0.9800 |
C4—C9 | 1.500 (4) | C10—H10C | 0.9800 |
C5—C10 | 1.502 (4) | ||
C5—Ru—C1 | 39.77 (10) | C3—C4—C5 | 107.7 (2) |
C5—Ru—C2 | 66.93 (11) | C3—C4—C9 | 127.0 (3) |
C1—Ru—C2 | 39.99 (11) | C5—C4—C9 | 125.1 (3) |
C5—Ru—C3 | 66.64 (10) | C3—C4—Ru | 70.17 (15) |
C1—Ru—C3 | 66.76 (11) | C5—C4—Ru | 69.66 (14) |
C2—Ru—C3 | 39.73 (11) | C9—C4—Ru | 129.3 (2) |
C5—Ru—C4 | 39.95 (10) | C1—C5—C4 | 108.1 (2) |
C1—Ru—C4 | 66.90 (10) | C1—C5—C10 | 126.2 (3) |
C2—Ru—C4 | 66.75 (10) | C4—C5—C10 | 125.7 (3) |
C3—Ru—C4 | 39.45 (11) | C1—C5—Ru | 70.13 (14) |
C5—Ru—Cl | 152.55 (7) | C4—C5—Ru | 70.39 (14) |
C1—Ru—Cl | 155.12 (8) | C10—C5—Ru | 125.47 (19) |
C2—Ru—Cl | 115.82 (8) | Ru—Cl—Ruiii | 97.092 (19) |
C3—Ru—Cl | 97.53 (7) | Ru—Cl—Ruii | 98.145 (18) |
C4—Ru—Cl | 113.84 (8) | Ruiii—Cl—Ruii | 96.627 (19) |
C5—Ru—Cli | 96.30 (8) | C1—C6—H6A | 109.5 |
C1—Ru—Cli | 121.70 (8) | C1—C6—H6B | 109.5 |
C2—Ru—Cli | 161.43 (8) | H6A—C6—H6B | 109.5 |
C3—Ru—Cli | 142.17 (8) | C1—C6—H6C | 109.5 |
C4—Ru—Cli | 105.99 (7) | H6A—C6—H6C | 109.5 |
Cl—Ru—Cli | 82.715 (19) | H6B—C6—H6C | 109.5 |
C5—Ru—Clii | 125.67 (7) | C2—C7—H7A | 109.5 |
C1—Ru—Clii | 96.09 (8) | C2—C7—H7B | 109.5 |
C2—Ru—Clii | 100.65 (7) | H7A—C7—H7B | 109.5 |
C3—Ru—Clii | 135.31 (8) | C2—C7—H7C | 109.5 |
C4—Ru—Clii | 162.99 (7) | H7A—C7—H7C | 109.5 |
Cl—Ru—Clii | 81.533 (18) | H7B—C7—H7C | 109.5 |
Cli—Ru—Clii | 82.354 (19) | C3—C8—H8A | 109.5 |
C5—C1—C2 | 107.9 (2) | C3—C8—H8B | 109.5 |
C5—C1—C6 | 126.1 (3) | H8A—C8—H8B | 109.5 |
C2—C1—C6 | 126.0 (3) | C3—C8—H8C | 109.5 |
C5—C1—Ru | 70.10 (13) | H8A—C8—H8C | 109.5 |
C2—C1—Ru | 70.12 (15) | H8B—C8—H8C | 109.5 |
C6—C1—Ru | 125.85 (19) | C4—C9—H9A | 109.5 |
C3—C2—C1 | 107.6 (2) | C4—C9—H9B | 109.5 |
C3—C2—C7 | 127.2 (3) | H9A—C9—H9B | 109.5 |
C1—C2—C7 | 125.1 (3) | C4—C9—H9C | 109.5 |
C3—C2—Ru | 70.27 (15) | H9A—C9—H9C | 109.5 |
C1—C2—Ru | 69.89 (14) | H9B—C9—H9C | 109.5 |
C7—C2—Ru | 127.5 (2) | C5—C10—H10A | 109.5 |
C4—C3—C2 | 108.6 (2) | C5—C10—H10B | 109.5 |
C4—C3—C8 | 125.5 (3) | H10A—C10—H10B | 109.5 |
C2—C3—C8 | 125.9 (3) | C5—C10—H10C | 109.5 |
C4—C3—Ru | 70.37 (15) | H10A—C10—H10C | 109.5 |
C2—C3—Ru | 70.00 (15) | H10B—C10—H10C | 109.5 |
C8—C3—Ru | 126.5 (2) | ||
C2—Ru—C1—C5 | −118.6 (2) | Ru—C3—C4—C5 | −59.79 (17) |
C3—Ru—C1—C5 | −80.87 (17) | C2—C3—C4—C9 | −175.4 (3) |
C4—Ru—C1—C5 | −37.79 (16) | C8—C3—C4—C9 | 3.3 (4) |
Cl—Ru—C1—C5 | −134.95 (17) | Ru—C3—C4—C9 | 124.8 (3) |
Cli—Ru—C1—C5 | 57.29 (17) | C2—C3—C4—Ru | 59.79 (18) |
Clii—Ru—C1—C5 | 142.05 (14) | C8—C3—C4—Ru | −121.5 (3) |
C5—Ru—C1—C2 | 118.6 (2) | C5—Ru—C4—C3 | −118.6 (2) |
C3—Ru—C1—C2 | 37.76 (16) | C1—Ru—C4—C3 | −80.99 (17) |
C4—Ru—C1—C2 | 80.84 (17) | C2—Ru—C4—C3 | −37.32 (15) |
Cl—Ru—C1—C2 | −16.3 (3) | Cl—Ru—C4—C3 | 71.86 (15) |
Cli—Ru—C1—C2 | 175.93 (12) | Cli—Ru—C4—C3 | 160.85 (13) |
Clii—Ru—C1—C2 | −99.32 (14) | Clii—Ru—C4—C3 | −81.5 (3) |
C5—Ru—C1—C6 | −120.8 (3) | C1—Ru—C4—C5 | 37.62 (16) |
C2—Ru—C1—C6 | 120.6 (3) | C2—Ru—C4—C5 | 81.29 (17) |
C3—Ru—C1—C6 | 158.4 (3) | C3—Ru—C4—C5 | 118.6 (2) |
C4—Ru—C1—C6 | −158.6 (3) | Cl—Ru—C4—C5 | −169.53 (13) |
Cl—Ru—C1—C6 | 104.3 (3) | Cli—Ru—C4—C5 | −80.54 (15) |
Cli—Ru—C1—C6 | −63.5 (3) | Clii—Ru—C4—C5 | 37.1 (4) |
Clii—Ru—C1—C6 | 21.3 (3) | C5—Ru—C4—C9 | 119.3 (4) |
C5—C1—C2—C3 | −0.3 (3) | C1—Ru—C4—C9 | 157.0 (3) |
C6—C1—C2—C3 | 179.1 (2) | C2—Ru—C4—C9 | −159.4 (3) |
Ru—C1—C2—C3 | −60.42 (18) | C3—Ru—C4—C9 | −122.1 (3) |
C5—C1—C2—C7 | −177.5 (3) | Cl—Ru—C4—C9 | −50.2 (3) |
C6—C1—C2—C7 | 1.9 (4) | Cli—Ru—C4—C9 | 38.8 (3) |
Ru—C1—C2—C7 | 122.3 (3) | Clii—Ru—C4—C9 | 156.4 (2) |
C5—C1—C2—Ru | 60.17 (17) | C2—C1—C5—C4 | 0.3 (3) |
C6—C1—C2—Ru | −120.5 (3) | C6—C1—C5—C4 | −179.1 (2) |
C5—Ru—C2—C3 | 80.69 (16) | Ru—C1—C5—C4 | 60.43 (17) |
C1—Ru—C2—C3 | 118.3 (2) | C2—C1—C5—C10 | 179.8 (2) |
C4—Ru—C2—C3 | 37.07 (16) | C6—C1—C5—C10 | 0.4 (4) |
Cl—Ru—C2—C3 | −69.24 (15) | Ru—C1—C5—C10 | −120.0 (3) |
Cli—Ru—C2—C3 | 107.4 (2) | C2—C1—C5—Ru | −60.18 (17) |
Clii—Ru—C2—C3 | −154.91 (14) | C6—C1—C5—Ru | 120.5 (3) |
C5—Ru—C2—C1 | −37.61 (15) | C3—C4—C5—C1 | −0.2 (3) |
C3—Ru—C2—C1 | −118.3 (2) | C9—C4—C5—C1 | 175.4 (2) |
C4—Ru—C2—C1 | −81.24 (17) | Ru—C4—C5—C1 | −60.27 (17) |
Cl—Ru—C2—C1 | 172.45 (13) | C3—C4—C5—C10 | −179.7 (2) |
Cli—Ru—C2—C1 | −10.9 (3) | C9—C4—C5—C10 | −4.2 (4) |
Clii—Ru—C2—C1 | 86.78 (15) | Ru—C4—C5—C10 | 120.2 (3) |
C5—Ru—C2—C7 | −157.0 (3) | C3—C4—C5—Ru | 60.12 (18) |
C1—Ru—C2—C7 | −119.4 (4) | C9—C4—C5—Ru | −124.4 (3) |
C3—Ru—C2—C7 | 122.3 (3) | C2—Ru—C5—C1 | 37.81 (16) |
C4—Ru—C2—C7 | 159.3 (3) | C3—Ru—C5—C1 | 81.21 (18) |
Cl—Ru—C2—C7 | 53.0 (3) | C4—Ru—C5—C1 | 118.6 (2) |
Cli—Ru—C2—C7 | −130.4 (3) | Cl—Ru—C5—C1 | 139.76 (16) |
Clii—Ru—C2—C7 | −32.6 (3) | Cli—Ru—C5—C1 | −133.92 (15) |
C1—C2—C3—C4 | 0.2 (3) | Clii—Ru—C5—C1 | −48.83 (18) |
C7—C2—C3—C4 | 177.3 (3) | C1—Ru—C5—C4 | −118.6 (2) |
Ru—C2—C3—C4 | −60.02 (18) | C2—Ru—C5—C4 | −80.82 (17) |
C1—C2—C3—C8 | −178.6 (3) | C3—Ru—C5—C4 | −37.42 (16) |
C7—C2—C3—C8 | −1.4 (5) | Cl—Ru—C5—C4 | 21.1 (3) |
Ru—C2—C3—C8 | 121.3 (3) | Cli—Ru—C5—C4 | 107.45 (15) |
C1—C2—C3—Ru | 60.18 (18) | Clii—Ru—C5—C4 | −167.46 (12) |
C7—C2—C3—Ru | −122.6 (3) | C1—Ru—C5—C10 | 121.0 (3) |
C5—Ru—C3—C4 | 37.88 (15) | C2—Ru—C5—C10 | 158.8 (3) |
C1—Ru—C3—C4 | 81.36 (17) | C3—Ru—C5—C10 | −157.8 (3) |
C2—Ru—C3—C4 | 119.4 (2) | C4—Ru—C5—C10 | −120.4 (3) |
Cl—Ru—C3—C4 | −118.75 (14) | Cl—Ru—C5—C10 | −99.3 (3) |
Cli—Ru—C3—C4 | −30.9 (2) | Cli—Ru—C5—C10 | −13.0 (2) |
Clii—Ru—C3—C4 | 155.70 (12) | Clii—Ru—C5—C10 | 72.1 (3) |
C5—Ru—C3—C2 | −81.48 (16) | C5—Ru—Cl—Ruiii | 81.26 (18) |
C1—Ru—C3—C2 | −38.00 (16) | C1—Ru—Cl—Ruiii | −177.91 (18) |
C4—Ru—C3—C2 | −119.4 (2) | C2—Ru—Cl—Ruiii | 170.52 (8) |
Cl—Ru—C3—C2 | 121.89 (14) | C3—Ru—Cl—Ruiii | 133.45 (8) |
Cli—Ru—C3—C2 | −150.30 (13) | C4—Ru—Cl—Ruiii | 95.92 (8) |
Clii—Ru—C3—C2 | 36.34 (19) | Cli—Ru—Cl—Ruiii | −8.388 (18) |
C5—Ru—C3—C8 | 158.1 (3) | Clii—Ru—Cl—Ruiii | −91.693 (16) |
C1—Ru—C3—C8 | −158.4 (3) | C5—Ru—Cl—Ruii | 179.04 (17) |
C2—Ru—C3—C8 | −120.4 (4) | C1—Ru—Cl—Ruii | −80.13 (18) |
C4—Ru—C3—C8 | 120.2 (3) | C2—Ru—Cl—Ruii | −91.70 (8) |
Cl—Ru—C3—C8 | 1.5 (3) | C3—Ru—Cl—Ruii | −128.78 (8) |
Cli—Ru—C3—C8 | 89.3 (3) | C4—Ru—Cl—Ruii | −166.30 (8) |
Clii—Ru—C3—C8 | −84.1 (3) | Cli—Ru—Cl—Ruii | 89.387 (18) |
C2—C3—C4—C5 | 0.0 (3) | Clii—Ru—Cl—Ruii | 6.08 (2) |
C8—C3—C4—C5 | 178.7 (3) |
Symmetry codes: (i) −y+3/2, x+1/2, −z+3/2; (ii) −x+1, −y+2, z; (iii) y−1/2, −x+3/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ru4(C10H15)4Cl4] |
Mr | 1086.96 |
Crystal system, space group | Tetragonal, I4 |
Temperature (K) | 133 |
a, c (Å) | 12.0733 (8), 14.9611 (15) |
V (Å3) | 2180.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.63 |
Crystal size (mm) | 0.30 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.530, 0.736 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13332, 3314, 3068 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.049, 1.07 |
No. of reflections | 3314 |
No. of parameters | 115 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.84, −0.33 |
Absolute structure | Flack (1983), 1573 Friedel pairs |
Absolute structure parameter | 0.43 (3) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Ru—C1 | 2.115 (3) | Ru—C5 | 2.114 (2) |
Ru—C2 | 2.118 (3) | Ru—Cl | 2.5245 (6) |
Ru—C3 | 2.122 (3) | Ru—Cli | 2.5350 (6) |
Ru—C4 | 2.124 (3) | Ru—Clii | 2.5427 (6) |
Cl—Ru—Cli | 82.715 (19) | Ru—Cl—Ruiii | 97.092 (19) |
Cl—Ru—Clii | 81.533 (18) | Ru—Cl—Ruii | 98.145 (18) |
Cli—Ru—Clii | 82.354 (19) | Ruiii—Cl—Ruii | 96.627 (19) |
Symmetry codes: (i) −y+3/2, x+1/2, −z+3/2; (ii) −x+1, −y+2, z; (iii) y−1/2, −x+3/2, −z+3/2. |
Fagan et al. (1990) reported two polymorphs of the title complex (I) [Cp*Ru(µ3-Cl)]4. At 201 K the crystal is triclinic with space group P1 (a = 11.281 (5), b = 11.354 (4), c = 18.846 (5) Å, α = 82.20 (2)°, β = 82.03 (3)°, γ = 65.45 (4) °; V = 2166.3 Å3) whereas at room temperature it adopts a monoclinic cell (a = 19.040; b = 12.240; c = 18.850 Å; β = 99.38°; V = 4334.2 Å3). Only the structure of the triclinic form was solved and refined; its Cambridge refcode (Allen, 2002) is JERTIJ.
Here we report the structure of a new, tetragonal polymorph of (I), which crystallizes in space group I4 (a = b = 12.0733 (8), c = 14.9611 (15) Å; V = 2180.8 (3) Å3). It is noteworthy that the new form has a significantly larger cell volume then the triclinic form despite the lower temperature. The tetrameric complex possesses imposed 4 symmetry (Fig. 1) and consists, as does the triclinic form, of a distorted cubic array of four Ru and Cl atoms, with angles at ruthenium ca 82° and angles at chlorine ca 97°. Each Ru atom in the complex adopts an 18-electron configuration in a pseudooctahedral environment. The C5Me5 ligand coordinates in η5 fashion to the Ru atom with a Cp* (centroid)—Ru distance of 1.727 Å, which is slightly longer than the average Cp*—Ru distance (1.720 Å) reported by Fagan et al. The C2—centroid vector eclipses the bond Ru···Cl (torsion angle 2.1°). The structure of the complex is closely similar to that of the triclinic form; a least-squares fit of the Ru4Cl4 core for one of the many possible atom permutations gave a r.m.s. deviation of 0.019 Å. In detail, the Ru—Cl bond lengths (av. 2.534 Å) are also slightly longer than in the triclinic form (av. 2.524 Å). The Ru···Ru distances are 3.8286 (4) to Ruii, 3.7920 (4) Å to Rui and Ruiii, cf. 3.776 (2)–3.821 Å (av. 3.797 Å) in the triclinic form. The thermal parameters of the Cp* rings are normal, but were high in the triclinic form; this and the above-mentioned bond lengthening effects (presumably attributable to reduced libration) may be a result of the lower measurement temperature of the current structure.