(E)-2-(2-Adamantylidene)-3-(1-ferrocenylethylidene)succinic anhydride

The title compound, [Fe(C₅H₅)(C₂₁H₂₁O₃)], was obtained from successive Stobbe condensations between ketones and di­methyl succinate. The succinic anhydride five-membered ring is distorted significantly from planarity, with the buta­diene moiety being twisted by 49.3 (2)° from planarity and the C atoms at the succinic anhydride end of the alkene bonds showing significant pyramidalization. The cyclo­penta­diene rings of the ferrocenyl moiety adopt an almost eclipsed conformation.

S1. Comment

Organic fulgides with an aryl ring undergo photochromic ring closure to give highly coloured tricyclic dihydronaphthalene derivatives (Hart & Heller, 1972). The fulgides themselves can be synthesized using successive Stobbe condensations between ketones or aldehydes and a succinate diester (Heller & Szewczyk, 1974). Touchard & Dabard (1975) reported that Stobbe condensations can be carried out using acetylferrocene, without affecting the ferrocene nucleus. However, these organometallic fulgides, unlike organic fulgides, do not undergo photochromic ring closure, and molecular orbital calculations have shown that the ring closure is actually forbidden (McCabe et al., 1993). Studies on the E/Z isomerization of ferrocenyl fulgides demonstrated that the preferred isomer was the E isomer in sterically hindered fulgide systems (McCabe et al., 1993). In the present work, the sterically hindered title fulgide, (III), was synthesized and its crystal structure determined (Fig. 1). \sch

In the solid state, the succinic anhydride five-membered ring of (III) is distorted significantly from planarity and adopts a half-chair conformation twisted on C12—C13, where the atoms C12 and C13 are 0.122 (3) and −0.156 (3) Å, respectively, from the plane defined by atoms C14, O15 and C16. This has consequences for the torsion angles about the C11═C12 and C13═C18 double bonds, which deviate by up to 24° from the normally expected values of 0 or 180° in an alkene system (Table 1). In addition, atoms C12 and C13 show significant pryamidalization from the expected trigonal planar conformation, with atom C12 lying 0.120 (1) Å from the plane defined by atoms C11, C13 and C16, while atom C13 lies 0.124 (1) Å from the plane defined by atoms C12, C14 and C18. In contrast, atoms C11 and C18 have almost no pyramidalization, being only 0.020 (1) and 0.038 (1) Å, respectively, from the planes defined by their three surrounding atoms.

The torsion angle of the butadiene fragment is also severely skewed [C11—C12—C13—C18 − 49.3 (2)°]. This is commonly observed in fulgides and has been attributed to steric congestion imposed by the rigidity of the alkene substituents (Kaftory, 1984; Kaftory et al., 1998). Of the 29 different fulgide structures currently stored in the Cambridge Structural Database (CSD; October 2002 release; Allen, 2002), the largest twist of the butadiene C—C bond is 56 (1)° in 2-(2-adamantylidene)-3-(9-fluorenylidene)succinic anhydride (Kaftory et al., 1998), which is a quite sterically crowded molecule and is the only other reported fulgide structure in which an adamantylidene moiety is present. Kaftory et al. (1998) have discussed this twist in more detail, but an interesting additional observation is that the twist is closely correlated with the degree of pyramidalization of the C atoms at the succinic anhydride end of the alkene bonds. For the 29 known fulgide structures, the deviations of these C atoms from the planes defined by their three surrounding C atoms are in the range 0.00–0.16 Å, with the largest value again being observed in the structure of 2-(2-adamantylidene)-3-(9-fluorenylidene)succinic anhydride.

The steric congestion between the adamantylidene and ferrocene moieties causes opening of the C11—C12—C13 and C12—C13—C18 angles, although these angles are close to the mean values derived from the other fulgide structures, in which these angles range from 124–139°. The bond lengths within the butadiene moiety are also close to the mean values derived from the reported fulgide structures.

The cyclopentadiene rings of the ferrocenyl moiety are rotated by only 8.03 (11)° from an eclipsed conformation and are tilted very slightly with respect to one another, so that the centres of gravity of the cyclopentadiene rings subtend an angle of 177.83 (3)° at the Fe atom. The distances between the Fe atom and the centres of gravity of the cyclopentadiene rings containing atoms C1 and C7 are 1.6460 (6) and 1.6552 (7) Å, respectively.

When the title compound (1 × 10⁻⁴ M in toluene) was irradiated at 366 nm for 2 h, no change was observed in the UV absorption spectrum of the solution. This is consistent with the expected absence of a photochromic ring-closure reaction. When the same solution was irradiated for 24 h, slightly shorter UV absorption wavelengths (4 nm) were recorded, which is presumed to be an indication of the formation of a small amount of the Z isomer. McCabe et al. (1993) reported that the irradiation of various E-ferrocenyl fulgide derivatives resulted in the formation of a photostationary equilibrium with the corresponding Z isomers, which were found to absorb at slightly shorter or longer UV wavelengths than the E isomers, depending on the derivative.

S2. Experimental

A mixture of dimethyl succinate (28 g, 0.2 mol), 2-adamantanone (36 g, 0.2 mol) and potassium tert-butoxide (22.4 g, 0.2 mol) in toluene (300 ml) was stirred at room temperature for 10 h. The resultant half-ester was then liberated by acidification with hydrochloric acid (5 M, Volume?) and extracted with ether (3 × 50 ml). The combined extracts were dried (MgSO₄), and then the ether was removed under reduced pressure to give the half-ester (38 g, 72%) as colorless cubes. Esterification of the half-ester (38 g) was conducted using acetyl chloride and methanol. The solvent was removed under reduced pressure and the residue was dissolved in ether and chromatographed on a short column (silica gel, petroleum ether, 2:1 Is a second solvent missing here?) to give dimethyl 2-(2-adamantylidene)succinate, (I), as a pale-yellow oil (27 g, 67%). Spectroscopic analysis: ¹H NMR (400 MHz, DMSO, δ, p.p.m.): 1.76–1.95, 2.84 (14H, m, adamantylidene H), 3.39 (2H, s, CH₂), 3.63 (3H, s, CH₃O), 3.68 (3H, s, CH₃O). A mixture of (I) (15 g, 0.05 mol), acetylferrocene (12 g, 0.05 mol) and potassium tert-butoxide (6.70 g, 0.06 moles) in toluene (200 ml) was stirred at room temperature for 10 h. Workup gave the half-ester in quantitative yield as a red gum. The half-ester was hydrolysed by boiling in 10% KOH. The crude diacid, (II), was dissolved in dichloromethane (100 ml) to give a red solution, which was cooled in an ice-salt-bath. Trifluoroacetic anhydride (3 ml) in dichloromethane (10 ml) was added dropwise and then stirred at room temperature for 3 h, after which the mixture was poured onto ice and extracted into ether. The ether solution was dried over MgSO₄ and evaporated to afford the title fulgide, (III), as red crystals (3.55 g, 16%), which were recrystallized from dichloromethane-petroleum ether (Ratio?) (m.p. 486–487 K). Spectroscopic analysis: ¹H NMR (400 MHz, DMSO, δ, p.p.m.): 1.49–1.88 (14H, m, adamantylidene H), 2.50 (3H, s, CH₃), 4.25 (5H, s, Cp' and 1H, s, Cp), 4.58 (3H, s, Cp); MS: m/z (ion, %I) 442 (M⁺, 100); UV: λ_max 339.5 and 494 nm. Elemental analysis, calculated for C₂₆H₂₆FeO₃: C 70.59, H 5.88%; found: C 70.76, H 5.94%.

S3. Refinement

The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the parent C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C). One low-angle reflection was omitted from the final cycles of refinement because its observed intensity was much lower than the calculated value, as a result of being partially obscured by the beam stop.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

Fig. 1. A view of the molecule of (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.

(E)-2-(2-adamantylidene)-3-(1-ferrocenylethylidene)succinic anhydride

Crystal data

[Fe(C5H5)(C21H21O3)]	Z = 2
Mr = 442.33	F(000) = 464
Triclinic, P1	Dx = 1.469 Mg m^−3
Hall symbol: -P 1	Melting point: 486 K
a = 9.5997 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4336 (1) Å	Cell parameters from 17312 reflections
c = 10.6348 (2) Å	θ = 2.0–30.0°
α = 72.0422 (6)°	µ = 0.78 mm^−1
β = 85.3458 (5)°	T = 160 K
γ = 80.8752 (6)°	Block, red
V = 999.87 (2) Å^3	0.35 × 0.22 × 0.17 mm

Data collection

Nonius KappaCCD area-detector diffractometer	5825 independent reflections
Radiation source: Nonius FR590 sealed tube generator	5116 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.037
Detector resolution: 9 pixels mm^-1	θmax = 30.0°, θmin = 2.0°
ϕ and ω scans with κ offsets	h = −13→13
Absorption correction: multi-scan (Blessing, 1995)	k = −13→14
Tmin = 0.831, Tmax = 0.880	l = −14→14
26888 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 0.3607P] where P = (Fo^2 + 2Fc^2)/3
5824 reflections	(Δ/σ)max = 0.003
272 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

Experimental. Solvent used: dichloromethane / petroleum ether Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.472 (1) Frames collected: 364 Seconds exposure per frame: 50 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

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
Fe	1.326588 (18)	0.111131 (17)	0.279157 (17)	0.01792 (6)
O14	0.77132 (12)	0.37033 (12)	−0.10442 (10)	0.0359 (2)
O15	0.80228 (10)	0.14439 (11)	−0.01723 (10)	0.0283 (2)
O16	0.85695 (12)	−0.07176 (11)	0.10713 (12)	0.0383 (3)
C1	1.11021 (12)	0.13127 (12)	0.30412 (12)	0.0168 (2)
C2	1.15578 (13)	0.25720 (12)	0.22544 (13)	0.0190 (2)
H2	1.1298	0.3059	0.1373	0.023*
C3	1.24655 (13)	0.29672 (13)	0.30201 (14)	0.0229 (3)
H3	1.2911	0.3764	0.2741	0.027*
C4	1.25878 (14)	0.19612 (14)	0.42725 (14)	0.0244 (3)
H4	1.3121	0.1976	0.4981	0.029*
C5	1.17793 (13)	0.09281 (13)	0.42874 (12)	0.0207 (2)
H5	1.1700	0.0122	0.4998	0.025*
C6	1.39674 (14)	−0.04508 (15)	0.19929 (15)	0.0285 (3)
H6	1.3414	−0.1059	0.1831	0.034*
C7	1.42381 (16)	0.08145 (17)	0.10937 (15)	0.0343 (3)
H7	1.3893	0.1206	0.0226	0.041*
C8	1.51136 (15)	0.13917 (16)	0.17178 (17)	0.0340 (3)
H8	1.5460	0.2237	0.1341	0.041*
C9	1.53814 (14)	0.04879 (15)	0.30024 (16)	0.0281 (3)
H9	1.5941	0.0620	0.3637	0.034*
C10	1.46684 (14)	−0.06462 (14)	0.31742 (14)	0.0254 (3)
H10	1.4661	−0.1406	0.3947	0.030*
C11	1.01897 (13)	0.05310 (12)	0.26188 (12)	0.0178 (2)
C12	0.91265 (13)	0.11649 (12)	0.17745 (12)	0.0186 (2)
C13	0.85500 (12)	0.26187 (12)	0.12224 (12)	0.0177 (2)
C14	0.80747 (13)	0.27488 (14)	−0.01122 (13)	0.0232 (3)
C16	0.85685 (14)	0.04523 (14)	0.09635 (14)	0.0251 (3)
C17	1.05176 (15)	−0.10034 (12)	0.31083 (14)	0.0240 (3)
H171	1.1228	−0.1269	0.3788	0.036*
H172	1.0882	−0.1347	0.2368	0.036*
H173	0.9655	−0.1388	0.3486	0.036*
C18	0.81401 (13)	0.35874 (12)	0.18345 (12)	0.0179 (2)
C19	0.74977 (14)	0.50308 (13)	0.11351 (14)	0.0233 (3)
H19	0.7530	0.5188	0.0157	0.028*
C20	0.83603 (16)	0.60018 (14)	0.14756 (15)	0.0294 (3)
H201	0.9356	0.5833	0.1172	0.035*
H202	0.7980	0.6956	0.1010	0.035*
C21	0.82918 (16)	0.57843 (14)	0.29693 (15)	0.0289 (3)
H21	0.8831	0.6439	0.3170	0.035*
C22	0.89524 (15)	0.43261 (14)	0.36680 (14)	0.0270 (3)
H221	0.8899	0.4164	0.4637	0.032*
H222	0.9959	0.4186	0.3386	0.032*
C23	0.81501 (14)	0.33213 (12)	0.33133 (13)	0.0218 (2)
H23	0.8583	0.2364	0.3749	0.026*
C24	0.59610 (15)	0.52715 (15)	0.16439 (16)	0.0315 (3)
H241	0.5536	0.6218	0.1201	0.038*
H242	0.5403	0.4648	0.1433	0.038*
C25	0.59240 (15)	0.50214 (15)	0.31359 (16)	0.0318 (3)
H25	0.4923	0.5161	0.3467	0.038*
C26	0.65953 (16)	0.35522 (14)	0.38044 (15)	0.0291 (3)
H261	0.6058	0.2911	0.3598	0.035*
H262	0.6556	0.3373	0.4776	0.035*
C27	0.67578 (17)	0.60134 (15)	0.34548 (17)	0.0340 (3)
H271	0.6334	0.6962	0.3018	0.041*
H272	0.6718	0.5867	0.4421	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.01559 (9)	0.01922 (9)	0.01859 (10)	0.00060 (6)	−0.00187 (6)	−0.00633 (7)
O14	0.0388 (6)	0.0435 (6)	0.0239 (5)	−0.0022 (5)	−0.0105 (4)	−0.0072 (5)
O15	0.0255 (5)	0.0384 (6)	0.0287 (5)	−0.0062 (4)	−0.0032 (4)	−0.0199 (4)
O16	0.0410 (6)	0.0319 (6)	0.0536 (7)	−0.0080 (5)	−0.0054 (5)	−0.0273 (5)
C1	0.0154 (5)	0.0162 (5)	0.0178 (5)	0.0003 (4)	0.0008 (4)	−0.0053 (4)
C2	0.0163 (5)	0.0163 (5)	0.0222 (6)	−0.0003 (4)	−0.0019 (4)	−0.0034 (4)
C3	0.0184 (6)	0.0194 (6)	0.0328 (7)	−0.0014 (4)	−0.0025 (5)	−0.0109 (5)
C4	0.0227 (6)	0.0287 (6)	0.0254 (7)	0.0023 (5)	−0.0050 (5)	−0.0154 (5)
C5	0.0225 (6)	0.0223 (6)	0.0159 (6)	0.0015 (5)	0.0002 (5)	−0.0061 (5)
C6	0.0198 (6)	0.0361 (7)	0.0375 (8)	0.0029 (5)	−0.0022 (5)	−0.0256 (6)
C7	0.0282 (7)	0.0482 (9)	0.0221 (7)	0.0102 (6)	0.0025 (5)	−0.0124 (6)
C8	0.0217 (7)	0.0314 (7)	0.0435 (9)	−0.0018 (6)	0.0114 (6)	−0.0076 (6)
C9	0.0154 (6)	0.0310 (7)	0.0416 (8)	0.0021 (5)	−0.0058 (5)	−0.0174 (6)
C10	0.0225 (6)	0.0223 (6)	0.0305 (7)	0.0048 (5)	−0.0033 (5)	−0.0100 (5)
C11	0.0191 (5)	0.0164 (5)	0.0187 (6)	−0.0032 (4)	0.0050 (4)	−0.0075 (4)
C12	0.0177 (5)	0.0197 (5)	0.0219 (6)	−0.0046 (4)	0.0030 (4)	−0.0112 (5)
C13	0.0151 (5)	0.0209 (5)	0.0178 (6)	−0.0037 (4)	−0.0009 (4)	−0.0062 (4)
C14	0.0171 (6)	0.0333 (7)	0.0218 (6)	−0.0039 (5)	−0.0009 (5)	−0.0117 (5)
C16	0.0204 (6)	0.0311 (7)	0.0303 (7)	−0.0059 (5)	0.0014 (5)	−0.0180 (6)
C17	0.0285 (7)	0.0165 (5)	0.0267 (7)	−0.0035 (5)	0.0054 (5)	−0.0076 (5)
C18	0.0164 (5)	0.0171 (5)	0.0196 (6)	−0.0035 (4)	−0.0003 (4)	−0.0040 (4)
C19	0.0248 (6)	0.0178 (5)	0.0242 (6)	−0.0012 (5)	−0.0032 (5)	−0.0023 (5)
C20	0.0329 (7)	0.0185 (6)	0.0351 (8)	−0.0076 (5)	0.0003 (6)	−0.0040 (5)
C21	0.0341 (7)	0.0199 (6)	0.0363 (8)	−0.0051 (5)	−0.0021 (6)	−0.0130 (5)
C22	0.0299 (7)	0.0257 (6)	0.0290 (7)	0.0013 (5)	−0.0056 (5)	−0.0149 (5)
C23	0.0284 (6)	0.0154 (5)	0.0206 (6)	0.0010 (5)	−0.0005 (5)	−0.0062 (4)
C24	0.0225 (6)	0.0260 (7)	0.0440 (9)	0.0036 (5)	−0.0062 (6)	−0.0101 (6)
C25	0.0231 (7)	0.0296 (7)	0.0434 (9)	0.0002 (5)	0.0068 (6)	−0.0161 (6)
C26	0.0348 (7)	0.0257 (6)	0.0281 (7)	−0.0080 (6)	0.0105 (6)	−0.0110 (5)
C27	0.0388 (8)	0.0217 (6)	0.0427 (9)	0.0035 (6)	0.0019 (7)	−0.0163 (6)

Geometric parameters (Å, º)

Fe—C5	2.0333 (13)	C11—C17	1.5119 (17)
Fe—C2	2.0397 (12)	C12—C16	1.4766 (17)
Fe—C9	2.0402 (13)	C12—C13	1.4795 (17)
Fe—C8	2.0410 (14)	C13—C18	1.3558 (17)
Fe—C10	2.0461 (13)	C13—C14	1.4859 (17)
Fe—C3	2.0462 (13)	C17—H171	0.9800
Fe—C4	2.0499 (13)	C17—H172	0.9800
Fe—C7	2.0511 (14)	C17—H173	0.9800
Fe—C1	2.0581 (12)	C18—C23	1.5109 (17)
Fe—C6	2.0601 (13)	C18—C19	1.5135 (17)
O14—C14	1.1967 (17)	C19—C24	1.5390 (19)
O15—C14	1.3914 (17)	C19—C20	1.5441 (19)
O15—C16	1.4015 (18)	C19—H19	1.0000
O16—C16	1.1902 (17)	C20—C21	1.531 (2)
C1—C2	1.4363 (16)	C20—H201	0.9900
C1—C5	1.4385 (17)	C20—H202	0.9900
C1—C11	1.4664 (17)	C21—C27	1.528 (2)
C2—C3	1.4243 (18)	C21—C22	1.5305 (19)
C2—H2	0.9500	C21—H21	1.0000
C3—C4	1.419 (2)	C22—C23	1.5432 (18)
C3—H3	0.9500	C22—H221	0.9900
C4—C5	1.4203 (19)	C22—H222	0.9900
C4—H4	0.9500	C23—C26	1.5478 (19)
C5—H5	0.9500	C23—H23	1.0000
C6—C10	1.417 (2)	C24—C25	1.525 (2)
C6—C7	1.419 (2)	C24—H241	0.9900
C6—H6	0.9500	C24—H242	0.9900
C7—C8	1.417 (2)	C25—C27	1.533 (2)
C7—H7	0.9500	C25—C26	1.536 (2)
C8—C9	1.417 (2)	C25—H25	1.0000
C8—H8	0.9500	C26—H261	0.9900
C9—C10	1.416 (2)	C26—H262	0.9900
C9—H9	0.9500	C27—H271	0.9900
C10—H10	0.9500	C27—H272	0.9900
C11—C12	1.3616 (17)
C5—Fe—C2	69.09 (5)	C9—C8—H8	126.0
C5—Fe—C9	125.81 (6)	Fe—C8—H8	125.8
C2—Fe—C9	152.57 (6)	C10—C9—C8	108.00 (13)
C5—Fe—C8	162.22 (6)	C10—C9—Fe	69.95 (7)
C2—Fe—C8	118.34 (6)	C8—C9—Fe	69.72 (8)
C9—Fe—C8	40.63 (6)	C10—C9—H9	126.0
C5—Fe—C10	108.88 (5)	C8—C9—H9	126.0
C2—Fe—C10	165.20 (5)	Fe—C9—H9	125.9
C9—Fe—C10	40.55 (6)	C9—C10—C6	108.10 (13)
C8—Fe—C10	68.22 (6)	C9—C10—Fe	69.50 (7)
C5—Fe—C3	68.78 (5)	C6—C10—Fe	70.34 (8)
C2—Fe—C3	40.80 (5)	C9—C10—H10	125.9
C9—Fe—C3	117.86 (5)	C6—C10—H10	125.9
C8—Fe—C3	105.53 (6)	Fe—C10—H10	125.8
C10—Fe—C3	153.37 (6)	C12—C11—C1	121.16 (11)
C5—Fe—C4	40.71 (5)	C12—C11—C17	121.38 (11)
C2—Fe—C4	68.45 (5)	C1—C11—C17	117.40 (11)
C9—Fe—C4	106.67 (6)	C11—C12—C16	120.95 (11)
C8—Fe—C4	124.30 (6)	C11—C12—C13	131.73 (11)
C10—Fe—C4	120.23 (6)	C16—C12—C13	105.75 (11)
C3—Fe—C4	40.54 (6)	C18—C13—C12	130.26 (11)
C5—Fe—C7	156.32 (6)	C18—C13—C14	122.51 (11)
C2—Fe—C7	107.55 (6)	C12—C13—C14	104.95 (10)
C9—Fe—C7	68.17 (6)	O14—C14—O15	118.95 (12)
C8—Fe—C7	40.51 (7)	O14—C14—C13	133.33 (13)
C10—Fe—C7	68.07 (6)	O15—C14—C13	107.67 (11)
C3—Fe—C7	124.90 (6)	O16—C16—O15	119.21 (12)
C4—Fe—C7	161.71 (7)	O16—C16—C12	133.29 (14)
C5—Fe—C1	41.16 (5)	O15—C16—C12	107.38 (11)
C2—Fe—C1	41.03 (5)	C11—C17—H171	109.5
C9—Fe—C1	164.50 (6)	C11—C17—H172	109.5
C8—Fe—C1	154.23 (6)	H171—C17—H172	109.5
C10—Fe—C1	127.93 (5)	C11—C17—H173	109.5
C3—Fe—C1	68.84 (5)	H171—C17—H173	109.5
C4—Fe—C1	68.62 (5)	H172—C17—H173	109.5
C7—Fe—C1	120.90 (6)	C13—C18—C23	123.91 (11)
C5—Fe—C6	121.94 (6)	C13—C18—C19	124.07 (11)
C2—Fe—C6	127.30 (5)	C23—C18—C19	111.82 (10)
C9—Fe—C6	68.02 (6)	C18—C19—C24	109.15 (11)
C8—Fe—C6	68.03 (6)	C18—C19—C20	107.74 (11)
C10—Fe—C6	40.38 (6)	C24—C19—C20	109.29 (12)
C3—Fe—C6	163.29 (6)	C18—C19—H19	110.2
C4—Fe—C6	155.77 (6)	C24—C19—H19	110.2
C7—Fe—C6	40.39 (7)	C20—C19—H19	110.2
C1—Fe—C6	109.83 (5)	C21—C20—C19	110.45 (11)
C14—O15—C16	111.23 (10)	C21—C20—H201	109.6
C2—C1—C5	106.90 (11)	C19—C20—H201	109.6
C2—C1—C11	126.27 (11)	C21—C20—H202	109.6
C5—C1—C11	126.72 (11)	C19—C20—H202	109.6
C2—C1—Fe	68.79 (7)	H201—C20—H202	108.1
C5—C1—Fe	68.49 (7)	C27—C21—C22	109.60 (12)
C11—C1—Fe	124.96 (8)	C27—C21—C20	110.04 (13)
C3—C2—C1	108.38 (11)	C22—C21—C20	108.86 (11)
C3—C2—Fe	69.85 (7)	C27—C21—H21	109.4
C1—C2—Fe	70.17 (7)	C22—C21—H21	109.4
C3—C2—H2	125.8	C20—C21—H21	109.4
C1—C2—H2	125.8	C21—C22—C23	109.23 (11)
Fe—C2—H2	125.8	C21—C22—H221	109.8
C4—C3—C2	108.00 (11)	C23—C22—H221	109.8
C4—C3—Fe	69.87 (7)	C21—C22—H222	109.8
C2—C3—Fe	69.35 (7)	C23—C22—H222	109.8
C4—C3—H3	126.0	H221—C22—H222	108.3
C2—C3—H3	126.0	C18—C23—C22	111.43 (11)
Fe—C3—H3	126.3	C18—C23—C26	107.12 (11)
C3—C4—C5	108.48 (11)	C22—C23—C26	107.92 (11)
C3—C4—Fe	69.59 (7)	C18—C23—H23	110.1
C5—C4—Fe	69.02 (7)	C22—C23—H23	110.1
C3—C4—H4	125.8	C26—C23—H23	110.1
C5—C4—H4	125.8	C25—C24—C19	109.75 (12)
Fe—C4—H4	127.2	C25—C24—H241	109.7
C4—C5—C1	108.19 (11)	C19—C24—H241	109.7
C4—C5—Fe	70.28 (8)	C25—C24—H242	109.7
C1—C5—Fe	70.35 (7)	C19—C24—H242	109.7
C4—C5—H5	125.9	H241—C24—H242	108.2
C1—C5—H5	125.9	C24—C25—C27	109.53 (13)
Fe—C5—H5	125.1	C24—C25—C26	108.96 (12)
C10—C6—C7	107.87 (13)	C27—C25—C26	109.55 (13)
C10—C6—Fe	69.28 (7)	C24—C25—H25	109.6
C7—C6—Fe	69.46 (8)	C27—C25—H25	109.6
C10—C6—H6	126.1	C26—C25—H25	109.6
C7—C6—H6	126.1	C25—C26—C23	110.31 (11)
Fe—C6—H6	126.8	C25—C26—H261	109.6
C8—C7—C6	107.99 (13)	C23—C26—H261	109.6
C8—C7—Fe	69.36 (8)	C25—C26—H262	109.6
C6—C7—Fe	70.14 (8)	C23—C26—H262	109.6
C8—C7—H7	126.0	H261—C26—H262	108.1
C6—C7—H7	126.0	C21—C27—C25	109.58 (11)
Fe—C7—H7	126.1	C21—C27—H271	109.8
C7—C8—C9	108.03 (13)	C25—C27—H271	109.8
C7—C8—Fe	70.13 (8)	C21—C27—H272	109.8
C9—C8—Fe	69.66 (8)	C25—C27—H272	109.8
C7—C8—H8	126.0	H271—C27—H272	108.2
C5—Fe—C1—C2	119.22 (10)	C3—Fe—C7—C8	71.70 (10)
C9—Fe—C1—C2	156.31 (18)	C4—Fe—C7—C8	39.0 (2)
C8—Fe—C1—C2	−44.20 (15)	C1—Fe—C7—C8	156.22 (8)
C10—Fe—C1—C2	−166.33 (8)	C6—Fe—C7—C8	−119.13 (12)
C3—Fe—C1—C2	37.67 (7)	C5—Fe—C7—C6	−49.70 (17)
C4—Fe—C1—C2	81.32 (8)	C2—Fe—C7—C6	−127.53 (8)
C7—Fe—C1—C2	−81.24 (9)	C9—Fe—C7—C6	81.30 (9)
C6—Fe—C1—C2	−124.54 (8)	C8—Fe—C7—C6	119.13 (12)
C2—Fe—C1—C5	−119.22 (10)	C10—Fe—C7—C6	37.44 (8)
C9—Fe—C1—C5	37.1 (2)	C3—Fe—C7—C6	−169.16 (8)
C8—Fe—C1—C5	−163.42 (12)	C4—Fe—C7—C6	158.16 (16)
C10—Fe—C1—C5	74.45 (9)	C1—Fe—C7—C6	−84.64 (9)
C3—Fe—C1—C5	−81.55 (8)	C6—C7—C8—C9	−0.17 (16)
C4—Fe—C1—C5	−37.90 (7)	Fe—C7—C8—C9	59.57 (10)
C7—Fe—C1—C5	159.54 (8)	C6—C7—C8—Fe	−59.74 (10)
C6—Fe—C1—C5	116.24 (8)	C5—Fe—C8—C7	165.24 (16)
C5—Fe—C1—C11	−120.58 (13)	C2—Fe—C8—C7	−84.05 (10)
C2—Fe—C1—C11	120.20 (13)	C9—Fe—C8—C7	119.02 (13)
C9—Fe—C1—C11	−83.5 (2)	C10—Fe—C8—C7	81.28 (10)
C8—Fe—C1—C11	76.00 (17)	C3—Fe—C8—C7	−126.08 (9)
C10—Fe—C1—C11	−46.13 (13)	C4—Fe—C8—C7	−166.16 (9)
C3—Fe—C1—C11	157.87 (12)	C1—Fe—C8—C7	−52.71 (16)
C4—Fe—C1—C11	−158.48 (12)	C6—Fe—C8—C7	37.62 (9)
C7—Fe—C1—C11	38.96 (13)	C5—Fe—C8—C9	46.2 (2)
C6—Fe—C1—C11	−4.34 (12)	C2—Fe—C8—C9	156.93 (8)
C5—C1—C2—C3	−1.55 (14)	C10—Fe—C8—C9	−37.74 (8)
C11—C1—C2—C3	−178.14 (11)	C3—Fe—C8—C9	114.90 (9)
Fe—C1—C2—C3	−59.62 (9)	C4—Fe—C8—C9	74.82 (10)
C5—C1—C2—Fe	58.06 (8)	C7—Fe—C8—C9	−119.02 (13)
C11—C1—C2—Fe	−118.52 (12)	C1—Fe—C8—C9	−171.73 (11)
C5—Fe—C2—C3	81.35 (8)	C6—Fe—C8—C9	−81.40 (9)
C9—Fe—C2—C3	−47.23 (15)	C7—C8—C9—C10	−0.17 (16)
C8—Fe—C2—C3	−80.85 (10)	Fe—C8—C9—C10	59.70 (9)
C10—Fe—C2—C3	166.2 (2)	C7—C8—C9—Fe	−59.87 (10)
C4—Fe—C2—C3	37.54 (8)	C5—Fe—C9—C10	76.72 (10)
C7—Fe—C2—C3	−123.51 (9)	C2—Fe—C9—C10	−167.51 (11)
C1—Fe—C2—C3	119.30 (11)	C8—Fe—C9—C10	−119.05 (13)
C6—Fe—C2—C3	−163.76 (8)	C3—Fe—C9—C10	159.63 (8)
C5—Fe—C2—C1	−37.95 (7)	C4—Fe—C9—C10	117.28 (9)
C9—Fe—C2—C1	−166.53 (11)	C7—Fe—C9—C10	−81.33 (10)
C8—Fe—C2—C1	159.85 (8)	C1—Fe—C9—C10	47.4 (2)
C10—Fe—C2—C1	46.9 (2)	C6—Fe—C9—C10	−37.63 (9)
C3—Fe—C2—C1	−119.30 (11)	C5—Fe—C9—C8	−164.22 (9)
C4—Fe—C2—C1	−81.76 (8)	C2—Fe—C9—C8	−48.46 (16)
C7—Fe—C2—C1	117.19 (8)	C10—Fe—C9—C8	119.05 (13)
C6—Fe—C2—C1	76.95 (9)	C3—Fe—C9—C8	−81.31 (10)
C1—C2—C3—C4	0.43 (14)	C4—Fe—C9—C8	−123.66 (9)
Fe—C2—C3—C4	−59.40 (9)	C7—Fe—C9—C8	37.73 (10)
C1—C2—C3—Fe	59.82 (8)	C1—Fe—C9—C8	166.47 (17)
C5—Fe—C3—C4	37.15 (8)	C6—Fe—C9—C8	81.42 (10)
C2—Fe—C3—C4	119.32 (11)	C8—C9—C10—C6	0.44 (15)
C9—Fe—C3—C4	−83.17 (9)	Fe—C9—C10—C6	60.00 (9)
C8—Fe—C3—C4	−125.09 (9)	C8—C9—C10—Fe	−59.56 (9)
C10—Fe—C3—C4	−52.84 (15)	C7—C6—C10—C9	−0.54 (15)
C7—Fe—C3—C4	−164.89 (8)	Fe—C6—C10—C9	−59.47 (9)
C1—Fe—C3—C4	81.45 (8)	C7—C6—C10—Fe	58.93 (10)
C6—Fe—C3—C4	170.04 (17)	C5—Fe—C10—C9	−123.48 (9)
C5—Fe—C3—C2	−82.18 (8)	C2—Fe—C10—C9	157.04 (19)
C9—Fe—C3—C2	157.51 (8)	C8—Fe—C10—C9	37.80 (9)
C8—Fe—C3—C2	115.59 (8)	C3—Fe—C10—C9	−43.36 (16)
C10—Fe—C3—C2	−172.17 (11)	C4—Fe—C10—C9	−80.19 (10)
C4—Fe—C3—C2	−119.32 (11)	C7—Fe—C10—C9	81.61 (10)
C7—Fe—C3—C2	75.79 (10)	C1—Fe—C10—C9	−165.56 (8)
C1—Fe—C3—C2	−37.87 (7)	C6—Fe—C10—C9	119.06 (13)
C6—Fe—C3—C2	50.7 (2)	C5—Fe—C10—C6	117.46 (9)
C2—C3—C4—C5	0.90 (15)	C2—Fe—C10—C6	38.0 (2)
Fe—C3—C4—C5	−58.18 (9)	C9—Fe—C10—C6	−119.06 (13)
C2—C3—C4—Fe	59.07 (9)	C8—Fe—C10—C6	−81.26 (10)
C5—Fe—C4—C3	−120.33 (11)	C3—Fe—C10—C6	−162.42 (12)
C2—Fe—C4—C3	−37.77 (7)	C4—Fe—C10—C6	160.74 (9)
C9—Fe—C4—C3	113.61 (8)	C7—Fe—C10—C6	−37.46 (9)
C8—Fe—C4—C3	72.62 (10)	C1—Fe—C10—C6	75.38 (10)
C10—Fe—C4—C3	155.58 (8)	C2—C1—C11—C12	−34.73 (18)
C7—Fe—C4—C3	42.9 (2)	C5—C1—C11—C12	149.34 (12)
C1—Fe—C4—C3	−82.02 (8)	Fe—C1—C11—C12	−122.76 (11)
C6—Fe—C4—C3	−173.04 (12)	C2—C1—C11—C17	142.59 (12)
C2—Fe—C4—C5	82.56 (8)	C5—C1—C11—C17	−33.34 (17)
C9—Fe—C4—C5	−126.05 (8)	Fe—C1—C11—C17	54.57 (14)
C8—Fe—C4—C5	−167.05 (8)	C1—C11—C12—C16	156.74 (12)
C10—Fe—C4—C5	−84.09 (9)	C17—C11—C12—C16	−20.47 (18)
C3—Fe—C4—C5	120.33 (11)	C1—C11—C12—C13	−6.8 (2)
C7—Fe—C4—C5	163.27 (16)	C17—C11—C12—C13	175.98 (12)
C1—Fe—C4—C5	38.32 (7)	C11—C12—C13—C18	−49.3 (2)
C6—Fe—C4—C5	−52.70 (16)	C16—C12—C13—C18	145.33 (13)
C3—C4—C5—C1	−1.87 (14)	C11—C12—C13—C14	147.95 (13)
Fe—C4—C5—C1	−60.40 (8)	C16—C12—C13—C14	−17.43 (13)
C3—C4—C5—Fe	58.53 (9)	C16—O15—C14—O14	176.11 (12)
C2—C1—C5—C4	2.10 (14)	C16—O15—C14—C13	−6.31 (14)
C11—C1—C5—C4	178.67 (11)	C18—C13—C14—O14	27.5 (2)
Fe—C1—C5—C4	60.36 (9)	C12—C13—C14—O14	−168.07 (15)
C2—C1—C5—Fe	−58.25 (8)	C18—C13—C14—O15	−149.59 (11)
C11—C1—C5—Fe	118.31 (12)	C12—C13—C14—O15	14.85 (13)
C2—Fe—C5—C4	−80.87 (8)	C14—O15—C16—O16	178.47 (13)
C9—Fe—C5—C4	72.76 (9)	C14—O15—C16—C12	−4.98 (14)
C8—Fe—C5—C4	37.3 (2)	C11—C12—C16—O16	22.7 (2)
C10—Fe—C5—C4	114.73 (8)	C13—C12—C16—O16	−169.98 (16)
C3—Fe—C5—C4	−37.00 (8)	C11—C12—C16—O15	−153.16 (11)
C7—Fe—C5—C4	−167.00 (13)	C13—C12—C16—O15	14.16 (13)
C1—Fe—C5—C4	−118.70 (10)	C12—C13—C18—C23	−2.5 (2)
C6—Fe—C5—C4	157.37 (8)	C14—C13—C18—C23	157.62 (12)
C2—Fe—C5—C1	37.83 (7)	C12—C13—C18—C19	−176.85 (12)
C9—Fe—C5—C1	−168.54 (7)	C14—C13—C18—C19	−16.70 (18)
C8—Fe—C5—C1	156.03 (17)	C13—C18—C19—C24	114.40 (14)
C10—Fe—C5—C1	−126.57 (7)	C23—C18—C19—C24	−60.52 (14)
C3—Fe—C5—C1	81.70 (8)	C13—C18—C19—C20	−127.02 (13)
C4—Fe—C5—C1	118.70 (10)	C23—C18—C19—C20	58.06 (14)
C7—Fe—C5—C1	−48.30 (16)	C18—C19—C20—C21	−60.80 (15)
C6—Fe—C5—C1	−83.92 (8)	C24—C19—C20—C21	57.68 (15)
C5—Fe—C6—C10	−81.68 (9)	C19—C20—C21—C27	−58.05 (15)
C2—Fe—C6—C10	−168.60 (8)	C19—C20—C21—C22	62.07 (15)
C9—Fe—C6—C10	37.79 (9)	C27—C21—C22—C23	62.04 (15)
C8—Fe—C6—C10	81.76 (9)	C20—C21—C22—C23	−58.35 (15)
C3—Fe—C6—C10	151.92 (17)	C13—C18—C23—C22	127.79 (13)
C4—Fe—C6—C10	−43.99 (17)	C19—C18—C23—C22	−57.28 (14)
C7—Fe—C6—C10	119.48 (12)	C13—C18—C23—C26	−114.40 (13)
C1—Fe—C6—C10	−125.77 (8)	C19—C18—C23—C26	60.54 (13)
C5—Fe—C6—C7	158.83 (9)	C21—C22—C23—C18	56.39 (14)
C2—Fe—C6—C7	71.91 (10)	C21—C22—C23—C26	−60.95 (14)
C9—Fe—C6—C7	−81.69 (10)	C18—C19—C24—C25	58.54 (15)
C8—Fe—C6—C7	−37.72 (9)	C20—C19—C24—C25	−59.06 (15)
C10—Fe—C6—C7	−119.48 (12)	C19—C24—C25—C27	60.82 (15)
C3—Fe—C6—C7	32.4 (2)	C19—C24—C25—C26	−59.00 (15)
C4—Fe—C6—C7	−163.47 (12)	C24—C25—C26—C23	60.60 (15)
C1—Fe—C6—C7	114.75 (9)	C27—C25—C26—C23	−59.21 (16)
C10—C6—C7—C8	0.44 (16)	C18—C23—C26—C25	−60.16 (14)
Fe—C6—C7—C8	59.25 (10)	C22—C23—C26—C25	59.92 (15)
C10—C6—C7—Fe	−58.81 (9)	C22—C21—C27—C25	−60.54 (16)
C5—Fe—C7—C8	−168.84 (12)	C20—C21—C27—C25	59.14 (16)
C2—Fe—C7—C8	113.34 (9)	C24—C25—C27—C21	−60.64 (16)
C9—Fe—C7—C8	−37.83 (9)	C26—C25—C27—C21	58.82 (16)
C10—Fe—C7—C8	−81.69 (9)