1-Ferrocenyl-3-(4-n-octoxylphen­yl)propane-1,3-dione

Shang, Y.; Li, B.; Hu, R.; Su, Y.; Tang, Q.

doi:10.1107/S1600536807057005

1-Ferrocenyl-3-(4-n-octoxylphenyl)propane-1,3-dione

Y. Shang, B. Li, R. Hu, Y. Su and Q. Tang

The title compound, [Fe(C₅H₅)(C₂₂H₂₇O₃)], which forms an extended conjugated system and appears in the enol form, is mainly stabilized by an intramolecular hydrogen bond. The Fe-C bond distances are nearly equal with a mean value of 2.0312 Å. The two cyclopentadienyl rings are almost parallel to each other, as shown by the dihedral angle of 0.97 (17)°. In the structure, ferrocenyl is the more powerful electron-donating group, with the result that the carbonyl group substituted on the benzene ring has the enol form.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057005/sf3061sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057005/sf3061Isup2.hkl Contains datablock I

CCDC reference: 628666

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.040
wR factor = 0.103
Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C1     -   C2      ..       8.43 su

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.752     1.000
            Tmin(prime) and Tmax expected:      0.718     0.854
            RR(prime) =      0.895
            Please check that your absorption correction is appropriate.
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.20 Sigma
PLAT048_ALERT_1_C MoietyFormula Not Given ........................          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.85
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          1
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C5      ..       5.02 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Fe

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.854
            Tmax scaled      0.854 Tmin scaled      0.642
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe          (3)       3.97
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

There has been a growing interest in functional liquid crystal materials (Kato,2002; Kato et al., 2006; Gin et al., 2001). For instance, incorporation of metal atoms into liquid crystalline materals (metallmesoges) provides new opportunities in materials science through tuning of anisotropic optical, electronic, and magnetic properties (Oriol & Serrano, 2005; Trzaska et al., 1999). Mixed ferrocene/beta-diketones mesogens have therefore attracted considerable attention for their potential redox switching activity and stability (Plazuk et al., 2001; Koizumi et al., 2002). In view of theapplications as the ligand of transition metal complexes which could be shown liquid crystalline properties, we have designed and synthesized the title compound,(I) (Figure. 1), derived by the condensation of actylferrocene and methyl 4-octanoxy benzonate.

From the crystal structure data, it is indicated that both cyclopentadienyl (Cp) groups of (I) are coplanar with the largest torsion angle 0.3 (3) ° between the two endocyclic C—C bonds for C2—C3—C4—C5 and the largest deviation of C atom of -0.0017(0.0014) for C3. The two Cp rings are almost parallel to each other as shown by the dihedral angle of 0.97 (0.17)°. The distances between Fe atom and two Cp planes are 1.6386 (0.0008) and 1.6436 (0.0010) Å,respectively and the distance between the two Cp rings is 3.2822 Å. The Fe—C bond distances are nearly equidistant and possess a mean value of 2.0312 Å and the mean distance of C—C bonds within Cp rings is 1.407 Å, whereas C6—C10 of 1.423 (2) Å and C9—C10 of 1.432 (2) Å are slightly longer due to the effect of substituted group. The mean value of bond angles of C—Fe—C is 40.53° and of Fe—C—C is 69.85° when the two carbon atoms are adjacent within the Cp rings. The bond angles of adjacent C—C—C in the same cyclopentadienyl ring have a mean value of 108.0°. The data above accord with the literature reported (Glidewell et al., 1996; Zhang et al., 2006). The bond length of C11—C12 (1.398 (3) Å) and C12—C13 (1.387 (2) Å) is shorter than the normal value of single C—C bond (1.54 Å) but close to the normal carbon-carbon double bond (1.34 Å) becaused of beta-diketone enolization. Enolization of the title compound (I) can also account for the bond length of O1—C11 and O2—C13 which is 1.285 (2) and 1.295 (2) Å respectively and remarkably shorter than the normal value of single O—C bond (1.42 Å) but a little longer than the normal C═O double bond (1.22 Å). Bond length O3—C17 of 1.395 (2) Å with partially double bonded properties results from conjugation of benzene ring and is shorter than the normal single O—C bond such as O3—C20 of 1.432 (2) Å. The ferrocenyl is a more powerful electron-donating group, resulting that the carbonyl group substituted on benzene ring favors the form of enol as shown in scheme below, which is also demonstrated by the shorter bond length of C12—C13 than that of C11—C12. The enol form of the beta-diketone is stabilized by an intramolecular hydrogen bonding (O1···H2A—O2: bond length 1.72 (2) Å, bond angle 151 (3) °, O2—H2A bond length 0.852 (17) Å, symmetry codes: (-x,y + 1/2,-z + 1/2). The bond angles around C11, C12 and C13 all averaging to 120° respectively demonstrated these atoms of sp² hybridization.

Related literature top

For related literature, see: Kato (2002); Koizumi et al. (2002); Plazuk et al. (2001); Zhang et al. (2006); Gin et al. (2001); Kato et al. (2006); Oriol & Serrano (2005); Shi et al. (2006); Trzaska et al. (1999).

Experimental top

The title compound was synthesized by dropwise additon of methyl 4-octanoxy benzonate (4 mmol) to a 25 ml dimethoxy-ethane solution of NaH (33 mmol) and acetylferrocene (4 mmol) under N₂. After the mixture were kept refluxing for 4 h, the solvent was evaporated, the remaining product was washed by 5% KOH solution for several times then extracted with benzene, the resulting product was purified by column chromatography (silica gel,100—200 meshes, eluant petroleum ether). The solid residue was recrystallized using petroleum ether by slow evaporation to afford dark red crystals (yield 76%, m.p.353 K). 1HNMR (CDCl₃, 500 MHz): delta 6.99 (m, 4H, Ar—H), 6.35 (s, 2H, COCH₂CO), 4.91—4.55 (m, 4H, C₅H₄), 4.24 (s, 5H, C₅H₅), 1.85—1.32 (m, 14 H, O(CH₂)₇), 0.92 (t, 3H, CH₃).

All H atoms were included in calculated positions as riding atoms, with C—H distance of 0.93 Å for aromatic H atoms, 0.893 Å for methine H atoms, 0.97 Å for methylene H atoms and 0.96 Å for the methyl H atom.

Computing details top

Data collection: SMART (Bruker 1997); cell refinement: SMART (Bruker 1997); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Sheldrick, 1997a); software used to prepare material for publication: SHELXTL (Sheldrick, 1997a).

Figures top

	Fig. 1. The X-ray crystal structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.
	Fig. 2. A packing diagram for (I), viewed along the c axis. The a axis is to the right and the b axis is upwards.
	Fig. 3. Reaction scheme.

1-Ferrocenyl-3-(4-n-octoxylphenyl)propane-1,3-dione top

Crystal data top

[Fe(C₅H₅)(C₂₂H₂₇O₃)]	D_x = 1.293 Mg m⁻³
M_r = 460.38	Melting point: 353 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.5985 (14) Å	Cell parameters from 5300 reflections
b = 10.5710 (8) Å	θ = 4.4–54.5°
c = 12.0814 (10) Å	µ = 0.66 mm⁻¹
β = 95.105 (1)°	T = 293 K
V = 2365.8 (3) Å³	Prismatic, red
Z = 4	0.49 × 0.42 × 0.24 mm
F(000) = 976

Data collection top

Bruker SMART CCD area-detector diffractometer	5151 independent reflections
Radiation source: fine-focus sealed tube	3981 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
phi and ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→20
T_min = 0.752, T_max = 1.000	k = −10→13
13567 measured reflections	l = −15→14

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0587P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.013
5151 reflections	Δρ_max = 0.44 e Å⁻³
290 parameters	Δρ_min = −0.34 e Å⁻³
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (5)

Crystal data top

[Fe(C₅H₅)(C₂₂H₂₇O₃)]	V = 2365.8 (3) Å³
M_r = 460.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.5985 (14) Å	µ = 0.66 mm⁻¹
b = 10.5710 (8) Å	T = 293 K
c = 12.0814 (10) Å	0.49 × 0.42 × 0.24 mm
β = 95.105 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5151 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3981 reflections with I > 2σ(I)
T_min = 0.752, T_max = 1.000	R_int = 0.056
13567 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	2 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.44 e Å⁻³
5151 reflections	Δρ_min = −0.34 e Å⁻³
290 parameters

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
Fe	0.410173 (12)	0.40073 (2)	0.66175 (2)	0.04243 (11)
O1	0.26966 (7)	0.25316 (14)	0.45703 (11)	0.0625 (4)
O2	0.16093 (8)	0.13125 (15)	0.50208 (12)	0.0596 (4)
O3	−0.06702 (8)	0.08529 (13)	0.85417 (12)	0.0643 (4)
C1	0.41834 (12)	0.2181 (2)	0.7121 (2)	0.0738 (7)
H1	0.3847	0.1548	0.6937	0.089*
C2	0.41979 (13)	0.2987 (2)	0.80485 (19)	0.0713 (6)
H2	0.3872	0.2979	0.8590	0.086*
C3	0.47802 (15)	0.3793 (2)	0.8014 (2)	0.0769 (7)
H3	0.4913	0.4424	0.8529	0.092*
C4	0.51349 (12)	0.3502 (3)	0.7082 (2)	0.0770 (7)
H4	0.5546	0.3905	0.6872	0.092*
C5	0.47771 (13)	0.2510 (2)	0.6515 (2)	0.0719 (6)
H5	0.4902	0.2134	0.5863	0.086*
C6	0.31896 (9)	0.50533 (17)	0.66238 (16)	0.0489 (4)
H6	0.2874	0.5058	0.7179	0.059*
C7	0.37895 (11)	0.58600 (16)	0.65660 (18)	0.0535 (5)
H7	0.3938	0.6487	0.7076	0.064*
C8	0.41245 (10)	0.55505 (17)	0.56015 (17)	0.0529 (5)
H8	0.4533	0.5940	0.5366	0.063*
C9	0.37379 (10)	0.45521 (18)	0.50528 (15)	0.0496 (4)
H9	0.3846	0.4169	0.4395	0.060*
C10	0.31494 (9)	0.42315 (16)	0.56879 (16)	0.0445 (4)
C11	0.26385 (9)	0.31945 (17)	0.54492 (15)	0.0460 (4)
C12	0.20941 (10)	0.29419 (18)	0.61446 (16)	0.0494 (4)
C13	0.15841 (9)	0.20017 (17)	0.59023 (15)	0.0452 (4)
C14	0.09937 (9)	0.17412 (16)	0.66001 (15)	0.0459 (4)
C15	0.09550 (10)	0.2317 (2)	0.76240 (18)	0.0601 (5)
H15	0.1308	0.2902	0.7868	0.072*
C16	0.04136 (10)	0.2051 (2)	0.82892 (18)	0.0611 (5)
H16	0.0406	0.2445	0.8976	0.073*
C17	−0.01206 (10)	0.11943 (18)	0.79344 (17)	0.0521 (5)
C18	−0.00993 (11)	0.0630 (2)	0.69056 (18)	0.0628 (5)
H18	−0.0462	0.0067	0.6652	0.075*
C19	0.04489 (11)	0.08889 (18)	0.62566 (17)	0.0565 (5)
H19	0.0458	0.0488	0.5573	0.068*
C20	−0.06966 (10)	0.1404 (2)	0.96201 (18)	0.0586 (5)
H20A	−0.0743	0.2316	0.9556	0.070*
H20B	−0.0255	0.1215	1.0080	0.070*
C21	−0.13316 (11)	0.08680 (19)	1.01395 (18)	0.0590 (5)
H21A	−0.1280	−0.0043	1.0194	0.071*
H21B	−0.1767	0.1046	0.9663	0.071*
C22	−0.14099 (10)	0.1403 (2)	1.12839 (17)	0.0599 (5)
H22A	−0.1444	0.2317	1.1231	0.072*
H22B	−0.0980	0.1200	1.1765	0.072*
C23	−0.20655 (11)	0.09033 (19)	1.18099 (17)	0.0577 (5)
H23A	−0.2496	0.1132	1.1341	0.069*
H23B	−0.2040	−0.0013	1.1836	0.069*
C24	−0.21352 (11)	0.1393 (2)	1.29670 (18)	0.0608 (5)
H24A	−0.2160	0.2309	1.2939	0.073*
H24B	−0.1703	0.1165	1.3434	0.073*
C25	−0.27851 (11)	0.09053 (19)	1.35034 (18)	0.0595 (5)
H25A	−0.3219	0.1165	1.3056	0.071*
H25B	−0.2772	−0.0012	1.3506	0.071*
C26	−0.28289 (13)	0.1364 (2)	1.46786 (19)	0.0704 (6)
H26A	−0.2403	0.1079	1.5133	0.085*
H26B	−0.2826	0.2281	1.4681	0.085*
C27	−0.34914 (17)	0.0907 (3)	1.5191 (2)	0.1007 (10)
H27A	−0.3916	0.1191	1.4751	0.121*
H27B	−0.3491	0.1239	1.5931	0.121*
H27C	−0.3489	−0.0001	1.5220	0.121*
H12	0.2083 (9)	0.3413 (16)	0.6756 (13)	0.046 (5)*
H2A	0.1963 (12)	0.156 (3)	0.468 (2)	0.107 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.03781 (16)	0.04017 (16)	0.04925 (18)	0.00032 (10)	0.00359 (11)	0.00728 (11)
O1	0.0600 (8)	0.0718 (9)	0.0564 (9)	−0.0068 (7)	0.0085 (7)	−0.0158 (7)
O2	0.0574 (9)	0.0673 (9)	0.0533 (9)	−0.0097 (7)	0.0001 (7)	−0.0133 (7)
O3	0.0587 (8)	0.0717 (10)	0.0635 (9)	−0.0214 (7)	0.0107 (7)	−0.0110 (7)
C1	0.0664 (14)	0.0423 (11)	0.109 (2)	−0.0009 (10)	−0.0108 (13)	0.0249 (12)
C2	0.0807 (15)	0.0706 (15)	0.0643 (15)	0.0110 (12)	0.0154 (12)	0.0283 (12)
C3	0.0842 (17)	0.0758 (16)	0.0648 (16)	−0.0036 (13)	−0.0255 (14)	0.0157 (12)
C4	0.0416 (11)	0.0894 (18)	0.098 (2)	0.0047 (12)	−0.0060 (12)	0.0356 (15)
C5	0.0711 (14)	0.0673 (14)	0.0782 (16)	0.0328 (12)	0.0119 (12)	0.0119 (12)
C6	0.0426 (9)	0.0457 (10)	0.0590 (12)	0.0043 (8)	0.0081 (8)	−0.0020 (9)
C7	0.0538 (11)	0.0381 (10)	0.0677 (13)	−0.0001 (8)	0.0008 (9)	−0.0013 (9)
C8	0.0534 (11)	0.0426 (10)	0.0633 (13)	−0.0022 (8)	0.0091 (9)	0.0143 (9)
C9	0.0539 (11)	0.0499 (11)	0.0454 (10)	0.0044 (9)	0.0058 (8)	0.0081 (8)
C10	0.0384 (9)	0.0440 (10)	0.0506 (11)	0.0050 (7)	0.0019 (8)	0.0019 (8)
C11	0.0406 (9)	0.0468 (10)	0.0491 (11)	0.0056 (7)	−0.0042 (8)	−0.0001 (8)
C12	0.0480 (10)	0.0499 (11)	0.0502 (11)	−0.0035 (8)	0.0026 (8)	−0.0116 (9)
C13	0.0416 (9)	0.0475 (10)	0.0451 (10)	0.0042 (8)	−0.0051 (7)	0.0004 (8)
C14	0.0419 (9)	0.0433 (10)	0.0507 (11)	−0.0017 (7)	−0.0065 (8)	0.0000 (8)
C15	0.0523 (11)	0.0621 (12)	0.0659 (13)	−0.0192 (9)	0.0056 (9)	−0.0181 (10)
C16	0.0563 (12)	0.0658 (13)	0.0618 (13)	−0.0163 (10)	0.0090 (10)	−0.0189 (10)
C17	0.0462 (10)	0.0512 (11)	0.0582 (12)	−0.0075 (8)	0.0008 (9)	−0.0013 (9)
C18	0.0602 (12)	0.0643 (13)	0.0631 (13)	−0.0228 (10)	0.0005 (10)	−0.0095 (10)
C19	0.0570 (12)	0.0604 (13)	0.0511 (12)	−0.0130 (9)	−0.0006 (9)	−0.0089 (9)
C20	0.0519 (11)	0.0627 (12)	0.0612 (13)	−0.0083 (10)	0.0047 (9)	−0.0044 (10)
C21	0.0532 (11)	0.0613 (13)	0.0625 (13)	−0.0097 (9)	0.0048 (10)	−0.0002 (10)
C22	0.0506 (11)	0.0634 (12)	0.0646 (14)	−0.0076 (9)	−0.0007 (10)	−0.0024 (10)
C23	0.0544 (11)	0.0598 (13)	0.0586 (13)	−0.0056 (9)	0.0024 (10)	0.0000 (9)
C24	0.0553 (12)	0.0619 (12)	0.0645 (14)	−0.0042 (10)	0.0018 (10)	−0.0034 (10)
C25	0.0542 (11)	0.0638 (13)	0.0598 (13)	0.0002 (9)	0.0013 (10)	0.0015 (10)
C26	0.0728 (15)	0.0758 (15)	0.0626 (15)	0.0071 (12)	0.0048 (12)	0.0001 (11)
C27	0.096 (2)	0.134 (3)	0.0759 (19)	0.0109 (17)	0.0303 (16)	0.0143 (16)

Geometric parameters (Å, º) top

Fe—C10	2.0250 (18)	C12—H12	0.893 (14)
Fe—C4	2.025 (2)	C13—C14	1.469 (2)
Fe—C6	2.0255 (17)	C14—C15	1.386 (3)
Fe—C1	2.026 (2)	C14—C19	1.391 (2)
Fe—C3	2.028 (2)	C15—C16	1.372 (3)
Fe—C5	2.031 (2)	C15—H15	0.9300
Fe—C2	2.032 (2)	C16—C17	1.384 (3)
Fe—C9	2.0336 (18)	C16—H16	0.9300
Fe—C7	2.0421 (17)	C17—C18	1.383 (3)
Fe—C8	2.0442 (18)	C18—C19	1.368 (3)
O1—C11	1.285 (2)	C18—H18	0.9300
O2—C13	1.295 (2)	C19—H19	0.9300
O2—H2A	0.852 (17)	C20—C21	1.497 (3)
O3—C17	1.359 (2)	C20—H20A	0.9700
O3—C20	1.432 (2)	C20—H20B	0.9700
C1—C2	1.406 (3)	C21—C22	1.513 (3)
C1—C5	1.421 (3)	C21—H21A	0.9700
C1—H1	0.9300	C21—H21B	0.9700
C2—C3	1.382 (3)	C22—C23	1.519 (3)
C2—H2	0.9300	C22—H22A	0.9700
C3—C4	1.389 (4)	C22—H22B	0.9700
C3—H3	0.9300	C23—C24	1.507 (3)
C4—C5	1.390 (4)	C23—H23A	0.9700
C4—H4	0.9300	C23—H23B	0.9700
C5—H5	0.9300	C24—C25	1.512 (3)
C6—C7	1.411 (3)	C24—H24A	0.9700
C6—C10	1.423 (2)	C24—H24B	0.9700
C6—H6	0.9300	C25—C26	1.509 (3)
C7—C8	1.408 (3)	C25—H25A	0.9700
C7—H7	0.9300	C25—H25B	0.9700
C8—C9	1.409 (3)	C26—C27	1.507 (3)
C8—H8	0.9300	C26—H26A	0.9700
C9—C10	1.432 (2)	C26—H26B	0.9700
C9—H9	0.9300	C27—H27A	0.9600
C10—C11	1.462 (2)	C27—H27B	0.9600
C11—C12	1.398 (3)	C27—H27C	0.9600
C12—C13	1.387 (2)

C10—Fe—C4	161.12 (10)	C9—C8—Fe	69.38 (10)
C10—Fe—C6	41.12 (7)	C7—C8—H8	125.7
C4—Fe—C6	156.54 (11)	C9—C8—H8	125.7
C10—Fe—C1	108.46 (8)	Fe—C8—H8	126.7
C4—Fe—C1	67.75 (10)	C8—C9—C10	107.91 (17)
C6—Fe—C1	124.02 (9)	C8—C9—Fe	70.19 (11)
C10—Fe—C3	157.43 (10)	C10—C9—Fe	69.02 (10)
C4—Fe—C3	40.09 (11)	C8—C9—H9	126.0
C6—Fe—C3	121.15 (10)	C10—C9—H9	126.0
C1—Fe—C3	67.61 (10)	Fe—C9—H9	126.3
C10—Fe—C5	124.92 (10)	C6—C10—C9	107.01 (16)
C4—Fe—C5	40.07 (10)	C6—C10—C11	126.99 (16)
C6—Fe—C5	161.49 (9)	C9—C10—C11	125.87 (17)
C1—Fe—C5	41.02 (9)	C6—C10—Fe	69.46 (10)
C3—Fe—C5	67.75 (11)	C9—C10—Fe	69.66 (10)
C10—Fe—C2	122.71 (9)	C11—C10—Fe	122.85 (12)
C4—Fe—C2	67.33 (10)	O1—C11—C12	120.75 (17)
C6—Fe—C2	107.27 (9)	O1—C11—C10	118.08 (16)
C1—Fe—C2	40.54 (10)	C12—C11—C10	121.16 (16)
C3—Fe—C2	39.79 (9)	C13—C12—C11	121.90 (17)
C5—Fe—C2	68.30 (9)	C13—C12—H12	120.6 (12)
C10—Fe—C9	41.33 (7)	C11—C12—H12	117.5 (12)
C4—Fe—C9	124.16 (10)	O2—C13—C12	120.18 (16)
C6—Fe—C9	68.86 (7)	O2—C13—C14	116.77 (16)
C1—Fe—C9	123.98 (10)	C12—C13—C14	123.05 (16)
C3—Fe—C9	159.41 (10)	C15—C14—C19	117.14 (17)
C5—Fe—C9	108.68 (9)	C15—C14—C13	122.06 (16)
C2—Fe—C9	159.72 (9)	C19—C14—C13	120.80 (17)
C10—Fe—C7	68.81 (8)	C16—C15—C14	122.14 (17)
C4—Fe—C7	121.45 (10)	C16—C15—H15	118.9
C6—Fe—C7	40.59 (8)	C14—C15—H15	118.9
C1—Fe—C7	159.49 (10)	C15—C16—C17	119.78 (19)
C3—Fe—C7	106.66 (10)	C15—C16—H16	120.1
C5—Fe—C7	157.09 (10)	C17—C16—H16	120.1
C2—Fe—C7	122.56 (9)	O3—C17—C18	116.99 (17)
C9—Fe—C7	68.28 (8)	O3—C17—C16	124.08 (18)
C10—Fe—C8	68.74 (7)	C18—C17—C16	118.92 (18)
C4—Fe—C8	107.89 (9)	C19—C18—C17	120.75 (18)
C6—Fe—C8	68.21 (8)	C19—C18—H18	119.6
C1—Fe—C8	159.36 (10)	C17—C18—H18	119.6
C3—Fe—C8	122.98 (9)	C18—C19—C14	121.25 (19)
C5—Fe—C8	122.63 (9)	C18—C19—H19	119.4
C2—Fe—C8	158.36 (10)	C14—C19—H19	119.4
C9—Fe—C8	40.43 (7)	O3—C20—C21	108.64 (16)
C7—Fe—C8	40.31 (8)	O3—C20—H20A	110.0
C13—O2—H2A	108 (2)	C21—C20—H20A	110.0
C17—O3—C20	118.13 (15)	O3—C20—H20B	110.0
C2—C1—C5	107.6 (2)	C21—C20—H20B	110.0
C2—C1—Fe	69.98 (12)	H20A—C20—H20B	108.3
C5—C1—Fe	69.70 (12)	C20—C21—C22	112.67 (17)
C2—C1—H1	126.2	C20—C21—H21A	109.1
C5—C1—H1	126.2	C22—C21—H21A	109.1
Fe—C1—H1	125.7	C20—C21—H21B	109.1
C3—C2—C1	108.0 (2)	C22—C21—H21B	109.1
C3—C2—Fe	69.94 (12)	H21A—C21—H21B	107.8
C1—C2—Fe	69.48 (12)	C21—C22—C23	113.50 (17)
C3—C2—H2	126.0	C21—C22—H22A	108.9
C1—C2—H2	126.0	C23—C22—H22A	108.9
Fe—C2—H2	126.2	C21—C22—H22B	108.9
C2—C3—C4	108.5 (2)	C23—C22—H22B	108.9
C2—C3—Fe	70.27 (13)	H22A—C22—H22B	107.7
C4—C3—Fe	69.85 (14)	C24—C23—C22	114.03 (17)
C2—C3—H3	125.7	C24—C23—H23A	108.7
C4—C3—H3	125.7	C22—C23—H23A	108.7
Fe—C3—H3	125.7	C24—C23—H23B	108.7
C3—C4—C5	109.0 (2)	C22—C23—H23B	108.7
C3—C4—Fe	70.06 (13)	H23A—C23—H23B	107.6
C5—C4—Fe	70.20 (12)	C23—C24—C25	114.73 (18)
C3—C4—H4	125.5	C23—C24—H24A	108.6
C5—C4—H4	125.5	C25—C24—H24A	108.6
Fe—C4—H4	125.8	C23—C24—H24B	108.6
C4—C5—C1	106.9 (2)	C25—C24—H24B	108.6
C4—C5—Fe	69.74 (13)	H24A—C24—H24B	107.6
C1—C5—Fe	69.28 (12)	C26—C25—C24	113.94 (19)
C4—C5—H5	126.6	C26—C25—H25A	108.8
C1—C5—H5	126.6	C24—C25—H25A	108.8
Fe—C5—H5	126.0	C26—C25—H25B	108.8
C7—C6—C10	108.40 (16)	C24—C25—H25B	108.8
C7—C6—Fe	70.34 (10)	H25A—C25—H25B	107.7
C10—C6—Fe	69.42 (10)	C27—C26—C25	113.5 (2)
C7—C6—H6	125.8	C27—C26—H26A	108.9
C10—C6—H6	125.8	C25—C26—H26A	108.9
Fe—C6—H6	126.0	C27—C26—H26B	108.9
C8—C7—C6	108.10 (17)	C25—C26—H26B	108.9
C8—C7—Fe	69.93 (10)	H26A—C26—H26B	107.7
C6—C7—Fe	69.07 (10)	C26—C27—H27A	109.5
C8—C7—H7	126.0	C26—C27—H27B	109.5
C6—C7—H7	126.0	H27A—C27—H27B	109.5
Fe—C7—H7	126.6	C26—C27—H27C	109.5
C7—C8—C9	108.58 (17)	H27A—C27—H27C	109.5
C7—C8—Fe	69.77 (10)	H27B—C27—H27C	109.5

C10—Fe—C1—C2	−119.09 (14)	C3—Fe—C7—C8	121.69 (14)
C4—Fe—C1—C2	80.65 (16)	C5—Fe—C7—C8	49.6 (3)
C6—Fe—C1—C2	−76.22 (16)	C2—Fe—C7—C8	162.18 (12)
C3—Fe—C1—C2	37.16 (15)	C9—Fe—C7—C8	−37.15 (11)
C5—Fe—C1—C2	118.5 (2)	C10—Fe—C7—C6	37.88 (11)
C9—Fe—C1—C2	−162.22 (12)	C4—Fe—C7—C6	−159.86 (13)
C7—Fe—C1—C2	−40.4 (3)	C1—Fe—C7—C6	−48.3 (3)
C8—Fe—C1—C2	162.3 (2)	C3—Fe—C7—C6	−118.71 (13)
C10—Fe—C1—C5	122.40 (15)	C5—Fe—C7—C6	169.2 (2)
C4—Fe—C1—C5	−37.86 (15)	C2—Fe—C7—C6	−78.23 (15)
C6—Fe—C1—C5	165.27 (14)	C9—Fe—C7—C6	82.44 (12)
C3—Fe—C1—C5	−81.35 (17)	C8—Fe—C7—C6	119.59 (17)
C2—Fe—C1—C5	−118.5 (2)	C6—C7—C8—C9	0.0 (2)
C9—Fe—C1—C5	79.26 (16)	Fe—C7—C8—C9	58.68 (13)
C7—Fe—C1—C5	−158.9 (2)	C6—C7—C8—Fe	−58.70 (13)
C8—Fe—C1—C5	43.8 (3)	C10—Fe—C8—C7	81.90 (12)
C5—C1—C2—C3	0.3 (2)	C4—Fe—C8—C7	−117.83 (15)
Fe—C1—C2—C3	−59.55 (15)	C6—Fe—C8—C7	37.54 (11)
C5—C1—C2—Fe	59.82 (14)	C1—Fe—C8—C7	167.9 (2)
C10—Fe—C2—C3	−160.68 (15)	C3—Fe—C8—C7	−76.33 (16)
C4—Fe—C2—C3	37.44 (16)	C5—Fe—C8—C7	−159.40 (14)
C6—Fe—C2—C3	−118.23 (16)	C2—Fe—C8—C7	−44.4 (3)
C1—Fe—C2—C3	119.2 (2)	C9—Fe—C8—C7	120.10 (16)
C5—Fe—C2—C3	80.85 (17)	C10—Fe—C8—C9	−38.20 (11)
C9—Fe—C2—C3	166.1 (2)	C4—Fe—C8—C9	122.07 (14)
C7—Fe—C2—C3	−76.40 (18)	C6—Fe—C8—C9	−82.56 (12)
C8—Fe—C2—C3	−43.9 (3)	C1—Fe—C8—C9	47.8 (3)
C10—Fe—C2—C1	80.10 (15)	C3—Fe—C8—C9	163.58 (14)
C4—Fe—C2—C1	−81.78 (16)	C5—Fe—C8—C9	80.50 (15)
C6—Fe—C2—C1	122.55 (13)	C2—Fe—C8—C9	−164.5 (2)
C3—Fe—C2—C1	−119.2 (2)	C7—Fe—C8—C9	−120.10 (16)
C5—Fe—C2—C1	−38.37 (14)	C7—C8—C9—C10	0.0 (2)
C9—Fe—C2—C1	46.9 (3)	Fe—C8—C9—C10	58.91 (12)
C7—Fe—C2—C1	164.38 (13)	C7—C8—C9—Fe	−58.91 (13)
C8—Fe—C2—C1	−163.2 (2)	C10—Fe—C9—C8	119.22 (16)
C1—C2—C3—C4	−0.3 (3)	C4—Fe—C9—C8	−77.06 (15)
Fe—C2—C3—C4	−59.59 (16)	C6—Fe—C9—C8	80.79 (12)
C1—C2—C3—Fe	59.26 (15)	C1—Fe—C9—C8	−161.63 (12)
C10—Fe—C3—C2	46.5 (3)	C3—Fe—C9—C8	−42.4 (3)
C4—Fe—C3—C2	−119.4 (2)	C5—Fe—C9—C8	−118.74 (13)
C6—Fe—C3—C2	79.42 (17)	C2—Fe—C9—C8	163.4 (2)
C1—Fe—C3—C2	−37.85 (14)	C7—Fe—C9—C8	37.05 (11)
C5—Fe—C3—C2	−82.36 (16)	C4—Fe—C9—C10	163.72 (13)
C9—Fe—C3—C2	−166.3 (2)	C6—Fe—C9—C10	−38.43 (10)
C7—Fe—C3—C2	121.23 (15)	C1—Fe—C9—C10	79.14 (14)
C8—Fe—C3—C2	162.24 (14)	C3—Fe—C9—C10	−161.6 (3)
C10—Fe—C3—C4	165.9 (2)	C5—Fe—C9—C10	122.04 (12)
C6—Fe—C3—C4	−161.16 (14)	C2—Fe—C9—C10	44.2 (3)
C1—Fe—C3—C4	81.57 (17)	C7—Fe—C9—C10	−82.18 (12)
C5—Fe—C3—C4	37.06 (15)	C8—Fe—C9—C10	−119.22 (16)
C2—Fe—C3—C4	119.4 (2)	C7—C6—C10—C9	−0.1 (2)
C9—Fe—C3—C4	−46.9 (3)	Fe—C6—C10—C9	−59.81 (12)
C7—Fe—C3—C4	−119.35 (16)	C7—C6—C10—C11	176.05 (17)
C8—Fe—C3—C4	−78.34 (18)	Fe—C6—C10—C11	116.30 (18)
C2—C3—C4—C5	0.3 (3)	C7—C6—C10—Fe	59.76 (13)
Fe—C3—C4—C5	−59.59 (15)	C8—C9—C10—C6	0.0 (2)
C2—C3—C4—Fe	59.85 (16)	Fe—C9—C10—C6	59.68 (12)
C10—Fe—C4—C3	−163.2 (2)	C8—C9—C10—C11	−176.12 (16)
C6—Fe—C4—C3	44.0 (3)	Fe—C9—C10—C11	−116.48 (18)
C1—Fe—C4—C3	−81.20 (17)	C8—C9—C10—Fe	−59.64 (12)
C5—Fe—C4—C3	−119.9 (2)	C4—Fe—C10—C6	−164.0 (3)
C2—Fe—C4—C3	−37.16 (15)	C1—Fe—C10—C6	120.97 (13)
C9—Fe—C4—C3	161.92 (14)	C3—Fe—C10—C6	45.1 (3)
C7—Fe—C4—C3	78.19 (17)	C5—Fe—C10—C6	163.49 (12)
C8—Fe—C4—C3	120.30 (15)	C2—Fe—C10—C6	78.52 (14)
C10—Fe—C4—C5	−43.2 (3)	C9—Fe—C10—C6	−118.18 (15)
C6—Fe—C4—C5	163.89 (18)	C7—Fe—C10—C6	−37.40 (11)
C1—Fe—C4—C5	38.74 (15)	C8—Fe—C10—C6	−80.78 (12)
C3—Fe—C4—C5	119.9 (2)	C4—Fe—C10—C9	−45.8 (3)
C2—Fe—C4—C5	82.77 (16)	C6—Fe—C10—C9	118.18 (15)
C9—Fe—C4—C5	−78.14 (17)	C1—Fe—C10—C9	−120.85 (13)
C7—Fe—C4—C5	−161.87 (13)	C3—Fe—C10—C9	163.2 (2)
C8—Fe—C4—C5	−119.76 (15)	C5—Fe—C10—C9	−78.33 (13)
C3—C4—C5—C1	−0.1 (3)	C2—Fe—C10—C9	−163.30 (12)
Fe—C4—C5—C1	−59.60 (14)	C7—Fe—C10—C9	80.78 (12)
C3—C4—C5—Fe	59.51 (16)	C8—Fe—C10—C9	37.39 (11)
C2—C1—C5—C4	−0.1 (2)	C4—Fe—C10—C11	74.5 (3)
Fe—C1—C5—C4	59.89 (15)	C6—Fe—C10—C11	−121.53 (19)
C2—C1—C5—Fe	−60.00 (14)	C1—Fe—C10—C11	−0.56 (18)
C10—Fe—C5—C4	164.31 (14)	C3—Fe—C10—C11	−76.5 (3)
C6—Fe—C5—C4	−159.6 (2)	C5—Fe—C10—C11	41.96 (19)
C1—Fe—C5—C4	−118.1 (2)	C2—Fe—C10—C11	−43.01 (18)
C3—Fe—C5—C4	−37.08 (15)	C9—Fe—C10—C11	120.29 (19)
C2—Fe—C5—C4	−80.13 (17)	C7—Fe—C10—C11	−158.93 (17)
C9—Fe—C5—C4	121.26 (15)	C8—Fe—C10—C11	157.69 (17)
C7—Fe—C5—C4	43.0 (3)	C6—C10—C11—O1	−178.33 (17)
C8—Fe—C5—C4	78.79 (18)	C9—C10—C11—O1	−2.9 (3)
C10—Fe—C5—C1	−77.63 (17)	Fe—C10—C11—O1	−90.42 (19)
C4—Fe—C5—C1	118.1 (2)	C6—C10—C11—C12	2.8 (3)
C6—Fe—C5—C1	−41.6 (3)	C9—C10—C11—C12	178.15 (17)
C3—Fe—C5—C1	80.98 (17)	Fe—C10—C11—C12	90.66 (19)
C2—Fe—C5—C1	37.93 (15)	O1—C11—C12—C13	−2.0 (3)
C9—Fe—C5—C1	−120.68 (15)	C10—C11—C12—C13	176.85 (17)
C7—Fe—C5—C1	161.1 (2)	C11—C12—C13—O2	1.1 (3)
C8—Fe—C5—C1	−163.15 (14)	C11—C12—C13—C14	−178.12 (17)
C10—Fe—C6—C7	−119.49 (16)	O2—C13—C14—C15	172.73 (18)
C4—Fe—C6—C7	47.5 (3)	C12—C13—C14—C15	−8.0 (3)
C1—Fe—C6—C7	161.61 (14)	O2—C13—C14—C19	−6.7 (3)
C3—Fe—C6—C7	79.02 (15)	C12—C13—C14—C19	172.56 (18)
C5—Fe—C6—C7	−166.7 (2)	C19—C14—C15—C16	1.1 (3)
C2—Fe—C6—C7	120.23 (13)	C13—C14—C15—C16	−178.35 (19)
C9—Fe—C6—C7	−80.87 (13)	C14—C15—C16—C17	−0.8 (3)
C8—Fe—C6—C7	−37.29 (12)	C20—O3—C17—C18	178.74 (19)
C4—Fe—C6—C10	167.0 (2)	C20—O3—C17—C16	−0.5 (3)
C1—Fe—C6—C10	−78.90 (15)	C15—C16—C17—O3	178.73 (19)
C3—Fe—C6—C10	−161.49 (12)	C15—C16—C17—C18	−0.5 (3)
C5—Fe—C6—C10	−47.2 (3)	O3—C17—C18—C19	−177.85 (19)
C2—Fe—C6—C10	−120.28 (12)	C16—C17—C18—C19	1.5 (3)
C9—Fe—C6—C10	38.61 (10)	C17—C18—C19—C14	−1.1 (3)
C7—Fe—C6—C10	119.49 (16)	C15—C14—C19—C18	−0.2 (3)
C8—Fe—C6—C10	82.20 (12)	C13—C14—C19—C18	179.31 (18)
C10—C6—C7—C8	0.0 (2)	C17—O3—C20—C21	−178.62 (17)
Fe—C6—C7—C8	59.23 (13)	O3—C20—C21—C22	−179.53 (17)
C10—C6—C7—Fe	−59.18 (12)	C20—C21—C22—C23	178.09 (18)
C10—Fe—C7—C8	−81.71 (12)	C21—C22—C23—C24	177.94 (18)
C4—Fe—C7—C8	80.55 (16)	C22—C23—C24—C25	180.00 (18)
C6—Fe—C7—C8	−119.59 (17)	C23—C24—C25—C26	177.61 (18)
C1—Fe—C7—C8	−167.9 (2)	C24—C25—C26—C27	178.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.85 (2)	1.72 (2)	2.499 (2)	151 (3)

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₂₂H₂₇O₃)]
M_r	460.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	18.5985 (14), 10.5710 (8), 12.0814 (10)
β (°)	95.105 (1)
V (Å³)	2365.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.49 × 0.42 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.752, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13567, 5151, 3981
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.103, 0.96
No. of reflections	5151
No. of parameters	290
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.34

Computer programs: SMART (Bruker 1997), SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b).