Crystal structure of 4-methyl-2-oxo-2H-chromen-7-yl ferrocene­carboxyl­ate

Abstract

The title mol­ecule, [Fe(C₅H₅)(C₁₆H₁₁O₄)], consists of a ferrocenyl moiety and a 4-methyl­coumarin group linked through an ester unit to one of the cyclo­penta­dienyl (Cp) rings. The two Cp rings are virually parallel, with an angle between the two least-squares planes of 0.74 (16)°. The distances between the Fe^II atom and the centroids of the two Cp rings are 1.639 (2) and 1.652 (2) Å. The conformation of the ferrocenyl moiety is slightly away from eclipsed. The dihedral angle between the coumarin ring system and the ferrocenyl ester moiety is 69.17 (19)°. π–π stacking inter­actions involving the benzene rings of neighbouring coumarin moieties, with centroid–centroid distances of 3.739 (2) Å, consolidate the crystal packing.

Related literature  

For background to ferrocene and its derivatives, see: Štěpnička (2002 ▶). For coumarin and its pharmacological activities, see: Peng et al. (2013 ▶). For the crystal structures of related ferrocenyl derivatives, see: Chen & Lu (2004 ▶); Imrie et al. (2002 ▶, 2005 ▶).

Experimental  

Crystal data  

• [Fe(C₅H₅)(C₁₆H₁₁O₄)]

• M _r = 388.19

• Monoclinic,

• a = 7.8678 (11) Å

• b = 20.294 (4) Å

• c = 11.1455 (18) Å

• β = 108.243 (14)°

• V = 1690.1 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.92 mm⁻¹

• T = 293 K

• 0.20 × 0.10 × 0.10 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.838, T _max = 0.914

• 11857 measured reflections

• 2979 independent reflections

• 2398 reflections with I > 2σ(I)

• R _int = 0.031

Refinement  

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.087

• S = 1.16

• 2979 reflections

• 236 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Supplementary Material

CCDC reference: 1027955

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

S1. Experimental

To a CH₂Cl₂ solution (30 ml) of ferrocenylcarboxylic acid (1.0 g, 4.3 mmol), 7-hydroxy-4-methylcoumarin (0.76 g, 4.3 mmol), 1-ethyl-3-(dimethylaminopropyl)carbodimide hydrochloride (EDCI) (0.89 g, 4.5 mmol) and N,N-dimethylaminopyridine (DMAP) (0.26 g, 2.2 mmol) were added into a 50 ml round bottom flask. Then the reaction mixture was stirred at room temperature. The reaction process was monitored by thin layer chromatography (TLC). After completion of the reaction, the product was extracted with ethyl acetate. The extracts were combined, washed with water and dried over anhydrous Na₂SO₄. After removing ethyl acetate under reduced pressure, the crude product was purified by column chromatography using petroleum ether/EtOAc (8:1) as eluent. Yellow crystals were obtained by slow evaporation of an ether/EtOAc (8:1) solution to give 1.03 g (62% yield) of the title compound, ¹H-NMR (CDCl₃, δ p.p.m.), 2.48 (s, 2H, CH₃), 4.34 (s, 5H, C₅H₅), 4.57 (s, 2H, C₅H₂), 5.00 (s, 2H, C₅H₂), 7.18–7.22 (m, 2H, ArH), 7.68 (d, 1H, ArH).

S2. Refinement

All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2 U_eq.

Figures

Fig. 1.

The molecular structure of the title compound showing atoms as ellipsoids at the 30% probability level.

Crystal data

[Fe(C5H5)(C16H11O4)]	F(000) = 800
Mr = 388.19	Dx = 1.526 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3613 reflections
a = 7.8678 (11) Å	θ = 2.7–23.4°
b = 20.294 (4) Å	µ = 0.92 mm−1
c = 11.1455 (18) Å	T = 293 K
β = 108.243 (14)°	Block, yellow
V = 1690.1 (5) Å3	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	2979 independent reflections
Radiation source: fine-focus sealed tube	2398 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
Tmin = 0.838, Tmax = 0.914	k = −24→24
11857 measured reflections	l = −13→12

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.16	w = 1/[σ2(Fo2) + (0.0432P)2] where P = (Fo2 + 2Fc2)/3
2979 reflections	(Δ/σ)max = 0.001
236 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.74731 (4)	0.157566 (14)	0.42513 (3)	0.04477 (13)
O1	0.4801 (2)	0.07407 (8)	0.61150 (16)	0.0717 (5)
O2	0.7574 (2)	0.09846 (8)	0.74074 (15)	0.0695 (5)
O3	0.7829 (2)	−0.13167 (8)	0.81894 (15)	0.0654 (5)
O4	0.7893 (3)	−0.23952 (9)	0.8434 (2)	0.0910 (6)
C1	0.7620 (3)	0.25205 (11)	0.4903 (2)	0.0620 (7)
H1	0.8464	0.2857	0.4811	0.074*
C2	0.5913 (3)	0.24019 (11)	0.4035 (2)	0.0616 (6)
H2	0.5372	0.2640	0.3242	0.074*
C3	0.5129 (3)	0.18719 (11)	0.4494 (2)	0.0549 (6)
H3	0.3943	0.1683	0.4083	0.066*
C4	0.6368 (3)	0.16608 (10)	0.5653 (2)	0.0490 (5)
C5	0.7925 (3)	0.20659 (10)	0.5906 (2)	0.0560 (6)
H5	0.9001	0.2037	0.6644	0.067*
C6	0.9160 (4)	0.15047 (13)	0.3194 (3)	0.0734 (8)
H6	0.9804	0.1869	0.2955	0.088*
C7	0.7462 (4)	0.12856 (15)	0.2511 (2)	0.0771 (8)
H7	0.6698	0.1464	0.1707	0.093*
C8	0.7034 (4)	0.07557 (13)	0.3160 (3)	0.0764 (8)
H8	0.5928	0.0497	0.2897	0.092*
C9	0.8462 (4)	0.06495 (12)	0.4251 (3)	0.0758 (9)
H9	0.8544	0.0310	0.4892	0.091*
C10	0.9783 (4)	0.11104 (14)	0.4274 (3)	0.0737 (8)
H10	1.0946	0.1155	0.4929	0.088*
C11	0.6091 (3)	0.10858 (11)	0.6366 (2)	0.0533 (6)
C12	0.7538 (3)	0.04467 (11)	0.8189 (2)	0.0573 (6)
C13	0.7677 (3)	−0.01842 (12)	0.7792 (2)	0.0586 (6)
H13	0.7736	−0.0268	0.6986	0.070*
C14	0.7727 (3)	−0.06931 (11)	0.8629 (2)	0.0497 (5)
C15	0.7663 (3)	−0.05849 (10)	0.9842 (2)	0.0478 (5)
C16	0.7540 (3)	0.00656 (11)	1.0201 (2)	0.0609 (6)
H16	0.7509	0.0155	1.1012	0.073*
C17	0.7463 (3)	0.05785 (12)	0.9382 (2)	0.0633 (7)
H17	0.7361	0.1010	0.9631	0.076*
C18	0.7724 (3)	−0.11504 (12)	1.0658 (2)	0.0528 (6)
C19	0.7797 (3)	−0.17514 (12)	1.0191 (3)	0.0624 (7)
H19	0.7826	−0.2113	1.0709	0.075*
C20	0.7833 (3)	−0.18689 (13)	0.8926 (3)	0.0674 (7)
C21	0.7700 (4)	−0.10441 (13)	1.1988 (2)	0.0731 (8)
H21A	0.7715	−0.1463	1.2392	0.110*
H21B	0.6636	−0.0808	1.1972	0.110*
H21C	0.8733	−0.0794	1.2449	0.110*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Fe1	0.0529 (2)	0.03700 (19)	0.0492 (2)	0.00541 (13)	0.02285 (16)	0.00617 (13)
O1	0.0629 (11)	0.0796 (12)	0.0749 (12)	−0.0128 (10)	0.0250 (10)	0.0156 (10)
O2	0.0814 (12)	0.0671 (11)	0.0539 (10)	−0.0207 (9)	0.0125 (9)	0.0164 (8)
O3	0.0824 (13)	0.0564 (10)	0.0612 (10)	0.0045 (9)	0.0279 (9)	−0.0112 (8)
O4	0.1009 (15)	0.0562 (11)	0.1085 (16)	0.0149 (10)	0.0219 (13)	−0.0211 (11)
C1	0.0792 (19)	0.0351 (11)	0.0761 (18)	0.0034 (11)	0.0306 (16)	0.0030 (12)
C2	0.0711 (17)	0.0467 (13)	0.0711 (17)	0.0193 (12)	0.0282 (14)	0.0145 (12)
C3	0.0530 (14)	0.0545 (13)	0.0617 (15)	0.0134 (11)	0.0244 (12)	0.0002 (12)
C4	0.0602 (15)	0.0440 (12)	0.0487 (13)	0.0060 (10)	0.0253 (12)	−0.0004 (10)
C5	0.0695 (16)	0.0426 (12)	0.0558 (14)	−0.0003 (11)	0.0196 (12)	−0.0036 (11)
C6	0.089 (2)	0.0639 (16)	0.090 (2)	0.0025 (15)	0.0609 (19)	0.0054 (15)
C7	0.100 (2)	0.0832 (19)	0.0534 (16)	0.0245 (17)	0.0307 (16)	−0.0026 (15)
C8	0.082 (2)	0.0568 (16)	0.106 (2)	−0.0087 (14)	0.052 (2)	−0.0307 (16)
C9	0.106 (2)	0.0499 (14)	0.096 (2)	0.0350 (16)	0.067 (2)	0.0242 (14)
C10	0.0569 (16)	0.089 (2)	0.0793 (19)	0.0225 (15)	0.0268 (15)	−0.0039 (16)
C11	0.0627 (16)	0.0550 (14)	0.0498 (14)	0.0015 (12)	0.0285 (13)	0.0003 (11)
C12	0.0632 (16)	0.0573 (14)	0.0481 (14)	−0.0121 (11)	0.0128 (12)	0.0100 (11)
C13	0.0683 (16)	0.0676 (16)	0.0429 (13)	−0.0056 (13)	0.0218 (12)	0.0003 (12)
C14	0.0499 (13)	0.0500 (12)	0.0511 (14)	−0.0007 (10)	0.0187 (11)	−0.0044 (11)
C15	0.0503 (13)	0.0486 (12)	0.0468 (13)	−0.0011 (10)	0.0184 (11)	−0.0001 (10)
C16	0.0886 (18)	0.0535 (14)	0.0466 (14)	−0.0041 (13)	0.0298 (13)	−0.0036 (11)
C17	0.092 (2)	0.0468 (13)	0.0555 (16)	−0.0043 (12)	0.0292 (14)	−0.0028 (11)
C18	0.0517 (14)	0.0540 (14)	0.0550 (14)	0.0031 (10)	0.0199 (12)	0.0082 (11)
C19	0.0591 (16)	0.0518 (14)	0.0778 (18)	0.0053 (12)	0.0234 (14)	0.0106 (13)
C20	0.0589 (16)	0.0546 (15)	0.085 (2)	0.0083 (12)	0.0177 (14)	−0.0042 (15)
C21	0.092 (2)	0.0718 (17)	0.0631 (17)	0.0049 (15)	0.0353 (15)	0.0209 (13)

Geometric parameters (Å, º)

Fe1—C4	2.019 (2)	C6—C10	1.400 (4)
Fe1—C7	2.024 (2)	C6—H6	0.9793
Fe1—C8	2.026 (2)	C7—C8	1.395 (4)
Fe1—C5	2.027 (2)	C7—H7	0.9791
Fe1—C9	2.034 (2)	C8—C9	1.390 (4)
Fe1—C6	2.037 (3)	C8—H8	0.9793
Fe1—C3	2.037 (2)	C9—C10	1.393 (4)
Fe1—C1	2.041 (2)	C9—H9	0.9794
Fe1—C10	2.042 (2)	C10—H10	0.9796
Fe1—C2	2.047 (2)	C12—C13	1.370 (3)
O1—C11	1.192 (3)	C12—C17	1.376 (3)
O2—C11	1.379 (3)	C13—C14	1.384 (3)
O2—C12	1.402 (3)	C13—H13	0.9300
O3—C14	1.368 (3)	C14—C15	1.387 (3)
O3—C20	1.388 (3)	C15—C16	1.391 (3)
O4—C20	1.208 (3)	C15—C18	1.456 (3)
C1—C2	1.408 (3)	C16—C17	1.373 (3)
C1—C5	1.411 (3)	C16—H16	0.9300
C1—H1	0.9799	C17—H17	0.9300
C2—C3	1.413 (3)	C18—C19	1.335 (3)
C2—H2	0.9799	C18—C21	1.503 (3)
C3—C4	1.419 (3)	C19—C20	1.439 (4)
C3—H3	0.9800	C19—H19	0.9300
C4—C5	1.428 (3)	C21—H21A	0.9600
C4—C11	1.466 (3)	C21—H21B	0.9600
C5—H5	0.9800	C21—H21C	0.9600
C6—C7	1.387 (4)
C4—Fe1—C7	153.19 (12)	C1—C5—Fe1	70.25 (13)
C4—Fe1—C8	120.07 (10)	C4—C5—Fe1	69.05 (13)
C7—Fe1—C8	40.29 (11)	C1—C5—H5	126.3
C4—Fe1—C5	41.35 (9)	C4—C5—H5	126.4
C7—Fe1—C5	164.06 (12)	Fe1—C5—H5	126.4
C8—Fe1—C5	153.89 (12)	C7—C6—C10	107.9 (3)
C4—Fe1—C9	109.67 (9)	C7—C6—Fe1	69.54 (16)
C7—Fe1—C9	67.55 (11)	C10—C6—Fe1	70.10 (15)
C8—Fe1—C9	40.03 (12)	C7—C6—H6	125.7
C5—Fe1—C9	119.71 (11)	C10—C6—H6	126.4
C4—Fe1—C6	165.92 (12)	Fe1—C6—H6	126.2
C7—Fe1—C6	39.94 (11)	C6—C7—C8	108.1 (3)
C8—Fe1—C6	67.30 (11)	C6—C7—Fe1	70.52 (15)
C5—Fe1—C6	126.92 (12)	C8—C7—Fe1	69.91 (15)
C9—Fe1—C6	67.43 (10)	C6—C7—H7	126.4
C4—Fe1—C3	40.94 (9)	C8—C7—H7	125.5
C7—Fe1—C3	118.74 (12)	Fe1—C7—H7	125.9
C8—Fe1—C3	109.32 (11)	C9—C8—C7	108.2 (3)
C5—Fe1—C3	69.04 (10)	C9—C8—Fe1	70.30 (15)
C9—Fe1—C3	129.41 (11)	C7—C8—Fe1	69.80 (15)
C6—Fe1—C3	151.50 (12)	C9—C8—H8	125.3
C4—Fe1—C1	68.54 (9)	C7—C8—H8	126.5
C7—Fe1—C1	126.66 (11)	Fe1—C8—H8	126.0
C8—Fe1—C1	164.88 (13)	C8—C9—C10	107.8 (2)
C5—Fe1—C1	40.59 (9)	C8—C9—Fe1	69.67 (14)
C9—Fe1—C1	152.77 (13)	C10—C9—Fe1	70.30 (14)
C6—Fe1—C1	107.33 (10)	C8—C9—H9	126.7
C3—Fe1—C1	68.16 (10)	C10—C9—H9	125.5
C4—Fe1—C10	128.88 (11)	Fe1—C9—H9	126.0
C7—Fe1—C10	67.28 (12)	C9—C10—C6	108.0 (3)
C8—Fe1—C10	67.12 (12)	C9—C10—Fe1	69.73 (14)
C5—Fe1—C10	108.31 (11)	C6—C10—Fe1	69.76 (15)
C9—Fe1—C10	39.97 (11)	C9—C10—H10	126.3
C6—Fe1—C10	40.14 (11)	C6—C10—H10	125.6
C3—Fe1—C10	167.07 (11)	Fe1—C10—H10	125.9
C1—Fe1—C10	118.65 (11)	O1—C11—O2	122.9 (2)
C4—Fe1—C2	68.50 (9)	O1—C11—C4	126.9 (2)
C7—Fe1—C2	107.62 (11)	O2—C11—C4	110.1 (2)
C8—Fe1—C2	128.22 (13)	C13—C12—C17	121.7 (2)
C5—Fe1—C2	68.47 (10)	C13—C12—O2	120.5 (2)
C9—Fe1—C2	166.40 (13)	C17—C12—O2	117.7 (2)
C6—Fe1—C2	117.71 (10)	C12—C13—C14	117.9 (2)
C3—Fe1—C2	40.49 (9)	C12—C13—H13	121.0
C1—Fe1—C2	40.30 (9)	C14—C13—H13	121.0
C10—Fe1—C2	151.52 (11)	O3—C14—C13	116.2 (2)
C11—O2—C12	117.52 (18)	O3—C14—C15	121.31 (19)
C14—O3—C20	121.64 (19)	C13—C14—C15	122.5 (2)
C2—C1—C5	108.8 (2)	C14—C15—C16	117.2 (2)
C2—C1—Fe1	70.10 (13)	C14—C15—C18	118.70 (19)
C5—C1—Fe1	69.16 (13)	C16—C15—C18	124.1 (2)
C2—C1—H1	125.3	C17—C16—C15	121.4 (2)
C5—C1—H1	125.9	C17—C16—H16	119.3
Fe1—C1—H1	125.6	C15—C16—H16	119.3
C1—C2—C3	108.1 (2)	C16—C17—C12	119.2 (2)
C1—C2—Fe1	69.60 (13)	C16—C17—H17	120.4
C3—C2—Fe1	69.36 (12)	C12—C17—H17	120.4
C1—C2—H2	125.9	C19—C18—C15	118.3 (2)
C3—C2—H2	125.9	C19—C18—C21	122.1 (2)
Fe1—C2—H2	125.8	C15—C18—C21	119.6 (2)
C2—C3—C4	107.8 (2)	C18—C19—C20	123.4 (2)
C2—C3—Fe1	70.14 (13)	C18—C19—H19	118.3
C4—C3—Fe1	68.86 (13)	C20—C19—H19	118.3
C2—C3—H3	126.0	O4—C20—O3	116.0 (3)
C4—C3—H3	126.1	O4—C20—C19	127.3 (3)
Fe1—C3—H3	126.3	O3—C20—C19	116.6 (2)
C3—C4—C5	108.0 (2)	C18—C21—H21A	109.5
C3—C4—C11	123.9 (2)	C18—C21—H21B	109.5
C5—C4—C11	127.9 (2)	H21A—C21—H21B	109.5
C3—C4—Fe1	70.20 (12)	C18—C21—H21C	109.5
C5—C4—Fe1	69.60 (13)	H21A—C21—H21C	109.5
C11—C4—Fe1	121.63 (15)	H21B—C21—H21C	109.5
C1—C5—C4	107.3 (2)
C4—Fe1—C1—C2	−81.64 (15)	C5—Fe1—C6—C10	73.7 (2)
C7—Fe1—C1—C2	72.90 (19)	C9—Fe1—C6—C10	−37.39 (17)
C8—Fe1—C1—C2	45.9 (5)	C3—Fe1—C6—C10	−169.9 (2)
C5—Fe1—C1—C2	−120.3 (2)	C1—Fe1—C6—C10	114.14 (18)
C9—Fe1—C1—C2	−173.15 (19)	C2—Fe1—C6—C10	156.54 (17)
C6—Fe1—C1—C2	112.64 (16)	C10—C6—C7—C8	−0.2 (3)
C3—Fe1—C1—C2	−37.43 (14)	Fe1—C6—C7—C8	−60.10 (18)
C10—Fe1—C1—C2	154.74 (15)	C10—C6—C7—Fe1	59.88 (19)
C4—Fe1—C1—C5	38.64 (14)	C4—Fe1—C7—C6	−170.58 (19)
C7—Fe1—C1—C5	−166.82 (16)	C8—Fe1—C7—C6	−118.6 (2)
C8—Fe1—C1—C5	166.2 (4)	C5—Fe1—C7—C6	39.2 (5)
C9—Fe1—C1—C5	−52.9 (3)	C9—Fe1—C7—C6	−81.18 (18)
C6—Fe1—C1—C5	−127.08 (17)	C3—Fe1—C7—C6	154.99 (15)
C3—Fe1—C1—C5	82.85 (16)	C1—Fe1—C7—C6	71.9 (2)
C10—Fe1—C1—C5	−84.98 (17)	C10—Fe1—C7—C6	−37.73 (16)
C2—Fe1—C1—C5	120.3 (2)	C2—Fe1—C7—C6	112.36 (17)
C5—C1—C2—C3	0.3 (3)	C4—Fe1—C7—C8	−51.9 (3)
Fe1—C1—C2—C3	58.83 (16)	C5—Fe1—C7—C8	157.9 (3)
C5—C1—C2—Fe1	−58.48 (16)	C9—Fe1—C7—C8	37.47 (18)
C4—Fe1—C2—C1	81.76 (15)	C6—Fe1—C7—C8	118.6 (2)
C7—Fe1—C2—C1	−126.44 (17)	C3—Fe1—C7—C8	−86.37 (19)
C8—Fe1—C2—C1	−166.21 (15)	C1—Fe1—C7—C8	−169.44 (17)
C5—Fe1—C2—C1	37.16 (14)	C10—Fe1—C7—C8	80.91 (19)
C9—Fe1—C2—C1	166.6 (4)	C2—Fe1—C7—C8	−128.99 (18)
C6—Fe1—C2—C1	−84.32 (18)	C6—C7—C8—C9	0.4 (3)
C3—Fe1—C2—C1	119.7 (2)	Fe1—C7—C8—C9	−60.04 (18)
C10—Fe1—C2—C1	−51.8 (3)	C6—C7—C8—Fe1	60.48 (18)
C4—Fe1—C2—C3	−37.91 (14)	C4—Fe1—C8—C9	−85.15 (18)
C7—Fe1—C2—C3	113.89 (17)	C7—Fe1—C8—C9	119.1 (2)
C8—Fe1—C2—C3	74.12 (19)	C5—Fe1—C8—C9	−47.3 (3)
C5—Fe1—C2—C3	−82.52 (15)	C6—Fe1—C8—C9	81.44 (18)
C9—Fe1—C2—C3	46.9 (5)	C3—Fe1—C8—C9	−128.94 (16)
C6—Fe1—C2—C3	156.00 (16)	C1—Fe1—C8—C9	153.4 (4)
C1—Fe1—C2—C3	−119.7 (2)	C10—Fe1—C8—C9	37.73 (16)
C10—Fe1—C2—C3	−171.4 (2)	C2—Fe1—C8—C9	−170.38 (15)
C1—C2—C3—C4	−0.2 (3)	C4—Fe1—C8—C7	155.77 (17)
Fe1—C2—C3—C4	58.74 (15)	C5—Fe1—C8—C7	−166.4 (2)
C1—C2—C3—Fe1	−58.98 (16)	C9—Fe1—C8—C7	−119.1 (2)
C4—Fe1—C3—C2	119.3 (2)	C6—Fe1—C8—C7	−37.64 (17)
C7—Fe1—C3—C2	−83.65 (19)	C3—Fe1—C8—C7	111.99 (18)
C8—Fe1—C3—C2	−126.80 (18)	C1—Fe1—C8—C7	34.3 (5)
C5—Fe1—C3—C2	81.00 (16)	C10—Fe1—C8—C7	−81.35 (18)
C9—Fe1—C3—C2	−167.16 (17)	C2—Fe1—C8—C7	70.5 (2)
C6—Fe1—C3—C2	−49.0 (3)	C7—C8—C9—C10	−0.5 (3)
C1—Fe1—C3—C2	37.26 (14)	Fe1—C8—C9—C10	−60.22 (18)
C10—Fe1—C3—C2	161.5 (4)	C7—C8—C9—Fe1	59.72 (18)
C7—Fe1—C3—C4	157.10 (15)	C4—Fe1—C9—C8	113.68 (17)
C8—Fe1—C3—C4	113.95 (16)	C7—Fe1—C9—C8	−37.70 (17)
C5—Fe1—C3—C4	−38.26 (13)	C5—Fe1—C9—C8	158.13 (16)
C9—Fe1—C3—C4	73.59 (19)	C6—Fe1—C9—C8	−81.09 (19)
C6—Fe1—C3—C4	−168.2 (2)	C3—Fe1—C9—C8	71.81 (19)
C1—Fe1—C3—C4	−81.99 (15)	C1—Fe1—C9—C8	−165.2 (2)
C10—Fe1—C3—C4	42.2 (5)	C10—Fe1—C9—C8	−118.6 (2)
C2—Fe1—C3—C4	−119.3 (2)	C2—Fe1—C9—C8	33.9 (5)
C2—C3—C4—C5	0.1 (3)	C4—Fe1—C9—C10	−127.68 (17)
Fe1—C3—C4—C5	59.59 (15)	C7—Fe1—C9—C10	80.94 (18)
C2—C3—C4—C11	−175.0 (2)	C8—Fe1—C9—C10	118.6 (2)
Fe1—C3—C4—C11	−115.4 (2)	C5—Fe1—C9—C10	−83.24 (18)
C2—C3—C4—Fe1	−59.54 (15)	C6—Fe1—C9—C10	37.54 (17)
C7—Fe1—C4—C3	−49.2 (3)	C3—Fe1—C9—C10	−169.56 (16)
C8—Fe1—C4—C3	−85.19 (17)	C1—Fe1—C9—C10	−46.6 (3)
C5—Fe1—C4—C3	118.92 (19)	C2—Fe1—C9—C10	152.6 (4)
C9—Fe1—C4—C3	−128.09 (16)	C8—C9—C10—C6	0.4 (3)
C6—Fe1—C4—C3	156.4 (4)	Fe1—C9—C10—C6	−59.46 (18)
C1—Fe1—C4—C3	80.97 (15)	C8—C9—C10—Fe1	59.82 (17)
C10—Fe1—C4—C3	−168.86 (15)	C7—C6—C10—C9	−0.1 (3)
C2—Fe1—C4—C3	37.51 (14)	Fe1—C6—C10—C9	59.44 (17)
C7—Fe1—C4—C5	−168.1 (2)	C7—C6—C10—Fe1	−59.53 (19)
C8—Fe1—C4—C5	155.88 (16)	C4—Fe1—C10—C9	73.2 (2)
C9—Fe1—C4—C5	112.99 (16)	C7—Fe1—C10—C9	−81.66 (19)
C6—Fe1—C4—C5	37.5 (4)	C8—Fe1—C10—C9	−37.79 (17)
C3—Fe1—C4—C5	−118.92 (19)	C5—Fe1—C10—C9	114.70 (18)
C1—Fe1—C4—C5	−37.95 (14)	C6—Fe1—C10—C9	−119.2 (2)
C10—Fe1—C4—C5	72.22 (18)	C3—Fe1—C10—C9	38.7 (5)
C2—Fe1—C4—C5	−81.41 (15)	C1—Fe1—C10—C9	157.75 (17)
C7—Fe1—C4—C11	69.1 (3)	C2—Fe1—C10—C9	−166.9 (2)
C8—Fe1—C4—C11	33.1 (3)	C4—Fe1—C10—C6	−167.59 (16)
C5—Fe1—C4—C11	−122.8 (3)	C7—Fe1—C10—C6	37.55 (17)
C9—Fe1—C4—C11	−9.8 (2)	C8—Fe1—C10—C6	81.42 (19)
C6—Fe1—C4—C11	−85.3 (4)	C5—Fe1—C10—C6	−126.09 (18)
C3—Fe1—C4—C11	118.3 (3)	C9—Fe1—C10—C6	119.2 (2)
C1—Fe1—C4—C11	−160.7 (2)	C3—Fe1—C10—C6	158.0 (4)
C10—Fe1—C4—C11	−50.6 (3)	C1—Fe1—C10—C6	−83.04 (19)
C2—Fe1—C4—C11	155.8 (2)	C2—Fe1—C10—C6	−47.7 (3)
C2—C1—C5—C4	−0.3 (3)	C12—O2—C11—O1	0.4 (3)
Fe1—C1—C5—C4	−59.37 (15)	C12—O2—C11—C4	−179.32 (19)
C2—C1—C5—Fe1	59.06 (16)	C3—C4—C11—O1	−3.3 (4)
C3—C4—C5—C1	0.2 (3)	C5—C4—C11—O1	−177.3 (2)
C11—C4—C5—C1	174.9 (2)	Fe1—C4—C11—O1	−89.5 (3)
Fe1—C4—C5—C1	60.13 (16)	C3—C4—C11—O2	176.36 (19)
C3—C4—C5—Fe1	−59.97 (15)	C5—C4—C11—O2	2.4 (3)
C11—C4—C5—Fe1	114.8 (2)	Fe1—C4—C11—O2	90.1 (2)
C4—Fe1—C5—C1	−118.4 (2)	C11—O2—C12—C13	72.1 (3)
C7—Fe1—C5—C1	41.8 (4)	C11—O2—C12—C17	−111.6 (3)
C8—Fe1—C5—C1	−171.8 (2)	C17—C12—C13—C14	0.5 (4)
C9—Fe1—C5—C1	155.16 (16)	O2—C12—C13—C14	176.7 (2)
C6—Fe1—C5—C1	72.29 (19)	C20—O3—C14—C13	−178.0 (2)
C3—Fe1—C5—C1	−80.49 (15)	C20—O3—C14—C15	1.4 (3)
C10—Fe1—C5—C1	112.95 (17)	C12—C13—C14—O3	178.7 (2)
C2—Fe1—C5—C1	−36.90 (14)	C12—C13—C14—C15	−0.8 (4)
C7—Fe1—C5—C4	160.2 (4)	O3—C14—C15—C16	−179.2 (2)
C8—Fe1—C5—C4	−53.5 (3)	C13—C14—C15—C16	0.2 (4)
C9—Fe1—C5—C4	−86.45 (17)	O3—C14—C15—C18	0.6 (3)
C6—Fe1—C5—C4	−169.33 (14)	C13—C14—C15—C18	180.0 (2)
C3—Fe1—C5—C4	37.89 (13)	C14—C15—C16—C17	0.8 (4)
C1—Fe1—C5—C4	118.4 (2)	C18—C15—C16—C17	−179.1 (2)
C10—Fe1—C5—C4	−128.67 (15)	C15—C16—C17—C12	−1.1 (4)
C2—Fe1—C5—C4	81.48 (15)	C13—C12—C17—C16	0.4 (4)
C4—Fe1—C6—C7	162.3 (3)	O2—C12—C17—C16	−175.9 (2)
C8—Fe1—C6—C7	37.96 (18)	C14—C15—C18—C19	−1.5 (3)
C5—Fe1—C6—C7	−167.46 (16)	C16—C15—C18—C19	178.3 (2)
C9—Fe1—C6—C7	81.50 (19)	C14—C15—C18—C21	178.6 (2)
C3—Fe1—C6—C7	−51.0 (3)	C16—C15—C18—C21	−1.6 (4)
C1—Fe1—C6—C7	−126.98 (17)	C15—C18—C19—C20	0.5 (4)
C10—Fe1—C6—C7	118.9 (2)	C21—C18—C19—C20	−179.6 (2)
C2—Fe1—C6—C7	−84.58 (19)	C14—O3—C20—O4	178.6 (2)
C4—Fe1—C6—C10	43.5 (5)	C14—O3—C20—C19	−2.4 (3)
C7—Fe1—C6—C10	−118.9 (2)	C18—C19—C20—O4	−179.7 (3)
C8—Fe1—C6—C10	−80.92 (19)	C18—C19—C20—O3	1.4 (4)