Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103008503/gd1249sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103008503/gd1249Isup2.hkl |
CCDC reference: 214367
The title compound (Woodward et al., 1952; Sonoda & Moritani, 1971) was prepared by refluxing a methanol solution of 1,1'-ferrocene dicarboxylic acid in the presence of BF3.Et2O. After purification on silica-gel plates (Merck, Kieselgel 60 HF254) using CH2Cl2 as eluant, (I) was obtained as orange crystals [97% yield, m.p. 388–390 K; literature m.p. 386–387 K (Sonoda et al., 1971)]. The single-crystal of (I) used for X-ray analysis was obtained by slow evaporation from a cyclohexane solution at room temperature. IR (CH2Cl2, υ, cm−1): 3090 (w, C–H, ferrocene), 1716 (s, C=O); 1H-NMR (CDCl3, p.p.m.): δ 4.80 (s), 4.43 (s), 4.34 (s), 4.25 (d, 8H, ferrocene), 3.84 (s, 6H, COOCH3); 13C-NMR (CDCl3, p.p.m.): δ 172.74, 172.72 (C=O), 71.59, 70.35 (ferrocene substituted ring), 51.73, 51.37 (OCH3).
All H atoms were included in calculated positions as riding atoms, with default parameters in SHELXL97 (Sheldrick, 1997).
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Fe(C7H7O2)2] | F(000) = 1248 |
Mr = 302.10 | Dx = 1.589 Mg m−3 |
Monoclinic, C2/c | Melting point = 388–390 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 32.7581 (10) Å | Cell parameters from 2802 reflections |
b = 5.9616 (2) Å | θ = 2.6–26.7° |
c = 13.3424 (5) Å | µ = 1.20 mm−1 |
β = 104.2847 (13)° | T = 293 K |
V = 2525.08 (15) Å3 | Irregular, orange |
Z = 8 | 0.30 × 0.20 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 2640 independent reflections |
Radiation source: fine-focus sealed tube | 2039 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ϕ and ω scans | θmax = 26.7°, θmin = 3.9° |
Absorption correction: multi-scan DENZO–SMN; Otwinovski & Minor, 1997 | h = −39→40 |
Tmin = 0.697, Tmax = 0.887 | k = −6→7 |
13701 measured reflections | l = −16→16 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.083P)2 + 3.7923P] where P = (Fo2 + 2Fc2)/3 |
2640 reflections | (Δ/σ)max = 0.001 |
174 parameters | Δρmax = 0.87 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Fe(C7H7O2)2] | V = 2525.08 (15) Å3 |
Mr = 302.10 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 32.7581 (10) Å | µ = 1.20 mm−1 |
b = 5.9616 (2) Å | T = 293 K |
c = 13.3424 (5) Å | 0.30 × 0.20 × 0.10 mm |
β = 104.2847 (13)° |
Nonius KappaCCD area-detector diffractometer | 2640 independent reflections |
Absorption correction: multi-scan DENZO–SMN; Otwinovski & Minor, 1997 | 2039 reflections with I > 2σ(I) |
Tmin = 0.697, Tmax = 0.887 | Rint = 0.066 |
13701 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.87 e Å−3 |
2640 reflections | Δρmin = −0.48 e Å−3 |
174 parameters |
x | y | z | Uiso*/Ueq | ||
Fe | 0.125946 (12) | 0.24707 (7) | 0.84995 (3) | 0.03629 (19) | |
O1 | 0.03032 (8) | 0.3410 (5) | 0.6250 (3) | 0.0740 (9) | |
O2 | 0.05414 (8) | 0.6812 (5) | 0.6784 (2) | 0.0573 (6) | |
O3 | 0.22026 (8) | 0.1719 (5) | 1.0947 (2) | 0.0634 (7) | |
O4 | 0.19679 (7) | 0.5233 (4) | 1.06339 (19) | 0.0506 (6) | |
C1 | 0.10225 (10) | 0.3876 (6) | 0.7083 (2) | 0.0430 (7) | |
C2 | 0.13730 (11) | 0.5165 (6) | 0.7657 (3) | 0.0480 (8) | |
H2 | 0.1369 | 0.6666 | 0.7844 | 0.058* | |
C3 | 0.17257 (11) | 0.3715 (7) | 0.7884 (3) | 0.0526 (9) | |
H3 | 0.1995 | 0.4108 | 0.8255 | 0.063* | |
C4 | 0.16048 (11) | 0.1594 (8) | 0.7460 (3) | 0.0544 (9) | |
H4 | 0.1781 | 0.0357 | 0.7498 | 0.065* | |
C5 | 0.11695 (11) | 0.1648 (7) | 0.6966 (2) | 0.0482 (8) | |
H5 | 0.1009 | 0.0460 | 0.6627 | 0.058* | |
C6 | 0.07851 (11) | 0.2361 (6) | 0.9259 (3) | 0.0528 (9) | |
H6 | 0.0508 | 0.2833 | 0.9005 | 0.063* | |
C7 | 0.11218 (10) | 0.3699 (6) | 0.9801 (2) | 0.0463 (8) | |
H7 | 0.1106 | 0.5211 | 0.9960 | 0.056* | |
C8 | 0.14913 (11) | 0.2333 (5) | 1.0066 (2) | 0.0423 (7) | |
C9 | 0.13774 (10) | 0.0146 (6) | 0.9664 (2) | 0.0461 (7) | |
H9 | 0.1557 | −0.1080 | 0.9719 | 0.055* | |
C10 | 0.09411 (11) | 0.0167 (6) | 0.9166 (3) | 0.0502 (8) | |
H10 | 0.0785 | −0.1043 | 0.8836 | 0.060* | |
C11 | 0.05887 (11) | 0.4610 (6) | 0.6672 (2) | 0.0482 (8) | |
C12 | 0.01300 (14) | 0.7711 (7) | 0.6289 (4) | 0.0707 (12) | |
H12A | 0.0071 | 0.7439 | 0.5558 | 0.106* | |
H12B | 0.0127 | 0.9296 | 0.6413 | 0.106* | |
H12C | −0.0080 | 0.6993 | 0.6568 | 0.106* | |
C13 | 0.19216 (10) | 0.3002 (6) | 1.0585 (2) | 0.0438 (7) | |
C14 | 0.23824 (11) | 0.6031 (7) | 1.1163 (3) | 0.0571 (9) | |
H14A | 0.2449 | 0.5521 | 1.1867 | 0.086* | |
H14B | 0.2386 | 0.7641 | 1.1150 | 0.086* | |
H14C | 0.2587 | 0.5460 | 1.0822 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0360 (3) | 0.0447 (3) | 0.0284 (3) | 0.00034 (17) | 0.00845 (18) | 0.00120 (17) |
O1 | 0.0600 (16) | 0.0634 (17) | 0.082 (2) | −0.0046 (15) | −0.0133 (15) | −0.0035 (16) |
O2 | 0.0546 (14) | 0.0571 (14) | 0.0554 (15) | 0.0036 (12) | 0.0043 (12) | 0.0007 (13) |
O3 | 0.0527 (15) | 0.0531 (14) | 0.0737 (19) | 0.0027 (13) | −0.0050 (13) | 0.0070 (14) |
O4 | 0.0508 (13) | 0.0456 (13) | 0.0497 (14) | 0.0013 (10) | 0.0017 (10) | −0.0037 (10) |
C1 | 0.0490 (17) | 0.0505 (18) | 0.0292 (14) | −0.0019 (14) | 0.0091 (13) | 0.0041 (13) |
C2 | 0.0532 (18) | 0.0527 (19) | 0.0390 (17) | −0.0073 (15) | 0.0130 (14) | 0.0035 (14) |
C3 | 0.0433 (17) | 0.073 (3) | 0.0444 (18) | −0.0070 (17) | 0.0156 (14) | 0.0074 (18) |
C4 | 0.0533 (19) | 0.072 (2) | 0.0440 (19) | 0.0131 (18) | 0.0238 (16) | 0.0025 (18) |
C5 | 0.0565 (19) | 0.0569 (19) | 0.0312 (16) | −0.0015 (17) | 0.0110 (14) | −0.0045 (15) |
C6 | 0.0382 (16) | 0.082 (3) | 0.0417 (18) | −0.0018 (16) | 0.0166 (14) | 0.0074 (17) |
C7 | 0.0505 (18) | 0.057 (2) | 0.0354 (16) | 0.0034 (15) | 0.0186 (14) | 0.0017 (15) |
C8 | 0.0466 (17) | 0.056 (2) | 0.0246 (14) | 0.0004 (14) | 0.0085 (13) | 0.0062 (12) |
C9 | 0.0517 (18) | 0.0449 (17) | 0.0412 (17) | 0.0003 (14) | 0.0106 (14) | 0.0094 (14) |
C10 | 0.0500 (18) | 0.056 (2) | 0.0445 (18) | −0.0102 (15) | 0.0110 (15) | 0.0056 (15) |
C11 | 0.0560 (19) | 0.054 (2) | 0.0328 (16) | −0.0023 (16) | 0.0075 (14) | 0.0016 (14) |
C12 | 0.064 (2) | 0.066 (3) | 0.075 (3) | 0.0168 (19) | 0.003 (2) | 0.003 (2) |
C13 | 0.0458 (17) | 0.0532 (18) | 0.0318 (15) | 0.0002 (14) | 0.0086 (13) | 0.0037 (14) |
C14 | 0.0539 (19) | 0.058 (2) | 0.055 (2) | −0.0058 (17) | 0.0048 (16) | −0.0073 (17) |
Fe—C7 | 2.035 (3) | C3—C4 | 1.402 (6) |
Fe—C1 | 2.038 (3) | C3—H3 | 0.93 |
Fe—C8 | 2.041 (3) | C4—C5 | 1.416 (5) |
Fe—C3 | 2.044 (3) | C4—H4 | 0.93 |
Fe—C9 | 2.047 (3) | C5—H5 | 0.93 |
Fe—C2 | 2.046 (3) | C6—C7 | 1.408 (5) |
Fe—C5 | 2.054 (3) | C6—C10 | 1.421 (5) |
Fe—C10 | 2.055 (3) | C6—H6 | 0.93 |
Fe—C6 | 2.055 (3) | C7—C8 | 1.429 (5) |
Fe—C4 | 2.061 (3) | C7—H7 | 0.93 |
O1—C11 | 1.202 (4) | C8—C9 | 1.424 (5) |
O2—C11 | 1.335 (5) | C8—C13 | 1.464 (5) |
O2—C12 | 1.449 (5) | C9—C10 | 1.420 (5) |
O3—C13 | 1.203 (4) | C9—H9 | 0.93 |
O4—C13 | 1.339 (4) | C10—H10 | 0.93 |
O4—C14 | 1.447 (4) | C12—H12A | 0.96 |
C1—C5 | 1.434 (5) | C12—H12B | 0.96 |
C1—C2 | 1.436 (5) | C12—H12C | 0.96 |
C1—C11 | 1.458 (5) | C14—H14A | 0.96 |
C2—C3 | 1.414 (5) | C14—H14B | 0.96 |
C2—H2 | 0.93 | C14—H14C | 0.96 |
C7—Fe—C1 | 121.99 (13) | C2—C3—H3 | 125.4 |
C7—Fe—C8 | 41.04 (13) | Fe—C3—H3 | 125.7 |
C1—Fe—C8 | 157.87 (13) | C3—C4—C5 | 108.6 (3) |
C7—Fe—C3 | 123.87 (15) | C3—C4—Fe | 69.37 (19) |
C1—Fe—C3 | 68.24 (13) | C5—C4—Fe | 69.58 (19) |
C8—Fe—C3 | 107.45 (14) | C3—C4—H4 | 125.7 |
C7—Fe—C9 | 68.64 (14) | C5—C4—H4 | 125.7 |
C1—Fe—C9 | 160.04 (14) | Fe—C4—H4 | 126.9 |
C8—Fe—C9 | 40.77 (13) | C4—C5—C1 | 107.3 (3) |
C3—Fe—C9 | 122.09 (14) | C4—C5—Fe | 70.15 (19) |
C7—Fe—C2 | 107.16 (14) | C1—C5—Fe | 68.88 (17) |
C1—Fe—C2 | 41.16 (13) | C4—C5—H5 | 126.4 |
C8—Fe—C2 | 121.45 (13) | C1—C5—H5 | 126.4 |
C3—Fe—C2 | 40.46 (15) | Fe—C5—H5 | 126.2 |
C9—Fe—C2 | 157.33 (14) | C7—C6—C10 | 108.3 (3) |
C7—Fe—C5 | 158.24 (14) | C7—C6—Fe | 69.12 (18) |
C1—Fe—C5 | 41.03 (15) | C10—C6—Fe | 69.76 (19) |
C8—Fe—C5 | 159.41 (14) | C7—C6—H6 | 125.9 |
C3—Fe—C5 | 67.90 (15) | C10—C6—H6 | 125.9 |
C9—Fe—C5 | 123.28 (15) | Fe—C6—H6 | 126.8 |
C2—Fe—C5 | 68.95 (15) | C6—C7—C8 | 108.2 (3) |
C7—Fe—C10 | 68.17 (15) | C6—C7—Fe | 70.6 (2) |
C1—Fe—C10 | 123.93 (13) | C8—C7—Fe | 69.70 (18) |
C8—Fe—C10 | 68.33 (14) | C6—C7—H7 | 125.9 |
C3—Fe—C10 | 157.83 (15) | C8—C7—H7 | 125.9 |
C9—Fe—C10 | 40.52 (13) | Fe—C7—H7 | 125.4 |
C2—Fe—C10 | 160.51 (14) | C9—C8—C7 | 107.5 (3) |
C5—Fe—C10 | 107.96 (15) | C9—C8—C13 | 124.0 (3) |
C7—Fe—C6 | 40.26 (14) | C7—C8—C13 | 128.3 (3) |
C1—Fe—C6 | 108.01 (14) | C9—C8—Fe | 69.81 (18) |
C8—Fe—C6 | 68.26 (14) | C7—C8—Fe | 69.26 (18) |
C3—Fe—C6 | 160.17 (16) | C13—C8—Fe | 123.1 (2) |
C9—Fe—C6 | 68.17 (14) | C10—C9—C8 | 107.9 (3) |
C2—Fe—C6 | 123.91 (15) | C10—C9—Fe | 70.05 (19) |
C5—Fe—C6 | 122.95 (15) | C8—C9—Fe | 69.41 (18) |
C10—Fe—C6 | 40.45 (15) | C10—C9—H9 | 126.0 |
C7—Fe—C4 | 159.89 (15) | C8—C9—H9 | 126.0 |
C1—Fe—C4 | 68.11 (14) | Fe—C9—H9 | 126.1 |
C8—Fe—C4 | 123.43 (14) | C9—C10—C6 | 108.0 (3) |
C3—Fe—C4 | 39.93 (17) | C9—C10—Fe | 69.44 (18) |
C9—Fe—C4 | 107.86 (15) | C6—C10—Fe | 69.79 (19) |
C2—Fe—C4 | 68.00 (16) | C9—C10—H10 | 126.0 |
C5—Fe—C4 | 40.26 (14) | C6—C10—H10 | 126.0 |
C10—Fe—C4 | 122.88 (16) | Fe—C10—H10 | 126.4 |
C6—Fe—C4 | 158.57 (17) | O1—C11—O2 | 122.7 (3) |
C11—O2—C12 | 115.7 (3) | O1—C11—C1 | 124.8 (3) |
C13—O4—C14 | 115.6 (3) | O2—C11—C1 | 112.5 (3) |
C5—C1—C2 | 107.9 (3) | O2—C12—H12A | 109.5 |
C5—C1—C11 | 124.0 (3) | O2—C12—H12B | 109.5 |
C2—C1—C11 | 128.1 (3) | H12A—C12—H12B | 109.5 |
C5—C1—Fe | 70.08 (17) | O2—C12—H12C | 109.5 |
C2—C1—Fe | 69.74 (18) | H12A—C12—H12C | 109.5 |
C11—C1—Fe | 125.8 (2) | H12B—C12—H12C | 109.5 |
C3—C2—C1 | 106.9 (3) | O3—C13—O4 | 123.1 (3) |
C3—C2—Fe | 69.7 (2) | O3—C13—C8 | 124.7 (3) |
C1—C2—Fe | 69.10 (18) | O4—C13—C8 | 112.2 (3) |
C3—C2—H2 | 126.6 | O4—C14—H14A | 109.5 |
C1—C2—H2 | 126.6 | O4—C14—H14B | 109.5 |
Fe—C2—H2 | 126.2 | H14A—C14—H14B | 109.5 |
C4—C3—C2 | 109.3 (3) | O4—C14—H14C | 109.5 |
C4—C3—Fe | 70.70 (19) | H14A—C14—H14C | 109.5 |
C2—C3—Fe | 69.86 (19) | H14B—C14—H14C | 109.5 |
C4—C3—H3 | 125.4 | ||
C7—Fe—C1—C5 | −161.8 (2) | C7—Fe—C6—C10 | −119.9 (3) |
C8—Fe—C1—C5 | 163.7 (3) | C1—Fe—C6—C10 | 121.6 (2) |
C3—Fe—C1—C5 | 80.9 (2) | C8—Fe—C6—C10 | −81.7 (2) |
C9—Fe—C1—C5 | −44.3 (5) | C3—Fe—C6—C10 | −162.8 (4) |
C2—Fe—C1—C5 | 118.9 (3) | C9—Fe—C6—C10 | −37.6 (2) |
C10—Fe—C1—C5 | −78.1 (2) | C2—Fe—C6—C10 | 164.2 (2) |
C6—Fe—C1—C5 | −119.8 (2) | C5—Fe—C6—C10 | 78.8 (3) |
C4—Fe—C1—C5 | 37.7 (2) | C4—Fe—C6—C10 | 45.7 (5) |
C7—Fe—C1—C2 | 79.3 (2) | C10—C6—C7—C8 | −0.9 (4) |
C8—Fe—C1—C2 | 44.9 (4) | Fe—C6—C7—C8 | −59.8 (2) |
C3—Fe—C1—C2 | −38.0 (2) | C10—C6—C7—Fe | 58.9 (2) |
C9—Fe—C1—C2 | −163.2 (4) | C1—Fe—C7—C6 | 80.0 (2) |
C5—Fe—C1—C2 | −118.9 (3) | C8—Fe—C7—C6 | −118.9 (3) |
C10—Fe—C1—C2 | 163.1 (2) | C3—Fe—C7—C6 | 163.9 (2) |
C6—Fe—C1—C2 | 121.3 (2) | C9—Fe—C7—C6 | −81.0 (2) |
C4—Fe—C1—C2 | −81.2 (2) | C2—Fe—C7—C6 | 122.6 (2) |
C7—Fe—C1—C11 | −43.7 (3) | C5—Fe—C7—C6 | 46.5 (5) |
C8—Fe—C1—C11 | −78.1 (5) | C10—Fe—C7—C6 | −37.3 (2) |
C3—Fe—C1—C11 | −160.9 (3) | C4—Fe—C7—C6 | −164.7 (4) |
C9—Fe—C1—C11 | 73.8 (5) | C1—Fe—C7—C8 | −161.08 (18) |
C2—Fe—C1—C11 | −123.0 (4) | C3—Fe—C7—C8 | −77.2 (2) |
C5—Fe—C1—C11 | 118.2 (4) | C9—Fe—C7—C8 | 37.89 (19) |
C10—Fe—C1—C11 | 40.1 (4) | C2—Fe—C7—C8 | −118.5 (2) |
C6—Fe—C1—C11 | −1.7 (3) | C5—Fe—C7—C8 | 165.4 (4) |
C4—Fe—C1—C11 | 155.9 (3) | C10—Fe—C7—C8 | 81.6 (2) |
C5—C1—C2—C3 | −0.2 (3) | C6—Fe—C7—C8 | 118.9 (3) |
C11—C1—C2—C3 | 179.9 (3) | C4—Fe—C7—C8 | −45.8 (5) |
Fe—C1—C2—C3 | 59.7 (2) | C6—C7—C8—C9 | 0.8 (4) |
C5—C1—C2—Fe | −59.9 (2) | Fe—C7—C8—C9 | −59.6 (2) |
C11—C1—C2—Fe | 120.2 (3) | C6—C7—C8—C13 | 176.7 (3) |
C7—Fe—C2—C3 | 122.5 (2) | Fe—C7—C8—C13 | 116.4 (3) |
C1—Fe—C2—C3 | −118.2 (3) | C6—C7—C8—Fe | 60.4 (2) |
C8—Fe—C2—C3 | 79.9 (2) | C7—Fe—C8—C9 | 118.9 (3) |
C9—Fe—C2—C3 | 46.9 (5) | C1—Fe—C8—C9 | 165.8 (3) |
C5—Fe—C2—C3 | −80.2 (2) | C3—Fe—C8—C9 | −119.2 (2) |
C10—Fe—C2—C3 | −164.6 (4) | C2—Fe—C8—C9 | −161.3 (2) |
C6—Fe—C2—C3 | 163.5 (2) | C5—Fe—C8—C9 | −45.8 (5) |
C4—Fe—C2—C3 | −36.8 (2) | C10—Fe—C8—C9 | 37.6 (2) |
C7—Fe—C2—C1 | −119.3 (2) | C6—Fe—C8—C9 | 81.3 (2) |
C8—Fe—C2—C1 | −161.85 (19) | C4—Fe—C8—C9 | −78.3 (3) |
C3—Fe—C2—C1 | 118.2 (3) | C1—Fe—C8—C7 | 46.9 (4) |
C9—Fe—C2—C1 | 165.2 (3) | C3—Fe—C8—C7 | 121.9 (2) |
C5—Fe—C2—C1 | 38.03 (19) | C9—Fe—C8—C7 | −118.9 (3) |
C10—Fe—C2—C1 | −46.4 (5) | C2—Fe—C8—C7 | 79.9 (2) |
C6—Fe—C2—C1 | −78.3 (2) | C5—Fe—C8—C7 | −164.6 (4) |
C4—Fe—C2—C1 | 81.4 (2) | C10—Fe—C8—C7 | −81.2 (2) |
C1—C2—C3—C4 | 0.6 (4) | C6—Fe—C8—C7 | −37.5 (2) |
Fe—C2—C3—C4 | 59.9 (2) | C4—Fe—C8—C7 | 162.8 (2) |
C1—C2—C3—Fe | −59.3 (2) | C7—Fe—C8—C13 | −123.0 (4) |
C7—Fe—C3—C4 | 163.8 (2) | C1—Fe—C8—C13 | −76.1 (5) |
C1—Fe—C3—C4 | −81.5 (2) | C3—Fe—C8—C13 | −1.1 (3) |
C8—Fe—C3—C4 | 121.6 (2) | C9—Fe—C8—C13 | 118.2 (4) |
C9—Fe—C3—C4 | 79.3 (2) | C2—Fe—C8—C13 | −43.1 (3) |
C2—Fe—C3—C4 | −120.1 (3) | C5—Fe—C8—C13 | 72.4 (5) |
C5—Fe—C3—C4 | −37.1 (2) | C10—Fe—C8—C13 | 155.8 (3) |
C10—Fe—C3—C4 | 46.4 (5) | C6—Fe—C8—C13 | −160.5 (3) |
C6—Fe—C3—C4 | −164.2 (4) | C4—Fe—C8—C13 | 39.9 (3) |
C7—Fe—C3—C2 | −76.1 (2) | C7—C8—C9—C10 | −0.5 (4) |
C1—Fe—C3—C2 | 38.6 (2) | C13—C8—C9—C10 | −176.6 (3) |
C8—Fe—C3—C2 | −118.3 (2) | Fe—C8—C9—C10 | −59.7 (2) |
C9—Fe—C3—C2 | −160.6 (2) | C7—C8—C9—Fe | 59.2 (2) |
C5—Fe—C3—C2 | 83.0 (2) | C13—C8—C9—Fe | −116.9 (3) |
C10—Fe—C3—C2 | 166.4 (3) | C7—Fe—C9—C10 | 81.0 (2) |
C6—Fe—C3—C2 | −44.2 (5) | C1—Fe—C9—C10 | −45.1 (5) |
C4—Fe—C3—C2 | 120.1 (3) | C8—Fe—C9—C10 | 119.1 (3) |
C2—C3—C4—C5 | −0.7 (4) | C3—Fe—C9—C10 | −161.6 (2) |
Fe—C3—C4—C5 | 58.7 (2) | C2—Fe—C9—C10 | 164.4 (3) |
C2—C3—C4—Fe | −59.4 (2) | C5—Fe—C9—C10 | −78.4 (2) |
C7—Fe—C4—C3 | −42.5 (6) | C6—Fe—C9—C10 | 37.5 (2) |
C1—Fe—C4—C3 | 81.8 (2) | C4—Fe—C9—C10 | −120.1 (2) |
C8—Fe—C4—C3 | −76.8 (3) | C7—Fe—C9—C8 | −38.1 (2) |
C9—Fe—C4—C3 | −119.0 (2) | C1—Fe—C9—C8 | −164.2 (3) |
C2—Fe—C4—C3 | 37.3 (2) | C3—Fe—C9—C8 | 79.3 (2) |
C5—Fe—C4—C3 | 120.2 (3) | C2—Fe—C9—C8 | 45.3 (4) |
C10—Fe—C4—C3 | −161.0 (2) | C5—Fe—C9—C8 | 162.5 (2) |
C6—Fe—C4—C3 | 165.4 (3) | C10—Fe—C9—C8 | −119.1 (3) |
C7—Fe—C4—C5 | −162.7 (4) | C6—Fe—C9—C8 | −81.6 (2) |
C1—Fe—C4—C5 | −38.4 (2) | C4—Fe—C9—C8 | 120.8 (2) |
C8—Fe—C4—C5 | 163.0 (2) | C8—C9—C10—C6 | 0.0 (4) |
C3—Fe—C4—C5 | −120.2 (3) | Fe—C9—C10—C6 | −59.3 (2) |
C9—Fe—C4—C5 | 120.8 (2) | C8—C9—C10—Fe | 59.3 (2) |
C2—Fe—C4—C5 | −83.0 (2) | C7—C6—C10—C9 | 0.6 (4) |
C10—Fe—C4—C5 | 78.7 (3) | Fe—C6—C10—C9 | 59.1 (2) |
C6—Fe—C4—C5 | 45.2 (5) | C7—C6—C10—Fe | −58.6 (2) |
C3—C4—C5—C1 | 0.6 (4) | C7—Fe—C10—C9 | −82.2 (2) |
Fe—C4—C5—C1 | 59.1 (2) | C1—Fe—C10—C9 | 163.0 (2) |
C3—C4—C5—Fe | −58.5 (2) | C8—Fe—C10—C9 | −37.9 (2) |
C2—C1—C5—C4 | −0.2 (4) | C3—Fe—C10—C9 | 45.2 (5) |
C11—C1—C5—C4 | 179.7 (3) | C2—Fe—C10—C9 | −161.9 (4) |
Fe—C1—C5—C4 | −59.9 (2) | C5—Fe—C10—C9 | 120.6 (2) |
C2—C1—C5—Fe | 59.7 (2) | C6—Fe—C10—C9 | −119.4 (3) |
C11—C1—C5—Fe | −120.4 (3) | C4—Fe—C10—C9 | 78.8 (2) |
C7—Fe—C5—C4 | 164.0 (4) | C7—Fe—C10—C6 | 37.1 (2) |
C1—Fe—C5—C4 | 118.6 (3) | C1—Fe—C10—C6 | −77.6 (3) |
C8—Fe—C5—C4 | −44.0 (5) | C8—Fe—C10—C6 | 81.5 (2) |
C3—Fe—C5—C4 | 36.8 (3) | C3—Fe—C10—C6 | 164.6 (3) |
C9—Fe—C5—C4 | −78.0 (3) | C9—Fe—C10—C6 | 119.4 (3) |
C2—Fe—C5—C4 | 80.4 (3) | C2—Fe—C10—C6 | −42.6 (5) |
C10—Fe—C5—C4 | −120.0 (3) | C5—Fe—C10—C6 | −120.1 (2) |
C6—Fe—C5—C4 | −162.0 (2) | C4—Fe—C10—C6 | −161.9 (2) |
C7—Fe—C5—C1 | 45.5 (5) | C12—O2—C11—O1 | −4.8 (6) |
C8—Fe—C5—C1 | −162.5 (3) | C12—O2—C11—C1 | 173.1 (3) |
C3—Fe—C5—C1 | −81.8 (2) | C5—C1—C11—O1 | 4.8 (5) |
C9—Fe—C5—C1 | 163.42 (19) | C2—C1—C11—O1 | −175.3 (4) |
C2—Fe—C5—C1 | −38.14 (19) | Fe—C1—C11—O1 | −84.1 (4) |
C10—Fe—C5—C1 | 121.4 (2) | C5—C1—C11—O2 | −173.1 (3) |
C6—Fe—C5—C1 | 79.4 (2) | C2—C1—C11—O2 | 6.8 (5) |
C4—Fe—C5—C1 | −118.6 (3) | Fe—C1—C11—O2 | 98.1 (3) |
C1—Fe—C6—C7 | −118.6 (2) | C14—O4—C13—O3 | −0.4 (5) |
C8—Fe—C6—C7 | 38.2 (2) | C14—O4—C13—C8 | 178.4 (3) |
C3—Fe—C6—C7 | −42.9 (5) | C9—C8—C13—O3 | −18.5 (5) |
C9—Fe—C6—C7 | 82.3 (2) | C7—C8—C13—O3 | 166.2 (4) |
C2—Fe—C6—C7 | −75.9 (2) | Fe—C8—C13—O3 | −105.2 (4) |
C5—Fe—C6—C7 | −161.3 (2) | C9—C8—C13—O4 | 162.8 (3) |
C10—Fe—C6—C7 | 119.9 (3) | C7—C8—C13—O4 | −12.6 (5) |
C4—Fe—C6—C7 | 165.6 (4) | Fe—C8—C13—O4 | 76.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12A···O1i | 0.96 | 2.47 | 3.401 (6) | 162 |
C12—H12B···O1ii | 0.96 | 2.54 | 3.447 (5) | 157 |
C14—H14B···O3ii | 0.96 | 2.50 | 3.442 (5) | 166 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C7H7O2)2] |
Mr | 302.10 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 32.7581 (10), 5.9616 (2), 13.3424 (5) |
β (°) | 104.2847 (13) |
V (Å3) | 2525.08 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.20 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan DENZO–SMN; Otwinovski & Minor, 1997 |
Tmin, Tmax | 0.697, 0.887 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13701, 2640, 2039 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.631 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.141, 1.03 |
No. of reflections | 2640 |
No. of parameters | 174 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.87, −0.48 |
Computer programs: COLLECT (Nonius, 2000), DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
O1—C11 | 1.202 (4) | O4—C13 | 1.339 (4) |
O2—C11 | 1.335 (5) | O4—C14 | 1.447 (4) |
O2—C12 | 1.449 (5) | C1—C11 | 1.458 (5) |
O3—C13 | 1.203 (4) | C8—C13 | 1.464 (5) |
C11—O2—C12 | 115.7 (3) | O1—C11—O2 | 122.7 (3) |
C13—O4—C14 | 115.6 (3) | O1—C11—C1 | 124.8 (3) |
C5—C1—C11 | 124.0 (3) | O2—C11—C1 | 112.5 (3) |
C2—C1—C11 | 128.1 (3) | O3—C13—O4 | 123.1 (3) |
C9—C8—C13 | 124.0 (3) | O3—C13—C8 | 124.7 (3) |
C7—C8—C13 | 128.3 (3) | O4—C13—C8 | 112.2 (3) |
C12—O2—C11—C1 | 173.1 (3) | C14—O4—C13—C8 | 178.4 (3) |
C2—C1—C11—O2 | 6.8 (5) | C7—C8—C13—O3 | 166.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12A···O1i | 0.96 | 2.47 | 3.401 (6) | 162 |
C12—H12B···O1ii | 0.96 | 2.54 | 3.447 (5) | 157 |
C14—H14B···O3ii | 0.96 | 2.50 | 3.442 (5) | 166 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z. |
The present study forms part of our wider research on differently homo- and heteroannularly disubstituted ferrocene compounds, viz. their synthesis, stereochemistry and structural analysis (Zorić et al., 1999; Lapić & Rapić, 2000; Cetina et al., 2002; Pavlović et al., 2002; Cetina et al., 2003). The applications of these complexes rely on their electronic properties, which depend on various functional groups on the cyclopentadienyl rings (Oberhoff et al., 1996). The study of these metallocenes led to important developments in the field of homogeneous catalysis, including carbonylation, hydrogenation and polymerization (Gonsalves & Chen, 1995; Severin et al., 1998; Patti & Nicolosi, 2000; Metzler-Nolte, 2001).
In the title compound, (I), the cyclopentadienyl rings bear two methoxycarbonyl groups in an anti arrangement (Fig. 1). The almost parallel cyclopentadienyl (Cp) rings [the dihedral angle is 1.0 (2)°] adopt an almost totally eclipsed conformation. The values of the corresponding pseudo-torsion angles defined by joining two eclipsing Cp C atoms through the ring centroids, viz. C—Cg1—Cg2–C (Cg1 and Cg2 are the centroids of the C1–C5 and C6–C10 rings, respectively), range from 1.3 (3) to 2.6 (3)°. The Fe atom is almost equidistant from the centroids [Fe—Cg1 = 1.654 (1) Å and Fe—Cg2 = 1.652 (1) Å], and the Cg1—Fe—Cg2 angle deviates very slightly from 180° [179.6 (1)°].
The C—C bond distances in the Cp rings are in the ranges 1.402 (6)–1.436 (5) Å for the C1–C5 ring and 1.408 (5)–1.429 (5) Å for the C6–C10 ring, with an average value of 1.419 (5) Å for both rings. The values of the bond angles in the Cp rings are in the range 106.9 (3)–109.3 (3)°. The structural parameters are consistent with those of similar structures that have a methoxycarbonyl group on one of the Cp rings (Luo et al., 1990; Podlaha et al., 1996; Hobi et al., 1997; Beck et al., 2001; Costa et al., 2001) and with the structure of methyl 3-ferrocenylpropanoate (Cetina et al., 2002). Selected geometric parameters for (I) are listed in Table 1.
The methoxycarbonyl groups and Cp rings form an extended π-conjugated system. The Cring—Ccarboxyl single bonds are shortened compared with the standard `unconjugated' Csp2—Csp2 bond [1.478 Å] and agree with the `conjugated' bond of 1.455 Å (Allen et al., 1987). The coplanar arrangement of a carbonyl group attached to the ring should allow the maximum interaction of two π-systems. In (I), the substituted groups are slightly twisted out of the plane of the Cp rings to which they are attached. The twisting is more pronounced for the C13/O3/O4 group with respect to the C6–C10 ring than for the C11/O1/O2 group with respect to the C1–C5 ring [15.7 (4) and 6.5 (4)°, respectively]. The π-conjugation also influences the Fe—C distances [2.035 (3)—2.061 (3) Å]. A survey of the Cambridge Structural Database (Allen, 2002) reveals that, in structures with efficient overlap of two π-systems, the shortest Fe—C distance is generally? Fe—Csubst [Fe—C1 = 2.038 (3) Å; Csubst is the substituted C atom of the Cp ring]. However, the shortest distance can also involve the nearest atom to Csubst, such as between the Fe atom and atom C7 of the C6–C10 ring in (I) [Fe–C7 = 2.035 (3) Å].
The molecules are bonded into dimers by very weak intermolecular C12—H12A···O1 hydrogen bonds forming? a ten-membered ring (Table 2 and Fig. 2). To our knowledge, two methoxycarbonyl groups attached to the Cp rings form such R22(10) rings in only two ferrocene structures (Luo et al., 1990; Podlaha et al., 1996). The dimers are connected by intermolecular C12—H12B···O1 hydrogen bonds, which form R24(8) rings, and C14—H14B···O3 hydrogen bonds, which form infinite chains along the b axis. The geometric centers of both rings coincide with a crystallographic center of inversion.