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Acta Cryst. (2007). E63, m2098    [ doi:10.1107/S160053680703262X ]

1,1'-Bis(ferrocenylphenylphosphino)ferrocene

L. S. von Chrzanowski, M. Lutz and A. L. Spek

Abstract top

In the title compound, [Fe3(C5H5)2(C16H13P)2], two (C6H5)P[(C5H4)Fe(C5H5)](C5H4) units are bridged by an Fe atom, located on an inversion center, giving a central third ferrocene unit. Each Fe atom is coordinated by two cyclopentadienyl rings in a parallel sandwich fashion, with twisted conformations. The geometry of the phosphine P atom is pseudo-tetrahedral, defined by a phenyl ring, two cyclopentadienyl rings and an electron pair.

Comment top

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].

Related literature top

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).

Experimental top

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).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. : Molecular structure of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) 1 − x, 1 − y, 1 − z]
[Figure 2] Fig. 2. : The conformation of the cyclopentadienyl (Cp) rings in (I). Hydrogen atoms have been omitted for clarity. A) View perpendicular to the Cp1-ring-plane. Color scheme: light blue Cp1, green Cp1i (Cp1 = C1–C5). B) View perpendicular to the Cp2- and Cp3-ring-plane. Color scheme: light green Cp2 and Cp2i, pink Cp3 and Cp3i (Cp2 = C6–C10 and Cp3 = C11–C15). [Symmetry code: (i) 1 − x, 1 − y, 1 − z]
1,1'-Bis(ferrocenylphenylphosphino)ferrocene top
Crystal data top
[Fe3(C5H5)2(C16H13P)2]Z = 1
Mr = 770.20F(000) = 396
Triclinic, P1Dx = 1.509 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.9308 (1) ÅCell parameters from 33761 reflections
b = 9.5875 (2) Åθ = 1.0–27.5°
c = 15.7529 (3) ŵ = 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
Data collection top
Nonius KappaCCD
diffractometer		3872 independent reflections
Radiation source: rotating anode3567 reflections with I > 2σ(I)
graphiteRint = 0.038
φ and ω scansθmax = 27.4°, θmin = 2.2°
Absorption correction: multi-scan
(MULABS routine of PLATON; Spek, 2003)		h = −7→7
Tmin = 0.77, Tmax = 0.84k = −12→12
19960 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: difference Fourier map
wR(F2) = 0.077All 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 parametersΔρmax = 1.02 e Å−3
0 restraintsΔρmin = −0.37 e Å−3
Crystal data top
[Fe3(C5H5)2(C16H13P)2]γ = 72.8206 (9)°
Mr = 770.20V = 847.58 (3) Å3
Triclinic, P1Z = 1
a = 5.9308 (1) ÅMo Kα radiation
b = 9.5875 (2) ŵ = 1.39 mm−1
c = 15.7529 (3) ÅT = 150 K
α = 82.2873 (10)°0.33 × 0.27 × 0.12 mm
β = 89.4928 (9)°
Data collection top
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 = 0.84Rint = 0.038
19960 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.030All H-atom parameters refined
wR(F2) = 0.077Δρmax = 1.02 e Å−3
S = 1.03Δρmin = −0.37 e Å−3
3872 reflectionsAbsolute structure: ?
286 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.50000.50000.50000.01673 (9)
Fe20.20709 (4)1.07610 (3)0.274313 (16)0.02367 (9)
P10.56465 (7)0.70824 (5)0.31173 (3)0.02101 (11)
C10.4763 (3)0.55601 (19)0.36935 (11)0.0191 (3)
C20.6404 (3)0.4122 (2)0.39305 (11)0.0228 (4)
C30.5199 (4)0.3205 (2)0.43963 (12)0.0263 (4)
C40.2802 (4)0.4057 (2)0.44521 (12)0.0256 (4)
C50.2523 (3)0.5499 (2)0.40199 (11)0.0212 (3)
C60.3239 (3)0.86348 (19)0.33599 (11)0.0203 (3)
C70.0769 (3)0.9040 (2)0.31389 (12)0.0228 (4)
C8−0.0417 (3)1.0281 (2)0.35466 (13)0.0273 (4)
C90.1280 (4)1.0664 (2)0.40202 (13)0.0278 (4)
C100.3532 (3)0.9663 (2)0.39040 (12)0.0249 (4)
C110.2321 (7)1.0950 (4)0.14502 (16)0.0615 (9)
C120.0377 (6)1.2089 (5)0.1681 (2)0.0776 (14)
C130.1247 (5)1.2925 (3)0.2200 (2)0.0550 (8)
C140.3699 (4)1.2309 (3)0.22715 (15)0.0399 (5)
C150.4347 (5)1.1115 (3)0.18153 (15)0.0432 (6)
C160.4953 (3)0.6923 (2)0.20074 (12)0.0266 (4)
C170.6397 (4)0.7335 (3)0.13786 (15)0.0407 (5)
C180.5986 (5)0.7260 (3)0.05218 (15)0.0544 (7)
C190.4187 (5)0.6751 (4)0.02877 (15)0.0565 (7)
C200.2766 (5)0.6306 (3)0.09029 (16)0.0495 (6)
C210.3154 (4)0.6396 (3)0.17618 (14)0.0344 (4)
H20.800 (4)0.391 (2)0.3808 (14)0.028 (6)*
H30.583 (4)0.225 (3)0.4641 (14)0.030 (6)*
H40.164 (5)0.376 (3)0.4752 (17)0.044 (7)*
H50.113 (4)0.623 (2)0.3968 (14)0.023 (5)*
H70.002 (4)0.857 (3)0.2789 (15)0.033 (6)*
H8−0.208 (4)1.077 (3)0.3502 (14)0.031 (6)*
H90.095 (4)1.144 (3)0.4345 (16)0.039 (7)*
H100.495 (4)0.967 (3)0.4117 (15)0.033 (6)*
H110.220 (7)1.020 (5)0.113 (3)0.098 (13)*
H12−0.091 (8)1.212 (5)0.154 (3)0.104 (14)*
H130.035 (6)1.375 (4)0.244 (2)0.081 (11)*
H140.478 (6)1.267 (4)0.254 (2)0.072 (10)*
H150.595 (6)1.038 (4)0.176 (2)0.067 (9)*
H170.766 (5)0.776 (3)0.1540 (18)0.052 (8)*
H180.695 (6)0.755 (4)0.011 (2)0.067 (9)*
H190.400 (5)0.668 (3)−0.030 (2)0.061 (8)*
H200.168 (5)0.591 (3)0.0761 (19)0.055 (8)*
H210.218 (5)0.613 (3)0.2145 (16)0.039 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.01851 (16)0.01506 (16)0.01460 (16)−0.00259 (12)0.00126 (12)−0.00050 (12)
Fe20.02421 (14)0.02186 (14)0.02401 (15)−0.00941 (10)−0.00277 (10)0.00620 (10)
P10.0170 (2)0.0244 (2)0.0203 (2)−0.00623 (17)0.00241 (16)0.00201 (17)
C10.0195 (8)0.0214 (8)0.0148 (7)−0.0042 (6)0.0009 (6)−0.0006 (6)
C20.0256 (9)0.0219 (8)0.0170 (8)−0.0006 (7)0.0021 (6)−0.0037 (6)
C30.0406 (10)0.0168 (8)0.0198 (8)−0.0057 (7)0.0008 (7)−0.0036 (7)
C40.0331 (10)0.0272 (9)0.0206 (9)−0.0155 (8)0.0021 (7)−0.0032 (7)
C50.0200 (8)0.0247 (9)0.0180 (8)−0.0067 (7)−0.0008 (6)−0.0001 (7)
C60.0217 (8)0.0196 (8)0.0193 (8)−0.0086 (6)0.0009 (6)0.0037 (6)
C70.0198 (8)0.0216 (8)0.0279 (9)−0.0091 (7)0.0008 (7)0.0006 (7)
C80.0252 (9)0.0220 (9)0.0327 (10)−0.0058 (7)0.0063 (7)0.0006 (7)
C90.0390 (11)0.0174 (8)0.0260 (9)−0.0081 (8)0.0020 (8)0.0002 (7)
C100.0306 (9)0.0233 (9)0.0220 (9)−0.0132 (7)−0.0034 (7)0.0049 (7)
C110.108 (3)0.0676 (19)0.0234 (12)−0.056 (2)−0.0078 (14)0.0117 (12)
C120.0470 (16)0.108 (3)0.070 (2)−0.0461 (19)−0.0363 (16)0.071 (2)
C130.0535 (15)0.0282 (12)0.0658 (18)0.0009 (11)0.0197 (13)0.0238 (12)
C140.0469 (13)0.0370 (12)0.0384 (12)−0.0247 (10)−0.0026 (10)0.0136 (9)
C150.0476 (13)0.0394 (12)0.0373 (12)−0.0126 (10)0.0127 (10)0.0117 (10)
C160.0285 (9)0.0273 (9)0.0196 (8)−0.0034 (7)0.0033 (7)0.0008 (7)
C170.0423 (12)0.0495 (13)0.0285 (11)−0.0136 (11)0.0112 (9)0.0006 (9)
C180.0616 (17)0.0714 (19)0.0244 (11)−0.0150 (14)0.0148 (11)0.0022 (11)
C190.0667 (18)0.0726 (19)0.0197 (11)−0.0037 (14)−0.0004 (11)−0.0081 (11)
C200.0539 (15)0.0633 (17)0.0326 (12)−0.0153 (13)−0.0045 (11)−0.0149 (11)
C210.0379 (11)0.0407 (12)0.0255 (10)−0.0122 (9)0.0043 (8)−0.0063 (8)
Geometric parameters (Å, °) top
Fe1—C22.0451 (17)C7—C81.423 (3)
Fe1—C42.0460 (19)C7—H70.94 (2)
Fe1—C32.0487 (18)C8—C91.418 (3)
Fe1—C52.0488 (17)C8—H80.96 (2)
Fe1—C12.0513 (16)C9—C101.422 (3)
Fe2—C112.028 (3)C9—H90.93 (3)
Fe2—C122.032 (2)C10—H100.91 (2)
Fe2—C102.0433 (18)C11—C151.396 (4)
Fe2—C72.0435 (18)C11—C121.418 (5)
Fe2—C152.044 (2)C11—H110.95 (4)
Fe2—C82.0502 (19)C12—C131.416 (5)
Fe2—C132.051 (2)C12—H120.79 (4)
Fe2—C142.055 (2)C13—C141.398 (4)
Fe2—C62.0556 (17)C13—H130.94 (4)
Fe2—C92.058 (2)C14—C151.389 (4)
P1—C61.8130 (18)C14—H140.94 (3)
P1—C11.8210 (18)C15—H151.01 (3)
P1—C161.8361 (19)C16—C211.386 (3)
C1—C51.435 (2)C16—C171.397 (3)
C1—C21.436 (2)C17—C181.389 (3)
C2—C31.418 (3)C17—H171.00 (3)
C2—H20.93 (2)C18—C191.370 (4)
C3—C41.423 (3)C18—H180.93 (3)
C3—H30.91 (2)C19—C201.385 (4)
C4—C51.420 (3)C19—H190.94 (3)
C4—H40.93 (3)C20—C211.393 (3)
C5—H50.91 (2)C20—H200.88 (3)
C6—C71.434 (2)C21—H210.90 (3)
C6—C101.438 (3)
C2i—Fe1—C2179.999 (1)C2—C3—Fe169.60 (10)
C2i—Fe1—C4111.69 (8)C4—C3—Fe169.56 (10)
C2—Fe1—C468.31 (8)C2—C3—H3127.2 (15)
C2—Fe1—C4i111.69 (8)C4—C3—H3124.8 (15)
C4—Fe1—C4i179.998 (1)Fe1—C3—H3124.4 (14)
C2i—Fe1—C3139.47 (8)C5—C4—C3108.31 (16)
C2—Fe1—C340.53 (8)C5—C4—Fe169.82 (10)
C4—Fe1—C340.69 (8)C3—C4—Fe169.76 (11)
C4i—Fe1—C3139.32 (8)C5—C4—H4125.1 (17)
C2—Fe1—C3i139.47 (8)C3—C4—H4126.4 (17)
C4—Fe1—C3i139.31 (8)Fe1—C4—H4122.7 (16)
C3—Fe1—C3i180.00 (8)C4—C5—C1108.37 (16)
C2i—Fe1—C5111.48 (7)C4—C5—Fe169.60 (10)
C2—Fe1—C568.51 (7)C1—C5—Fe169.61 (9)
C4—Fe1—C540.58 (7)C4—C5—H5123.9 (14)
C4i—Fe1—C5139.42 (7)C1—C5—H5127.7 (14)
C3—Fe1—C568.46 (7)Fe1—C5—H5126.8 (14)
C3i—Fe1—C5111.54 (7)C7—C6—C10106.61 (16)
C2—Fe1—C5i111.49 (7)C7—C6—P1130.23 (14)
C4—Fe1—C5i139.42 (7)C10—C6—P1123.00 (13)
C3—Fe1—C5i111.54 (7)C7—C6—Fe269.07 (10)
C5—Fe1—C5i179.998 (2)C10—C6—Fe269.00 (10)
C2—Fe1—C1i138.95 (7)P1—C6—Fe2130.26 (9)
C4—Fe1—C1i111.19 (7)C8—C7—C6108.44 (16)
C3—Fe1—C1i111.09 (7)C8—C7—Fe269.91 (11)
C5—Fe1—C1i139.03 (7)C6—C7—Fe269.98 (10)
C2i—Fe1—C1138.95 (7)C8—C7—H7124.7 (15)
C2—Fe1—C141.05 (7)C6—C7—H7126.8 (15)
C4—Fe1—C168.81 (7)Fe2—C7—H7126.3 (14)
C4i—Fe1—C1111.19 (7)C9—C8—C7108.42 (17)
C3—Fe1—C168.90 (7)C9—C8—Fe270.10 (11)
C3i—Fe1—C1111.10 (7)C7—C8—Fe269.40 (10)
C5—Fe1—C140.97 (7)C9—C8—H8126.3 (14)
C5i—Fe1—C1139.03 (7)C7—C8—H8125.3 (14)
C1i—Fe1—C1180.00 (10)Fe2—C8—H8125.9 (14)
C11—Fe2—C1240.86 (16)C8—C9—C10107.81 (17)
C11—Fe2—C10146.78 (13)C8—C9—Fe269.52 (11)
C12—Fe2—C10171.90 (15)C10—C9—Fe269.16 (11)
C11—Fe2—C7108.50 (10)C8—C9—H9125.1 (15)
C12—Fe2—C7113.95 (11)C10—C9—H9127.1 (16)
C10—Fe2—C768.58 (7)Fe2—C9—H9126.5 (15)
C11—Fe2—C1540.11 (12)C9—C10—C6108.72 (17)
C12—Fe2—C1567.42 (12)C9—C10—Fe270.26 (11)
C10—Fe2—C15116.96 (9)C6—C10—Fe269.93 (10)
C7—Fe2—C15133.60 (9)C9—C10—H10126.9 (15)
C11—Fe2—C8132.21 (11)C6—C10—H10124.3 (15)
C12—Fe2—C8108.31 (11)Fe2—C10—H10124.2 (15)
C10—Fe2—C868.20 (8)C15—C11—C12107.0 (3)
C7—Fe2—C840.68 (7)C15—C11—Fe270.54 (14)
C15—Fe2—C8171.86 (10)C12—C11—Fe269.72 (17)
C11—Fe2—C1368.42 (14)C15—C11—H11128 (3)
C12—Fe2—C1340.56 (15)C12—C11—H11125 (3)
C10—Fe2—C13133.29 (12)Fe2—C11—H11122 (2)
C7—Fe2—C13145.35 (10)C13—C12—C11108.1 (2)
C15—Fe2—C1367.20 (10)C13—C12—Fe270.44 (14)
C8—Fe2—C13114.51 (9)C11—C12—Fe269.42 (15)
C11—Fe2—C1467.45 (11)C13—C12—H12133 (3)
C12—Fe2—C1467.22 (11)C11—C12—H12119 (3)
C10—Fe2—C14111.30 (9)Fe2—C12—H12123 (3)
C7—Fe2—C14172.87 (9)C14—C13—C12107.1 (3)
C15—Fe2—C1439.63 (10)C14—C13—Fe270.26 (13)
C8—Fe2—C14146.35 (10)C12—C13—Fe269.01 (15)
C13—Fe2—C1439.80 (10)C14—C13—H13126 (2)
C11—Fe2—C6114.47 (11)C12—C13—H13127 (2)
C12—Fe2—C6145.58 (14)Fe2—C13—H13127 (2)
C10—Fe2—C641.07 (7)C15—C14—C13108.8 (2)
C7—Fe2—C640.94 (7)C15—C14—Fe269.74 (13)
C15—Fe2—C6110.53 (9)C13—C14—Fe269.94 (13)
C8—Fe2—C668.73 (7)C15—C14—H14124 (2)
C13—Fe2—C6173.03 (11)C13—C14—H14127 (2)
C14—Fe2—C6134.39 (8)Fe2—C14—H14130 (2)
C11—Fe2—C9171.42 (13)C14—C15—C11109.0 (3)
C12—Fe2—C9132.17 (14)C14—C15—Fe270.64 (13)
C10—Fe2—C940.59 (8)C11—C15—Fe269.35 (15)
C7—Fe2—C968.37 (8)C14—C15—H15130.1 (19)
C15—Fe2—C9147.56 (10)C11—C15—H15120.8 (19)
C8—Fe2—C940.37 (8)Fe2—C15—H15122.5 (18)
C13—Fe2—C9109.29 (10)C21—C16—C17118.7 (2)
C14—Fe2—C9116.51 (9)C21—C16—P1124.65 (15)
C6—Fe2—C968.82 (7)C17—C16—P1116.63 (17)
C6—P1—C1100.46 (8)C18—C17—C16120.4 (2)
C6—P1—C16103.22 (8)C18—C17—H17119.5 (16)
C1—P1—C16100.66 (9)C16—C17—H17119.9 (16)
C5—C1—C2106.76 (15)C19—C18—C17120.2 (2)
C5—C1—P1130.84 (13)C19—C18—H18120 (2)
C2—C1—P1122.37 (13)C17—C18—H18119 (2)
C5—C1—Fe169.42 (9)C18—C19—C20120.3 (2)
C2—C1—Fe169.24 (10)C18—C19—H19117.6 (19)
P1—C1—Fe1124.65 (9)C20—C19—H19122.0 (19)
C3—C2—C1108.69 (16)C19—C20—C21119.7 (3)
C3—C2—Fe169.87 (10)C19—C20—H20121 (2)
C1—C2—Fe169.71 (10)C21—C20—H20120 (2)
C3—C2—H2129.3 (14)C16—C21—C20120.6 (2)
C1—C2—H2121.9 (14)C16—C21—H21121.5 (16)
Fe1—C2—H2123.4 (14)C20—C21—H21117.8 (16)
C2—C3—C4107.86 (16)
C6—P1—C1—C517.63 (18)C6—C7—C8—Fe259.60 (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—C294.14 (15)C10—Fe2—C8—C937.60 (11)
C6—P1—C1—Fe1−74.25 (11)C7—Fe2—C8—C9119.67 (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—C5118.15 (15)C6—Fe2—C8—C981.91 (12)
C4—Fe1—C1—C537.26 (11)C11—Fe2—C8—C766.55 (19)
C4i—Fe1—C1—C5−142.74 (11)C12—Fe2—C8—C7105.71 (18)
C3—Fe1—C1—C581.03 (11)C10—Fe2—C8—C7−82.07 (12)
C3i—Fe1—C1—C5−98.97 (11)C13—Fe2—C8—C7148.94 (15)
C5i—Fe1—C1—C5180.001 (1)C14—Fe2—C8—C7−178.10 (14)
C2i—Fe1—C1—C2180.0C6—Fe2—C8—C7−37.76 (11)
C4—Fe1—C1—C2−80.89 (12)C9—Fe2—C8—C7−119.67 (16)
C4i—Fe1—C1—C299.11 (12)C7—C8—C9—C100.3 (2)
C3—Fe1—C1—C2−37.12 (11)Fe2—C8—C9—C10−58.74 (13)
C3i—Fe1—C1—C2142.88 (11)C7—C8—C9—Fe259.01 (13)
C5—Fe1—C1—C2−118.15 (15)C12—Fe2—C9—C865.74 (18)
C5i—Fe1—C1—C261.85 (15)C10—Fe2—C9—C8−119.45 (16)
C2i—Fe1—C1—P164.28 (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—P1163.39 (13)C13—Fe2—C9—C8105.48 (14)
C4i—Fe1—C1—P1−16.61 (13)C14—Fe2—C9—C8148.16 (12)
C3—Fe1—C1—P1−152.84 (13)C6—Fe2—C9—C8−81.67 (11)
C3i—Fe1—C1—P127.16 (13)C12—Fe2—C9—C10−174.81 (16)
C5—Fe1—C1—P1126.13 (16)C7—Fe2—C9—C1081.90 (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—C10119.45 (16)
P1—C1—C2—C3177.83 (13)C13—Fe2—C9—C10−135.08 (13)
Fe1—C1—C2—C359.17 (13)C14—Fe2—C9—C10−92.39 (13)
C5—C1—C2—Fe1−59.56 (12)C6—Fe2—C9—C1037.78 (11)
P1—C1—C2—Fe1118.66 (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—C3142.24 (11)C8—C9—C10—Fe258.96 (13)
C3i—Fe1—C2—C3180.0C7—C6—C10—C90.7 (2)
C5—Fe1—C2—C3−81.56 (12)P1—C6—C10—C9−175.06 (13)
C5i—Fe1—C2—C398.44 (12)Fe2—C6—C10—C959.77 (13)
C1i—Fe1—C2—C360.03 (16)C7—C6—C10—Fe2−59.09 (12)
C1—Fe1—C2—C3−119.97 (16)P1—C6—C10—Fe2125.17 (13)
C4—Fe1—C2—C182.20 (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—C1119.97 (16)C15—Fe2—C10—C9149.51 (13)
C3i—Fe1—C2—C1−60.03 (16)C8—Fe2—C10—C9−37.41 (11)
C5—Fe1—C2—C138.41 (10)C13—Fe2—C10—C966.30 (16)
C5i—Fe1—C2—C1−141.59 (10)C14—Fe2—C10—C9106.33 (13)
C1i—Fe1—C2—C1179.999 (2)C6—Fe2—C10—C9−119.61 (15)
C1—C2—C3—C40.2 (2)C11—Fe2—C10—C6−53.0 (2)
Fe1—C2—C3—C459.24 (13)C7—Fe2—C10—C638.29 (10)
C1—C2—C3—Fe1−59.07 (12)C15—Fe2—C10—C6−90.88 (13)
C2i—Fe1—C3—C2179.999 (1)C8—Fe2—C10—C682.20 (11)
C4—Fe1—C3—C2119.20 (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—C281.70 (11)C9—Fe2—C10—C6119.61 (15)
C5i—Fe1—C3—C2−98.30 (11)C12—Fe2—C11—C15117.5 (3)
C1i—Fe1—C3—C2−142.42 (10)C10—Fe2—C11—C15−58.1 (3)
C1—Fe1—C3—C237.58 (10)C7—Fe2—C11—C15−137.02 (16)
C2i—Fe1—C3—C460.80 (15)C8—Fe2—C11—C15−176.11 (13)
C2—Fe1—C3—C4−119.20 (15)C13—Fe2—C11—C1579.80 (18)
C4i—Fe1—C3—C4180.0C14—Fe2—C11—C1536.72 (16)
C5—Fe1—C3—C4−37.50 (11)C6—Fe2—C11—C15−93.31 (17)
C5i—Fe1—C3—C4142.50 (11)C10—Fe2—C11—C12−175.56 (17)
C1i—Fe1—C3—C498.37 (11)C7—Fe2—C11—C12105.51 (18)
C1—Fe1—C3—C4−81.63 (11)C15—Fe2—C11—C12−117.5 (2)
C2—C3—C4—C50.1 (2)C8—Fe2—C11—C1266.4 (2)
Fe1—C3—C4—C559.38 (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—C598.14 (11)C6—Fe2—C11—C12149.22 (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—C1360.05 (18)
C3i—Fe1—C4—C560.51 (15)C15—C11—C12—Fe2−61.02 (16)
C5i—Fe1—C4—C5180.0C11—Fe2—C12—C13−119.1 (2)
C1i—Fe1—C4—C5142.39 (10)C7—Fe2—C12—C13149.94 (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—C13106.57 (17)
C2—Fe1—C4—C337.63 (11)C14—Fe2—C12—C13−37.72 (16)
C3i—Fe1—C4—C3180.000 (1)C6—Fe2—C12—C13−174.55 (14)
C5—Fe1—C4—C3119.49 (15)C9—Fe2—C12—C1368.1 (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—C1138.24 (17)
C1—Fe1—C4—C381.89 (11)C8—Fe2—C12—C11−134.35 (16)
C3—C4—C5—C1−0.4 (2)C13—Fe2—C12—C11119.1 (2)
Fe1—C4—C5—C158.99 (12)C14—Fe2—C12—C1181.35 (18)
C3—C4—C5—Fe1−59.34 (13)C6—Fe2—C12—C11−55.5 (2)
C2—C1—C5—C40.5 (2)C9—Fe2—C12—C11−172.82 (15)
P1—C1—C5—C4−177.56 (14)C11—C12—C13—C140.8 (3)
Fe1—C1—C5—C4−58.99 (12)Fe2—C12—C13—C1460.23 (17)
C2—C1—C5—Fe159.44 (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—C481.31 (12)C10—Fe2—C13—C1469.4 (2)
C4i—Fe1—C5—C4180.0C7—Fe2—C13—C14−171.83 (15)
C3—Fe1—C5—C437.59 (11)C15—Fe2—C13—C14−36.79 (16)
C3i—Fe1—C5—C4−142.41 (11)C8—Fe2—C13—C14151.90 (15)
C1i—Fe1—C5—C4−60.20 (15)C9—Fe2—C13—C14108.58 (17)
C1—Fe1—C5—C4119.80 (15)C11—Fe2—C13—C1237.9 (2)
C2i—Fe1—C5—C1141.51 (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—C1281.4 (2)
C4i—Fe1—C5—C160.20 (15)C8—Fe2—C13—C12−89.9 (2)
C3—Fe1—C5—C1−82.21 (11)C14—Fe2—C13—C12118.2 (3)
C3i—Fe1—C5—C197.79 (11)C9—Fe2—C13—C12−133.23 (19)
C1i—Fe1—C5—C1180.0C12—C13—C14—C15−0.3 (3)
C1—P1—C6—C7−63.73 (17)Fe2—C13—C14—C1559.08 (16)
C16—P1—C6—C739.95 (18)C12—C13—C14—Fe2−59.43 (16)
C1—P1—C6—C10110.91 (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—C15106.98 (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—C1565.63 (19)
C10—Fe2—C6—C7118.33 (15)C9—Fe2—C14—C15151.22 (14)
C15—Fe2—C6—C7−133.79 (13)C11—Fe2—C14—C1382.9 (2)
C8—Fe2—C6—C737.53 (11)C12—Fe2—C14—C1338.4 (2)
C14—Fe2—C6—C7−172.13 (13)C10—Fe2—C14—C13−132.98 (18)
C9—Fe2—C6—C780.98 (12)C15—Fe2—C14—C13120.0 (2)
C11—Fe2—C6—C10151.25 (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—C10107.88 (13)C13—C14—C15—C11−0.3 (3)
C8—Fe2—C6—C10−80.80 (12)Fe2—C14—C15—C1158.94 (16)
C14—Fe2—C6—C1069.54 (16)C13—C14—C15—Fe2−59.21 (16)
C9—Fe2—C6—C10−37.34 (11)C12—C11—C15—C140.8 (3)
C11—Fe2—C6—P135.19 (17)Fe2—C11—C15—C14−59.73 (16)
C12—Fe2—C6—P171.5 (2)C12—C11—C15—Fe260.49 (17)
C10—Fe2—C6—P1−116.07 (17)C11—Fe2—C15—C14120.0 (2)
C7—Fe2—C6—P1125.61 (18)C12—Fe2—C15—C1481.1 (2)
C15—Fe2—C6—P1−8.18 (16)C10—Fe2—C15—C14−91.42 (15)
C8—Fe2—C6—P1163.13 (15)C7—Fe2—C15—C14−176.75 (12)
C14—Fe2—C6—P1−46.52 (19)C13—Fe2—C15—C1436.94 (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—C8174.81 (14)C12—Fe2—C15—C11−39.0 (2)
Fe2—C6—C7—C8−59.55 (13)C10—Fe2—C15—C11148.55 (18)
C10—C6—C7—Fe259.04 (12)C7—Fe2—C15—C1163.2 (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—C11104.01 (19)
C10—Fe2—C7—C881.05 (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—C2130.64 (19)
C6—Fe2—C7—C8119.45 (16)C6—P1—C16—C17108.67 (17)
C9—Fe2—C7—C837.27 (11)C1—P1—C16—C17−147.80 (17)
C11—Fe2—C7—C6106.32 (16)C21—C16—C17—C182.0 (3)
C12—Fe2—C7—C6149.93 (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—C668.98 (16)C17—C18—C19—C20−0.1 (5)
C8—Fe2—C7—C6−119.45 (16)C18—C19—C20—C210.8 (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—C90.1 (2)C19—C20—C21—C16−0.2 (4)
Fe2—C7—C8—C9−59.45 (13)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Fe1—C22.0451 (17)Fe2—C152.044 (2)
Fe1—C42.0460 (19)Fe2—C82.0502 (19)
Fe1—C32.0487 (18)Fe2—C132.051 (2)
Fe1—C52.0488 (17)Fe2—C142.055 (2)
Fe1—C12.0513 (16)Fe2—C62.0556 (17)
Fe2—C112.028 (3)Fe2—C92.058 (2)
Fe2—C122.032 (2)P1—C61.8130 (18)
Fe2—C102.0433 (18)P1—C11.8210 (18)
Fe2—C72.0435 (18)P1—C161.8361 (19)
C6—P1—C1100.46 (8)C1—P1—C16100.66 (9)
C6—P1—C16103.22 (8)
Acknowledgements top

This work was supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO) (ML and ALS). Crystals were kindly supplied by Professor Piet W. N. M. van Leeuwen and Dr Ulrike Nettekoven, University of Amsterdam, The Netherlands.

references
References top

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