Acta Cryst. (2007). E63, m3067 [ doi:10.1107/S1600536807053391 ]
In the title compound, [Fe(C5H5)(C12H7Cl2O)], the cyclopentadienyl rings are almost parallel and eclipsed as typically found for similar monosubstituted ferrocene derivatives. Weak C-H
O and C-HCl hydrogen bonds link molecules into two-dimensional layers parallel to the ac plane in the crystal structure.
The title compound was synthesized from ferrocene and 3,4-dichlorobenzoyl chloride in the presence of AlCl3 following the procedure described by Reeves (1977). Melting point, IR and NMR spectra confirmed identity and purity of prepared compound. Crystals suitable for X-ray diffraction analysis were grown by sublimation in a sealed ampoule at 0.1 Pa and 380 K.
All H atoms were positioned geometrically and refined as riding on their parent C atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: enCIFer (Allen et al., 2004).
![[Figure 1]](./bh2140fig1thm.gif)
| Fig. 1. ORTEP view of the title compound with displacement ellipsoids drawn at the 50% probability level. |
| [Fe(C5H5)(C12H7Cl2O)] | Z = 2 |
| Mr = 359.02 | F000 = 364 |
| Triclinic, P1 | Dx = 1.719 Mg m−3 |
| Hall symbol: -P 1 | Melting point: 426 K |
| a = 6.1970 (3) Å | Mo Kα radiation λ = 0.71073 Å |
| b = 10.0720 (5) Å | Cell parameters from 11119 reflections |
| c = 11.8160 (7) Å | θ = 1–27.5º |
| α = 78.098 (4)º | µ = 1.47 mm−1 |
| β = 76.452 (4)º | T = 150 (1) K |
| γ = 78.903 (3)º | Plate, red |
| V = 693.47 (6) Å3 | 0.40 × 0.30 × 0.06 mm |
| Bruker–Nonius KappaCCD area-detector diffractometer | 3169 independent reflections |
| Monochromator: graphite | 2773 reflections with I > 2σ(I) |
| Detector resolution: 9.091 pixels mm-1 | Rint = 0.133 |
| T = 150(1) K | θmax = 27.5º |
| φ and ω scans to fill the Ewald sphere | θmin = 3.0º |
| Absorption correction: integration Gaussian integration (Coppens et al., 1970) | h = −7→8 |
| Tmin = 0.551, Tmax = 0.916 | k = −13→12 |
| 11098 measured reflections | l = −15→15 |
| 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)] = 0.042 | H-atom parameters constrained |
| wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0055P)2 + 0.7487P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.15 | (Δ/σ)max < 0.001 |
| 3169 reflections | Δρmax = 0.72 e Å−3 |
| 190 parameters | Δρmin = −0.74 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Fe(C5H5)(C12H7Cl2O)] | γ = 78.903 (3)º |
| Mr = 359.02 | V = 693.47 (6) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.1970 (3) Å | Mo Kα |
| b = 10.0720 (5) Å | µ = 1.47 mm−1 |
| c = 11.8160 (7) Å | T = 150 (1) K |
| α = 78.098 (4)º | 0.40 × 0.30 × 0.06 mm |
| β = 76.452 (4)º |
| Bruker–Nonius KappaCCD area-detector diffractometer | 3169 independent reflections |
| Absorption correction: integration Gaussian integration (Coppens et al., 1970) | 2773 reflections with I > 2σ(I) |
| Tmin = 0.551, Tmax = 0.916 | Rint = 0.133 |
| 11098 measured reflections |
| R[F2 > 2σ(F2)] = 0.042 | 190 parameters |
| wR(F2) = 0.102 | H-atom parameters constrained |
| S = 1.15 | Δρmax = 0.72 e Å−3 |
| 3169 reflections | Δρmin = −0.74 e Å−3 |
Experimental. Melting point: 426–427 K. Spectroscopic analysis: 1H NMR (benzene-d6, δ, p.p.m.): 3.84 (s, 5H), 4.09 (m, 2H), 4.66 (m, 2H), 6.95 (m, 1H), 7.44 (m, 1H), 8.04 (d, 1H). 13C NMR (benzene-d6, δ, p.p.m.): 67.0, 71.1, 72.3, 77.8, 129.5, 130.2, 132.3, 135.4, 139.3, 184.5. Uv-Vis (cyclohexane, maxima at nm): 473, 369, 284 (sh). IR (KBr disc, cm−1): 3108 (m), 1625 (s), 1581 (m), 1555 (m), 1533 (w), 1455 (m), 1445 (s), 1385 (s), 1289 (s), 1246 (m), 1172 (m), 1131 (w), 1106 (m), 1054 (m), 1028 (m), 1002 (w), 969 (m), 907 (m), 877 (w), 848 (w), 829 (s), 767 (m), 752 (m), 678 (m), 667 (w), 579 (w), 538 (m), 501 (m), 486 (m), 442 (w). |
| x | y | z | Uiso*/Ueq | ||
| Fe1 | 0.83358 (6) | 0.22818 (4) | 0.27185 (4) | 0.01123 (12) | |
| Cl2 | 0.33933 (12) | 0.18553 (8) | 0.93854 (7) | 0.02494 (19) | |
| Cl1 | 0.76392 (12) | 0.31674 (8) | 0.92710 (7) | 0.02464 (19) | |
| O1 | 1.1551 (3) | 0.3333 (3) | 0.4841 (2) | 0.0256 (5) | |
| C4 | 0.9628 (5) | 0.3893 (3) | 0.1563 (3) | 0.0178 (6) | |
| H4 | 1.0332 | 0.3891 | 0.0776 | 0.021* | |
| C13 | 0.8399 (4) | 0.3279 (3) | 0.6918 (3) | 0.0138 (6) | |
| H13 | 0.9690 | 0.3638 | 0.6888 | 0.017* | |
| C1 | 0.9018 (4) | 0.3649 (3) | 0.3600 (3) | 0.0133 (6) | |
| C15 | 0.5085 (4) | 0.2371 (3) | 0.8039 (3) | 0.0138 (6) | |
| C16 | 0.4526 (4) | 0.2223 (3) | 0.7020 (3) | 0.0149 (6) | |
| H16 | 0.3223 | 0.1873 | 0.7056 | 0.018* | |
| C7 | 0.6071 (5) | 0.0945 (3) | 0.3417 (3) | 0.0181 (6) | |
| H7 | 0.4651 | 0.1143 | 0.3879 | 0.022* | |
| C11 | 0.9590 (4) | 0.3365 (3) | 0.4761 (3) | 0.0149 (6) | |
| C14 | 0.6996 (4) | 0.2925 (3) | 0.7995 (3) | 0.0140 (6) | |
| C12 | 0.7887 (4) | 0.3099 (3) | 0.5885 (3) | 0.0129 (6) | |
| C17 | 0.5904 (4) | 0.2596 (3) | 0.5934 (3) | 0.0139 (6) | |
| H17 | 0.5513 | 0.2512 | 0.5241 | 0.017* | |
| C5 | 1.0691 (5) | 0.3524 (3) | 0.2539 (3) | 0.0173 (6) | |
| H5 | 1.2222 | 0.3245 | 0.2502 | 0.021* | |
| C10 | 0.9866 (5) | 0.0274 (3) | 0.2838 (3) | 0.0198 (7) | |
| H10 | 1.1371 | −0.0044 | 0.2858 | 0.024* | |
| C2 | 0.6896 (4) | 0.4111 (3) | 0.3241 (3) | 0.0153 (6) | |
| H2 | 0.5507 | 0.4278 | 0.3740 | 0.018* | |
| C9 | 0.8939 (5) | 0.0678 (3) | 0.1809 (3) | 0.0191 (6) | |
| H9 | 0.9731 | 0.0672 | 0.1037 | 0.023* | |
| C8 | 0.6603 (5) | 0.1094 (3) | 0.2159 (3) | 0.0181 (6) | |
| H8 | 0.5591 | 0.1410 | 0.1657 | 0.022* | |
| C3 | 0.7291 (5) | 0.4269 (3) | 0.1992 (3) | 0.0186 (6) | |
| H3 | 0.6206 | 0.4568 | 0.1531 | 0.022* | |
| C6 | 0.8093 (5) | 0.0440 (3) | 0.3838 (3) | 0.0198 (7) | |
| H6 | 0.8235 | 0.0252 | 0.4624 | 0.024* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.0107 (2) | 0.00976 (18) | 0.0112 (2) | −0.00165 (14) | 0.00060 (14) | −0.00050 (15) |
| Cl2 | 0.0214 (4) | 0.0346 (4) | 0.0160 (4) | −0.0112 (3) | 0.0055 (3) | −0.0020 (3) |
| Cl1 | 0.0274 (4) | 0.0353 (4) | 0.0144 (4) | −0.0120 (3) | −0.0057 (3) | −0.0030 (3) |
| O1 | 0.0101 (9) | 0.0460 (14) | 0.0210 (14) | −0.0065 (9) | −0.0018 (8) | −0.0056 (11) |
| C4 | 0.0257 (14) | 0.0134 (12) | 0.0114 (16) | −0.0076 (11) | 0.0017 (11) | 0.0025 (11) |
| C13 | 0.0099 (11) | 0.0157 (12) | 0.0152 (16) | −0.0029 (10) | −0.0030 (10) | −0.0001 (11) |
| C1 | 0.0139 (12) | 0.0111 (12) | 0.0138 (16) | −0.0039 (10) | 0.0005 (10) | −0.0015 (11) |
| C15 | 0.0117 (12) | 0.0131 (12) | 0.0140 (16) | −0.0013 (10) | 0.0015 (10) | −0.0017 (11) |
| C16 | 0.0104 (12) | 0.0154 (12) | 0.0182 (17) | −0.0022 (10) | −0.0019 (10) | −0.0023 (11) |
| C7 | 0.0173 (13) | 0.0173 (13) | 0.0197 (17) | −0.0099 (11) | 0.0000 (11) | −0.0009 (12) |
| C11 | 0.0120 (12) | 0.0155 (12) | 0.0171 (16) | −0.0025 (10) | −0.0027 (11) | −0.0023 (11) |
| C14 | 0.0153 (12) | 0.0147 (12) | 0.0125 (16) | −0.0006 (10) | −0.0057 (10) | −0.0020 (11) |
| C12 | 0.0103 (12) | 0.0122 (12) | 0.0137 (16) | 0.0001 (10) | −0.0009 (10) | 0.0002 (10) |
| C17 | 0.0099 (11) | 0.0163 (12) | 0.0155 (16) | −0.0012 (10) | −0.0028 (10) | −0.0034 (11) |
| C5 | 0.0158 (13) | 0.0180 (13) | 0.0163 (16) | −0.0069 (11) | 0.0039 (11) | −0.0029 (11) |
| C10 | 0.0189 (13) | 0.0099 (12) | 0.027 (2) | 0.0023 (10) | −0.0034 (12) | −0.0010 (12) |
| C2 | 0.0149 (12) | 0.0089 (11) | 0.0212 (17) | 0.0003 (10) | −0.0038 (11) | −0.0020 (11) |
| C9 | 0.0263 (15) | 0.0162 (13) | 0.0133 (16) | −0.0060 (12) | 0.0045 (12) | −0.0065 (11) |
| C8 | 0.0225 (14) | 0.0163 (13) | 0.0173 (17) | −0.0063 (11) | −0.0053 (11) | −0.0020 (12) |
| C3 | 0.0228 (14) | 0.0115 (12) | 0.0203 (18) | −0.0002 (11) | −0.0054 (12) | −0.0009 (11) |
| C6 | 0.0271 (15) | 0.0122 (12) | 0.0182 (17) | −0.0069 (11) | −0.0023 (12) | 0.0025 (12) |
| Fe1—C2 | 2.037 (3) | C15—C16 | 1.372 (4) |
| Fe1—C8 | 2.043 (3) | C15—C14 | 1.390 (4) |
| Fe1—C1 | 2.045 (3) | C16—C17 | 1.389 (4) |
| Fe1—C5 | 2.046 (3) | C16—H16 | 0.9300 |
| Fe1—C7 | 2.047 (2) | C7—C6 | 1.421 (4) |
| Fe1—C9 | 2.049 (3) | C7—C8 | 1.428 (5) |
| Fe1—C4 | 2.053 (2) | C7—H7 | 0.9300 |
| Fe1—C6 | 2.053 (3) | C11—C12 | 1.502 (4) |
| Fe1—C10 | 2.053 (3) | C12—C17 | 1.402 (3) |
| Fe1—C3 | 2.053 (3) | C17—H17 | 0.9300 |
| Cl2—C15 | 1.728 (3) | C5—H5 | 0.9300 |
| Cl1—C14 | 1.720 (3) | C10—C9 | 1.417 (5) |
| O1—C11 | 1.235 (3) | C10—C6 | 1.426 (4) |
| C4—C5 | 1.409 (4) | C10—H10 | 0.9300 |
| C4—C3 | 1.422 (4) | C2—C3 | 1.419 (5) |
| C4—H4 | 0.9300 | C2—H2 | 0.9300 |
| C13—C12 | 1.384 (4) | C9—C8 | 1.414 (4) |
| C13—C14 | 1.385 (4) | C9—H9 | 0.9300 |
| C13—H13 | 0.9300 | C8—H8 | 0.9300 |
| C1—C5 | 1.439 (4) | C3—H3 | 0.9300 |
| C1—C2 | 1.439 (4) | C6—H6 | 0.9300 |
| C1—C11 | 1.454 (4) | ||
| C2—Fe1—C8 | 122.72 (11) | C15—C16—C17 | 120.0 (2) |
| C2—Fe1—C1 | 41.27 (11) | C15—C16—H16 | 120.0 |
| C8—Fe1—C1 | 160.73 (11) | C17—C16—H16 | 120.0 |
| C2—Fe1—C5 | 68.79 (11) | C6—C7—C8 | 108.0 (3) |
| C8—Fe1—C5 | 155.61 (13) | C6—C7—Fe1 | 69.95 (14) |
| C1—Fe1—C5 | 41.17 (11) | C8—C7—Fe1 | 69.44 (14) |
| C2—Fe1—C7 | 107.01 (11) | C6—C7—H7 | 126.0 |
| C8—Fe1—C7 | 40.86 (12) | C8—C7—H7 | 126.0 |
| C1—Fe1—C7 | 124.75 (12) | Fe1—C7—H7 | 126.2 |
| C5—Fe1—C7 | 162.75 (13) | O1—C11—C1 | 119.5 (3) |
| C2—Fe1—C9 | 159.04 (13) | O1—C11—C12 | 117.7 (3) |
| C8—Fe1—C9 | 40.44 (12) | C1—C11—C12 | 122.8 (2) |
| C1—Fe1—C9 | 158.00 (12) | C13—C14—C15 | 119.7 (3) |
| C5—Fe1—C9 | 121.68 (12) | C13—C14—Cl1 | 119.8 (2) |
| C7—Fe1—C9 | 68.28 (12) | C15—C14—Cl1 | 120.5 (2) |
| C2—Fe1—C4 | 68.58 (12) | C13—C12—C17 | 119.6 (3) |
| C8—Fe1—C4 | 119.76 (13) | C13—C12—C11 | 117.6 (2) |
| C1—Fe1—C4 | 68.83 (12) | C17—C12—C11 | 122.7 (3) |
| C5—Fe1—C4 | 40.22 (12) | C16—C17—C12 | 119.8 (3) |
| C7—Fe1—C4 | 155.46 (13) | C16—C17—H17 | 120.1 |
| C9—Fe1—C4 | 106.74 (12) | C12—C17—H17 | 120.1 |
| C2—Fe1—C6 | 122.28 (13) | C4—C5—C1 | 108.8 (2) |
| C8—Fe1—C6 | 68.47 (12) | C4—C5—Fe1 | 70.13 (15) |
| C1—Fe1—C6 | 108.89 (12) | C1—C5—Fe1 | 69.37 (14) |
| C5—Fe1—C6 | 126.45 (12) | C4—C5—H5 | 125.6 |
| C7—Fe1—C6 | 40.56 (12) | C1—C5—H5 | 125.6 |
| C9—Fe1—C6 | 68.30 (13) | Fe1—C5—H5 | 126.5 |
| C4—Fe1—C6 | 162.02 (12) | C9—C10—C6 | 108.2 (3) |
| C2—Fe1—C10 | 158.73 (14) | C9—C10—Fe1 | 69.63 (16) |
| C8—Fe1—C10 | 68.11 (12) | C6—C10—Fe1 | 69.67 (16) |
| C1—Fe1—C10 | 123.20 (12) | C9—C10—H10 | 125.9 |
| C5—Fe1—C10 | 109.30 (12) | C6—C10—H10 | 125.9 |
| C7—Fe1—C10 | 68.18 (11) | Fe1—C10—H10 | 126.4 |
| C9—Fe1—C10 | 40.41 (13) | C3—C2—C1 | 108.1 (2) |
| C4—Fe1—C10 | 124.55 (12) | C3—C2—Fe1 | 70.31 (17) |
| C6—Fe1—C10 | 40.65 (12) | C1—C2—Fe1 | 69.65 (16) |
| C2—Fe1—C3 | 40.58 (13) | C3—C2—H2 | 125.9 |
| C8—Fe1—C3 | 105.76 (12) | C1—C2—H2 | 125.9 |
| C1—Fe1—C3 | 68.74 (12) | Fe1—C2—H2 | 125.7 |
| C5—Fe1—C3 | 67.95 (12) | C8—C9—C10 | 108.2 (3) |
| C7—Fe1—C3 | 120.48 (11) | C8—C9—Fe1 | 69.58 (17) |
| C9—Fe1—C3 | 122.75 (14) | C10—C9—Fe1 | 69.96 (18) |
| C4—Fe1—C3 | 40.52 (11) | C8—C9—H9 | 125.9 |
| C6—Fe1—C3 | 156.78 (12) | C10—C9—H9 | 125.9 |
| C10—Fe1—C3 | 159.99 (14) | Fe1—C9—H9 | 126.2 |
| C5—C4—C3 | 108.0 (3) | C9—C8—C7 | 108.0 (3) |
| C5—C4—Fe1 | 69.65 (15) | C9—C8—Fe1 | 69.98 (16) |
| C3—C4—Fe1 | 69.76 (14) | C7—C8—Fe1 | 69.70 (16) |
| C5—C4—H4 | 126.0 | C9—C8—H8 | 126.0 |
| C3—C4—H4 | 126.0 | C7—C8—H8 | 126.0 |
| Fe1—C4—H4 | 126.2 | Fe1—C8—H8 | 125.9 |
| C12—C13—C14 | 120.2 (2) | C2—C3—C4 | 108.4 (3) |
| C12—C13—H13 | 119.9 | C2—C3—Fe1 | 69.11 (16) |
| C14—C13—H13 | 119.9 | C4—C3—Fe1 | 69.72 (15) |
| C5—C1—C2 | 106.6 (3) | C2—C3—H3 | 125.8 |
| C5—C1—C11 | 122.2 (2) | C4—C3—H3 | 125.8 |
| C2—C1—C11 | 131.2 (3) | Fe1—C3—H3 | 127.0 |
| C5—C1—Fe1 | 69.46 (17) | C7—C6—C10 | 107.6 (3) |
| C2—C1—Fe1 | 69.07 (16) | C7—C6—Fe1 | 69.49 (15) |
| C11—C1—Fe1 | 127.36 (18) | C10—C6—Fe1 | 69.68 (15) |
| C16—C15—C14 | 120.6 (3) | C7—C6—H6 | 126.2 |
| C16—C15—Cl2 | 119.39 (19) | C10—C6—H6 | 126.2 |
| C14—C15—Cl2 | 120.0 (2) | Fe1—C6—H6 | 126.2 |
| Fe1···Cg1 | 1.6505 (10) |
| Fe1···Cg2 | 1.6479 (10) |
| Cg1···Fe1···Cg2 | 177.94 (8) |
| Cg1 and Cg2 are the centroids defined by atoms C1–C5 and C6–C10, respectively. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C17—H17···O1i | 0.93 | 2.56 | 3.156 (4) | 123 |
| C9—H9···Cl2ii | 0.93 | 2.90 | 3.658 (3) | 140 |
| Symmetry codes: (i) x − 1, −y + 1, z; (ii) x − 1, y, z + 1. |
The authors thank the Ministry of Education, Youth and Sports of the Czech Republic for financial support of this work within the framework of research project MSM 0021627501.
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Ferrocene complexes are widely used in homogenous catalysis, organic or organometallic synthesis and in material science. The use of ferrocene and its derivatives as catalyst in drying process of oxidizable paints was investigated recently (Šťáva et al., 2007) and it was observed that ferrocenes bearing electron-withdrawing substituents show the highest activity. As a part of our investigation of ferrocene derivatives, we have prepared the title compound, (I), and determined its structure in the solid state.
As Figure 1 shows, the title compound displays a structure typical for monosubstituted acylferrocenes. The cyclopentadienyl (Cp) rings are almost parallel, making a dihedral angle of 2.0 (2)°, and are eclipsed as viewed down the normal of Cp rings. The dihedral angle between a ring C atom, the two ring centroids and the C atom of opposite ring varies from 3.1 (2)° to 3.9 (3)°. The interatomic distances and angles in (I) are very close to those found in benzoylferrocene (Butler et al., 1988), see Table 1.
The angle between the plane defined by ring of 3,4-dichlorobenzoyl group and Cp ring bonded to this group is found to be 39.5 (2)°, validating that Cp and benzene ring π-systems are not conjugated. Carbonyl atom C11 is displaced slightly out of the Cp ring away from the Fe atom, with an angle of 1.3 (2)° between the ring plane and C1—C11 bond.
Geometric parameters of weak intermolecular interactions observed in the crystal of (I) are listed in the Table 2. Atom O1 of the molecule at (−1 + x, 1 − y, z) serves as an acceptor for atom C17 of the molecule in the asymmetric unit, generating molecular wires along the [100] axis. Atom C9 of the asymmetric unit serves as a donor to atom Cl2 of the molecule at (−1 + x, y, 1 + z), linking the above mentioned molecular wires into two-dimensional layers parallel to the ac plane.