Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004732/lh6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004732/lh6042Isup2.hkl |
CCDC reference: 209881
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.024
- wR factor = 0.062
- Data-to-parameter ratio = 25.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.71 From the CIF: _reflns_number_total 5254 Count of symmetry unique reflns 3183 Completeness (_total/calc) 165.06% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2071 Fraction of Friedel pairs measured 0.651 Are heavy atom types Z>Si present yes 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.
Compound (I) was prepared according to a reported procedure (Archer et al., 1991) and crystals were grown by a slow diffusion, over several days, of a threefold excess of hexane into a concentrated solution of (I) in dichloromethane held at 263 K.
H atoms were placed in calculated positions, with C—H = 0.99 and 0.95 Å for methylene and cyclopentadienyl H atoms, respectively. All H atoms were refined with a riding model, with Uiso = 1.2Ueq of the C atom to which they are attached. The extent of disorder of Fe and Ru was established by refinement of a free variable occupancy factor, x [final refined value 0.7592 (17)], for sites of the form Fex/Ru1 - x and Rux/Fe1 - x with SHELXL97 EXYZ and EADP instructions rigorously enforcing identical atomic coordinates and displacement parameters for both atoms in the site.
Data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
[RuFe(C3H6)(C5H5)2(CO)4] | F(000) = 880 |
Mr = 441.22 | Dx = 1.772 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 15516 reflections |
a = 6.834 (3) Å | θ = 4.1–31.7° |
b = 11.358 (4) Å | µ = 1.81 mm−1 |
c = 21.303 (9) Å | T = 100 K |
V = 1653.6 (12) Å3 | Plate, yellow |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Oxford Diffraction Xcalibur 2 CCD area-detector diffractometer | 5017 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 31.7°, θmin = 4.1° |
ω–2θ scans | h = −9→10 |
15516 measured reflections | k = 0→16 |
5254 independent reflections | l = 0→30 |
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)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0308P)2 + 0.3168P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.002 |
5254 reflections | Δρmax = 0.54 e Å−3 |
209 parameters | Δρmin = −0.81 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2204 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.040 (18) |
[RuFe(C3H6)(C5H5)2(CO)4] | V = 1653.6 (12) Å3 |
Mr = 441.22 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.834 (3) Å | µ = 1.81 mm−1 |
b = 11.358 (4) Å | T = 100 K |
c = 21.303 (9) Å | 0.40 × 0.20 × 0.20 mm |
Oxford Diffraction Xcalibur 2 CCD area-detector diffractometer | 5017 reflections with I > 2σ(I) |
15516 measured reflections | Rint = 0.053 |
5254 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.062 | Δρmax = 0.54 e Å−3 |
S = 1.11 | Δρmin = −0.81 e Å−3 |
5254 reflections | Absolute structure: Flack (1983), 2204 Friedel pairs |
209 parameters | Absolute structure parameter: 0.040 (18) |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 5.6450 (0.0049) x - 4.7849 (0.0115) y + 7.9775 (0.0225) z = 6.8563 (0.0087) * -0.0049 (0.0013) C1_a * 0.0022 (0.0014) C2_a * 0.0014 (0.0014) C3_a * -0.0044 (0.0014) C4_a * 0.0058 (0.0013) C5_a -1.7881 (0.0013) Fe1_a Rms deviation of fitted atoms = 0.0041 6.6465 (0.0035) x + 0.1866 (0.0143) y + 4.9431 (0.0256) z = 6.8644 (0.0099) Angle to previous plane (with approximate e.s.d.) = 27.95 (0.10) * 0.0065 (0.0014) C1A_a * 0.0004 (0.0016) C2A_a * -0.0074 (0.0016) C3A_a * 0.0115 (0.0016) C4A_a * -0.0110 (0.0015) C5A_a -1.8805 (0.0013) Ru1_a Rms deviation of fitted atoms = 0.0084 |
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) | |
Fe1 | 0.21839 (3) | −0.13426 (2) | 0.400252 (10) | 0.01211 (8) | 0.7592 (17) |
Ru1A | 0.21839 (3) | −0.13426 (2) | 0.400252 (10) | 0.01211 (8) | 0.2408 (17) |
C1 | 0.4699 (3) | −0.11100 (18) | 0.45976 (9) | 0.0173 (4) | |
H1 | 0.4961 | −0.0405 | 0.4822 | 0.021* | |
C2 | 0.3566 (3) | −0.20921 (19) | 0.48189 (10) | 0.0179 (4) | |
H2 | 0.2957 | −0.2155 | 0.5218 | 0.021* | |
C3 | 0.3520 (3) | −0.29428 (19) | 0.43401 (11) | 0.0196 (4) | |
H3 | 0.2871 | −0.3681 | 0.4360 | 0.023* | |
C4 | 0.4614 (3) | −0.25101 (19) | 0.38186 (10) | 0.0206 (4) | |
H4 | 0.4811 | −0.2906 | 0.3431 | 0.025* | |
C5 | 0.5355 (3) | −0.13848 (19) | 0.39818 (10) | 0.0185 (4) | |
H5 | 0.6152 | −0.0899 | 0.3724 | 0.022* | |
C6 | 0.0415 (3) | −0.04504 (19) | 0.43712 (9) | 0.0178 (4) | |
O1 | −0.0754 (3) | 0.01541 (16) | 0.45860 (8) | 0.0268 (4) | |
C7 | 0.0424 (3) | −0.20557 (19) | 0.35258 (10) | 0.0195 (4) | |
O2 | −0.0727 (3) | −0.25321 (16) | 0.32244 (9) | 0.0285 (4) | |
C8 | 0.2395 (3) | 0.00338 (18) | 0.33556 (9) | 0.0152 (4) | |
H8A | 0.3261 | −0.0214 | 0.3007 | 0.018* | |
H8B | 0.1083 | 0.0189 | 0.3177 | 0.018* | |
C9 | 0.3194 (3) | 0.11766 (19) | 0.36395 (9) | 0.0161 (4) | |
H9A | 0.2270 | 0.1473 | 0.3961 | 0.019* | |
H9B | 0.4461 | 0.1016 | 0.3848 | 0.019* | |
Ru1 | 0.48086 (2) | 0.369182 (15) | 0.347747 (8) | 0.01301 (6) | 0.7592 (17) |
Fe1A | 0.48086 (2) | 0.369182 (15) | 0.347747 (8) | 0.01301 (6) | 0.2408 (17) |
C1A | 0.7669 (3) | 0.46428 (19) | 0.34127 (11) | 0.0216 (4) | |
H1A | 0.7823 | 0.5377 | 0.3205 | 0.026* | |
C2A | 0.7190 (4) | 0.4481 (2) | 0.40503 (12) | 0.0261 (5) | |
H2A | 0.6954 | 0.5088 | 0.4348 | 0.031* | |
C3A | 0.7123 (4) | 0.3247 (3) | 0.41716 (11) | 0.0265 (5) | |
H3A | 0.6820 | 0.2888 | 0.4562 | 0.032* | |
C4A | 0.7584 (3) | 0.2657 (2) | 0.36119 (11) | 0.0220 (5) | |
H4A | 0.7681 | 0.1828 | 0.3562 | 0.026* | |
C5A | 0.7882 (3) | 0.3505 (2) | 0.31342 (10) | 0.0213 (4) | |
H5A | 0.8170 | 0.3347 | 0.2706 | 0.026* | |
C6A | 0.2762 (3) | 0.38190 (19) | 0.40304 (10) | 0.0193 (4) | |
O1A | 0.1544 (2) | 0.38925 (17) | 0.43959 (8) | 0.0281 (4) | |
C7A | 0.3455 (4) | 0.4477 (2) | 0.28598 (11) | 0.0222 (4) | |
O2A | 0.2614 (3) | 0.49664 (18) | 0.24772 (9) | 0.0331 (4) | |
C8A | 0.3480 (3) | 0.21119 (19) | 0.31342 (9) | 0.0160 (4) | |
H8C | 0.2191 | 0.2309 | 0.2950 | 0.019* | |
H8D | 0.4308 | 0.1782 | 0.2796 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01250 (12) | 0.01073 (11) | 0.01309 (11) | −0.00212 (9) | −0.00027 (7) | −0.00059 (9) |
Ru1A | 0.01250 (12) | 0.01073 (11) | 0.01309 (11) | −0.00212 (9) | −0.00027 (7) | −0.00059 (9) |
C1 | 0.0157 (8) | 0.0151 (9) | 0.0209 (9) | −0.0001 (7) | −0.0043 (7) | 0.0002 (7) |
C2 | 0.0186 (10) | 0.0170 (9) | 0.0182 (9) | 0.0011 (8) | −0.0025 (7) | 0.0039 (7) |
C3 | 0.0200 (10) | 0.0125 (9) | 0.0262 (11) | 0.0020 (8) | −0.0011 (8) | 0.0014 (7) |
C4 | 0.0186 (10) | 0.0180 (10) | 0.0251 (10) | 0.0041 (8) | 0.0016 (8) | −0.0031 (7) |
C5 | 0.0142 (8) | 0.0181 (9) | 0.0234 (9) | 0.0006 (8) | 0.0002 (7) | 0.0026 (8) |
C6 | 0.0200 (10) | 0.0201 (9) | 0.0133 (8) | −0.0070 (8) | −0.0005 (7) | 0.0011 (7) |
O1 | 0.0274 (9) | 0.0256 (9) | 0.0274 (9) | −0.0011 (7) | 0.0075 (7) | −0.0026 (7) |
C7 | 0.0253 (10) | 0.0163 (9) | 0.0169 (9) | −0.0042 (8) | 0.0046 (8) | 0.0001 (7) |
O2 | 0.0317 (10) | 0.0266 (9) | 0.0273 (8) | −0.0121 (7) | −0.0028 (7) | −0.0035 (7) |
C8 | 0.0174 (9) | 0.0136 (8) | 0.0147 (9) | −0.0036 (7) | −0.0010 (7) | −0.0009 (6) |
C9 | 0.0197 (9) | 0.0148 (9) | 0.0138 (8) | −0.0032 (8) | −0.0007 (6) | 0.0008 (7) |
Ru1 | 0.01264 (8) | 0.01049 (8) | 0.01590 (8) | −0.00021 (6) | −0.00059 (6) | 0.00026 (6) |
Fe1A | 0.01264 (8) | 0.01049 (8) | 0.01590 (8) | −0.00021 (6) | −0.00059 (6) | 0.00026 (6) |
C1A | 0.0181 (10) | 0.0178 (9) | 0.0289 (11) | −0.0041 (8) | −0.0008 (9) | 0.0041 (8) |
C2A | 0.0213 (11) | 0.0300 (12) | 0.0270 (11) | −0.0024 (9) | −0.0034 (10) | −0.0083 (10) |
C3A | 0.0182 (11) | 0.0415 (14) | 0.0198 (10) | −0.0029 (10) | −0.0020 (8) | 0.0096 (9) |
C4A | 0.0145 (10) | 0.0195 (10) | 0.0320 (12) | 0.0019 (8) | −0.0008 (9) | 0.0046 (8) |
C5A | 0.0187 (10) | 0.0233 (11) | 0.0220 (10) | −0.0002 (8) | 0.0039 (8) | 0.0024 (8) |
C6A | 0.0188 (9) | 0.0166 (10) | 0.0225 (9) | −0.0012 (8) | −0.0057 (8) | −0.0052 (8) |
O1A | 0.0189 (8) | 0.0347 (10) | 0.0309 (9) | −0.0005 (7) | 0.0023 (6) | −0.0119 (7) |
C7A | 0.0236 (11) | 0.0170 (10) | 0.0260 (11) | −0.0050 (8) | 0.0001 (9) | 0.0022 (8) |
O2A | 0.0327 (10) | 0.0279 (9) | 0.0385 (10) | 0.0013 (8) | −0.0051 (8) | 0.0125 (8) |
C8A | 0.0186 (10) | 0.0142 (9) | 0.0152 (9) | 0.0003 (7) | −0.0020 (7) | 0.0005 (7) |
Fe1—C6 | 1.762 (2) | C9—H9A | 0.9900 |
Fe1—C7 | 1.770 (2) | C9—H9B | 0.9900 |
Fe1—C8 | 2.089 (2) | Ru1—C6A | 1.834 (2) |
Fe1—C1 | 2.152 (2) | Ru1—C7A | 1.839 (2) |
Fe1—C2 | 2.154 (2) | Ru1—C8A | 2.140 (2) |
Fe1—C3 | 2.157 (2) | Ru1—C2A | 2.223 (2) |
Fe1—C4 | 2.161 (2) | Ru1—C3A | 2.223 (3) |
Fe1—C5 | 2.168 (2) | Ru1—C5A | 2.234 (2) |
C1—C5 | 1.421 (3) | Ru1—C1A | 2.238 (2) |
C1—C2 | 1.437 (3) | Ru1—C4A | 2.250 (2) |
C1—H1 | 0.9500 | C1A—C2A | 1.409 (3) |
C2—C3 | 1.405 (3) | C1A—C5A | 1.429 (3) |
C2—H2 | 0.9500 | C1A—H1A | 0.9500 |
C3—C4 | 1.426 (3) | C2A—C3A | 1.426 (4) |
C3—H3 | 0.9500 | C2A—H2A | 0.9500 |
C4—C5 | 1.418 (3) | C3A—C4A | 1.404 (4) |
C4—H4 | 0.9500 | C3A—H3A | 0.9500 |
C5—H5 | 0.9500 | C4A—C5A | 1.416 (3) |
C6—O1 | 1.148 (3) | C4A—H4A | 0.9500 |
C7—O2 | 1.151 (3) | C5A—H5A | 0.9500 |
C8—C9 | 1.533 (3) | C6A—O1A | 1.143 (3) |
C8—H8A | 0.9900 | C7A—O2A | 1.142 (3) |
C8—H8B | 0.9900 | C8A—H8C | 0.9900 |
C9—C8A | 1.525 (3) | C8A—H8D | 0.9900 |
C6—Fe1—C7 | 93.02 (11) | C8A—C9—H9B | 109.5 |
C6—Fe1—C8 | 84.90 (9) | C8—C9—H9B | 109.5 |
C7—Fe1—C8 | 90.62 (9) | H9A—C9—H9B | 108.0 |
C6—Fe1—C1 | 102.41 (9) | C6A—Ru1—C7A | 92.17 (11) |
C7—Fe1—C1 | 159.51 (9) | C6A—Ru1—C8A | 87.82 (9) |
C8—Fe1—C1 | 103.98 (8) | C7A—Ru1—C8A | 87.07 (9) |
C6—Fe1—C2 | 99.69 (9) | C6A—Ru1—C2A | 100.02 (10) |
C7—Fe1—C2 | 125.47 (9) | C7A—Ru1—C2A | 124.43 (11) |
C8—Fe1—C2 | 142.93 (8) | C8A—Ru1—C2A | 146.76 (9) |
C1—Fe1—C2 | 38.99 (8) | C6A—Ru1—C3A | 97.65 (10) |
C6—Fe1—C3 | 128.78 (9) | C7A—Ru1—C3A | 160.68 (10) |
C7—Fe1—C3 | 95.36 (10) | C8A—Ru1—C3A | 109.80 (10) |
C8—Fe1—C3 | 145.19 (9) | C2A—Ru1—C3A | 37.40 (10) |
C1—Fe1—C3 | 64.46 (8) | C6A—Ru1—C5A | 159.15 (9) |
C2—Fe1—C3 | 38.04 (8) | C7A—Ru1—C5A | 106.53 (10) |
C6—Fe1—C4 | 163.93 (9) | C8A—Ru1—C5A | 101.98 (9) |
C7—Fe1—C4 | 97.89 (10) | C2A—Ru1—C5A | 61.94 (9) |
C8—Fe1—C4 | 106.64 (9) | C3A—Ru1—C5A | 61.79 (9) |
C1—Fe1—C4 | 64.43 (9) | C6A—Ru1—C1A | 131.89 (9) |
C2—Fe1—C4 | 64.34 (9) | C7A—Ru1—C1A | 99.27 (10) |
C3—Fe1—C4 | 38.57 (9) | C8A—Ru1—C1A | 138.97 (8) |
C6—Fe1—C5 | 135.03 (9) | C2A—Ru1—C1A | 36.83 (9) |
C7—Fe1—C5 | 131.09 (9) | C3A—Ru1—C1A | 61.91 (9) |
C8—Fe1—C5 | 86.21 (8) | C5A—Ru1—C1A | 37.27 (8) |
C1—Fe1—C5 | 38.40 (8) | C6A—Ru1—C4A | 127.03 (9) |
C2—Fe1—C5 | 64.49 (8) | C7A—Ru1—C4A | 140.22 (10) |
C3—Fe1—C5 | 64.21 (9) | C8A—Ru1—C4A | 87.90 (9) |
C4—Fe1—C5 | 38.24 (8) | C2A—Ru1—C4A | 61.53 (10) |
C5—C1—C2 | 107.60 (18) | C3A—Ru1—C4A | 36.57 (9) |
C5—C1—Fe1 | 71.42 (12) | C5A—Ru1—C4A | 36.81 (8) |
C2—C1—Fe1 | 70.60 (12) | C1A—Ru1—C4A | 61.53 (9) |
C5—C1—H1 | 126.2 | C2A—C1A—C5A | 107.8 (2) |
C2—C1—H1 | 126.2 | C2A—C1A—Ru1 | 71.02 (13) |
Fe1—C1—H1 | 123.4 | C5A—C1A—Ru1 | 71.22 (12) |
C3—C2—C1 | 107.92 (19) | C2A—C1A—H1A | 126.1 |
C3—C2—Fe1 | 71.10 (13) | C5A—C1A—H1A | 126.1 |
C1—C2—Fe1 | 70.41 (12) | Ru1—C1A—H1A | 123.3 |
C3—C2—H2 | 126.0 | C1A—C2A—C3A | 108.1 (2) |
C1—C2—H2 | 126.0 | C1A—C2A—Ru1 | 72.15 (13) |
Fe1—C2—H2 | 124.1 | C3A—C2A—Ru1 | 71.31 (14) |
C2—C3—C4 | 108.5 (2) | C1A—C2A—H2A | 126.0 |
C2—C3—Fe1 | 70.86 (12) | C3A—C2A—H2A | 126.0 |
C4—C3—Fe1 | 70.85 (13) | Ru1—C2A—H2A | 122.3 |
C2—C3—H3 | 125.8 | C4A—C3A—C2A | 107.9 (2) |
C4—C3—H3 | 125.8 | C4A—C3A—Ru1 | 72.73 (14) |
Fe1—C3—H3 | 124.1 | C2A—C3A—Ru1 | 71.29 (15) |
C5—C4—C3 | 107.86 (19) | C4A—C3A—H3A | 126.0 |
C5—C4—Fe1 | 71.16 (12) | C2A—C3A—H3A | 126.0 |
C3—C4—Fe1 | 70.58 (13) | Ru1—C3A—H3A | 121.7 |
C5—C4—H4 | 126.1 | C3A—C4A—C5A | 108.5 (2) |
C3—C4—H4 | 126.1 | C3A—C4A—Ru1 | 70.70 (14) |
Fe1—C4—H4 | 123.8 | C5A—C4A—Ru1 | 70.99 (13) |
C4—C5—C1 | 108.15 (18) | C3A—C4A—H4A | 125.7 |
C4—C5—Fe1 | 70.60 (12) | C5A—C4A—H4A | 125.7 |
C1—C5—Fe1 | 70.18 (12) | Ru1—C4A—H4A | 124.2 |
C4—C5—H5 | 125.9 | C4A—C5A—C1A | 107.6 (2) |
C1—C5—H5 | 125.9 | C4A—C5A—Ru1 | 72.19 (13) |
Fe1—C5—H5 | 124.9 | C1A—C5A—Ru1 | 71.51 (13) |
O1—C6—Fe1 | 176.95 (19) | C4A—C5A—H5A | 126.2 |
O2—C7—Fe1 | 178.8 (2) | C1A—C5A—H5A | 126.2 |
C9—C8—Fe1 | 113.45 (12) | Ru1—C5A—H5A | 121.8 |
C9—C8—H8A | 108.9 | O1A—C6A—Ru1 | 177.00 (19) |
Fe1—C8—H8A | 108.9 | O2A—C7A—Ru1 | 179.87 (16) |
C9—C8—H8B | 108.9 | C9—C8A—Ru1 | 113.41 (13) |
Fe1—C8—H8B | 108.9 | C9—C8A—H8C | 108.9 |
H8A—C8—H8B | 107.7 | Ru1—C8A—H8C | 108.9 |
C8A—C9—C8 | 110.91 (16) | C9—C8A—H8D | 108.9 |
C8A—C9—H9A | 109.5 | Ru1—C8A—H8D | 108.9 |
C8—C9—H9A | 109.5 | H8C—C8A—H8D | 107.7 |
Fe1—C8—C9—C8A | 175.08 (14) | C2—C3—C4—C5 | 0.6 (3) |
C6—Fe1—C8—C9 | 65.20 (16) | C3—C4—C5—C1 | −1.0 (2) |
C7—Fe1—C8—C9 | 158.18 (16) | C4—C5—C1—C2 | 1.0 (2) |
Ru1—C8A—C9—C8 | −175.36 (14) | C5A—C1A—C2A—C3A | 0.6 (3) |
C6A—Ru1—C8A—C9 | −58.35 (16) | C1A—C2A—C3A—C4A | 0.8 (3) |
C7A—Ru1—C8A—C9 | −150.64 (17) | C2A—C3A—C4A—C5A | −1.8 (3) |
C5—C1—C2—C3 | −0.7 (2) | C3A—C4A—C5A—C1A | 2.1 (3) |
C1—C2—C3—C4 | 0.1 (3) | C4A—C5A—C1A—C2A | −1.7 (3) |
Experimental details
Crystal data | |
Chemical formula | [RuFe(C3H6)(C5H5)2(CO)4] |
Mr | 441.22 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 6.834 (3), 11.358 (4), 21.303 (9) |
V (Å3) | 1653.6 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.81 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur 2 CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15516, 5254, 5017 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.740 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.062, 1.11 |
No. of reflections | 5254 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.81 |
Absolute structure | Flack (1983), 2204 Friedel pairs |
Absolute structure parameter | 0.040 (18) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2001), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).
Fe1—C8—C9—C8A | 175.08 (14) | Ru1—C8A—C9—C8 | −175.36 (14) |
C6—Fe1—C8—C9 | 65.20 (16) | C6A—Ru1—C8A—C9 | −58.35 (16) |
C7—Fe1—C8—C9 | 158.18 (16) | C7A—Ru1—C8A—C9 | −150.64 (17) |
I | IIb | IIIb | |||
M = Fe1 | M = Ru1 | M = Fe1 | M = Ru1 | M = Ru2 | |
Cg—M | 1.7880 (12) | 1.8805 (13) | 1.737 | 1.936 | 1.942 |
C6—M | 1.762 (2) | 1.834 (2) | 1.738 | 1.860 (8) | 1.868 (8) |
C7—M | 1.770 (2) | 1.839 (2) | 1.753 | 1.871 (9) | 1.888 (8) |
C8—M | 2.089 (2) | 2.140 (2) | 2.0815 | 2.179 (8) | 2.164 (8) |
Cg—M—C6 | 130.33 | 126.71 | 127.2 | 129.6 | 127.3 |
Cg—M—C7 | 125.48 | 130.29 | 127.6 | 128.3 | 129.8 |
Cg—M—C8 | 120.12 | 119.85 | 122.4 | 120.9 | 123.5 |
C6—M—C7 | 93.02 (11) | 92.17 (11) | 92.8 | 90.2 (4) | 89.3 (4) |
C6—M—C8 | 84.90 (9) | 87.82 (9) | 87.2 | 86.1 (3) | 88.2 (3) |
C7—M—C8 | 90.62 (9) | 87.07 (9) | 87.0 | 88.4 (4) | 85.2 (3) |
Notes: (a) atom designations are precisely as for Fe and, neglecting the suffix A, for Ru in (I). Distances and angles involving the cyclopentadienyl ligand are expressed in terms of its centroid, Cg, and mostly lack s.u. values as a consequence. (b) Values calculated (PLATON; Spek, 2003) from CIF data (PRCFEC; Pope et al. 1976), which lacks s.u. values, for (II) and for (III) (JEHVUN; Finch et al. 1989), extracted from the Cambridge Structural Database (Version 24; Allen, 2002), accessed at the Chemical Database Service (Fletcher et al., 1996) of the EPSRC at Daresbury, England. |
C1A—H1A···O2iv | C2—H2···Cgv | |
Type Hydrogen bond | C—H···πa | |
C—H | 0.95 | 0.95 |
H···A | 2.57 | 2.82 |
Hperpb | 2.81 | |
C···A | 3.414 (3) | 3.574 |
C—H···A | 148 | 137 |
γc | 5.6 |
Notes: (a) acceptor A is the centroid of the five membered ring C1 to C5; (b) perpendicular from H2 to the ring plane; (c) angle between H···A and Hperp. Symmetry codes: (iv) 1+x, 1+y, z; (v) x-1/2, -y-1/2, 1-z. |
This structure determination was undertaken in the context of an ongoing study of heterobimetallic compounds (Friedrich & Moss, 1993). The connectivity and atom labelling of the molecule of the title compound, (I), is shown in Fig. 1. The coordination of Fe and Ru in (I) is compared to that in the closely analogous (propane-1,3-diyl)-bis[dicarbonyl(η-5-cyclopentadienyl)iron], (II) (PRCFEC; Pope et al., 1976) and (pentane-1,5-diyl)-bis[dicarbonyl(η-5-cyclopentadienyl)ruthenium], (III) (JEHVUN; Finch et al., 1989) in Table 1. There it is clear that whereas the effectively tetrahedral coordination of the metal atoms is very similar throughout in (I) the bonds to Fe tend to be slightly longer than in (II) and the bonds to Ru somewhat shorter than they are in (III). In a previous structural model where twin refinement, but no other form of disorder, had been introduced a concern, not noted in the checkCIF validation report obtained at that time, was the disparity between the Ueq values for Fe1 and Ru1 of 0.0038 (1) and 0.0168 (1) Å2, respectively. This prompted the rerefinement presented here in which disorder by partial replacement of Ru by Fe and vice versa was introduced and twin refinement abandoned. Precisely this form of disorder is found but in a much more extreme form in the structure of the wholly analogous [dicarbonyl(η5-cyclopentadienyl)iron(II)]-µ21,6-n-hexandiyl- [dicarbonyl(η5-cyclopentadienyl)ruthenium(II)] (Archer et al., 1991). The disordered model has proved to be technically superior on every count, i.e. giving much better R factors, much lower residual electron densities, lower s.u. values and a satisfactory estimate of the Flack x parameter with no indication of the need for twin refinement. Clearly it also accounts for the bond-length differences between (I) and (II) and (III).
The C—C and C—O bonds in (I) are unexceptional and are not discussed further. Selected torsion angles are given in Table 2. In the cell of (I) (Fig. 2), aside from the weak intermolecular interactions given in Table 3, the packing of the molecules involves only van der Waals contacts.