Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103006309/de1207sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103006309/de1207Isup2.hkl |
CCDC reference: 214139
The title compound was synthesized and purified following the procedure of Suzuki et al. (1993). It was then further purified using column chromatography (hexanes/diethyl ether, 9:1). Crystals used for X-ray analysis where grown from a hexanes/diethyl ether (9:1) solution.
H atoms were placed in calculated positions, with C—H bond lengths in the range 0.95–0.99 Å and O—H distances of 0.84 Å, and with Uiso = 1.2Ueq of the attached atom (1.5Ueq for OH groups), and thereafter treated as riding. A torsional parameter was refined for each OH group. The carboxyl groups are disordered, with the H atoms half populated and lying near inversion centers.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2002).
[Fe(C5H5)(C9H9O3)] | F(000) = 592 |
Mr = 286.10 | Dx = 1.631 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2661 reflections |
a = 5.673 (2) Å | θ = 2.5–27.5° |
b = 26.892 (6) Å | µ = 1.29 mm−1 |
c = 7.764 (2) Å | T = 120 K |
β = 100.433 (10)° | Prism, orange |
V = 1164.9 (6) Å3 | 0.20 × 0.13 × 0.07 mm |
Z = 4 |
Nonius KappaCCD (fitted with an Oxford Cryosystems Cryostream cooler) diffractometer | 2673 independent reflections |
Radiation source: fine-focus sealed tube | 2059 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | h = −7→7 |
Tmin = 0.804, Tmax = 0.914 | k = −34→34 |
13367 measured reflections | l = −10→10 |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.015P)2 + 1.1438P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2673 reflections | Δρmax = 0.39 e Å−3 |
166 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0019 (5) |
[Fe(C5H5)(C9H9O3)] | V = 1164.9 (6) Å3 |
Mr = 286.10 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.673 (2) Å | µ = 1.29 mm−1 |
b = 26.892 (6) Å | T = 120 K |
c = 7.764 (2) Å | 0.20 × 0.13 × 0.07 mm |
β = 100.433 (10)° |
Nonius KappaCCD (fitted with an Oxford Cryosystems Cryostream cooler) diffractometer | 2673 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | 2059 reflections with I > 2σ(I) |
Tmin = 0.804, Tmax = 0.914 | Rint = 0.025 |
13367 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.39 e Å−3 |
2673 reflections | Δρmin = −0.33 e Å−3 |
166 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) | |
Fe1 | 0.54330 (5) | 0.334308 (12) | 0.70899 (4) | 0.01418 (11) | |
O1 | 0.1573 (3) | 0.37150 (6) | 0.2794 (2) | 0.0218 (4) | |
O2 | −0.0120 (3) | 0.49756 (6) | 0.1697 (2) | 0.0226 (4) | |
H2O | 0.0118 | 0.4967 | 0.0661 | 0.034* | 0.50 |
O3 | 0.1794 (3) | 0.47965 (6) | 0.4363 (2) | 0.0224 (4) | |
H3O | 0.0587 | 0.4944 | 0.4601 | 0.034* | 0.50 |
C1 | 0.4930 (4) | 0.33179 (9) | 0.4433 (3) | 0.0151 (5) | |
C2 | 0.3736 (4) | 0.29077 (8) | 0.5086 (3) | 0.0176 (5) | |
H2 | 0.2067 | 0.2839 | 0.4813 | 0.021* | |
C3 | 0.5467 (4) | 0.26217 (9) | 0.6208 (3) | 0.0192 (5) | |
H3 | 0.5161 | 0.2329 | 0.6817 | 0.023* | |
C4 | 0.7750 (4) | 0.28488 (9) | 0.6267 (3) | 0.0193 (5) | |
H4 | 0.9227 | 0.2734 | 0.6922 | 0.023* | |
C5 | 0.7439 (4) | 0.32771 (9) | 0.5176 (3) | 0.0173 (5) | |
H5 | 0.8669 | 0.3497 | 0.4974 | 0.021* | |
C6 | 0.3717 (4) | 0.37340 (9) | 0.3403 (3) | 0.0160 (5) | |
C7 | 0.5189 (4) | 0.41877 (9) | 0.3153 (3) | 0.0182 (5) | |
H7A | 0.6572 | 0.4085 | 0.2620 | 0.022* | |
H7B | 0.5824 | 0.4336 | 0.4311 | 0.022* | |
C8 | 0.3741 (4) | 0.45786 (9) | 0.1991 (3) | 0.0191 (5) | |
H8A | 0.4823 | 0.4855 | 0.1809 | 0.023* | |
H8B | 0.3124 | 0.4429 | 0.0833 | 0.023* | |
C9 | 0.1673 (4) | 0.47871 (9) | 0.2713 (3) | 0.0190 (5) | |
C10 | 0.4095 (4) | 0.40089 (9) | 0.7748 (3) | 0.0233 (6) | |
H10 | 0.3385 | 0.4257 | 0.6949 | 0.028* | |
C11 | 0.2885 (4) | 0.36111 (10) | 0.8404 (3) | 0.0267 (6) | |
H11 | 0.1213 | 0.3546 | 0.8129 | 0.032* | |
C12 | 0.4600 (5) | 0.33267 (9) | 0.9542 (3) | 0.0244 (6) | |
H12 | 0.4283 | 0.3036 | 1.0159 | 0.029* | |
C13 | 0.6871 (4) | 0.35507 (9) | 0.9600 (3) | 0.0221 (5) | |
H13 | 0.8346 | 0.3438 | 1.0266 | 0.027* | |
C14 | 0.6553 (4) | 0.39696 (9) | 0.8495 (3) | 0.0221 (6) | |
H14 | 0.7783 | 0.4189 | 0.8287 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01359 (17) | 0.01571 (18) | 0.01326 (18) | 0.00013 (14) | 0.00252 (12) | −0.00178 (15) |
O1 | 0.0167 (9) | 0.0283 (10) | 0.0188 (9) | −0.0002 (7) | −0.0007 (7) | 0.0016 (7) |
O2 | 0.0229 (9) | 0.0256 (10) | 0.0191 (9) | 0.0071 (7) | 0.0030 (7) | 0.0054 (8) |
O3 | 0.0248 (9) | 0.0279 (10) | 0.0149 (9) | 0.0103 (8) | 0.0046 (7) | 0.0000 (7) |
C1 | 0.0170 (11) | 0.0180 (12) | 0.0107 (11) | 0.0013 (10) | 0.0033 (9) | −0.0028 (10) |
C2 | 0.0182 (12) | 0.0198 (13) | 0.0147 (12) | −0.0026 (10) | 0.0023 (10) | −0.0055 (10) |
C3 | 0.0262 (13) | 0.0159 (13) | 0.0155 (12) | −0.0001 (10) | 0.0042 (10) | −0.0044 (10) |
C4 | 0.0171 (12) | 0.0216 (13) | 0.0193 (13) | 0.0052 (10) | 0.0032 (10) | −0.0024 (10) |
C5 | 0.0165 (11) | 0.0202 (13) | 0.0165 (12) | 0.0015 (10) | 0.0062 (9) | −0.0024 (10) |
C6 | 0.0187 (12) | 0.0203 (13) | 0.0101 (12) | 0.0010 (10) | 0.0052 (10) | −0.0029 (9) |
C7 | 0.0192 (12) | 0.0203 (13) | 0.0159 (13) | 0.0023 (10) | 0.0053 (10) | −0.0013 (10) |
C8 | 0.0242 (13) | 0.0183 (13) | 0.0164 (13) | 0.0023 (10) | 0.0080 (10) | 0.0016 (10) |
C9 | 0.0207 (13) | 0.0134 (12) | 0.0234 (14) | −0.0009 (10) | 0.0049 (10) | 0.0001 (10) |
C10 | 0.0324 (15) | 0.0215 (13) | 0.0155 (13) | 0.0122 (11) | 0.0034 (11) | −0.0037 (10) |
C11 | 0.0163 (12) | 0.0401 (17) | 0.0252 (14) | −0.0033 (11) | 0.0076 (11) | −0.0157 (12) |
C12 | 0.0403 (15) | 0.0185 (13) | 0.0186 (13) | −0.0044 (12) | 0.0166 (11) | −0.0023 (11) |
C13 | 0.0236 (13) | 0.0268 (14) | 0.0135 (12) | 0.0049 (11) | −0.0032 (10) | −0.0054 (11) |
C14 | 0.0256 (13) | 0.0196 (13) | 0.0228 (14) | −0.0064 (10) | 0.0091 (11) | −0.0089 (11) |
Fe1—C1 | 2.032 (2) | C3—H3 | 0.9500 |
Fe1—C2 | 2.043 (2) | C4—C5 | 1.421 (3) |
Fe1—C3 | 2.058 (2) | C4—H4 | 0.9500 |
Fe1—C4 | 2.051 (2) | C5—H5 | 0.9500 |
Fe1—C5 | 2.036 (2) | C6—C7 | 1.511 (3) |
Fe1—C10 | 2.045 (2) | C7—C8 | 1.525 (3) |
Fe1—C11 | 2.046 (2) | C7—H7A | 0.9900 |
Fe1—C12 | 2.043 (2) | C7—H7B | 0.9900 |
Fe1—C13 | 2.049 (2) | C8—C9 | 1.498 (3) |
Fe1—C14 | 2.045 (2) | C8—H8A | 0.9900 |
O1—C6 | 1.224 (3) | C8—H8B | 0.9900 |
O2—C9 | 1.274 (3) | C10—C14 | 1.414 (3) |
O2—H2O | 0.8400 | C10—C11 | 1.415 (4) |
O3—C9 | 1.271 (3) | C10—H10 | 0.9500 |
O3—H3O | 0.8400 | C11—C12 | 1.414 (4) |
C1—C2 | 1.435 (3) | C11—H11 | 0.9500 |
C1—C5 | 1.440 (3) | C12—C13 | 1.416 (3) |
C1—C6 | 1.472 (3) | C12—H12 | 0.9500 |
C2—C3 | 1.416 (3) | C13—C14 | 1.408 (3) |
C2—H2 | 0.9500 | C13—H13 | 0.9500 |
C3—C4 | 1.425 (3) | C14—H14 | 0.9500 |
C1—Fe1—C5 | 41.46 (9) | C4—C3—H3 | 125.9 |
C1—Fe1—C2 | 41.22 (9) | Fe1—C3—H3 | 127.0 |
C5—Fe1—C2 | 69.10 (9) | C5—C4—C3 | 108.3 (2) |
C1—Fe1—C12 | 158.68 (10) | C5—C4—Fe1 | 69.09 (13) |
C5—Fe1—C12 | 158.75 (10) | C3—C4—Fe1 | 69.99 (13) |
C2—Fe1—C12 | 122.70 (10) | C5—C4—H4 | 125.8 |
C1—Fe1—C14 | 122.83 (10) | C3—C4—H4 | 125.8 |
C5—Fe1—C14 | 107.49 (10) | Fe1—C4—H4 | 126.7 |
C2—Fe1—C14 | 159.44 (10) | C4—C5—C1 | 107.9 (2) |
C12—Fe1—C14 | 67.83 (10) | C4—C5—Fe1 | 70.22 (13) |
C1—Fe1—C10 | 107.01 (9) | C1—C5—Fe1 | 69.11 (12) |
C5—Fe1—C10 | 122.70 (10) | C4—C5—H5 | 126.0 |
C2—Fe1—C10 | 123.14 (10) | C1—C5—H5 | 126.0 |
C12—Fe1—C10 | 68.12 (10) | Fe1—C5—H5 | 126.2 |
C14—Fe1—C10 | 40.44 (10) | O1—C6—C1 | 120.9 (2) |
C1—Fe1—C11 | 122.42 (10) | O1—C6—C7 | 121.2 (2) |
C5—Fe1—C11 | 158.98 (10) | C1—C6—C7 | 117.96 (19) |
C2—Fe1—C11 | 107.66 (10) | C6—C7—C8 | 112.43 (19) |
C12—Fe1—C11 | 40.48 (10) | C6—C7—H7A | 109.1 |
C14—Fe1—C11 | 67.84 (10) | C8—C7—H7A | 109.1 |
C10—Fe1—C11 | 40.48 (10) | C6—C7—H7B | 109.1 |
C1—Fe1—C13 | 158.93 (10) | C8—C7—H7B | 109.1 |
C5—Fe1—C13 | 122.61 (10) | H7A—C7—H7B | 107.8 |
C2—Fe1—C13 | 158.69 (10) | C9—C8—C7 | 114.30 (19) |
C12—Fe1—C13 | 40.47 (10) | C9—C8—H8A | 108.7 |
C14—Fe1—C13 | 40.22 (10) | C7—C8—H8A | 108.7 |
C10—Fe1—C13 | 68.02 (10) | C9—C8—H8B | 108.7 |
C11—Fe1—C13 | 67.99 (10) | C7—C8—H8B | 108.7 |
C1—Fe1—C4 | 69.03 (9) | H8A—C8—H8B | 107.6 |
C5—Fe1—C4 | 40.69 (9) | O3—C9—O2 | 120.5 (2) |
C2—Fe1—C4 | 68.39 (9) | O3—C9—C8 | 118.8 (2) |
C12—Fe1—C4 | 123.07 (10) | O2—C9—C8 | 120.6 (2) |
C14—Fe1—C4 | 123.06 (10) | C14—C10—C11 | 107.6 (2) |
C10—Fe1—C4 | 158.88 (10) | C14—C10—Fe1 | 69.77 (13) |
C11—Fe1—C4 | 159.12 (11) | C11—C10—Fe1 | 69.77 (14) |
C13—Fe1—C4 | 107.81 (10) | C14—C10—H10 | 126.2 |
C1—Fe1—C3 | 68.84 (9) | C11—C10—H10 | 126.2 |
C5—Fe1—C3 | 68.59 (9) | Fe1—C10—H10 | 125.8 |
C2—Fe1—C3 | 40.39 (9) | C12—C11—C10 | 108.1 (2) |
C12—Fe1—C3 | 107.89 (10) | C12—C11—Fe1 | 69.68 (13) |
C14—Fe1—C3 | 158.94 (10) | C10—C11—Fe1 | 69.75 (13) |
C10—Fe1—C3 | 159.13 (10) | C12—C11—H11 | 126.0 |
C11—Fe1—C3 | 123.23 (10) | C10—C11—H11 | 126.0 |
C13—Fe1—C3 | 123.16 (10) | Fe1—C11—H11 | 126.2 |
C4—Fe1—C3 | 40.58 (9) | C11—C12—C13 | 108.0 (2) |
C9—O2—H2O | 109.5 | C11—C12—Fe1 | 69.84 (14) |
C9—O3—H3O | 109.5 | C13—C12—Fe1 | 69.99 (13) |
C2—C1—C5 | 107.2 (2) | C11—C12—H12 | 126.0 |
C2—C1—C6 | 124.9 (2) | C13—C12—H12 | 126.0 |
C5—C1—C6 | 127.4 (2) | Fe1—C12—H12 | 125.7 |
C2—C1—Fe1 | 69.83 (12) | C14—C13—C12 | 107.8 (2) |
C5—C1—Fe1 | 69.43 (12) | C14—C13—Fe1 | 69.73 (13) |
C6—C1—Fe1 | 119.47 (15) | C12—C13—Fe1 | 69.54 (14) |
C3—C2—C1 | 108.4 (2) | C14—C13—H13 | 126.1 |
C3—C2—Fe1 | 70.37 (13) | C12—C13—H13 | 126.1 |
C1—C2—Fe1 | 68.95 (12) | Fe1—C13—H13 | 126.2 |
C3—C2—H2 | 125.8 | C13—C14—C10 | 108.5 (2) |
C1—C2—H2 | 125.8 | C13—C14—Fe1 | 70.06 (14) |
Fe1—C2—H2 | 126.4 | C10—C14—Fe1 | 69.79 (14) |
C2—C3—C4 | 108.2 (2) | C13—C14—H14 | 125.7 |
C2—C3—Fe1 | 69.24 (13) | C10—C14—H14 | 125.7 |
C4—C3—Fe1 | 69.43 (13) | Fe1—C14—H14 | 126.0 |
C2—C3—H3 | 125.9 | ||
C5—Fe1—C1—C2 | 118.31 (19) | C3—Fe1—C5—C1 | 81.84 (14) |
C12—Fe1—C1—C2 | −48.0 (3) | C2—C1—C6—O1 | −11.9 (3) |
C14—Fe1—C1—C2 | −162.65 (13) | C5—C1—C6—O1 | 177.5 (2) |
C10—Fe1—C1—C2 | −121.23 (14) | Fe1—C1—C6—O1 | −96.8 (2) |
C11—Fe1—C1—C2 | −79.65 (16) | C2—C1—C6—C7 | 167.0 (2) |
C13—Fe1—C1—C2 | 165.9 (2) | C5—C1—C6—C7 | −3.6 (3) |
C4—Fe1—C1—C2 | 80.73 (14) | Fe1—C1—C6—C7 | 82.1 (2) |
C3—Fe1—C1—C2 | 37.11 (13) | O1—C6—C7—C8 | −3.9 (3) |
C2—Fe1—C1—C5 | −118.31 (19) | C1—C6—C7—C8 | 177.24 (18) |
C12—Fe1—C1—C5 | −166.3 (2) | C6—C7—C8—C9 | 62.3 (3) |
C14—Fe1—C1—C5 | 79.04 (16) | C7—C8—C9—O3 | 27.9 (3) |
C10—Fe1—C1—C5 | 120.47 (14) | C7—C8—C9—O2 | −155.7 (2) |
C11—Fe1—C1—C5 | 162.04 (14) | C1—Fe1—C10—C14 | −121.01 (15) |
C13—Fe1—C1—C5 | 47.6 (3) | C5—Fe1—C10—C14 | −78.31 (17) |
C4—Fe1—C1—C5 | −37.57 (13) | C2—Fe1—C10—C14 | −163.31 (14) |
C3—Fe1—C1—C5 | −81.20 (14) | C12—Fe1—C10—C14 | 81.03 (16) |
C5—Fe1—C1—C6 | −122.2 (2) | C11—Fe1—C10—C14 | 118.6 (2) |
C2—Fe1—C1—C6 | 119.5 (2) | C13—Fe1—C10—C14 | 37.25 (14) |
C12—Fe1—C1—C6 | 71.5 (3) | C4—Fe1—C10—C14 | −45.3 (3) |
C14—Fe1—C1—C6 | −43.1 (2) | C3—Fe1—C10—C14 | 163.9 (2) |
C10—Fe1—C1—C6 | −1.7 (2) | C1—Fe1—C10—C11 | 120.35 (15) |
C11—Fe1—C1—C6 | 39.9 (2) | C5—Fe1—C10—C11 | 163.05 (14) |
C13—Fe1—C1—C6 | −74.6 (3) | C2—Fe1—C10—C11 | 78.06 (17) |
C4—Fe1—C1—C6 | −159.8 (2) | C12—Fe1—C10—C11 | −37.60 (15) |
C3—Fe1—C1—C6 | 156.6 (2) | C14—Fe1—C10—C11 | −118.6 (2) |
C5—C1—C2—C3 | 0.1 (2) | C13—Fe1—C10—C11 | −81.38 (16) |
C6—C1—C2—C3 | −172.0 (2) | C4—Fe1—C10—C11 | −163.9 (2) |
Fe1—C1—C2—C3 | −59.52 (16) | C3—Fe1—C10—C11 | 45.3 (3) |
C5—C1—C2—Fe1 | 59.64 (15) | C14—C10—C11—C12 | −0.4 (3) |
C6—C1—C2—Fe1 | −112.5 (2) | Fe1—C10—C11—C12 | 59.36 (17) |
C1—Fe1—C2—C3 | 119.74 (19) | C14—C10—C11—Fe1 | −59.77 (16) |
C5—Fe1—C2—C3 | 81.14 (14) | C1—Fe1—C11—C12 | 162.89 (14) |
C12—Fe1—C2—C3 | −78.98 (16) | C5—Fe1—C11—C12 | −162.4 (2) |
C14—Fe1—C2—C3 | 165.3 (2) | C2—Fe1—C11—C12 | 120.02 (15) |
C10—Fe1—C2—C3 | −162.68 (14) | C14—Fe1—C11—C12 | −81.34 (16) |
C11—Fe1—C2—C3 | −120.88 (15) | C10—Fe1—C11—C12 | −119.3 (2) |
C13—Fe1—C2—C3 | −46.3 (3) | C13—Fe1—C11—C12 | −37.78 (15) |
C4—Fe1—C2—C3 | 37.33 (14) | C4—Fe1—C11—C12 | 44.5 (3) |
C5—Fe1—C2—C1 | −38.61 (13) | C3—Fe1—C11—C12 | 78.35 (17) |
C12—Fe1—C2—C1 | 161.28 (13) | C1—Fe1—C11—C10 | −77.84 (17) |
C14—Fe1—C2—C1 | 45.5 (3) | C5—Fe1—C11—C10 | −43.2 (3) |
C10—Fe1—C2—C1 | 77.57 (16) | C2—Fe1—C11—C10 | −120.71 (15) |
C11—Fe1—C2—C1 | 119.37 (14) | C12—Fe1—C11—C10 | 119.3 (2) |
C13—Fe1—C2—C1 | −166.1 (2) | C14—Fe1—C11—C10 | 37.93 (14) |
C4—Fe1—C2—C1 | −82.41 (14) | C13—Fe1—C11—C10 | 81.49 (16) |
C3—Fe1—C2—C1 | −119.74 (19) | C4—Fe1—C11—C10 | 163.8 (2) |
C1—C2—C3—C4 | 0.0 (3) | C3—Fe1—C11—C10 | −162.38 (14) |
Fe1—C2—C3—C4 | −58.67 (16) | C10—C11—C12—C13 | 0.4 (3) |
C1—C2—C3—Fe1 | 58.64 (15) | Fe1—C11—C12—C13 | 59.84 (16) |
C1—Fe1—C3—C2 | −37.85 (13) | C10—C11—C12—Fe1 | −59.41 (16) |
C5—Fe1—C3—C2 | −82.50 (14) | C1—Fe1—C12—C11 | −43.1 (3) |
C12—Fe1—C3—C2 | 119.78 (14) | C5—Fe1—C12—C11 | 162.6 (2) |
C14—Fe1—C3—C2 | −165.6 (2) | C2—Fe1—C12—C11 | −78.64 (17) |
C10—Fe1—C3—C2 | 44.4 (3) | C14—Fe1—C12—C11 | 81.39 (16) |
C11—Fe1—C3—C2 | 77.86 (17) | C10—Fe1—C12—C11 | 37.61 (15) |
C13—Fe1—C3—C2 | 161.70 (13) | C13—Fe1—C12—C11 | 118.9 (2) |
C4—Fe1—C3—C2 | −119.9 (2) | C4—Fe1—C12—C11 | −162.66 (14) |
C1—Fe1—C3—C4 | 82.07 (15) | C3—Fe1—C12—C11 | −120.58 (15) |
C5—Fe1—C3—C4 | 37.42 (14) | C1—Fe1—C12—C13 | −162.0 (2) |
C2—Fe1—C3—C4 | 119.9 (2) | C5—Fe1—C12—C13 | 43.7 (3) |
C12—Fe1—C3—C4 | −120.31 (15) | C2—Fe1—C12—C13 | 162.42 (14) |
C14—Fe1—C3—C4 | −45.7 (3) | C14—Fe1—C12—C13 | −37.55 (15) |
C10—Fe1—C3—C4 | 164.3 (2) | C10—Fe1—C12—C13 | −81.33 (16) |
C11—Fe1—C3—C4 | −162.23 (15) | C11—Fe1—C12—C13 | −118.9 (2) |
C13—Fe1—C3—C4 | −78.38 (17) | C4—Fe1—C12—C13 | 78.40 (17) |
C2—C3—C4—C5 | −0.1 (3) | C3—Fe1—C12—C13 | 120.48 (15) |
Fe1—C3—C4—C5 | −58.62 (16) | C11—C12—C13—C14 | −0.3 (3) |
C2—C3—C4—Fe1 | 58.55 (16) | Fe1—C12—C13—C14 | 59.46 (16) |
C1—Fe1—C4—C5 | 38.26 (13) | C11—C12—C13—Fe1 | −59.74 (17) |
C2—Fe1—C4—C5 | 82.65 (15) | C1—Fe1—C13—C14 | 42.7 (3) |
C12—Fe1—C4—C5 | −161.54 (14) | C5—Fe1—C13—C14 | 78.23 (16) |
C14—Fe1—C4—C5 | −78.06 (17) | C2—Fe1—C13—C14 | −163.4 (2) |
C10—Fe1—C4—C5 | −44.7 (3) | C12—Fe1—C13—C14 | −119.1 (2) |
C11—Fe1—C4—C5 | 165.6 (2) | C10—Fe1—C13—C14 | −37.45 (14) |
C13—Fe1—C4—C5 | −119.65 (14) | C11—Fe1—C13—C14 | −81.26 (16) |
C3—Fe1—C4—C5 | 119.8 (2) | C4—Fe1—C13—C14 | 120.51 (15) |
C1—Fe1—C4—C3 | −81.56 (15) | C3—Fe1—C13—C14 | 162.51 (14) |
C5—Fe1—C4—C3 | −119.8 (2) | C1—Fe1—C13—C12 | 161.8 (2) |
C2—Fe1—C4—C3 | −37.17 (14) | C5—Fe1—C13—C12 | −162.72 (14) |
C12—Fe1—C4—C3 | 78.65 (17) | C2—Fe1—C13—C12 | −44.4 (3) |
C14—Fe1—C4—C3 | 162.13 (14) | C14—Fe1—C13—C12 | 119.1 (2) |
C10—Fe1—C4—C3 | −164.5 (2) | C10—Fe1—C13—C12 | 81.60 (16) |
C11—Fe1—C4—C3 | 45.8 (3) | C11—Fe1—C13—C12 | 37.79 (15) |
C13—Fe1—C4—C3 | 120.54 (15) | C4—Fe1—C13—C12 | −120.44 (15) |
C3—C4—C5—C1 | 0.2 (3) | C3—Fe1—C13—C12 | −78.44 (17) |
Fe1—C4—C5—C1 | −59.03 (15) | C12—C13—C14—C10 | 0.0 (3) |
C3—C4—C5—Fe1 | 59.18 (16) | Fe1—C13—C14—C10 | 59.38 (16) |
C2—C1—C5—C4 | −0.2 (2) | C12—C13—C14—Fe1 | −59.34 (16) |
C6—C1—C5—C4 | 171.7 (2) | C11—C10—C14—C13 | 0.2 (3) |
Fe1—C1—C5—C4 | 59.72 (15) | Fe1—C10—C14—C13 | −59.54 (17) |
C2—C1—C5—Fe1 | −59.89 (15) | C11—C10—C14—Fe1 | 59.77 (16) |
C6—C1—C5—Fe1 | 112.0 (2) | C1—Fe1—C14—C13 | −163.12 (13) |
C1—Fe1—C5—C4 | −119.16 (19) | C5—Fe1—C14—C13 | −120.16 (14) |
C2—Fe1—C5—C4 | −80.77 (15) | C2—Fe1—C14—C13 | 162.8 (2) |
C12—Fe1—C5—C4 | 47.1 (3) | C12—Fe1—C14—C13 | 37.78 (14) |
C14—Fe1—C5—C4 | 120.72 (15) | C10—Fe1—C14—C13 | 119.6 (2) |
C10—Fe1—C5—C4 | 162.48 (14) | C11—Fe1—C14—C13 | 81.65 (16) |
C11—Fe1—C5—C4 | −165.7 (2) | C4—Fe1—C14—C13 | −78.18 (17) |
C13—Fe1—C5—C4 | 79.21 (16) | C3—Fe1—C14—C13 | −44.4 (3) |
C3—Fe1—C5—C4 | −37.32 (14) | C1—Fe1—C14—C10 | 77.26 (17) |
C2—Fe1—C5—C1 | 38.39 (13) | C5—Fe1—C14—C10 | 120.23 (15) |
C12—Fe1—C5—C1 | 166.2 (2) | C2—Fe1—C14—C10 | 43.2 (3) |
C14—Fe1—C5—C1 | −120.12 (14) | C12—Fe1—C14—C10 | −81.83 (16) |
C10—Fe1—C5—C1 | −78.36 (16) | C11—Fe1—C14—C10 | −37.97 (15) |
C11—Fe1—C5—C1 | −46.5 (3) | C13—Fe1—C14—C10 | −119.6 (2) |
C13—Fe1—C5—C1 | −161.63 (14) | C4—Fe1—C14—C10 | 162.20 (14) |
C4—Fe1—C5—C1 | 119.16 (19) | C3—Fe1—C14—C10 | −164.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O2i | 0.84 | 1.84 | 2.667 (3) | 169 |
O3—H3O···O3ii | 0.84 | 1.83 | 2.655 (3) | 166 |
C10—H10···O3 | 0.95 | 2.51 | 3.443 (3) | 168 |
C13—H13···O1iii | 0.95 | 2.54 | 3.326 (3) | 140 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) x+1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C9H9O3)] |
Mr | 286.10 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 5.673 (2), 26.892 (6), 7.764 (2) |
β (°) | 100.433 (10) |
V (Å3) | 1164.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.29 |
Crystal size (mm) | 0.20 × 0.13 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD (fitted with an Oxford Cryosystems Cryostream cooler) diffractometer |
Absorption correction | Multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.804, 0.914 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13367, 2673, 2059 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.073, 1.02 |
No. of reflections | 2673 |
No. of parameters | 166 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.33 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2002).
Fe1—C1 | 2.032 (2) | Fe1—C12 | 2.043 (2) |
Fe1—C2 | 2.043 (2) | Fe1—C13 | 2.049 (2) |
Fe1—C3 | 2.058 (2) | Fe1—C14 | 2.045 (2) |
Fe1—C4 | 2.051 (2) | O1—C6 | 1.224 (3) |
Fe1—C5 | 2.036 (2) | O2—C9 | 1.274 (3) |
Fe1—C10 | 2.045 (2) | O3—C9 | 1.271 (3) |
Fe1—C11 | 2.046 (2) | ||
O3—C9—O2 | 120.5 (2) | O2—C9—C8 | 120.6 (2) |
O3—C9—C8 | 118.8 (2) | ||
C2—C1—C6—O1 | −11.9 (3) | C7—C8—C9—O2 | −155.7 (2) |
C6—C7—C8—C9 | 62.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O2i | 0.84 | 1.84 | 2.667 (3) | 169 |
O3—H3O···O3ii | 0.84 | 1.83 | 2.655 (3) | 166 |
C10—H10···O3 | 0.95 | 2.51 | 3.443 (3) | 168 |
C13—H13···O1iii | 0.95 | 2.54 | 3.326 (3) | 140 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) x+1, y, z+1. |
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In the process of preparing 2-propenyl 4-ferrocenyl-4-oxobutanoate, reported earlier by our group (Giraldés et al., 2001), the title compound, (I), was used as a starting material. It is a common, commercially available, ferrocene, but its crystal structure has not been reported previously, only that of a complex of its carboxylate with a zirconocene (Ma et al., 1989). Thus, we undertook to determine its structure at low temperature.
The molecule is depicted in Fig. 1, which shows the normal eclipsed conformation of the cyclopentadienyl (Cp) rings. The Fe–centroid distance to the unsubstituted ring is 1.6551 (11) Å, while that to the substituted ring is slightly shorter, at 1.6445 (11) Å, and the centroid–Fe–centroid angle is linear, 179.95 (7)°. The unsubstituted Cp ring forms a weak intramolecular C—H···O hydrogen bond (Steiner & Desiraju, 1998) with the carboxyl group (Table 2). This hydrogen bond was also present in 2-propenyl 4-ferrocenyl-4-oxobutanoate (Giraldés et al., 2001), but involved an ester carbonyl O atom, and was somewhat shorter [3.289 (2) Å] but slightly less linear (159°).
The carboxyl group is disordered, with equal C—O distances midway between those expected for ordered COOH groups (Borthwick, 1980). The carboxyl H atoms must also be disordered over two half-populated positions, and both sites were clearly visible in difference maps. The half H atom on O3 lies in the synplanar position usually observed in carboxylic acids, while that on O2 lies in the rare antiplanar position normally found only in intramolecular hydrogen bonds (Leiserowitz, 1976). The synplanar conformation is more stable by 8.37–16.74 kJ mol−1 (Miyazawa & Pitzer, 1959; Lide, 1964; Karpfen, 1984; Marcoccia et al., 1990). The antiplanar conformation was apparently unknown in intermolecular hydrogen bonds before about 1980 (Fujinaga & James, 1980). We have previously encountered it in hydrogen bonds to water molecules from carboxyl groups on crown ethers and their metal ion complexes (Dutton et al., 1990, 1993). In those cases, the water molecule was encapsulated by the crown, which had insufficient flexibility to allow a syn-H atom on the carboxyl group to donate to the water molecule. This could only happen with the antiplanar conformation, so those cases were somewhat analogous to intramolecular hydrogen bonds.
Hydrogen bonding involving the carboxyl groups is illustrated in Fig. 2. Both partially occupied carboxyl H-atom positions lie near inversion centers, that on O2 near 0,1/2,0, and that on O3 near 0,1/2,1/2. Thus, the carboxyl groups form disordered hydrogen-bonded chains running in the [001] direction, and these chains are of the rare syn–anti type, similar to that seen in the isostructural compounds 4-bromocubane-1-carboxylic acid and its iodo analog (Kuduva et al., 1999). Ordered syn–anti chains are also present in other cubane carboxylic acids (Ermer & Lex, 1987) and seem to be the dominant pattern in that class of compounds, despite occurring for an estimated 0.15% of all organic carboxylic acids (Kuduva et al., 1999). The existence of the antiplanar conformation in the carboxyl group of the cubane acids was attributed to its allowance of C—H···O hydrogen bonding by the acidic cubane H atoms, an idea which is supported by the structure of formic acid–HF (Wiechert et al., 1997), which is able to form C—H···O hydrogen bonds in conjunction with anti–anti carboxyl chains. The role of C—H···O hydrogen bonding in allowing the less stable anti carboxyl group conformation in (I) is less clear. In addition to the intramolecular interaction mentioned above, (I) has a shorter but less linear intermolecular hydrogen bond involving atom C13 and ketone atom O1 (Table 2). However, it is not obvious why (I) could not form the ubiquitous syn–syn carboxyl dimers or syn–syn chains and still be able to form both the observed intramolecular and intermolecular C—H···O hydrogen bonds.
The cell dimensions at 292 K, measured using a CAD-4 diffractometer with Cu Kα radiation (25 reflections, 14 < θ < 27°), are a = 5.7331 (4), b = 27.099 (3), c = 7.7730 (6) Å and β = 100.622 (5)°.