Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014659/om6053sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014659/om6053Isup2.hkl |
CCDC reference: 175323
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.039
- wR factor = 0.091
- Data-to-parameter ratio = 23.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.90 From the CIF: _reflns_number_total 4409 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4942 Completeness (_total/calc) 89.21% Alert B: < 90% complete (theta max?)
Author response: We were not able to measure the 10 k l and 11 k l data at very
high angle. The data are 94% complete to theta=30 degrees. Including the
30.0 |
General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.90 From the CIF: _reflns_number_total 4409 From the CIF: _diffrn_reflns_limit_ max hkl 9. 16. 49. From the CIF: _diffrn_reflns_limit_ min hkl -9. -16. -48. TEST1: Expected hkl limits for theta max Calculated maximum hkl 11. 16. 50. Calculated minimum hkl -11. -16. -50. ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
To a solution of 4-ferrocenyl-4-oxobutanoic acid (0.95 g, 3.3 mmol) in 20 ml acetone, K2CO3 (1.58 g,12 mmol) and allyl bromide (2.66 g, 22 mmol) were added under argon. The mixture was refluxed at 373 K overnight. After cooling, HCl (10 ml, 4 N) was added to the mixture and extracted with (3 x 20 ml) dichloromethane. The organic layers were combined and dried over sodium sulfate and evaporated in vacuo. The product was purified by column chromatography (2:1, hexane–ethyl acetate). Diffraction-quality crystals were grown by dissolving the solid material in a hot ethanol solution, followed by slow evaporation of the solvent. Yield 0.91 g (85%). MS, m/e (M+): 326.
H atoms were placed in calculated positions with C—H bond distances in the range 0.95–0.99 Å and Uiso = 1.2Ueq of the attached atom, and thereafter treated as riding.
Data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Fe(C5H5)(C12H13O3)] | Dx = 1.508 Mg m−3 |
Mr = 326.16 | Melting point: 313 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7561 (1) Å | Cell parameters from 4495 reflections |
b = 10.8931 (2) Å | θ = 2.5–31.9° |
c = 34.0120 (6) Å | µ = 1.06 mm−1 |
V = 2873.60 (8) Å3 | T = 120 K |
Z = 8 | Plate, orange |
F(000) = 1360 | 0.32 × 0.20 × 0.05 mm |
KappaCCD diffractometer (with Oxford Cryosystems Cryostream cooler) | 4409 independent reflections |
Radiation source: fine-focus sealed tube | 3031 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans with κ offsets | θmax = 31.9°, θmin = 2.9° |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | h = −9→9 |
Tmin = 0.844, Tmax = 0.949 | k = −16→16 |
19653 measured reflections | l = −48→49 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0325P)2 + 1.0286P] where P = (Fo2 + 2Fc2)/3 |
4409 reflections | (Δ/σ)max = 0.003 |
190 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[Fe(C5H5)(C12H13O3)] | V = 2873.60 (8) Å3 |
Mr = 326.16 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.7561 (1) Å | µ = 1.06 mm−1 |
b = 10.8931 (2) Å | T = 120 K |
c = 34.0120 (6) Å | 0.32 × 0.20 × 0.05 mm |
KappaCCD diffractometer (with Oxford Cryosystems Cryostream cooler) | 4409 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | 3031 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.949 | Rint = 0.038 |
19653 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.33 e Å−3 |
4409 reflections | Δρmin = −0.58 e Å−3 |
190 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 | ||
Fe1 | 0.45489 (4) | 0.14941 (2) | 0.568335 (7) | 0.01796 (8) | |
O1 | 0.54470 (18) | 0.15132 (11) | 0.67736 (4) | 0.0251 (3) | |
O2 | 0.50402 (18) | 0.49114 (12) | 0.71968 (4) | 0.0254 (3) | |
O3 | 0.4741 (2) | 0.48972 (13) | 0.65390 (4) | 0.0338 (4) | |
C1 | 0.6237 (2) | 0.10907 (15) | 0.61192 (5) | 0.0181 (4) | |
C2 | 0.7139 (3) | 0.13360 (15) | 0.57593 (5) | 0.0212 (4) | |
H2 | 0.7967 | 0.1966 | 0.5719 | 0.025* | |
C3 | 0.6580 (3) | 0.04753 (16) | 0.54745 (5) | 0.0232 (4) | |
H3 | 0.6974 | 0.0426 | 0.5211 | 0.028* | |
C4 | 0.5327 (3) | −0.03033 (15) | 0.56508 (5) | 0.0208 (4) | |
H4 | 0.4740 | −0.0959 | 0.5524 | 0.025* | |
C5 | 0.5103 (2) | 0.00670 (15) | 0.60477 (5) | 0.0196 (4) | |
H5 | 0.4341 | −0.0295 | 0.6233 | 0.024* | |
C6 | 0.6245 (2) | 0.18366 (15) | 0.64817 (5) | 0.0193 (4) | |
C7 | 0.7320 (3) | 0.29945 (15) | 0.64771 (5) | 0.0213 (4) | |
H7A | 0.7013 | 0.3480 | 0.6241 | 0.026* | |
H7B | 0.8551 | 0.2764 | 0.6454 | 0.026* | |
C8 | 0.7092 (3) | 0.37977 (16) | 0.68389 (5) | 0.0226 (4) | |
H8A | 0.7056 | 0.3265 | 0.7075 | 0.027* | |
H8B | 0.8109 | 0.4341 | 0.6864 | 0.027* | |
C9 | 0.5496 (3) | 0.45745 (15) | 0.68308 (5) | 0.0217 (4) | |
C10 | 0.3607 (3) | 0.57710 (16) | 0.72340 (6) | 0.0277 (4) | |
H10A | 0.2994 | 0.5618 | 0.7485 | 0.033* | |
H10B | 0.2782 | 0.5636 | 0.7016 | 0.033* | |
C11 | 0.4224 (3) | 0.70637 (16) | 0.72243 (6) | 0.0249 (4) | |
H11 | 0.5161 | 0.7285 | 0.7390 | 0.030* | |
C12 | 0.3547 (3) | 0.79118 (18) | 0.70000 (6) | 0.0327 (5) | |
H12A | 0.2609 | 0.7715 | 0.6832 | 0.039* | |
H12B | 0.3992 | 0.8724 | 0.7006 | 0.039* | |
C13 | 0.3238 (3) | 0.30135 (17) | 0.58654 (6) | 0.0307 (5) | |
H13 | 0.3439 | 0.3460 | 0.6101 | 0.037* | |
C14 | 0.4030 (3) | 0.32361 (17) | 0.54977 (7) | 0.0325 (5) | |
H14 | 0.4857 | 0.3857 | 0.5443 | 0.039* | |
C15 | 0.3378 (3) | 0.23740 (18) | 0.52256 (6) | 0.0334 (5) | |
H15 | 0.3688 | 0.2313 | 0.4956 | 0.040* | |
C16 | 0.2181 (3) | 0.16173 (17) | 0.54248 (6) | 0.0310 (5) | |
H16 | 0.1546 | 0.0960 | 0.5312 | 0.037* | |
C17 | 0.2097 (3) | 0.20114 (19) | 0.58213 (6) | 0.0299 (5) | |
H17 | 0.1397 | 0.1664 | 0.6022 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01903 (17) | 0.01857 (11) | 0.01628 (13) | 0.00217 (10) | −0.00046 (11) | 0.00120 (9) |
O1 | 0.0276 (9) | 0.0277 (6) | 0.0198 (6) | −0.0050 (6) | 0.0036 (6) | 0.0010 (5) |
O2 | 0.0268 (9) | 0.0261 (6) | 0.0234 (7) | 0.0046 (6) | 0.0025 (6) | −0.0003 (5) |
O3 | 0.0407 (10) | 0.0358 (7) | 0.0247 (8) | 0.0118 (7) | −0.0091 (7) | −0.0033 (6) |
C1 | 0.0167 (10) | 0.0180 (7) | 0.0196 (9) | 0.0038 (7) | −0.0007 (8) | 0.0023 (6) |
C2 | 0.0166 (11) | 0.0222 (8) | 0.0247 (10) | 0.0012 (7) | 0.0045 (8) | 0.0008 (6) |
C3 | 0.0246 (12) | 0.0237 (8) | 0.0214 (9) | 0.0040 (8) | 0.0033 (8) | −0.0017 (7) |
C4 | 0.0221 (11) | 0.0175 (7) | 0.0229 (9) | 0.0028 (7) | −0.0021 (8) | −0.0019 (6) |
C5 | 0.0205 (11) | 0.0179 (7) | 0.0204 (9) | 0.0004 (7) | −0.0010 (7) | 0.0041 (6) |
C6 | 0.0162 (10) | 0.0214 (7) | 0.0202 (9) | 0.0030 (7) | −0.0004 (8) | 0.0030 (6) |
C7 | 0.0194 (11) | 0.0229 (8) | 0.0216 (9) | −0.0017 (7) | 0.0023 (8) | −0.0006 (7) |
C8 | 0.0234 (12) | 0.0222 (8) | 0.0221 (9) | −0.0012 (7) | −0.0020 (8) | −0.0012 (6) |
C9 | 0.0232 (11) | 0.0190 (7) | 0.0228 (9) | −0.0030 (7) | 0.0001 (8) | −0.0017 (6) |
C10 | 0.0235 (12) | 0.0284 (9) | 0.0314 (11) | 0.0023 (8) | 0.0072 (9) | 0.0000 (7) |
C11 | 0.0221 (12) | 0.0285 (9) | 0.0242 (10) | 0.0010 (8) | 0.0021 (8) | −0.0073 (7) |
C12 | 0.0271 (12) | 0.0312 (10) | 0.0400 (12) | 0.0025 (9) | 0.0032 (10) | −0.0005 (8) |
C13 | 0.0308 (13) | 0.0298 (9) | 0.0315 (11) | 0.0145 (9) | −0.0086 (10) | −0.0091 (8) |
C14 | 0.0317 (13) | 0.0212 (8) | 0.0445 (13) | 0.0059 (8) | −0.0012 (11) | 0.0073 (8) |
C15 | 0.0431 (15) | 0.0366 (10) | 0.0206 (10) | 0.0175 (10) | −0.0029 (10) | 0.0042 (8) |
C16 | 0.0270 (13) | 0.0287 (9) | 0.0372 (11) | 0.0052 (9) | −0.0147 (10) | −0.0044 (8) |
C17 | 0.0191 (12) | 0.0380 (10) | 0.0327 (11) | 0.0110 (9) | 0.0005 (9) | 0.0054 (8) |
Fe1—C1 | 2.0260 (18) | C6—C7 | 1.512 (2) |
Fe1—C2 | 2.033 (2) | C7—C8 | 1.520 (2) |
Fe1—C5 | 2.0339 (17) | C7—H7A | 0.9900 |
Fe1—C17 | 2.038 (2) | C7—H7B | 0.9900 |
Fe1—C13 | 2.0386 (18) | C8—C9 | 1.500 (3) |
Fe1—C14 | 2.0399 (18) | C8—H8A | 0.9900 |
Fe1—C16 | 2.040 (2) | C8—H8B | 0.9900 |
Fe1—C15 | 2.0415 (19) | C10—C11 | 1.488 (3) |
Fe1—C4 | 2.0517 (16) | C10—H10A | 0.9900 |
Fe1—C3 | 2.0534 (19) | C10—H10B | 0.9900 |
O1—C6 | 1.222 (2) | C11—C12 | 1.308 (3) |
O2—C9 | 1.345 (2) | C11—H11 | 0.9500 |
O2—C10 | 1.459 (2) | C12—H12A | 0.9500 |
O3—C9 | 1.205 (2) | C12—H12B | 0.9500 |
C1—C2 | 1.435 (2) | C13—C17 | 1.414 (3) |
C1—C5 | 1.441 (3) | C13—C14 | 1.414 (3) |
C1—C6 | 1.477 (2) | C13—H13 | 0.9500 |
C2—C3 | 1.416 (2) | C14—C15 | 1.412 (3) |
C2—H2 | 0.9500 | C14—H14 | 0.9500 |
C3—C4 | 1.422 (3) | C15—C16 | 1.414 (3) |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.420 (2) | C16—C17 | 1.417 (3) |
C4—H4 | 0.9500 | C16—H16 | 0.9500 |
C5—H5 | 0.9500 | C17—H17 | 0.9500 |
C1—Fe1—C2 | 41.41 (7) | C3—C4—H4 | 125.8 |
C1—Fe1—C5 | 41.58 (7) | Fe1—C4—H4 | 127.0 |
C2—Fe1—C5 | 69.46 (7) | C4—C5—C1 | 107.79 (16) |
C1—Fe1—C17 | 119.64 (8) | C4—C5—Fe1 | 70.35 (10) |
C2—Fe1—C17 | 156.39 (8) | C1—C5—Fe1 | 68.92 (10) |
C5—Fe1—C17 | 105.55 (8) | C4—C5—H5 | 126.1 |
C1—Fe1—C13 | 106.02 (8) | C1—C5—H5 | 126.1 |
C2—Fe1—C13 | 121.53 (8) | Fe1—C5—H5 | 126.2 |
C5—Fe1—C13 | 122.73 (8) | O1—C6—C1 | 121.18 (16) |
C17—Fe1—C13 | 40.57 (8) | O1—C6—C7 | 121.89 (16) |
C1—Fe1—C14 | 123.75 (8) | C1—C6—C7 | 116.92 (15) |
C2—Fe1—C14 | 108.24 (8) | C6—C7—C8 | 114.06 (15) |
C5—Fe1—C14 | 160.26 (8) | C6—C7—H7A | 108.7 |
C17—Fe1—C14 | 68.29 (9) | C8—C7—H7A | 108.7 |
C13—Fe1—C14 | 40.58 (9) | C6—C7—H7B | 108.7 |
C1—Fe1—C16 | 155.67 (9) | C8—C7—H7B | 108.7 |
C2—Fe1—C16 | 161.76 (8) | H7A—C7—H7B | 107.6 |
C5—Fe1—C16 | 120.19 (8) | C9—C8—C7 | 113.93 (16) |
C17—Fe1—C16 | 40.64 (8) | C9—C8—H8A | 108.8 |
C13—Fe1—C16 | 68.21 (8) | C7—C8—H8A | 108.8 |
C14—Fe1—C16 | 68.16 (9) | C9—C8—H8B | 108.8 |
C1—Fe1—C15 | 161.32 (8) | C7—C8—H8B | 108.8 |
C2—Fe1—C15 | 125.19 (9) | H8A—C8—H8B | 107.7 |
C5—Fe1—C15 | 156.56 (8) | O3—C9—O2 | 123.69 (18) |
C17—Fe1—C15 | 68.32 (9) | O3—C9—C8 | 125.53 (18) |
C13—Fe1—C15 | 68.20 (8) | O2—C9—C8 | 110.73 (16) |
C14—Fe1—C15 | 40.49 (9) | O2—C10—C11 | 111.11 (17) |
C16—Fe1—C15 | 40.54 (9) | O2—C10—H10A | 109.4 |
C1—Fe1—C4 | 69.05 (7) | C11—C10—H10A | 109.4 |
C2—Fe1—C4 | 68.62 (7) | O2—C10—H10B | 109.4 |
C5—Fe1—C4 | 40.66 (7) | C11—C10—H10B | 109.4 |
C17—Fe1—C4 | 123.41 (8) | H10A—C10—H10B | 108.0 |
C13—Fe1—C4 | 159.68 (9) | C12—C11—C10 | 123.5 (2) |
C14—Fe1—C4 | 158.28 (8) | C12—C11—H11 | 118.3 |
C16—Fe1—C4 | 107.71 (8) | C10—C11—H11 | 118.3 |
C15—Fe1—C4 | 122.53 (8) | C11—C12—H12A | 120.0 |
C1—Fe1—C3 | 68.91 (7) | C11—C12—H12B | 120.0 |
C2—Fe1—C3 | 40.55 (7) | H12A—C12—H12B | 120.0 |
C5—Fe1—C3 | 68.64 (7) | C17—C13—C14 | 108.09 (18) |
C17—Fe1—C3 | 160.85 (8) | C17—C13—Fe1 | 69.70 (11) |
C13—Fe1—C3 | 157.86 (9) | C14—C13—Fe1 | 69.76 (11) |
C14—Fe1—C3 | 123.16 (8) | C17—C13—H13 | 126.0 |
C16—Fe1—C3 | 125.22 (8) | C14—C13—H13 | 126.0 |
C15—Fe1—C3 | 109.34 (8) | Fe1—C13—H13 | 126.2 |
C4—Fe1—C3 | 40.54 (7) | C15—C14—C13 | 108.06 (19) |
C9—O2—C10 | 117.11 (15) | C15—C14—Fe1 | 69.82 (11) |
C2—C1—C5 | 107.32 (15) | C13—C14—Fe1 | 69.66 (11) |
C2—C1—C6 | 127.43 (16) | C15—C14—H14 | 126.0 |
C5—C1—C6 | 124.70 (17) | C13—C14—H14 | 126.0 |
C2—C1—Fe1 | 69.54 (11) | Fe1—C14—H14 | 126.1 |
C5—C1—Fe1 | 69.50 (10) | C14—C15—C16 | 107.97 (19) |
C6—C1—Fe1 | 119.63 (12) | C14—C15—Fe1 | 69.69 (11) |
C3—C2—C1 | 108.10 (16) | C16—C15—Fe1 | 69.68 (11) |
C3—C2—Fe1 | 70.51 (12) | C14—C15—H15 | 126.0 |
C1—C2—Fe1 | 69.04 (11) | C16—C15—H15 | 126.0 |
C3—C2—H2 | 125.9 | Fe1—C15—H15 | 126.2 |
C1—C2—H2 | 125.9 | C15—C16—C17 | 108.06 (18) |
Fe1—C2—H2 | 126.1 | C15—C16—Fe1 | 69.78 (12) |
C2—C3—C4 | 108.41 (16) | C17—C16—Fe1 | 69.60 (12) |
C2—C3—Fe1 | 68.94 (11) | C15—C16—H16 | 126.0 |
C4—C3—Fe1 | 69.67 (11) | C17—C16—H16 | 126.0 |
C2—C3—H3 | 125.8 | Fe1—C16—H16 | 126.2 |
C4—C3—H3 | 125.8 | C13—C17—C16 | 107.83 (19) |
Fe1—C3—H3 | 127.2 | C13—C17—Fe1 | 69.73 (12) |
C5—C4—C3 | 108.37 (16) | C16—C17—Fe1 | 69.75 (12) |
C5—C4—Fe1 | 68.99 (9) | C13—C17—H17 | 126.1 |
C3—C4—Fe1 | 69.79 (10) | C16—C17—H17 | 126.1 |
C5—C4—H4 | 125.8 | Fe1—C17—H17 | 126.0 |
C5—Fe1—C1—C2 | 118.61 (14) | C5—C1—C6—O1 | 11.2 (3) |
C17—Fe1—C1—C2 | −161.56 (10) | Fe1—C1—C6—O1 | 95.69 (18) |
C13—Fe1—C1—C2 | −119.79 (11) | C2—C1—C6—C7 | 0.1 (3) |
C14—Fe1—C1—C2 | −79.13 (13) | C5—C1—C6—C7 | −170.34 (16) |
C16—Fe1—C1—C2 | 167.80 (16) | Fe1—C1—C6—C7 | −85.86 (19) |
C15—Fe1—C1—C2 | −50.7 (3) | O1—C6—C7—C8 | −8.9 (3) |
C4—Fe1—C1—C2 | 81.02 (11) | C1—C6—C7—C8 | 172.68 (16) |
C3—Fe1—C1—C2 | 37.44 (10) | C6—C7—C8—C9 | −79.7 (2) |
C2—Fe1—C1—C5 | −118.61 (14) | C10—O2—C9—O3 | −3.6 (3) |
C17—Fe1—C1—C5 | 79.83 (13) | C10—O2—C9—C8 | 174.14 (15) |
C13—Fe1—C1—C5 | 121.60 (12) | C7—C8—C9—O3 | −24.3 (3) |
C14—Fe1—C1—C5 | 162.27 (12) | C7—C8—C9—O2 | 158.09 (15) |
C16—Fe1—C1—C5 | 49.2 (2) | C9—O2—C10—C11 | −89.2 (2) |
C15—Fe1—C1—C5 | −169.3 (2) | O2—C10—C11—C12 | 131.0 (2) |
C4—Fe1—C1—C5 | −37.59 (11) | C1—Fe1—C13—C17 | −117.11 (12) |
C3—Fe1—C1—C5 | −81.16 (11) | C2—Fe1—C13—C17 | −159.45 (12) |
C2—Fe1—C1—C6 | 122.28 (18) | C5—Fe1—C13—C17 | −74.89 (14) |
C5—Fe1—C1—C6 | −119.11 (19) | C14—Fe1—C13—C17 | 119.29 (18) |
C17—Fe1—C1—C6 | −39.28 (17) | C16—Fe1—C13—C17 | 37.87 (12) |
C13—Fe1—C1—C6 | 2.49 (16) | C15—Fe1—C13—C17 | 81.68 (13) |
C14—Fe1—C1—C6 | 43.16 (18) | C4—Fe1—C13—C17 | −44.3 (3) |
C16—Fe1—C1—C6 | −69.9 (2) | C3—Fe1—C13—C17 | 169.59 (18) |
C15—Fe1—C1—C6 | 71.6 (3) | C1—Fe1—C13—C14 | 123.60 (13) |
C4—Fe1—C1—C6 | −156.70 (16) | C2—Fe1—C13—C14 | 81.27 (14) |
C3—Fe1—C1—C6 | 159.73 (16) | C5—Fe1—C13—C14 | 165.82 (13) |
C5—C1—C2—C3 | −0.5 (2) | C17—Fe1—C13—C14 | −119.29 (18) |
C6—C1—C2—C3 | −172.20 (18) | C16—Fe1—C13—C14 | −81.42 (14) |
Fe1—C1—C2—C3 | −59.93 (13) | C15—Fe1—C13—C14 | −37.60 (14) |
C5—C1—C2—Fe1 | 59.48 (12) | C4—Fe1—C13—C14 | −163.6 (2) |
C6—C1—C2—Fe1 | −112.27 (19) | C3—Fe1—C13—C14 | 50.3 (3) |
C1—Fe1—C2—C3 | 119.24 (14) | C17—C13—C14—C15 | 0.1 (2) |
C5—Fe1—C2—C3 | 80.76 (11) | Fe1—C13—C14—C15 | 59.47 (14) |
C17—Fe1—C2—C3 | 162.59 (18) | C17—C13—C14—Fe1 | −59.38 (13) |
C13—Fe1—C2—C3 | −162.65 (11) | C1—Fe1—C14—C15 | 166.41 (13) |
C14—Fe1—C2—C3 | −120.04 (12) | C2—Fe1—C14—C15 | 123.26 (14) |
C16—Fe1—C2—C3 | −44.6 (3) | C5—Fe1—C14—C15 | −156.8 (2) |
C15—Fe1—C2—C3 | −78.41 (13) | C17—Fe1—C14—C15 | −81.61 (15) |
C4—Fe1—C2—C3 | 37.09 (11) | C13—Fe1—C14—C15 | −119.2 (2) |
C5—Fe1—C2—C1 | −38.48 (10) | C16—Fe1—C14—C15 | −37.69 (13) |
C17—Fe1—C2—C1 | 43.4 (2) | C4—Fe1—C14—C15 | 45.4 (3) |
C13—Fe1—C2—C1 | 78.11 (12) | C3—Fe1—C14—C15 | 81.02 (15) |
C14—Fe1—C2—C1 | 120.72 (11) | C1—Fe1—C14—C13 | −74.34 (15) |
C16—Fe1—C2—C1 | −163.9 (2) | C2—Fe1—C14—C13 | −117.49 (13) |
C15—Fe1—C2—C1 | 162.35 (10) | C5—Fe1—C14—C13 | −37.6 (3) |
C4—Fe1—C2—C1 | −82.15 (10) | C17—Fe1—C14—C13 | 37.63 (13) |
C3—Fe1—C2—C1 | −119.24 (14) | C16—Fe1—C14—C13 | 81.56 (14) |
C1—C2—C3—C4 | 0.4 (2) | C15—Fe1—C14—C13 | 119.2 (2) |
Fe1—C2—C3—C4 | −58.63 (13) | C4—Fe1—C14—C13 | 164.6 (2) |
C1—C2—C3—Fe1 | 59.01 (13) | C3—Fe1—C14—C13 | −159.73 (12) |
C1—Fe1—C3—C2 | −38.21 (10) | C13—C14—C15—C16 | 0.0 (2) |
C5—Fe1—C3—C2 | −82.98 (11) | Fe1—C14—C15—C16 | 59.39 (14) |
C17—Fe1—C3—C2 | −158.6 (2) | C13—C14—C15—Fe1 | −59.38 (14) |
C13—Fe1—C3—C2 | 42.4 (2) | C1—Fe1—C15—C14 | −37.6 (3) |
C14—Fe1—C3—C2 | 79.13 (13) | C2—Fe1—C15—C14 | −76.35 (15) |
C16—Fe1—C3—C2 | 164.39 (11) | C5—Fe1—C15—C14 | 160.48 (19) |
C15—Fe1—C3—C2 | 121.95 (12) | C17—Fe1—C15—C14 | 81.51 (15) |
C4—Fe1—C3—C2 | −120.24 (15) | C13—Fe1—C15—C14 | 37.68 (14) |
C1—Fe1—C3—C4 | 82.03 (12) | C16—Fe1—C15—C14 | 119.19 (18) |
C2—Fe1—C3—C4 | 120.24 (15) | C4—Fe1—C15—C14 | −161.79 (13) |
C5—Fe1—C3—C4 | 37.26 (11) | C3—Fe1—C15—C14 | −118.79 (14) |
C17—Fe1—C3—C4 | −38.3 (3) | C1—Fe1—C15—C16 | −156.8 (2) |
C13—Fe1—C3—C4 | 162.66 (19) | C2—Fe1—C15—C16 | 164.46 (11) |
C14—Fe1—C3—C4 | −160.62 (12) | C5—Fe1—C15—C16 | 41.3 (3) |
C16—Fe1—C3—C4 | −75.37 (14) | C17—Fe1—C15—C16 | −37.68 (12) |
C15—Fe1—C3—C4 | −117.80 (12) | C13—Fe1—C15—C16 | −81.51 (13) |
C2—C3—C4—C5 | −0.2 (2) | C14—Fe1—C15—C16 | −119.19 (18) |
Fe1—C3—C4—C5 | −58.35 (12) | C4—Fe1—C15—C16 | 79.02 (14) |
C2—C3—C4—Fe1 | 58.18 (13) | C3—Fe1—C15—C16 | 122.02 (12) |
C1—Fe1—C4—C5 | 38.42 (11) | C14—C15—C16—C17 | −0.1 (2) |
C2—Fe1—C4—C5 | 82.98 (12) | Fe1—C15—C16—C17 | 59.28 (14) |
C17—Fe1—C4—C5 | −74.04 (14) | C14—C15—C16—Fe1 | −59.40 (14) |
C13—Fe1—C4—C5 | −41.1 (3) | C1—Fe1—C16—C15 | 162.14 (16) |
C14—Fe1—C4—C5 | 168.7 (2) | C2—Fe1—C16—C15 | −44.4 (3) |
C16—Fe1—C4—C5 | −116.00 (12) | C5—Fe1—C16—C15 | −162.32 (11) |
C15—Fe1—C4—C5 | −158.06 (12) | C17—Fe1—C16—C15 | 119.30 (16) |
C3—Fe1—C4—C5 | 120.07 (16) | C13—Fe1—C16—C15 | 81.50 (13) |
C1—Fe1—C4—C3 | −81.66 (12) | C14—Fe1—C16—C15 | 37.64 (12) |
C2—Fe1—C4—C3 | −37.10 (11) | C4—Fe1—C16—C15 | −119.67 (12) |
C5—Fe1—C4—C3 | −120.07 (16) | C3—Fe1—C16—C15 | −78.35 (13) |
C17—Fe1—C4—C3 | 165.89 (11) | C1—Fe1—C16—C17 | 42.8 (2) |
C13—Fe1—C4—C3 | −161.1 (2) | C2—Fe1—C16—C17 | −163.7 (2) |
C14—Fe1—C4—C3 | 48.6 (3) | C5—Fe1—C16—C17 | 78.38 (13) |
C16—Fe1—C4—C3 | 123.93 (12) | C13—Fe1—C16—C17 | −37.80 (12) |
C15—Fe1—C4—C3 | 81.87 (14) | C14—Fe1—C16—C17 | −81.66 (13) |
C3—C4—C5—C1 | −0.1 (2) | C15—Fe1—C16—C17 | −119.30 (16) |
Fe1—C4—C5—C1 | −58.95 (12) | C4—Fe1—C16—C17 | 121.03 (12) |
C3—C4—C5—Fe1 | 58.84 (13) | C3—Fe1—C16—C17 | 162.34 (11) |
C2—C1—C5—C4 | 0.3 (2) | C14—C13—C17—C16 | −0.2 (2) |
C6—C1—C5—C4 | 172.37 (16) | Fe1—C13—C17—C16 | −59.58 (14) |
Fe1—C1—C5—C4 | 59.85 (12) | C14—C13—C17—Fe1 | 59.42 (14) |
C2—C1—C5—Fe1 | −59.50 (12) | C15—C16—C17—C13 | 0.2 (2) |
C6—C1—C5—Fe1 | 112.52 (17) | Fe1—C16—C17—C13 | 59.56 (13) |
C1—Fe1—C5—C4 | −119.04 (16) | C15—C16—C17—Fe1 | −59.39 (14) |
C2—Fe1—C5—C4 | −80.71 (12) | C1—Fe1—C17—C13 | 79.85 (14) |
C17—Fe1—C5—C4 | 123.59 (12) | C2—Fe1—C17—C13 | 48.3 (2) |
C13—Fe1—C5—C4 | 164.27 (12) | C5—Fe1—C17—C13 | 122.54 (12) |
C14—Fe1—C5—C4 | −167.6 (2) | C14—Fe1—C17—C13 | −37.64 (13) |
C16—Fe1—C5—C4 | 82.11 (13) | C16—Fe1—C17—C13 | −118.96 (17) |
C15—Fe1—C5—C4 | 52.4 (3) | C15—Fe1—C17—C13 | −81.37 (13) |
C3—Fe1—C5—C4 | −37.16 (11) | C4—Fe1—C17—C13 | 163.10 (12) |
C2—Fe1—C5—C1 | 38.33 (10) | C3—Fe1—C17—C13 | −168.0 (2) |
C17—Fe1—C5—C1 | −117.38 (12) | C1—Fe1—C17—C16 | −161.20 (11) |
C13—Fe1—C5—C1 | −76.70 (13) | C2—Fe1—C17—C16 | 167.30 (17) |
C14—Fe1—C5—C1 | −48.6 (3) | C5—Fe1—C17—C16 | −118.50 (12) |
C16—Fe1—C5—C1 | −158.85 (11) | C13—Fe1—C17—C16 | 118.96 (17) |
C15—Fe1—C5—C1 | 171.40 (19) | C14—Fe1—C17—C16 | 81.32 (13) |
C4—Fe1—C5—C1 | 119.04 (16) | C15—Fe1—C17—C16 | 37.59 (12) |
C3—Fe1—C5—C1 | 81.88 (12) | C4—Fe1—C17—C16 | −77.94 (13) |
C2—C1—C6—O1 | −178.39 (18) | C3—Fe1—C17—C16 | −49.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C12H13O3)] |
Mr | 326.16 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 7.7561 (1), 10.8931 (2), 34.0120 (6) |
V (Å3) | 2873.60 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.32 × 0.20 × 0.05 |
Data collection | |
Diffractometer | KappaCCD diffractometer (with Oxford Cryosystems Cryostream cooler) |
Absorption correction | Multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.844, 0.949 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19653, 4409, 3031 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.744 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.091, 1.01 |
No. of reflections | 4409 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.58 |
Computer programs: COLLECT (Nonius, 1999), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
Fe1—C1 | 2.0260 (18) | Fe1—C4 | 2.0517 (16) |
Fe1—C2 | 2.033 (2) | Fe1—C3 | 2.0534 (19) |
Fe1—C5 | 2.0339 (17) | O1—C6 | 1.222 (2) |
Fe1—C17 | 2.038 (2) | O2—C9 | 1.345 (2) |
Fe1—C13 | 2.0386 (18) | O2—C10 | 1.459 (2) |
Fe1—C14 | 2.0399 (18) | O3—C9 | 1.205 (2) |
Fe1—C16 | 2.040 (2) | C11—C12 | 1.308 (3) |
Fe1—C15 | 2.0415 (19) | ||
C5—C1—C6—O1 | 11.2 (3) | C10—O2—C9—C8 | 174.14 (15) |
O1—C6—C7—C8 | −8.9 (3) | C7—C8—C9—O2 | 158.09 (15) |
C6—C7—C8—C9 | −79.7 (2) | O2—C10—C11—C12 | 131.0 (2) |
With the rapid development of solid-phase synthesis, there is a great deal of interest in developing new solid-phase linkers. We report here the synthesis of 2-propenyl 4-ferrocenyl-4-oxobutanoate, (I), a ferrocenylamide-based linker precursor. This allyl ester ferrocene derivative was prepared to be used as a linker in solid-phase peptide synthesis (SPPS). The mild conditions used to remove allyl groups are compatible with classical Fmoc/tBu methods (Kates et al., 1993; Trzeciak & Bannwarth, 1992; Merrifield, 1995). The allyl ester serves as a protecting group and is easily cleaved without disrupting the other protecting groups by using palladium catalysts under neutral conditions. Upon reductive amination of the ketone and peptide synthesis, the ferrocenyl–amine bond will be easily cleaved (Blanchet et al., 2000) making the ferrocenyl cation which is more stable than the traditional benzylic cations used in SPPS (Watts, 1979). The crystal structure of the title compound was determined to prove its successful synthesis.
The cyclopentadienyl (Cp) rings are essentially eclipsed, forming C—Centroid—Centroid—C torsion angles which average 3.3 (2)°. The rings are nearly parallel, forming a 2.5 (2)° dihedral angle. The Fe atom lies 1.6388 (8) Å out of Cp ring C1–C5 and 1.6472 (9) Å out of Cp ring C13–C17. These are typical geometric features [see, for example, Gallagher et al. (1997)]. The carbonyl C6═O1 is twisted by 11.2 (3)° out of the Cp ring to which it is attached. The conformation of the remainder of the substituent on Cp ring C1—C5 (Table 1) is such that the ester carbonyl O3 atom forms an intramolecular C—H···O hydrogen bond with the unsubstituted Cp ring. The C13···O3 distance is 3.289 (2) Å, the H···O distance is 2.39 Å, and the angle about H is 159°.