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
Key indicators
- Single-crystal X-ray study
- T = 133 K
- Mean (C-C) = 0.004 Å
- R factor = 0.024
- wR factor = 0.049
- Data-to-parameter ratio = 28.8
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.530 0.736 Tmin(prime) and Tmax expected: 0.607 0.722 RR(prime) = 0.856 Please check that your absorption correction is appropriate. STRVA01_ALERT_4_C Flack test results are ambiguous. From the CIF: _refine_ls_abs_structure_Flack 0.430 From the CIF: _refine_ls_abs_structure_Flack_su 0.030 PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.84 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.57 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru - Cl .. 9.58 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru - Cl_a .. 6.04 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru - Cl_c .. 9.18 su PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 54.00 A 3 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.11 Ratio
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 30.52 From the CIF: _reflns_number_total 3314 Count of symmetry unique reflns 1741 Completeness (_total/calc) 190.35% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1573 Fraction of Friedel pairs measured 0.904 Are heavy atom types Z>Si present yes PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero. 0.43
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.