Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703262X/nc2045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703262X/nc2045Isup2.hkl |
CCDC reference: 657551
The synthesis of the title compound, (I), is described by Nettekoven et al. (2001). Orange crystals for data collection were obtained after recrystallization from CH2Cl2/hexane (ratio 1:1).
All hydrogen atoms were located in the difference Fourier map and where refined freely with isotropic displacement parameters.
The final residual density of 1.021 e Å-3 is located 1.77 Å from C20.
Atoms C11–C13 belong to the unsubstituted, only to Fe2 coordinated Cp ring C11–C15 and show anomalous anisotropic displacement parameters along their chemical bonds. This is due to the higher ability of rotation compared to Cp rings C1–C5 and C6–C10.
Phosphorous-chiral ligands based on ferrocene play important roles in stereoselective synthesis and asymmetric catalysis. In this context we report here the crystal structure of (I).
The title compound, (I), consists of two (C6H5)P[(C5H4)Fe(C5H4)](C5H4) units, which are connected via Fe1 into a substituted ferrocene (Fig. 1). Fe1 is located on an inversion center. Each Fe atom is coordinated in a sandwich fashion by two cyclopentadienyl (Cp) rings. Fe1—C(Cp) distances range from 2.0451 (17) to 2.0513 (16) Å, the variation of the Fe2—C(Cp) bond length is with 2.028 (3) to 2.058 (2) Å wider. This ranges compares well to the related (Ph)P[(Cp)Fe(Cp)]2 complex [Fe—C = 1.999 (12) – 2.060 (11)] reported by Houlton et al. (1990).
The planes of the Cp rings are standing parallel on top of each other, with the largest deviation from parallelity of 2.24 (15) ° for Cp2 (C6–C10) with respect to Cp3 (C11—C15). The conformation of the Cp rings are twisted, the Cp–C atoms do not cover each other as can be seen in plots viewed perpendicular to the Cp rings in Fig. 2. This rotation is expressed by variation of the C—Cg—Cg—C (Cg is the centroid of the Cp rings) torsions angles. The rotation of Cp2 with respect to Cp3 is with 23.13 [C6—Cg3—Cg1—C15] to 23.61 ° [C7—Cg2—Cg3—C11] smaller compared to the rotation of Cg1 to Cg1i [symmetry code: (i) 1 - x, 1 - y, 1 - z] with 35.48 ° [C2—Cg1—Cg1i—C4i] to 36.01 ° [C1—Cg1—Cg1i—C4i]. Since the first structure determinations on metallocenes there have been discussions, whether the Cp–H atoms are bent away from or towards to the metal (Haaland, 1979). In (I) all Cp–H atoms are found in the planes of the corresponding Cp–C atoms within standard uncertainties.
The phosphine P is in a tetrahedral environment, defined by a phenyl (Ph) ring, two cyclopentadienyl rings and an electron pair. C—P—C angles are less than the ideal value of 109°, they vary between 100.46 (8) and 103.22 (8)°. P—C(Cp) distances are with 1.8130 (18) and 1.8210 (18) Å shorter than the P—C(Ph) distance [1.8361 (19) Å]. Again the P geometry is similar to the related (Ph)P[(Cp)Fe(Cp)]2 complex, where bond lengths and angles agree well with those in (I), the longest P—C distance [1.843 (11) Å] corresponds again to P—C(Ph).
In a similar structure, where the phosphine P is protected by a BH3 group (Nettekoven et al., 2003), the C—P—C angles range from 102.29 (12) to 108.10 (11)° and the P geometry is therefore closer to tetrahedral. P—C(Cp) and P—C(Ph) bond distances are shorter than in (I) [P—C(Cp) = 1.786 (3), 1.798 (3) Å; P—C(Ph) = 1.820 (2) Å].
The synthesis of the title compound is described by Nettekoven et al. (2001). Related structures are reported by Houlton et al. (1990) and Nettekoven et al. (2003).
For related literature, see: Haaland (1979).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Version 1.11.0; Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: DIRDIF97 (Beurskens et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
[Fe3(C5H5)2(C16H13P)2] | Z = 1 |
Mr = 770.20 | F(000) = 396 |
Triclinic, P1 | Dx = 1.509 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9308 (1) Å | Cell parameters from 33761 reflections |
b = 9.5875 (2) Å | θ = 1.0–27.5° |
c = 15.7529 (3) Å | µ = 1.39 mm−1 |
α = 82.2873 (10)° | T = 150 K |
β = 89.4928 (9)° | Block, orange |
γ = 72.8206 (9)° | 0.33 × 0.27 × 0.12 mm |
V = 847.58 (3) Å3 |
Nonius KappaCCD diffractometer | 3872 independent reflections |
Radiation source: rotating anode | 3567 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
φ and ω scans | θmax = 27.4°, θmin = 2.2° |
Absorption correction: multi-scan (MULABS routine of PLATON; Spek, 2003) | h = −7→7 |
Tmin = 0.77, Tmax = 0.84 | k = −12→12 |
19960 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.077 | All H-atom parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0331P)2 + 0.7293P] where P = (Fo2 + 2Fc2)/3 |
3872 reflections | (Δ/σ)max = 0.004 |
286 parameters | Δρmax = 1.02 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Fe3(C5H5)2(C16H13P)2] | γ = 72.8206 (9)° |
Mr = 770.20 | V = 847.58 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.9308 (1) Å | Mo Kα radiation |
b = 9.5875 (2) Å | µ = 1.39 mm−1 |
c = 15.7529 (3) Å | T = 150 K |
α = 82.2873 (10)° | 0.33 × 0.27 × 0.12 mm |
β = 89.4928 (9)° |
Nonius KappaCCD diffractometer | 3872 independent reflections |
Absorption correction: multi-scan (MULABS routine of PLATON; Spek, 2003) | 3567 reflections with I > 2σ(I) |
Tmin = 0.77, Tmax = 0.84 | Rint = 0.038 |
19960 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.077 | All H-atom parameters refined |
S = 1.03 | Δρmax = 1.02 e Å−3 |
3872 reflections | Δρmin = −0.37 e Å−3 |
286 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 I>2σ(I) 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 | 0.5000 | 0.5000 | 0.5000 | 0.01673 (9) | |
Fe2 | 0.20709 (4) | 1.07610 (3) | 0.274313 (16) | 0.02367 (9) | |
P1 | 0.56465 (7) | 0.70824 (5) | 0.31173 (3) | 0.02101 (11) | |
C1 | 0.4763 (3) | 0.55601 (19) | 0.36935 (11) | 0.0191 (3) | |
C2 | 0.6404 (3) | 0.4122 (2) | 0.39305 (11) | 0.0228 (4) | |
C3 | 0.5199 (4) | 0.3205 (2) | 0.43963 (12) | 0.0263 (4) | |
C4 | 0.2802 (4) | 0.4057 (2) | 0.44521 (12) | 0.0256 (4) | |
C5 | 0.2523 (3) | 0.5499 (2) | 0.40199 (11) | 0.0212 (3) | |
C6 | 0.3239 (3) | 0.86348 (19) | 0.33599 (11) | 0.0203 (3) | |
C7 | 0.0769 (3) | 0.9040 (2) | 0.31389 (12) | 0.0228 (4) | |
C8 | −0.0417 (3) | 1.0281 (2) | 0.35466 (13) | 0.0273 (4) | |
C9 | 0.1280 (4) | 1.0664 (2) | 0.40202 (13) | 0.0278 (4) | |
C10 | 0.3532 (3) | 0.9663 (2) | 0.39040 (12) | 0.0249 (4) | |
C11 | 0.2321 (7) | 1.0950 (4) | 0.14502 (16) | 0.0615 (9) | |
C12 | 0.0377 (6) | 1.2089 (5) | 0.1681 (2) | 0.0776 (14) | |
C13 | 0.1247 (5) | 1.2925 (3) | 0.2200 (2) | 0.0550 (8) | |
C14 | 0.3699 (4) | 1.2309 (3) | 0.22715 (15) | 0.0399 (5) | |
C15 | 0.4347 (5) | 1.1115 (3) | 0.18153 (15) | 0.0432 (6) | |
C16 | 0.4953 (3) | 0.6923 (2) | 0.20074 (12) | 0.0266 (4) | |
C17 | 0.6397 (4) | 0.7335 (3) | 0.13786 (15) | 0.0407 (5) | |
C18 | 0.5986 (5) | 0.7260 (3) | 0.05218 (15) | 0.0544 (7) | |
C19 | 0.4187 (5) | 0.6751 (4) | 0.02877 (15) | 0.0565 (7) | |
C20 | 0.2766 (5) | 0.6306 (3) | 0.09029 (16) | 0.0495 (6) | |
C21 | 0.3154 (4) | 0.6396 (3) | 0.17618 (14) | 0.0344 (4) | |
H2 | 0.800 (4) | 0.391 (2) | 0.3808 (14) | 0.028 (6)* | |
H3 | 0.583 (4) | 0.225 (3) | 0.4641 (14) | 0.030 (6)* | |
H4 | 0.164 (5) | 0.376 (3) | 0.4752 (17) | 0.044 (7)* | |
H5 | 0.113 (4) | 0.623 (2) | 0.3968 (14) | 0.023 (5)* | |
H7 | 0.002 (4) | 0.857 (3) | 0.2789 (15) | 0.033 (6)* | |
H8 | −0.208 (4) | 1.077 (3) | 0.3502 (14) | 0.031 (6)* | |
H9 | 0.095 (4) | 1.144 (3) | 0.4345 (16) | 0.039 (7)* | |
H10 | 0.495 (4) | 0.967 (3) | 0.4117 (15) | 0.033 (6)* | |
H11 | 0.220 (7) | 1.020 (5) | 0.113 (3) | 0.098 (13)* | |
H12 | −0.091 (8) | 1.212 (5) | 0.154 (3) | 0.104 (14)* | |
H13 | 0.035 (6) | 1.375 (4) | 0.244 (2) | 0.081 (11)* | |
H14 | 0.478 (6) | 1.267 (4) | 0.254 (2) | 0.072 (10)* | |
H15 | 0.595 (6) | 1.038 (4) | 0.176 (2) | 0.067 (9)* | |
H17 | 0.766 (5) | 0.776 (3) | 0.1540 (18) | 0.052 (8)* | |
H18 | 0.695 (6) | 0.755 (4) | 0.011 (2) | 0.067 (9)* | |
H19 | 0.400 (5) | 0.668 (3) | −0.030 (2) | 0.061 (8)* | |
H20 | 0.168 (5) | 0.591 (3) | 0.0761 (19) | 0.055 (8)* | |
H21 | 0.218 (5) | 0.613 (3) | 0.2145 (16) | 0.039 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01851 (16) | 0.01506 (16) | 0.01460 (16) | −0.00259 (12) | 0.00126 (12) | −0.00050 (12) |
Fe2 | 0.02421 (14) | 0.02186 (14) | 0.02401 (15) | −0.00941 (10) | −0.00277 (10) | 0.00620 (10) |
P1 | 0.0170 (2) | 0.0244 (2) | 0.0203 (2) | −0.00623 (17) | 0.00241 (16) | 0.00201 (17) |
C1 | 0.0195 (8) | 0.0214 (8) | 0.0148 (7) | −0.0042 (6) | 0.0009 (6) | −0.0006 (6) |
C2 | 0.0256 (9) | 0.0219 (8) | 0.0170 (8) | −0.0006 (7) | 0.0021 (6) | −0.0037 (6) |
C3 | 0.0406 (10) | 0.0168 (8) | 0.0198 (8) | −0.0057 (7) | 0.0008 (7) | −0.0036 (7) |
C4 | 0.0331 (10) | 0.0272 (9) | 0.0206 (9) | −0.0155 (8) | 0.0021 (7) | −0.0032 (7) |
C5 | 0.0200 (8) | 0.0247 (9) | 0.0180 (8) | −0.0067 (7) | −0.0008 (6) | −0.0001 (7) |
C6 | 0.0217 (8) | 0.0196 (8) | 0.0193 (8) | −0.0086 (6) | 0.0009 (6) | 0.0037 (6) |
C7 | 0.0198 (8) | 0.0216 (8) | 0.0279 (9) | −0.0091 (7) | 0.0008 (7) | 0.0006 (7) |
C8 | 0.0252 (9) | 0.0220 (9) | 0.0327 (10) | −0.0058 (7) | 0.0063 (7) | 0.0006 (7) |
C9 | 0.0390 (11) | 0.0174 (8) | 0.0260 (9) | −0.0081 (8) | 0.0020 (8) | 0.0002 (7) |
C10 | 0.0306 (9) | 0.0233 (9) | 0.0220 (9) | −0.0132 (7) | −0.0034 (7) | 0.0049 (7) |
C11 | 0.108 (3) | 0.0676 (19) | 0.0234 (12) | −0.056 (2) | −0.0078 (14) | 0.0117 (12) |
C12 | 0.0470 (16) | 0.108 (3) | 0.070 (2) | −0.0461 (19) | −0.0363 (16) | 0.071 (2) |
C13 | 0.0535 (15) | 0.0282 (12) | 0.0658 (18) | 0.0009 (11) | 0.0197 (13) | 0.0238 (12) |
C14 | 0.0469 (13) | 0.0370 (12) | 0.0384 (12) | −0.0247 (10) | −0.0026 (10) | 0.0136 (9) |
C15 | 0.0476 (13) | 0.0394 (12) | 0.0373 (12) | −0.0126 (10) | 0.0127 (10) | 0.0117 (10) |
C16 | 0.0285 (9) | 0.0273 (9) | 0.0196 (8) | −0.0034 (7) | 0.0033 (7) | 0.0008 (7) |
C17 | 0.0423 (12) | 0.0495 (13) | 0.0285 (11) | −0.0136 (11) | 0.0112 (9) | 0.0006 (9) |
C18 | 0.0616 (17) | 0.0714 (19) | 0.0244 (11) | −0.0150 (14) | 0.0148 (11) | 0.0022 (11) |
C19 | 0.0667 (18) | 0.0726 (19) | 0.0197 (11) | −0.0037 (14) | −0.0004 (11) | −0.0081 (11) |
C20 | 0.0539 (15) | 0.0633 (17) | 0.0326 (12) | −0.0153 (13) | −0.0045 (11) | −0.0149 (11) |
C21 | 0.0379 (11) | 0.0407 (12) | 0.0255 (10) | −0.0122 (9) | 0.0043 (8) | −0.0063 (8) |
Fe1—C2 | 2.0451 (17) | C7—C8 | 1.423 (3) |
Fe1—C4 | 2.0460 (19) | C7—H7 | 0.94 (2) |
Fe1—C3 | 2.0487 (18) | C8—C9 | 1.418 (3) |
Fe1—C5 | 2.0488 (17) | C8—H8 | 0.96 (2) |
Fe1—C1 | 2.0513 (16) | C9—C10 | 1.422 (3) |
Fe2—C11 | 2.028 (3) | C9—H9 | 0.93 (3) |
Fe2—C12 | 2.032 (2) | C10—H10 | 0.91 (2) |
Fe2—C10 | 2.0433 (18) | C11—C15 | 1.396 (4) |
Fe2—C7 | 2.0435 (18) | C11—C12 | 1.418 (5) |
Fe2—C15 | 2.044 (2) | C11—H11 | 0.95 (4) |
Fe2—C8 | 2.0502 (19) | C12—C13 | 1.416 (5) |
Fe2—C13 | 2.051 (2) | C12—H12 | 0.79 (4) |
Fe2—C14 | 2.055 (2) | C13—C14 | 1.398 (4) |
Fe2—C6 | 2.0556 (17) | C13—H13 | 0.94 (4) |
Fe2—C9 | 2.058 (2) | C14—C15 | 1.389 (4) |
P1—C6 | 1.8130 (18) | C14—H14 | 0.94 (3) |
P1—C1 | 1.8210 (18) | C15—H15 | 1.01 (3) |
P1—C16 | 1.8361 (19) | C16—C21 | 1.386 (3) |
C1—C5 | 1.435 (2) | C16—C17 | 1.397 (3) |
C1—C2 | 1.436 (2) | C17—C18 | 1.389 (3) |
C2—C3 | 1.418 (3) | C17—H17 | 1.00 (3) |
C2—H2 | 0.93 (2) | C18—C19 | 1.370 (4) |
C3—C4 | 1.423 (3) | C18—H18 | 0.93 (3) |
C3—H3 | 0.91 (2) | C19—C20 | 1.385 (4) |
C4—C5 | 1.420 (3) | C19—H19 | 0.94 (3) |
C4—H4 | 0.93 (3) | C20—C21 | 1.393 (3) |
C5—H5 | 0.91 (2) | C20—H20 | 0.88 (3) |
C6—C7 | 1.434 (2) | C21—H21 | 0.90 (3) |
C6—C10 | 1.438 (3) | ||
C2i—Fe1—C2 | 179.999 (1) | C2—C3—Fe1 | 69.60 (10) |
C2i—Fe1—C4 | 111.69 (8) | C4—C3—Fe1 | 69.56 (10) |
C2—Fe1—C4 | 68.31 (8) | C2—C3—H3 | 127.2 (15) |
C2—Fe1—C4i | 111.69 (8) | C4—C3—H3 | 124.8 (15) |
C4—Fe1—C4i | 179.998 (1) | Fe1—C3—H3 | 124.4 (14) |
C2i—Fe1—C3 | 139.47 (8) | C5—C4—C3 | 108.31 (16) |
C2—Fe1—C3 | 40.53 (8) | C5—C4—Fe1 | 69.82 (10) |
C4—Fe1—C3 | 40.69 (8) | C3—C4—Fe1 | 69.76 (11) |
C4i—Fe1—C3 | 139.32 (8) | C5—C4—H4 | 125.1 (17) |
C2—Fe1—C3i | 139.47 (8) | C3—C4—H4 | 126.4 (17) |
C4—Fe1—C3i | 139.31 (8) | Fe1—C4—H4 | 122.7 (16) |
C3—Fe1—C3i | 180.00 (8) | C4—C5—C1 | 108.37 (16) |
C2i—Fe1—C5 | 111.48 (7) | C4—C5—Fe1 | 69.60 (10) |
C2—Fe1—C5 | 68.51 (7) | C1—C5—Fe1 | 69.61 (9) |
C4—Fe1—C5 | 40.58 (7) | C4—C5—H5 | 123.9 (14) |
C4i—Fe1—C5 | 139.42 (7) | C1—C5—H5 | 127.7 (14) |
C3—Fe1—C5 | 68.46 (7) | Fe1—C5—H5 | 126.8 (14) |
C3i—Fe1—C5 | 111.54 (7) | C7—C6—C10 | 106.61 (16) |
C2—Fe1—C5i | 111.49 (7) | C7—C6—P1 | 130.23 (14) |
C4—Fe1—C5i | 139.42 (7) | C10—C6—P1 | 123.00 (13) |
C3—Fe1—C5i | 111.54 (7) | C7—C6—Fe2 | 69.07 (10) |
C5—Fe1—C5i | 179.998 (2) | C10—C6—Fe2 | 69.00 (10) |
C2—Fe1—C1i | 138.95 (7) | P1—C6—Fe2 | 130.26 (9) |
C4—Fe1—C1i | 111.19 (7) | C8—C7—C6 | 108.44 (16) |
C3—Fe1—C1i | 111.09 (7) | C8—C7—Fe2 | 69.91 (11) |
C5—Fe1—C1i | 139.03 (7) | C6—C7—Fe2 | 69.98 (10) |
C2i—Fe1—C1 | 138.95 (7) | C8—C7—H7 | 124.7 (15) |
C2—Fe1—C1 | 41.05 (7) | C6—C7—H7 | 126.8 (15) |
C4—Fe1—C1 | 68.81 (7) | Fe2—C7—H7 | 126.3 (14) |
C4i—Fe1—C1 | 111.19 (7) | C9—C8—C7 | 108.42 (17) |
C3—Fe1—C1 | 68.90 (7) | C9—C8—Fe2 | 70.10 (11) |
C3i—Fe1—C1 | 111.10 (7) | C7—C8—Fe2 | 69.40 (10) |
C5—Fe1—C1 | 40.97 (7) | C9—C8—H8 | 126.3 (14) |
C5i—Fe1—C1 | 139.03 (7) | C7—C8—H8 | 125.3 (14) |
C1i—Fe1—C1 | 180.00 (10) | Fe2—C8—H8 | 125.9 (14) |
C11—Fe2—C12 | 40.86 (16) | C8—C9—C10 | 107.81 (17) |
C11—Fe2—C10 | 146.78 (13) | C8—C9—Fe2 | 69.52 (11) |
C12—Fe2—C10 | 171.90 (15) | C10—C9—Fe2 | 69.16 (11) |
C11—Fe2—C7 | 108.50 (10) | C8—C9—H9 | 125.1 (15) |
C12—Fe2—C7 | 113.95 (11) | C10—C9—H9 | 127.1 (16) |
C10—Fe2—C7 | 68.58 (7) | Fe2—C9—H9 | 126.5 (15) |
C11—Fe2—C15 | 40.11 (12) | C9—C10—C6 | 108.72 (17) |
C12—Fe2—C15 | 67.42 (12) | C9—C10—Fe2 | 70.26 (11) |
C10—Fe2—C15 | 116.96 (9) | C6—C10—Fe2 | 69.93 (10) |
C7—Fe2—C15 | 133.60 (9) | C9—C10—H10 | 126.9 (15) |
C11—Fe2—C8 | 132.21 (11) | C6—C10—H10 | 124.3 (15) |
C12—Fe2—C8 | 108.31 (11) | Fe2—C10—H10 | 124.2 (15) |
C10—Fe2—C8 | 68.20 (8) | C15—C11—C12 | 107.0 (3) |
C7—Fe2—C8 | 40.68 (7) | C15—C11—Fe2 | 70.54 (14) |
C15—Fe2—C8 | 171.86 (10) | C12—C11—Fe2 | 69.72 (17) |
C11—Fe2—C13 | 68.42 (14) | C15—C11—H11 | 128 (3) |
C12—Fe2—C13 | 40.56 (15) | C12—C11—H11 | 125 (3) |
C10—Fe2—C13 | 133.29 (12) | Fe2—C11—H11 | 122 (2) |
C7—Fe2—C13 | 145.35 (10) | C13—C12—C11 | 108.1 (2) |
C15—Fe2—C13 | 67.20 (10) | C13—C12—Fe2 | 70.44 (14) |
C8—Fe2—C13 | 114.51 (9) | C11—C12—Fe2 | 69.42 (15) |
C11—Fe2—C14 | 67.45 (11) | C13—C12—H12 | 133 (3) |
C12—Fe2—C14 | 67.22 (11) | C11—C12—H12 | 119 (3) |
C10—Fe2—C14 | 111.30 (9) | Fe2—C12—H12 | 123 (3) |
C7—Fe2—C14 | 172.87 (9) | C14—C13—C12 | 107.1 (3) |
C15—Fe2—C14 | 39.63 (10) | C14—C13—Fe2 | 70.26 (13) |
C8—Fe2—C14 | 146.35 (10) | C12—C13—Fe2 | 69.01 (15) |
C13—Fe2—C14 | 39.80 (10) | C14—C13—H13 | 126 (2) |
C11—Fe2—C6 | 114.47 (11) | C12—C13—H13 | 127 (2) |
C12—Fe2—C6 | 145.58 (14) | Fe2—C13—H13 | 127 (2) |
C10—Fe2—C6 | 41.07 (7) | C15—C14—C13 | 108.8 (2) |
C7—Fe2—C6 | 40.94 (7) | C15—C14—Fe2 | 69.74 (13) |
C15—Fe2—C6 | 110.53 (9) | C13—C14—Fe2 | 69.94 (13) |
C8—Fe2—C6 | 68.73 (7) | C15—C14—H14 | 124 (2) |
C13—Fe2—C6 | 173.03 (11) | C13—C14—H14 | 127 (2) |
C14—Fe2—C6 | 134.39 (8) | Fe2—C14—H14 | 130 (2) |
C11—Fe2—C9 | 171.42 (13) | C14—C15—C11 | 109.0 (3) |
C12—Fe2—C9 | 132.17 (14) | C14—C15—Fe2 | 70.64 (13) |
C10—Fe2—C9 | 40.59 (8) | C11—C15—Fe2 | 69.35 (15) |
C7—Fe2—C9 | 68.37 (8) | C14—C15—H15 | 130.1 (19) |
C15—Fe2—C9 | 147.56 (10) | C11—C15—H15 | 120.8 (19) |
C8—Fe2—C9 | 40.37 (8) | Fe2—C15—H15 | 122.5 (18) |
C13—Fe2—C9 | 109.29 (10) | C21—C16—C17 | 118.7 (2) |
C14—Fe2—C9 | 116.51 (9) | C21—C16—P1 | 124.65 (15) |
C6—Fe2—C9 | 68.82 (7) | C17—C16—P1 | 116.63 (17) |
C6—P1—C1 | 100.46 (8) | C18—C17—C16 | 120.4 (2) |
C6—P1—C16 | 103.22 (8) | C18—C17—H17 | 119.5 (16) |
C1—P1—C16 | 100.66 (9) | C16—C17—H17 | 119.9 (16) |
C5—C1—C2 | 106.76 (15) | C19—C18—C17 | 120.2 (2) |
C5—C1—P1 | 130.84 (13) | C19—C18—H18 | 120 (2) |
C2—C1—P1 | 122.37 (13) | C17—C18—H18 | 119 (2) |
C5—C1—Fe1 | 69.42 (9) | C18—C19—C20 | 120.3 (2) |
C2—C1—Fe1 | 69.24 (10) | C18—C19—H19 | 117.6 (19) |
P1—C1—Fe1 | 124.65 (9) | C20—C19—H19 | 122.0 (19) |
C3—C2—C1 | 108.69 (16) | C19—C20—C21 | 119.7 (3) |
C3—C2—Fe1 | 69.87 (10) | C19—C20—H20 | 121 (2) |
C1—C2—Fe1 | 69.71 (10) | C21—C20—H20 | 120 (2) |
C3—C2—H2 | 129.3 (14) | C16—C21—C20 | 120.6 (2) |
C1—C2—H2 | 121.9 (14) | C16—C21—H21 | 121.5 (16) |
Fe1—C2—H2 | 123.4 (14) | C20—C21—H21 | 117.8 (16) |
C2—C3—C4 | 107.86 (16) | ||
C6—P1—C1—C5 | 17.63 (18) | C6—C7—C8—Fe2 | 59.60 (12) |
C16—P1—C1—C5 | −88.12 (17) | C11—Fe2—C8—C9 | −173.79 (16) |
C6—P1—C1—C2 | −160.12 (15) | C12—Fe2—C8—C9 | −134.62 (18) |
C16—P1—C1—C2 | 94.14 (15) | C10—Fe2—C8—C9 | 37.60 (11) |
C6—P1—C1—Fe1 | −74.25 (11) | C7—Fe2—C8—C9 | 119.67 (16) |
C16—P1—C1—Fe1 | −179.99 (10) | C13—Fe2—C8—C9 | −91.39 (15) |
C2i—Fe1—C1—C5 | −61.85 (15) | C14—Fe2—C8—C9 | −58.43 (19) |
C2—Fe1—C1—C5 | 118.15 (15) | C6—Fe2—C8—C9 | 81.91 (12) |
C4—Fe1—C1—C5 | 37.26 (11) | C11—Fe2—C8—C7 | 66.55 (19) |
C4i—Fe1—C1—C5 | −142.74 (11) | C12—Fe2—C8—C7 | 105.71 (18) |
C3—Fe1—C1—C5 | 81.03 (11) | C10—Fe2—C8—C7 | −82.07 (12) |
C3i—Fe1—C1—C5 | −98.97 (11) | C13—Fe2—C8—C7 | 148.94 (15) |
C5i—Fe1—C1—C5 | 180.001 (1) | C14—Fe2—C8—C7 | −178.10 (14) |
C2i—Fe1—C1—C2 | 180.0 | C6—Fe2—C8—C7 | −37.76 (11) |
C4—Fe1—C1—C2 | −80.89 (12) | C9—Fe2—C8—C7 | −119.67 (16) |
C4i—Fe1—C1—C2 | 99.11 (12) | C7—C8—C9—C10 | 0.3 (2) |
C3—Fe1—C1—C2 | −37.12 (11) | Fe2—C8—C9—C10 | −58.74 (13) |
C3i—Fe1—C1—C2 | 142.88 (11) | C7—C8—C9—Fe2 | 59.01 (13) |
C5—Fe1—C1—C2 | −118.15 (15) | C12—Fe2—C9—C8 | 65.74 (18) |
C5i—Fe1—C1—C2 | 61.85 (15) | C10—Fe2—C9—C8 | −119.45 (16) |
C2i—Fe1—C1—P1 | 64.28 (16) | C7—Fe2—C9—C8 | −37.54 (11) |
C2—Fe1—C1—P1 | −115.72 (16) | C15—Fe2—C9—C8 | −176.92 (15) |
C4—Fe1—C1—P1 | 163.39 (13) | C13—Fe2—C9—C8 | 105.48 (14) |
C4i—Fe1—C1—P1 | −16.61 (13) | C14—Fe2—C9—C8 | 148.16 (12) |
C3—Fe1—C1—P1 | −152.84 (13) | C6—Fe2—C9—C8 | −81.67 (11) |
C3i—Fe1—C1—P1 | 27.16 (13) | C12—Fe2—C9—C10 | −174.81 (16) |
C5—Fe1—C1—P1 | 126.13 (16) | C7—Fe2—C9—C10 | 81.90 (11) |
C5i—Fe1—C1—P1 | −53.87 (16) | C15—Fe2—C9—C10 | −57.5 (2) |
C5—C1—C2—C3 | −0.4 (2) | C8—Fe2—C9—C10 | 119.45 (16) |
P1—C1—C2—C3 | 177.83 (13) | C13—Fe2—C9—C10 | −135.08 (13) |
Fe1—C1—C2—C3 | 59.17 (13) | C14—Fe2—C9—C10 | −92.39 (13) |
C5—C1—C2—Fe1 | −59.56 (12) | C6—Fe2—C9—C10 | 37.78 (11) |
P1—C1—C2—Fe1 | 118.66 (13) | C8—C9—C10—C6 | −0.6 (2) |
C4—Fe1—C2—C3 | −37.76 (11) | Fe2—C9—C10—C6 | −59.56 (12) |
C4i—Fe1—C2—C3 | 142.24 (11) | C8—C9—C10—Fe2 | 58.96 (13) |
C3i—Fe1—C2—C3 | 180.0 | C7—C6—C10—C9 | 0.7 (2) |
C5—Fe1—C2—C3 | −81.56 (12) | P1—C6—C10—C9 | −175.06 (13) |
C5i—Fe1—C2—C3 | 98.44 (12) | Fe2—C6—C10—C9 | 59.77 (13) |
C1i—Fe1—C2—C3 | 60.03 (16) | C7—C6—C10—Fe2 | −59.09 (12) |
C1—Fe1—C2—C3 | −119.97 (16) | P1—C6—C10—Fe2 | 125.17 (13) |
C4—Fe1—C2—C1 | 82.20 (11) | C11—Fe2—C10—C9 | −172.65 (18) |
C4i—Fe1—C2—C1 | −97.80 (11) | C7—Fe2—C10—C9 | −81.32 (12) |
C3—Fe1—C2—C1 | 119.97 (16) | C15—Fe2—C10—C9 | 149.51 (13) |
C3i—Fe1—C2—C1 | −60.03 (16) | C8—Fe2—C10—C9 | −37.41 (11) |
C5—Fe1—C2—C1 | 38.41 (10) | C13—Fe2—C10—C9 | 66.30 (16) |
C5i—Fe1—C2—C1 | −141.59 (10) | C14—Fe2—C10—C9 | 106.33 (13) |
C1i—Fe1—C2—C1 | 179.999 (2) | C6—Fe2—C10—C9 | −119.61 (15) |
C1—C2—C3—C4 | 0.2 (2) | C11—Fe2—C10—C6 | −53.0 (2) |
Fe1—C2—C3—C4 | 59.24 (13) | C7—Fe2—C10—C6 | 38.29 (10) |
C1—C2—C3—Fe1 | −59.07 (12) | C15—Fe2—C10—C6 | −90.88 (13) |
C2i—Fe1—C3—C2 | 179.999 (1) | C8—Fe2—C10—C6 | 82.20 (11) |
C4—Fe1—C3—C2 | 119.20 (15) | C13—Fe2—C10—C6 | −174.09 (13) |
C4i—Fe1—C3—C2 | −60.80 (15) | C14—Fe2—C10—C6 | −134.06 (12) |
C5—Fe1—C3—C2 | 81.70 (11) | C9—Fe2—C10—C6 | 119.61 (15) |
C5i—Fe1—C3—C2 | −98.30 (11) | C12—Fe2—C11—C15 | 117.5 (3) |
C1i—Fe1—C3—C2 | −142.42 (10) | C10—Fe2—C11—C15 | −58.1 (3) |
C1—Fe1—C3—C2 | 37.58 (10) | C7—Fe2—C11—C15 | −137.02 (16) |
C2i—Fe1—C3—C4 | 60.80 (15) | C8—Fe2—C11—C15 | −176.11 (13) |
C2—Fe1—C3—C4 | −119.20 (15) | C13—Fe2—C11—C15 | 79.80 (18) |
C4i—Fe1—C3—C4 | 180.0 | C14—Fe2—C11—C15 | 36.72 (16) |
C5—Fe1—C3—C4 | −37.50 (11) | C6—Fe2—C11—C15 | −93.31 (17) |
C5i—Fe1—C3—C4 | 142.50 (11) | C10—Fe2—C11—C12 | −175.56 (17) |
C1i—Fe1—C3—C4 | 98.37 (11) | C7—Fe2—C11—C12 | 105.51 (18) |
C1—Fe1—C3—C4 | −81.63 (11) | C15—Fe2—C11—C12 | −117.5 (2) |
C2—C3—C4—C5 | 0.1 (2) | C8—Fe2—C11—C12 | 66.4 (2) |
Fe1—C3—C4—C5 | 59.38 (13) | C13—Fe2—C11—C12 | −37.67 (17) |
C2—C3—C4—Fe1 | −59.27 (13) | C14—Fe2—C11—C12 | −80.75 (19) |
C2i—Fe1—C4—C5 | 98.14 (11) | C6—Fe2—C11—C12 | 149.22 (17) |
C2—Fe1—C4—C5 | −81.86 (11) | C15—C11—C12—C13 | −1.0 (3) |
C3—Fe1—C4—C5 | −119.49 (15) | Fe2—C11—C12—C13 | 60.05 (18) |
C3i—Fe1—C4—C5 | 60.51 (15) | C15—C11—C12—Fe2 | −61.02 (16) |
C5i—Fe1—C4—C5 | 180.0 | C11—Fe2—C12—C13 | −119.1 (2) |
C1i—Fe1—C4—C5 | 142.39 (10) | C7—Fe2—C12—C13 | 149.94 (15) |
C1—Fe1—C4—C5 | −37.61 (10) | C15—Fe2—C12—C13 | −80.83 (17) |
C2i—Fe1—C4—C3 | −142.37 (11) | C8—Fe2—C12—C13 | 106.57 (17) |
C2—Fe1—C4—C3 | 37.63 (11) | C14—Fe2—C12—C13 | −37.72 (16) |
C3i—Fe1—C4—C3 | 180.000 (1) | C6—Fe2—C12—C13 | −174.55 (14) |
C5—Fe1—C4—C3 | 119.49 (15) | C9—Fe2—C12—C13 | 68.1 (2) |
C5i—Fe1—C4—C3 | −60.51 (15) | C7—Fe2—C12—C11 | −90.99 (17) |
C1i—Fe1—C4—C3 | −98.12 (11) | C15—Fe2—C12—C11 | 38.24 (17) |
C1—Fe1—C4—C3 | 81.89 (11) | C8—Fe2—C12—C11 | −134.35 (16) |
C3—C4—C5—C1 | −0.4 (2) | C13—Fe2—C12—C11 | 119.1 (2) |
Fe1—C4—C5—C1 | 58.99 (12) | C14—Fe2—C12—C11 | 81.35 (18) |
C3—C4—C5—Fe1 | −59.34 (13) | C6—Fe2—C12—C11 | −55.5 (2) |
C2—C1—C5—C4 | 0.5 (2) | C9—Fe2—C12—C11 | −172.82 (15) |
P1—C1—C5—C4 | −177.56 (14) | C11—C12—C13—C14 | 0.8 (3) |
Fe1—C1—C5—C4 | −58.99 (12) | Fe2—C12—C13—C14 | 60.23 (17) |
C2—C1—C5—Fe1 | 59.44 (12) | C11—C12—C13—Fe2 | −59.41 (17) |
P1—C1—C5—Fe1 | −118.57 (15) | C11—Fe2—C13—C14 | −80.24 (19) |
C2i—Fe1—C5—C4 | −98.69 (12) | C12—Fe2—C13—C14 | −118.2 (3) |
C2—Fe1—C5—C4 | 81.31 (12) | C10—Fe2—C13—C14 | 69.4 (2) |
C4i—Fe1—C5—C4 | 180.0 | C7—Fe2—C13—C14 | −171.83 (15) |
C3—Fe1—C5—C4 | 37.59 (11) | C15—Fe2—C13—C14 | −36.79 (16) |
C3i—Fe1—C5—C4 | −142.41 (11) | C8—Fe2—C13—C14 | 151.90 (15) |
C1i—Fe1—C5—C4 | −60.20 (15) | C9—Fe2—C13—C14 | 108.58 (17) |
C1—Fe1—C5—C4 | 119.80 (15) | C11—Fe2—C13—C12 | 37.9 (2) |
C2i—Fe1—C5—C1 | 141.51 (10) | C10—Fe2—C13—C12 | −172.36 (18) |
C2—Fe1—C5—C1 | −38.49 (10) | C7—Fe2—C13—C12 | −53.6 (3) |
C4—Fe1—C5—C1 | −119.80 (15) | C15—Fe2—C13—C12 | 81.4 (2) |
C4i—Fe1—C5—C1 | 60.20 (15) | C8—Fe2—C13—C12 | −89.9 (2) |
C3—Fe1—C5—C1 | −82.21 (11) | C14—Fe2—C13—C12 | 118.2 (3) |
C3i—Fe1—C5—C1 | 97.79 (11) | C9—Fe2—C13—C12 | −133.23 (19) |
C1i—Fe1—C5—C1 | 180.0 | C12—C13—C14—C15 | −0.3 (3) |
C1—P1—C6—C7 | −63.73 (17) | Fe2—C13—C14—C15 | 59.08 (16) |
C16—P1—C6—C7 | 39.95 (18) | C12—C13—C14—Fe2 | −59.43 (16) |
C1—P1—C6—C10 | 110.91 (15) | C11—Fe2—C14—C15 | −37.15 (18) |
C16—P1—C6—C10 | −145.40 (15) | C12—Fe2—C14—C15 | −81.6 (2) |
C1—P1—C6—Fe2 | −159.66 (12) | C10—Fe2—C14—C15 | 106.98 (15) |
C16—P1—C6—Fe2 | −55.97 (14) | C8—Fe2—C14—C15 | −170.70 (15) |
C11—Fe2—C6—C7 | −90.42 (15) | C13—Fe2—C14—C15 | −120.0 (2) |
C12—Fe2—C6—C7 | −54.1 (2) | C6—Fe2—C14—C15 | 65.63 (19) |
C10—Fe2—C6—C7 | 118.33 (15) | C9—Fe2—C14—C15 | 151.22 (14) |
C15—Fe2—C6—C7 | −133.79 (13) | C11—Fe2—C14—C13 | 82.9 (2) |
C8—Fe2—C6—C7 | 37.53 (11) | C12—Fe2—C14—C13 | 38.4 (2) |
C14—Fe2—C6—C7 | −172.13 (13) | C10—Fe2—C14—C13 | −132.98 (18) |
C9—Fe2—C6—C7 | 80.98 (12) | C15—Fe2—C14—C13 | 120.0 (2) |
C11—Fe2—C6—C10 | 151.25 (14) | C8—Fe2—C14—C13 | −50.7 (3) |
C12—Fe2—C6—C10 | −172.4 (2) | C6—Fe2—C14—C13 | −174.33 (17) |
C7—Fe2—C6—C10 | −118.33 (15) | C9—Fe2—C14—C13 | −88.74 (19) |
C15—Fe2—C6—C10 | 107.88 (13) | C13—C14—C15—C11 | −0.3 (3) |
C8—Fe2—C6—C10 | −80.80 (12) | Fe2—C14—C15—C11 | 58.94 (16) |
C14—Fe2—C6—C10 | 69.54 (16) | C13—C14—C15—Fe2 | −59.21 (16) |
C9—Fe2—C6—C10 | −37.34 (11) | C12—C11—C15—C14 | 0.8 (3) |
C11—Fe2—C6—P1 | 35.19 (17) | Fe2—C11—C15—C14 | −59.73 (16) |
C12—Fe2—C6—P1 | 71.5 (2) | C12—C11—C15—Fe2 | 60.49 (17) |
C10—Fe2—C6—P1 | −116.07 (17) | C11—Fe2—C15—C14 | 120.0 (2) |
C7—Fe2—C6—P1 | 125.61 (18) | C12—Fe2—C15—C14 | 81.1 (2) |
C15—Fe2—C6—P1 | −8.18 (16) | C10—Fe2—C15—C14 | −91.42 (15) |
C8—Fe2—C6—P1 | 163.13 (15) | C7—Fe2—C15—C14 | −176.75 (12) |
C14—Fe2—C6—P1 | −46.52 (19) | C13—Fe2—C15—C14 | 36.94 (16) |
C9—Fe2—C6—P1 | −153.41 (15) | C6—Fe2—C15—C14 | −135.96 (14) |
C10—C6—C7—C8 | −0.5 (2) | C9—Fe2—C15—C14 | −53.4 (2) |
P1—C6—C7—C8 | 174.81 (14) | C12—Fe2—C15—C11 | −39.0 (2) |
Fe2—C6—C7—C8 | −59.55 (13) | C10—Fe2—C15—C11 | 148.55 (18) |
C10—C6—C7—Fe2 | 59.04 (12) | C7—Fe2—C15—C11 | 63.2 (2) |
P1—C6—C7—Fe2 | −125.64 (15) | C13—Fe2—C15—C11 | −83.1 (2) |
C11—Fe2—C7—C8 | −134.23 (16) | C14—Fe2—C15—C11 | −120.0 (2) |
C12—Fe2—C7—C8 | −90.62 (19) | C6—Fe2—C15—C11 | 104.01 (19) |
C10—Fe2—C7—C8 | 81.05 (12) | C9—Fe2—C15—C11 | −173.47 (19) |
C15—Fe2—C7—C8 | −171.57 (13) | C6—P1—C16—C21 | −72.89 (19) |
C13—Fe2—C7—C8 | −55.7 (2) | C1—P1—C16—C21 | 30.64 (19) |
C6—Fe2—C7—C8 | 119.45 (16) | C6—P1—C16—C17 | 108.67 (17) |
C9—Fe2—C7—C8 | 37.27 (11) | C1—P1—C16—C17 | −147.80 (17) |
C11—Fe2—C7—C6 | 106.32 (16) | C21—C16—C17—C18 | 2.0 (3) |
C12—Fe2—C7—C6 | 149.93 (17) | P1—C16—C17—C18 | −179.5 (2) |
C10—Fe2—C7—C6 | −38.41 (11) | C16—C17—C18—C19 | −1.3 (4) |
C15—Fe2—C7—C6 | 68.98 (16) | C17—C18—C19—C20 | −0.1 (5) |
C8—Fe2—C7—C6 | −119.45 (16) | C18—C19—C20—C21 | 0.8 (4) |
C13—Fe2—C7—C6 | −175.11 (18) | C17—C16—C21—C20 | −1.2 (3) |
C9—Fe2—C7—C6 | −82.18 (12) | P1—C16—C21—C20 | −179.61 (19) |
C6—C7—C8—C9 | 0.1 (2) | C19—C20—C21—C16 | −0.2 (4) |
Fe2—C7—C8—C9 | −59.45 (13) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Fe3(C5H5)2(C16H13P)2] |
Mr | 770.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 5.9308 (1), 9.5875 (2), 15.7529 (3) |
α, β, γ (°) | 82.2873 (10), 89.4928 (9), 72.8206 (9) |
V (Å3) | 847.58 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.39 |
Crystal size (mm) | 0.33 × 0.27 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (MULABS routine of PLATON; Spek, 2003) |
Tmin, Tmax | 0.77, 0.84 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19960, 3872, 3567 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.077, 1.03 |
No. of reflections | 3872 |
No. of parameters | 286 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.02, −0.37 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Version 1.11.0; Otwinowski & Minor, 1997), DENZO, DIRDIF97 (Beurskens et al., 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
Fe1—C2 | 2.0451 (17) | Fe2—C15 | 2.044 (2) |
Fe1—C4 | 2.0460 (19) | Fe2—C8 | 2.0502 (19) |
Fe1—C3 | 2.0487 (18) | Fe2—C13 | 2.051 (2) |
Fe1—C5 | 2.0488 (17) | Fe2—C14 | 2.055 (2) |
Fe1—C1 | 2.0513 (16) | Fe2—C6 | 2.0556 (17) |
Fe2—C11 | 2.028 (3) | Fe2—C9 | 2.058 (2) |
Fe2—C12 | 2.032 (2) | P1—C6 | 1.8130 (18) |
Fe2—C10 | 2.0433 (18) | P1—C1 | 1.8210 (18) |
Fe2—C7 | 2.0435 (18) | P1—C16 | 1.8361 (19) |
C6—P1—C1 | 100.46 (8) | C1—P1—C16 | 100.66 (9) |
C6—P1—C16 | 103.22 (8) |
Phosphorous-chiral ligands based on ferrocene play important roles in stereoselective synthesis and asymmetric catalysis. In this context we report here the crystal structure of (I).
The title compound, (I), consists of two (C6H5)P[(C5H4)Fe(C5H4)](C5H4) units, which are connected via Fe1 into a substituted ferrocene (Fig. 1). Fe1 is located on an inversion center. Each Fe atom is coordinated in a sandwich fashion by two cyclopentadienyl (Cp) rings. Fe1—C(Cp) distances range from 2.0451 (17) to 2.0513 (16) Å, the variation of the Fe2—C(Cp) bond length is with 2.028 (3) to 2.058 (2) Å wider. This ranges compares well to the related (Ph)P[(Cp)Fe(Cp)]2 complex [Fe—C = 1.999 (12) – 2.060 (11)] reported by Houlton et al. (1990).
The planes of the Cp rings are standing parallel on top of each other, with the largest deviation from parallelity of 2.24 (15) ° for Cp2 (C6–C10) with respect to Cp3 (C11—C15). The conformation of the Cp rings are twisted, the Cp–C atoms do not cover each other as can be seen in plots viewed perpendicular to the Cp rings in Fig. 2. This rotation is expressed by variation of the C—Cg—Cg—C (Cg is the centroid of the Cp rings) torsions angles. The rotation of Cp2 with respect to Cp3 is with 23.13 [C6—Cg3—Cg1—C15] to 23.61 ° [C7—Cg2—Cg3—C11] smaller compared to the rotation of Cg1 to Cg1i [symmetry code: (i) 1 - x, 1 - y, 1 - z] with 35.48 ° [C2—Cg1—Cg1i—C4i] to 36.01 ° [C1—Cg1—Cg1i—C4i]. Since the first structure determinations on metallocenes there have been discussions, whether the Cp–H atoms are bent away from or towards to the metal (Haaland, 1979). In (I) all Cp–H atoms are found in the planes of the corresponding Cp–C atoms within standard uncertainties.
The phosphine P is in a tetrahedral environment, defined by a phenyl (Ph) ring, two cyclopentadienyl rings and an electron pair. C—P—C angles are less than the ideal value of 109°, they vary between 100.46 (8) and 103.22 (8)°. P—C(Cp) distances are with 1.8130 (18) and 1.8210 (18) Å shorter than the P—C(Ph) distance [1.8361 (19) Å]. Again the P geometry is similar to the related (Ph)P[(Cp)Fe(Cp)]2 complex, where bond lengths and angles agree well with those in (I), the longest P—C distance [1.843 (11) Å] corresponds again to P—C(Ph).
In a similar structure, where the phosphine P is protected by a BH3 group (Nettekoven et al., 2003), the C—P—C angles range from 102.29 (12) to 108.10 (11)° and the P geometry is therefore closer to tetrahedral. P—C(Cp) and P—C(Ph) bond distances are shorter than in (I) [P—C(Cp) = 1.786 (3), 1.798 (3) Å; P—C(Ph) = 1.820 (2) Å].