Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048842/om2164sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048842/om2164Isup2.hkl |
CCDC reference: 667143
A solution of tert-butyllithium in n-pentane (1.59 M; 17.3 ml, 27.5 mmol) was added to a THF (25 ml)/n-hexane (25 ml) solution of ferrocene (4.63 mg, 25.0 mmol) at 273 K. After stirring at the same temperature for 3 h, 1,2-dibromo-1,1,2,2-tetrafluoroethane (4.41 ml, 37.5 mmol) was added to the reaction mixture. After stirring at the same temperature for 1 h, the solution was allowed to be warmed up to room temperature for 12 h. After the removal of solvents, n-hexane was added to the residue and the mixture was filtered through Celite. The filtrate was purified by silica-gel column chromatography (eluting with n-hexane and chloroform) to afford the title compound (350 mg, 0.810 mmol, 5.9% based on the ferrocene) as an orange solid [m.p. 473 K (decomposition)]. Single crystals suitable for X-ray crystallographic analysis were obtained by slow recrystallization of its chloroform solution at room temperature.
All H atoms were treated as riding with C—H distances of 0.95 Å, while all the other atoms were refined anisotropically.
Although a number of synthetic works on ferrocenyl substituted ethenes have been reported, only three reports are known for the crystalline structures of trans-1,2-diferrocenylethene derivatives, that is, trans-1,2-diferrocenylethene (Denifl et al., 1996), trans-1,2-diferrocenyl-1,2-dimethylethene (Chen et al., 2000), and trans-1,2-diferrocenyl-1,2-diphenylethene (Skibar et al., 2004). During our course of studies on the syntheses of new π-conjugated compounds bearing ferrocenyl groups (Nagahora et al., 2004), the crystal structure of trans-1,2-diferrocenyl-1,2-difluoroethene has been revealed.
The title compound was synthesized in 6% yield by the treatment of ferrocenyllithium, which was prepared by the reaction of ferrocene with tert-butyllithium, with 1,2-dibromo-1,1,2,2-tetrafluoroethane. The molecular structure of the title compound is shown in Fig. 1. It was found that two fluoro and ferrocenyl groups are located as trans configuration, respectively, with respect to the ethene framework. It has a center of symmetry in the middle of the C1—C1i bond. The C1—C1i and C1—C2 bond lengths (1.331 (5) and 1.448 (2) Å) of the title compound are in the range of those for the previously reported trans-Fc(R)C=C(R)Fc (Fc = ferrocenyl) (1.17 (1) and 1.47 (6) Å for R = H, 1.354 (4) and 1.517 (3) Å for R = Me, 1.29 (4) and 1.51 Å for R = Ph). The F1—C1 distance (1.365 (3) Å) is similar to that of trans-F(H)C=C(H)F (1.1349 (1) Å) (Lentz et al., 2004). The dihedral angle between the least squares of C2—C3—C4—C5—C6 and C2i—C3i—C4i—C5i—C6i (the cyclopentadienyl rings) is 18.6°, which is similar to that of the reported trans-Fc(H)C=C(H)Fc (15.1°). The shortest intermolecular contacts were found to be F1—H1iii (2.4885 (15) Å) and F1—F1ii (2.704 (2) Å), which are shorter than the sum of van der Waals radii between fluoro and hydrogen atoms (2.67 Å) and two fluoro atoms (2.94 Å), respectively (Fig. 2).
For related literature, see: Chen et al. (2000); Denifl et al. (1996); Lentz et al. (2004); Nagahora et al. (2004); Skibar et al. (2004).
Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: yadokari-XG (Wakita, 2005).
[Fe2(C5H5)2(C6H4F)2] | Dx = 1.699 Mg m−3 |
Mr = 432.06 | Mo Kα radiation, λ = 0.71070 Å |
Tetragonal, P42/n | Cell parameters from 1483 reflections |
Hall symbol: -P 4bc | θ = 3.4–25.0° |
a = 16.968 (6) Å | µ = 1.74 mm−1 |
c = 5.8668 (17) Å | T = 103 K |
V = 1689.2 (9) Å3 | Needle, orange |
Z = 4 | 0.30 × 0.10 × 0.10 mm |
F(000) = 880 |
Rigaku Mercury CCD diffractometer | 1483 independent reflections |
Radiation source: fine-focus sealed tube | 1361 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.0°, θmin = 3.4° |
ω scans | h = −20→20 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −20→19 |
Tmin = 0.623, Tmax = 0.845 | l = −6→6 |
10691 measured reflections |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.22 | w = 1/[σ2(Fo2) + (0.0205P)2 + 1.7668P] where P = (Fo2 + 2Fc2)/3 |
1483 reflections | (Δ/σ)max = 0.001 |
118 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Fe2(C5H5)2(C6H4F)2] | Z = 4 |
Mr = 432.06 | Mo Kα radiation |
Tetragonal, P42/n | µ = 1.74 mm−1 |
a = 16.968 (6) Å | T = 103 K |
c = 5.8668 (17) Å | 0.30 × 0.10 × 0.10 mm |
V = 1689.2 (9) Å3 |
Rigaku Mercury CCD diffractometer | 1483 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 1361 reflections with I > 2σ(I) |
Tmin = 0.623, Tmax = 0.845 | Rint = 0.040 |
10691 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.22 | Δρmax = 0.25 e Å−3 |
1483 reflections | Δρmin = −0.25 e Å−3 |
118 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 | 0.00676 (2) | 0.71464 (2) | 0.01662 (6) | 0.01341 (13) | |
F1 | 0.01687 (9) | 0.52552 (9) | −0.2872 (2) | 0.0201 (4) | |
C1 | 0.01534 (15) | 0.53068 (15) | −0.0550 (4) | 0.0149 (5) | |
C2 | 0.05082 (15) | 0.60226 (15) | 0.0318 (4) | 0.0149 (6) | |
C3 | 0.04486 (16) | 0.63610 (15) | 0.2559 (5) | 0.0165 (6) | |
H1 | 0.0145 | 0.6159 | 0.3788 | 0.020* | |
C4 | 0.09205 (16) | 0.70469 (15) | 0.2614 (5) | 0.0192 (6) | |
H2 | 0.0992 | 0.7383 | 0.3891 | 0.023* | |
C5 | 0.12706 (15) | 0.71477 (15) | 0.0434 (5) | 0.0186 (6) | |
H3 | 0.1617 | 0.7562 | 0.0006 | 0.022* | |
C6 | 0.10137 (15) | 0.65216 (15) | −0.0999 (5) | 0.0172 (6) | |
H4 | 0.1153 | 0.6448 | −0.2553 | 0.021* | |
C7 | −0.10232 (17) | 0.71039 (17) | −0.1308 (6) | 0.0285 (7) | |
H5 | −0.1283 | 0.6643 | −0.1836 | 0.034* | |
C8 | −0.10795 (16) | 0.74232 (16) | 0.0892 (5) | 0.0245 (7) | |
H6 | −0.1383 | 0.7215 | 0.2111 | 0.029* | |
C9 | −0.06075 (16) | 0.81070 (16) | 0.0981 (5) | 0.0223 (6) | |
H7 | −0.0540 | 0.8440 | 0.2268 | 0.027* | |
C10 | −0.02530 (16) | 0.82111 (16) | −0.1169 (5) | 0.0230 (7) | |
H8 | 0.0096 | 0.8624 | −0.1586 | 0.028* | |
C11 | −0.05117 (18) | 0.75871 (18) | −0.2605 (5) | 0.0271 (7) | |
H9 | −0.0367 | 0.7509 | −0.4153 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0127 (2) | 0.0098 (2) | 0.0177 (2) | 0.00023 (15) | −0.00097 (16) | 0.00126 (15) |
F1 | 0.0289 (9) | 0.0176 (8) | 0.0136 (8) | −0.0035 (7) | 0.0007 (7) | 0.0001 (6) |
C1 | 0.0166 (13) | 0.0157 (13) | 0.0125 (14) | 0.0038 (10) | −0.0015 (11) | −0.0008 (10) |
C2 | 0.0145 (13) | 0.0111 (12) | 0.0191 (15) | 0.0038 (10) | −0.0028 (11) | 0.0015 (11) |
C3 | 0.0210 (14) | 0.0133 (13) | 0.0152 (14) | 0.0036 (11) | −0.0022 (11) | 0.0017 (11) |
C4 | 0.0219 (15) | 0.0151 (14) | 0.0204 (15) | 0.0039 (11) | −0.0082 (12) | −0.0015 (11) |
C5 | 0.0117 (13) | 0.0139 (13) | 0.0303 (17) | 0.0010 (11) | −0.0020 (11) | 0.0021 (12) |
C6 | 0.0141 (13) | 0.0158 (14) | 0.0218 (15) | 0.0035 (11) | 0.0016 (11) | 0.0011 (12) |
C7 | 0.0192 (15) | 0.0178 (15) | 0.048 (2) | 0.0014 (12) | −0.0167 (14) | −0.0025 (14) |
C8 | 0.0149 (14) | 0.0209 (15) | 0.0378 (18) | 0.0041 (12) | 0.0040 (13) | 0.0062 (13) |
C9 | 0.0217 (15) | 0.0146 (14) | 0.0307 (16) | 0.0075 (11) | −0.0019 (13) | −0.0024 (12) |
C10 | 0.0186 (15) | 0.0137 (14) | 0.0368 (18) | 0.0038 (11) | −0.0012 (13) | 0.0111 (13) |
C11 | 0.0284 (16) | 0.0330 (17) | 0.0198 (16) | 0.0163 (14) | −0.0064 (13) | 0.0023 (13) |
Fe1—C3 | 2.041 (3) | C3—H1 | 0.9500 |
Fe1—C6 | 2.042 (3) | C4—C5 | 1.420 (4) |
Fe1—C11 | 2.042 (3) | C4—H2 | 0.9500 |
Fe1—C10 | 2.043 (3) | C5—C6 | 1.423 (4) |
Fe1—C7 | 2.044 (3) | C5—H3 | 0.9500 |
Fe1—C4 | 2.046 (3) | C6—H4 | 0.9500 |
Fe1—C8 | 2.047 (3) | C7—C8 | 1.403 (4) |
Fe1—C5 | 2.047 (3) | C7—C11 | 1.416 (4) |
Fe1—C9 | 2.049 (3) | C7—H5 | 0.9500 |
Fe1—C2 | 2.050 (3) | C8—C9 | 1.411 (4) |
F1—C1 | 1.365 (3) | C8—H6 | 0.9500 |
C1—C1i | 1.331 (5) | C9—C10 | 1.408 (4) |
C1—C2 | 1.448 (4) | C9—H7 | 0.9500 |
C2—C6 | 1.432 (4) | C10—C11 | 1.422 (4) |
C2—C3 | 1.439 (4) | C10—H8 | 0.9500 |
C3—C4 | 1.413 (4) | C11—H9 | 0.9500 |
C3—Fe1—C6 | 69.03 (11) | C4—C3—C2 | 108.0 (2) |
C3—Fe1—C11 | 159.96 (12) | C4—C3—Fe1 | 69.95 (15) |
C6—Fe1—C11 | 107.59 (12) | C2—C3—Fe1 | 69.76 (14) |
C3—Fe1—C10 | 157.77 (11) | C4—C3—H1 | 126.0 |
C6—Fe1—C10 | 122.70 (11) | C2—C3—H1 | 126.0 |
C11—Fe1—C10 | 40.76 (12) | Fe1—C3—H1 | 125.9 |
C3—Fe1—C7 | 123.69 (12) | C3—C4—C5 | 108.4 (2) |
C6—Fe1—C7 | 123.51 (12) | C3—C4—Fe1 | 69.59 (15) |
C11—Fe1—C7 | 40.55 (12) | C5—C4—Fe1 | 69.75 (15) |
C10—Fe1—C7 | 68.15 (11) | C3—C4—H2 | 125.8 |
C3—Fe1—C4 | 40.46 (11) | C5—C4—H2 | 125.8 |
C6—Fe1—C4 | 68.65 (11) | Fe1—C4—H2 | 126.4 |
C11—Fe1—C4 | 158.40 (12) | C4—C5—C6 | 108.3 (2) |
C10—Fe1—C4 | 122.05 (11) | C4—C5—Fe1 | 69.63 (15) |
C7—Fe1—C4 | 159.15 (13) | C6—C5—Fe1 | 69.42 (15) |
C3—Fe1—C8 | 107.93 (11) | C4—C5—H3 | 125.9 |
C6—Fe1—C8 | 159.45 (11) | C6—C5—H3 | 125.9 |
C11—Fe1—C8 | 67.89 (12) | Fe1—C5—H3 | 126.7 |
C10—Fe1—C8 | 67.89 (11) | C5—C6—C2 | 107.8 (2) |
C7—Fe1—C8 | 40.10 (13) | C5—C6—Fe1 | 69.85 (15) |
C4—Fe1—C8 | 123.07 (12) | C2—C6—Fe1 | 69.85 (14) |
C3—Fe1—C5 | 68.41 (11) | C5—C6—H4 | 126.1 |
C6—Fe1—C5 | 40.73 (11) | C2—C6—H4 | 126.1 |
C11—Fe1—C5 | 122.74 (12) | Fe1—C6—H4 | 125.8 |
C10—Fe1—C5 | 107.10 (11) | C8—C7—C11 | 108.2 (3) |
C7—Fe1—C5 | 159.27 (13) | C8—C7—Fe1 | 70.06 (17) |
C4—Fe1—C5 | 40.61 (11) | C11—C7—Fe1 | 69.62 (16) |
C8—Fe1—C5 | 158.73 (12) | C8—C7—H5 | 125.9 |
C3—Fe1—C9 | 122.43 (11) | C11—C7—H5 | 125.9 |
C6—Fe1—C9 | 158.57 (11) | Fe1—C7—H5 | 126.0 |
C11—Fe1—C9 | 67.98 (12) | C7—C8—C9 | 108.2 (3) |
C10—Fe1—C9 | 40.27 (12) | C7—C8—Fe1 | 69.84 (16) |
C7—Fe1—C9 | 67.69 (12) | C9—C8—Fe1 | 69.91 (16) |
C4—Fe1—C9 | 107.31 (11) | C7—C8—H6 | 125.9 |
C8—Fe1—C9 | 40.30 (11) | C9—C8—H6 | 125.9 |
C5—Fe1—C9 | 122.60 (11) | Fe1—C8—H6 | 125.9 |
C3—Fe1—C2 | 41.17 (10) | C10—C9—C8 | 108.2 (3) |
C6—Fe1—C2 | 40.96 (10) | C10—C9—Fe1 | 69.64 (15) |
C11—Fe1—C2 | 123.42 (11) | C8—C9—Fe1 | 69.79 (16) |
C10—Fe1—C2 | 159.43 (12) | C10—C9—H7 | 125.9 |
C7—Fe1—C2 | 108.40 (11) | C8—C9—H7 | 125.9 |
C4—Fe1—C2 | 68.58 (10) | Fe1—C9—H7 | 126.2 |
C8—Fe1—C2 | 123.44 (11) | C9—C10—C11 | 107.8 (3) |
C5—Fe1—C2 | 68.53 (10) | C9—C10—Fe1 | 70.09 (15) |
C9—Fe1—C2 | 159.04 (11) | C11—C10—Fe1 | 69.57 (16) |
C1i—C1—F1 | 116.2 (3) | C9—C10—H8 | 126.1 |
C1i—C1—C2 | 130.4 (3) | C11—C10—H8 | 126.1 |
F1—C1—C2 | 113.4 (2) | Fe1—C10—H8 | 125.8 |
C6—C2—C3 | 107.4 (2) | C7—C11—C10 | 107.6 (3) |
C6—C2—C1 | 123.7 (2) | C7—C11—Fe1 | 69.83 (16) |
C3—C2—C1 | 128.8 (2) | C10—C11—Fe1 | 69.67 (16) |
C6—C2—Fe1 | 69.20 (14) | C7—C11—H9 | 126.2 |
C3—C2—Fe1 | 69.06 (14) | C10—C11—H9 | 126.2 |
C1—C2—Fe1 | 127.83 (18) | Fe1—C11—H9 | 125.9 |
C1i—C1—C2—C6 | 161.0 (3) | C2—Fe1—C6—C5 | −118.8 (2) |
F1—C1—C2—C6 | −16.4 (4) | C3—Fe1—C6—C2 | 37.98 (15) |
C1i—C1—C2—C3 | −17.7 (6) | C11—Fe1—C6—C2 | −121.08 (17) |
F1—C1—C2—C3 | 164.9 (2) | C10—Fe1—C6—C2 | −163.28 (16) |
C1i—C1—C2—Fe1 | −110.3 (4) | C7—Fe1—C6—C2 | −79.33 (19) |
F1—C1—C2—Fe1 | 72.3 (3) | C4—Fe1—C6—C2 | 81.50 (17) |
C3—Fe1—C2—C6 | −119.2 (2) | C8—Fe1—C6—C2 | −47.3 (4) |
C11—Fe1—C2—C6 | 78.00 (19) | C5—Fe1—C6—C2 | 118.8 (2) |
C10—Fe1—C2—C6 | 43.6 (4) | C9—Fe1—C6—C2 | 164.5 (3) |
C7—Fe1—C2—C6 | 120.28 (18) | C3—Fe1—C7—C8 | 77.46 (19) |
C4—Fe1—C2—C6 | −81.68 (17) | C6—Fe1—C7—C8 | 163.19 (16) |
C8—Fe1—C2—C6 | 162.00 (17) | C11—Fe1—C7—C8 | −119.3 (2) |
C5—Fe1—C2—C6 | −37.89 (16) | C10—Fe1—C7—C8 | −81.18 (18) |
C9—Fe1—C2—C6 | −164.2 (3) | C4—Fe1—C7—C8 | 42.4 (4) |
C6—Fe1—C2—C3 | 119.2 (2) | C5—Fe1—C7—C8 | −161.7 (3) |
C11—Fe1—C2—C3 | −162.78 (17) | C9—Fe1—C7—C8 | −37.57 (16) |
C10—Fe1—C2—C3 | 162.8 (3) | C2—Fe1—C7—C8 | 120.43 (17) |
C7—Fe1—C2—C3 | −120.50 (17) | C3—Fe1—C7—C11 | −163.24 (16) |
C4—Fe1—C2—C3 | 37.54 (16) | C6—Fe1—C7—C11 | −77.5 (2) |
C8—Fe1—C2—C3 | −78.78 (19) | C10—Fe1—C7—C11 | 38.12 (17) |
C5—Fe1—C2—C3 | 81.32 (17) | C4—Fe1—C7—C11 | 161.7 (3) |
C9—Fe1—C2—C3 | −45.0 (4) | C8—Fe1—C7—C11 | 119.3 (2) |
C3—Fe1—C2—C1 | 123.6 (3) | C5—Fe1—C7—C11 | −42.4 (4) |
C6—Fe1—C2—C1 | −117.2 (3) | C9—Fe1—C7—C11 | 81.73 (18) |
C11—Fe1—C2—C1 | −39.2 (3) | C2—Fe1—C7—C11 | −120.27 (17) |
C10—Fe1—C2—C1 | −73.6 (4) | C11—C7—C8—C9 | 0.2 (3) |
C7—Fe1—C2—C1 | 3.1 (3) | Fe1—C7—C8—C9 | 59.59 (19) |
C4—Fe1—C2—C1 | 161.1 (3) | C11—C7—C8—Fe1 | −59.38 (19) |
C8—Fe1—C2—C1 | 44.8 (3) | C3—Fe1—C8—C7 | −121.39 (17) |
C5—Fe1—C2—C1 | −155.1 (3) | C6—Fe1—C8—C7 | −43.4 (4) |
C9—Fe1—C2—C1 | 78.6 (4) | C11—Fe1—C8—C7 | 37.73 (18) |
C6—C2—C3—C4 | −0.9 (3) | C10—Fe1—C8—C7 | 81.88 (19) |
C1—C2—C3—C4 | 177.9 (3) | C4—Fe1—C8—C7 | −163.35 (17) |
Fe1—C2—C3—C4 | −59.72 (18) | C5—Fe1—C8—C7 | 162.2 (3) |
C6—C2—C3—Fe1 | 58.77 (17) | C9—Fe1—C8—C7 | 119.3 (3) |
C1—C2—C3—Fe1 | −122.3 (3) | C2—Fe1—C8—C7 | −78.6 (2) |
C6—Fe1—C3—C4 | 81.28 (17) | C3—Fe1—C8—C9 | 119.33 (18) |
C11—Fe1—C3—C4 | 165.2 (3) | C6—Fe1—C8—C9 | −162.7 (3) |
C10—Fe1—C3—C4 | −45.0 (4) | C11—Fe1—C8—C9 | −81.56 (19) |
C7—Fe1—C3—C4 | −161.65 (17) | C10—Fe1—C8—C9 | −37.41 (18) |
C8—Fe1—C3—C4 | −120.29 (17) | C7—Fe1—C8—C9 | −119.3 (3) |
C5—Fe1—C3—C4 | 37.42 (16) | C4—Fe1—C8—C9 | 77.4 (2) |
C9—Fe1—C3—C4 | −78.37 (19) | C5—Fe1—C8—C9 | 42.9 (4) |
C2—Fe1—C3—C4 | 119.1 (2) | C2—Fe1—C8—C9 | 162.07 (17) |
C6—Fe1—C3—C2 | −37.78 (15) | C7—C8—C9—C10 | −0.3 (3) |
C11—Fe1—C3—C2 | 46.1 (4) | Fe1—C8—C9—C10 | 59.25 (19) |
C10—Fe1—C3—C2 | −164.1 (3) | C7—C8—C9—Fe1 | −59.55 (19) |
C7—Fe1—C3—C2 | 79.28 (19) | C3—Fe1—C9—C10 | 161.21 (16) |
C4—Fe1—C3—C2 | −119.1 (2) | C6—Fe1—C9—C10 | 43.9 (4) |
C8—Fe1—C3—C2 | 120.65 (16) | C11—Fe1—C9—C10 | −38.12 (18) |
C5—Fe1—C3—C2 | −81.64 (16) | C7—Fe1—C9—C10 | −82.06 (19) |
C9—Fe1—C3—C2 | 162.57 (15) | C4—Fe1—C9—C10 | 119.47 (17) |
C2—C3—C4—C5 | 0.5 (3) | C8—Fe1—C9—C10 | −119.5 (3) |
Fe1—C3—C4—C5 | −59.14 (18) | C5—Fe1—C9—C10 | 77.6 (2) |
C2—C3—C4—Fe1 | 59.60 (18) | C2—Fe1—C9—C10 | −165.3 (3) |
C6—Fe1—C4—C3 | −82.31 (16) | C3—Fe1—C9—C8 | −79.3 (2) |
C11—Fe1—C4—C3 | −166.2 (3) | C6—Fe1—C9—C8 | 163.4 (3) |
C10—Fe1—C4—C3 | 161.61 (16) | C11—Fe1—C9—C8 | 81.3 (2) |
C7—Fe1—C4—C3 | 47.4 (4) | C10—Fe1—C9—C8 | 119.5 (3) |
C8—Fe1—C4—C3 | 78.63 (19) | C7—Fe1—C9—C8 | 37.39 (18) |
C5—Fe1—C4—C3 | −119.8 (2) | C4—Fe1—C9—C8 | −121.07 (18) |
C9—Fe1—C4—C3 | 120.01 (16) | C5—Fe1—C9—C8 | −162.96 (17) |
C2—Fe1—C4—C3 | −38.18 (16) | C2—Fe1—C9—C8 | −45.9 (4) |
C3—Fe1—C4—C5 | 119.8 (2) | C8—C9—C10—C11 | 0.3 (3) |
C6—Fe1—C4—C5 | 37.44 (16) | Fe1—C9—C10—C11 | 59.61 (18) |
C11—Fe1—C4—C5 | −46.5 (4) | C8—C9—C10—Fe1 | −59.34 (19) |
C10—Fe1—C4—C5 | −78.64 (19) | C3—Fe1—C10—C9 | −45.9 (4) |
C7—Fe1—C4—C5 | 167.2 (3) | C6—Fe1—C10—C9 | −162.47 (16) |
C8—Fe1—C4—C5 | −161.61 (16) | C11—Fe1—C10—C9 | 118.8 (2) |
C9—Fe1—C4—C5 | −120.23 (16) | C7—Fe1—C10—C9 | 80.83 (19) |
C2—Fe1—C4—C5 | 81.58 (17) | C4—Fe1—C10—C9 | −78.70 (19) |
C3—C4—C5—C6 | 0.2 (3) | C8—Fe1—C10—C9 | 37.44 (17) |
Fe1—C4—C5—C6 | −58.83 (18) | C5—Fe1—C10—C9 | −120.59 (17) |
C3—C4—C5—Fe1 | 59.03 (18) | C2—Fe1—C10—C9 | 165.1 (3) |
C3—Fe1—C5—C4 | −37.29 (15) | C3—Fe1—C10—C11 | −164.7 (3) |
C6—Fe1—C5—C4 | −119.8 (2) | C6—Fe1—C10—C11 | 78.8 (2) |
C11—Fe1—C5—C4 | 161.50 (16) | C7—Fe1—C10—C11 | −37.93 (18) |
C10—Fe1—C5—C4 | 119.61 (17) | C4—Fe1—C10—C11 | 162.54 (17) |
C7—Fe1—C5—C4 | −167.1 (3) | C8—Fe1—C10—C11 | −81.33 (19) |
C8—Fe1—C5—C4 | 46.8 (4) | C5—Fe1—C10—C11 | 120.65 (18) |
C9—Fe1—C5—C4 | 78.27 (19) | C9—Fe1—C10—C11 | −118.8 (2) |
C2—Fe1—C5—C4 | −81.71 (17) | C2—Fe1—C10—C11 | 46.3 (4) |
C3—Fe1—C5—C6 | 82.51 (17) | C8—C7—C11—C10 | 0.0 (3) |
C11—Fe1—C5—C6 | −78.70 (19) | Fe1—C7—C11—C10 | −59.69 (19) |
C10—Fe1—C5—C6 | −120.59 (17) | C8—C7—C11—Fe1 | 59.7 (2) |
C7—Fe1—C5—C6 | −47.3 (4) | C9—C10—C11—C7 | −0.1 (3) |
C4—Fe1—C5—C6 | 119.8 (2) | Fe1—C10—C11—C7 | 59.79 (19) |
C8—Fe1—C5—C6 | 166.6 (3) | C9—C10—C11—Fe1 | −59.94 (18) |
C9—Fe1—C5—C6 | −161.93 (16) | C3—Fe1—C11—C7 | 44.4 (4) |
C2—Fe1—C5—C6 | 38.09 (16) | C6—Fe1—C11—C7 | 121.34 (17) |
C4—C5—C6—C2 | −0.8 (3) | C10—Fe1—C11—C7 | −118.6 (2) |
Fe1—C5—C6—C2 | −59.76 (17) | C4—Fe1—C11—C7 | −162.4 (3) |
C4—C5—C6—Fe1 | 58.96 (18) | C8—Fe1—C11—C7 | −37.32 (17) |
C3—C2—C6—C5 | 1.1 (3) | C5—Fe1—C11—C7 | 163.51 (17) |
C1—C2—C6—C5 | −177.9 (2) | C9—Fe1—C11—C7 | −80.96 (18) |
Fe1—C2—C6—C5 | 59.76 (18) | C2—Fe1—C11—C7 | 79.1 (2) |
C3—C2—C6—Fe1 | −58.68 (17) | C3—Fe1—C11—C10 | 163.1 (3) |
C1—C2—C6—Fe1 | 122.4 (2) | C6—Fe1—C11—C10 | −120.02 (17) |
C3—Fe1—C6—C5 | −80.86 (17) | C7—Fe1—C11—C10 | 118.6 (2) |
C11—Fe1—C6—C5 | 120.08 (17) | C4—Fe1—C11—C10 | −43.7 (4) |
C10—Fe1—C6—C5 | 77.88 (19) | C8—Fe1—C11—C10 | 81.32 (18) |
C7—Fe1—C6—C5 | 161.83 (17) | C5—Fe1—C11—C10 | −77.85 (19) |
C4—Fe1—C6—C5 | −37.34 (16) | C9—Fe1—C11—C10 | 37.67 (17) |
C8—Fe1—C6—C5 | −166.1 (3) | C2—Fe1—C11—C10 | −162.29 (16) |
C9—Fe1—C6—C5 | 45.7 (4) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Fe2(C5H5)2(C6H4F)2] |
Mr | 432.06 |
Crystal system, space group | Tetragonal, P42/n |
Temperature (K) | 103 |
a, c (Å) | 16.968 (6), 5.8668 (17) |
V (Å3) | 1689.2 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.623, 0.845 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10691, 1483, 1361 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.067, 1.22 |
No. of reflections | 1483 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.25 |
Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), yadokari-XG (Wakita, 2005).
F1—C1 | 1.365 (3) | C1—C2 | 1.448 (4) |
C1—C1i | 1.331 (5) | ||
C1i—C1—F1 | 116.2 (3) | F1—C1—C2 | 113.4 (2) |
C1i—C1—C2 | 130.4 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Although a number of synthetic works on ferrocenyl substituted ethenes have been reported, only three reports are known for the crystalline structures of trans-1,2-diferrocenylethene derivatives, that is, trans-1,2-diferrocenylethene (Denifl et al., 1996), trans-1,2-diferrocenyl-1,2-dimethylethene (Chen et al., 2000), and trans-1,2-diferrocenyl-1,2-diphenylethene (Skibar et al., 2004). During our course of studies on the syntheses of new π-conjugated compounds bearing ferrocenyl groups (Nagahora et al., 2004), the crystal structure of trans-1,2-diferrocenyl-1,2-difluoroethene has been revealed.
The title compound was synthesized in 6% yield by the treatment of ferrocenyllithium, which was prepared by the reaction of ferrocene with tert-butyllithium, with 1,2-dibromo-1,1,2,2-tetrafluoroethane. The molecular structure of the title compound is shown in Fig. 1. It was found that two fluoro and ferrocenyl groups are located as trans configuration, respectively, with respect to the ethene framework. It has a center of symmetry in the middle of the C1—C1i bond. The C1—C1i and C1—C2 bond lengths (1.331 (5) and 1.448 (2) Å) of the title compound are in the range of those for the previously reported trans-Fc(R)C=C(R)Fc (Fc = ferrocenyl) (1.17 (1) and 1.47 (6) Å for R = H, 1.354 (4) and 1.517 (3) Å for R = Me, 1.29 (4) and 1.51 Å for R = Ph). The F1—C1 distance (1.365 (3) Å) is similar to that of trans-F(H)C=C(H)F (1.1349 (1) Å) (Lentz et al., 2004). The dihedral angle between the least squares of C2—C3—C4—C5—C6 and C2i—C3i—C4i—C5i—C6i (the cyclopentadienyl rings) is 18.6°, which is similar to that of the reported trans-Fc(H)C=C(H)Fc (15.1°). The shortest intermolecular contacts were found to be F1—H1iii (2.4885 (15) Å) and F1—F1ii (2.704 (2) Å), which are shorter than the sum of van der Waals radii between fluoro and hydrogen atoms (2.67 Å) and two fluoro atoms (2.94 Å), respectively (Fig. 2).