Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106025662/sq3026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106025662/sq3026Isup2.hkl |
CCDC reference: 618612
In a Schlenk tube under argon, (2S, 4S, SFc)-2-(diphenylphosphinoferrocenyl)-4-methoxymethyl-1,3-dioxane (16.5 g, 33.1 mmol; prepared according to Riant et al. (1997)] was dissolved in dry dichloromethane (1.3 l). Sulfur (5.7 g, 178 mmol, 5.4 equivalents) was then added and the solution was kept at reflux for 2 h. After cooling back to room temperature, dichloromethane (Volume?) was added to the suspension and the mixture was filtered on Celite with washings by dichloromethane. After evaporation of the solvent, the crude material was purified by flash chromatography on silica gel, eluted with a pentane–diethyl? ether mixture (80:20 v/v), to yield 14.8 g (84%) of an orange solid. Single crystals of (I) suitable for X-ray diffraction studies were obtained by slow diffusion of hexane into a CH2Cl2 solution of (2S, 4S, SFc)-2-(diphenylphosphinoferrocenyl)-4-methoxymethyl-1,3-dioxane.
All H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H = 0.93 (Caromatic) or 0.96 Å (Cmethyl) and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(Caromatic,O) or 1.5Ueq(Cmethyl).
Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software; data reduction: X-RED (Stoe & Cie, 1996); 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) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Fe(C5H5)(C23H24O3PS)] | F(000) = 1112 |
Mr = 532.39 | Dx = 1.434 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8000 reflections |
a = 9.4886 (12) Å | θ = 1.8–24.3° |
b = 15.2217 (17) Å | µ = 0.79 mm−1 |
c = 17.071 (2) Å | T = 180 K |
V = 2465.7 (5) Å3 | Needle, yellow |
Z = 4 | 0.49 × 0.09 × 0.06 mm |
Stoe IPDS diffractometer | 3962 independent reflections |
Radiation source: fine-focus sealed tube | 3266 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ϕ scans | θmax = 24.3°, θmin = 1.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −10→10 |
Tmin = 0.561, Tmax = 0.865 | k = 0→17 |
19961 measured reflections | l = 0→19 |
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)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0172P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
3962 reflections | Δρmax = 0.21 e Å−3 |
308 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.016 (17) |
[Fe(C5H5)(C23H24O3PS)] | V = 2465.7 (5) Å3 |
Mr = 532.39 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.4886 (12) Å | µ = 0.79 mm−1 |
b = 15.2217 (17) Å | T = 180 K |
c = 17.071 (2) Å | 0.49 × 0.09 × 0.06 mm |
Stoe IPDS diffractometer | 3962 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3266 reflections with I > 2σ(I) |
Tmin = 0.561, Tmax = 0.865 | Rint = 0.047 |
19961 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.056 | Δρmax = 0.21 e Å−3 |
S = 0.96 | Δρmin = −0.31 e Å−3 |
3962 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
308 parameters | Absolute structure parameter: −0.016 (17) |
0 restraints |
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 80 mm. 125 frames (5 min per frame) were obtained with 0 < ϕ < 250° and with the crystals rotated through 2.0° in ϕ. Coverage of the unique set was over 98.8% complete to at least 24.33°. Crystal decay was monitored by measuring 200 reflections per frame. Spectroscopic and analytical characterization: 1H NMR (S)-(2) (acetone-d6, δ, p.p.m.): 7.9–7.8 (2H, m, PPh2), 7.7–7.4 (8H, m, PPh2), 6.02 (1H, s, O—CH—O), 4.77 (1H, m, subst Cp), 4.41 (1H, m, subst Cp), 4.32 (5H, s, Cp), 4.17 (1H, dd, ABX syst, J = 12.4 and 5 Hz, OCH2CH2), 3.88 (1H, dd, ABX syst, J = 12.4 and 2.8 Hz, OCH2CH2), 3.83 (1H, m, subst Cp), 3.64 (1H, m, CH), 2.89 (3H, s, OCH3), 2.77 (1H, dd, ABX syst, J = 10.1 and 4.5 Hz, CH2OCH3), 2.69 (1H, dd, ABX syst, J = 10.1 and 5.5 Hz, CH2OCH3), 1.62 (1H, qd, J =13.3 and 5.5 Hz, CH2), 1.38 (1H, br d, J = 13.3 Hz, CH2); 13C NMR (acetone-d6, δ, p.p.m.): 135.8 (JPC = 88.5 Hz, quat PPh2), 134.1 (JPC = 86.1 Hz, quat PPh2), 132.5 (JPC = 10.6 Hz, PPh2), 132.3 (JPC = 10.7 Hz, PPh2), 131.5 (JPC = 3.0 Hz, PPh2), 131.1 (JPC = 3.1 Hz, PPh2), 128.2 (JPC = 12.2 Hz, PPh2), 128.0 (JPC = 12.6 Hz, PPh2), 98.3 (O—CH—O), 90.1 (JPC = 10.9 Hz, quat Cp), 75.2 (JPC = 12.3 Hz, subst Cp), 75.1, 74.6, 74.4 (JPC = 94.? Hz, quat Cp), 71.0 (Cp), 70.9 (JPC = 8.7 Hz, subst Cp), 69.4 (JPC = 10.3 Hz, subst Cp), 67.8, 65.5, 58.3 (OCH3), 15.0 (CH2); 31P NMR (acetone-d6, δ, p.p.m.): 47.9. [α]D = −9.72 (CHCl3, c = 0.36). MS (DCI, NH3) m/e: 533 (M+1, 100%). Analysis, found: C 63.13, H 4.90, S 5.29%; calculated for C28H29FeO3PS: C 63.16, H 5.48, S 6.02%. |
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 | 0.44353 (5) | 0.10794 (3) | 0.94796 (3) | 0.01799 (11) | |
S1 | 0.86914 (10) | 0.05679 (6) | 0.90433 (5) | 0.0245 (2) | |
P1 | 0.75005 (9) | 0.12341 (5) | 0.83239 (5) | 0.01670 (18) | |
O1 | 0.4108 (3) | 0.21193 (14) | 0.71221 (12) | 0.0244 (6) | |
O2 | 0.2482 (2) | 0.12014 (16) | 0.77315 (12) | 0.0223 (5) | |
O3 | 0.3405 (4) | 0.2627 (2) | 0.50854 (17) | 0.0551 (10) | |
C11 | 0.5875 (3) | 0.1622 (2) | 0.87428 (18) | 0.0161 (8) | |
C12 | 0.4467 (4) | 0.17102 (19) | 0.84335 (17) | 0.0156 (7) | |
C13 | 0.3663 (4) | 0.2200 (2) | 0.89868 (19) | 0.0195 (7) | |
H13 | 0.2700 | 0.2359 | 0.8932 | 0.023* | |
C14 | 0.4532 (4) | 0.2411 (2) | 0.96286 (19) | 0.0241 (8) | |
H14 | 0.4255 | 0.2734 | 1.0079 | 0.029* | |
C15 | 0.5890 (3) | 0.20594 (19) | 0.9489 (2) | 0.0181 (7) | |
H15 | 0.6678 | 0.2105 | 0.9830 | 0.022* | |
C16 | 0.5024 (4) | −0.0156 (2) | 0.9826 (2) | 0.0283 (9) | |
H16 | 0.5906 | −0.0430 | 0.9728 | 0.034* | |
C17 | 0.4688 (4) | 0.0354 (2) | 1.0480 (2) | 0.0335 (9) | |
H17 | 0.5300 | 0.0486 | 1.0904 | 0.040* | |
C18 | 0.3285 (5) | 0.0639 (3) | 1.0400 (2) | 0.0416 (11) | |
H18 | 0.2788 | 0.1001 | 1.0759 | 0.050* | |
C19 | 0.2751 (4) | 0.0297 (3) | 0.9700 (3) | 0.0455 (13) | |
H19 | 0.1824 | 0.0382 | 0.9504 | 0.055* | |
C20 | 0.3828 (5) | −0.0195 (2) | 0.9337 (2) | 0.0387 (11) | |
H20 | 0.3760 | −0.0497 | 0.8851 | 0.046* | |
C2 | 0.3919 (3) | 0.1407 (2) | 0.76523 (18) | 0.0164 (7) | |
H2 | 0.4457 | 0.0881 | 0.7469 | 0.020* | |
C3 | 0.1910 (4) | 0.0915 (3) | 0.6996 (2) | 0.0293 (9) | |
H3A | 0.0896 | 0.0780 | 0.7059 | 0.035* | |
H3B | 0.2397 | 0.0373 | 0.6825 | 0.035* | |
C5 | 0.2094 (4) | 0.1625 (2) | 0.6380 (2) | 0.0303 (9) | |
H5A | 0.1790 | 0.1401 | 0.5862 | 0.036* | |
H5B | 0.1503 | 0.2140 | 0.6513 | 0.036* | |
C4 | 0.3632 (4) | 0.1895 (2) | 0.63460 (19) | 0.0264 (9) | |
H4 | 0.4210 | 0.1398 | 0.6137 | 0.032* | |
C111 | 0.7064 (3) | 0.0605 (2) | 0.74640 (19) | 0.0173 (8) | |
C112 | 0.6548 (4) | −0.0247 (2) | 0.7570 (2) | 0.0236 (8) | |
H112 | 0.6491 | −0.0486 | 0.8083 | 0.028* | |
C113 | 0.6122 (4) | −0.0745 (2) | 0.6939 (2) | 0.0264 (9) | |
H113 | 0.5753 | −0.1318 | 0.7019 | 0.032* | |
C114 | 0.6234 (4) | −0.0409 (2) | 0.6191 (2) | 0.0324 (9) | |
H114 | 0.5948 | −0.0753 | 0.5755 | 0.039* | |
C115 | 0.6761 (4) | 0.0425 (2) | 0.6075 (2) | 0.0298 (9) | |
H115 | 0.6837 | 0.0652 | 0.5558 | 0.036* | |
C116 | 0.7181 (4) | 0.0936 (2) | 0.67064 (19) | 0.0236 (8) | |
H116 | 0.7547 | 0.1510 | 0.6622 | 0.028* | |
C121 | 0.8322 (4) | 0.2243 (2) | 0.7988 (2) | 0.0191 (8) | |
C122 | 0.7508 (4) | 0.2921 (2) | 0.7661 (2) | 0.0256 (8) | |
H122 | 0.6515 | 0.2862 | 0.7618 | 0.031* | |
C123 | 0.8171 (4) | 0.3676 (2) | 0.7401 (2) | 0.0307 (9) | |
H123 | 0.7627 | 0.4134 | 0.7175 | 0.037* | |
C124 | 0.9616 (4) | 0.3773 (2) | 0.7466 (2) | 0.0295 (9) | |
H124 | 1.0057 | 0.4297 | 0.7288 | 0.035* | |
C125 | 1.0413 (4) | 0.3111 (2) | 0.7788 (2) | 0.0323 (9) | |
H125 | 1.1405 | 0.3176 | 0.7831 | 0.039* | |
C126 | 0.9768 (4) | 0.2347 (2) | 0.8052 (2) | 0.0245 (9) | |
H126 | 1.0322 | 0.1892 | 0.8277 | 0.029* | |
C41 | 0.3885 (6) | 0.2702 (3) | 0.5864 (2) | 0.0487 (13) | |
H41A | 0.3405 | 0.3206 | 0.6115 | 0.058* | |
H41B | 0.4908 | 0.2829 | 0.5858 | 0.058* | |
C42 | 0.4237 (6) | 0.2052 (3) | 0.4637 (2) | 0.0648 (15) | |
H42A | 0.5236 | 0.2180 | 0.4728 | 0.097* | |
H42B | 0.4018 | 0.2130 | 0.4081 | 0.097* | |
H42C | 0.4036 | 0.1445 | 0.4791 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0183 (2) | 0.0193 (2) | 0.0164 (2) | −0.0001 (2) | 0.0011 (2) | 0.0015 (2) |
S1 | 0.0236 (5) | 0.0250 (5) | 0.0248 (5) | 0.0049 (4) | −0.0031 (4) | 0.0010 (4) |
P1 | 0.0154 (4) | 0.0180 (4) | 0.0167 (4) | −0.0006 (4) | 0.0005 (4) | −0.0028 (4) |
O1 | 0.0380 (17) | 0.0189 (12) | 0.0162 (11) | −0.0072 (11) | −0.0051 (11) | 0.0037 (10) |
O2 | 0.0164 (11) | 0.0312 (13) | 0.0192 (11) | −0.0040 (12) | −0.0035 (10) | −0.0030 (11) |
O3 | 0.097 (3) | 0.0462 (19) | 0.0216 (15) | −0.0159 (19) | −0.0114 (17) | 0.0078 (14) |
C11 | 0.0165 (19) | 0.0175 (17) | 0.0144 (17) | −0.0010 (14) | −0.0006 (14) | 0.0025 (13) |
C12 | 0.0185 (17) | 0.0108 (15) | 0.0175 (16) | 0.0000 (15) | 0.0033 (16) | 0.0023 (13) |
C13 | 0.0218 (19) | 0.0180 (17) | 0.0188 (17) | 0.0052 (15) | 0.0032 (17) | −0.0004 (15) |
C14 | 0.0282 (19) | 0.0218 (17) | 0.0222 (19) | 0.0018 (17) | 0.0040 (18) | −0.0046 (14) |
C15 | 0.0199 (19) | 0.0209 (16) | 0.0136 (15) | −0.0031 (13) | −0.0055 (16) | −0.0003 (15) |
C16 | 0.035 (2) | 0.0169 (18) | 0.033 (2) | −0.0026 (16) | −0.0027 (17) | 0.0097 (16) |
C17 | 0.053 (3) | 0.0255 (18) | 0.0219 (18) | −0.0004 (18) | −0.001 (2) | 0.0036 (18) |
C18 | 0.050 (3) | 0.038 (2) | 0.037 (3) | 0.009 (2) | 0.027 (2) | 0.015 (2) |
C19 | 0.021 (2) | 0.046 (3) | 0.070 (4) | −0.006 (2) | −0.002 (2) | 0.037 (2) |
C20 | 0.051 (3) | 0.026 (2) | 0.039 (3) | −0.018 (2) | −0.002 (2) | 0.0063 (17) |
C2 | 0.0135 (17) | 0.0184 (17) | 0.0175 (16) | 0.0047 (13) | 0.0005 (14) | 0.0010 (13) |
C3 | 0.022 (2) | 0.038 (2) | 0.027 (2) | −0.0083 (18) | −0.0049 (17) | −0.0043 (17) |
C5 | 0.037 (2) | 0.032 (2) | 0.0223 (19) | 0.0082 (18) | −0.0092 (17) | −0.0029 (17) |
C4 | 0.041 (2) | 0.023 (2) | 0.0156 (17) | −0.0075 (18) | −0.0089 (17) | 0.0013 (14) |
C111 | 0.0148 (18) | 0.0159 (17) | 0.0213 (18) | −0.0007 (14) | −0.0001 (14) | −0.0070 (15) |
C112 | 0.025 (2) | 0.0202 (19) | 0.026 (2) | 0.0056 (16) | −0.0023 (17) | 0.0005 (15) |
C113 | 0.028 (2) | 0.0191 (18) | 0.032 (2) | −0.0021 (16) | 0.0021 (18) | −0.0063 (15) |
C114 | 0.038 (2) | 0.028 (2) | 0.031 (2) | 0.0032 (19) | −0.0052 (19) | −0.0196 (17) |
C115 | 0.039 (2) | 0.031 (2) | 0.0189 (19) | 0.0025 (18) | 0.0020 (18) | −0.0031 (17) |
C116 | 0.028 (2) | 0.0228 (19) | 0.0206 (18) | −0.0014 (15) | 0.0058 (16) | −0.0006 (16) |
C121 | 0.018 (2) | 0.0170 (18) | 0.0221 (19) | −0.0029 (15) | −0.0020 (15) | −0.0066 (14) |
C122 | 0.025 (2) | 0.0267 (19) | 0.0255 (19) | 0.0010 (18) | −0.0010 (17) | −0.0001 (16) |
C123 | 0.044 (2) | 0.025 (2) | 0.023 (2) | −0.0040 (18) | −0.0083 (18) | 0.0029 (16) |
C124 | 0.038 (2) | 0.019 (2) | 0.0319 (19) | −0.0119 (19) | 0.0054 (19) | −0.0039 (17) |
C125 | 0.025 (2) | 0.034 (2) | 0.038 (2) | −0.0072 (19) | 0.0016 (19) | −0.0057 (18) |
C126 | 0.024 (2) | 0.0218 (19) | 0.028 (2) | −0.0015 (16) | 0.0024 (16) | −0.0017 (16) |
C41 | 0.093 (4) | 0.035 (2) | 0.0179 (19) | −0.016 (2) | −0.015 (2) | 0.0049 (17) |
C42 | 0.091 (4) | 0.079 (3) | 0.024 (2) | −0.025 (3) | 0.008 (3) | 0.006 (2) |
Fe1—C18 | 2.027 (4) | C20—H20 | 0.9500 |
Fe1—C12 | 2.028 (3) | C2—H2 | 1.0000 |
Fe1—C19 | 2.028 (4) | C3—C5 | 1.518 (5) |
Fe1—C11 | 2.032 (3) | C3—H3A | 0.9900 |
Fe1—C15 | 2.033 (3) | C3—H3B | 0.9900 |
Fe1—C20 | 2.038 (4) | C5—C4 | 1.518 (6) |
Fe1—C13 | 2.038 (3) | C5—H5A | 0.9900 |
Fe1—C14 | 2.044 (3) | C5—H5B | 0.9900 |
Fe1—C17 | 2.047 (4) | C4—C41 | 1.498 (5) |
Fe1—C16 | 2.049 (3) | C4—H4 | 1.0000 |
S1—P1 | 1.9529 (12) | C111—C116 | 1.393 (5) |
P1—C11 | 1.800 (3) | C111—C112 | 1.399 (4) |
P1—C111 | 1.801 (3) | C112—C113 | 1.377 (5) |
P1—C121 | 1.816 (3) | C112—H112 | 0.9500 |
O1—C2 | 1.423 (4) | C113—C114 | 1.380 (5) |
O1—C4 | 1.441 (4) | C113—H113 | 0.9500 |
O2—C2 | 1.406 (4) | C114—C115 | 1.379 (5) |
O2—C3 | 1.435 (4) | C114—H114 | 0.9500 |
O3—C42 | 1.405 (6) | C115—C116 | 1.388 (5) |
O3—C41 | 1.409 (4) | C115—H115 | 0.9500 |
C11—C15 | 1.437 (4) | C116—H116 | 0.9500 |
C11—C12 | 1.443 (5) | C121—C126 | 1.386 (5) |
C12—C13 | 1.425 (4) | C121—C122 | 1.405 (5) |
C12—C2 | 1.504 (4) | C122—C123 | 1.383 (5) |
C13—C14 | 1.409 (5) | C122—H122 | 0.9500 |
C13—H13 | 0.9500 | C123—C124 | 1.383 (5) |
C14—C15 | 1.415 (5) | C123—H123 | 0.9500 |
C14—H14 | 0.9500 | C124—C125 | 1.375 (5) |
C15—H15 | 0.9500 | C124—H124 | 0.9500 |
C16—C17 | 1.396 (5) | C125—C126 | 1.389 (5) |
C16—C20 | 1.410 (5) | C125—H125 | 0.9500 |
C16—H16 | 0.9500 | C126—H126 | 0.9500 |
C17—C18 | 1.407 (6) | C41—H41A | 0.9900 |
C17—H17 | 0.9500 | C41—H41B | 0.9900 |
C18—C19 | 1.397 (6) | C42—H42A | 0.9800 |
C18—H18 | 0.9500 | C42—H42B | 0.9800 |
C19—C20 | 1.412 (6) | C42—H42C | 0.9800 |
C19—H19 | 0.9500 | ||
C18—Fe1—C12 | 147.91 (16) | C16—C17—H17 | 126.0 |
C18—Fe1—C19 | 40.31 (17) | C18—C17—H17 | 126.0 |
C12—Fe1—C19 | 116.96 (16) | Fe1—C17—H17 | 126.4 |
C18—Fe1—C11 | 167.42 (16) | C19—C18—C17 | 108.2 (4) |
C12—Fe1—C11 | 41.63 (13) | C19—C18—Fe1 | 69.9 (2) |
C19—Fe1—C11 | 152.04 (16) | C17—C18—Fe1 | 70.6 (2) |
C18—Fe1—C15 | 127.05 (16) | C19—C18—H18 | 125.9 |
C12—Fe1—C15 | 69.46 (14) | C17—C18—H18 | 125.9 |
C19—Fe1—C15 | 164.69 (17) | Fe1—C18—H18 | 125.2 |
C11—Fe1—C15 | 41.41 (13) | C18—C19—C20 | 108.1 (4) |
C18—Fe1—C20 | 68.02 (17) | C18—C19—Fe1 | 69.8 (2) |
C12—Fe1—C20 | 110.45 (14) | C20—C19—Fe1 | 70.1 (2) |
C19—Fe1—C20 | 40.62 (17) | C18—C19—H19 | 126.0 |
C11—Fe1—C20 | 120.18 (15) | C20—C19—H19 | 126.0 |
C15—Fe1—C20 | 153.05 (16) | Fe1—C19—H19 | 125.8 |
C18—Fe1—C13 | 113.78 (15) | C16—C20—C19 | 107.5 (4) |
C12—Fe1—C13 | 41.03 (13) | C16—C20—Fe1 | 70.2 (2) |
C19—Fe1—C13 | 106.53 (16) | C19—C20—Fe1 | 69.3 (2) |
C11—Fe1—C13 | 69.29 (13) | C16—C20—H20 | 126.3 |
C15—Fe1—C13 | 68.48 (14) | C19—C20—H20 | 126.3 |
C20—Fe1—C13 | 130.20 (16) | Fe1—C20—H20 | 125.8 |
C18—Fe1—C14 | 104.82 (15) | O2—C2—O1 | 110.7 (3) |
C12—Fe1—C14 | 68.88 (13) | O2—C2—C12 | 108.6 (3) |
C19—Fe1—C14 | 126.44 (17) | O1—C2—C12 | 106.7 (2) |
C11—Fe1—C14 | 69.15 (13) | O2—C2—H2 | 110.3 |
C15—Fe1—C14 | 40.62 (14) | O1—C2—H2 | 110.3 |
C20—Fe1—C14 | 166.16 (17) | C12—C2—H2 | 110.3 |
C13—Fe1—C14 | 40.36 (13) | O2—C3—C5 | 110.3 (3) |
C18—Fe1—C17 | 40.39 (16) | O2—C3—H3A | 109.6 |
C12—Fe1—C17 | 171.12 (15) | C5—C3—H3A | 109.6 |
C19—Fe1—C17 | 67.72 (16) | O2—C3—H3B | 109.6 |
C11—Fe1—C17 | 131.03 (15) | C5—C3—H3B | 109.6 |
C15—Fe1—C17 | 108.04 (15) | H3A—C3—H3B | 108.1 |
C20—Fe1—C17 | 67.65 (16) | C4—C5—C3 | 109.2 (3) |
C13—Fe1—C17 | 146.89 (14) | C4—C5—H5A | 109.8 |
C14—Fe1—C17 | 115.18 (14) | C3—C5—H5A | 109.8 |
C18—Fe1—C16 | 67.63 (16) | C4—C5—H5B | 109.8 |
C12—Fe1—C16 | 133.22 (14) | C3—C5—H5B | 109.8 |
C19—Fe1—C16 | 67.83 (16) | H5A—C5—H5B | 108.3 |
C11—Fe1—C16 | 111.61 (14) | O1—C4—C41 | 105.1 (3) |
C15—Fe1—C16 | 119.08 (14) | O1—C4—C5 | 109.3 (3) |
C20—Fe1—C16 | 40.38 (15) | C41—C4—C5 | 113.4 (4) |
C13—Fe1—C16 | 170.16 (15) | O1—C4—H4 | 109.7 |
C14—Fe1—C16 | 149.48 (15) | C41—C4—H4 | 109.7 |
C17—Fe1—C16 | 39.86 (14) | C5—C4—H4 | 109.7 |
C11—P1—C111 | 107.52 (15) | C116—C111—C112 | 119.0 (3) |
C11—P1—C121 | 102.48 (15) | C116—C111—P1 | 123.1 (3) |
C111—P1—C121 | 106.92 (15) | C112—C111—P1 | 117.9 (3) |
C11—P1—S1 | 114.60 (11) | C113—C112—C111 | 120.8 (3) |
C111—P1—S1 | 111.69 (12) | C113—C112—H112 | 119.6 |
C121—P1—S1 | 112.94 (12) | C111—C112—H112 | 119.6 |
C2—O1—C4 | 111.4 (2) | C112—C113—C114 | 119.8 (3) |
C2—O2—C3 | 110.5 (2) | C112—C113—H113 | 120.1 |
C42—O3—C41 | 112.5 (4) | C114—C113—H113 | 120.1 |
C15—C11—C12 | 106.9 (3) | C115—C114—C113 | 120.2 (3) |
C15—C11—P1 | 119.7 (2) | C115—C114—H114 | 119.9 |
C12—C11—P1 | 132.7 (2) | C113—C114—H114 | 119.9 |
C15—C11—Fe1 | 69.31 (17) | C114—C115—C116 | 120.5 (3) |
C12—C11—Fe1 | 69.02 (17) | C114—C115—H115 | 119.7 |
P1—C11—Fe1 | 133.54 (17) | C116—C115—H115 | 119.7 |
C13—C12—C11 | 107.6 (3) | C115—C116—C111 | 119.7 (3) |
C13—C12—C2 | 124.3 (3) | C115—C116—H116 | 120.1 |
C11—C12—C2 | 128.0 (3) | C111—C116—H116 | 120.1 |
C13—C12—Fe1 | 69.88 (18) | C126—C121—C122 | 119.5 (3) |
C11—C12—Fe1 | 69.35 (17) | C126—C121—P1 | 119.8 (3) |
C2—C12—Fe1 | 129.1 (2) | C122—C121—P1 | 120.8 (3) |
C14—C13—C12 | 108.7 (3) | C123—C122—C121 | 119.2 (4) |
C14—C13—Fe1 | 70.05 (19) | C123—C122—H122 | 120.4 |
C12—C13—Fe1 | 69.09 (18) | C121—C122—H122 | 120.4 |
C14—C13—H13 | 125.6 | C122—C123—C124 | 120.9 (4) |
C12—C13—H13 | 125.6 | C122—C123—H123 | 119.6 |
Fe1—C13—H13 | 126.8 | C124—C123—H123 | 119.6 |
C13—C14—C15 | 108.4 (3) | C125—C124—C123 | 119.9 (3) |
C13—C14—Fe1 | 69.58 (18) | C125—C124—H124 | 120.0 |
C15—C14—Fe1 | 69.24 (17) | C123—C124—H124 | 120.0 |
C13—C14—H14 | 125.8 | C124—C125—C126 | 120.1 (4) |
C15—C14—H14 | 125.8 | C124—C125—H125 | 119.9 |
Fe1—C14—H14 | 127.0 | C126—C125—H125 | 119.9 |
C14—C15—C11 | 108.4 (3) | C121—C126—C125 | 120.4 (4) |
C14—C15—Fe1 | 70.14 (18) | C121—C126—H126 | 119.8 |
C11—C15—Fe1 | 69.28 (17) | C125—C126—H126 | 119.8 |
C14—C15—H15 | 125.8 | O3—C41—C4 | 113.6 (3) |
C11—C15—H15 | 125.8 | O3—C41—H41A | 108.9 |
Fe1—C15—H15 | 126.4 | C4—C41—H41A | 108.9 |
C17—C16—C20 | 108.2 (4) | O3—C41—H41B | 108.9 |
C17—C16—Fe1 | 70.0 (2) | C4—C41—H41B | 108.9 |
C20—C16—Fe1 | 69.4 (2) | H41A—C41—H41B | 107.7 |
C17—C16—H16 | 125.9 | O3—C42—H42A | 109.5 |
C20—C16—H16 | 125.9 | O3—C42—H42B | 109.5 |
Fe1—C16—H16 | 126.3 | H42A—C42—H42B | 109.5 |
C16—C17—C18 | 108.0 (4) | O3—C42—H42C | 109.5 |
C16—C17—Fe1 | 70.1 (2) | H42A—C42—H42C | 109.5 |
C18—C17—Fe1 | 69.0 (2) | H42B—C42—H42C | 109.5 |
C4—C41—O3—C42 | −71.0 (5) | C13—C12—C2—O2 | −34.5 (4) |
C13—C12—C2—O1 | 84.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C126—H126···O2i | 0.95 | 2.48 | 3.157 (4) | 128 |
C122—H122···O1 | 0.95 | 2.69 | 3.570 (5) | 155 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C23H24O3PS)] |
Mr | 532.39 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 180 |
a, b, c (Å) | 9.4886 (12), 15.2217 (17), 17.071 (2) |
V (Å3) | 2465.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.49 × 0.09 × 0.06 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.561, 0.865 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19961, 3962, 3266 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.580 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.056, 0.96 |
No. of reflections | 3962 |
No. of parameters | 308 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.31 |
Absolute structure | Flack (1983), with how many Friedel pairs |
Absolute structure parameter | −0.016 (17) |
Computer programs: IPDS Software (Stoe & Cie, 2000), IPDS Software, X-RED (Stoe & Cie, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C126—H126···O2i | 0.95 | 2.48 | 3.157 (4) | 127.8 |
C122—H122···O1 | 0.95 | 2.69 | 3.570 (5) | 155.2 |
Symmetry code: (i) x+1, y, z. |
Ref | Δ | Ψ1* | Ψ2** | Θ | Q |
(I)a | 63.3 (1) | -90.8 (4) | 149.9 (3) | 177.1 (3) | 0.569 (3) |
Aa | 75.9 | -101.0 | 138.1 | 175.86 | 0.562 |
Bb | 75.4 | 103.7 | -135.4 | 178.15 | 0.562 |
Cc | 39.8 | 68.6 | -169.8 | 176.26 | 0.557 |
Cc | 56.6 | -93.3 | 28.0 | 177.23 | 0.551 |
Dd | 48.2 | 103.1 | -18.6 | 2.73 | 0.551 |
Dd | 10.2 | -38.5 | -162.2 | 2.58 | 0.551 |
Ed | 8.3 | 36.3 | 159.2 | 2.90 | 0.562 |
Fd | 35.9 | -113.3 | 6.4 | 179.35 | 0.567 |
Fd | 7.9 | 148.4 | 26.4 | 4.32 | 0.560 |
Fd | 36.3 | 174.0 | -65.0 | 178.70 | 0.571 |
Fd | 39.9 | -110.2 | 10.5 | 175.59 | 0.564 |
Fd | 44.7 | -164.8 | 74.4 | 173.75 | 0.562 |
Ge | 41.4 | 70.8 | -166.7 | 174.4 | 0.567 |
Notes: (*) Ψ1 is the C2—C1—C11—O1 torsion angle. (**) Ψ2 is the C2—C1—C11—O2 torsion angle. (***) Δ is the dihedral angle between the C2O2 plane and the Cp ring. (a) 1,2-disubstituted ferrocenyl derivatives. (b) 1,2,1'-trisubstituted ferrocenyl derivatives. (c) 1,2,5-trisubstituted ferrocenyl derivatives. (d) 1,1'-disubstituted ferrocenyl derivatives. (e) 1-monosubstituted ferrocenyl derivatives. References: (A) Riant et al. (1997); (B) Iftime et al. (1996); (C) Chiffre et al. (2002); (C) Chiffre et al. (2002); (D) Iftime et al. (1998); (E) Chiffre et al. (2001); (F) Hartinger et al. (2003); (F) Hartinger et al. (2003); (F) Hartinger et al. (2003); (G) Chiffre et al. (1999). |
Compound | Fe—Cg1 | Fe—Cg2 | Cg1—Fe—Cg2 | C2—P | P—S | δ |
(I) | 1.639 (5) | 1.653 (5) | 176.16 (3) | 1.800 (3) | 1.9529 (13) | 0.879 (7) |
a | 1.627 | 1.647 | 178.2 | 1.792 | 1.944 | 1.063 |
a | 1.636 | 1.652 | 175.7 | 1.811 | 1.951 | 1.395 |
b | 1.638 | 1.656 | 177.1 | 1.790 | 1.957 | 0.543 |
c | 1.644 | 1.660 | 175.4 | 1.795 | 1.956 | 1.270 |
d | 1.650 | 1.650 | 180.0 | 1.795 | 1.938 | 0.886 |
e | 1.653 | 1.653 | 180.0 | 1.795 | 1.944 | 0.891 |
Notes: (a) Butler et al. (1986); (b) Stepnicka & Císarová (2002); (c) Stepnicka & Císarová (2003); (d) Fang et al. (1995); (e) Pilloni et al. (1997) |
In recent decades, ferrocene derivatives have attracted tremendous interest (Togni & Hayashi, 1995) because of their numerous fields of application. Among these compounds, those which exhibit planar chirality are especially important because of their involvement in asymmetric catalysis and materials chemistry (Richards & Locke, 1998; Balavoine et al., 1998; Riant & Kagan, 1997). One of the most efficient methods to synthesize enantiomerically pure ferrocene derivatives has been developed by Kagan et al. (Riant et al., 1997). We used this method to synthesize the title compound, (I). This compound proved to be a very useful intermediate for the synthesis of enantiomerically pure (S)-2-(diphenylthiophosphinoferrocenyl)methanol or (S)-2-(diphenylthiophosphino)ferrocenecarboxaldehyde, which we have used to develop new ligands for asymmetric catalysis (Routaboul et al., 2005; Mateus et al., 2006; Malacea et al., 2006).
A molecular view of compound (I) is shown in Fig. 1. Atom P1 is slightly exo by 0.237 (5) Å with respect to the Cp ring to which it is attached. This slight deviation from planarity with the Cp ring may be related to steric hindrance occurring between the dioxane ring and the phenyl rings. Indeed, there is a short contact of 2.51 Å between atom C111 and the H atom attached to atom C2. However, it could also result from an intramolecular C—H···O interaction between atom C122 of one of the phenyl rings and atom O1 of the dioxane (Table 1). As observed in related (diphenylthiophosphino)ferrocenyl derivatives (López Cortés et al., 2006, and references therein), atom S1 is endo by 0.878 (7) Å with respect to this Cp ring.
The dioxane ring is distorted and the puckering parameters (Cremer & Pople, 1975) show that its conformation is close to that of a chair: the total puckering amplitude Q and the θ angle calculated for the atom sequence C2/O2/C3/C5/C4/O1 are 0.569 (3) and 177.1 (3)°, respectively. Such a chair conformation seems to be general for a dioxane ring attached to ferrocenyl derivatives, whatever the number of substituents on the ferrocene framework (Table 2). Owing to steric hindrance, the dioxane ring is twisted with respect to the Cp ring, with C13—C12—C2—O1 and C13—C12—C2—O2 torsion angles of 84.8 (4) and −34.5 (4)°, respectively. This twist is also reflected by the dihedral angle of 63.3 (1)° between the Cp ring and the O1/C3/C4/O2 mean plane. These different geometric parameters are greatly dependent on the nature of the substituted ferrocenyl derivatives (Table 2). The larger twist is observed for the 1,2-di-substituted ferrocene with bulky substituents in the 2 position on the same Cp ring, as underlined in Table 2 [Cambridge Structural Database (CSD), Version 5.27; Allen, 2002]. The terminal methoxy group is twisted with respect to the C4—C41 bond, with a torsion angle of −71.0 (5)°.
The two Cp rings are twisted with respect to each other by 16.0 (3)°, and so have a conformation which might be regarded as intermediate between eclipsed and staggered. Such a conformation may be induced by the occurrence of an intermolecular C—H···O hydrogen-bonding interaction, which links the molecules into a C(8) chain (Etter et al., 1990) running parallel to the a axis (Table 1, Fig. 2).
The geometry within the (diphenylthiophosphino)ferrocenyl framework agrees with related compounds found in the CSD. Some selected bond distances, angles and puckering parameters are reported in Table 3. In all of these compounds, the S atoms appear to be endo with respect to the Cp ring bearing the phosphino group.
The refinement of the Flack parameter (Flack, 1983; Bernardinelli & Flack, 1985) allowed the determination of the absolute configuration and fully confirmed the stereochemistry expected from the chemical pathway. The two chiral centres, C2 and C4, have an S configuration, and the chiral planarity is S.