Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106010833/sk3012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106010833/sk3012IIIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106010833/sk3012Vsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106010833/sk3012VIIIsup4.hkl |
CCDC references: 609398; 609399; 609400
Compounds (III), (V) and (VIII) were synthesized according to procedure reported by Lopez Cortés et al. (2006). The scheme gives an outline of the synthesis, with steps as follows. (i) t-BuLi, 195 K to room temperature; 1-cyanophosphole, 243 K; S8, CH2Cl2, room temperature. (ii) H+, H2O/CH2Cl2, reflux. (iii) NaBH4, room temperature. (iv) AcCl/NEt3, 273 K to room temperature, CH2Cl2. (v) R2PH, toluene, reflux, S8, CH2Cl2, room temperature. (vi) P(NMe2)3, toluene reflux. Intermediate products (IV), (VI) and (VII) were obtained as oils, whereas crystals of (III), (V) and (VIII) suitable for X-ray analyses were obtained by slow diffusion of pentane into dichloromethane solutions.
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: CrysAlis CCD (Oxford Diffraction, 2003) for (III); IPDS Software (Stoe & Cie, 2000) for (V), (VIII). Cell refinement: CrysAlis RED (Oxford Diffraction, 2003) for (III); IPDS Software for (V), (VIII). Data reduction: CrysAlis RED for (III); X-RED (Stoe & Cie, 1996) for (V), (VIII). For all compounds, 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) for (III), (VIII); ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003) for (V). For all compounds, software used to prepare material for publication: WinGX (Farrugia, 1999).
[Fe(C5H5)(C23H22O3PS)] | F(000) = 552 |
Mr = 530.38 | Dx = 1.470 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3139 reflections |
a = 7.4885 (7) Å | θ = 3.6–31.6° |
b = 9.5175 (8) Å | µ = 0.81 mm−1 |
c = 16.8193 (13) Å | T = 180 K |
β = 91.067 (7)° | Prism, yellow |
V = 1198.53 (18) Å3 | 0.36 × 0.28 × 0.22 mm |
Z = 2 |
Oxford XCALIBUR diffractometer | 4045 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 28.3°, θmin = 3.2° |
Detector resolution: 8.2632 pixels mm-1 | h = −9→9 |
ω and ϕ scans | k = −12→10 |
10617 measured reflections | l = −22→22 |
4383 independent reflections |
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)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0401P)2 + 0.0522P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
4383 reflections | Δρmax = 0.33 e Å−3 |
308 parameters | Δρmin = −0.33 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1249 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (1) |
[Fe(C5H5)(C23H22O3PS)] | V = 1198.53 (18) Å3 |
Mr = 530.38 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.4885 (7) Å | µ = 0.81 mm−1 |
b = 9.5175 (8) Å | T = 180 K |
c = 16.8193 (13) Å | 0.36 × 0.28 × 0.22 mm |
β = 91.067 (7)° |
Oxford XCALIBUR diffractometer | 4045 reflections with I > 2σ(I) |
10617 measured reflections | Rint = 0.023 |
4383 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.066 | Δρmax = 0.33 e Å−3 |
S = 1.07 | Δρmin = −0.33 e Å−3 |
4383 reflections | Absolute structure: Flack (1983), with 1249 Friedel pairs |
308 parameters | Absolute structure parameter: 0.00 (1) |
1 restraint |
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 | 0.80570 (4) | 0.53939 (3) | 0.734270 (16) | 0.01884 (8) | |
P1 | 0.78732 (7) | 0.90456 (6) | 0.73444 (3) | 0.01810 (11) | |
S1 | 0.71485 (8) | 0.94431 (7) | 0.84217 (3) | 0.02705 (13) | |
O21 | 1.1755 (2) | 0.59496 (16) | 0.88366 (9) | 0.0248 (3) | |
O22 | 1.1587 (2) | 0.83298 (16) | 0.85032 (9) | 0.0207 (3) | |
O26 | 1.1561 (2) | 1.12476 (18) | 0.90846 (11) | 0.0324 (4) | |
C1 | 0.8935 (2) | 0.7384 (2) | 0.71717 (11) | 0.0175 (4) | |
C2 | 1.0154 (3) | 0.6636 (2) | 0.76842 (12) | 0.0186 (4) | |
C3 | 1.0785 (2) | 0.5440 (3) | 0.72635 (11) | 0.0212 (4) | |
H3 | 1.1603 | 0.4758 | 0.7464 | 0.025* | |
C4 | 0.9979 (3) | 0.5443 (3) | 0.64908 (11) | 0.0226 (4) | |
H4 | 1.0169 | 0.4765 | 0.6086 | 0.027* | |
C5 | 0.8842 (3) | 0.6633 (2) | 0.64289 (12) | 0.0211 (4) | |
H5 | 0.8140 | 0.6889 | 0.5975 | 0.025* | |
C6 | 0.5659 (3) | 0.5491 (3) | 0.79046 (14) | 0.0326 (5) | |
H6 | 0.5052 | 0.6317 | 0.8065 | 0.039* | |
C7 | 0.5457 (3) | 0.4804 (3) | 0.71572 (16) | 0.0326 (5) | |
H7 | 0.4704 | 0.5098 | 0.6728 | 0.039* | |
C8 | 0.6579 (3) | 0.3600 (3) | 0.71654 (17) | 0.0346 (6) | |
H8 | 0.6704 | 0.2946 | 0.6743 | 0.041* | |
C9 | 0.7475 (4) | 0.3546 (3) | 0.79086 (16) | 0.0364 (6) | |
H9 | 0.8304 | 0.2847 | 0.8077 | 0.044* | |
C10 | 0.6918 (4) | 0.4729 (3) | 0.83655 (15) | 0.0354 (6) | |
H10 | 0.7325 | 0.4961 | 0.8888 | 0.042* | |
C11 | 0.9308 (3) | 1.0287 (2) | 0.68432 (11) | 0.0217 (4) | |
C12 | 0.8615 (3) | 1.0586 (2) | 0.60804 (12) | 0.0264 (5) | |
C13 | 0.6847 (3) | 0.9947 (2) | 0.59147 (13) | 0.0283 (5) | |
C14 | 0.6202 (3) | 0.9148 (2) | 0.65512 (13) | 0.0254 (5) | |
C21 | 1.0668 (3) | 0.7033 (2) | 0.85227 (11) | 0.0198 (4) | |
H21 | 0.9570 | 0.7130 | 0.8848 | 0.024* | |
C22 | 1.2274 (3) | 0.6261 (3) | 0.96438 (13) | 0.0282 (5) | |
H22A | 1.3104 | 0.5527 | 0.9844 | 0.034* | |
H22B | 1.1205 | 0.6255 | 0.9982 | 0.034* | |
C23 | 1.3174 (3) | 0.7683 (3) | 0.96985 (13) | 0.0263 (5) | |
H23A | 1.4344 | 0.7645 | 0.9435 | 0.032* | |
H23B | 1.3385 | 0.7934 | 1.0264 | 0.032* | |
C24 | 1.1999 (3) | 0.8790 (2) | 0.92996 (13) | 0.0222 (4) | |
H24 | 1.0862 | 0.8869 | 0.9599 | 0.027* | |
C25 | 1.2861 (3) | 1.0227 (3) | 0.92612 (13) | 0.0246 (4) | |
H25A | 1.3452 | 1.0446 | 0.9778 | 0.029* | |
H25B | 1.3781 | 1.0232 | 0.8846 | 0.029* | |
C26 | 1.2296 (4) | 1.2612 (3) | 0.9035 (2) | 0.0498 (8) | |
H26A | 1.2827 | 1.2873 | 0.9551 | 0.075* | |
H26B | 1.1352 | 1.3283 | 0.8891 | 0.075* | |
H26C | 1.3219 | 1.2626 | 0.8630 | 0.075* | |
C111 | 1.0897 (3) | 1.0856 (2) | 0.71198 (14) | 0.0271 (5) | |
H111 | 1.1333 | 1.0652 | 0.7641 | 0.033* | |
C112 | 1.1853 (4) | 1.1740 (3) | 0.66158 (15) | 0.0331 (5) | |
H112 | 1.2947 | 1.2147 | 0.6794 | 0.040* | |
C113 | 1.1200 (4) | 1.2021 (3) | 0.58569 (14) | 0.0365 (6) | |
H113 | 1.1869 | 1.2608 | 0.5516 | 0.044* | |
C114 | 0.9589 (4) | 1.1464 (3) | 0.55817 (14) | 0.0343 (6) | |
H114 | 0.9155 | 1.1677 | 0.5061 | 0.041* | |
C411 | 0.4531 (3) | 0.8537 (3) | 0.65205 (16) | 0.0325 (6) | |
H411 | 0.4105 | 0.8016 | 0.6960 | 0.039* | |
C412 | 0.3481 (4) | 0.8699 (3) | 0.58340 (18) | 0.0413 (7) | |
H412 | 0.2317 | 0.8302 | 0.5806 | 0.050* | |
C413 | 0.4137 (4) | 0.9439 (4) | 0.51907 (16) | 0.0450 (7) | |
H413 | 0.3433 | 0.9508 | 0.4717 | 0.054* | |
C414 | 0.5787 (4) | 1.0077 (3) | 0.52262 (15) | 0.0403 (7) | |
H414 | 0.6202 | 1.0601 | 0.4786 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01991 (14) | 0.01598 (14) | 0.02068 (14) | −0.00138 (13) | 0.00213 (10) | −0.00135 (13) |
P1 | 0.0208 (3) | 0.0151 (3) | 0.0183 (2) | 0.0016 (2) | 0.00039 (19) | −0.00107 (19) |
S1 | 0.0278 (3) | 0.0289 (3) | 0.0247 (3) | 0.0030 (2) | 0.0073 (2) | −0.0050 (2) |
O21 | 0.0307 (8) | 0.0182 (8) | 0.0252 (8) | 0.0048 (7) | −0.0057 (6) | 0.0007 (6) |
O22 | 0.0221 (7) | 0.0180 (7) | 0.0217 (7) | −0.0021 (6) | −0.0017 (6) | −0.0016 (6) |
O26 | 0.0296 (9) | 0.0194 (8) | 0.0483 (10) | 0.0000 (7) | −0.0029 (7) | −0.0039 (7) |
C1 | 0.0169 (9) | 0.0171 (11) | 0.0187 (8) | −0.0016 (8) | 0.0025 (7) | −0.0015 (8) |
C2 | 0.0166 (9) | 0.0172 (10) | 0.0221 (10) | −0.0018 (8) | 0.0028 (7) | 0.0002 (8) |
C3 | 0.0176 (8) | 0.0195 (10) | 0.0267 (9) | 0.0021 (10) | 0.0043 (7) | −0.0002 (10) |
C4 | 0.0242 (9) | 0.0201 (10) | 0.0239 (9) | −0.0008 (10) | 0.0073 (7) | −0.0048 (10) |
C5 | 0.0261 (10) | 0.0199 (10) | 0.0175 (9) | 0.0003 (9) | 0.0030 (8) | −0.0019 (8) |
C6 | 0.0284 (11) | 0.0276 (13) | 0.0425 (12) | −0.0055 (11) | 0.0195 (9) | −0.0065 (12) |
C7 | 0.0218 (11) | 0.0338 (13) | 0.0421 (14) | −0.0064 (10) | 0.0012 (9) | −0.0016 (11) |
C8 | 0.0321 (13) | 0.0232 (12) | 0.0486 (15) | −0.0115 (10) | 0.0062 (11) | −0.0104 (11) |
C9 | 0.0381 (14) | 0.0244 (13) | 0.0468 (16) | −0.0074 (11) | 0.0065 (12) | 0.0121 (11) |
C10 | 0.0418 (14) | 0.0384 (15) | 0.0263 (12) | −0.0125 (12) | 0.0120 (11) | 0.0043 (10) |
C11 | 0.0297 (10) | 0.0133 (9) | 0.0223 (9) | 0.0034 (10) | 0.0074 (7) | −0.0028 (9) |
C12 | 0.0376 (12) | 0.0188 (12) | 0.0230 (9) | 0.0095 (10) | 0.0056 (8) | 0.0005 (8) |
C13 | 0.0376 (12) | 0.0222 (11) | 0.0251 (11) | 0.0147 (10) | −0.0025 (9) | −0.0043 (8) |
C14 | 0.0278 (11) | 0.0201 (11) | 0.0283 (11) | 0.0096 (9) | −0.0032 (8) | −0.0043 (9) |
C21 | 0.0185 (9) | 0.0192 (11) | 0.0217 (9) | −0.0002 (8) | −0.0004 (7) | 0.0011 (8) |
C22 | 0.0368 (13) | 0.0234 (12) | 0.0243 (11) | 0.0014 (10) | −0.0058 (9) | 0.0026 (9) |
C23 | 0.0292 (12) | 0.0272 (12) | 0.0224 (10) | 0.0022 (9) | −0.0046 (9) | −0.0040 (8) |
C24 | 0.0212 (10) | 0.0213 (11) | 0.0240 (10) | −0.0007 (9) | 0.0005 (8) | −0.0031 (9) |
C25 | 0.0227 (9) | 0.0237 (12) | 0.0272 (10) | 0.0002 (10) | −0.0017 (8) | −0.0046 (9) |
C26 | 0.0553 (19) | 0.0220 (14) | 0.071 (2) | −0.0053 (12) | −0.0172 (15) | −0.0002 (13) |
C111 | 0.0338 (11) | 0.0186 (10) | 0.0291 (11) | −0.0012 (9) | 0.0051 (9) | −0.0014 (9) |
C112 | 0.0405 (14) | 0.0198 (11) | 0.0396 (13) | −0.0039 (10) | 0.0139 (11) | −0.0017 (10) |
C113 | 0.0539 (15) | 0.0185 (12) | 0.0379 (12) | −0.0003 (11) | 0.0230 (11) | 0.0029 (10) |
C114 | 0.0532 (16) | 0.0256 (13) | 0.0245 (11) | 0.0126 (12) | 0.0116 (11) | 0.0054 (9) |
C411 | 0.0273 (12) | 0.0275 (13) | 0.0422 (14) | 0.0073 (10) | −0.0073 (10) | −0.0072 (10) |
C412 | 0.0347 (14) | 0.0339 (14) | 0.0546 (18) | 0.0091 (11) | −0.0171 (12) | −0.0157 (13) |
C413 | 0.0492 (16) | 0.0455 (16) | 0.0394 (14) | 0.0234 (14) | −0.0210 (12) | −0.0128 (13) |
C414 | 0.0537 (16) | 0.0393 (18) | 0.0275 (12) | 0.0203 (13) | −0.0083 (11) | −0.0027 (11) |
Fe1—C1 | 2.028 (2) | C9—H9 | 0.9500 |
Fe1—C5 | 2.033 (2) | C10—H10 | 0.9500 |
Fe1—C10 | 2.035 (2) | C11—C111 | 1.380 (3) |
Fe1—C2 | 2.039 (2) | C11—C12 | 1.404 (3) |
Fe1—C7 | 2.045 (2) | C12—C114 | 1.399 (3) |
Fe1—C6 | 2.047 (2) | C12—C13 | 1.479 (3) |
Fe1—C4 | 2.0502 (19) | C13—C414 | 1.397 (3) |
Fe1—C9 | 2.050 (2) | C13—C14 | 1.406 (3) |
Fe1—C3 | 2.0503 (19) | C14—C411 | 1.380 (3) |
Fe1—C8 | 2.053 (2) | C21—H21 | 1.0000 |
P1—C1 | 1.796 (2) | C22—C23 | 1.514 (3) |
P1—C14 | 1.815 (2) | C22—H22A | 0.9900 |
P1—C11 | 1.815 (2) | C22—H22B | 0.9900 |
P1—S1 | 1.9384 (7) | C23—C24 | 1.521 (3) |
O21—C21 | 1.410 (3) | C23—H23A | 0.9900 |
O21—C22 | 1.436 (3) | C23—H23B | 0.9900 |
O22—C21 | 1.414 (3) | C24—C25 | 1.514 (3) |
O22—C24 | 1.437 (3) | C24—H24 | 1.0000 |
O26—C25 | 1.403 (3) | C25—H25A | 0.9900 |
O26—C26 | 1.413 (3) | C25—H25B | 0.9900 |
C1—C2 | 1.433 (3) | C26—H26A | 0.9800 |
C1—C5 | 1.440 (3) | C26—H26B | 0.9800 |
C2—C3 | 1.425 (3) | C26—H26C | 0.9800 |
C2—C21 | 1.503 (3) | C111—C112 | 1.401 (3) |
C3—C4 | 1.423 (3) | C111—H111 | 0.9500 |
C3—H3 | 0.9500 | C112—C113 | 1.384 (4) |
C4—C5 | 1.420 (3) | C112—H112 | 0.9500 |
C4—H4 | 0.9500 | C113—C114 | 1.389 (4) |
C5—H5 | 0.9500 | C113—H113 | 0.9500 |
C6—C10 | 1.410 (4) | C114—H114 | 0.9500 |
C6—C7 | 1.423 (4) | C411—C412 | 1.394 (4) |
C6—H6 | 0.9500 | C411—H411 | 0.9500 |
C7—C8 | 1.421 (4) | C412—C413 | 1.389 (5) |
C7—H7 | 0.9500 | C412—H412 | 0.9500 |
C8—C9 | 1.409 (4) | C413—C414 | 1.377 (4) |
C8—H8 | 0.9500 | C413—H413 | 0.9500 |
C9—C10 | 1.430 (4) | C414—H414 | 0.9500 |
C1—Fe1—C5 | 41.55 (8) | C8—C7—H7 | 126.0 |
C1—Fe1—C10 | 123.53 (10) | C6—C7—H7 | 126.0 |
C5—Fe1—C10 | 162.01 (10) | Fe1—C7—H7 | 125.8 |
C1—Fe1—C2 | 41.28 (8) | C9—C8—C7 | 108.0 (2) |
C5—Fe1—C2 | 69.20 (8) | C9—C8—Fe1 | 69.80 (14) |
C10—Fe1—C2 | 105.94 (10) | C7—C8—Fe1 | 69.39 (14) |
C1—Fe1—C7 | 123.04 (10) | C9—C8—H8 | 126.0 |
C5—Fe1—C7 | 109.38 (10) | C7—C8—H8 | 126.0 |
C10—Fe1—C7 | 68.33 (11) | Fe1—C8—H8 | 126.4 |
C2—Fe1—C7 | 158.15 (10) | C8—C9—C10 | 108.0 (2) |
C1—Fe1—C6 | 108.24 (10) | C8—C9—Fe1 | 70.05 (14) |
C5—Fe1—C6 | 126.26 (10) | C10—C9—Fe1 | 68.95 (14) |
C10—Fe1—C6 | 40.42 (11) | C8—C9—H9 | 126.0 |
C2—Fe1—C6 | 121.43 (9) | C10—C9—H9 | 126.0 |
C7—Fe1—C6 | 40.69 (10) | Fe1—C9—H9 | 126.6 |
C1—Fe1—C4 | 69.27 (9) | C6—C10—C9 | 107.9 (2) |
C5—Fe1—C4 | 40.69 (9) | C6—C10—Fe1 | 70.25 (13) |
C10—Fe1—C4 | 155.30 (11) | C9—C10—Fe1 | 70.08 (13) |
C2—Fe1—C4 | 68.71 (8) | C6—C10—H10 | 126.0 |
C7—Fe1—C4 | 125.34 (9) | C9—C10—H10 | 126.0 |
C6—Fe1—C4 | 162.74 (9) | Fe1—C10—H10 | 125.2 |
C1—Fe1—C9 | 159.97 (10) | C111—C11—C12 | 122.0 (2) |
C5—Fe1—C9 | 156.28 (10) | C111—C11—P1 | 127.81 (17) |
C10—Fe1—C9 | 40.97 (11) | C12—C11—P1 | 110.13 (16) |
C2—Fe1—C9 | 122.38 (10) | C114—C12—C11 | 118.7 (2) |
C7—Fe1—C9 | 67.99 (11) | C114—C12—C13 | 127.5 (2) |
C6—Fe1—C9 | 68.19 (12) | C11—C12—C13 | 113.77 (19) |
C4—Fe1—C9 | 120.13 (10) | C414—C13—C14 | 118.8 (2) |
C1—Fe1—C3 | 69.19 (9) | C414—C13—C12 | 127.8 (2) |
C5—Fe1—C3 | 68.66 (9) | C14—C13—C12 | 113.44 (19) |
C10—Fe1—C3 | 119.69 (10) | C411—C14—C13 | 121.5 (2) |
C2—Fe1—C3 | 40.80 (9) | C411—C14—P1 | 128.12 (19) |
C7—Fe1—C3 | 160.58 (9) | C13—C14—P1 | 110.32 (17) |
C6—Fe1—C3 | 155.91 (9) | O21—C21—O22 | 111.66 (15) |
C4—Fe1—C3 | 40.61 (8) | O21—C21—C2 | 107.65 (17) |
C9—Fe1—C3 | 105.61 (11) | O22—C21—C2 | 108.30 (16) |
C1—Fe1—C8 | 158.68 (10) | O21—C21—H21 | 109.7 |
C5—Fe1—C8 | 122.35 (10) | O22—C21—H21 | 109.7 |
C10—Fe1—C8 | 68.36 (12) | C2—C21—H21 | 109.7 |
C2—Fe1—C8 | 158.89 (10) | O21—C22—C23 | 110.73 (19) |
C7—Fe1—C8 | 40.57 (11) | O21—C22—H22A | 109.5 |
C6—Fe1—C8 | 68.25 (11) | C23—C22—H22A | 109.5 |
C4—Fe1—C8 | 107.50 (10) | O21—C22—H22B | 109.5 |
C9—Fe1—C8 | 40.15 (12) | C23—C22—H22B | 109.5 |
C3—Fe1—C8 | 122.91 (10) | H22A—C22—H22B | 108.1 |
C1—P1—C14 | 103.27 (10) | C22—C23—C24 | 109.85 (18) |
C1—P1—C11 | 103.30 (9) | C22—C23—H23A | 109.7 |
C14—P1—C11 | 91.70 (10) | C24—C23—H23A | 109.7 |
C1—P1—S1 | 117.10 (7) | C22—C23—H23B | 109.7 |
C14—P1—S1 | 118.40 (8) | C24—C23—H23B | 109.7 |
C11—P1—S1 | 119.05 (7) | H23A—C23—H23B | 108.2 |
C21—O21—C22 | 110.34 (16) | O22—C24—C25 | 108.65 (18) |
C21—O22—C24 | 109.91 (16) | O22—C24—C23 | 108.21 (18) |
C25—O26—C26 | 112.30 (19) | C25—C24—C23 | 113.66 (18) |
C2—C1—C5 | 107.14 (18) | O22—C24—H24 | 108.7 |
C2—C1—P1 | 128.27 (15) | C25—C24—H24 | 108.7 |
C5—C1—P1 | 124.28 (16) | C23—C24—H24 | 108.7 |
C2—C1—Fe1 | 69.80 (12) | O26—C25—C24 | 109.88 (17) |
C5—C1—Fe1 | 69.41 (12) | O26—C25—H25A | 109.7 |
P1—C1—Fe1 | 130.85 (10) | C24—C25—H25A | 109.7 |
C3—C2—C1 | 108.17 (17) | O26—C25—H25B | 109.7 |
C3—C2—C21 | 125.81 (19) | C24—C25—H25B | 109.7 |
C1—C2—C21 | 126.02 (19) | H25A—C25—H25B | 108.2 |
C3—C2—Fe1 | 70.01 (12) | O26—C26—H26A | 109.5 |
C1—C2—Fe1 | 68.92 (11) | O26—C26—H26B | 109.5 |
C21—C2—Fe1 | 126.31 (14) | H26A—C26—H26B | 109.5 |
C4—C3—C2 | 108.23 (19) | O26—C26—H26C | 109.5 |
C4—C3—Fe1 | 69.69 (11) | H26A—C26—H26C | 109.5 |
C2—C3—Fe1 | 69.19 (11) | H26B—C26—H26C | 109.5 |
C4—C3—H3 | 125.9 | C11—C111—C112 | 118.6 (2) |
C2—C3—H3 | 125.9 | C11—C111—H111 | 120.7 |
Fe1—C3—H3 | 126.8 | C112—C111—H111 | 120.7 |
C5—C4—C3 | 108.20 (19) | C113—C112—C111 | 119.9 (3) |
C5—C4—Fe1 | 68.99 (11) | C113—C112—H112 | 120.1 |
C3—C4—Fe1 | 69.70 (10) | C111—C112—H112 | 120.1 |
C5—C4—H4 | 125.9 | C112—C113—C114 | 121.5 (2) |
C3—C4—H4 | 125.9 | C112—C113—H113 | 119.2 |
Fe1—C4—H4 | 127.0 | C114—C113—H113 | 119.2 |
C4—C5—C1 | 108.27 (18) | C113—C114—C12 | 119.2 (2) |
C4—C5—Fe1 | 70.32 (12) | C113—C114—H114 | 120.4 |
C1—C5—Fe1 | 69.04 (11) | C12—C114—H114 | 120.4 |
C4—C5—H5 | 125.9 | C14—C411—C412 | 118.8 (3) |
C1—C5—H5 | 125.9 | C14—C411—H411 | 120.6 |
Fe1—C5—H5 | 126.3 | C412—C411—H411 | 120.6 |
C10—C6—C7 | 108.0 (3) | C413—C412—C411 | 119.9 (3) |
C10—C6—Fe1 | 69.33 (13) | C413—C412—H412 | 120.0 |
C7—C6—Fe1 | 69.57 (12) | C411—C412—H412 | 120.0 |
C10—C6—H6 | 126.0 | C414—C413—C412 | 121.3 (2) |
C7—C6—H6 | 126.0 | C414—C413—H413 | 119.3 |
Fe1—C6—H6 | 126.7 | C412—C413—H413 | 119.3 |
C8—C7—C6 | 108.0 (2) | C413—C414—C13 | 119.5 (3) |
C8—C7—Fe1 | 70.04 (14) | C413—C414—H414 | 120.3 |
C6—C7—Fe1 | 69.74 (13) | C13—C414—H414 | 120.3 |
C3—C2—C21—O22 | 115.8 (2) | C3—C2—C21—O21 | −5.0 (3) |
[Fe(C5H5)(C18H14OPS)] | F(000) = 444 |
Mr = 430.26 | Dx = 1.539 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 8000 reflections |
a = 7.1110 (13) Å | θ = 2.6–26.1° |
b = 12.862 (3) Å | µ = 1.02 mm−1 |
c = 10.223 (2) Å | T = 180 K |
β = 96.73 (2)° | Needle, yellow |
V = 928.6 (3) Å3 | 0.48 × 0.13 × 0.12 mm |
Z = 2 |
Stoe IPDS diffractometer | 3619 independent reflections |
Radiation source: fine-focus sealed tube | 3380 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ϕ scans | θmax = 26.1°, θmin = 2.6° |
Absorption correction: multi-scan (Blessing, 1995) | h = −8→8 |
Tmin = 0.598, Tmax = 0.873 | k = −15→15 |
9253 measured reflections | l = −12→12 |
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0359P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.001 |
3619 reflections | Δρmax = 0.36 e Å−3 |
245 parameters | Δρmin = −0.25 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1722 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.015 (12) |
[Fe(C5H5)(C18H14OPS)] | V = 928.6 (3) Å3 |
Mr = 430.26 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.1110 (13) Å | µ = 1.02 mm−1 |
b = 12.862 (3) Å | T = 180 K |
c = 10.223 (2) Å | 0.48 × 0.13 × 0.12 mm |
β = 96.73 (2)° |
Stoe IPDS diffractometer | 3619 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3380 reflections with I > 2σ(I) |
Tmin = 0.598, Tmax = 0.873 | Rint = 0.050 |
9253 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.061 | Δρmax = 0.36 e Å−3 |
S = 0.98 | Δρmin = −0.25 e Å−3 |
3619 reflections | Absolute structure: Flack (1983), with 1722 Friedel pairs |
245 parameters | Absolute structure parameter: −0.015 (12) |
1 restraint |
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 70 mm. 167 frames (3 min per frame) were obtained with 0 < ϕ < 250.5° and with the crystals rotated through 1.5° in ϕ. Coverage of the unique set was over 98.5% complete to at least 26.08°. Crystal decay was monitored by measuring 200 reflections per frame. |
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 | 0.95509 (4) | 0.27803 (2) | 1.10011 (3) | 0.01710 (9) | |
P1 | 0.98411 (8) | 0.25396 (4) | 0.76524 (6) | 0.01874 (13) | |
S1 | 1.10129 (9) | 0.11644 (5) | 0.76488 (7) | 0.02777 (15) | |
O21 | 0.5810 (3) | 0.08178 (15) | 0.8284 (2) | 0.0341 (4) | |
H21 | 0.4845 | 0.1161 | 0.8318 | 0.051* | |
C1 | 0.8638 (3) | 0.2824 (2) | 0.9048 (2) | 0.0186 (4) | |
C2 | 0.7467 (3) | 0.2122 (2) | 0.9715 (2) | 0.0210 (5) | |
C3 | 0.6672 (3) | 0.2727 (2) | 1.0687 (2) | 0.0256 (5) | |
H3 | 0.5869 | 0.2475 | 1.1269 | 0.031* | |
C4 | 0.7295 (3) | 0.3765 (2) | 1.0628 (3) | 0.0248 (5) | |
H4 | 0.6973 | 0.4309 | 1.1159 | 0.030* | |
C5 | 0.8502 (3) | 0.38368 (19) | 0.9617 (2) | 0.0207 (5) | |
H5 | 0.9099 | 0.4436 | 0.9368 | 0.025* | |
C6 | 1.2154 (4) | 0.2088 (2) | 1.1316 (3) | 0.0255 (5) | |
H6 | 1.2771 | 0.1743 | 1.0689 | 0.031* | |
C7 | 1.2297 (4) | 0.3160 (2) | 1.1619 (3) | 0.0244 (6) | |
H7 | 1.3025 | 0.3644 | 1.1228 | 0.029* | |
C8 | 1.1129 (3) | 0.3367 (2) | 1.2630 (3) | 0.0254 (5) | |
H8 | 1.0957 | 0.4010 | 1.3015 | 0.030* | |
C9 | 1.0276 (4) | 0.2419 (2) | 1.2943 (2) | 0.0260 (5) | |
H9 | 0.9445 | 0.2331 | 1.3572 | 0.031* | |
C10 | 1.0901 (4) | 0.1629 (2) | 1.2138 (3) | 0.0260 (5) | |
H10 | 1.0556 | 0.0932 | 1.2144 | 0.031* | |
C11 | 0.8150 (3) | 0.2916 (2) | 0.6268 (2) | 0.0207 (5) | |
C12 | 0.8729 (3) | 0.38479 (18) | 0.5721 (2) | 0.0206 (5) | |
C13 | 1.0609 (3) | 0.42100 (19) | 0.6312 (2) | 0.0205 (5) | |
C14 | 1.1390 (3) | 0.36087 (18) | 0.7384 (2) | 0.0201 (5) | |
C21 | 0.7096 (4) | 0.0997 (2) | 0.9451 (3) | 0.0295 (6) | |
H21A | 0.8286 | 0.0650 | 0.9361 | 0.035* | |
H21B | 0.6576 | 0.0692 | 1.0199 | 0.035* | |
C111 | 0.6443 (3) | 0.24475 (19) | 0.5808 (2) | 0.0251 (5) | |
H111 | 0.6080 | 0.1827 | 0.6172 | 0.030* | |
C112 | 0.5291 (3) | 0.2923 (2) | 0.4797 (3) | 0.0299 (6) | |
H112 | 0.4146 | 0.2616 | 0.4472 | 0.036* | |
C113 | 0.5833 (4) | 0.3854 (2) | 0.4262 (3) | 0.0298 (6) | |
H113 | 0.5043 | 0.4170 | 0.3588 | 0.036* | |
C114 | 0.7537 (4) | 0.4316 (2) | 0.4726 (3) | 0.0272 (5) | |
H114 | 0.7882 | 0.4942 | 0.4368 | 0.033* | |
C411 | 1.3197 (3) | 0.3800 (2) | 0.8003 (3) | 0.0229 (5) | |
H411 | 1.3714 | 0.3385 | 0.8698 | 0.027* | |
C412 | 1.4224 (4) | 0.4626 (2) | 0.7562 (3) | 0.0273 (6) | |
H412 | 1.5433 | 0.4771 | 0.7970 | 0.033* | |
C413 | 1.3446 (4) | 0.5227 (2) | 0.6521 (3) | 0.0290 (6) | |
H413 | 1.4141 | 0.5779 | 0.6241 | 0.035* | |
C414 | 1.1655 (4) | 0.5031 (2) | 0.5879 (3) | 0.0252 (5) | |
H414 | 1.1160 | 0.5440 | 0.5171 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01541 (14) | 0.02014 (16) | 0.01570 (15) | 0.00009 (13) | 0.00159 (11) | −0.00024 (14) |
P1 | 0.0213 (3) | 0.0188 (3) | 0.0156 (3) | 0.0015 (2) | 0.0001 (2) | −0.0002 (2) |
S1 | 0.0319 (3) | 0.0214 (3) | 0.0294 (3) | 0.0068 (3) | 0.0010 (3) | −0.0043 (3) |
O21 | 0.0310 (10) | 0.0322 (10) | 0.0377 (11) | −0.0085 (8) | −0.0024 (8) | −0.0063 (9) |
C1 | 0.0179 (9) | 0.0208 (10) | 0.0161 (10) | 0.0013 (10) | −0.0017 (8) | −0.0004 (11) |
C2 | 0.0172 (11) | 0.0238 (13) | 0.0214 (12) | −0.0024 (10) | −0.0004 (9) | 0.0007 (10) |
C3 | 0.0160 (9) | 0.0378 (13) | 0.0232 (11) | −0.0026 (12) | 0.0024 (8) | −0.0015 (13) |
C4 | 0.0207 (11) | 0.0283 (13) | 0.0248 (13) | 0.0062 (10) | 0.0002 (10) | −0.0076 (11) |
C5 | 0.0217 (11) | 0.0185 (11) | 0.0207 (12) | 0.0016 (9) | −0.0024 (10) | 0.0011 (10) |
C6 | 0.0185 (12) | 0.0352 (15) | 0.0228 (13) | 0.0051 (11) | 0.0018 (10) | 0.0009 (12) |
C7 | 0.0169 (11) | 0.0308 (13) | 0.0245 (14) | −0.0010 (9) | −0.0011 (10) | 0.0015 (11) |
C8 | 0.0238 (13) | 0.0282 (13) | 0.0223 (13) | 0.0027 (10) | −0.0052 (10) | −0.0046 (11) |
C9 | 0.0268 (12) | 0.0343 (14) | 0.0168 (11) | 0.0018 (10) | 0.0026 (9) | 0.0004 (10) |
C10 | 0.0292 (13) | 0.0231 (13) | 0.0246 (13) | 0.0015 (10) | −0.0019 (11) | 0.0035 (11) |
C11 | 0.0249 (10) | 0.0207 (12) | 0.0164 (10) | 0.0050 (10) | 0.0019 (8) | −0.0015 (10) |
C12 | 0.0240 (11) | 0.0235 (11) | 0.0152 (11) | 0.0031 (9) | 0.0059 (9) | −0.0009 (10) |
C13 | 0.0235 (11) | 0.0212 (11) | 0.0177 (12) | 0.0044 (10) | 0.0063 (9) | −0.0018 (10) |
C14 | 0.0245 (12) | 0.0196 (12) | 0.0166 (12) | 0.0023 (9) | 0.0034 (9) | −0.0021 (9) |
C21 | 0.0312 (13) | 0.0268 (14) | 0.0292 (14) | −0.0068 (11) | −0.0010 (11) | 0.0038 (11) |
C111 | 0.0300 (12) | 0.0246 (12) | 0.0205 (12) | −0.0021 (9) | 0.0013 (10) | −0.0036 (10) |
C112 | 0.0260 (11) | 0.0359 (15) | 0.0260 (12) | 0.0012 (11) | −0.0043 (10) | −0.0057 (12) |
C113 | 0.0270 (13) | 0.0381 (14) | 0.0225 (13) | 0.0059 (11) | −0.0048 (10) | 0.0016 (12) |
C114 | 0.0322 (13) | 0.0285 (13) | 0.0211 (13) | 0.0047 (11) | 0.0039 (10) | 0.0039 (11) |
C411 | 0.0212 (11) | 0.0268 (12) | 0.0199 (12) | 0.0021 (9) | −0.0009 (10) | 0.0005 (10) |
C412 | 0.0235 (12) | 0.0289 (12) | 0.0299 (15) | −0.0014 (10) | 0.0046 (11) | −0.0032 (12) |
C413 | 0.0313 (14) | 0.0252 (13) | 0.0324 (15) | −0.0032 (10) | 0.0127 (11) | 0.0003 (12) |
C414 | 0.0282 (13) | 0.0247 (12) | 0.0234 (14) | 0.0021 (10) | 0.0056 (10) | 0.0031 (10) |
Fe1—C1 | 2.027 (2) | C7—H7 | 0.9300 |
Fe1—C3 | 2.036 (2) | C8—C9 | 1.415 (4) |
Fe1—C5 | 2.039 (2) | C8—H8 | 0.9300 |
Fe1—C7 | 2.040 (3) | C9—C10 | 1.412 (4) |
Fe1—C8 | 2.040 (3) | C9—H9 | 0.9300 |
Fe1—C4 | 2.044 (3) | C10—H10 | 0.9300 |
Fe1—C9 | 2.045 (3) | C11—C111 | 1.387 (3) |
Fe1—C6 | 2.045 (3) | C11—C12 | 1.405 (3) |
Fe1—C2 | 2.046 (2) | C12—C114 | 1.383 (4) |
Fe1—C10 | 2.050 (3) | C12—C13 | 1.476 (4) |
P1—C1 | 1.785 (2) | C13—C414 | 1.393 (4) |
P1—C14 | 1.803 (2) | C13—C14 | 1.402 (3) |
P1—C11 | 1.812 (2) | C14—C411 | 1.386 (4) |
P1—S1 | 1.9555 (9) | C21—H21A | 0.9700 |
O21—C21 | 1.434 (3) | C21—H21B | 0.9700 |
O21—H21 | 0.8200 | C111—C112 | 1.384 (4) |
C1—C5 | 1.435 (4) | C111—H111 | 0.9300 |
C1—C2 | 1.452 (3) | C112—C113 | 1.390 (4) |
C2—C3 | 1.430 (3) | C112—H112 | 0.9300 |
C2—C21 | 1.490 (4) | C113—C114 | 1.382 (4) |
C3—C4 | 1.410 (4) | C113—H113 | 0.9300 |
C3—H3 | 0.9300 | C114—H114 | 0.9300 |
C4—C5 | 1.421 (4) | C411—C412 | 1.394 (4) |
C4—H4 | 0.9300 | C411—H411 | 0.9300 |
C5—H5 | 0.9300 | C412—C413 | 1.378 (4) |
C6—C7 | 1.414 (4) | C412—H412 | 0.9300 |
C6—C10 | 1.422 (4) | C413—C414 | 1.386 (4) |
C6—H6 | 0.9300 | C413—H413 | 0.9300 |
C7—C8 | 1.425 (4) | C414—H414 | 0.9300 |
C1—Fe1—C3 | 69.24 (9) | C4—C5—Fe1 | 69.84 (14) |
C1—Fe1—C5 | 41.33 (10) | C1—C5—Fe1 | 68.87 (13) |
C3—Fe1—C5 | 68.49 (11) | C4—C5—H5 | 125.9 |
C1—Fe1—C7 | 118.89 (10) | C1—C5—H5 | 125.9 |
C3—Fe1—C7 | 164.85 (11) | Fe1—C5—H5 | 126.9 |
C5—Fe1—C7 | 108.35 (11) | C7—C6—C10 | 108.0 (2) |
C1—Fe1—C8 | 151.15 (11) | C7—C6—Fe1 | 69.53 (16) |
C3—Fe1—C8 | 125.99 (10) | C10—C6—Fe1 | 69.87 (15) |
C5—Fe1—C8 | 116.19 (10) | C7—C6—H6 | 126.0 |
C7—Fe1—C8 | 40.88 (11) | C10—C6—H6 | 126.0 |
C1—Fe1—C4 | 69.23 (10) | Fe1—C6—H6 | 126.2 |
C3—Fe1—C4 | 40.44 (11) | C6—C7—C8 | 108.0 (2) |
C5—Fe1—C4 | 40.73 (10) | C6—C7—Fe1 | 69.96 (16) |
C7—Fe1—C4 | 127.67 (11) | C8—C7—Fe1 | 69.58 (14) |
C8—Fe1—C4 | 105.51 (11) | C6—C7—H7 | 126.0 |
C1—Fe1—C9 | 167.90 (11) | C8—C7—H7 | 126.0 |
C3—Fe1—C9 | 106.26 (10) | Fe1—C7—H7 | 126.0 |
C5—Fe1—C9 | 148.77 (10) | C9—C8—C7 | 107.7 (2) |
C7—Fe1—C9 | 68.30 (11) | C9—C8—Fe1 | 69.92 (15) |
C8—Fe1—C9 | 40.52 (11) | C7—C8—Fe1 | 69.54 (15) |
C4—Fe1—C9 | 115.15 (11) | C9—C8—H8 | 126.1 |
C1—Fe1—C6 | 110.27 (10) | C7—C8—H8 | 126.1 |
C3—Fe1—C6 | 152.25 (11) | Fe1—C8—H8 | 126.0 |
C5—Fe1—C6 | 130.56 (11) | C10—C9—C8 | 108.4 (2) |
C7—Fe1—C6 | 40.51 (11) | C10—C9—Fe1 | 70.03 (15) |
C8—Fe1—C6 | 68.39 (11) | C8—C9—Fe1 | 69.56 (15) |
C4—Fe1—C6 | 167.15 (11) | C10—C9—H9 | 125.8 |
C9—Fe1—C6 | 68.15 (11) | C8—C9—H9 | 125.8 |
C1—Fe1—C2 | 41.76 (10) | Fe1—C9—H9 | 126.2 |
C3—Fe1—C2 | 41.01 (10) | C9—C10—C6 | 107.9 (2) |
C5—Fe1—C2 | 69.59 (10) | C9—C10—Fe1 | 69.63 (15) |
C7—Fe1—C2 | 153.28 (10) | C6—C10—Fe1 | 69.49 (15) |
C8—Fe1—C2 | 164.83 (10) | C9—C10—H10 | 126.0 |
C4—Fe1—C2 | 69.09 (10) | C6—C10—H10 | 126.0 |
C9—Fe1—C2 | 127.66 (10) | Fe1—C10—H10 | 126.4 |
C6—Fe1—C2 | 119.66 (11) | C111—C11—C12 | 121.4 (2) |
C1—Fe1—C10 | 130.76 (11) | C111—C11—P1 | 128.54 (19) |
C3—Fe1—C10 | 117.44 (11) | C12—C11—P1 | 109.88 (18) |
C5—Fe1—C10 | 169.60 (10) | C114—C12—C11 | 118.7 (2) |
C7—Fe1—C10 | 68.25 (11) | C114—C12—C13 | 127.7 (2) |
C8—Fe1—C10 | 68.18 (11) | C11—C12—C13 | 113.6 (2) |
C4—Fe1—C10 | 149.14 (11) | C414—C13—C14 | 119.3 (2) |
C9—Fe1—C10 | 40.34 (10) | C414—C13—C12 | 126.9 (2) |
C6—Fe1—C10 | 40.63 (11) | C14—C13—C12 | 113.8 (2) |
C2—Fe1—C10 | 108.73 (11) | C411—C14—C13 | 121.3 (2) |
C1—P1—C14 | 108.90 (12) | C411—C14—P1 | 128.0 (2) |
C1—P1—C11 | 103.48 (10) | C13—C14—P1 | 110.28 (18) |
C14—P1—C11 | 92.23 (11) | O21—C21—C2 | 112.9 (2) |
C1—P1—S1 | 115.52 (9) | O21—C21—H21A | 109.0 |
C14—P1—S1 | 114.94 (8) | C2—C21—H21A | 109.0 |
C11—P1—S1 | 118.96 (9) | O21—C21—H21B | 109.0 |
C21—O21—H21 | 109.5 | C2—C21—H21B | 109.0 |
C5—C1—C2 | 107.7 (2) | H21A—C21—H21B | 107.8 |
C5—C1—P1 | 124.86 (19) | C112—C111—C11 | 118.6 (2) |
C2—C1—P1 | 127.1 (2) | C112—C111—H111 | 120.7 |
C5—C1—Fe1 | 69.80 (13) | C11—C111—H111 | 120.7 |
C2—C1—Fe1 | 69.84 (13) | C111—C112—C113 | 120.5 (2) |
P1—C1—Fe1 | 130.82 (11) | C111—C112—H112 | 119.8 |
C3—C2—C1 | 106.4 (2) | C113—C112—H112 | 119.8 |
C3—C2—C21 | 125.4 (2) | C114—C113—C112 | 120.5 (2) |
C1—C2—C21 | 128.2 (2) | C114—C113—H113 | 119.7 |
C3—C2—Fe1 | 69.10 (13) | C112—C113—H113 | 119.7 |
C1—C2—Fe1 | 68.41 (12) | C113—C114—C12 | 120.2 (2) |
C21—C2—Fe1 | 128.15 (18) | C113—C114—H114 | 119.9 |
C4—C3—C2 | 109.5 (2) | C12—C114—H114 | 119.9 |
C4—C3—Fe1 | 70.12 (14) | C14—C411—C412 | 118.7 (2) |
C2—C3—Fe1 | 69.88 (13) | C14—C411—H411 | 120.6 |
C4—C3—H3 | 125.2 | C412—C411—H411 | 120.6 |
C2—C3—H3 | 125.2 | C413—C412—C411 | 120.0 (2) |
Fe1—C3—H3 | 126.3 | C413—C412—H412 | 120.0 |
C3—C4—C5 | 108.2 (2) | C411—C412—H412 | 120.0 |
C3—C4—Fe1 | 69.44 (14) | C412—C413—C414 | 121.8 (2) |
C5—C4—Fe1 | 69.42 (14) | C412—C413—H413 | 119.1 |
C3—C4—H4 | 125.9 | C414—C413—H413 | 119.1 |
C5—C4—H4 | 125.9 | C413—C414—C13 | 118.9 (2) |
Fe1—C4—H4 | 126.8 | C413—C414—H414 | 120.6 |
C4—C5—C1 | 108.2 (2) | C13—C414—H414 | 120.6 |
C3—C2—C21—O21 | 103.5 (3) | C1—C2—C21—O21 | −75.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21···S1i | 0.82 | 2.73 | 3.426 (2) | 144 |
C114—H114···S1ii | 0.93 | 2.78 | 3.633 (3) | 153 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y+1/2, −z+1. |
[Fe(C5H5)(C30H23P2)] | F(000) = 1176 |
Mr = 566.36 | Dx = 1.369 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8000 reflections |
a = 10.9693 (10) Å | θ = 2.1–26.1° |
b = 11.0436 (10) Å | µ = 0.69 mm−1 |
c = 22.678 (2) Å | T = 180 K |
V = 2747.2 (4) Å3 | Prism, yellow |
Z = 4 | 0.2 × 0.12 × 0.1 mm |
Stoe IPDS diffractometer | 5395 independent reflections |
Radiation source: fine-focus sealed tube | 3205 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.145 |
ϕ scans | θmax = 26.1°, θmin = 2.1° |
Absorption correction: multi-scan (Blessing, 1995) | h = −13→13 |
Tmin = 0.852, Tmax = 0.894 | k = −13→13 |
22007 measured reflections | l = −27→27 |
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)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0476P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max = 0.004 |
5395 reflections | Δρmax = 0.97 e Å−3 |
343 parameters | Δρmin = −0.47 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 2333 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (3) |
[Fe(C5H5)(C30H23P2)] | V = 2747.2 (4) Å3 |
Mr = 566.36 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.9693 (10) Å | µ = 0.69 mm−1 |
b = 11.0436 (10) Å | T = 180 K |
c = 22.678 (2) Å | 0.2 × 0.12 × 0.1 mm |
Stoe IPDS diffractometer | 5395 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3205 reflections with I > 2σ(I) |
Tmin = 0.852, Tmax = 0.894 | Rint = 0.145 |
22007 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.126 | Δρmax = 0.97 e Å−3 |
S = 0.93 | Δρmin = −0.47 e Å−3 |
5395 reflections | Absolute structure: Flack (1983), with 2333 Friedel pairs |
343 parameters | Absolute structure parameter: 0.01 (3) |
0 restraints |
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 70 mm. 179 frames (5 min per frame) were obtained with 0 < ϕ < 250.6° and with the crystals oscillated through 1.4° in ϕ. Coverage of the unique set was over 99.4% complete to at least 26.06°. Crystal decay was monitored by measuring 200 reflections per frame. |
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 | 0.78911 (8) | 0.88531 (7) | 0.46301 (4) | 0.0263 (2) | |
P1 | 0.62209 (16) | 0.82877 (15) | 0.33563 (8) | 0.0348 (4) | |
P2 | 0.76292 (14) | 0.49338 (13) | 0.37331 (7) | 0.0314 (4) | |
C1 | 0.6596 (5) | 0.8045 (5) | 0.4121 (3) | 0.0278 (14) | |
C2 | 0.7485 (5) | 0.7162 (5) | 0.4324 (3) | 0.0267 (13) | |
C3 | 0.7465 (6) | 0.7179 (5) | 0.4958 (3) | 0.0319 (15) | |
H3 | 0.7938 | 0.6699 | 0.5205 | 0.038* | |
C4 | 0.6601 (6) | 0.8056 (5) | 0.5139 (3) | 0.0348 (16) | |
H4 | 0.6420 | 0.8256 | 0.5528 | 0.042* | |
C5 | 0.6055 (5) | 0.8581 (5) | 0.4633 (3) | 0.0323 (14) | |
H5 | 0.5450 | 0.9171 | 0.4634 | 0.039* | |
C6 | 0.9671 (6) | 0.9196 (5) | 0.4426 (3) | 0.0354 (16) | |
H6 | 1.0204 | 0.8664 | 0.4240 | 0.042* | |
C7 | 0.9487 (6) | 0.9291 (5) | 0.5036 (3) | 0.0368 (16) | |
H7 | 0.9880 | 0.8835 | 0.5324 | 0.044* | |
C8 | 0.8605 (6) | 1.0197 (6) | 0.5139 (3) | 0.0387 (16) | |
H8 | 0.8315 | 1.0442 | 0.5506 | 0.046* | |
C9 | 0.8234 (5) | 1.0671 (5) | 0.4582 (3) | 0.0349 (15) | |
H9 | 0.7659 | 1.1276 | 0.4519 | 0.042* | |
C10 | 0.8908 (5) | 1.0048 (5) | 0.4140 (3) | 0.0300 (14) | |
H10 | 0.8856 | 1.0177 | 0.3736 | 0.036* | |
C11 | 0.5585 (6) | 0.9812 (6) | 0.3312 (3) | 0.0360 (15) | |
C12 | 0.4327 (6) | 0.9794 (6) | 0.3202 (3) | 0.0388 (16) | |
C13 | 0.3809 (6) | 0.8549 (6) | 0.3212 (3) | 0.0359 (15) | |
C14 | 0.4690 (6) | 0.7654 (5) | 0.3307 (3) | 0.0346 (15) | |
C21 | 0.8310 (6) | 0.6416 (5) | 0.3945 (3) | 0.0331 (15) | |
H21A | 0.9066 | 0.6272 | 0.4155 | 0.040* | |
H21B | 0.8502 | 0.6868 | 0.3590 | 0.040* | |
C111 | 0.6198 (7) | 1.0916 (5) | 0.3314 (3) | 0.0404 (15) | |
H111 | 0.7035 | 1.0931 | 0.3380 | 0.048* | |
C112 | 0.5581 (8) | 1.1986 (6) | 0.3222 (3) | 0.0452 (19) | |
H112 | 0.5993 | 1.2721 | 0.3238 | 0.054* | |
C113 | 0.4332 (8) | 1.1957 (7) | 0.3103 (3) | 0.049 (2) | |
H113 | 0.3917 | 1.2677 | 0.3032 | 0.059* | |
C114 | 0.3699 (7) | 1.0861 (6) | 0.3091 (3) | 0.0469 (18) | |
H114 | 0.2868 | 1.0846 | 0.3010 | 0.056* | |
C211 | 0.7625 (5) | 0.4160 (4) | 0.4447 (3) | 0.0298 (14) | |
C212 | 0.6541 (5) | 0.3681 (5) | 0.4649 (3) | 0.0346 (14) | |
H212 | 0.5855 | 0.3707 | 0.4408 | 0.041* | |
C213 | 0.6454 (6) | 0.3158 (6) | 0.5208 (3) | 0.0417 (17) | |
H213 | 0.5715 | 0.2845 | 0.5339 | 0.050* | |
C214 | 0.7461 (7) | 0.3110 (6) | 0.5561 (3) | 0.0442 (18) | |
H214 | 0.7406 | 0.2774 | 0.5936 | 0.053* | |
C215 | 0.8568 (6) | 0.3561 (5) | 0.5361 (3) | 0.0404 (15) | |
H215 | 0.9256 | 0.3514 | 0.5599 | 0.049* | |
C216 | 0.8650 (6) | 0.4082 (5) | 0.4804 (3) | 0.0347 (15) | |
H216 | 0.9394 | 0.4379 | 0.4671 | 0.042* | |
C221 | 0.8944 (6) | 0.4230 (5) | 0.3373 (3) | 0.0281 (13) | |
C222 | 0.9589 (6) | 0.4865 (6) | 0.2933 (3) | 0.0382 (16) | |
H222 | 0.9373 | 0.5656 | 0.2840 | 0.046* | |
C223 | 1.0547 (7) | 0.4309 (6) | 0.2639 (3) | 0.0424 (17) | |
H223 | 1.0979 | 0.4743 | 0.2357 | 0.051* | |
C224 | 1.0869 (6) | 0.3127 (6) | 0.2758 (3) | 0.0394 (16) | |
H224 | 1.1506 | 0.2765 | 0.2553 | 0.047* | |
C225 | 1.0245 (6) | 0.2485 (6) | 0.3181 (3) | 0.0417 (18) | |
H225 | 1.0462 | 0.1691 | 0.3268 | 0.050* | |
C226 | 0.9276 (6) | 0.3044 (5) | 0.3478 (3) | 0.0367 (16) | |
H226 | 0.8842 | 0.2600 | 0.3757 | 0.044* | |
C411 | 0.4343 (6) | 0.6449 (6) | 0.3326 (3) | 0.0419 (17) | |
H411 | 0.4927 | 0.5850 | 0.3383 | 0.050* | |
C412 | 0.3123 (7) | 0.6131 (7) | 0.3260 (3) | 0.0533 (19) | |
H412 | 0.2885 | 0.5324 | 0.3279 | 0.064* | |
C413 | 0.2263 (7) | 0.7043 (7) | 0.3164 (3) | 0.0531 (19) | |
H413 | 0.1449 | 0.6832 | 0.3115 | 0.064* | |
C414 | 0.2588 (6) | 0.8233 (7) | 0.3141 (3) | 0.0490 (18) | |
H414 | 0.2002 | 0.8827 | 0.3079 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0289 (4) | 0.0225 (4) | 0.0276 (4) | −0.0013 (4) | −0.0009 (4) | 0.0000 (4) |
P1 | 0.0337 (9) | 0.0381 (9) | 0.0327 (9) | −0.0017 (7) | −0.0058 (8) | 0.0026 (8) |
P2 | 0.0344 (10) | 0.0249 (7) | 0.0351 (8) | 0.0005 (6) | −0.0047 (8) | 0.0015 (6) |
C1 | 0.024 (3) | 0.024 (3) | 0.036 (4) | 0.005 (2) | 0.001 (3) | 0.001 (2) |
C2 | 0.024 (3) | 0.031 (3) | 0.025 (3) | −0.004 (2) | 0.004 (3) | 0.001 (2) |
C3 | 0.032 (4) | 0.029 (3) | 0.034 (4) | −0.005 (3) | 0.002 (3) | 0.008 (3) |
C4 | 0.040 (4) | 0.037 (4) | 0.028 (3) | −0.008 (3) | 0.003 (3) | −0.003 (3) |
C5 | 0.030 (3) | 0.034 (3) | 0.034 (3) | 0.003 (2) | −0.002 (3) | −0.003 (3) |
C6 | 0.039 (4) | 0.026 (3) | 0.042 (4) | 0.005 (3) | 0.003 (3) | −0.003 (3) |
C7 | 0.043 (4) | 0.035 (3) | 0.033 (4) | 0.000 (3) | −0.009 (3) | 0.004 (3) |
C8 | 0.041 (4) | 0.039 (4) | 0.036 (4) | −0.001 (3) | −0.001 (3) | −0.006 (3) |
C9 | 0.037 (4) | 0.025 (3) | 0.043 (4) | 0.001 (2) | −0.007 (3) | −0.001 (3) |
C10 | 0.035 (4) | 0.022 (3) | 0.033 (3) | 0.002 (3) | −0.003 (3) | 0.001 (2) |
C11 | 0.044 (4) | 0.046 (4) | 0.018 (3) | −0.001 (3) | −0.005 (3) | 0.004 (3) |
C12 | 0.040 (4) | 0.049 (4) | 0.028 (4) | 0.007 (3) | −0.009 (3) | 0.004 (3) |
C13 | 0.027 (3) | 0.051 (4) | 0.029 (4) | 0.000 (3) | −0.003 (3) | 0.001 (3) |
C14 | 0.040 (4) | 0.037 (3) | 0.027 (3) | 0.002 (3) | 0.000 (3) | −0.002 (3) |
C21 | 0.037 (4) | 0.024 (3) | 0.038 (4) | 0.003 (2) | 0.003 (3) | 0.001 (3) |
C111 | 0.042 (4) | 0.038 (4) | 0.041 (4) | 0.003 (3) | −0.005 (3) | 0.011 (3) |
C112 | 0.062 (5) | 0.042 (4) | 0.031 (4) | −0.001 (3) | 0.000 (4) | 0.012 (3) |
C113 | 0.068 (6) | 0.052 (5) | 0.028 (4) | 0.013 (4) | −0.004 (4) | 0.003 (3) |
C114 | 0.052 (4) | 0.058 (5) | 0.031 (4) | 0.016 (4) | −0.009 (4) | 0.004 (3) |
C211 | 0.030 (3) | 0.022 (3) | 0.038 (3) | 0.001 (2) | −0.005 (3) | −0.005 (2) |
C212 | 0.032 (3) | 0.032 (3) | 0.040 (3) | 0.002 (2) | 0.007 (3) | −0.004 (3) |
C213 | 0.040 (4) | 0.039 (4) | 0.046 (5) | 0.002 (3) | 0.015 (4) | −0.005 (3) |
C214 | 0.057 (5) | 0.042 (4) | 0.034 (4) | 0.003 (3) | 0.007 (3) | 0.003 (3) |
C215 | 0.044 (4) | 0.048 (4) | 0.030 (3) | 0.007 (3) | −0.005 (4) | 0.000 (3) |
C216 | 0.033 (3) | 0.032 (3) | 0.039 (4) | −0.003 (3) | −0.001 (3) | 0.003 (3) |
C221 | 0.042 (4) | 0.023 (3) | 0.020 (3) | −0.006 (2) | −0.007 (3) | 0.000 (2) |
C222 | 0.055 (4) | 0.029 (3) | 0.031 (4) | −0.003 (3) | 0.004 (3) | 0.005 (3) |
C223 | 0.053 (4) | 0.043 (4) | 0.032 (4) | −0.011 (3) | 0.012 (4) | 0.000 (3) |
C224 | 0.040 (4) | 0.045 (4) | 0.033 (4) | 0.004 (3) | 0.004 (3) | −0.008 (3) |
C225 | 0.047 (5) | 0.031 (3) | 0.047 (5) | 0.004 (3) | 0.000 (4) | −0.006 (3) |
C226 | 0.051 (4) | 0.020 (3) | 0.039 (4) | −0.007 (3) | 0.006 (3) | −0.002 (3) |
C411 | 0.038 (4) | 0.049 (4) | 0.039 (4) | −0.007 (3) | −0.011 (3) | 0.005 (3) |
C412 | 0.051 (5) | 0.067 (4) | 0.042 (4) | −0.023 (4) | −0.014 (4) | 0.004 (4) |
C413 | 0.041 (5) | 0.075 (5) | 0.043 (4) | −0.014 (4) | −0.006 (4) | 0.007 (4) |
C414 | 0.036 (4) | 0.066 (5) | 0.045 (4) | −0.002 (3) | −0.009 (3) | −0.001 (4) |
Fe1—C4 | 2.027 (6) | C13—C14 | 1.400 (9) |
Fe1—C1 | 2.036 (6) | C14—C411 | 1.384 (9) |
Fe1—C5 | 2.036 (6) | C21—H21A | 0.9700 |
Fe1—C7 | 2.037 (7) | C21—H21B | 0.9700 |
Fe1—C8 | 2.037 (6) | C111—C112 | 1.378 (9) |
Fe1—C2 | 2.042 (5) | C111—H111 | 0.9300 |
Fe1—C6 | 2.042 (7) | C112—C113 | 1.396 (10) |
Fe1—C9 | 2.046 (5) | C112—H112 | 0.9300 |
Fe1—C3 | 2.046 (5) | C113—C114 | 1.396 (10) |
Fe1—C10 | 2.054 (6) | C113—H113 | 0.9300 |
P1—C1 | 1.803 (6) | C114—H114 | 0.9300 |
P1—C14 | 1.823 (7) | C211—C212 | 1.380 (8) |
P1—C11 | 1.825 (7) | C211—C216 | 1.388 (8) |
P2—C221 | 1.830 (6) | C212—C213 | 1.398 (9) |
P2—C211 | 1.831 (6) | C212—H212 | 0.9300 |
P2—C21 | 1.862 (6) | C213—C214 | 1.365 (9) |
C1—C5 | 1.432 (9) | C213—H213 | 0.9300 |
C1—C2 | 1.454 (8) | C214—C215 | 1.389 (9) |
C2—C3 | 1.437 (8) | C214—H214 | 0.9300 |
C2—C21 | 1.496 (8) | C215—C216 | 1.389 (9) |
C3—C4 | 1.417 (8) | C215—H215 | 0.9300 |
C3—H3 | 0.9300 | C216—H216 | 0.9300 |
C4—C5 | 1.417 (9) | C221—C226 | 1.381 (8) |
C4—H4 | 0.9300 | C221—C222 | 1.409 (8) |
C5—H5 | 0.9300 | C222—C223 | 1.387 (9) |
C6—C7 | 1.403 (9) | C222—H222 | 0.9300 |
C6—C10 | 1.416 (8) | C223—C224 | 1.379 (9) |
C6—H6 | 0.9300 | C223—H223 | 0.9300 |
C7—C8 | 1.411 (9) | C224—C225 | 1.374 (9) |
C7—H7 | 0.9300 | C224—H224 | 0.9300 |
C8—C9 | 1.428 (9) | C225—C226 | 1.402 (9) |
C8—H8 | 0.9300 | C225—H225 | 0.9300 |
C9—C10 | 1.421 (9) | C226—H226 | 0.9300 |
C9—H9 | 0.9300 | C411—C412 | 1.391 (9) |
C10—H10 | 0.9300 | C411—H411 | 0.9300 |
C11—C111 | 1.392 (9) | C412—C413 | 1.396 (11) |
C11—C12 | 1.402 (9) | C412—H412 | 0.9300 |
C12—C114 | 1.388 (9) | C413—C414 | 1.363 (10) |
C12—C13 | 1.488 (9) | C413—H413 | 0.9300 |
C13—C414 | 1.393 (9) | C414—H414 | 0.9300 |
C4—Fe1—C1 | 69.2 (2) | C9—C8—Fe1 | 69.9 (3) |
C4—Fe1—C5 | 40.8 (3) | C7—C8—H8 | 126.0 |
C1—Fe1—C5 | 41.2 (2) | C9—C8—H8 | 126.0 |
C4—Fe1—C7 | 116.5 (3) | Fe1—C8—H8 | 126.0 |
C1—Fe1—C7 | 163.8 (2) | C10—C9—C8 | 107.3 (5) |
C5—Fe1—C7 | 152.1 (3) | C10—C9—Fe1 | 70.0 (3) |
C4—Fe1—C8 | 105.2 (3) | C8—C9—Fe1 | 69.2 (3) |
C1—Fe1—C8 | 155.3 (2) | C10—C9—H9 | 126.3 |
C5—Fe1—C8 | 119.1 (3) | C8—C9—H9 | 126.3 |
C7—Fe1—C8 | 40.5 (2) | Fe1—C9—H9 | 126.0 |
C4—Fe1—C2 | 69.1 (2) | C6—C10—C9 | 107.9 (5) |
C1—Fe1—C2 | 41.8 (2) | C6—C10—Fe1 | 69.3 (4) |
C5—Fe1—C2 | 69.5 (2) | C9—C10—Fe1 | 69.4 (3) |
C7—Fe1—C2 | 124.0 (2) | C6—C10—H10 | 126.1 |
C8—Fe1—C2 | 160.6 (2) | C9—C10—H10 | 126.1 |
C4—Fe1—C6 | 151.3 (3) | Fe1—C10—H10 | 126.8 |
C1—Fe1—C6 | 128.3 (2) | C111—C11—C12 | 119.2 (6) |
C5—Fe1—C6 | 166.9 (3) | C111—C11—P1 | 128.6 (5) |
C7—Fe1—C6 | 40.2 (3) | C12—C11—P1 | 111.9 (5) |
C8—Fe1—C6 | 68.0 (3) | C114—C12—C11 | 120.6 (7) |
C2—Fe1—C6 | 107.5 (2) | C114—C12—C13 | 126.7 (6) |
C4—Fe1—C9 | 125.8 (3) | C11—C12—C13 | 112.7 (6) |
C1—Fe1—C9 | 121.9 (2) | C414—C13—C14 | 120.3 (6) |
C5—Fe1—C9 | 109.1 (2) | C414—C13—C12 | 126.7 (6) |
C7—Fe1—C9 | 68.5 (2) | C14—C13—C12 | 113.0 (6) |
C8—Fe1—C9 | 40.9 (3) | C411—C14—C13 | 119.5 (6) |
C2—Fe1—C9 | 156.9 (3) | C411—C14—P1 | 128.4 (5) |
C6—Fe1—C9 | 68.3 (2) | C13—C14—P1 | 112.0 (5) |
C4—Fe1—C3 | 40.7 (2) | C2—C21—P2 | 112.9 (4) |
C1—Fe1—C3 | 69.6 (2) | C2—C21—H21A | 109.0 |
C5—Fe1—C3 | 68.9 (2) | P2—C21—H21A | 109.0 |
C7—Fe1—C3 | 104.3 (2) | C2—C21—H21B | 109.0 |
C8—Fe1—C3 | 122.7 (3) | P2—C21—H21B | 109.0 |
C2—Fe1—C3 | 41.2 (2) | H21A—C21—H21B | 107.8 |
C6—Fe1—C3 | 117.9 (2) | C112—C111—C11 | 120.9 (7) |
C9—Fe1—C3 | 161.5 (3) | C112—C111—H111 | 119.6 |
C4—Fe1—C10 | 165.0 (2) | C11—C111—H111 | 119.6 |
C1—Fe1—C10 | 110.7 (2) | C111—C112—C113 | 119.5 (7) |
C5—Fe1—C10 | 129.3 (2) | C111—C112—H112 | 120.3 |
C7—Fe1—C10 | 68.0 (3) | C113—C112—H112 | 120.3 |
C8—Fe1—C10 | 68.3 (2) | C112—C113—C114 | 120.8 (7) |
C2—Fe1—C10 | 121.5 (2) | C112—C113—H113 | 119.6 |
C6—Fe1—C10 | 40.5 (2) | C114—C113—H113 | 119.6 |
C9—Fe1—C10 | 40.6 (2) | C12—C114—C113 | 119.0 (7) |
C3—Fe1—C10 | 154.3 (2) | C12—C114—H114 | 120.5 |
C1—P1—C14 | 102.2 (3) | C113—C114—H114 | 120.5 |
C1—P1—C11 | 106.1 (3) | C212—C211—C216 | 118.7 (6) |
C14—P1—C11 | 89.9 (3) | C212—C211—P2 | 118.3 (5) |
C221—P2—C211 | 101.4 (3) | C216—C211—P2 | 122.9 (5) |
C221—P2—C21 | 99.9 (3) | C211—C212—C213 | 121.2 (6) |
C211—P2—C21 | 100.6 (3) | C211—C212—H212 | 119.4 |
C5—C1—C2 | 107.4 (5) | C213—C212—H212 | 119.4 |
C5—C1—P1 | 128.7 (4) | C214—C213—C212 | 119.5 (6) |
C2—C1—P1 | 123.8 (4) | C214—C213—H213 | 120.3 |
C5—C1—Fe1 | 69.4 (3) | C212—C213—H213 | 120.3 |
C2—C1—Fe1 | 69.3 (3) | C213—C214—C215 | 120.2 (6) |
P1—C1—Fe1 | 129.8 (3) | C213—C214—H214 | 119.9 |
C3—C2—C1 | 107.3 (5) | C215—C214—H214 | 119.9 |
C3—C2—C21 | 126.2 (5) | C214—C215—C216 | 120.1 (6) |
C1—C2—C21 | 126.4 (5) | C214—C215—H215 | 119.9 |
C3—C2—Fe1 | 69.6 (3) | C216—C215—H215 | 119.9 |
C1—C2—Fe1 | 68.9 (3) | C211—C216—C215 | 120.2 (6) |
C21—C2—Fe1 | 124.5 (4) | C211—C216—H216 | 119.9 |
C4—C3—C2 | 108.0 (6) | C215—C216—H216 | 119.9 |
C4—C3—Fe1 | 68.9 (3) | C226—C221—C222 | 117.5 (6) |
C2—C3—Fe1 | 69.2 (3) | C226—C221—P2 | 122.2 (5) |
C4—C3—H3 | 126.0 | C222—C221—P2 | 120.0 (4) |
C2—C3—H3 | 126.0 | C223—C222—C221 | 120.1 (6) |
Fe1—C3—H3 | 127.4 | C223—C222—H222 | 120.0 |
C3—C4—C5 | 109.1 (6) | C221—C222—H222 | 120.0 |
C3—C4—Fe1 | 70.4 (3) | C224—C223—C222 | 121.2 (6) |
C5—C4—Fe1 | 69.9 (4) | C224—C223—H223 | 119.4 |
C3—C4—H4 | 125.4 | C222—C223—H223 | 119.4 |
C5—C4—H4 | 125.4 | C225—C224—C223 | 119.8 (6) |
Fe1—C4—H4 | 125.8 | C225—C224—H224 | 120.1 |
C4—C5—C1 | 108.2 (5) | C223—C224—H224 | 120.1 |
C4—C5—Fe1 | 69.2 (3) | C224—C225—C226 | 119.1 (6) |
C1—C5—Fe1 | 69.4 (3) | C224—C225—H225 | 120.4 |
C4—C5—H5 | 125.9 | C226—C225—H225 | 120.4 |
C1—C5—H5 | 125.9 | C221—C226—C225 | 122.3 (6) |
Fe1—C5—H5 | 127.0 | C221—C226—H226 | 118.9 |
C7—C6—C10 | 108.5 (6) | C225—C226—H226 | 118.9 |
C7—C6—Fe1 | 69.7 (4) | C14—C411—C412 | 120.3 (7) |
C10—C6—Fe1 | 70.2 (4) | C14—C411—H411 | 119.9 |
C7—C6—H6 | 125.8 | C412—C411—H411 | 119.9 |
C10—C6—H6 | 125.8 | C411—C412—C413 | 119.0 (7) |
Fe1—C6—H6 | 125.9 | C411—C412—H412 | 120.5 |
C6—C7—C8 | 108.3 (6) | C413—C412—H412 | 120.5 |
C6—C7—Fe1 | 70.1 (4) | C414—C413—C412 | 121.6 (7) |
C8—C7—Fe1 | 69.7 (4) | C414—C413—H413 | 119.2 |
C6—C7—H7 | 125.8 | C412—C413—H413 | 119.2 |
C8—C7—H7 | 125.8 | C413—C414—C13 | 119.3 (7) |
Fe1—C7—H7 | 125.9 | C413—C414—H414 | 120.4 |
C7—C8—C9 | 108.0 (6) | C13—C414—H414 | 120.4 |
C7—C8—Fe1 | 69.7 (4) |
Experimental details
(III) | (V) | (VIII) | |
Crystal data | |||
Chemical formula | [Fe(C5H5)(C23H22O3PS)] | [Fe(C5H5)(C18H14OPS)] | [Fe(C5H5)(C30H23P2)] |
Mr | 530.38 | 430.26 | 566.36 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 180 | 180 | 180 |
a, b, c (Å) | 7.4885 (7), 9.5175 (8), 16.8193 (13) | 7.1110 (13), 12.862 (3), 10.223 (2) | 10.9693 (10), 11.0436 (10), 22.678 (2) |
α, β, γ (°) | 90, 91.067 (7), 90 | 90, 96.73 (2), 90 | 90, 90, 90 |
V (Å3) | 1198.53 (18) | 928.6 (3) | 2747.2 (4) |
Z | 2 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.81 | 1.02 | 0.69 |
Crystal size (mm) | 0.36 × 0.28 × 0.22 | 0.48 × 0.13 × 0.12 | 0.2 × 0.12 × 0.1 |
Data collection | |||
Diffractometer | Oxford XCALIBUR diffractometer | Stoe IPDS diffractometer | Stoe IPDS diffractometer |
Absorption correction | – | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | – | 0.598, 0.873 | 0.852, 0.894 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10617, 4383, 4045 | 9253, 3619, 3380 | 22007, 5395, 3205 |
Rint | 0.023 | 0.050 | 0.145 |
(sin θ/λ)max (Å−1) | 0.667 | 0.619 | 0.618 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.066, 1.07 | 0.026, 0.061, 0.98 | 0.057, 0.126, 0.93 |
No. of reflections | 4383 | 3619 | 5395 |
No. of parameters | 308 | 245 | 343 |
No. of restraints | 1 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.33 | 0.36, −0.25 | 0.97, −0.47 |
Absolute structure | Flack (1983), with 1249 Friedel pairs | Flack (1983), with 1722 Friedel pairs | Flack (1983), with 2333 Friedel pairs |
Absolute structure parameter | 0.00 (1) | −0.015 (12) | 0.01 (3) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), IPDS Software (Stoe & Cie, 2000), CrysAlis RED (Oxford Diffraction, 2003), IPDS Software, CrysAlis RED, 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 |
O21—H21···S1i | 0.82 | 2.73 | 3.426 (2) | 144 |
C114—H114···S1ii | 0.93 | 2.78 | 3.633 (3) | 153 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y+1/2, −z+1. |
Compound | Fe1-Cg1 | Fe1-Cg2 | C1-P1 | P1-S1 | C2-C21 |
(III) | 1.639 (5) | 1.653 (5) | 1.796 (2) | 1.9384 (7) | 1.503 (3) |
c | 1.645 (9) | 1.660 (10) | 1.790 (3) | 1.9487 (11) | 1.504 (4) |
(V) | 1.636 (2) | 1.651 (2) | 1.785 (2) | 1.9555 (9) | 1.490 (4) |
c | 1.636 (8) | 1.646 (8) | 1.7901 (18) | 1.9677 (6) | 1.505 (3) |
d | 1.633 (2) | 1.652 (2) | 1.7885 (14) | 1.9645 (6) | 1.489 (2) |
(VIII) | 1.6337 (8) | 1.6503 (8) | 1.803 (6) | 1.496 (8) | |
c | 1.6392 (4) | 1.6588 (4) | 1.809 (3) | 1.515 (5) | |
a | 1.6375 (8) | 1.656 (1) | 1.790 (2) | 1.9567 (6) | 1.485 (2) |
b | 1.6443 (7) | 1.6596 (7) | 1.795 (3) | 1.9561 (5) | 1.505 (2) |
References: (a) Stepnicka & Císarová (2002). (b) Stepnicka & Císarová (2003). (c) Lopez Cortés et al. (2006). (d) Mourgues et al. (2003). |
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Considerable efforts have been devoted to the development of new chiral ligands owing to the growing importance of transition metal-catalysed asymmetric synthesis (Ojima, 2000; Jacobsen et al., 1999; Noyori, 1994). Among these chiral ligands, ferrocene-containing ligands are among the most interesting because of their stability, the easy introduction of planar chirality and the special electronic and stereoproperties of the ferrocene skeleton (Togni & Hayashi, 1995; Borman, 1996; Togni, 1996; Atkinson et al., 2004). Among the chiral ferrocene-based ligands, enantiopure 1,2-disubstituted ferrocene derivatives, especially ferrocenyldiphosphine ligands, have played a dominant role (Colacot, 2003; Tang et al., 2003; Barbaro et al., 2004). Typical examples are TRAP ligands (Sawamura et al., 1996; Kuwano et al., 1999, 2000), and the diphosphine Josiphos ligands (Blaser et al., 2002), in particular the industrially important Xyliphos (Blaser, 2002), Taniaphos (Lotz et al., 2002; Spindler et al., 2004) or Walphos-type ligands (Sturm et al., 2003). Common characteristics of these ligands include the ferrocenylethyl backbone and the presence of both planar and central chiralities. Little attention has been paid to ligands based on the ferrocenylmethyl backbone or, more generally, to ferrocenes possessing planar chirality as their only element of chirality. Thus, we have recently investigated the family of 1,2-disubstituted planar chiral ferrocenes by the introduction of a phosphole group, leading to planar chiral ferrocenyl phosphole amine ligands (Lopez Cortés et al., 2006). We report here the structural characterization of three enantiomerically pure ferrocenyl derivatives containing the dibenzophosphole moiety, (III), (V) and (VIII).
A molecular view of compound (III) is shown in Fig. 1. As expected, the phosphole ring is planar, with the largest deviation being 0.068 (2) Å for atom C112. Atom P1 deviates slightly by 0.204 (2) Å from the Cp ring to which it is attached, whereas atom S1 is endo with respect to this Cp ring by 1.026 (3) Å. The dibenzyl phosphole and the Cp rings are nearly perpendicular, making a dihedral angle of 88.21 (5)°. The dioxane ring is distorted and the puckering parameters (Cremer & Pople, 1975) show that its conformation is close to that of a chair: the θ and ϕ angles calculated for the atom sequence C21/O21/C22/C23/C24/O22 are 175.4 (2)° and 133 (2)°, respectively. Owing to steric hindrance, the dioxane ring is twisted with respect to the Cp ring, with C3—C2—C21—O21 and C3—C2—C21—O22 torsion angles of −5.0 (3) and 115.8 (2)°, respectively. The two Cp rings are nearly eclipsed, with a twisted angle of only 3.5°.
A molecular view of alcohol (V) is shown in Fig. 2. As previously noticed, the dibenzyl phosphole is roughly planar, with the largest deviation being 0.109 (2) Å for atom C14, and it makes a dihedral angle of 87.34 (7)° with the Cp ring to which it is attached. Atom P1 is nearly coplanar with the Cp ring, deviating by only 0.088 (2) Å. Atom S1 is endo by 1.333 (3) Å with respect to this Cp ring. An interesting feature is the occurrence of an O—H···S intermolecular hydrogen bond linking the molecules to form a chain developing parallel to the a axis. It is worth pointing out that, in the related compound (SFc)-[2-(3,4-dimethyl-1-thio-1H-1λ5-phosphol-1-yl)ferrocenyl]methanol (Mourgues et al., 2003), the O—H···S interaction is only intramolecular. Moreover, in (V) the chains are interconnected by weak C—H···S hydrogen bonds to form a two-dimensional network parallel to (001) (Table 1, Fig. 3). The two Cp rings are twisted with respect to each other by 13.9°. This larger value compared with compound (III) [Please check - was originally (I)] might be related to the occurrence of the hydrogen bond. The alcohol group is twisted with respect to the Cp plane, with a C3—C2—C21—O21 torsion angle of 103.1 (3)°. A similar conformation of the alcohol group has been found in the related compound rac-2-(diphenylthiophosphoryl)ferrocenylmethanol (Stepnicka & Císarová, 2002). However, the O—H···S hydrogen bonds in that compound resulted in the formation of pseudo dimer through an inversion centre.
A molecular view of complex (VIII) is shown in Fig. 4. As already observed in free phosphole ligands (Tissot et al., 2000; Ogasawara et al., 2001; Hydrio et al., 2002; Melaimi et al., 2002), the P atom is located slightly above the butadiene fragment [0.129 (5) Å]. Atom P1 is roughly in the plane of the Cp ring, with a deviation from the mean plane of 0.09 (1) Å. Atom P2 is oriented exo with respect to the Cp ring and is located 1.62 (1) Å above it. The two Cp rings are perfectly eclipsed, with a twist angle of 0.5°. The two phenyl rings make a dihedral angle of 65.7 (2)°. It is interesting to note that the lone pairs of the two P atoms are in the correct arrangement for chelating on a metal precursor.
In all three compounds, the geometry within the ferrocene frameworks is roughly identical (Table 2) and agrees with that of related compounds found in the Cambridge Structural Database (CSD; Version 5.27; Allen, 2002). For these three compounds, the refinement of the Flack parameter (Flack, 1983; Bernardinelli & Flack, 1985) allowed the determination of the absolute configuration.