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Acta Cryst. (2007). E63, m2499-m2500    [ doi:10.1107/S160053680704305X ]

(S,S,Rp)-(+)-2-{1-[1-(2-Diphenylphosphinoferrocenyl)ethyl]pyrrolidin-2-yl}propan-2-ol

J.-T. Liu, Y.-J. Mao, R.-M. Xi and W.-L. Dong

Abstract top

The title compound, [Fe(C5H5)(C26H31NOP)], contains one planar and two central chiral centers. It is of interest with respect to asymmetric catalysis. In the ferrocenyl moiety, the cyclopentadienyl (Cp) rings are twisted from the eclipsed conformation by 15.83° (average value). The two Cp rings make a dihedral angle of 5.24 (10)°. There are intramolecular O-H...N, C-H...P and C-H...[pi] hydrogen bonds. The structure is packed by one prominent and other weak C-H...[pi] contacts and hydrophobic interactions.

Comment top

The application of ferrocenyl ligands possessing planar chirality in asymmetric catalysis has received considerable interest (Dai et al., 2003). Ferrocenyl ligands with planar and central chirality have shown efficiency as ligands for catalytic asymmetric synthesis both in research and industrial processes (Togni, 1996). The molecule of the title compound contains one planar and two central chiral centers (I) (Scheme 1).

The X-ray structure analysis of the title compound (Figure 2) proves the absolute configuration shown in Scheme 1. The diastereomeric ferrocenyl ligand (I) was prepared from enantiopure (S, Rp)-1-(2-diphenylphosphinoferrocenyl)ethyl acetate by replacement of the acetoxy group by (S)-2-(pyrrolidine-2-yl)propane-2-ol with retention of the configuration on the α-carbon atom.

In the ferrocenyl moiety, the cyclopentadienyl (Cp) rings are twisted from the eclipsed conformation·The values of the torsion angles defined with C atoms of Cp rings in opposite position and ring centroids (C– Cg3- Cg4- C) are in the range 15.20- 16.63° (Table 1)·The rings are nearly parallel with dihedral angle of 5.24°between the two best planes.

The pyrrolidine ring adopts an envelope conformation. The methylene group is inclined to the atoms defining the planar part of the five member ring by 40.71° or 38.36°.

The structure has intramolecular hydrogen bonds such as O1—H1A···N1, C11—H11···P1 and C16—H16···P1 (Table 2). Furthermore, there is one intramoleculear C—H···π contact C1—H1···Cg6 with distances C1···Cg6 3.66 (3) Å, angle around H1 131 °, and Cg6 is the centroid (centre of gravity) of the π-ring system C26 to C31 (Table 3).

The intermolecular C–H···π contact which connects molecules is C30—H30···Cg3 with distances C30···Cg3 3.864 (3) Å, angle around H30 165 °. The symmetry operation of the intermolecular contact for Cg3 is (−1/2 + x, 1/2 − y, 1 − z), which represents a 21 axis helical chain as shown in Table 3 and Fig. 3.

Related literature top

For related literature, see: Dai et al. (2003); Togni (1996).

Experimental top

(S)- 2-(pyrrolidine-2-yl)propane-2-ol(0.645 g, 5 mmol) and (S, Rp)-1-(2-diphenylphosphinoferrocenyl)ethyl acetate(0.228 g, 0.5 mmol) were dissolved in methanol(3 mL) and the reaction mixture was gently refluxed in an oil bath heated to 347–352 K under N2-atmosphere for 7 h (Fig. 1). The solvent was evaporated in vacuo and the residue was purified by chromatography on Al2O3-column with ethyl acetate–petroleum ether(1:20) as eluent. The title compound (0.234 g, 89%) was obtained as a yellow solid, mp 439.7- 440.2 K. Crystals suitable for X-ray diffraction analysis were grown from cyclohexane- DCM (20:1) solution at 277 K. Spectroscopic analysis: 1H NMR (300 MHz, CDCl3, TMS p.p.m.): d 0.607 (s, 3H), 0.750 (m, 1H), 0.938(m, 1H), 1.119(s, 3H), 1.135(m, 1H), 1.283(m, 1H), 1.639(d, 3H), 2.584(m, 2H), 2.734(m, 1H), 3.833(s, 5H), 4.208(m, 1H), 4.211(m, 1H), 4.439(m, 1H), 4.512(m, 1H), 7.218–7.767(m, 10H).

Refinement top

All H atoms were placed in geometrically calculated positions(C—H = 0.93–0.98 Å and O—H = 0.82 Å) and refined using a riding model, their isotropic displacement parameters were set to 1.2 times (1.5 times for CH3 groups) the equivalent displacement parameter of their parent atoms.

The pyrrolidine ring shows positional disorder of atom C14. The flipping of H atoms at C13 and C15 were also considered in the refinement. The final site occupatio ratio of the related atoms was 0.6:0.4.

The absolute configuration of the structure of the crystal could be determined reliably; the Flack parameter (Flack, 1983) was refined using 2685 Friedel opposite reflections.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Reaction scheme.
[Figure 2] Fig. 2. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level and H atoms omitted.
[Figure 3] Fig. 3. View of the structure along the a axis. H atoms were omitted for clarity except those which were involved with X—H···Cg(π-ring) interactions.
(S,S,Rp)-(+)-2-{1-[1-(2-diphenylphosphino ferrocenyl)ethyl]pyrrolidin-2-yl}propan-2-ol top
Crystal data top
[Fe(C5H5)(C26H31NOP)]Dx = 1.300 Mg m−3
Mr = 525.43Melting point: 440.0 K
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
a = 10.1102 (4) ÅCell parameters from 5318 reflections
b = 13.6587 (5) Åθ = 2.3–26.6º
c = 19.4363 (8) ŵ = 0.65 mm−1
V = 2684.00 (18) Å3T = 293 (2) K
Z = 4Prism, yellow
F000 = 11120.31 × 0.25 × 0.17 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6152 independent reflections
Radiation source: fine-focus sealed tube5154 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 293(2) Kθmax = 27.5º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(APEX2; Bruker, 2005)		h = −13→12
Tmin = 0.825, Tmax = 0.898k = −17→16
16205 measured reflectionsl = −24→25
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033  w = 1/[σ2(Fo2) + (0.0576P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.088(Δ/σ)max = 0.001
S = 0.92Δρmax = 0.28 e Å−3
6152 reflectionsΔρmin = −0.14 e Å−3
330 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack, 1983
Secondary atom site location: difference Fourier mapFlack parameter: 0.022 (12)
Crystal data top
[Fe(C5H5)(C26H31NOP)]V = 2684.00 (18) Å3
Mr = 525.43Z = 4
Orthorhombic, P212121Mo Kα
a = 10.1102 (4) ŵ = 0.65 mm−1
b = 13.6587 (5) ÅT = 293 (2) K
c = 19.4363 (8) Å0.31 × 0.25 × 0.17 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6152 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2005)		5154 reflections with I > 2σ(I)
Tmin = 0.825, Tmax = 0.898Rint = 0.026
16205 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.088Δρmax = 0.28 e Å−3
S = 0.92Δρmin = −0.14 e Å−3
6152 reflectionsAbsolute structure: Flack, 1983
330 parametersFlack parameter: 0.022 (12)
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 F2 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.3621 (3)0.4260 (2)0.54550 (16)0.0660 (8)
H10.26590.42980.55140.079*
C20.4284 (3)0.38314 (16)0.49015 (16)0.0586 (7)
H20.38650.35250.45010.070*
C30.5653 (3)0.39228 (16)0.50107 (16)0.0561 (6)
H30.63520.36890.47030.067*
C40.5839 (3)0.44111 (18)0.56433 (14)0.0610 (7)
H40.66920.45740.58530.073*
C50.4588 (3)0.4623 (2)0.59210 (14)0.0711 (8)
H50.44140.49520.63600.085*
C60.4875 (3)0.67342 (16)0.52054 (11)0.0493 (6)
H60.49750.70210.56650.059*
C70.3657 (2)0.65036 (14)0.48780 (11)0.0425 (5)
H70.27720.66050.50710.051*
C80.3952 (2)0.60983 (14)0.42156 (10)0.0353 (4)
C90.5380 (2)0.60872 (15)0.41390 (10)0.0387 (4)
C100.5916 (2)0.64693 (16)0.47607 (12)0.0470 (5)
H100.68600.65360.48640.056*
C110.6132 (2)0.58181 (15)0.34878 (11)0.0422 (5)
H110.55400.54090.32110.051*
C120.7380 (3)0.5216 (2)0.36188 (15)0.0698 (8)
H12A0.77860.50510.31870.105*
H12B0.71510.46260.38600.105*
H12C0.79880.55910.38920.105*
C160.5389 (2)0.71609 (15)0.27045 (12)0.0436 (5)
H160.45590.69660.29260.052*
C170.5344 (3)0.68590 (18)0.19393 (12)0.0514 (6)
C180.5072 (4)0.57731 (19)0.18663 (13)0.0742 (9)
H18A0.49850.56110.13880.111*
H18B0.42670.56120.21030.111*
H18C0.57910.54080.20620.111*
C190.4297 (3)0.7435 (3)0.15570 (15)0.0805 (9)
H19A0.45430.81140.15450.121*
H19B0.34630.73670.17880.121*
H19C0.42210.71900.10960.121*
C200.1972 (2)0.66731 (17)0.32383 (11)0.0423 (5)
C210.2223 (3)0.76359 (18)0.34252 (13)0.0503 (6)
H210.27990.77670.37860.060*
C220.1622 (3)0.8404 (2)0.30780 (15)0.0649 (8)
H220.18030.90470.32060.078*
C230.0764 (3)0.8222 (3)0.25479 (16)0.0727 (9)
H230.03690.87420.23170.087*
C240.0487 (3)0.7287 (3)0.23584 (17)0.0799 (9)
H24−0.01010.71650.20010.096*
C250.1085 (3)0.6517 (2)0.27006 (14)0.0647 (7)
H250.08900.58790.25680.078*
C260.1488 (2)0.50485 (16)0.41030 (11)0.0426 (5)
C270.0678 (2)0.55690 (18)0.45498 (12)0.0496 (5)
H270.07590.62460.45820.060*
C28−0.0248 (2)0.5084 (2)0.49475 (13)0.0632 (6)
H28−0.07710.54360.52540.076*
C29−0.0403 (3)0.4090 (2)0.48939 (15)0.0693 (8)
H29−0.10170.37670.51680.083*
C300.0356 (3)0.3577 (2)0.44329 (15)0.0668 (8)
H300.02310.29060.43840.080*
C310.1301 (3)0.40437 (18)0.40422 (13)0.0530 (6)
H310.18170.36850.37360.064*
Fe10.47849 (3)0.528215 (19)0.498686 (16)0.04009 (9)
N10.6497 (2)0.66738 (15)0.30560 (10)0.0468 (5)
P10.28173 (6)0.55894 (4)0.35818 (3)0.03890 (13)
O10.6585 (2)0.70818 (16)0.16220 (11)0.0733 (6)
H1A0.71720.67600.18050.110*
C130.7295 (3)0.7435 (2)0.34085 (17)0.0690 (9)0.606 (5)
H13A0.80570.76180.31340.083*0.606 (5)
H13B0.75960.72080.38550.083*0.606 (5)
C140.6346 (6)0.8288 (3)0.3484 (3)0.0771 (17)0.606 (5)
H14A0.57560.81950.38720.092*0.606 (5)
H14B0.68180.89010.35400.092*0.606 (5)
C150.5603 (3)0.82650 (19)0.28158 (16)0.0694 (8)0.606 (5)
H15A0.61200.85490.24460.083*0.606 (5)
H15B0.47670.86100.28520.083*0.606 (5)
C13'0.7295 (3)0.7435 (2)0.34085 (17)0.0690 (9)0.394 (5)
H13C0.82230.72550.34150.083*0.394 (5)
H13D0.69950.75270.38780.083*0.394 (5)
C14'0.7082 (10)0.8361 (6)0.2987 (5)0.084 (3)0.394 (5)
H14C0.76220.83650.25750.101*0.394 (5)
H14D0.72620.89460.32540.101*0.394 (5)
C15'0.5603 (3)0.82650 (19)0.28158 (16)0.0694 (8)0.394 (5)
H15C0.53850.86300.24030.083*0.394 (5)
H15D0.50630.85030.31930.083*0.394 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0695 (17)0.0564 (17)0.0721 (19)−0.0025 (14)0.0044 (15)0.0300 (14)
C20.0778 (16)0.0351 (11)0.0628 (17)−0.0028 (11)−0.0135 (14)0.0124 (12)
C30.0721 (15)0.0395 (11)0.0567 (14)0.0100 (10)−0.0116 (15)0.0056 (13)
C40.0739 (17)0.0536 (15)0.0556 (15)0.0058 (14)−0.0211 (13)0.0114 (12)
C50.108 (2)0.0671 (18)0.0387 (13)0.0085 (17)0.0035 (14)0.0204 (12)
C60.0722 (16)0.0385 (11)0.0372 (11)−0.0027 (11)−0.0073 (10)−0.0052 (8)
C70.0571 (13)0.0330 (10)0.0374 (12)0.0051 (9)−0.0019 (9)−0.0019 (8)
C80.0447 (11)0.0285 (10)0.0327 (10)0.0026 (8)−0.0033 (8)0.0026 (8)
C90.0459 (12)0.0325 (10)0.0375 (10)−0.0015 (9)−0.0036 (9)0.0022 (8)
C100.0512 (13)0.0432 (12)0.0466 (12)−0.0040 (10)−0.0085 (10)0.0017 (9)
C110.0443 (11)0.0427 (12)0.0396 (11)0.0020 (9)0.0002 (9)0.0017 (9)
C120.0602 (15)0.083 (2)0.0659 (17)0.0234 (15)0.0025 (13)0.0093 (16)
C160.0506 (12)0.0369 (11)0.0432 (11)−0.0014 (10)0.0082 (10)0.0040 (9)
C170.0657 (15)0.0491 (13)0.0394 (12)−0.0024 (12)0.0078 (11)0.0079 (10)
C180.128 (3)0.0558 (16)0.0388 (13)−0.0158 (18)0.0062 (16)−0.0057 (11)
C190.092 (2)0.095 (2)0.0543 (18)0.0138 (19)−0.0033 (16)0.0224 (16)
C200.0432 (12)0.0457 (13)0.0379 (11)0.0022 (10)0.0021 (9)0.0077 (9)
C210.0545 (14)0.0512 (14)0.0451 (14)0.0096 (13)0.0017 (11)0.0048 (10)
C220.0781 (19)0.0485 (16)0.0680 (18)0.0153 (15)0.0144 (15)0.0100 (13)
C230.0628 (17)0.084 (2)0.0714 (19)0.0225 (16)0.0024 (15)0.0325 (17)
C240.0631 (18)0.102 (3)0.075 (2)0.0004 (18)−0.0233 (15)0.0265 (19)
C250.0667 (17)0.0670 (17)0.0603 (16)−0.0095 (14)−0.0186 (13)0.0135 (13)
C260.0482 (12)0.0403 (12)0.0393 (11)−0.0042 (9)−0.0071 (9)0.0060 (9)
C270.0477 (12)0.0504 (13)0.0507 (13)0.0014 (11)−0.0006 (10)0.0061 (11)
C280.0494 (12)0.0930 (19)0.0472 (13)0.0017 (13)0.0017 (12)0.0107 (14)
C290.0616 (16)0.0818 (19)0.0646 (18)−0.0210 (14)−0.0123 (14)0.0327 (16)
C300.0746 (18)0.0529 (15)0.0729 (18)−0.0203 (15)−0.0180 (16)0.0186 (13)
C310.0616 (15)0.0445 (13)0.0528 (14)−0.0085 (12)−0.0131 (12)0.0020 (11)
Fe10.05131 (17)0.03507 (15)0.03388 (15)0.00183 (12)−0.00484 (15)0.00278 (13)
N10.0480 (11)0.0493 (12)0.0430 (10)−0.0080 (9)0.0028 (8)0.0024 (9)
P10.0447 (3)0.0374 (3)0.0345 (3)−0.0005 (2)−0.0015 (2)−0.0021 (2)
O10.0793 (13)0.0776 (14)0.0631 (13)−0.0072 (11)0.0299 (11)0.0018 (10)
C130.0708 (19)0.075 (2)0.0614 (19)−0.0344 (18)−0.0015 (14)0.0037 (14)
C140.110 (4)0.050 (3)0.071 (3)−0.029 (3)0.005 (3)−0.013 (2)
C150.093 (2)0.0421 (14)0.0734 (19)−0.0022 (15)0.0080 (16)−0.0028 (13)
C13'0.0708 (19)0.075 (2)0.0614 (19)−0.0344 (18)−0.0015 (14)0.0037 (14)
C14'0.098 (6)0.070 (5)0.083 (6)−0.045 (5)0.003 (5)−0.003 (4)
C15'0.093 (2)0.0421 (14)0.0734 (19)−0.0022 (15)0.0080 (16)−0.0028 (13)
Geometric parameters (Å, °) top
C1—C21.397 (4)C18—H18A0.96
C1—C51.422 (4)C18—H18B0.96
C1—Fe12.040 (3)C18—H18C0.96
C1—H10.98C19—H19A0.96
C2—C31.405 (4)C19—H19B0.96
C2—Fe12.052 (2)C19—H19C0.96
C2—H20.98C20—C211.388 (3)
C3—C41.411 (4)C20—C251.393 (3)
C3—Fe12.054 (2)C20—P11.835 (2)
C3—H30.98C21—C221.388 (4)
C4—C51.405 (4)C21—H210.93
C4—Fe12.044 (2)C22—C231.370 (4)
C4—H40.98C22—H220.93
C5—Fe12.037 (2)C23—C241.358 (5)
C5—H50.98C23—H230.93
C6—C101.409 (3)C24—C251.383 (4)
C6—C71.421 (3)C24—H240.93
C6—Fe12.030 (2)C25—H250.93
C6—H60.98C26—C271.389 (3)
C7—C81.433 (3)C26—C311.390 (3)
C7—Fe12.032 (2)C26—P11.838 (2)
C7—H70.98C27—C281.383 (3)
C8—C91.451 (3)C27—H270.93
C8—P11.821 (2)C28—C291.370 (4)
C8—Fe12.0491 (19)C28—H280.93
C9—C101.424 (3)C29—C301.373 (4)
C9—C111.522 (3)C29—H290.93
C9—Fe12.070 (2)C30—C311.377 (4)
C10—Fe12.032 (2)C30—H300.93
C10—H100.98C31—H310.93
C11—N11.485 (3)N1—C131.485 (3)
C11—C121.528 (3)O1—H1A0.82
C11—H110.98C13—C141.517 (6)
C12—H12A0.96C13—H13A0.97
C12—H12B0.96C13—H13B0.97
C12—H12C0.96C14—C151.500 (6)
C16—N11.471 (3)C14—H14A0.97
C16—C151.539 (3)C14—H14B0.97
C16—C171.544 (3)C15—H15A0.97
C16—H160.98C15—H15B0.97
C17—O11.430 (3)C14'—H14C0.97
C17—C191.514 (4)C14'—H14D0.97
C17—C181.515 (3)
C2—C1—C5107.8 (3)C23—C22—C21120.4 (3)
C2—C1—Fe170.51 (15)C23—C22—H22119.8
C5—C1—Fe169.46 (15)C21—C22—H22119.8
C2—C1—H1126.1C24—C23—C22120.3 (3)
C5—C1—H1126.1C24—C23—H23119.8
Fe1—C1—H1126.1C22—C23—H23119.8
C1—C2—C3108.6 (3)C23—C24—C25119.6 (3)
C1—C2—Fe169.57 (15)C23—C24—H24120.2
C3—C2—Fe170.07 (13)C25—C24—H24120.2
C1—C2—H2125.7C24—C25—C20121.7 (3)
C3—C2—H2125.7C24—C25—H25119.2
Fe1—C2—H2125.7C20—C25—H25119.2
C2—C3—C4107.7 (3)C27—C26—C31118.6 (2)
C2—C3—Fe169.90 (13)C27—C26—P1124.74 (17)
C4—C3—Fe169.47 (14)C31—C26—P1116.7 (2)
C2—C3—H3126.1C28—C27—C26120.2 (2)
C4—C3—H3126.1C28—C27—H27119.9
Fe1—C3—H3126.1C26—C27—H27119.9
C5—C4—C3108.2 (3)C29—C28—C27120.6 (3)
C5—C4—Fe169.57 (15)C29—C28—H28119.7
C3—C4—Fe170.24 (13)C27—C28—H28119.7
C5—C4—H4125.9C28—C29—C30119.5 (3)
C3—C4—H4125.9C28—C29—H29120.2
Fe1—C4—H4125.9C30—C29—H29120.2
C4—C5—C1107.6 (3)C29—C30—C31120.7 (3)
C4—C5—Fe170.15 (15)C29—C30—H30119.6
C1—C5—Fe169.71 (14)C31—C30—H30119.6
C4—C5—H5126.2C30—C31—C26120.3 (3)
C1—C5—H5126.2C30—C31—H31119.9
Fe1—C5—H5126.2C26—C31—H31119.9
C10—C6—C7108.38 (19)C6—Fe1—C740.96 (9)
C10—C6—Fe169.78 (13)C6—Fe1—C1040.58 (10)
C7—C6—Fe169.57 (12)C7—Fe1—C1068.77 (9)
C10—C6—H6125.8C6—Fe1—C5104.48 (11)
C7—C6—H6125.8C7—Fe1—C5113.65 (11)
Fe1—C6—H6125.8C10—Fe1—C5126.93 (12)
C6—C7—C8107.9 (2)C6—Fe1—C1126.94 (12)
C6—C7—Fe169.47 (12)C7—Fe1—C1106.53 (11)
C8—C7—Fe170.10 (11)C10—Fe1—C1165.25 (11)
C6—C7—H7126.0C5—Fe1—C140.82 (12)
C8—C7—H7126.0C6—Fe1—C4114.49 (10)
Fe1—C7—H7126.0C7—Fe1—C4146.66 (10)
C7—C8—C9107.64 (18)C10—Fe1—C4107.83 (11)
C7—C8—P1128.64 (17)C5—Fe1—C440.28 (12)
C9—C8—P1123.58 (15)C1—Fe1—C467.92 (12)
C7—C8—Fe168.79 (11)C6—Fe1—C868.91 (8)
C9—C8—Fe170.17 (11)C7—Fe1—C841.10 (8)
P1—C8—Fe1123.09 (10)C10—Fe1—C868.83 (9)
C10—C9—C8106.72 (19)C5—Fe1—C8148.50 (11)
C10—C9—C11127.2 (2)C1—Fe1—C8117.48 (10)
C8—C9—C11125.81 (18)C4—Fe1—C8170.91 (10)
C10—C9—Fe168.26 (12)C6—Fe1—C2166.26 (11)
C8—C9—Fe168.59 (11)C7—Fe1—C2130.26 (10)
C11—C9—Fe1132.76 (14)C10—Fe1—C2153.11 (11)
C6—C10—C9109.3 (2)C5—Fe1—C267.72 (12)
C6—C10—Fe169.64 (13)C1—Fe1—C239.92 (12)
C9—C10—Fe171.15 (12)C4—Fe1—C267.48 (11)
C6—C10—H10125.3C8—Fe1—C2111.40 (10)
C9—C10—H10125.3C6—Fe1—C3149.21 (10)
Fe1—C10—H10125.3C7—Fe1—C3169.83 (9)
N1—C11—C9113.82 (17)C10—Fe1—C3119.07 (11)
N1—C11—C12108.2 (2)C5—Fe1—C367.78 (12)
C9—C11—C12113.85 (19)C1—Fe1—C367.54 (12)
N1—C11—H11106.8C4—Fe1—C340.29 (11)
C9—C11—H11106.8C8—Fe1—C3133.14 (10)
C12—C11—H11106.8C2—Fe1—C340.03 (11)
C11—C12—H12A109.5C6—Fe1—C968.57 (9)
C11—C12—H12B109.5C7—Fe1—C969.14 (9)
H12A—C12—H12B109.5C10—Fe1—C940.59 (8)
C11—C12—H12C109.5C5—Fe1—C9166.64 (11)
H12A—C12—H12C109.5C1—Fe1—C9152.38 (11)
H12B—C12—H12C109.5C4—Fe1—C9130.89 (11)
N1—C16—C15105.7 (2)C8—Fe1—C941.25 (8)
N1—C16—C17110.43 (19)C2—Fe1—C9121.35 (10)
C15—C16—C17113.7 (2)C3—Fe1—C9111.96 (10)
N1—C16—H16109.0C16—N1—C13108.1 (2)
C15—C16—H16109.0C16—N1—C11115.44 (18)
C17—C16—H16109.0C13—N1—C11115.2 (2)
O1—C17—C19106.9 (2)C8—P1—C20103.40 (10)
O1—C17—C18109.1 (2)C8—P1—C26103.96 (10)
C19—C17—C18109.6 (3)C20—P1—C26100.60 (10)
O1—C17—C16109.4 (2)C17—O1—H1A109.5
C19—C17—C16110.8 (2)N1—C13—C14103.8 (3)
C18—C17—C16110.91 (18)N1—C13—H13A111.0
C17—C18—H18A109.5C14—C13—H13A111.0
C17—C18—H18B109.5N1—C13—H13B111.0
H18A—C18—H18B109.5C14—C13—H13B111.0
C17—C18—H18C109.5H13A—C13—H13B109.0
H18A—C18—H18C109.5C15—C14—C13102.5 (3)
H18B—C18—H18C109.5C15—C14—H14A111.3
C17—C19—H19A109.5C13—C14—H14A111.3
C17—C19—H19B109.5C15—C14—H14B111.3
H19A—C19—H19B109.5C13—C14—H14B111.3
C17—C19—H19C109.5H14A—C14—H14B109.2
H19A—C19—H19C109.5C14—C15—C16102.3 (3)
H19B—C19—H19C109.5C14—C15—H15A111.3
C21—C20—C25117.3 (2)C16—C15—H15A111.3
C21—C20—P1125.72 (19)C14—C15—H15B111.3
C25—C20—P1116.70 (19)C16—C15—H15B111.3
C20—C21—C22120.6 (3)H15A—C15—H15B109.2
C20—C21—H21119.7H14C—C14'—H14D109.4
C22—C21—H21119.7
C5—C1—C2—C3−0.3 (3)C2—C1—Fe1—C10−156.8 (4)
Fe1—C1—C2—C359.38 (17)C5—C1—Fe1—C10−38.1 (5)
C5—C1—C2—Fe1−59.68 (18)C2—C1—Fe1—C5−118.7 (2)
C1—C2—C3—C40.3 (3)C2—C1—Fe1—C4−80.83 (17)
Fe1—C2—C3—C459.40 (17)C5—C1—Fe1—C437.83 (17)
C1—C2—C3—Fe1−59.08 (17)C2—C1—Fe1—C891.11 (17)
C2—C3—C4—C5−0.2 (3)C5—C1—Fe1—C8−150.23 (16)
Fe1—C3—C4—C559.45 (18)C5—C1—Fe1—C2118.7 (2)
C2—C3—C4—Fe1−59.67 (17)C2—C1—Fe1—C3−37.14 (17)
C3—C4—C5—C10.0 (3)C5—C1—Fe1—C381.52 (19)
Fe1—C4—C5—C159.90 (17)C2—C1—Fe1—C957.6 (3)
C3—C4—C5—Fe1−59.86 (18)C5—C1—Fe1—C9176.3 (2)
C2—C1—C5—C40.2 (3)C5—C4—Fe1—C683.5 (2)
Fe1—C1—C5—C4−60.18 (18)C3—C4—Fe1—C6−157.28 (16)
C2—C1—C5—Fe160.34 (17)C5—C4—Fe1—C748.3 (3)
C10—C6—C7—C8−0.6 (2)C3—C4—Fe1—C7167.53 (17)
Fe1—C6—C7—C8−59.79 (14)C5—C4—Fe1—C10126.63 (18)
C10—C6—C7—Fe159.18 (15)C3—C4—Fe1—C10−114.19 (17)
C6—C7—C8—C9−0.3 (2)C3—C4—Fe1—C5119.2 (3)
Fe1—C7—C8—C9−59.65 (14)C5—C4—Fe1—C1−38.33 (18)
C6—C7—C8—P1175.47 (15)C3—C4—Fe1—C180.85 (19)
Fe1—C7—C8—P1116.08 (16)C5—C4—Fe1—C2−81.6 (2)
C6—C7—C8—Fe159.39 (15)C3—C4—Fe1—C237.55 (18)
C7—C8—C9—C101.0 (2)C5—C4—Fe1—C3−119.2 (3)
P1—C8—C9—C10−174.98 (14)C5—C4—Fe1—C9165.67 (17)
Fe1—C8—C9—C10−57.78 (14)C3—C4—Fe1—C9−75.1 (2)
C7—C8—C9—C11−173.17 (18)C7—C8—Fe1—C6−37.91 (14)
P1—C8—C9—C1110.8 (3)C9—C8—Fe1—C681.13 (14)
Fe1—C8—C9—C11128.0 (2)P1—C8—Fe1—C6−161.04 (15)
C7—C8—C9—Fe158.79 (14)C9—C8—Fe1—C7119.05 (18)
P1—C8—C9—Fe1−117.21 (15)P1—C8—Fe1—C7−123.13 (19)
C7—C6—C10—C91.3 (2)C7—C8—Fe1—C10−81.56 (14)
Fe1—C6—C10—C960.32 (15)C9—C8—Fe1—C1037.49 (13)
C7—C6—C10—Fe1−59.04 (15)P1—C8—Fe1—C10155.31 (16)
C8—C9—C10—C6−1.4 (2)C7—C8—Fe1—C545.4 (2)
C11—C9—C10—C6172.7 (2)C9—C8—Fe1—C5164.4 (2)
Fe1—C9—C10—C6−59.39 (16)P1—C8—Fe1—C5−77.7 (2)
C8—C9—C10—Fe157.98 (14)C7—C8—Fe1—C183.78 (16)
C11—C9—C10—Fe1−127.9 (2)C9—C8—Fe1—C1−157.17 (14)
C10—C9—C11—N1−78.3 (3)P1—C8—Fe1—C1−39.34 (18)
C8—C9—C11—N194.7 (3)C7—C8—Fe1—C2127.34 (14)
Fe1—C9—C11—N1−172.24 (16)C9—C8—Fe1—C2−113.61 (15)
C10—C9—C11—C1246.4 (3)P1—C8—Fe1—C24.21 (17)
C8—C9—C11—C12−140.6 (2)C7—C8—Fe1—C3167.89 (14)
Fe1—C9—C11—C12−47.5 (3)C9—C8—Fe1—C3−73.06 (17)
N1—C16—C17—O1−56.6 (2)P1—C8—Fe1—C344.76 (19)
C15—C16—C17—O162.1 (3)C7—C8—Fe1—C9−119.05 (18)
N1—C16—C17—C19−174.2 (2)P1—C8—Fe1—C9117.82 (18)
C15—C16—C17—C19−55.6 (3)C1—C2—Fe1—C6−19.1 (5)
N1—C16—C17—C1863.9 (3)C3—C2—Fe1—C6−138.9 (4)
C15—C16—C17—C18−177.5 (3)C1—C2—Fe1—C7−64.5 (2)
C25—C20—C21—C22−1.0 (4)C3—C2—Fe1—C7175.71 (17)
P1—C20—C21—C22173.03 (19)C1—C2—Fe1—C10167.2 (2)
C20—C21—C22—C230.4 (4)C3—C2—Fe1—C1047.3 (3)
C21—C22—C23—C240.3 (5)C1—C2—Fe1—C538.31 (17)
C22—C23—C24—C25−0.5 (5)C3—C2—Fe1—C5−81.5 (2)
C23—C24—C25—C20−0.1 (5)C3—C2—Fe1—C1−119.8 (3)
C21—C20—C25—C240.8 (4)C1—C2—Fe1—C482.04 (18)
P1—C20—C25—C24−173.7 (2)C3—C2—Fe1—C4−37.79 (19)
C31—C26—C27—C283.0 (3)C1—C2—Fe1—C8−107.69 (16)
P1—C26—C27—C28−176.45 (18)C3—C2—Fe1—C8132.48 (18)
C26—C27—C28—C29−1.7 (4)C1—C2—Fe1—C3119.8 (3)
C27—C28—C29—C30−1.0 (4)C1—C2—Fe1—C9−152.71 (16)
C28—C29—C30—C312.3 (4)C3—C2—Fe1—C987.5 (2)
C29—C30—C31—C26−0.9 (4)C2—C3—Fe1—C6162.26 (19)
C27—C26—C31—C30−1.8 (3)C4—C3—Fe1—C643.3 (3)
P1—C26—C31—C30177.75 (18)C2—C3—Fe1—C7−18.9 (7)
C10—C6—Fe1—C7−119.72 (19)C4—C3—Fe1—C7−137.8 (6)
C7—C6—Fe1—C10119.72 (19)C2—C3—Fe1—C10−157.63 (18)
C10—C6—Fe1—C5130.73 (16)C4—C3—Fe1—C1083.46 (19)
C7—C6—Fe1—C5−109.55 (16)C2—C3—Fe1—C581.3 (2)
C10—C6—Fe1—C1169.13 (15)C4—C3—Fe1—C5−37.57 (19)
C7—C6—Fe1—C1−71.15 (17)C2—C3—Fe1—C137.04 (19)
C10—C6—Fe1—C489.16 (16)C4—C3—Fe1—C1−81.87 (19)
C7—C6—Fe1—C4−151.11 (15)C2—C3—Fe1—C4118.9 (3)
C10—C6—Fe1—C8−81.68 (14)C2—C3—Fe1—C8−70.2 (2)
C7—C6—Fe1—C838.04 (13)C4—C3—Fe1—C8170.86 (16)
C10—C6—Fe1—C2−175.6 (4)C4—C3—Fe1—C2−118.9 (3)
C7—C6—Fe1—C2−55.9 (5)C2—C3—Fe1—C9−113.08 (19)
C10—C6—Fe1—C360.0 (3)C4—C3—Fe1—C9128.01 (17)
C10—C6—Fe1—C9−37.27 (13)C10—C9—Fe1—C637.26 (14)
C7—C6—Fe1—C982.45 (14)C8—C9—Fe1—C6−82.02 (14)
C8—C7—Fe1—C6119.02 (19)C11—C9—Fe1—C6158.4 (2)
C6—C7—Fe1—C10−37.30 (14)C10—C9—Fe1—C781.32 (14)
C8—C7—Fe1—C1081.72 (13)C8—C9—Fe1—C7−37.96 (12)
C6—C7—Fe1—C584.94 (17)C11—C9—Fe1—C7−157.5 (2)
C8—C7—Fe1—C5−156.04 (15)C8—C9—Fe1—C10−119.28 (18)
C6—C7—Fe1—C1127.91 (15)C11—C9—Fe1—C10121.2 (3)
C8—C7—Fe1—C1−113.07 (15)C10—C9—Fe1—C5−23.4 (5)
C6—C7—Fe1—C453.1 (2)C8—C9—Fe1—C5−142.6 (4)
C8—C7—Fe1—C4172.13 (18)C11—C9—Fe1—C597.8 (5)
C6—C7—Fe1—C8−119.02 (19)C10—C9—Fe1—C1167.2 (2)
C6—C7—Fe1—C2165.06 (15)C8—C9—Fe1—C147.9 (3)
C8—C7—Fe1—C2−75.92 (17)C11—C9—Fe1—C1−71.6 (3)
C8—C7—Fe1—C3−60.1 (7)C10—C9—Fe1—C4−67.17 (17)
C6—C7—Fe1—C9−80.93 (14)C8—C9—Fe1—C4173.55 (13)
C8—C7—Fe1—C938.08 (12)C11—C9—Fe1—C454.0 (2)
C9—C10—Fe1—C6−119.96 (19)C10—C9—Fe1—C8119.28 (18)
C6—C10—Fe1—C737.65 (13)C11—C9—Fe1—C8−119.6 (3)
C9—C10—Fe1—C7−82.32 (13)C10—C9—Fe1—C2−153.39 (14)
C6—C10—Fe1—C5−66.62 (19)C8—C9—Fe1—C287.33 (15)
C9—C10—Fe1—C5173.42 (15)C11—C9—Fe1—C2−32.2 (2)
C6—C10—Fe1—C1−36.3 (5)C10—C9—Fe1—C3−109.54 (14)
C9—C10—Fe1—C1−156.3 (4)C8—C9—Fe1—C3131.18 (13)
C6—C10—Fe1—C4−107.09 (15)C11—C9—Fe1—C311.6 (2)
C9—C10—Fe1—C4132.95 (14)C15—C16—N1—C133.9 (3)
C6—C10—Fe1—C881.89 (14)C17—C16—N1—C13127.2 (2)
C9—C10—Fe1—C8−38.08 (12)C15—C16—N1—C11134.6 (2)
C6—C10—Fe1—C2177.7 (2)C17—C16—N1—C11−102.1 (2)
C9—C10—Fe1—C257.7 (3)C9—C11—N1—C16−70.4 (2)
C6—C10—Fe1—C3−149.53 (14)C12—C11—N1—C16161.9 (2)
C9—C10—Fe1—C390.51 (15)C9—C11—N1—C1356.8 (3)
C6—C10—Fe1—C9119.96 (19)C12—C11—N1—C13−70.8 (3)
C4—C5—Fe1—C6−110.95 (18)C7—C8—P1—C2072.69 (19)
C1—C5—Fe1—C6130.59 (18)C9—C8—P1—C20−112.20 (18)
C4—C5—Fe1—C7−153.36 (16)Fe1—C8—P1—C20160.86 (12)
C1—C5—Fe1—C788.17 (19)C7—C8—P1—C26−32.0 (2)
C4—C5—Fe1—C10−72.9 (2)C9—C8—P1—C26143.08 (17)
C1—C5—Fe1—C10168.66 (16)Fe1—C8—P1—C2656.14 (14)
C4—C5—Fe1—C1118.5 (2)C21—C20—P1—C82.0 (2)
C1—C5—Fe1—C4−118.5 (2)C25—C20—P1—C8175.99 (19)
C4—C5—Fe1—C8175.91 (16)C21—C20—P1—C26109.2 (2)
C1—C5—Fe1—C857.4 (3)C25—C20—P1—C26−76.7 (2)
C4—C5—Fe1—C280.98 (18)C27—C26—P1—C861.2 (2)
C1—C5—Fe1—C2−37.48 (17)C31—C26—P1—C8−118.32 (18)
C4—C5—Fe1—C337.58 (16)C27—C26—P1—C20−45.6 (2)
C1—C5—Fe1—C3−80.89 (18)C31—C26—P1—C20134.86 (18)
C4—C5—Fe1—C9−54.0 (5)C16—N1—C13—C1421.5 (3)
C1—C5—Fe1—C9−172.5 (4)C11—N1—C13—C14−109.4 (3)
C2—C1—Fe1—C6174.42 (15)N1—C13—C14—C15−38.8 (4)
C5—C1—Fe1—C6−66.9 (2)C13—C14—C15—C1640.7 (4)
C2—C1—Fe1—C7134.09 (15)N1—C16—C15—C14−27.9 (4)
C5—C1—Fe1—C7−107.25 (18)C17—C16—C15—C14−149.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N10.822.532.844 (2)104
C11—H11···P10.982.863.371 (2)114
C16—H16···P10.982.873.778 (2)154
Selected torsion angles (°) top
C1—Cg3—Cg4—C716.63C4—Cg3—Cg4—C1015.63
C2—Cg3—Cg4—C815.99C5—Cg3—Cg4—C615.80
C3—Cg3—Cg4—C915.20
Cg3 is the centroid of the Cp ring system C1 to C5, Cg4 is the centroid of the Cp ring system C6 to C10.
X—H···Cg (π-ring) interaction geometry (Å, °) top
X—H···CgX—HH···CgX···CgX—H···Cg
C1—H1···Cg60.982.953.66 (3)131
C30—H30···Cg3(i)0.982.963.864 (3)165
Cg6 is the centroid of the π-ring system C26 to C31. Cg3 is the centroid of the Cp ring system C1 to C5. Symmetry code: (i) −1/2 + x, 1/2 − y, 1 − z.
Acknowledgements top

We thank the Scientific Reseach Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for support of this work.

references
References top

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.

Bruker (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005). APEX2. Version 2.0-2. Bruker AXS Inc., Madison, Wisconsin, USA.

Dai, L. X., Tu, T., You, S. L., Deng, W. P. & Hou, X. L. (2003). Acc. Chem. Res. 36, 659–667.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (1997). SHELX97. University of Göttingen, Germany.

Togni, A. (1996). Angew. Chem. Int. Ed. 35, 1475–1477.