The twinned structure of ferricenyl­tri­fluoro­borate

Crystals of the title compound, [Fe(C₅H₅)(C₅H₄BF₃)], are monoclinic and twinned. The twinning initially resulted in a misleading unit-cell assignment. The formal oxi­dation state of Fe is 3+, and the crystal packing consists of intermolecular C—H...F and π–π interactions.

S1. Comment

Oligonuclear aggregates of organometallic compounds are increasingly receiving attention becasue of their potential applications as magnetic, electronic and liquid crystalline materials. We have recently synthesized the trinuclear ferrocene complex 1,3,5-tri(4-methoxyphenyl)-2,4,6-triferrocenylborazine, in order to investigate the efficiency of a borazine bridging unit as a transmitter of electronic interactions (Ma et al., 2002). Partial oxidation of that compound was expected to lead to a mixed-valence state with interesting electronic and spectroscopic properties. For this reason, the compound was treated with the oxidizing agent AgBF₄ in various stoichiometric ratios. In most cases, a small number of dark colored crystals of (I) were obtained from the reaction mixture. Thus, 1,3,5-tri(4-methoxyphenyl)-2,4,6-triferrocenylborazine is apparently not stable in the presence of AgBF₄, but decomposes to give ferricenyltrifluoroborate, (I).

Crystals of (I) were found to be twinned. The twinned cell can be obtained by the unit-cell transformation a_twin = −a, b_twin = −b and c_twin = c + 2a/3 (see Fig. 1). Reflections of the major domain perfectly coincide with reflections of the twin domain for h = 3n. Reflections of both major and twin domains were measured and used for the structure refinement. Initially the unit cell assignment resulted in an orthogonal cell with a volume three times that of the correct monoclinic unit cell. This pseudo-orthorhombic lattice is related to the monoclinic cell by the transformation a_ortho = a_mono, b_ortho = b_mono and c_ortho = a_mono + 3c_mono. The β_ortho angle of the pseudo-orthogonal cell at 146 K was calculated as 90.001 (13)°. Thus the assignment of the correct crystal system was only possible after the structure had been determined and refined. This ambiguity could have been avoided if the structure determination had been performed at a higher temperature. Cell measurements at different temperatures gave β_ortho angles of 90.241 (13), 90.111 (11) and 90.047 (12)° at 294, 224 and 174 K, respectively. At room temperature several reflection profiles were split and the twinning of the crystal was quite obvious.

The ferrocene group has an eclipsed conformation (Fig. 2). The C—Cg1—Cg2—C torsion angles range from 3.6 to 4.1° for the five eclipsed atom pairs (Cg1 and Cg2 are the centroids of the two five-membered rings). The angle between the two cyclopentadienyl planes is 1.64 (8)°. The B atom deviates 0.027 (5) Å from the C11/C12/C13/C14/C15 plane and is slightly tilted toward the center of the molecule. The Fe—C11 bond length (involving the BF₃ substituted C atom) is about 0.02 Å longer than the remaining nine Fe—C bond lengths. The ring bond angle at C11 [105.8 (2)°] is 2° smaller than the value of 108.0° in unsubstituted ferrocene (Seiler & Dunitz, 1979, 1982). The average Fe—C bond length [2.084 (s.u. value?) Å] is comparable to Fe—C bond lengths in ferrocenium cations, but is about 0.04–0.05 Å longer than Fe—C bond lengths in neutral ferrocene groups. As Fe—C bonds in several ferrocenyl and ferrocene groups are considerably affected by libration, however, it appears more realistic to consider the distances from the Fe atom to the centers of the cyclopentadiene rings as a measure of the formal oxidation state of the Fe atom. Values of 1.697 and 1.703 Å are observed in (I). These values are in very good agreement with the values 1.686–1.702 Å (mean 1.696 Å) for a number of ferrocenium cations (Sullivan & Foxman, 1983; Rheingold et al., 1983; Bullen et al. 1986; Cotton et al., 1998). This confirms the formal oxidation state of Fe in (I) as 3+. The distances of the Fe²⁺ ions from the centers of the cyclopentadiene rings in the crystal structure of ferrocene are between 1.646 and 1.661 Å, with a mean value of 1.653 Å (Seiler & Dunitz, 1979, 1982). A mean value of 1.646 Å was found in a recent determination of a ferrocenyltrifluoroborate anion (Quach et al., 2001a), in which Fe has a formal oxidation state of 2+. Otherwise, the dimensions of the neutral molecule and the anion are similar. The B—C bond distance is little affected by the charge of the ferrocene group. The value of 1.616 (4) Å in (I) agrees within the experimental uncertainty with the values of 1.605 (4) and 1.608 (3) Å that were found for the anion and is also similar to the values of 1.600 (3) and 1.610 (10) Å found in phenyltrifluoroborate anions (Conole et al., 1995; Quach et al., 2001b). Longer B—C distances of 1.63, 1.64, 1.65 and 1.66 Å have, however, been observed in ferricenyl-tri-ferrocenylborate (Cowan et al., 1979). Thus the difference in electronegativity between fluorine and ferrocene has a measurable influence on the B—C bond length.

There are no short intramolecular contacts. The crystal packing shows four intermolecular C—H···F interactions, with H···F distances of less than 2.6 Å (Fig. 3 and Table 1). One C—H···F interaction (C13—H13···F2) has an H···F distance of only 2.24 Å and is very short. The other three C—H···F interactions have H···F distances of 2.43, 2.53 and 2.58 Å. Neighboring ferrocenyl groups translated in the a direction are connected by π–π interactions between the cyclopentadiene rings. The shortest contact is 3.251 (4) Å, between atom C13 and atom C24 at (x − 1, y, z).

S2. Experimental

A dry solution of AgBF₄ (25 mg, 0.139 mmol) in THF (2.0 ml) was added dropwise at room temperature, with stirring, to a solution of 1,3,5-tri(4-methoxyphenyl)-2,4,6-triferrocenylborazine (40 mg, 0.042 mmol) in THF (about 3.0 ml). The color of the solution changed gradually from yellow to blue and the resulting mixture was stirred at room temperature for about 2 h. After all insolubles had been removed by filtration, the filtrate was evaporated in vacuo to yield a deep-blue solid. The crude material was dissolved in dry acetonitrile (about 10 ml). Deep-blue, almost black, crystals of (I) were obtained by gas-phase diffusion (at room temperature) of dry diethyl ether into the acetonitrile solution of (I) over a period of one month.

S3. Refinement

The initial unit-cell determination of (I) revealed an orthogonal cell [a = 6.8615 (7) Å, b = 11.2481 (16) Å, c = 37.781 (6) Å, α = β = γ = 90° and V = 2915.9 (9) ų]. Merging of the equivalent reflections showed the crystal system to be monoclinic (R_int = 0.054) rather than orthorhombic (R_int = 0.211). The systematic absences indicated the monoclinic space group P2₁/c. No acceptable orthorhombic space group could be found. Initially, the structure was determined and refined assuming the space group to be P2₁/c. Each reflection, hkl, coincided with a twin reflection, h-k-l. The twin fraction refined to 0.369 (1). Refinement in P2₁/c converged at wR2 = 0.167 and R1 = 0.099. The resulting structure contained three independent molecules, which were found to be related by translation vectors of 2/3 0 1/3 and 1/3 0 2/3. Thus, the pseudo-orthogonal cell is an artefact of the twinning and the correct unit cell only has a volume of one third of the observed cell. The new monoclinic unit cell can be obtained from the pseudo-orthogonal cell by the transformation a_new = a_ortho, b_new = b_ortho and c_new = −a_ortho/3 + c_ortho/3, while the unit cell of the twin domain is obtained by the trnsformation a_twin = −a_ortho, b_twin = −b_ortho and c_twin = a_ortho/3 + c_ortho/3. Reflections hkl of the main domain coincide with reflections −h −k l+2 h/3 of the twin domain for h = 3n, while no overlap occurs for reflections with h = 3n+1 or h = 3n+2. Reflections with h = 3n were omitted from the final cell refinement so that lattice constants unbiased by twinning could be obtained. The space group of the new cell is P2₁/n. H atoms were positioned geometrically and were refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C)] using a riding model, with a fixed H—C distance of 0.95 Å. Reflections of both the major domain and the twin domain were used for the structure refinement. The final value of the twin fraction refined to 0.371 (1).

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A projection of the structure along b. The monoclinic lattice defined by vectors a and c is represented by solid lines, the twin lattice defined by a' and c' is represented by broken lines, and the pseudo-orthogonal lattice defined by a and c" is indicated by bold lines.
	Fig. 2. The molecular structure, with displacement ellipsoids shown at the 50% probability level.
	Fig. 3. The crystal packing of (I) viewed along a.

ferricenyltrifluoroborate

Crystal data

[Fe(C5H5)(C5H4BF3)]	F(000) = 508
Mr = 252.83	Dx = 1.728 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 118 reflections
a = 6.8603 (10) Å	θ = 3–23°
b = 11.248 (2) Å	µ = 1.55 mm^−1
c = 12.804 (3) Å	T = 146 K
β = 100.290 (13)°	Rod, black
V = 972.1 (3) Å^3	0.45 × 0.12 × 0.08 mm
Z = 4

Data collection

SIEMENS SMART 1K CCD diffractometer	5254 independent reflections
Radiation source: normal-focus sealed tube	4283 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω scans	θmax = 32.0°, θmin = 2.4°
Absorption correction: numerical SHELXTL (Sheldrick, 1996)	h = −9→10
Tmin = 0.596, Tmax = 0.886	k = −16→16
20212 measured reflections	l = −18→18

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.30	w = 1/[σ^2(Fo^2) + (0.03P)^2 + P] where P = (Fo^2 + 2Fc^2)/3
5254 reflections	(Δ/σ)max = 0.002
137 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.58 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
Fe	0.18541 (5)	0.24868 (3)	0.57430 (3)	0.01972 (9)
F1	0.0642 (3)	−0.04420 (15)	0.66658 (13)	0.0415 (4)
F2	0.1561 (3)	0.06773 (15)	0.81460 (13)	0.0385 (4)
F3	−0.1676 (3)	0.02025 (17)	0.75898 (15)	0.0437 (5)
C11	−0.0237 (3)	0.1719 (2)	0.65545 (18)	0.0187 (4)
C12	−0.1016 (3)	0.1821 (2)	0.5447 (2)	0.0237 (5)
H12	−0.1458	0.1177	0.4985	0.028*
C13	−0.1027 (4)	0.3039 (3)	0.5143 (2)	0.0324 (6)
H13	−0.1475	0.3347	0.4451	0.039*
C14	−0.0250 (4)	0.3706 (2)	0.6057 (2)	0.0312 (6)
H14	−0.0082	0.4545	0.6089	0.037*
C15	0.0236 (4)	0.2906 (2)	0.6920 (2)	0.0245 (5)
H15	0.0788	0.3122	0.7628	0.029*
C21	0.4318 (4)	0.1372 (3)	0.5958 (3)	0.0377 (7)
H21	0.4426	0.0638	0.6331	0.045*
C22	0.3584 (4)	0.1529 (3)	0.4861 (3)	0.0352 (7)
H22	0.3104	0.0921	0.4367	0.042*
C23	0.3695 (4)	0.2757 (3)	0.4633 (2)	0.0322 (6)
H23	0.3307	0.3117	0.3956	0.039*
C24	0.4477 (4)	0.3348 (3)	0.5581 (2)	0.0341 (6)
H24	0.4708	0.4179	0.5657	0.041*
C25	0.4860 (4)	0.2498 (3)	0.6397 (2)	0.0364 (7)
H25	0.5392	0.2657	0.7120	0.044*
B	0.0098 (4)	0.0513 (3)	0.7249 (2)	0.0226 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.01394 (14)	0.02361 (16)	0.02243 (16)	−0.00048 (14)	0.00548 (12)	0.00041 (16)
F1	0.0696 (13)	0.0244 (8)	0.0305 (8)	0.0066 (9)	0.0093 (9)	−0.0033 (7)
F2	0.0453 (10)	0.0344 (9)	0.0282 (8)	−0.0078 (8)	−0.0144 (7)	0.0036 (7)
F3	0.0324 (9)	0.0475 (11)	0.0537 (11)	−0.0049 (8)	0.0143 (8)	0.0224 (9)
C11	0.0133 (9)	0.0244 (11)	0.0191 (10)	−0.0012 (8)	0.0049 (8)	0.0003 (9)
C12	0.0123 (10)	0.0352 (14)	0.0232 (12)	−0.0025 (9)	0.0020 (8)	0.0034 (10)
C13	0.0189 (12)	0.0441 (17)	0.0344 (15)	0.0069 (11)	0.0052 (11)	0.0187 (13)
C14	0.0270 (13)	0.0242 (12)	0.0462 (16)	0.0071 (10)	0.0167 (12)	0.0088 (12)
C15	0.0231 (11)	0.0250 (11)	0.0277 (12)	0.0012 (9)	0.0113 (10)	−0.0021 (10)
C21	0.0215 (13)	0.0393 (16)	0.0535 (19)	0.0102 (12)	0.0105 (13)	0.0084 (14)
C22	0.0229 (13)	0.0373 (15)	0.0483 (17)	−0.0043 (11)	0.0142 (12)	−0.0182 (14)
C23	0.0277 (13)	0.0421 (17)	0.0307 (13)	−0.0021 (11)	0.0155 (11)	0.0002 (12)
C24	0.0239 (13)	0.0363 (15)	0.0461 (17)	−0.0100 (11)	0.0175 (12)	−0.0116 (13)
C25	0.0143 (10)	0.0597 (19)	0.0346 (14)	0.0002 (13)	0.0028 (10)	−0.0109 (15)
B	0.0234 (12)	0.0243 (13)	0.0195 (12)	−0.0015 (10)	0.0022 (10)	0.0006 (10)

Geometric parameters (Å, º)

Fe—C12	2.077 (2)	C12—H12	0.9500
Fe—C15	2.079 (2)	C13—C14	1.413 (4)
Fe—C22	2.079 (3)	C13—H13	0.9500
Fe—C14	2.082 (3)	C14—C15	1.418 (4)
Fe—C25	2.082 (3)	C14—H14	0.9500
Fe—C21	2.083 (3)	C15—H15	0.9500
Fe—C13	2.083 (3)	C21—C25	1.408 (5)
Fe—C23	2.085 (3)	C21—C22	1.416 (5)
Fe—C24	2.086 (3)	C21—H21	0.9500
Fe—C11	2.102 (2)	C22—C23	1.416 (4)
F1—B	1.397 (3)	C22—H22	0.9500
F2—B	1.396 (3)	C23—C24	1.404 (4)
F3—B	1.408 (3)	C23—H23	0.9500
C11—C12	1.428 (3)	C24—C25	1.406 (5)
C11—C15	1.433 (4)	C24—H24	0.9500
C11—B	1.616 (4)	C25—H25	0.9500
C12—C13	1.425 (4)
C12—Fe—C15	66.57 (10)	Fe—C12—H12	125.1
C12—Fe—C22	109.19 (11)	C14—C13—C12	107.5 (2)
C15—Fe—C22	160.33 (12)	C14—C13—Fe	70.12 (15)
C12—Fe—C14	66.78 (11)	C12—C13—Fe	69.74 (15)
C15—Fe—C14	39.84 (11)	C14—C13—H13	126.2
C22—Fe—C14	158.28 (13)	C12—C13—H13	126.2
C12—Fe—C25	156.04 (12)	Fe—C13—H13	125.5
C15—Fe—C25	109.01 (11)	C13—C14—C15	108.0 (2)
C22—Fe—C25	66.50 (12)	C13—C14—Fe	70.23 (16)
C14—Fe—C25	126.08 (12)	C15—C14—Fe	69.97 (14)
C12—Fe—C21	121.83 (12)	C13—C14—H14	126.0
C15—Fe—C21	124.50 (12)	C15—C14—H14	126.0
C22—Fe—C21	39.79 (13)	Fe—C14—H14	125.4
C14—Fe—C21	160.95 (13)	C14—C15—C11	109.3 (2)
C25—Fe—C21	39.53 (13)	C14—C15—Fe	70.19 (15)
C12—Fe—C13	40.05 (11)	C11—C15—Fe	70.81 (13)
C15—Fe—C13	66.77 (11)	C14—C15—H15	125.4
C22—Fe—C13	123.37 (13)	C11—C15—H15	125.4
C14—Fe—C13	39.65 (12)	Fe—C15—H15	125.2
C25—Fe—C13	162.26 (13)	C25—C21—C22	107.8 (3)
C21—Fe—C13	157.27 (14)	C25—C21—Fe	70.20 (16)
C12—Fe—C23	126.71 (11)	C22—C21—Fe	69.96 (16)
C15—Fe—C23	158.10 (12)	C25—C21—H21	126.1
C22—Fe—C23	39.74 (12)	C22—C21—H21	126.1
C14—Fe—C23	124.12 (12)	Fe—C21—H21	125.3
C25—Fe—C23	66.21 (12)	C23—C22—C21	107.7 (3)
C21—Fe—C23	66.54 (12)	C23—C22—Fe	70.36 (15)
C13—Fe—C23	110.80 (12)	C21—C22—Fe	70.25 (16)
C12—Fe—C24	162.85 (11)	C23—C22—H22	126.2
C15—Fe—C24	123.27 (11)	C21—C22—H22	126.2
C22—Fe—C24	66.43 (12)	Fe—C22—H22	124.8
C14—Fe—C24	110.69 (12)	C24—C23—C22	108.0 (3)
C25—Fe—C24	39.42 (13)	C24—C23—Fe	70.37 (15)
C21—Fe—C24	66.34 (13)	C22—C23—Fe	69.89 (15)
C13—Fe—C24	127.08 (12)	C24—C23—H23	126.0
C23—Fe—C24	39.34 (11)	C22—C23—H23	126.0
C12—Fe—C11	39.95 (9)	Fe—C23—H23	125.3
C15—Fe—C11	40.08 (10)	C23—C24—C25	108.2 (3)
C22—Fe—C11	124.20 (11)	C23—C24—Fe	70.29 (15)
C14—Fe—C11	67.50 (10)	C25—C24—Fe	70.13 (15)
C25—Fe—C11	121.21 (11)	C23—C24—H24	125.9
C21—Fe—C11	107.26 (11)	C25—C24—H24	125.9
C13—Fe—C11	67.58 (10)	Fe—C24—H24	125.3
C23—Fe—C11	161.23 (11)	C24—C25—C21	108.3 (3)
C24—Fe—C11	156.51 (11)	C24—C25—Fe	70.45 (16)
C12—C11—C15	105.8 (2)	C21—C25—Fe	70.27 (15)
C12—C11—B	127.3 (2)	C24—C25—H25	125.8
C15—C11—B	126.9 (2)	C21—C25—H25	125.8
C12—C11—Fe	69.11 (13)	Fe—C25—H25	125.0
C15—C11—Fe	69.11 (13)	F2—B—F1	108.7 (2)
B—C11—Fe	125.09 (16)	F2—B—F3	108.2 (2)
C13—C12—C11	109.4 (2)	F1—B—F3	107.7 (2)
C13—C12—Fe	70.21 (15)	F2—B—C11	110.6 (2)
C11—C12—Fe	70.94 (13)	F1—B—C11	112.1 (2)
C13—C12—H12	125.3	F3—B—C11	109.4 (2)
C11—C12—H12	125.3
C15—Fe—C11—C12	117.2 (2)	C23—Fe—C15—C11	170.5 (3)
C22—Fe—C11—C12	−78.91 (19)	C24—Fe—C15—C11	−157.52 (15)
C14—Fe—C11—C12	80.21 (17)	C12—Fe—C21—C25	−159.66 (17)
C25—Fe—C11—C12	−160.17 (16)	C15—Fe—C21—C25	−77.8 (2)
C21—Fe—C11—C12	−119.29 (17)	C22—Fe—C21—C25	118.4 (3)
C13—Fe—C11—C12	37.14 (17)	C14—Fe—C21—C25	−47.6 (4)
C23—Fe—C11—C12	−51.7 (4)	C13—Fe—C21—C25	168.6 (3)
C24—Fe—C11—C12	170.6 (3)	C23—Fe—C21—C25	80.5 (2)
C12—Fe—C11—C15	−117.2 (2)	C24—Fe—C21—C25	37.42 (18)
C22—Fe—C11—C15	163.89 (16)	C11—Fe—C21—C25	−118.42 (18)
C14—Fe—C11—C15	−37.00 (16)	C12—Fe—C21—C22	81.9 (2)
C25—Fe—C11—C15	82.62 (18)	C15—Fe—C21—C22	163.78 (17)
C21—Fe—C11—C15	123.50 (17)	C14—Fe—C21—C22	−166.0 (3)
C13—Fe—C11—C15	−80.07 (17)	C25—Fe—C21—C22	−118.4 (3)
C23—Fe—C11—C15	−168.9 (3)	C13—Fe—C21—C22	50.1 (4)
C24—Fe—C11—C15	53.3 (3)	C23—Fe—C21—C22	−37.94 (17)
C12—Fe—C11—B	121.6 (3)	C24—Fe—C21—C22	−81.03 (19)
C15—Fe—C11—B	−121.2 (3)	C11—Fe—C21—C22	123.14 (17)
C22—Fe—C11—B	42.7 (2)	C25—C21—C22—C23	0.4 (3)
C14—Fe—C11—B	−158.2 (2)	Fe—C21—C22—C23	60.71 (19)
C25—Fe—C11—B	−38.6 (2)	C25—C21—C22—Fe	−60.31 (19)
C21—Fe—C11—B	2.3 (2)	C12—Fe—C22—C23	124.85 (17)
C13—Fe—C11—B	158.7 (2)	C15—Fe—C22—C23	−161.2 (3)
C23—Fe—C11—B	69.9 (4)	C14—Fe—C22—C23	49.6 (4)
C24—Fe—C11—B	−67.9 (4)	C25—Fe—C22—C23	−80.5 (2)
C15—C11—C12—C13	−0.2 (3)	C21—Fe—C22—C23	−118.1 (3)
B—C11—C12—C13	−178.8 (2)	C13—Fe—C22—C23	82.7 (2)
Fe—C11—C12—C13	−59.92 (17)	C24—Fe—C22—C23	−37.33 (18)
C15—C11—C12—Fe	59.71 (15)	C11—Fe—C22—C23	166.70 (16)
B—C11—C12—Fe	−118.9 (2)	C12—Fe—C22—C21	−117.06 (18)
C15—Fe—C12—C13	81.22 (17)	C15—Fe—C22—C21	−43.1 (4)
C22—Fe—C12—C13	−119.42 (18)	C14—Fe—C22—C21	167.7 (3)
C14—Fe—C12—C13	37.66 (17)	C25—Fe—C22—C21	37.60 (19)
C25—Fe—C12—C13	165.4 (3)	C13—Fe—C22—C21	−159.21 (18)
C21—Fe—C12—C13	−161.56 (18)	C23—Fe—C22—C21	118.1 (3)
C23—Fe—C12—C13	−78.5 (2)	C24—Fe—C22—C21	80.8 (2)
C24—Fe—C12—C13	−47.4 (4)	C11—Fe—C22—C21	−75.2 (2)
C11—Fe—C12—C13	119.8 (2)	C21—C22—C23—C24	−0.3 (3)
C15—Fe—C12—C11	−38.61 (15)	Fe—C22—C23—C24	60.29 (19)
C22—Fe—C12—C11	120.75 (17)	C21—C22—C23—Fe	−60.64 (19)
C14—Fe—C12—C11	−82.17 (16)	C12—Fe—C23—C24	166.06 (18)
C25—Fe—C12—C11	45.6 (3)	C15—Fe—C23—C24	44.4 (4)
C21—Fe—C12—C11	78.62 (18)	C22—Fe—C23—C24	−118.7 (3)
C13—Fe—C12—C11	−119.8 (2)	C14—Fe—C23—C24	81.2 (2)
C23—Fe—C12—C11	161.63 (16)	C25—Fe—C23—C24	−37.44 (19)
C24—Fe—C12—C11	−167.2 (3)	C21—Fe—C23—C24	−80.8 (2)
C11—C12—C13—C14	0.2 (3)	C13—Fe—C23—C24	123.6 (2)
Fe—C12—C13—C14	−60.21 (18)	C11—Fe—C23—C24	−155.0 (3)
C11—C12—C13—Fe	60.37 (17)	C12—Fe—C23—C22	−75.2 (2)
C12—Fe—C13—C14	118.4 (2)	C15—Fe—C23—C22	163.1 (3)
C15—Fe—C13—C14	37.67 (16)	C14—Fe—C23—C22	−160.10 (18)
C22—Fe—C13—C14	−161.54 (17)	C25—Fe—C23—C22	81.3 (2)
C25—Fe—C13—C14	−42.0 (4)	C21—Fe—C23—C22	37.98 (18)
C21—Fe—C13—C14	162.4 (3)	C13—Fe—C23—C22	−117.62 (19)
C23—Fe—C13—C14	−118.82 (17)	C24—Fe—C23—C22	118.7 (3)
C24—Fe—C13—C14	−77.4 (2)	C11—Fe—C23—C22	−36.2 (4)
C11—Fe—C13—C14	81.31 (16)	C22—C23—C24—C25	0.2 (3)
C15—Fe—C13—C12	−80.70 (16)	Fe—C23—C24—C25	60.15 (19)
C22—Fe—C13—C12	80.09 (18)	C22—C23—C24—Fe	−59.99 (19)
C14—Fe—C13—C12	−118.4 (2)	C12—Fe—C24—C23	−40.9 (5)
C25—Fe—C13—C12	−160.4 (3)	C15—Fe—C24—C23	−161.81 (17)
C21—Fe—C13—C12	44.1 (4)	C22—Fe—C24—C23	37.71 (18)
C23—Fe—C13—C12	122.81 (16)	C14—Fe—C24—C23	−119.03 (19)
C24—Fe—C13—C12	164.22 (15)	C25—Fe—C24—C23	118.8 (3)
C11—Fe—C13—C12	−37.06 (14)	C21—Fe—C24—C23	81.3 (2)
C12—C13—C14—C15	0.0 (3)	C13—Fe—C24—C23	−77.3 (2)
Fe—C13—C14—C15	−60.01 (18)	C11—Fe—C24—C23	160.0 (2)
C12—C13—C14—Fe	59.97 (18)	C12—Fe—C24—C25	−159.7 (3)
C12—Fe—C14—C13	−38.03 (15)	C15—Fe—C24—C25	79.4 (2)
C15—Fe—C14—C13	−118.8 (2)	C22—Fe—C24—C25	−81.1 (2)
C22—Fe—C14—C13	45.6 (4)	C14—Fe—C24—C25	122.14 (18)
C25—Fe—C14—C13	165.38 (17)	C21—Fe—C24—C25	−37.52 (18)
C21—Fe—C14—C13	−159.1 (3)	C13—Fe—C24—C25	163.88 (18)
C23—Fe—C14—C13	81.64 (19)	C23—Fe—C24—C25	−118.8 (3)
C24—Fe—C14—C13	123.67 (17)	C11—Fe—C24—C25	41.2 (3)
C11—Fe—C14—C13	−81.54 (17)	C23—C24—C25—C21	0.1 (3)
C12—Fe—C14—C15	80.73 (17)	Fe—C24—C25—C21	60.34 (19)
C22—Fe—C14—C15	164.4 (3)	C23—C24—C25—Fe	−60.25 (19)
C25—Fe—C14—C15	−75.9 (2)	C22—C21—C25—C24	−0.3 (3)
C21—Fe—C14—C15	−40.3 (4)	Fe—C21—C25—C24	−60.46 (19)
C13—Fe—C14—C15	118.8 (2)	C22—C21—C25—Fe	60.15 (19)
C23—Fe—C14—C15	−159.60 (16)	C12—Fe—C25—C24	165.4 (2)
C24—Fe—C14—C15	−117.57 (17)	C15—Fe—C25—C24	−119.64 (17)
C11—Fe—C14—C15	37.22 (15)	C22—Fe—C25—C24	80.93 (19)
C13—C14—C15—C11	−0.1 (3)	C14—Fe—C25—C24	−78.6 (2)
Fe—C14—C15—C11	−60.27 (17)	C21—Fe—C25—C24	118.8 (3)
C13—C14—C15—Fe	60.17 (18)	C13—Fe—C25—C24	−46.6 (4)
C12—C11—C15—C14	0.2 (3)	C23—Fe—C25—C24	37.37 (17)
B—C11—C15—C14	178.8 (2)	C11—Fe—C25—C24	−162.12 (16)
Fe—C11—C15—C14	59.89 (17)	C12—Fe—C25—C21	46.7 (4)
C12—C11—C15—Fe	−59.70 (15)	C15—Fe—C25—C21	121.58 (19)
B—C11—C15—Fe	118.9 (2)	C22—Fe—C25—C21	−37.85 (19)
C12—Fe—C15—C14	−81.29 (18)	C14—Fe—C25—C21	162.66 (17)
C22—Fe—C15—C14	−162.8 (3)	C13—Fe—C25—C21	−165.4 (3)
C25—Fe—C15—C14	124.01 (18)	C23—Fe—C25—C21	−81.4 (2)
C21—Fe—C15—C14	165.15 (18)	C24—Fe—C25—C21	−118.8 (3)
C13—Fe—C15—C14	−37.50 (17)	C11—Fe—C25—C21	79.1 (2)
C23—Fe—C15—C14	50.7 (3)	C12—C11—B—F2	155.8 (2)
C24—Fe—C15—C14	82.7 (2)	C15—C11—B—F2	−22.5 (3)
C11—Fe—C15—C14	−119.8 (2)	Fe—C11—B—F2	66.6 (3)
C12—Fe—C15—C11	38.49 (14)	C12—C11—B—F1	34.3 (3)
C22—Fe—C15—C11	−43.0 (4)	C15—C11—B—F1	−143.9 (2)
C14—Fe—C15—C11	119.8 (2)	Fe—C11—B—F1	−54.9 (3)
C25—Fe—C15—C11	−116.21 (16)	C12—C11—B—F3	−85.0 (3)
C21—Fe—C15—C11	−75.07 (18)	C15—C11—B—F3	96.7 (3)
C13—Fe—C15—C11	82.28 (16)	Fe—C11—B—F3	−174.28 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···F1^i	0.95	2.43	3.168 (3)	135
C13—H13···F2^ii	0.95	2.24	3.138 (3)	158
C23—H23···F3^iii	0.95	2.58	3.455 (4)	154
C24—H24···F2^iv	0.95	2.53	3.232 (4)	130

Symmetry codes: (i) −x, −y, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2.