Crystal structure of tricarbon­yl[η4-6-exo-(tri­phenyl­phosphino)cyclo­hepta-2,4-dien-1-one]iron(0) tetra­fluoro­borate

Wong, K.C.; Reinheimer, E.W.; Nataro, C.; Griffith, D.R.

doi:10.1107/S2056989024005747

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ISSN: 2056-9890

Volume 80| Part 7| July 2024| Pages 746-750

https://doi.org/10.1107/S2056989024005747

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Crystal structure of tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluoroborate

Kelsey C. Wong,^a Eric W. Reinheimer,^b Chip Nataro ^a and Daniel R. Griffith ^a ^*

^aDepartment of Chemistry, Lafayette College, Hugel Science Center, Easton, PA 18042-1768, USA, and ^bRigaku Americas Corporation, 9009 New Trails Dr., The Woodlands, TX 77381, USA
^*Correspondence e-mail: griffitd@lafayette.edu

Edited by F. Di Salvo, University of Buenos Aires, Argentina (Received 19 October 2023; accepted 13 June 2024; online 18 June 2024)

The molecular structure of tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluoroborate dichloromethane hemisolvate, [Fe(C₂₈H₂₂O₄)(CO)₃]BF₄·0.5CH₂Cl₂, as determined by single-crystal X-ray diffraction is reported. The two independent tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one] iron(0) cations and their corresponding anions form dimers, which constitute the asymmetric unit of the structure parallel to the (100) plane. Solid-state stability within that asymmetric unit as well as between neighboring dimeric units is afforded by C—H⋯O and C—H⋯F hydrogen bonds and C—H⋯π and Y—X⋯π (Y = B, C; X = F, O) interactions, which yield diperiodic sheets and a three-dimensional extended network.

Keywords: crystal structure; phosphine; undergraduate; iron carbonyl; piano stool; η⁴-cyclohepta-2,4-dien-1-one.

CCDC reference: 2362680

1. Chemical context

This compound was prepared as part of a Course-based Undergraduate Research Experience (CURE) (Stone et al., 2020 ; Huang et al., 2019 ). The foundation of this CURE was to further examine addition reactions to tricarbonyl(tropone)iron(0) (I) and tricarbonyl(η⁵-ketocycloheptadienyl)iron(0) tetrafluoroborate (II) (Fig. 1). The research focus of one author lies in the synthesis of unique and diverse azapolycyclic skeletons from common synthetic building blocks such as compound I due to the biological importance of such scaffolds. Although seven-membered carbocyclic rings are found in a number of biologically active natural products (Shoemaker & Griffith, 2021 ), their synthesis tends to present a greater challenge compared to similar five- or six-membered rings because of the increased enthalpic and entropic barriers associated with their formation (Phelan et al., 2020 ; Huang et al., 2018 ). The addition of a number of different nucleophiles to compound II has previously been reported, including amines (Phelan et al., 2020), azide, and cyanide (Eisenstadt, 1975 ). This raised the question as to whether or not triphenylphosphine would be sufficiently nucleophilic to react with compound II. Previously, the reaction of several phosphines (PEt₃, PⁿPr₃, PⁿBu₃ or PMe₂Ph) with tricarbonyl(η⁵-cycloheptadienyl)iron(II) tetrafluoroborate in methylene chloride resulted in the formation of the corresponding tricarbonyl[η⁴-(5-exo-phosphine)cycloheptadiene]iron(0) tetrafluoroborate (Brown et al., 1982 ). Similar to that system, the reaction of compound II and triphenylphosphine resulted in the formation of tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluoroborate (III) (Fig. 1). Ultimately, this and similar phosphonium salts could be a precursor for Wittig olefinations that would provide efficient access to tropone rings with diverse substituents.

Figure 1
Tricarbonyl(tropone)iron(0) (I), tricarbonyl(η⁵-ketocycloheptadienyl)iron(II) tetrafluoroborate (II), and tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluoroborate (III) and the procedure outlining the synthesis of III from I and II.

2. Structural commentary

The single crystal X-ray structure of III crystallizes in the centrosymmetric triclinic space group P $[\overline{1}]$ (Fig. 2). The asymmetric unit consists of two tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) cations, two tetrafluoroborate anions (to balance the charge), and an interstitial CH₂Cl₂ solvent molecule lying in solvent-accessible voids of ∼101 Å³. The iron tricarbonyl moieties adopt piano stool orientations with the cyclohepta-2,4-dien-1-one group (Fig. 2). Closer analysis of the thermal parameters of the [BF₄]⁻ anions and CH₂Cl₂ solvent molecule within the asymmetric unit showed no qualitative evidence of disorder.

Figure 2
Single-crystal structure of one tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluoroborate (III) from the asymmetric unit with anisotropic displacement ellipsoids at the 50% probability level. The interstitial CH₂Cl₂ has been removed for the sake of clarity.

3. Supramolecular features

Solid-state stability between the molecules of III within the asymmetric unit is afforded by an array of C—H⋯O and C—H⋯F hydrogen bonds (Table 1) as determined through PLATON analysis (Spek, 2020 ). The two independent tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) cations from the asymmetric unit lie parallel to the (100) plane and are stabilized by intermolecular C—H⋯O hydrogen bonds. The addition of C—H⋯F hydrogen bonding involving the [BF₄]⁻ anions increases the dimensionality of the solid-state structure into both diperiodic sheets and extended 3D networks, which also contain C—H⋯π and Y—X⋯π (Y = B,C; X = F, O) interactions (Table 2) according to PLATON (Spek, 2020) (Figs. 3 and 4). The resulting 3D network was also found to contain solvent-accessible voids of ∼101 Å³ within which the interstitial CH₂Cl₂ was located (Fig. 5).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32⋯F5	1.00	2.37	3.198 (3)	140
C43—H43⋯F6ⁱ	0.95	2.33	3.240 (3)	160
C44—H44⋯O8ⁱⁱ	0.95	2.56	3.467 (3)	159
C46—H46⋯F7ⁱⁱⁱ	0.95	2.40	3.151 (3)	136
C49—H49⋯O7^iv	0.95	2.60	3.339 (3)	135
C50—H50⋯F6^iv	0.95	2.53	3.471 (3)	169
C52—H52⋯O1	0.95	2.37	3.286 (3)	161
C53—H53⋯F4ⁱⁱⁱ	0.95	2.66	3.500 (3)	148
C56—H56⋯F6^iv	0.95	2.48	3.362 (3)	155
C2—H2⋯F3^v	1.00	2.50	3.493 (3)	170
C4—H4⋯F4ⁱⁱⁱ	1.00	2.42	3.393 (3)	165
C7—H7⋯O5	1.00	2.34	3.192 (3)	143
C13—H13⋯F1^v	0.95	2.41	3.232 (3)	144
C19—H19⋯O2^vi	0.95	2.51	3.393 (3)	154
C28—H28⋯O5	0.95	2.41	3.319 (4)	161
C57A—H57A⋯F4	0.99	2.47	3.276 (4)	139
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Table 2
Phenyl ring torsion angles (°)

Cation 1		Cation 2
Torsion angle	Value	Torsion angle	Value
Ring 1
P1—C11—C16—C15	175.9 (2)	P2—C39—C40—C41	−176.5 (2)
C11—C16—C15—C14	−0.7 (4)	C39—C40—C41—C42	1.0 (4)
C16—C15—C14—C13	−0.7 (4)	C40—C41—C42—C43	1.2 (4)
C15—C14—C13—C12	1.2 (4)	C41—C42—C43—C44	−2.2 (4)
C14—C13—C12—C11	−0.2 (4)	C42—C43—C44—C39	0.9 (4)
C13—C12—C11—P1	−175.4 (2)	C43—C44—C39—P2	175.6 (2)

Ring 2
P1—C17—C18—C19	−175.5 (2)	P2—C45—C50—C49	178.8 (2)
C17—C18—C19—C20	−0.1 (4)	C45—C50—C49—C48	0.8 (4)
C18—C19—C20—C21	0.4 (4)	C50—C49—C48—C47	−0.1 (4)
C19—C20—C21—C22	−0.2 (5)	C49—C48—C47—C46	−1.5 (4)
C20—C21—C22—C17	−1.2 (4)	C48—C47—C46—C45	2.3 (4)
C21—C22—C17—P1	176.0 (2)	C47—C46—C45—P2	179.7 (2)

Ring 3
P1—C23—C28—C27	−170.3 (2)	P2—C51—C52—C53	176.9 (2)
C23—C28—C27—C26	−1.1 (4)	C51—C52—C53—C54	0.1 (4)
C28—C27—C26—C25	1.1 (4)	C52—C53—C54—C55	−0.5 (4)
C27—C26—C25—C24	0.1 (5)	C53—C54—C55—C56	−0.1 (5)
C26—C25—C24—C23	−1.3 (5)	C54—C55—C56—C51	1.2 (5)
C25—C24—C23—P1	171.4 (2)	C55—C56—C51—P2	−177.7 (2)

Figure 3
View of the C—H⋯O and C—H⋯F hydrogen bonds from the (101) plane of III. When coupled with the C—H⋯π and Y—X⋯π (Y = B, C; X = F, O) interactions, this repeat unit extends into a three-dimensional network. Anisotropic displacement ellipsoids have been set to the 50% probability level.

Figure 4
Projection of the C—H⋯π and Y—X⋯π (Y = B, C; X = F, O) interactions in the ac plane of III. Their combination with the hydrogen bonds yields a three-dimensional extended network in the solid state. Anisotropic displacement ellipsoids have been set to the 50% probability level (C_g = ring centroids).

Figure 5
View into the (120) plane showing the interstitial CH₂Cl₂ solvent molecules lying within the solvent-accessible voids of III. These voids are generated from the packing supported by the C—H⋯O and C—H⋯F hydrogen bonds and C—H⋯π and Y—X⋯π (Y = B, C; X = F, O) interactions. The anisotropic displacement ellipsoids for CH₂Cl₂ have been set to the 50% probability level.

The Z′ > 1 nature of the structural model for III suggests the presence of structural differences between molecules within the asymmetric unit. Barring differences in the thermal parameters for the various atoms within the independent components, overlaying the tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) cations and [BF₄]⁻ anions showed that the anions had better alignment while differences in the some of the constituent torsion angles within phenyl rings from the tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) cations were more pronounced visually (Fig. 6). Table 3 summarizes the torsion angles from the phenyl rings of the tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) cations.

Table 3
X—Y⋯π interactions (Å,°)

Cg1–Cg5 are the centroids of the C11–C16, C17–C22, C39–C44 and C45–C50 rings, respectively.

X—Y⋯Cg	Y⋯Cg	X⋯Cg	X—H⋯Cg
C54—H54⋯Cg2ⁱ	2.99	3.929 (3)	171
B1—F1⋯Cg1ⁱⁱ	3.429 (2)	4.790 (3)	165.56 (17)
B2—F6⋯Cg3ⁱⁱⁱ	3.653 (2)	4.913 (3)	150.99 (17)
C9—O3⋯Cg2^iv	3.393 (2)	3.858 (3)	105.37 (19)
C38—08⋯Cg4^v	3.467 (2)	3.925 (3)	105.10 (18)
Symmetry codes: (i) −1 + x, 1 + y, z; (ii) x, 1 + y, z; (iii) 1 + x, −1 + y, z; (iv) 2 − x, 1 − y, 1 − z; (v) 1 − x, 1 − y, 2 − z.

Figure 6
Molecular overlay of between both cations constituting the symmetric unit of III demonstrating that the greatest disparity between them exists within the torsion angles of the the phenyl rings. The first tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluorrborate is in black while the second is in yellow. Anisotropic displacement ellipsoids have been set to the 50% probability level.

4. Database survey

The structure of this report is not found in the Cambridge Structural Database (CSD version 5.43; Groom et al., 2016 ). To date, the structures of six tricarbonyl(η⁴-tropone derivative)iron(0) compounds have been reported. In addition to the structure of compound I (Dodge, 1964 ), three of the remaining reports have one additional substituent in the 6-position, H (Sotokawa et al., 1987 ), t-Bu (Coquerel et al., 2002 ) and morpholi-4-yl (Huang et al., 2018). From the various reports, comparison of their structural features suggested that the presence of the formally cationic phosphorous had minimal impact on the bond lengths.

5. Synthesis and crystallization

All chemicals were purchased from commercial vendors and used as is. Compounds I and II were prepared according to literature procedures (Huang et al., 2019). NMR spectra were obtained in d₃-acetonitrile using a Bruker Avance III HD 400 FT-NMR spectrometer. The synthesis was performed using standard Schlenk conditions as outlined in Fig. 1, but all subsequent manipulations of the product were conducted in air. Compound II (0.0054 g, 0.016 mmol) and triphenylphosphine (0.0043 g, 0.016 mmol) were added to a 50 mL round-bottom flask along with a stir bar. Methylene chloride (12 mL) was added, and the reaction mixture was stirred at room temperature for 30 minutes. A color change from pastel yellow to a darker yellow was observed. The solution was reduced in vacuo to approximately 5 mL and the resulting solution was layered with diethyl ether (7 mL) before being placed in the freezer for 48 h. The sample formed a pastel yellow solid and was filtered via cannula. The solid was dried in vacuo to give the desired product (0.0085 g, 88% yield). Crystals were grown by slow vapor diffusion of diethyl ether at room temperature into a solution of the compound in methylene chloride. ¹H NMR (400 MHz, CD₃CN): δ 7.87 (m, 9H, H_meta, H_para), 7.75 (m, 6H, H_ortho), 5.80 (t, J = 6.2 Hz, 1H, H4), 5.20 (t, J = 7.0 Hz, 1H, H1), 4.86 (td, J = 12.7, 4.7 Hz, 1H, H7), 3.21 (dd, J = 13.0, 7.5 Hz, 1H, H3), 3.16 (d, J = 6.6 Hz, 1H, H2), 2.18 (m, 1H, H6A/B), 1.99 (q, J = 12.2 Hz, 1H, H6A/B); ³¹P{¹H} NMR (162 MHz, CD₃CN): δ 23.3 (s); ¹³C{¹H} NMR (100 MHz, CD₃CN): δ 207.9 (s, No DEPT, C8–10), 202.6 (d, J = 15.4 Hz, No DEPT, C5), 135.9 (d, J = 3.2 Hz, DEPT +, C_para), 134.8 (d, J = 9.5 Hz, DEPT +, C_meta), 131.1 (d, J = 12.7 Hz, DEPT +, C_ortho), 117.2 (d, J = 81.6 Hz, No DEPT, C_ipso), 94.6 (s, DEPT +, C4), 89.8 (s, DEPT +, C1), 56.7 (s, DEPT +, C2), 49.5 (d, J = 7.4 Hz, DEPT +, C3), 41.2 (d, J = 31.8 Hz, DEPT +, C7), 37.2 (s, DEPT –, C6). Peaks were assigned using COSY, HMBC and HSQC NMR spectra. Protons of the tropone ring are labeled by the number of the carbon atom to which they are bonded. IR (cm⁻¹, CH₃CN): 2059 (m, Fe—C≡O), 2014 (m, Fe—C≡O), 1966 (vs, Fe—C≡O), 1710 (m, C=O), 1609 (m, C=C).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All non-hydrogen atoms were refined anisotropically. H atoms bound to carbon were positioned geometrically and constrained to ride on their parent atoms. U_iso(H) values were set to a multiple of U_eq(C) with 1.2 times all CH and CH₂ groups.

Table 4
Experimental details

Crystal data
Chemical formula	[Fe(C₂₈H₂₂O₄)(CO)₃]BF₄·0.5CH₂Cl₂
M_r	638.57
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.9343 (2), 10.9767 (3), 26.4168 (6)
α, β, γ (°)	86.993 (2), 82.468 (2), 77.300 (2)
V (Å³)	2785.09 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.76
Crystal size (mm)	0.3 × 0.14 × 0.08

Data collection
Diffractometer	Rigaku Oxford Diffraction XtaLAB Mini II
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.841, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	59046, 9882, 7785
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.103, 1.03
No. of reflections	9882
No. of parameters	730
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.43
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2362680

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005747/vu2002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005747/vu2002Isup2.hkl

checkCIF report

Computing details top

Tricarbonyl[η⁴-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]\ iron(0) tetrafluoroborate dichloromethane hemisolvate top

Crystal data top

[Fe(C₂₈H₂₂O₄)(CO)₃]BF₄·0.5CH₂Cl₂	Z = 4
M_r = 638.57	F(000) = 1300
Triclinic, P1	D_x = 1.523 Mg m⁻³
a = 9.9343 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9767 (3) Å	Cell parameters from 14608 reflections
c = 26.4168 (6) Å	θ = 2.3–25.9°
α = 86.993 (2)°	µ = 0.76 mm⁻¹
β = 82.468 (2)°	T = 100 K
γ = 77.300 (2)°	Block, yellow
V = 2785.09 (12) Å³	0.3 × 0.14 × 0.08 mm

Data collection top

Rigaku Oxford Diffraction XtaLAB Mini II diffractometer	9882 independent reflections
Radiation source: fine-focus sealed X-ray tube, Rigaku (Mo) X-ray Source	7785 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 10.0000 pixels mm^-1	θ_max = 25.1°, θ_min = 2.0°
ω scans	h = −11→11
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2023)	k = −13→13
T_min = 0.841, T_max = 0.969	l = −31→31
59046 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0554P)² + 0.9998P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
9882 reflections	Δρ_max = 0.54 e Å⁻³
730 parameters	Δρ_min = −0.43 e Å⁻³
9 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P2	0.49890 (7)	0.80234 (6)	0.85505 (2)	0.01236 (16)
Fe2	0.76338 (4)	0.40071 (4)	0.89551 (2)	0.01306 (11)
O5	0.8797 (2)	0.49399 (18)	0.75394 (7)	0.0214 (5)
O6	0.6413 (2)	0.28814 (19)	0.81779 (7)	0.0266 (5)
O7	0.9804 (2)	0.18494 (18)	0.92305 (7)	0.0231 (5)
O8	0.5743 (2)	0.3482 (2)	0.98587 (7)	0.0285 (5)
C29	0.6417 (3)	0.5823 (2)	0.89315 (10)	0.0145 (6)
H29	0.556816	0.593076	0.918838	0.017*
C30	0.7655 (3)	0.5796 (2)	0.91661 (10)	0.0149 (6)
H30	0.756979	0.598566	0.953652	0.018*
C31	0.8961 (3)	0.5230 (2)	0.89111 (10)	0.0159 (6)
H31	0.977935	0.502297	0.910803	0.019*
C32	0.9086 (3)	0.4713 (3)	0.84151 (10)	0.0160 (6)
H32	0.997745	0.409752	0.832129	0.019*
C33	0.8442 (3)	0.5353 (3)	0.79735 (10)	0.0155 (6)
C34	0.7409 (3)	0.6599 (2)	0.80507 (10)	0.0165 (6)
H34A	0.713284	0.694001	0.771616	0.020*
H34B	0.786063	0.719880	0.819411	0.020*
C35	0.6098 (3)	0.6455 (2)	0.84144 (9)	0.0136 (6)
H35	0.556541	0.595660	0.824317	0.016*
C36	0.6867 (3)	0.3314 (3)	0.84864 (10)	0.0175 (6)
C37	0.8977 (3)	0.2693 (3)	0.91181 (10)	0.0173 (6)
C38	0.6482 (3)	0.3682 (3)	0.95096 (10)	0.0173 (6)
C39	0.5932 (3)	0.8834 (2)	0.89063 (9)	0.0122 (6)
C40	0.6901 (3)	0.9485 (2)	0.86506 (10)	0.0166 (6)
H40	0.702505	0.953906	0.828798	0.020*
C41	0.7676 (3)	1.0048 (3)	0.89304 (10)	0.0192 (6)
H41	0.832112	1.049971	0.875878	0.023*
C42	0.7511 (3)	0.9952 (3)	0.94643 (11)	0.0200 (7)
H42	0.803154	1.035219	0.965383	0.024*
C43	0.6592 (3)	0.9277 (3)	0.97171 (10)	0.0157 (6)
H43	0.650592	0.919132	1.007893	0.019*
C44	0.5792 (3)	0.8722 (2)	0.94406 (10)	0.0139 (6)
H44	0.515241	0.826836	0.961476	0.017*
C45	0.3386 (3)	0.7855 (2)	0.89292 (10)	0.0134 (6)
C46	0.3015 (3)	0.6696 (3)	0.90128 (10)	0.0169 (6)
H46	0.361384	0.596876	0.886685	0.020*
C47	0.1768 (3)	0.6603 (3)	0.93104 (11)	0.0205 (7)
H47	0.153518	0.581082	0.937688	0.025*
C48	0.0867 (3)	0.7676 (3)	0.95092 (11)	0.0201 (7)
H48	0.000884	0.761797	0.970466	0.024*
C49	0.1227 (3)	0.8837 (3)	0.94208 (10)	0.0183 (6)
H49	0.060856	0.956466	0.955709	0.022*
C50	0.2479 (3)	0.8940 (3)	0.91362 (10)	0.0160 (6)
H50	0.272247	0.973078	0.908149	0.019*
C51	0.4586 (3)	0.8938 (2)	0.79783 (9)	0.0142 (6)
C52	0.4425 (3)	0.8367 (3)	0.75349 (10)	0.0169 (6)
H52	0.456999	0.748360	0.752392	0.020*
C53	0.4047 (3)	0.9112 (3)	0.71075 (10)	0.0218 (7)
H53	0.393439	0.873265	0.680526	0.026*
C54	0.3839 (3)	1.0399 (3)	0.71241 (11)	0.0262 (7)
H54	0.359061	1.089691	0.683175	0.031*
C55	0.3990 (3)	1.0971 (3)	0.75671 (11)	0.0268 (7)
H55	0.384692	1.185501	0.757477	0.032*
C56	0.4353 (3)	1.0245 (3)	0.79987 (10)	0.0199 (7)
H56	0.444019	1.063075	0.830287	0.024*
P1	0.94285 (7)	0.20756 (6)	0.64553 (2)	0.01226 (16)
O1	0.5518 (2)	0.53885 (18)	0.72809 (7)	0.0245 (5)
Fe1	0.70408 (4)	0.60845 (4)	0.59115 (2)	0.01357 (11)
C1	0.8213 (3)	0.4256 (2)	0.60006 (9)	0.0126 (6)
H1	0.913470	0.411913	0.578387	0.015*
C2	0.7095 (3)	0.4278 (2)	0.57052 (10)	0.0160 (6)
H2	0.731133	0.405510	0.533685	0.019*
O2	0.4934 (2)	0.81613 (18)	0.55330 (8)	0.0254 (5)
C3	0.5726 (3)	0.4871 (3)	0.58972 (11)	0.0185 (6)
H3	0.499787	0.506083	0.565967	0.022*
O3	0.9219 (2)	0.6536 (2)	0.50941 (8)	0.0273 (5)
C4	0.5435 (3)	0.5435 (3)	0.63893 (10)	0.0174 (6)
H4	0.453410	0.606242	0.643897	0.021*
O4	0.7946 (2)	0.73153 (19)	0.67411 (8)	0.0272 (5)
C5	0.5929 (3)	0.4868 (3)	0.68714 (10)	0.0174 (6)
C6	0.6918 (3)	0.3593 (3)	0.68483 (10)	0.0171 (6)
H6A	0.649606	0.299488	0.668921	0.021*
H6B	0.707112	0.328216	0.719929	0.021*
C7	0.8327 (3)	0.3667 (2)	0.65366 (9)	0.0130 (6)
H7	0.880827	0.416729	0.672986	0.016*
C8	0.5753 (3)	0.7365 (3)	0.56836 (10)	0.0173 (6)
C9	0.8363 (3)	0.6373 (3)	0.54088 (11)	0.0186 (6)
C10	0.7618 (3)	0.6834 (3)	0.64182 (11)	0.0181 (6)
C11	0.8592 (3)	0.1224 (2)	0.60744 (10)	0.0125 (6)
C12	0.8886 (3)	0.1261 (2)	0.55398 (10)	0.0133 (6)
H12	0.957399	0.168329	0.538081	0.016*
C13	0.8167 (3)	0.0676 (2)	0.52443 (10)	0.0159 (6)
H13	0.836029	0.070149	0.488247	0.019*
C14	0.7169 (3)	0.0058 (3)	0.54771 (10)	0.0186 (6)
H14	0.669280	−0.035317	0.527338	0.022*
C15	0.6853 (3)	0.0030 (3)	0.60082 (10)	0.0177 (6)
H15	0.615918	−0.039006	0.616404	0.021*
C16	0.7559 (3)	0.0620 (2)	0.63085 (10)	0.0150 (6)
H16	0.734259	0.061266	0.666957	0.018*
C17	1.1110 (3)	0.2205 (2)	0.61364 (9)	0.0139 (6)
C18	1.2036 (3)	0.1120 (3)	0.59409 (9)	0.0155 (6)
H18	1.175348	0.034497	0.595495	0.019*
C19	1.3374 (3)	0.1205 (3)	0.57264 (10)	0.0189 (7)
H19	1.400826	0.047994	0.559412	0.023*
C20	1.3790 (3)	0.2337 (3)	0.57043 (11)	0.0221 (7)
H20	1.470133	0.238330	0.555546	0.026*
C21	1.2875 (3)	0.3400 (3)	0.58992 (11)	0.0236 (7)
H21	1.316252	0.417319	0.588198	0.028*
C22	1.1544 (3)	0.3338 (3)	0.61191 (10)	0.0188 (6)
H22	1.092670	0.406478	0.625785	0.023*
C23	0.9730 (3)	0.1234 (3)	0.70496 (10)	0.0157 (6)
C24	0.9921 (3)	−0.0070 (3)	0.70735 (11)	0.0226 (7)
H24	0.976679	−0.050371	0.679188	0.027*
C25	1.0334 (3)	−0.0724 (3)	0.75100 (12)	0.0298 (8)
H25	1.044555	−0.160654	0.753021	0.036*
C26	1.0588 (3)	−0.0089 (3)	0.79202 (11)	0.0272 (8)
H26	1.087283	−0.054269	0.821806	0.033*
C27	1.0425 (3)	0.1197 (3)	0.78950 (10)	0.0253 (7)
H27	1.061477	0.162045	0.817316	0.030*
C28	0.9983 (3)	0.1875 (3)	0.74612 (10)	0.0194 (6)
H28	0.985532	0.275874	0.744555	0.023*
B1	1.1632 (3)	0.7161 (3)	0.59857 (12)	0.0190 (7)
F1	1.06555 (19)	0.81871 (17)	0.58349 (7)	0.0392 (5)
F2	1.09598 (19)	0.62678 (16)	0.62366 (7)	0.0344 (5)
F3	1.25338 (19)	0.66298 (17)	0.55619 (6)	0.0332 (5)
F4	1.24188 (19)	0.75704 (18)	0.63210 (7)	0.0371 (5)
B2	1.2845 (4)	0.2994 (3)	0.90769 (14)	0.0241 (8)
F5	1.2026 (2)	0.3128 (2)	0.86803 (8)	0.0563 (6)
F6	1.3542 (2)	0.17533 (15)	0.91095 (6)	0.0358 (5)
F7	1.38046 (19)	0.37573 (18)	0.89795 (8)	0.0454 (5)
F8	1.1993 (2)	0.33346 (18)	0.95371 (7)	0.0453 (5)
Cl1A	1.25733 (10)	0.41520 (8)	0.72180 (3)	0.0411 (2)
Cl2A	1.18892 (9)	0.61367 (8)	0.79693 (3)	0.0331 (2)
C57A	1.1926 (4)	0.5766 (3)	0.73249 (11)	0.0316 (7)
H57A	1.251916	0.624921	0.710549	0.038*
H57B	1.097398	0.601362	0.722659	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P2	0.0146 (4)	0.0111 (4)	0.0105 (3)	−0.0010 (3)	−0.0010 (3)	−0.0018 (3)
Fe2	0.0128 (2)	0.0127 (2)	0.0132 (2)	−0.00214 (16)	−0.00068 (16)	−0.00078 (15)
O5	0.0223 (11)	0.0224 (12)	0.0170 (10)	−0.0010 (9)	0.0020 (9)	−0.0053 (8)
O6	0.0321 (13)	0.0305 (13)	0.0221 (11)	−0.0144 (10)	−0.0070 (10)	−0.0037 (10)
O7	0.0209 (11)	0.0180 (12)	0.0293 (11)	−0.0023 (10)	−0.0039 (9)	0.0023 (9)
O8	0.0297 (13)	0.0345 (14)	0.0203 (11)	−0.0111 (11)	0.0054 (10)	0.0043 (10)
C29	0.0149 (15)	0.0135 (15)	0.0123 (13)	−0.0005 (12)	0.0044 (11)	−0.0014 (11)
C30	0.0204 (15)	0.0107 (14)	0.0149 (13)	−0.0050 (12)	−0.0041 (12)	−0.0002 (11)
C31	0.0180 (15)	0.0121 (15)	0.0194 (14)	−0.0062 (12)	−0.0051 (12)	0.0019 (11)
C32	0.0106 (14)	0.0142 (15)	0.0230 (15)	−0.0035 (12)	0.0009 (12)	−0.0011 (12)
C33	0.0137 (14)	0.0141 (15)	0.0185 (14)	−0.0059 (12)	0.0034 (12)	−0.0006 (11)
C34	0.0195 (15)	0.0147 (15)	0.0128 (13)	−0.0009 (12)	0.0029 (11)	−0.0003 (11)
C35	0.0151 (14)	0.0111 (14)	0.0127 (13)	0.0011 (11)	−0.0014 (11)	−0.0019 (11)
C36	0.0163 (15)	0.0162 (16)	0.0181 (15)	−0.0027 (12)	0.0015 (12)	0.0036 (12)
C37	0.0190 (16)	0.0166 (16)	0.0171 (14)	−0.0066 (13)	0.0003 (12)	−0.0024 (12)
C38	0.0187 (16)	0.0125 (15)	0.0204 (15)	−0.0002 (12)	−0.0075 (13)	0.0006 (12)
C39	0.0112 (14)	0.0103 (14)	0.0140 (13)	0.0010 (11)	−0.0025 (11)	−0.0017 (10)
C40	0.0203 (15)	0.0146 (15)	0.0132 (13)	−0.0024 (12)	0.0013 (12)	−0.0007 (11)
C41	0.0157 (15)	0.0205 (16)	0.0219 (15)	−0.0079 (13)	0.0039 (12)	−0.0027 (12)
C42	0.0164 (15)	0.0222 (17)	0.0215 (15)	−0.0020 (13)	−0.0035 (12)	−0.0089 (12)
C43	0.0154 (15)	0.0174 (16)	0.0122 (13)	0.0011 (12)	−0.0009 (11)	−0.0029 (11)
C44	0.0146 (14)	0.0104 (14)	0.0149 (13)	−0.0006 (11)	0.0022 (11)	−0.0018 (11)
C45	0.0139 (14)	0.0151 (15)	0.0121 (13)	−0.0029 (12)	−0.0055 (11)	−0.0006 (11)
C46	0.0157 (15)	0.0161 (16)	0.0189 (14)	−0.0025 (12)	−0.0023 (12)	−0.0042 (12)
C47	0.0202 (16)	0.0203 (17)	0.0241 (15)	−0.0091 (13)	−0.0076 (13)	0.0030 (12)
C48	0.0120 (15)	0.0276 (18)	0.0216 (15)	−0.0054 (13)	−0.0027 (12)	−0.0015 (13)
C49	0.0144 (15)	0.0215 (17)	0.0170 (14)	0.0016 (12)	−0.0022 (12)	−0.0040 (12)
C50	0.0192 (15)	0.0127 (15)	0.0164 (14)	−0.0019 (12)	−0.0055 (12)	−0.0021 (11)
C51	0.0151 (14)	0.0132 (15)	0.0126 (13)	−0.0005 (12)	−0.0003 (11)	−0.0002 (11)
C52	0.0161 (15)	0.0173 (16)	0.0174 (14)	−0.0041 (12)	0.0000 (12)	−0.0042 (12)
C53	0.0190 (16)	0.0320 (19)	0.0136 (14)	−0.0036 (14)	−0.0025 (12)	−0.0015 (13)
C54	0.0269 (18)	0.033 (2)	0.0160 (15)	−0.0023 (15)	−0.0049 (13)	0.0083 (13)
C55	0.0343 (19)	0.0172 (17)	0.0269 (17)	−0.0002 (14)	−0.0066 (14)	0.0023 (13)
C56	0.0286 (17)	0.0125 (15)	0.0175 (14)	−0.0005 (13)	−0.0050 (13)	−0.0004 (12)
P1	0.0142 (4)	0.0106 (4)	0.0114 (3)	−0.0015 (3)	−0.0006 (3)	−0.0023 (3)
O1	0.0242 (12)	0.0230 (12)	0.0231 (11)	−0.0030 (9)	0.0086 (9)	−0.0082 (9)
Fe1	0.0123 (2)	0.0118 (2)	0.0157 (2)	−0.00230 (16)	0.00080 (16)	−0.00029 (16)
C1	0.0148 (14)	0.0106 (14)	0.0109 (12)	−0.0016 (11)	0.0028 (11)	−0.0023 (10)
C2	0.0225 (16)	0.0093 (14)	0.0171 (14)	−0.0055 (12)	−0.0020 (12)	−0.0013 (11)
O2	0.0208 (12)	0.0184 (12)	0.0360 (12)	−0.0016 (10)	−0.0063 (10)	0.0042 (10)
C3	0.0164 (15)	0.0165 (16)	0.0246 (15)	−0.0080 (12)	−0.0049 (12)	0.0059 (12)
O3	0.0255 (12)	0.0338 (14)	0.0228 (11)	−0.0115 (10)	0.0045 (10)	0.0023 (9)
C4	0.0087 (14)	0.0159 (16)	0.0258 (15)	−0.0025 (12)	0.0033 (12)	0.0025 (12)
O4	0.0359 (13)	0.0264 (13)	0.0219 (11)	−0.0117 (10)	−0.0031 (10)	−0.0035 (10)
C5	0.0112 (14)	0.0169 (16)	0.0230 (15)	−0.0059 (12)	0.0066 (12)	0.0000 (12)
C6	0.0187 (15)	0.0176 (16)	0.0130 (13)	−0.0031 (12)	0.0047 (12)	−0.0009 (11)
C7	0.0158 (14)	0.0106 (14)	0.0122 (13)	−0.0021 (11)	0.0004 (11)	−0.0031 (11)
C8	0.0152 (15)	0.0172 (16)	0.0205 (15)	−0.0087 (13)	0.0038 (12)	−0.0022 (12)
C9	0.0209 (16)	0.0161 (16)	0.0191 (15)	−0.0027 (13)	−0.0057 (13)	−0.0001 (12)
C10	0.0178 (15)	0.0135 (15)	0.0193 (15)	−0.0012 (12)	0.0058 (12)	0.0038 (12)
C11	0.0132 (14)	0.0097 (14)	0.0139 (13)	−0.0005 (11)	−0.0018 (11)	−0.0017 (11)
C12	0.0123 (14)	0.0115 (15)	0.0148 (13)	−0.0017 (11)	0.0019 (11)	−0.0012 (11)
C13	0.0170 (15)	0.0168 (15)	0.0124 (13)	0.0002 (12)	−0.0016 (11)	−0.0026 (11)
C14	0.0190 (16)	0.0179 (16)	0.0205 (14)	−0.0052 (13)	−0.0044 (12)	−0.0058 (12)
C15	0.0163 (15)	0.0154 (15)	0.0209 (14)	−0.0053 (12)	0.0025 (12)	−0.0011 (12)
C16	0.0185 (15)	0.0134 (15)	0.0126 (13)	−0.0026 (12)	−0.0010 (11)	−0.0014 (11)
C17	0.0146 (14)	0.0155 (15)	0.0111 (13)	−0.0011 (12)	−0.0026 (11)	−0.0019 (11)
C18	0.0174 (15)	0.0162 (15)	0.0139 (13)	−0.0036 (12)	−0.0045 (11)	−0.0028 (11)
C19	0.0129 (15)	0.0249 (17)	0.0161 (14)	0.0047 (13)	−0.0049 (12)	−0.0039 (12)
C20	0.0118 (15)	0.0287 (18)	0.0256 (16)	−0.0050 (13)	−0.0007 (12)	−0.0007 (13)
C21	0.0170 (16)	0.0215 (17)	0.0341 (17)	−0.0074 (13)	−0.0035 (13)	−0.0022 (14)
C22	0.0169 (15)	0.0156 (16)	0.0242 (15)	−0.0025 (12)	−0.0038 (12)	−0.0055 (12)
C23	0.0139 (14)	0.0177 (15)	0.0126 (13)	0.0000 (12)	0.0023 (11)	0.0015 (11)
C24	0.0269 (17)	0.0185 (17)	0.0221 (15)	−0.0032 (13)	−0.0052 (13)	−0.0004 (12)
C25	0.0345 (19)	0.0215 (18)	0.0311 (18)	−0.0018 (15)	−0.0054 (15)	0.0066 (14)
C26	0.0226 (17)	0.038 (2)	0.0151 (15)	0.0037 (15)	−0.0015 (13)	0.0095 (14)
C27	0.0242 (17)	0.034 (2)	0.0129 (14)	0.0034 (14)	0.0005 (12)	−0.0068 (13)
C28	0.0185 (16)	0.0220 (17)	0.0156 (14)	−0.0003 (13)	−0.0004 (12)	−0.0040 (12)
B1	0.0183 (18)	0.0163 (18)	0.0203 (17)	0.0000 (14)	−0.0015 (14)	−0.0007 (14)
F1	0.0316 (11)	0.0366 (12)	0.0390 (11)	0.0082 (9)	0.0001 (9)	0.0159 (9)
F2	0.0425 (12)	0.0244 (10)	0.0363 (10)	−0.0137 (9)	0.0039 (9)	0.0046 (8)
F3	0.0360 (11)	0.0324 (11)	0.0274 (10)	−0.0036 (9)	0.0068 (8)	−0.0092 (8)
F4	0.0352 (11)	0.0458 (13)	0.0344 (10)	−0.0141 (9)	−0.0067 (9)	−0.0093 (9)
B2	0.0226 (19)	0.0179 (19)	0.0313 (19)	−0.0027 (15)	−0.0054 (16)	0.0039 (15)
F5	0.0337 (12)	0.0883 (18)	0.0516 (13)	−0.0204 (12)	−0.0224 (10)	0.0308 (12)
F6	0.0588 (13)	0.0175 (10)	0.0240 (9)	0.0039 (9)	−0.0005 (9)	0.0003 (7)
F7	0.0285 (11)	0.0290 (12)	0.0799 (16)	−0.0121 (9)	0.0014 (10)	−0.0064 (11)
F8	0.0466 (13)	0.0345 (12)	0.0496 (12)	−0.0045 (10)	0.0119 (10)	−0.0154 (10)
Cl1A	0.0475 (6)	0.0249 (5)	0.0523 (5)	−0.0028 (4)	−0.0173 (4)	−0.0064 (4)
Cl2A	0.0452 (5)	0.0323 (5)	0.0239 (4)	−0.0120 (4)	−0.0065 (4)	0.0026 (3)
C57A	0.041 (2)	0.0278 (15)	0.0252 (14)	−0.0055 (15)	−0.0040 (14)	0.0010 (13)

Geometric parameters (Å, º) top

P2—C35	1.853 (3)	Fe1—C2	2.071 (3)
P2—C39	1.799 (3)	Fe1—C3	2.065 (3)
P2—C45	1.807 (3)	Fe1—C4	2.127 (3)
P2—C51	1.810 (3)	Fe1—C8	1.816 (3)
Fe2—C29	2.094 (3)	Fe1—C9	1.809 (3)
Fe2—C30	2.074 (3)	Fe1—C10	1.822 (3)
Fe2—C31	2.068 (3)	C1—H1	1.0000
Fe2—C32	2.134 (3)	C1—C2	1.434 (4)
Fe2—C36	1.815 (3)	C1—C7	1.533 (3)
Fe2—C37	1.812 (3)	C2—H2	1.0000
Fe2—C38	1.808 (3)	C2—C3	1.412 (4)
O5—C33	1.234 (3)	O2—C8	1.149 (3)
O6—C36	1.150 (3)	C3—H3	1.0000
O7—C37	1.149 (3)	C3—C4	1.436 (4)
O8—C38	1.145 (3)	O3—C9	1.145 (3)
C29—H29	1.0000	C4—H4	1.0000
C29—C30	1.442 (4)	C4—C5	1.482 (4)
C29—C35	1.538 (3)	O4—C10	1.144 (3)
C30—H30	1.0000	C5—C6	1.522 (4)
C30—C31	1.408 (4)	C6—H6A	0.9900
C31—H31	1.0000	C6—H6B	0.9900
C31—C32	1.435 (4)	C6—C7	1.544 (4)
C32—H32	1.0000	C7—H7	1.0000
C32—C33	1.475 (4)	C11—C12	1.404 (3)
C33—C34	1.524 (4)	C11—C16	1.402 (4)
C34—H34A	0.9900	C12—H12	0.9500
C34—H34B	0.9900	C12—C13	1.390 (4)
C34—C35	1.546 (4)	C13—H13	0.9500
C35—H35	1.0000	C13—C14	1.384 (4)
C39—C40	1.405 (4)	C14—H14	0.9500
C39—C44	1.401 (3)	C14—C15	1.397 (4)
C40—H40	0.9500	C15—H15	0.9500
C40—C41	1.388 (4)	C15—C16	1.393 (4)
C41—H41	0.9500	C16—H16	0.9500
C41—C42	1.399 (4)	C17—C18	1.411 (4)
C42—H42	0.9500	C17—C22	1.400 (4)
C42—C43	1.383 (4)	C18—H18	0.9500
C43—H43	0.9500	C18—C19	1.396 (4)
C43—C44	1.396 (4)	C19—H19	0.9500
C44—H44	0.9500	C19—C20	1.389 (4)
C45—C46	1.399 (4)	C20—H20	0.9500
C45—C50	1.413 (4)	C20—C21	1.388 (4)
C46—H46	0.9500	C21—H21	0.9500
C46—C47	1.399 (4)	C21—C22	1.388 (4)
C47—H47	0.9500	C22—H22	0.9500
C47—C48	1.393 (4)	C23—C24	1.402 (4)
C48—H48	0.9500	C23—C28	1.403 (4)
C48—C49	1.398 (4)	C24—H24	0.9500
C49—H49	0.9500	C24—C25	1.386 (4)
C49—C50	1.390 (4)	C25—H25	0.9500
C50—H50	0.9500	C25—C26	1.397 (4)
C51—C52	1.400 (4)	C26—H26	0.9500
C51—C56	1.405 (4)	C26—C27	1.384 (4)
C52—H52	0.9500	C27—H27	0.9500
C52—C53	1.401 (4)	C27—C28	1.400 (4)
C53—H53	0.9500	C28—H28	0.9500
C53—C54	1.384 (4)	B1—F1	1.394 (4)
C54—H54	0.9500	B1—F2	1.396 (4)
C54—C55	1.397 (4)	B1—F3	1.404 (3)
C55—H55	0.9500	B1—F4	1.406 (4)
C55—C56	1.397 (4)	B2—F5	1.392 (4)
C56—H56	0.9500	B2—F6	1.389 (4)
P1—C7	1.853 (3)	B2—F7	1.393 (4)
P1—C11	1.799 (3)	B2—F8	1.405 (4)
P1—C17	1.801 (3)	Cl1A—C57A	1.771 (3)
P1—C23	1.805 (3)	Cl2A—C57A	1.765 (3)
O1—C5	1.229 (3)	C57A—H57A	0.9900
Fe1—C1	2.106 (3)	C57A—H57B	0.9900

C39—P2—C35	107.22 (12)	C3—Fe1—C1	72.32 (11)
C39—P2—C45	109.80 (12)	C3—Fe1—C2	39.93 (11)
C39—P2—C51	108.45 (12)	C3—Fe1—C4	40.04 (10)
C45—P2—C35	109.27 (12)	C8—Fe1—C1	159.35 (11)
C45—P2—C51	109.02 (12)	C8—Fe1—C2	119.34 (12)
C51—P2—C35	113.05 (12)	C8—Fe1—C3	90.88 (12)
C29—Fe2—C32	85.14 (10)	C8—Fe1—C4	89.74 (11)
C30—Fe2—C29	40.48 (10)	C8—Fe1—C10	101.08 (12)
C30—Fe2—C32	72.09 (10)	C9—Fe1—C1	89.05 (11)
C31—Fe2—C29	72.52 (11)	C9—Fe1—C2	95.78 (12)
C31—Fe2—C30	39.75 (10)	C9—Fe1—C3	127.05 (12)
C31—Fe2—C32	39.90 (10)	C9—Fe1—C4	167.04 (12)
C36—Fe2—C29	98.70 (11)	C9—Fe1—C8	91.88 (12)
C36—Fe2—C30	136.74 (11)	C9—Fe1—C10	96.79 (12)
C36—Fe2—C31	134.13 (11)	C10—Fe1—C1	99.29 (11)
C36—Fe2—C32	95.62 (11)	C10—Fe1—C2	137.07 (11)
C37—Fe2—C29	160.40 (12)	C10—Fe1—C3	134.26 (11)
C37—Fe2—C30	120.23 (12)	C10—Fe1—C4	95.51 (11)
C37—Fe2—C31	92.41 (12)	Fe1—C1—H1	112.0
C37—Fe2—C32	91.19 (11)	C2—C1—Fe1	68.62 (15)
C37—Fe2—C36	100.82 (12)	C2—C1—H1	112.0
C38—Fe2—C29	88.42 (11)	C2—C1—C7	125.5 (2)
C38—Fe2—C30	95.26 (11)	C7—C1—Fe1	119.90 (17)
C38—Fe2—C31	126.49 (11)	C7—C1—H1	112.0
C38—Fe2—C32	166.34 (12)	Fe1—C2—H2	119.4
C38—Fe2—C36	97.26 (12)	C1—C2—Fe1	71.24 (15)
C38—Fe2—C37	90.87 (12)	C1—C2—H2	119.4
Fe2—C29—H29	111.9	C3—C2—Fe1	69.78 (15)
C30—C29—Fe2	69.04 (15)	C3—C2—C1	119.7 (2)
C30—C29—H29	111.9	C3—C2—H2	119.4
C30—C29—C35	125.5 (2)	Fe1—C3—H3	118.9
C35—C29—Fe2	119.85 (17)	C2—C3—Fe1	70.29 (15)
C35—C29—H29	111.9	C2—C3—H3	118.9
Fe2—C30—H30	119.5	C2—C3—C4	120.8 (2)
C29—C30—Fe2	70.48 (15)	C4—C3—Fe1	72.34 (16)
C29—C30—H30	119.5	C4—C3—H3	118.9
C31—C30—Fe2	69.88 (15)	Fe1—C4—H4	114.0
C31—C30—C29	119.4 (2)	C3—C4—Fe1	67.62 (15)
C31—C30—H30	119.5	C3—C4—H4	114.0
Fe2—C31—H31	118.8	C3—C4—C5	126.6 (2)
C30—C31—Fe2	70.37 (16)	C5—C4—Fe1	111.10 (18)
C30—C31—H31	118.8	C5—C4—H4	114.0
C30—C31—C32	121.2 (2)	O1—C5—C4	121.2 (3)
C32—C31—Fe2	72.50 (15)	O1—C5—C6	120.7 (3)
C32—C31—H31	118.8	C4—C5—C6	118.0 (2)
Fe2—C32—H32	114.1	C5—C6—H6A	109.4
C31—C32—Fe2	67.59 (15)	C5—C6—H6B	109.4
C31—C32—H32	114.1	C5—C6—C7	111.0 (2)
C31—C32—C33	125.5 (2)	H6A—C6—H6B	108.0
C33—C32—Fe2	112.39 (18)	C7—C6—H6A	109.4
C33—C32—H32	114.1	C7—C6—H6B	109.4
O5—C33—C32	121.1 (2)	P1—C7—H7	108.6
O5—C33—C34	119.6 (2)	C1—C7—P1	106.93 (17)
C32—C33—C34	119.1 (2)	C1—C7—C6	114.4 (2)
C33—C34—H34A	109.3	C1—C7—H7	108.6
C33—C34—H34B	109.3	C6—C7—P1	109.73 (18)
C33—C34—C35	111.5 (2)	C6—C7—H7	108.6
H34A—C34—H34B	108.0	O2—C8—Fe1	178.8 (3)
C35—C34—H34A	109.3	O3—C9—Fe1	178.6 (3)
C35—C34—H34B	109.3	O4—C10—Fe1	178.2 (3)
P2—C35—H35	108.9	C12—C11—P1	119.8 (2)
C29—C35—P2	107.10 (17)	C16—C11—P1	119.85 (19)
C29—C35—C34	113.7 (2)	C16—C11—C12	120.1 (2)
C29—C35—H35	108.9	C11—C12—H12	120.1
C34—C35—P2	109.12 (18)	C13—C12—C11	119.8 (2)
C34—C35—H35	108.9	C13—C12—H12	120.1
O6—C36—Fe2	177.8 (2)	C12—C13—H13	120.0
O7—C37—Fe2	178.2 (3)	C14—C13—C12	120.0 (2)
O8—C38—Fe2	179.3 (3)	C14—C13—H13	120.0
C40—C39—P2	120.3 (2)	C13—C14—H14	119.6
C44—C39—P2	119.8 (2)	C13—C14—C15	120.8 (3)
C44—C39—C40	119.7 (2)	C15—C14—H14	119.6
C39—C40—H40	120.2	C14—C15—H15	120.1
C41—C40—C39	119.7 (2)	C16—C15—C14	119.8 (3)
C41—C40—H40	120.2	C16—C15—H15	120.1
C40—C41—H41	119.9	C11—C16—H16	120.2
C40—C41—C42	120.3 (3)	C15—C16—C11	119.6 (2)
C42—C41—H41	119.9	C15—C16—H16	120.2
C41—C42—H42	119.9	C18—C17—P1	118.9 (2)
C43—C42—C41	120.3 (3)	C22—C17—P1	120.9 (2)
C43—C42—H42	119.9	C22—C17—C18	120.0 (2)
C42—C43—H43	120.0	C17—C18—H18	120.6
C42—C43—C44	120.0 (2)	C19—C18—C17	118.8 (3)
C44—C43—H43	120.0	C19—C18—H18	120.6
C39—C44—H44	120.0	C18—C19—H19	119.6
C43—C44—C39	120.1 (3)	C20—C19—C18	120.7 (3)
C43—C44—H44	120.0	C20—C19—H19	119.6
C46—C45—P2	122.0 (2)	C19—C20—H20	119.9
C46—C45—C50	119.8 (3)	C21—C20—C19	120.2 (3)
C50—C45—P2	118.2 (2)	C21—C20—H20	119.9
C45—C46—H46	119.9	C20—C21—H21	119.9
C47—C46—C45	120.3 (3)	C22—C21—C20	120.3 (3)
C47—C46—H46	119.9	C22—C21—H21	119.9
C46—C47—H47	120.1	C17—C22—H22	120.0
C48—C47—C46	119.8 (3)	C21—C22—C17	120.0 (3)
C48—C47—H47	120.1	C21—C22—H22	120.0
C47—C48—H48	120.0	C24—C23—P1	120.0 (2)
C47—C48—C49	119.9 (3)	C24—C23—C28	120.2 (3)
C49—C48—H48	120.0	C28—C23—P1	119.0 (2)
C48—C49—H49	119.6	C23—C24—H24	120.2
C50—C49—C48	120.9 (3)	C25—C24—C23	119.7 (3)
C50—C49—H49	119.6	C25—C24—H24	120.2
C45—C50—H50	120.4	C24—C25—H25	119.9
C49—C50—C45	119.2 (3)	C24—C25—C26	120.2 (3)
C49—C50—H50	120.4	C26—C25—H25	119.9
C52—C51—P2	121.0 (2)	C25—C26—H26	119.8
C52—C51—C56	120.5 (2)	C27—C26—C25	120.4 (3)
C56—C51—P2	118.3 (2)	C27—C26—H26	119.8
C51—C52—H52	120.3	C26—C27—H27	119.9
C51—C52—C53	119.3 (3)	C26—C27—C28	120.2 (3)
C53—C52—H52	120.3	C28—C27—H27	119.9
C52—C53—H53	119.9	C23—C28—H28	120.4
C54—C53—C52	120.2 (3)	C27—C28—C23	119.3 (3)
C54—C53—H53	119.9	C27—C28—H28	120.4
C53—C54—H54	119.7	F1—B1—F2	110.1 (3)
C53—C54—C55	120.6 (3)	F1—B1—F3	110.7 (2)
C55—C54—H54	119.7	F1—B1—F4	108.4 (3)
C54—C55—H55	120.0	F2—B1—F3	109.8 (2)
C56—C55—C54	120.1 (3)	F2—B1—F4	109.3 (2)
C56—C55—H55	120.0	F3—B1—F4	108.6 (2)
C51—C56—H56	120.4	F5—B2—F7	109.7 (3)
C55—C56—C51	119.3 (3)	F5—B2—F8	109.4 (3)
C55—C56—H56	120.4	F6—B2—F5	108.6 (3)
C11—P1—C7	107.74 (12)	F6—B2—F7	109.7 (3)
C11—P1—C17	110.56 (12)	F6—B2—F8	109.9 (3)
C11—P1—C23	109.76 (13)	F7—B2—F8	109.5 (3)
C17—P1—C7	108.54 (12)	Cl1A—C57A—H57A	109.2
C17—P1—C23	106.44 (12)	Cl1A—C57A—H57B	109.2
C23—P1—C7	113.81 (12)	Cl2A—C57A—Cl1A	112.05 (17)
C1—Fe1—C4	84.95 (10)	Cl2A—C57A—H57A	109.2
C2—Fe1—C1	40.14 (10)	Cl2A—C57A—H57B	109.2
C2—Fe1—C4	72.30 (11)	H57A—C57A—H57B	107.9

P2—C39—C40—C41	−176.5 (2)	P1—C11—C12—C13	−175.4 (2)
P2—C39—C44—C43	175.57 (19)	P1—C11—C16—C15	175.9 (2)
P2—C45—C46—C47	179.7 (2)	P1—C17—C18—C19	−175.46 (19)
P2—C45—C50—C49	178.8 (2)	P1—C17—C22—C21	176.0 (2)
P2—C51—C52—C53	176.9 (2)	P1—C23—C24—C25	171.4 (2)
P2—C51—C56—C55	−177.7 (2)	P1—C23—C28—C27	−170.3 (2)
Fe2—C29—C30—C31	51.8 (2)	O1—C5—C6—C7	−116.4 (3)
Fe2—C29—C35—P2	179.24 (13)	Fe1—C1—C2—C3	−52.1 (2)
Fe2—C29—C35—C34	−60.1 (3)	Fe1—C1—C7—P1	179.98 (13)
Fe2—C30—C31—C32	53.9 (2)	Fe1—C1—C7—C6	58.3 (3)
Fe2—C31—C32—C33	102.3 (3)	Fe1—C2—C3—C4	−53.9 (2)
Fe2—C32—C33—O5	−115.5 (2)	Fe1—C3—C4—C5	−100.3 (3)
Fe2—C32—C33—C34	69.6 (3)	Fe1—C4—C5—O1	109.3 (3)
O5—C33—C34—C35	121.2 (3)	Fe1—C4—C5—C6	−73.2 (3)
C29—C30—C31—Fe2	−52.0 (2)	C1—C2—C3—Fe1	52.8 (2)
C29—C30—C31—C32	1.9 (4)	C1—C2—C3—C4	−1.1 (4)
C30—C29—C35—P2	−96.3 (3)	C2—C1—C7—P1	96.1 (3)
C30—C29—C35—C34	24.3 (4)	C2—C1—C7—C6	−25.6 (4)
C30—C31—C32—Fe2	−53.0 (2)	C2—C3—C4—Fe1	53.0 (2)
C30—C31—C32—C33	49.3 (4)	C2—C3—C4—C5	−47.4 (4)
C31—C32—C33—O5	166.8 (3)	C3—C4—C5—O1	−173.5 (3)
C31—C32—C33—C34	−8.1 (4)	C3—C4—C5—C6	4.0 (4)
C32—C33—C34—C35	−63.8 (3)	C4—C5—C6—C7	66.0 (3)
C33—C34—C35—P2	173.40 (18)	C5—C6—C7—P1	−173.67 (18)
C33—C34—C35—C29	53.9 (3)	C5—C6—C7—C1	−53.5 (3)
C35—P2—C39—C40	85.3 (2)	C7—P1—C11—C12	89.3 (2)
C35—P2—C39—C44	−88.9 (2)	C7—P1—C11—C16	−85.0 (2)
C35—P2—C45—C46	−10.1 (3)	C7—P1—C17—C18	−167.5 (2)
C35—P2—C45—C50	171.1 (2)	C7—P1—C17—C22	17.9 (3)
C35—P2—C51—C52	33.2 (3)	C7—P1—C23—C24	149.2 (2)
C35—P2—C51—C56	−150.7 (2)	C7—P1—C23—C28	−40.5 (3)
C35—C29—C30—Fe2	−112.4 (2)	C7—C1—C2—Fe1	112.2 (2)
C35—C29—C30—C31	−60.7 (4)	C7—C1—C2—C3	60.1 (4)
C39—P2—C35—C29	57.4 (2)	C11—P1—C7—C1	−59.7 (2)
C39—P2—C35—C34	−66.1 (2)	C11—P1—C7—C6	64.9 (2)
C39—P2—C45—C46	−127.4 (2)	C11—P1—C17—C18	−49.5 (2)
C39—P2—C45—C50	53.8 (2)	C11—P1—C17—C22	135.9 (2)
C39—P2—C51—C52	151.9 (2)	C11—P1—C23—C24	28.4 (3)
C39—P2—C51—C56	−32.0 (3)	C11—P1—C23—C28	−161.3 (2)
C39—C40—C41—C42	1.0 (4)	C11—C12—C13—C14	−0.2 (4)
C40—C39—C44—C43	1.3 (4)	C12—C11—C16—C15	1.6 (4)
C40—C41—C42—C43	1.2 (4)	C12—C13—C14—C15	1.2 (4)
C41—C42—C43—C44	−2.1 (4)	C13—C14—C15—C16	−0.7 (4)
C42—C43—C44—C39	0.9 (4)	C14—C15—C16—C11	−0.7 (4)
C44—C39—C40—C41	−2.2 (4)	C16—C11—C12—C13	−1.2 (4)
C45—P2—C35—C29	−61.5 (2)	C17—P1—C7—C1	60.1 (2)
C45—P2—C35—C34	174.99 (17)	C17—P1—C7—C6	−175.37 (18)
C45—P2—C39—C40	−156.1 (2)	C17—P1—C11—C12	−29.1 (2)
C45—P2—C39—C44	29.7 (2)	C17—P1—C11—C16	156.6 (2)
C45—P2—C51—C52	−88.5 (2)	C17—P1—C23—C24	−91.3 (2)
C45—P2—C51—C56	87.5 (2)	C17—P1—C23—C28	79.0 (2)
C45—C46—C47—C48	2.3 (4)	C17—C18—C19—C20	−0.1 (4)
C46—C45—C50—C49	0.0 (4)	C18—C17—C22—C21	1.4 (4)
C46—C47—C48—C49	−1.5 (4)	C18—C19—C20—C21	0.4 (4)
C47—C48—C49—C50	−0.1 (4)	C19—C20—C21—C22	0.3 (4)
C48—C49—C50—C45	0.8 (4)	C20—C21—C22—C17	−1.2 (4)
C50—C45—C46—C47	−1.5 (4)	C22—C17—C18—C19	−0.8 (4)
C51—P2—C35—C29	176.90 (17)	C23—P1—C7—C1	178.39 (18)
C51—P2—C35—C34	53.4 (2)	C23—P1—C7—C6	−57.1 (2)
C51—P2—C39—C40	−37.1 (2)	C23—P1—C11—C12	−146.3 (2)
C51—P2—C39—C44	148.7 (2)	C23—P1—C11—C16	39.5 (2)
C51—P2—C45—C46	113.9 (2)	C23—P1—C17—C18	69.6 (2)
C51—P2—C45—C50	−64.9 (2)	C23—P1—C17—C22	−105.0 (2)
C51—C52—C53—C54	0.1 (4)	C23—C24—C25—C26	−1.3 (5)
C52—C51—C56—C55	−1.6 (4)	C24—C23—C28—C27	0.0 (4)
C52—C53—C54—C55	−0.5 (4)	C24—C25—C26—C27	0.1 (5)
C53—C54—C55—C56	−0.1 (5)	C25—C26—C27—C28	1.1 (4)
C54—C55—C56—C51	1.2 (5)	C26—C27—C28—C23	−1.1 (4)
C56—C51—C52—C53	1.0 (4)	C28—C23—C24—C25	1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32···F5	1.00	2.37	3.198 (3)	140
C43—H43···F6ⁱ	0.95	2.33	3.240 (3)	160
C44—H44···O8ⁱⁱ	0.95	2.56	3.467 (3)	159
C46—H46···F7ⁱⁱⁱ	0.95	2.40	3.151 (3)	136
C49—H49···O7^iv	0.95	2.60	3.339 (3)	135
C50—H50···F6^iv	0.95	2.53	3.471 (3)	169
C52—H52···O1	0.95	2.37	3.286 (3)	161
C53—H53···F4ⁱⁱⁱ	0.95	2.66	3.500 (3)	148
C56—H56···F6^iv	0.95	2.48	3.362 (3)	155
C2—H2···F3^v	1.00	2.50	3.493 (3)	170
C4—H4···F4ⁱⁱⁱ	1.00	2.42	3.393 (3)	165
C7—H7···O5	1.00	2.34	3.192 (3)	143
C13—H13···F1^v	0.95	2.41	3.232 (3)	144
C19—H19···O2^vi	0.95	2.51	3.393 (3)	154
C28—H28···O5	0.95	2.41	3.319 (4)	161
C57A—H57A···F4	0.99	2.47	3.276 (4)	139

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

Phenyl ring torsion angles (°) top

Cation 1		Cation 2
Torsion angle	Value	Torsion angle	Value
Ring 1
P1—C11—C16—C15	175.9 (2)	P2—C39—C40—C41	-176.5 (2)
C11—C16—C15—C14	-0.7 (4)	C39—C40—C41—C42	1.0 (4)
C16—C15—C14—C13	-0.7 (4)	C40—C41—C42—C43	1.2 (4)
C15—C14—C13—C12	1.2 (4)	C41—C42—C43—C44	-2.2 (4)
C14—C13—C12—C11	-0.2 (4)	C42—C43—C44—C39	0.9 (4)
C13—C12—C11—P1	-175.4 (2)	C43—C44—C39—P2	175.6 (2)

Ring 2
P1—C17—C18—C19	-175.5 (2)	P2—C45—C50—C49	178.8 (2)
C17—C18—C19—C20	-0.1 (4)	C45—C50—C49—C48	0.8 (4)
C18—C19—C20—C21	0.4 (4)	C50—C49—C48—C47	-0.1 (4)
C19—C20—C21—C22	-0.2 (5)	C49—C48—C47—C46	-1.5 (4)
C20—C21—C22—C17	-1.2 (4)	C48—C47—C46—C45	2.3 (4)
C21—C22—C17—P1	176.0 (2)	C47—C46—C45—P2	179.7 (2)

Ring 3
P1—C23—C28—C27	-170.3 (2)	P2—C51—C52—C53	176.9 (2)
C23—C28—C27—C26	-1.1 (4)	C51—C52—C53—C54	0.1 (4)
C28—C27—C26—C25	1.1 (4)	C52—C53—C54—C55	-0.5 (4)
C27—C26—C25—C24	0.1 (5)	C53—C54—C55—C56	-0.1 (5)
C26—C25—C24—C23	-1.3 (5)	C54—C55—C56—C51	1.2 (5)
C25—C24—C23—P1	171.4 (2)	C55—C56—C51—P2	-177.7 (2)

X—Y···π interactions (Å,°) top

Cg1–Cg5 are the centroids of the C11–C16, C17–C22, C39–C44 and C45–C50 rings, respectively.

X—Y···Cg	Y···Cg	X···Cg	X—H···Cg
C54—H54···Cg2ⁱ	2.99	3.929 (3)	171
B1—F1···Cg1ⁱⁱ	3.429 (2)	4.790 (3)	165.56 (17)
B2—F6···Cg3ⁱⁱⁱ	3.653 (2)	4.913 (3)	150.99 (17)
C9—O3···Cg2^iv	3.393 (2)	3.858 (3)	105.37 (19)
C38—08···Cg4^v	3.467 (2)	3.925 (3)	105.10 (18)

Symmetry codes: (i) -1 + x, 1 + y, z; (ii) x, 1 + y, z; (iii) 1 + x, -1 + y, z; (iv) 2 - x, 1 - y, 1 - z; (v) 1 - x, 1 - y, 2 - z.

Funding information

The authors gratefully acknowledge the McCutchen Foundation for partial support of the X-ray diffractometer.

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