(R,SP)-1-Diphenyl­phosphino-2-(1-ethoxy­ethyl)ferrocene

Yuan, H.; Zhou, Z.-M.

doi:10.1107/S1600536808033618

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1448

doi:10.1107/S1600536808033618

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(R,S_P)-1-Diphenylphosphino-2-(1-ethoxyethyl)ferrocene

Hao Yuan ^a and Zhi-Ming Zhou ^a ^*

^aSchool of Chemical Engineering and the Enviroment, Beijing Institute of Technology, Beijing 100081, People's Republic of China
^*Correspondence e-mail: zzm@bit.edu.cn

(Received 12 July 2008; accepted 15 October 2008; online 22 October 2008)

In the crystal structure of the title compound, [Fe(C₅H₅)(C₂₁H₂₂OP)], the cyclopentadienyl (Cp) rings are almost parallel and are essentially eclipsed. The absolute configuration was determined as S for the planar and R for the central chirality.

Related literature

For background to ferrocene derivatives applied as catalysts, see: Blaser & Schmidt (2004 ); Gomez Arrayas et al. (2006 ); Hayashi et al. (1988 ); Ohmura et al. (1995 ); Ojima (2000 ). For the structures of closely related compounds, see: Jin et al. (2004 ); Cheelama & Knochel (2007 ); Podlaha et al. (1996 ).

Experimental

Crystal data

[Fe(C₅H₅)(C₂₁H₂₂OP)]
M_r = 442.30
Orthorhombic, P 2₁ 2₁ 2₁
a = 11.003 (2) Å
b = 12.191 (2) Å
c = 16.599 (3) Å
V = 2226.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 113 (2) K
0.12 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2001 ) T_min = 0.914, T_max = 0.942
22928 measured reflections
3929 independent reflections
3847 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.062
S = 1.05
3929 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), with 1688 Friedel pairs
Flack parameter: 0.019 (12)

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033618/nc2112sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033618/nc2112Isup2.hkl

checkCIF report

Comment top

Asymmetric metal catalysis is one of the most active areas in modern organic chemistry, and considerable efforts have been made to the development of novel ligands for catalytic asymmetric transformations (Ojima, 2000). In this context, ferrocene-based ligands incorporating both chirality are very important (Gomez Arrayas et al., 2006) and some of them have already been applied in industrial processes because of their stability, low price and unique structure (Blaser & Schmidt, 2004).

(S,R_p)-1-(diphenylphosphino)-2-(1-ethoxyethyl)-ferrocene, the enantiomorph of title compound, has been used to synthesize 1,1'-binaphthyls via asymmetric Ni-catalysed Grignard cross-coupling with up to 68% ee, and the (S,R_p)-1-(diphenylphosphino)-2-(1-methoxyethyl)-ferrocene provided axially chiral binaphthalenes in enantioselectivities up to 95% ee (Hayashi et al., 1988). In addition, the (R,S_p)-1-(diphenylphosphino)-2-(1-ethoxyethyl)-ferrocene was also used in asymmetric hydrosilyation (Ohmura et al., 1995).

The Fe—C bond distances within the ferrocene group are in the range of 2.038 (2)–2.050 (2) Å for the unsubstituted cyclopentadienyl (Cp) ring [C1–C5] and 2.025 (2)–2.046 (2) Å for the substituted Cp ring [C6–C10]. The Cp rings are almost parallel, the dihedral angle between the Cp ring planes is 1.80 (10)°. The Cp rings are essentially eclipsed and the Fe–centroid distances are 1.654 (9) (Cg1) and 1.639 (9) Å (Cg2) with Cg1 and Cg2 are the centroids of the [C1–C5] and [C6–C10] rings. The [Cg1—Fe1—Cg2] angle is 178.60 (18)°. The C11 atom is almost in the plane of their carrier Cp ring, while the P1 atom is tilted slightly out of the plane by 0.102 (10) Å.

The two phenyl rings are oriented almost perpendicular, with a dihedral angle of 90.90 (10)°. The O1—C11 and C10—C11 bonds lengths are in agreement with those in the related complex 1-(1-Ferrocenyl-1-methoxy-3-phenyl-2-propyl)-1H-1,2,4-triazole (Jin et al., 2004) and the geometric parameters of the PPh₂ group are in agreement with those in the similar structure 1-carboxy-1'-(diphenylphosphino)-ferrocene (Podlaha et al., 1996).

The title compound has both central chirality and planar chirality with the configuration of C11 atom being R, and the configuration of planar chirality being S.

Related literature top

For background to ferrocene derivatives applied as catalysts, see: Blaser & Schmidt (2004); Gomez Arrayas et al. (2006); Hayashi et al. (1988); Ohmura et al. (1995); Ojima (2000). For the structures of closely related compounds, see: Jin et al. (2004); Cheelama & Knochel (2007); Podlaha et al. (1996).

Experimental top

The title compound was prepared from (R,S_p)-1-[1-(acetyloxy)ethyl]-2-(diphenylphosphino)-ferrocene according to literature procedures (Hayashi et al., 1988). Single crystals of the title compound suitable for X-ray diffraction analysis were obtained by slow evaporation of a hexane solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalClear (Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A molecular view of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are draw at the 30% probability level.

(R,S_P)-1-Diphenylphosphino-2-(1-ethoxyethyl)ferrocene top

Crystal data top

[Fe(C₅H₅)(C₂₁H₂₂OP)]	F(000) = 928
M_r = 442.30	D_x = 1.319 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7176 reflections
a = 11.003 (2) Å	θ = 2.2–27.9°
b = 12.191 (2) Å	µ = 0.76 mm⁻¹
c = 16.599 (3) Å	T = 113 K
V = 2226.6 (8) Å³	Block, red
Z = 4	0.12 × 0.10 × 0.08 mm

Data collection top

Rigaku Saturn diffractometer	3929 independent reflections
Radiation source: rotating anode	3847 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.050
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2001)	h = −13→12
T_min = 0.914, T_max = 0.942	k = −14→14
22928 measured reflections	l = −19→19

Refinement top

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) = 0.062	w = 1/[σ²(F_o²) + (0.0301P)² + 0.2869P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
3929 reflections	Δρ_max = 0.18 e Å⁻³
262 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Absolute structure: Flack (1983), with 1688 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.019 (12)

Crystal data top

[Fe(C₅H₅)(C₂₁H₂₂OP)]	V = 2226.6 (8) Å³
M_r = 442.30	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 11.003 (2) Å	µ = 0.76 mm⁻¹
b = 12.191 (2) Å	T = 113 K
c = 16.599 (3) Å	0.12 × 0.10 × 0.08 mm

Data collection top

Rigaku Saturn diffractometer	3929 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2001)	3847 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.942	R_int = 0.050
22928 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.062	Δρ_max = 0.18 e Å⁻³
S = 1.05	Δρ_min = −0.28 e Å⁻³
3929 reflections	Absolute structure: Flack (1983), with 1688 Friedel pairs
262 parameters	Absolute structure parameter: 0.019 (12)
0 restraints

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	−0.03864 (3)	0.77799 (2)	0.905322 (18)	0.02169 (9)
P1	0.07707 (4)	0.98992 (4)	1.01327 (3)	0.01930 (12)
O1	0.18641 (12)	1.04499 (11)	0.82901 (9)	0.0230 (3)
C1	0.09790 (19)	0.66545 (15)	0.91286 (14)	0.0272 (5)
H1A	0.1815	0.6758	0.8941	0.033*
C2	0.0010 (2)	0.62243 (18)	0.86702 (16)	0.0358 (6)
H2A	0.0055	0.5980	0.8108	0.043*
C3	−0.1039 (2)	0.62123 (19)	0.9163 (2)	0.0513 (8)
H3A	−0.1850	0.5958	0.9004	0.062*
C4	−0.0708 (3)	0.6634 (2)	0.99241 (18)	0.0517 (8)
H4A	−0.1254	0.6724	1.0386	0.062*
C5	0.0538 (2)	0.69041 (18)	0.99089 (14)	0.0373 (6)
H5A	0.1011	0.7209	1.0356	0.045*
C6	−0.01527 (17)	0.94062 (15)	0.93016 (11)	0.0178 (4)
C7	−0.14254 (18)	0.91375 (16)	0.92785 (12)	0.0210 (4)
H7A	−0.2004	0.9224	0.9723	0.025*
C8	−0.16938 (19)	0.87040 (17)	0.84996 (13)	0.0260 (5)
H8A	−0.2489	0.8442	0.8315	0.031*
C9	−0.06047 (19)	0.87097 (17)	0.80413 (12)	0.0230 (4)
H9A	−0.0519	0.8449	0.7486	0.028*
C10	0.03465 (19)	0.91267 (15)	0.85299 (11)	0.0198 (4)
C11	0.16655 (19)	0.92877 (16)	0.83152 (12)	0.0204 (4)
H11A	0.2167	0.8975	0.8746	0.024*
C12	0.2039 (2)	0.87699 (19)	0.75210 (13)	0.0306 (5)
H12A	0.2887	0.8903	0.7428	0.046*
H12B	0.1572	0.9086	0.7091	0.046*
H12C	0.1894	0.7994	0.7542	0.046*
C13	0.3051 (2)	1.07659 (18)	0.85426 (15)	0.0291 (5)
H13A	0.3658	1.0419	0.8204	0.035*
H13B	0.3188	1.0538	0.9095	0.035*
C14	0.3145 (2)	1.19937 (17)	0.84759 (15)	0.0334 (5)
H14A	0.3939	1.2225	0.8645	0.050*
H14B	0.2541	1.2329	0.8813	0.050*
H14C	0.3014	1.2210	0.7927	0.050*
C15	0.06768 (17)	1.14024 (16)	1.00256 (11)	0.0189 (4)
C16	0.1436 (2)	1.20172 (18)	1.05214 (12)	0.0253 (5)
H16A	0.1945	1.1661	1.0885	0.030*
C17	0.1443 (2)	1.31563 (18)	1.04809 (13)	0.0308 (5)
H17A	0.1950	1.3558	1.0819	0.037*
C18	0.0702 (2)	1.36905 (18)	0.99405 (13)	0.0300 (5)
H18A	0.0702	1.4452	0.9913	0.036*
C19	−0.0040 (2)	1.30890 (18)	0.94408 (14)	0.0305 (5)
H19A	−0.0540	1.3448	0.9074	0.037*
C20	−0.00485 (19)	1.19497 (17)	0.94788 (13)	0.0263 (5)
H20A	−0.0547	1.1553	0.9133	0.032*
C21	−0.02654 (17)	0.96925 (15)	1.09878 (11)	0.0203 (4)
C22	−0.13214 (18)	1.03066 (16)	1.10886 (12)	0.0231 (5)
H22A	−0.1524	1.0840	1.0711	0.028*
C23	−0.2073 (2)	1.01308 (18)	1.17447 (13)	0.0277 (5)
H23A	−0.2772	1.0551	1.1809	0.033*
C24	−0.1788 (2)	0.93330 (19)	1.23050 (13)	0.0303 (5)
H24A	−0.2297	0.9215	1.2744	0.036*
C25	−0.0752 (2)	0.8714 (2)	1.22134 (13)	0.0319 (5)
H25A	−0.0562	0.8173	1.2588	0.038*
C26	0.0012 (2)	0.88959 (18)	1.15610 (12)	0.0281 (5)
H26A	0.0716	0.8481	1.1506	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02261 (15)	0.01571 (14)	0.02675 (16)	−0.00025 (12)	0.00374 (13)	0.00058 (13)
P1	0.0201 (3)	0.0192 (3)	0.0186 (3)	0.0020 (2)	−0.0007 (2)	0.0016 (2)
O1	0.0219 (7)	0.0174 (7)	0.0297 (8)	−0.0010 (6)	0.0016 (6)	0.0015 (6)
C1	0.0283 (11)	0.0154 (10)	0.0378 (12)	0.0046 (9)	0.0035 (11)	0.0019 (10)
C2	0.0387 (14)	0.0162 (11)	0.0525 (15)	0.0022 (10)	0.0012 (12)	−0.0069 (10)
C3	0.0332 (14)	0.0176 (12)	0.103 (3)	−0.0032 (10)	0.0143 (17)	0.0083 (16)
C4	0.066 (2)	0.0258 (13)	0.0637 (19)	0.0156 (12)	0.0410 (16)	0.0200 (13)
C5	0.0570 (16)	0.0207 (11)	0.0343 (13)	0.0130 (11)	0.0039 (13)	0.0061 (10)
C6	0.0184 (10)	0.0137 (9)	0.0212 (10)	0.0026 (8)	0.0010 (8)	0.0027 (8)
C7	0.0203 (10)	0.0186 (10)	0.0240 (11)	0.0018 (8)	0.0014 (9)	0.0005 (8)
C8	0.0229 (11)	0.0258 (11)	0.0292 (12)	−0.0001 (10)	−0.0050 (10)	0.0000 (10)
C9	0.0275 (11)	0.0218 (10)	0.0196 (10)	0.0000 (9)	−0.0023 (9)	−0.0007 (8)
C10	0.0247 (11)	0.0148 (10)	0.0198 (10)	0.0011 (9)	0.0010 (9)	0.0004 (8)
C11	0.0243 (11)	0.0159 (10)	0.0209 (10)	0.0003 (9)	−0.0016 (9)	0.0005 (8)
C12	0.0309 (12)	0.0322 (12)	0.0287 (12)	0.0012 (10)	0.0077 (10)	−0.0052 (10)
C13	0.0230 (11)	0.0258 (12)	0.0386 (13)	−0.0053 (9)	0.0007 (11)	0.0006 (10)
C14	0.0289 (12)	0.0259 (12)	0.0454 (14)	−0.0053 (10)	0.0065 (11)	−0.0037 (11)
C15	0.0182 (11)	0.0198 (10)	0.0188 (10)	−0.0007 (8)	0.0048 (8)	−0.0003 (8)
C16	0.0269 (11)	0.0293 (12)	0.0198 (10)	−0.0029 (9)	−0.0046 (9)	0.0015 (9)
C17	0.0350 (13)	0.0291 (12)	0.0282 (12)	−0.0125 (10)	−0.0001 (11)	−0.0055 (10)
C18	0.0364 (14)	0.0188 (11)	0.0349 (13)	−0.0005 (9)	0.0095 (11)	0.0023 (10)
C19	0.0310 (12)	0.0240 (12)	0.0366 (12)	0.0028 (9)	−0.0037 (11)	0.0091 (10)
C20	0.0267 (11)	0.0229 (11)	0.0292 (11)	−0.0015 (9)	−0.0055 (10)	0.0005 (9)
C21	0.0235 (10)	0.0193 (10)	0.0181 (9)	−0.0017 (8)	−0.0012 (10)	0.0015 (8)
C22	0.0309 (12)	0.0192 (10)	0.0190 (10)	0.0000 (9)	−0.0003 (9)	0.0004 (8)
C23	0.0291 (12)	0.0276 (12)	0.0264 (11)	−0.0029 (10)	0.0045 (10)	−0.0071 (10)
C24	0.0346 (13)	0.0367 (13)	0.0196 (11)	−0.0114 (11)	0.0040 (10)	−0.0014 (10)
C25	0.0382 (14)	0.0332 (13)	0.0243 (12)	−0.0045 (11)	−0.0031 (10)	0.0095 (10)
C26	0.0313 (12)	0.0285 (12)	0.0245 (11)	0.0005 (10)	−0.0039 (10)	0.0038 (9)

Geometric parameters (Å, º) top

Fe1—C10	2.025 (2)	C11—C12	1.518 (3)
Fe1—C1	2.038 (2)	C11—H11A	0.9800
Fe1—C9	2.041 (2)	C12—H12A	0.9600
Fe1—C6	2.041 (2)	C12—H12B	0.9600
Fe1—C4	2.042 (2)	C12—H12C	0.9600
Fe1—C8	2.045 (2)	C13—C14	1.505 (3)
Fe1—C7	2.046 (2)	C13—H13A	0.9700
Fe1—C2	2.047 (2)	C13—H13B	0.9700
Fe1—C5	2.047 (2)	C14—H14A	0.9600
Fe1—C3	2.050 (2)	C14—H14B	0.9600
P1—C6	1.816 (2)	C14—H14C	0.9600
P1—C21	1.838 (2)	C15—C20	1.381 (3)
P1—C15	1.844 (2)	C15—C16	1.392 (3)
O1—C13	1.424 (3)	C16—C17	1.390 (3)
O1—C11	1.434 (2)	C16—H16A	0.9300
C1—C2	1.411 (3)	C17—C18	1.376 (3)
C1—C5	1.416 (3)	C17—H17A	0.9300
C1—H1A	0.9800	C18—C19	1.375 (3)
C2—C3	1.415 (4)	C18—H18A	0.9300
C2—H2A	0.9800	C19—C20	1.390 (3)
C3—C4	1.412 (4)	C19—H19A	0.9300
C3—H3A	0.9800	C20—H20A	0.9300
C4—C5	1.410 (4)	C21—C22	1.392 (3)
C4—H4A	0.9800	C21—C26	1.393 (3)
C5—H5A	0.9800	C22—C23	1.384 (3)
C6—C10	1.435 (3)	C22—H22A	0.9300
C6—C7	1.439 (3)	C23—C24	1.382 (3)
C7—C8	1.428 (3)	C23—H23A	0.9300
C7—H7A	0.9800	C24—C25	1.376 (3)
C8—C9	1.419 (3)	C24—H24A	0.9300
C8—H8A	0.9800	C25—C26	1.388 (3)
C9—C10	1.418 (3)	C25—H25A	0.9300
C9—H9A	0.9800	C26—H26A	0.9300
C10—C11	1.507 (3)

C10—Fe1—C1	106.17 (9)	C8—C7—C6	108.05 (18)
C10—Fe1—C9	40.83 (8)	C8—C7—Fe1	69.55 (12)
C1—Fe1—C9	120.74 (9)	C6—C7—Fe1	69.22 (11)
C10—Fe1—C6	41.32 (7)	C8—C7—H7A	126.0
C1—Fe1—C6	123.26 (8)	C6—C7—H7A	126.0
C9—Fe1—C6	68.99 (8)	Fe1—C7—H7A	126.0
C10—Fe1—C4	158.10 (11)	C9—C8—C7	107.99 (18)
C1—Fe1—C4	67.90 (9)	C9—C8—Fe1	69.49 (12)
C9—Fe1—C4	160.50 (11)	C7—C8—Fe1	69.60 (12)
C6—Fe1—C4	122.93 (10)	C9—C8—H8A	126.0
C10—Fe1—C8	68.94 (9)	C7—C8—H8A	126.0
C1—Fe1—C8	156.45 (9)	Fe1—C8—H8A	126.0
C9—Fe1—C8	40.66 (8)	C10—C9—C8	108.57 (18)
C6—Fe1—C8	69.17 (8)	C10—C9—Fe1	69.00 (11)
C4—Fe1—C8	124.97 (10)	C8—C9—Fe1	69.86 (12)
C10—Fe1—C7	69.21 (8)	C10—C9—H9A	125.7
C1—Fe1—C7	160.92 (8)	C8—C9—H9A	125.7
C9—Fe1—C7	68.61 (8)	Fe1—C9—H9A	125.7
C6—Fe1—C7	41.22 (8)	C9—C10—C6	108.25 (18)
C4—Fe1—C7	109.11 (9)	C9—C10—C11	128.47 (18)
C8—Fe1—C7	40.85 (8)	C6—C10—C11	123.28 (18)
C10—Fe1—C2	122.21 (9)	C9—C10—Fe1	70.17 (12)
C1—Fe1—C2	40.41 (9)	C6—C10—Fe1	69.95 (11)
C9—Fe1—C2	106.50 (9)	C11—C10—Fe1	126.19 (14)
C6—Fe1—C2	159.33 (9)	O1—C11—C10	106.40 (16)
C4—Fe1—C2	67.84 (10)	O1—C11—C12	110.14 (17)
C8—Fe1—C2	121.37 (10)	C10—C11—C12	114.32 (17)
C7—Fe1—C2	157.70 (9)	O1—C11—H11A	108.6
C10—Fe1—C5	121.51 (10)	C10—C11—H11A	108.6
C1—Fe1—C5	40.56 (9)	C12—C11—H11A	108.6
C9—Fe1—C5	156.82 (9)	C11—C12—H12A	109.5
C6—Fe1—C5	107.69 (9)	C11—C12—H12B	109.5
C4—Fe1—C5	40.35 (11)	H12A—C12—H12B	109.5
C8—Fe1—C5	161.50 (9)	C11—C12—H12C	109.5
C7—Fe1—C5	124.93 (9)	H12A—C12—H12C	109.5
C2—Fe1—C5	68.07 (10)	H12B—C12—H12C	109.5
C10—Fe1—C3	158.99 (11)	O1—C13—C14	108.08 (18)
C1—Fe1—C3	68.00 (9)	O1—C13—H13A	110.1
C9—Fe1—C3	123.33 (12)	C14—C13—H13A	110.1
C6—Fe1—C3	158.72 (10)	O1—C13—H13B	110.1
C4—Fe1—C3	40.39 (12)	C14—C13—H13B	110.1
C8—Fe1—C3	107.86 (10)	H13A—C13—H13B	108.4
C7—Fe1—C3	122.83 (10)	C13—C14—H14A	109.5
C2—Fe1—C3	40.40 (10)	C13—C14—H14B	109.5
C5—Fe1—C3	68.07 (11)	H14A—C14—H14B	109.5
C6—P1—C21	101.20 (9)	C13—C14—H14C	109.5
C6—P1—C15	102.97 (9)	H14A—C14—H14C	109.5
C21—P1—C15	100.13 (8)	H14B—C14—H14C	109.5
C13—O1—C11	113.47 (16)	C20—C15—C16	118.39 (19)
C2—C1—C5	108.3 (2)	C20—C15—P1	125.17 (15)
C2—C1—Fe1	70.13 (13)	C16—C15—P1	116.40 (15)
C5—C1—Fe1	70.05 (12)	C17—C16—C15	120.8 (2)
C2—C1—H1A	125.9	C17—C16—H16A	119.6
C5—C1—H1A	125.9	C15—C16—H16A	119.6
Fe1—C1—H1A	125.9	C18—C17—C16	120.0 (2)
C1—C2—C3	108.0 (2)	C18—C17—H17A	120.0
C1—C2—Fe1	69.47 (12)	C16—C17—H17A	120.0
C3—C2—Fe1	69.90 (13)	C19—C18—C17	119.5 (2)
C1—C2—H2A	126.0	C19—C18—H18A	120.2
C3—C2—H2A	126.0	C17—C18—H18A	120.2
Fe1—C2—H2A	126.0	C18—C19—C20	120.6 (2)
C4—C3—C2	107.6 (2)	C18—C19—H19A	119.7
C4—C3—Fe1	69.49 (14)	C20—C19—H19A	119.7
C2—C3—Fe1	69.70 (13)	C15—C20—C19	120.57 (19)
C4—C3—H3A	126.2	C15—C20—H20A	119.7
C2—C3—H3A	126.2	C19—C20—H20A	119.7
Fe1—C3—H3A	126.2	C22—C21—C26	118.38 (19)
C5—C4—C3	108.6 (2)	C22—C21—P1	122.46 (15)
C5—C4—Fe1	70.04 (14)	C26—C21—P1	119.16 (15)
C3—C4—Fe1	70.12 (15)	C23—C22—C21	120.66 (19)
C5—C4—H4A	125.7	C23—C22—H22A	119.7
C3—C4—H4A	125.7	C21—C22—H22A	119.7
Fe1—C4—H4A	125.7	C24—C23—C22	120.2 (2)
C4—C5—C1	107.4 (2)	C24—C23—H23A	119.9
C4—C5—Fe1	69.61 (15)	C22—C23—H23A	119.9
C1—C5—Fe1	69.39 (13)	C25—C24—C23	120.0 (2)
C4—C5—H5A	126.3	C25—C24—H24A	120.0
C1—C5—H5A	126.3	C23—C24—H24A	120.0
Fe1—C5—H5A	126.3	C24—C25—C26	120.0 (2)
C10—C6—C7	107.14 (18)	C24—C25—H25A	120.0
C10—C6—P1	122.87 (15)	C26—C25—H25A	120.0
C7—C6—P1	129.82 (15)	C25—C26—C21	120.8 (2)
C10—C6—Fe1	68.73 (11)	C25—C26—H26A	119.6
C7—C6—Fe1	69.57 (11)	C21—C26—H26A	119.6
P1—C6—Fe1	123.06 (10)

C10—Fe1—C1—C2	−121.03 (14)	Fe1—C6—C7—C8	−58.89 (14)
C9—Fe1—C1—C2	−79.11 (16)	C10—C6—C7—Fe1	58.67 (13)
C6—Fe1—C1—C2	−162.88 (13)	P1—C6—C7—Fe1	−116.57 (17)
C4—Fe1—C1—C2	81.32 (16)	C10—Fe1—C7—C8	81.47 (13)
C8—Fe1—C1—C2	−46.7 (3)	C1—Fe1—C7—C8	160.7 (2)
C7—Fe1—C1—C2	166.0 (2)	C9—Fe1—C7—C8	37.56 (12)
C5—Fe1—C1—C2	119.1 (2)	C6—Fe1—C7—C8	119.68 (17)
C3—Fe1—C1—C2	37.59 (16)	C4—Fe1—C7—C8	−121.79 (15)
C10—Fe1—C1—C5	119.87 (14)	C2—Fe1—C7—C8	−43.7 (3)
C9—Fe1—C1—C5	161.79 (14)	C5—Fe1—C7—C8	−163.90 (13)
C6—Fe1—C1—C5	78.03 (16)	C3—Fe1—C7—C8	−79.16 (17)
C4—Fe1—C1—C5	−37.78 (16)	C10—Fe1—C7—C6	−38.21 (11)
C8—Fe1—C1—C5	−165.8 (2)	C1—Fe1—C7—C6	41.0 (3)
C7—Fe1—C1—C5	46.9 (3)	C9—Fe1—C7—C6	−82.12 (12)
C2—Fe1—C1—C5	−119.1 (2)	C4—Fe1—C7—C6	118.53 (14)
C3—Fe1—C1—C5	−81.51 (17)	C8—Fe1—C7—C6	−119.68 (17)
C5—C1—C2—C3	0.4 (2)	C2—Fe1—C7—C6	−163.4 (2)
Fe1—C1—C2—C3	−59.49 (16)	C5—Fe1—C7—C6	76.41 (15)
C5—C1—C2—Fe1	59.89 (14)	C3—Fe1—C7—C6	161.16 (15)
C10—Fe1—C2—C1	76.58 (16)	C6—C7—C8—C9	−0.4 (2)
C9—Fe1—C2—C1	118.33 (14)	Fe1—C7—C8—C9	−59.09 (14)
C6—Fe1—C2—C1	44.2 (3)	C6—C7—C8—Fe1	58.68 (13)
C4—Fe1—C2—C1	−81.47 (16)	C10—Fe1—C8—C9	37.24 (12)
C8—Fe1—C2—C1	160.08 (13)	C1—Fe1—C8—C9	−44.9 (3)
C7—Fe1—C2—C1	−167.9 (2)	C6—Fe1—C8—C9	81.63 (13)
C5—Fe1—C2—C1	−37.77 (14)	C4—Fe1—C8—C9	−162.03 (14)
C3—Fe1—C2—C1	−119.2 (2)	C7—Fe1—C8—C9	119.40 (17)
C10—Fe1—C2—C3	−164.18 (16)	C2—Fe1—C8—C9	−78.50 (15)
C1—Fe1—C2—C3	119.2 (2)	C5—Fe1—C8—C9	165.2 (3)
C9—Fe1—C2—C3	−122.42 (17)	C3—Fe1—C8—C9	−120.72 (15)
C6—Fe1—C2—C3	163.5 (3)	C10—Fe1—C8—C7	−82.16 (12)
C4—Fe1—C2—C3	37.78 (18)	C1—Fe1—C8—C7	−164.33 (19)
C8—Fe1—C2—C3	−80.68 (19)	C9—Fe1—C8—C7	−119.40 (17)
C7—Fe1—C2—C3	−48.7 (3)	C6—Fe1—C8—C7	−37.77 (12)
C5—Fe1—C2—C3	81.48 (18)	C4—Fe1—C8—C7	78.57 (16)
C1—C2—C3—C4	−0.2 (3)	C2—Fe1—C8—C7	162.10 (12)
Fe1—C2—C3—C4	−59.38 (16)	C5—Fe1—C8—C7	45.8 (3)
C1—C2—C3—Fe1	59.22 (15)	C3—Fe1—C8—C7	119.88 (15)
C10—Fe1—C3—C4	158.9 (2)	C7—C8—C9—C10	0.9 (2)
C1—Fe1—C3—C4	81.29 (16)	Fe1—C8—C9—C10	−58.27 (14)
C9—Fe1—C3—C4	−165.50 (15)	C7—C8—C9—Fe1	59.16 (14)
C6—Fe1—C3—C4	−45.1 (4)	C1—Fe1—C9—C10	−78.90 (14)
C8—Fe1—C3—C4	−123.40 (15)	C6—Fe1—C9—C10	38.18 (11)
C7—Fe1—C3—C4	−80.96 (18)	C4—Fe1—C9—C10	169.5 (3)
C2—Fe1—C3—C4	118.9 (2)	C8—Fe1—C9—C10	120.27 (18)
C5—Fe1—C3—C4	37.39 (15)	C7—Fe1—C9—C10	82.54 (13)
C10—Fe1—C3—C2	40.1 (3)	C2—Fe1—C9—C10	−120.49 (13)
C1—Fe1—C3—C2	−37.59 (15)	C5—Fe1—C9—C10	−47.8 (3)
C9—Fe1—C3—C2	75.63 (18)	C3—Fe1—C9—C10	−161.40 (12)
C6—Fe1—C3—C2	−163.9 (2)	C10—Fe1—C9—C8	−120.27 (18)
C4—Fe1—C3—C2	−118.9 (2)	C1—Fe1—C9—C8	160.83 (12)
C8—Fe1—C3—C2	117.72 (16)	C6—Fe1—C9—C8	−82.09 (13)
C7—Fe1—C3—C2	160.17 (14)	C4—Fe1—C9—C8	49.2 (3)
C5—Fe1—C3—C2	−81.48 (16)	C7—Fe1—C9—C8	−37.73 (12)
C2—C3—C4—C5	−0.1 (3)	C2—Fe1—C9—C8	119.24 (13)
Fe1—C3—C4—C5	−59.65 (16)	C5—Fe1—C9—C8	−168.1 (2)
C2—C3—C4—Fe1	59.51 (16)	C3—Fe1—C9—C8	78.33 (16)
C10—Fe1—C4—C5	−40.2 (3)	C8—C9—C10—C6	−1.0 (2)
C1—Fe1—C4—C5	37.97 (14)	Fe1—C9—C10—C6	−59.82 (13)
C9—Fe1—C4—C5	158.4 (2)	C8—C9—C10—C11	179.80 (19)
C6—Fe1—C4—C5	−78.28 (16)	Fe1—C9—C10—C11	121.0 (2)
C8—Fe1—C4—C5	−164.60 (13)	C8—C9—C10—Fe1	58.80 (15)
C7—Fe1—C4—C5	−121.88 (14)	C7—C6—C10—C9	0.8 (2)
C2—Fe1—C4—C5	81.75 (15)	P1—C6—C10—C9	176.41 (14)
C3—Fe1—C4—C5	119.5 (2)	Fe1—C6—C10—C9	59.96 (14)
C10—Fe1—C4—C3	−159.8 (2)	C7—C6—C10—C11	179.99 (17)
C1—Fe1—C4—C3	−81.58 (15)	P1—C6—C10—C11	−4.4 (3)
C9—Fe1—C4—C3	38.8 (3)	Fe1—C6—C10—C11	−120.81 (18)
C6—Fe1—C4—C3	162.18 (14)	C7—C6—C10—Fe1	−59.20 (13)
C8—Fe1—C4—C3	75.85 (17)	P1—C6—C10—Fe1	116.45 (14)
C7—Fe1—C4—C3	118.57 (15)	C1—Fe1—C10—C9	118.58 (13)
C2—Fe1—C4—C3	−37.80 (15)	C6—Fe1—C10—C9	−119.07 (17)
C5—Fe1—C4—C3	−119.5 (2)	C4—Fe1—C10—C9	−170.6 (2)
C3—C4—C5—C1	0.4 (3)	C8—Fe1—C10—C9	−37.08 (12)
Fe1—C4—C5—C1	−59.31 (15)	C7—Fe1—C10—C9	−80.95 (13)
C3—C4—C5—Fe1	59.71 (17)	C2—Fe1—C10—C9	77.55 (15)
C2—C1—C5—C4	−0.5 (2)	C5—Fe1—C10—C9	159.99 (13)
Fe1—C1—C5—C4	59.45 (16)	C3—Fe1—C10—C9	48.0 (3)
C2—C1—C5—Fe1	−59.94 (15)	C1—Fe1—C10—C6	−122.34 (12)
C10—Fe1—C5—C4	163.58 (15)	C9—Fe1—C10—C6	119.07 (17)
C1—Fe1—C5—C4	−118.8 (2)	C4—Fe1—C10—C6	−51.5 (3)
C9—Fe1—C5—C4	−161.8 (2)	C8—Fe1—C10—C6	81.99 (12)
C6—Fe1—C5—C4	120.39 (16)	C7—Fe1—C10—C6	38.12 (11)
C8—Fe1—C5—C4	43.3 (4)	C2—Fe1—C10—C6	−163.37 (12)
C7—Fe1—C5—C4	78.15 (18)	C5—Fe1—C10—C6	−80.93 (14)
C2—Fe1—C5—C4	−81.13 (16)	C3—Fe1—C10—C6	167.1 (2)
C3—Fe1—C5—C4	−37.42 (16)	C1—Fe1—C10—C11	−5.16 (19)
C10—Fe1—C5—C1	−77.66 (15)	C9—Fe1—C10—C11	−123.7 (2)
C9—Fe1—C5—C1	−43.0 (3)	C6—Fe1—C10—C11	117.2 (2)
C6—Fe1—C5—C1	−120.84 (13)	C4—Fe1—C10—C11	65.6 (3)
C4—Fe1—C5—C1	118.8 (2)	C8—Fe1—C10—C11	−160.82 (19)
C8—Fe1—C5—C1	162.1 (2)	C7—Fe1—C10—C11	155.30 (19)
C7—Fe1—C5—C1	−163.08 (12)	C2—Fe1—C10—C11	−46.2 (2)
C2—Fe1—C5—C1	37.63 (13)	C5—Fe1—C10—C11	36.2 (2)
C3—Fe1—C5—C1	81.34 (15)	C3—Fe1—C10—C11	−75.7 (3)
C21—P1—C6—C10	−163.25 (16)	C13—O1—C11—C10	146.74 (17)
C15—P1—C6—C10	93.47 (17)	C13—O1—C11—C12	−88.9 (2)
C21—P1—C6—C7	11.3 (2)	C9—C10—C11—O1	111.4 (2)
C15—P1—C6—C7	−91.94 (19)	C6—C10—C11—O1	−67.6 (2)
C21—P1—C6—Fe1	−78.69 (12)	Fe1—C10—C11—O1	−156.03 (13)
C15—P1—C6—Fe1	178.04 (11)	C9—C10—C11—C12	−10.4 (3)
C1—Fe1—C6—C10	76.02 (14)	C6—C10—C11—C12	170.58 (18)
C9—Fe1—C6—C10	−37.74 (12)	Fe1—C10—C11—C12	82.2 (2)
C4—Fe1—C6—C10	159.63 (14)	C11—O1—C13—C14	179.14 (17)
C8—Fe1—C6—C10	−81.41 (12)	C6—P1—C15—C20	5.9 (2)
C7—Fe1—C6—C10	−118.85 (17)	C21—P1—C15—C20	−98.16 (18)
C2—Fe1—C6—C10	43.3 (3)	C6—P1—C15—C16	−171.67 (15)
C5—Fe1—C6—C10	117.91 (13)	C21—P1—C15—C16	84.23 (16)
C3—Fe1—C6—C10	−167.2 (3)	C20—C15—C16—C17	1.5 (3)
C10—Fe1—C6—C7	118.85 (16)	P1—C15—C16—C17	179.30 (17)
C1—Fe1—C6—C7	−165.12 (12)	C15—C16—C17—C18	−0.6 (3)
C9—Fe1—C6—C7	81.11 (12)	C16—C17—C18—C19	−0.3 (3)
C4—Fe1—C6—C7	−81.52 (15)	C17—C18—C19—C20	0.2 (3)
C8—Fe1—C6—C7	37.44 (12)	C16—C15—C20—C19	−1.6 (3)
C2—Fe1—C6—C7	162.1 (2)	P1—C15—C20—C19	−179.18 (17)
C5—Fe1—C6—C7	−123.24 (13)	C18—C19—C20—C15	0.8 (3)
C3—Fe1—C6—C7	−48.4 (3)	C6—P1—C21—C22	−68.60 (17)
C10—Fe1—C6—P1	−116.20 (17)	C15—P1—C21—C22	36.93 (18)
C1—Fe1—C6—P1	−40.17 (16)	C6—P1—C21—C26	111.64 (17)
C9—Fe1—C6—P1	−153.94 (14)	C15—P1—C21—C26	−142.83 (16)
C4—Fe1—C6—P1	43.43 (16)	C26—C21—C22—C23	0.3 (3)
C8—Fe1—C6—P1	162.39 (14)	P1—C21—C22—C23	−179.51 (16)
C7—Fe1—C6—P1	124.95 (17)	C21—C22—C23—C24	−0.6 (3)
C2—Fe1—C6—P1	−72.9 (3)	C22—C23—C24—C25	0.3 (3)
C5—Fe1—C6—P1	1.71 (14)	C23—C24—C25—C26	0.4 (3)
C3—Fe1—C6—P1	76.6 (3)	C24—C25—C26—C21	−0.8 (3)
C10—C6—C7—C8	−0.2 (2)	C22—C21—C26—C25	0.5 (3)
P1—C6—C7—C8	−175.46 (15)	P1—C21—C26—C25	−179.76 (17)

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₂₁H₂₂OP)]
M_r	442.30
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	113
a, b, c (Å)	11.003 (2), 12.191 (2), 16.599 (3)
V (Å³)	2226.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2001)
T_min, T_max	0.914, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	22928, 3929, 3847
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.062, 1.05
No. of reflections	3929
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.28
Absolute structure	Flack (1983), with 1688 Friedel pairs
Absolute structure parameter	0.019 (12)

Computer programs: CrystalClear (Rigaku, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

P1—C6	1.816 (2)	O1—C11	1.434 (2)
P1—C21	1.838 (2)	C10—C11	1.507 (3)
P1—C15	1.844 (2)	C11—C12	1.518 (3)
O1—C13	1.424 (3)

C6—P1—C21	101.20 (9)	C7—C6—P1	129.82 (15)
C6—P1—C15	102.97 (9)	O1—C11—C10	106.40 (16)
C13—O1—C11	113.47 (16)	C10—C11—C12	114.32 (17)
C10—C6—P1	122.87 (15)

C15—P1—C6—C10	93.47 (17)	C6—P1—C15—C16	−171.67 (15)

Acknowledgements

The authors thank the Natural Science Foundation of China (grant No. 20572009) and the Basic Research Fund of Beijing Institute of Technology (grant No. 000Y05 for financial support of this work.

References

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