Methoxy[meso-5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]­iron(III), [Fe(TDFPP)(OCH₃)]

The crystal structure of the title compound, [Fe(C₄₄H₂₀F₈N₄)(CH₃O)], has been determined. The Fe atom lies 0.485 (1) Å out of the plane of the four N atoms to which it is coordinated and from the inversion centre at the origin of the unit cell. The methoxy group is axially coordinated to the Fe atom with O-Fe-N angles of 106.3 (2) and 102.4 (2)°, a C-O-Fe angle of 128.3 (5)° and an Fe-O distance of 1.788 (5) Å. Di­fluoro­phenyl rings are tilted from the porphyrin (por) plane with torsion angles of -68.1 (6) and 77.7 (5)° across the two C_por-­C-C-C_ar systems.

S1. Comment

The active site of heme-dependent enzymes is composed of an iron(III) ion coordinated in the equatorial plane to the four N atoms of protoporphyrin IX and two possible coordination sites of the metal ion in axial positions. The axial sites of electron-transfer enzymes are occupied by two amino acid residues while only one aminoacid is coordinated to the metal for peroxidase, catalase, and P-450 monooxygenase. The latter enzymes can have one labile position for coordination of substrates or oxidants (Andersson & Dawson, 1991). The most important difference among the various heme-dependent enzymes is the nature of their axial ligands. The coordinated atom in peroxidase, catalase and P-450 is the N of histidine (Chung & Van Wart, 1992), O^- of tyrosine (Chung & Van Wart, 1992; Benecky et al., 1993), and S^- of cysteine (Egawa et al., 1994), respectively. The specific chemical property of each enzyme may be due to its axial ligand. We have elucidated that the cysteinate ligand of P-450 plays an important role in the catalytic cycle of P-450. Also, we recently observed that the reactive oxygenating intermediates of iron(III) porphyrin complexes as model compounds of P-450 are altered by anionic axial ligands (Nam, Lim, Oh et al., 2000; Nam, Lim & Oh et al., 2000; Nam, Lim, Moon & Kim et al., 2000). During the study of the anionic acid ligand effect, we obtained the crystal of an iron(III) porphyrin complex with a methoxy ligand in the axial position. We now report the structure of an electron-deficient iron porphyrin complex, Fe(TDFPP)(OCH₃) [TDFPP = meso-tetrakis(2,6-diflorophenyl)porphyrinato dianion], (I). \sch

In space group P2₁/n with Z = 2, the molecules lie on inversion centers as might be expected for some symmetrically substituted square-planar molecules. In the case of (I) the basic geometry of the molecule is square-pyramidal and the Fe atom lies 0.485 (1) Å out of the plane of the four N atoms to which it is coordinated and from the inversion center at the origin of the unit cell. The Fe atom (and the coordinated –OCH₃ ligand) is thus disordered over two sites (50:50) by the inversion symmetry. There is additional conformational disorder in one of the substituted phenyl rings which is disordered over two sites with occupancies in ratio 0.69:0.31. Difluorophenyl rings are tilted from the porphyrinato plane with torsional angles of -68.1 (6) and 77.7 (5)° for C10—C1—C11—C12 and C7—C2—C21—C22, respectively. The Fe—N bond lengths of 2.051 (4) and 2.104 (4) Å are longer than those of low-spin complexes (average 1.986 Å). The –OCH₃ group is axially coordinated to the Fe atom with angles of 106.3 (2) and 102.4 (2)° for O1—Fe1—N1 and O1—Fe1—N2, respectively. The Fe1—O1 distance is 1.788 (5) Å which is a little shorter than that of the methoxyiron(III)mesoporphyrin-IX complex (Fe—O 1.842 Å) (Hoard et al., 1965).

Related literature

For related literature, see: Andersson & Dawson (1991); Benecky et al. (1993); Chung & Van Wart (1992); Egawa et al. (1994); Hoard et al. (1965); Nam, Lim & Oh (2000); Nam, Lim, Moon & Kim (2000); Nam, Lim, Oh, Lee, Woo, Kim & Shin (2000).

S2. Experimental

To a solution of Fe(TDFPP)Cl (4.0 mg, 0.0042 mmol) in CH₂Cl₂ (0.5 ml) was added sodium 2-methyl-2-propane thiolate (52 mg, 0.042 mmol) at room temperature. After the reaction mixture was stirred for 3 h and then filtered through a 0.45 filter, methanol (3 ml) was added to the filtered solution. The fitrate was allowed to stand at room temperature for two weeks and crystals of compound (I) were then obtained.

S3. Refinement

All H atoms except water molecule hydrogen atoms were inserted at calculated positions and treated as riding with isotropic displacement parameters.

Computing details

Data collection: Kappa-CCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. View of the molecule showing the labelling scheme. Ellipsoids are drawn at the 30% probability level. All H atoms are omitted for clarity and only one component of disorder is shown. Atoms labelled with a hash are related by inversion symmetry.

(I)

Crystal data

[Fe(C44H20F8N4)(CH3O)]	F(000) = 854
Mr = 843.3	Dx = 1.542 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.4526 (4) Å	Cell parameters from 11483 reflections
b = 12.6673 (5) Å	θ = 3.0–25.0°
c = 12.6426 (5) Å	µ = 0.50 mm^−1
β = 114.39 (3)°	T = 150 K
V = 1816.31 (12) Å^3	Plate, dark brown
Z = 2	0.18 × 0.18 × 0.08 mm

Data collection

Kappa-CCD diffractometer	3198 independent reflections
Radiation source: fine-focus sealed tube	2188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.08
Detector resolution: 9 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ϕ scans ω scans with κ offsets	h = −14→14
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	k = −15→15
Tmin = 0.915, Tmax = 0.961	l = −15→13
11483 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.079	H-atom parameters constrained
wR(F^2) = 0.207	w = 1/[σ^2(Fo^2) + (0.0657P)^2 + 4.6789P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3198 reflections	Δρmax = 0.44 e Å^−3
251 parameters	Δρmin = −0.48 e Å^−3
16 restraints	Extinction correction: SHELXL97 (Sheldrick, 1998), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (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	Occ. (<1)
Fe1	0.01072 (12)	0.01855 (11)	0.03678 (11)	0.0329 (4)	0.50
N1	−0.0667 (3)	0.1312 (3)	−0.0954 (3)	0.0353 (10)
N2	0.1636 (3)	0.0414 (3)	0.0154 (3)	0.0347 (10)
C1	0.1154 (4)	0.2070 (4)	−0.0976 (4)	0.0363 (11)
C2	−0.2776 (4)	0.1028 (4)	−0.1423 (4)	0.0367 (12)
C3	0.1940 (4)	0.1285 (4)	−0.0321 (4)	0.0351 (11)
C4	0.3189 (4)	0.1278 (4)	−0.0023 (4)	0.0383 (12)
H4A	0.3616	0.1777	−0.0260	0.046*
C5	0.3637 (4)	0.0418 (4)	0.0663 (4)	0.0394 (12)
H5A	0.4441	0.0208	0.1004	0.047*
C6	0.2669 (4)	−0.0115 (4)	0.0776 (4)	0.0345 (11)
C7	−0.1840 (4)	0.1588 (4)	−0.1486 (4)	0.0374 (12)
C8	−0.1959 (5)	0.2571 (4)	−0.2114 (4)	0.0412 (12)
H8A	−0.2671	0.2937	−0.2550	0.049*
C9	−0.0873 (5)	0.2862 (4)	−0.1964 (4)	0.0414 (12)
H9A	−0.0674	0.3482	−0.2266	0.050*
C10	−0.0064 (4)	0.2077 (4)	−0.1267 (4)	0.0369 (11)
F1	0.0696 (3)	0.2351 (3)	−0.3330 (3)	0.0594 (9)
F2	0.2682 (3)	0.3636 (3)	0.0456 (3)	0.0692 (11)
C11	0.1632 (4)	0.2964 (4)	−0.1427 (4)	0.0404 (12)
C12	0.1373 (5)	0.3101 (4)	−0.2590 (5)	0.0452 (13)
C13	0.1764 (5)	0.3938 (5)	−0.3030 (5)	0.0544 (16)
H13A	0.1550	0.4003	−0.3841	0.065*
C14	0.2469 (6)	0.4671 (5)	−0.2270 (6)	0.0609 (17)
H14A	0.2740	0.5258	−0.2560	0.073*
C15	0.2802 (6)	0.4579 (5)	−0.1079 (6)	0.0640 (18)
H15A	0.3303	0.5085	−0.0551	0.077*
C16	0.2374 (5)	0.3723 (4)	−0.0697 (5)	0.0508 (14)
F3	−0.3936 (5)	0.0517 (4)	−0.3786 (5)	0.0524 (16)*	0.691 (10)
F4	−0.4216 (4)	0.2219 (4)	−0.0602 (3)	0.0458 (15)*	0.691 (10)
C21	−0.4051 (4)	0.1360 (4)	−0.2182 (5)	0.040 (3)*	0.691 (10)
C22	−0.4550 (6)	0.1090 (3)	−0.3352 (5)	0.053 (5)*	0.691 (10)
C23	−0.5689 (6)	0.1415 (4)	−0.4058 (3)	0.049 (4)*	0.691 (10)
H23	−0.6031	0.1230	−0.4857	0.059*	0.691 (10)
C24	−0.6328 (4)	0.2012 (5)	−0.3594 (4)	0.045 (2)*	0.691 (10)
H24	−0.7106	0.2234	−0.4077	0.054*	0.691 (10)
C25	−0.5828 (4)	0.2283 (4)	−0.2425 (4)	0.0392 (19)*	0.691 (10)
H25	−0.6264	0.2690	−0.2108	0.047*	0.691 (10)
C26	−0.4689 (4)	0.1957 (4)	−0.1718 (3)	0.0350 (17)*	0.691 (10)
F3*	−0.4155 (10)	0.0286 (7)	−0.3637 (10)	0.043 (3)*	0.309 (10)
F4*	−0.3854 (10)	0.2759 (10)	−0.0730 (8)	0.061 (4)*	0.309 (10)
C21*	−0.3967 (7)	0.1500 (8)	−0.2172 (9)	0.032 (7)*	0.309 (10)
C22*	−0.4597 (11)	0.1094 (6)	−0.3279 (10)	0.019 (6)*	0.309 (10)
C23*	−0.5679 (11)	0.1532 (9)	−0.3994 (7)	0.044 (9)*	0.309 (10)
H23*	−0.6110	0.1255	−0.4750	0.053*	0.309 (10)
C24*	−0.6129 (10)	0.2375 (11)	−0.3602 (10)	0.057 (6)*	0.309 (10)
H24*	−0.6868	0.2675	−0.4090	0.068*	0.309 (10)
C25*	−0.5499 (11)	0.2781 (10)	−0.2494 (10)	0.069 (6)*	0.309 (10)
H25*	−0.5807	0.3358	−0.2226	0.083*	0.309 (10)
C26*	−0.4418 (10)	0.2344 (9)	−0.1780 (7)	0.045 (5)*	0.309 (10)
O1	0.0410 (5)	0.0851 (4)	0.1708 (4)	0.0226 (12)	0.50
C27	0.0773 (9)	0.0412 (8)	0.2826 (8)	0.037 (2)	0.50
H27A	0.0668	0.0934	0.3348	0.055*	0.50
H27B	0.1606	0.0212	0.3121	0.055*	0.50
H27C	0.0297	−0.0214	0.2788	0.055*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0303 (8)	0.0368 (9)	0.0290 (8)	0.0065 (6)	0.0097 (7)	0.0035 (6)
N1	0.034 (2)	0.038 (2)	0.033 (2)	0.0074 (18)	0.0133 (19)	0.0013 (18)
N2	0.034 (2)	0.036 (2)	0.031 (2)	0.0045 (18)	0.0101 (19)	0.0038 (17)
C1	0.042 (3)	0.037 (3)	0.029 (3)	0.003 (2)	0.014 (2)	−0.001 (2)
C2	0.036 (3)	0.042 (3)	0.030 (3)	0.009 (2)	0.011 (2)	0.001 (2)
C3	0.038 (3)	0.037 (3)	0.029 (3)	−0.001 (2)	0.013 (2)	0.001 (2)
C4	0.040 (3)	0.037 (3)	0.037 (3)	0.000 (2)	0.015 (2)	−0.001 (2)
C5	0.030 (3)	0.045 (3)	0.038 (3)	0.000 (2)	0.009 (2)	−0.004 (2)
C6	0.033 (3)	0.041 (3)	0.028 (2)	0.002 (2)	0.011 (2)	−0.004 (2)
C7	0.040 (3)	0.042 (3)	0.030 (3)	0.010 (2)	0.013 (2)	0.003 (2)
C8	0.042 (3)	0.047 (3)	0.034 (3)	0.012 (2)	0.015 (2)	0.010 (2)
C9	0.050 (3)	0.040 (3)	0.036 (3)	0.008 (2)	0.020 (3)	0.012 (2)
C10	0.042 (3)	0.040 (3)	0.032 (3)	0.006 (2)	0.018 (2)	0.006 (2)
F1	0.059 (2)	0.079 (2)	0.0378 (18)	−0.0013 (18)	0.0179 (16)	0.0048 (17)
F2	0.092 (3)	0.062 (2)	0.055 (2)	−0.016 (2)	0.031 (2)	−0.0059 (17)
C11	0.038 (3)	0.042 (3)	0.042 (3)	0.005 (2)	0.017 (2)	0.008 (2)
C12	0.038 (3)	0.051 (3)	0.050 (3)	0.011 (3)	0.022 (3)	0.014 (3)
C13	0.049 (3)	0.065 (4)	0.056 (4)	0.018 (3)	0.028 (3)	0.029 (3)
C14	0.058 (4)	0.049 (4)	0.085 (5)	0.013 (3)	0.039 (4)	0.023 (4)
C15	0.068 (4)	0.046 (4)	0.084 (5)	−0.002 (3)	0.037 (4)	0.005 (3)
C16	0.057 (4)	0.046 (3)	0.055 (4)	0.003 (3)	0.028 (3)	0.003 (3)
O1	0.027 (3)	0.025 (3)	0.012 (3)	0.006 (2)	0.005 (2)	0.001 (2)
C27	0.051 (6)	0.034 (5)	0.024 (5)	0.009 (5)	0.014 (5)	0.002 (4)

Geometric parameters (Å, º)

Fe1—Fe1^i	0.976 (3)	C7—C8	1.451 (7)
Fe1—O1	1.788 (5)	C8—C9	1.337 (7)
Fe1—N2	2.051 (4)	C9—C10	1.431 (7)
Fe1—N1^i	2.051 (4)	F1—C12	1.356 (7)
Fe1—N1	2.104 (4)	F2—C16	1.350 (7)
Fe1—N2^i	2.131 (4)	C11—C12	1.381 (7)
N1—C7	1.378 (6)	C11—C16	1.387 (8)
N1—C10	1.380 (6)	C12—C13	1.376 (8)
N1—Fe1^i	2.051 (4)	C13—C14	1.364 (9)
N2—C6	1.374 (6)	C14—C15	1.391 (9)
N2—C3	1.382 (6)	C15—C16	1.381 (8)
N2—Fe1^i	2.131 (4)	F3—C22	1.327 (3)
C1—C3	1.401 (7)	F4—C26	1.327 (3)
C1—C10	1.405 (7)	C21—C22	1.3900
C1—C11	1.498 (7)	C21—C26	1.3900
C2—C6^i	1.390 (7)	C22—C23	1.3900
C2—C7	1.395 (7)	C23—C24	1.3900
C2—C21*	1.515 (9)	C24—C25	1.3900
C2—C21	1.536 (6)	C25—C26	1.3900
C3—C4	1.441 (7)	F3*—C22*	1.328 (3)
C4—C5	1.361 (7)	F4*—C26*	1.327 (3)
C5—C6	1.439 (7)	O1—C27	1.409 (10)
C6—C2^i	1.390 (7)
Fe1^i—Fe1—O1	176.5 (3)	C5—C4—C3	106.6 (4)
Fe1^i—Fe1—N2	81.1 (2)	C4—C5—C6	107.4 (4)
O1—Fe1—N2	102.4 (2)	N2—C6—C2^i	125.6 (4)
Fe1^i—Fe1—N1^i	79.5 (2)	N2—C6—C5	109.8 (4)
O1—Fe1—N1^i	100.8 (2)	C2^i—C6—C5	124.6 (4)
N2—Fe1—N1^i	89.02 (16)	N1—C7—C2	125.9 (4)
Fe1^i—Fe1—N1	73.42 (19)	N1—C7—C8	109.4 (4)
O1—Fe1—N1	106.3 (2)	C2—C7—C8	124.7 (4)
N2—Fe1—N1	86.86 (16)	C9—C8—C7	106.9 (4)
N1^i—Fe1—N1	152.88 (8)	C8—C9—C10	108.0 (5)
Fe1^i—Fe1—N2^i	71.96 (19)	N1—C10—C1	125.2 (4)
O1—Fe1—N2^i	104.5 (2)	N1—C10—C9	109.7 (4)
N2—Fe1—N2^i	153.11 (8)	C1—C10—C9	125.1 (5)
N1^i—Fe1—N2^i	86.14 (16)	C12—C11—C16	114.8 (5)
N1—Fe1—N2^i	85.53 (16)	C12—C11—C1	123.1 (5)
C7—N1—C10	106.0 (4)	C16—C11—C1	122.1 (5)
C7—N1—Fe1^i	123.0 (3)	F1—C12—C13	118.9 (5)
C10—N1—Fe1^i	127.5 (3)	F1—C12—C11	116.9 (5)
C7—N1—Fe1	127.3 (3)	C13—C12—C11	124.2 (6)
C10—N1—Fe1	125.4 (3)	C14—C13—C12	118.1 (6)
Fe1^i—N1—Fe1	27.12 (8)	C13—C14—C15	121.5 (6)
C6—N2—C3	106.2 (4)	C16—C15—C14	117.4 (6)
C6—N2—Fe1	123.8 (3)	F2—C16—C15	117.6 (6)
C3—N2—Fe1	127.3 (3)	F2—C16—C11	118.5 (5)
C6—N2—Fe1^i	126.6 (3)	C15—C16—C11	123.9 (6)
C3—N2—Fe1^i	125.2 (3)	C22—C21—C2	119.4 (4)
Fe1—N2—Fe1^i	26.89 (8)	C26—C21—C2	120.6 (4)
C3—C1—C10	125.1 (5)	F3—C22—C23	120.4 (5)
C3—C1—C11	118.1 (4)	F3—C22—C21	119.6 (5)
C10—C1—C11	116.8 (4)	F4—C26—C25	119.7 (4)
C6^i—C2—C7	125.3 (4)	F4—C26—C21	120.3 (4)
C6^i—C2—C21*	121.8 (5)	C22*—C21*—C2	118.9 (8)
C7—C2—C21*	112.9 (5)	C26*—C21*—C2	121.0 (8)
C6^i—C2—C21	114.8 (4)	F3*—C22*—C21*	119.2 (10)
C7—C2—C21	119.8 (4)	F3*—C22*—C23*	120.8 (10)
C21*—C2—C21	7.6 (4)	F4*—C26*—C25*	117.5 (10)
N2—C3—C1	125.0 (4)	F4*—C26*—C21*	122.5 (10)
N2—C3—C4	110.0 (4)	C27—O1—Fe1	128.3 (5)
C1—C3—C4	125.0 (4)
Fe1^i—Fe1—N1—C7	90.9 (4)	C7—C8—C9—C10	0.9 (6)
O1—Fe1—N1—C7	−85.5 (4)	C7—N1—C10—C1	−175.8 (5)
N2—Fe1—N1—C7	172.6 (4)	Fe1^i—N1—C10—C1	−16.8 (7)
N1^i—Fe1—N1—C7	90.9 (4)	Fe1—N1—C10—C1	17.0 (7)
N2^i—Fe1—N1—C7	18.4 (4)	C7—N1—C10—C9	2.5 (5)
Fe1^i—Fe1—N1—C10	−104.6 (4)	Fe1^i—N1—C10—C9	161.5 (3)
O1—Fe1—N1—C10	79.1 (4)	Fe1—N1—C10—C9	−164.7 (3)
N2—Fe1—N1—C10	−22.9 (4)	C3—C1—C10—N1	−0.1 (8)
N1^i—Fe1—N1—C10	−104.6 (4)	C11—C1—C10—N1	178.6 (4)
N2^i—Fe1—N1—C10	−177.1 (4)	C3—C1—C10—C9	−178.1 (5)
O1—Fe1—N1—Fe1^i	−176.4 (3)	C11—C1—C10—C9	0.6 (7)
N2—Fe1—N1—Fe1^i	81.69 (19)	C8—C9—C10—N1	−2.2 (6)
N2^i—Fe1—N1—Fe1^i	−72.50 (19)	C8—C9—C10—C1	176.1 (5)
Fe1^i—Fe1—N2—C6	−105.4 (4)	C3—C1—C11—C12	110.7 (6)
O1—Fe1—N2—C6	74.8 (4)	C10—C1—C11—C12	−68.1 (6)
N1^i—Fe1—N2—C6	−26.0 (4)	C3—C1—C11—C16	−69.5 (7)
N1—Fe1—N2—C6	−179.1 (4)	C10—C1—C11—C16	111.8 (6)
N2^i—Fe1—N2—C6	−105.4 (4)	C16—C11—C12—F1	177.0 (5)
Fe1^i—Fe1—N2—C3	95.8 (4)	C1—C11—C12—F1	−3.1 (7)
O1—Fe1—N2—C3	−83.9 (4)	C16—C11—C12—C13	−2.4 (8)
N1^i—Fe1—N2—C3	175.3 (4)	C1—C11—C12—C13	177.4 (5)
N1—Fe1—N2—C3	22.1 (4)	F1—C12—C13—C14	−178.4 (5)
N2^i—Fe1—N2—C3	95.8 (4)	C11—C12—C13—C14	1.1 (8)
O1—Fe1—N2—Fe1^i	−179.7 (3)	C12—C13—C14—C15	0.8 (9)
N1^i—Fe1—N2—Fe1^i	79.48 (19)	C13—C14—C15—C16	−1.0 (9)
N1—Fe1—N2—Fe1^i	−73.70 (19)	C14—C15—C16—F2	−179.2 (5)
C6—N2—C3—C1	−176.7 (5)	C14—C15—C16—C11	−0.5 (9)
Fe1—N2—C3—C1	−15.0 (7)	C12—C11—C16—F2	−179.2 (5)
Fe1^i—N2—C3—C1	18.5 (7)	C1—C11—C16—F2	1.0 (8)
C6—N2—C3—C4	2.1 (5)	C12—C11—C16—C15	2.2 (8)
Fe1—N2—C3—C4	163.8 (3)	C1—C11—C16—C15	−177.7 (5)
Fe1^i—N2—C3—C4	−162.7 (3)	C6^i—C2—C21—C22	−97.8 (4)
C10—C1—C3—N2	−1.4 (8)	C7—C2—C21—C22	77.7 (5)
C11—C1—C3—N2	179.9 (4)	C6^i—C2—C21—C26	84.3 (5)
C10—C1—C3—C4	180.0 (5)	C7—C2—C21—C26	−100.1 (5)
C11—C1—C3—C4	1.3 (7)	C21*—C2—C21—C26	−75 (4)
N2—C3—C4—C5	−1.9 (5)	C26—C21—C22—F3	−179.7 (3)
C1—C3—C4—C5	176.9 (5)	C2—C21—C22—F3	2.4 (4)
C3—C4—C5—C6	0.8 (5)	C2—C21—C22—C23	−177.9 (4)
C3—N2—C6—C2^i	178.2 (4)	F3—C22—C23—C24	179.7 (3)
Fe1—N2—C6—C2^i	15.7 (7)	C24—C25—C26—F4	179.9 (3)
Fe1^i—N2—C6—C2^i	−17.2 (7)	C22—C21—C26—F4	−179.9 (3)
C3—N2—C6—C5	−1.6 (5)	C2—C21—C26—F4	−2.1 (4)
Fe1—N2—C6—C5	−164.1 (3)	C2—C21—C26—C25	177.8 (4)
Fe1^i—N2—C6—C5	163.0 (3)	C6^i—C2—C21*—C22*	−82.8 (7)
C4—C5—C6—N2	0.4 (6)	C7—C2—C21*—C22*	95.7 (6)
C4—C5—C6—C2^i	−179.4 (5)	C21—C2—C21*—C22*	−61 (4)
C10—N1—C7—C2	179.0 (5)	C6^i—C2—C21*—C26*	98.8 (7)
Fe1^i—N1—C7—C2	18.9 (7)	C7—C2—C21*—C26*	−82.6 (7)
Fe1—N1—C7—C2	−14.0 (7)	C26*—C21*—C22*—F3*	−179.7 (3)
C10—N1—C7—C8	−1.9 (5)	C2—C21*—C22*—F3*	1.9 (7)
Fe1^i—N1—C7—C8	−162.1 (3)	C2—C21*—C22*—C23*	−178.4 (7)
Fe1—N1—C7—C8	165.0 (3)	F3*—C22*—C23*—C24*	179.7 (3)
C6^i—C2—C7—N1	2.4 (8)	C24*—C25*—C26*—F4*	−179.8 (3)
C21*—C2—C7—N1	−176.1 (6)	C22*—C21*—C26*—F4*	179.8 (3)
C21—C2—C7—N1	−172.6 (4)	C2—C21*—C26*—F4*	−1.9 (8)
C6^i—C2—C7—C8	−176.5 (5)	C2—C21*—C26*—C25*	178.3 (8)
C21*—C2—C7—C8	5.0 (8)	N2—Fe1—O1—C27	−99.4 (7)
C21—C2—C7—C8	8.5 (7)	N1^i—Fe1—O1—C27	−8.0 (7)
N1—C7—C8—C9	0.6 (6)	N1—Fe1—O1—C27	170.3 (7)
C2—C7—C8—C9	179.7 (5)	N2^i—Fe1—O1—C27	80.7 (7)

Symmetry code: (i) −x, −y, −z.