Hydrogen bis­[tris­(4-fluoro­phenyl)­phosphane oxide] triiodide

In the title compound, C₃₆H₂₅F₆O₂P₂⁺·I₃⁻, hydrogen-bonded [{(p-FC₆H₄)₃PO}₂H]⁺ dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I—I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter-ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å⁻³. The inclusion of two low-occupancy I-atom sites (total 1.7%), which can be inter­preted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å⁻³. The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin.

S1. Comment

The title structure, (I), consists of triiodide anions and proton counterions that link pairs of tris(4-fluorophenyl)phosphane oxide molecules into hydrogen-bonded dimers (Fig. 1). The two crystallographically unique (p-FC₆H₄)₃PO molecules have similar conformations, as indicated by their O—P—C—C torsions angles of 3.9 (11), 78.0 (12) and -13.7 (13)° around O1—P1, and 80.2 (12), 10.1 (13) and -15.5 (12)° around O2—P2. This type of parallel, parallel, orthogonal conformation has been named `orthogonal flipper' by Dance & Scudder (2000) and is also the conformation adopted in an analogous unfluorinated structure with FeBr₄^- as the counterion (corresponding torsion angles 19.5, 27.3 and 83.2, and 19.5, 27.3 and 83.2°; Lane et al., 1994). However, when the counterion is ClO₄^-, a rotor-type conformation is adopted (corresponding torsion angles 29.9, 37.3 and 64.1, and 16.2, 30.0 and 42.7°; Antipin et al. 1980). In the structure of (I) the orthogonal rings are opposite each other in the hydrogen-bonded dimers and participate in face-to-face π interactions. In contrast, each orthogonal ring is opposite a parallel one in the unfluorinated dimer reported by Lane et al., (1994), facilitating edge-to-face π interactions.

In the structure of (I), the P—O bonds of 1.526 (10) and 1.530 (10) Å are significantly longer than typical double P═O bonds of e.g. 1.487 (3) Å in (C₆H₅)₃P═O (Thomas & Hamor, 1993) and 1.467 (2) Å in (C₆F₅)₃P═O (Nicholson & Thwaite, 2003). However, they are shorter than the single P—O bonds of 1.581 (4), 1.579 (4) and 1.553 (3) Å in triphenylphosphane oxyl derivatives (Kunnari et al., 2001; Carcedo et al. 2004; Chow et al. 1996), which average 1.571 Å. As the P—O bond lengths fall midway between single- and double-bond values, it is clear that the correct depiction of these bonds should be as intermediate single/double bonds. Because of this, and as the H atom was not found in the difference electron-density map, it has been fixed at the initial halfway position between the O atoms in this strong hydrogen bond, with its displacement parameter refined freely. Although this is reasonable it may not be strictly correct, as asymmetric positioning of the H atom is common in even the strongest hydrogen bonds. See, for example, Konu & Chivers (2006) and Antipin et al. (1980), who found that the O···H···O bond in [{(C₆H₅)₃P═O}₂H]⁺.ClO₄^- changes from symmetric at room temperature to asymmetric on cooling.

Packing of the hydrogen-bonded dimers of (I) forms tunnels parallel to the crystallographic c axis (Fig. 2). The tunnels house triiodide anions, which are also aligned along the crystallographic c axis. Within each tunnel, adjacent iodide anions are related by crystallographic c-glide operations. In stacked structures or structures with channels, triiodides often form infinite linear chains with weak I₃^-···I₃^- interactions, with typical I···I separations ≥ 3.6 Å (Svensson & Kloo, 2003). The I···I distance of 3.5774 (11) Å seen in (I) is a rare example of an interionic I₃^-···I₃^- separation of less than 3.6 Å. In contrast, the most significant contact between the triiodide anion and the surrounding tunnel atoms is 3.156 Å between phenyl atom H32 and central iodine I1, which is only marginally shorter than the van der Waals contact (3.35 Å; Harrison, 1978).

The two I—I bonds [2.9023 (15) and 2.9452 (14) Å] show significant asymmetry. This is not unusual and is caused by nonbonded interaction within the crystal structure. In the case of (I), the most significant sub-van der Waals contacts involving the terminal triiodide I atoms are I···I contacts, which are of equal length for symmetry reasons. However, atom I2 has five I···H contacts shorter than the sum of the van der Waals radii (3.283–3.347 Å), compared with only two for I3 (3.222 and 3.291 Å).

Related literature

For related literature, see: Antipin et al. (1980); Carcedo et al. (2004); Chow et al. (1996); Dance & Scudder (2000); Harrison (1978); Konu & Chivers (2006); Kunnari et al. (2001); Lane et al. (1994); Nicholson & Thwaite (2003); Spek (2009); Svensson & Kloo (2003); Thomas & Hamor (1993).

S2. Experimental

The title compound was synthesized from (p-FC₆H₄)₃P (0.418 g, 1.32 mmol) dissolved in anhydrous diethyl ether (30 ml). To this was added iodine (two equivalents, 0.671 g, 2.64 mmol), which caused rapid precipitation of a brown solid. The reaction was stirred for 48 h, after which time the solid was isolated by standard Schlenk techniques. Crystals were prepared by dissolving the brown solid in dichloromethane (5 ml) in a Rotaflo tube. Hexane (15 ml) was layered on top of the solution and the layers were allowed to diffuse slowly over 48 h, after which time purple–brown [Yellow given in CIF - please clarify] crystals of (I) had formed.

S3. Refinement

C-bound H atoms were idealized with C—H bond lengths of 0.95 Å and with the H atom on the external bisector of the C—C—C angle, with U_iso(H) = 1.2U_eq(C). Initial refinement with anisotropic displacement parameters for all non-H atoms converged to R₁ = 0.0659, with a maximum Δρ_max of 5.79 e Å^-3.

A posteriori screening for twinning by looking for F_o² >> F_c² was carried out using PLATON (Spek, 2009). A nonmerohedral twin with twin matrix (1 0 0.459, 0 -1 0, 0 0 -1) was identified and used to construct expanded reflection files, in which overlapping reflections were assigned indices for each contributing twin domain. The inclusion of racemic twins gave a total of four domains: (i) the initial domain, (1 0 0, 0 1 0, 0 0 1); (ii) the inverse of (i), (-1 0 0, 0 -1 0, 0 0 -1); (iii) a nonmerohedral twin, (1 0 0.459, 0 -1 0, 0 0 -1); and (iv) the inverse of (iii), (-1 0 -0.459, 0 1 0, 0 0 1).

Three expanded reflection files were generated using three different 2θ resolution tolerance criteria for establishing nonmerohedral reflection overlap, namely 0.05, 0.10 and 0.15°, which gave 465, 863 and 1210 overlapping reflections, respectively. Refinements carried out using these reflection files, in which the fractional contribution volumes of the above domains were allowed to vary, were compared on the basis of R factors, bond-length s.u. values, mean (F_o²)/mean (F_c²) distribution versus F_c/F_c(max) and Δρ_max, and, in each case, the 0.05° data were found to be the best, e.g. Δρ_max values for the 0.05, 0.10 and 0.15° 2θ tolerance data were 3.24, 4.02 and 5.28 e Å^-3, respectively. All further structure refinement was therefore carried out using the 0.05° data. The fractional contribution volumes refined to 0.37 (3), 0.38 (3), 0.124 (6) and 0.123 (6) for domains (i), (ii), (iii) and (iv), respectively. The last two numbers were restrained to be equal because of the high correlation between the two parameters (-0.99).

Ideally, twinning should be dealt with at the data-processing stage, but this was not possible with the version of diffractometer software being used in the current case. Given the rudimentary method used to assign non-merohedral reflection overlap, i.e. a global 2θ tolerance parameter, which assumes average reflection width, shape and twin obliquity, it is reasonable to anticipate that further improvements could be achieved if the software examined each reflection on a more individual basis, allowing for crystal anisotropy and the way the area detector intersects the Ewald sphere. Also, the small changes that are automatically made to the orientation matrix to compensate for slight crystal movement during the data collection could also be taken into account, rather than assuming a fixed orientation matrix.

In fact, the nonmerohedral twin correction was only partially successful and left rows of residual electron-density peaks spanning the cell in the z direction near the triiodide ions, with an inter-peak separation of approximately half an I—I bond, which also approximates to c/12. The two highest remaining peaks in the residual electron-density map were suitably positioned to be modelled as a translational disorder of the triiodide anions along the channels. They were therefore treated as disordered minor I-atom sites, I2B and I3B, whose occupancies refined to 0.021 (4) and 0.030 (4), respectively, reducing Δρ_max to 2.03 e Å^-3. The minor site displacement parameters were subjected to `rigid body' restraints, in which the anisotropic displacement parameters in the direction of their I—I bonds, I2—I3B and I3—I2B, were restrained to be equal. Also, the U^ij values for the minor I-atom sites were restrained to be equal to those of the major I-atom sites they are bonded to, as the I atoms in the minor sites are generated from those in the major sites by translation of the triiodide along the channels parallel to c.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: DIRDIF08 (Beurskens et al., 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the [{(p-FC6H4)3PO}2H]^+ dimer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the ?0% probability level [Please complete].
	Fig. 2. A packing diagram for (I), viewed down the c axis, showing the channels that house the triiodide anions.
	Fig. 3. A layer of molecules of (I) in the vicinity of the bc plane, showing local noncrystallographic twofold and mirror symmetries, which act as a twinning plane.

µ-hydrogen-bis[tris(4-fluorophenyl)phosphane oxide] triiodide

Crystal data

C36H25F6O2P2^+·I3^−	F(000) = 2000
Mr = 1046	Dx = 1.872 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3916 reflections
a = 13.2153 (4) Å	θ = 2–27°
b = 15.9752 (6) Å	µ = 2.68 mm^−1
c = 18.5695 (6) Å	T = 100 K
β = 108.818 (2)°	Plate, purple–brown
V = 3710.8 (2) Å^3	0.18 × 0.15 × 0.06 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	5376 independent reflections
Radiation source: Enraf–Nonius FR590	4363 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
Detector resolution: 9 pixels mm^-1	θmax = 25.5°, θmin = 3.3°
CCD rotation images, thick slices scans	h = −15→15
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −19→19
Tmin = 0.645, Tmax = 0.856	l = −22→22
14255 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)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0392P)^2 + 81.0459P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
5376 reflections	Δρmax = 2.03 e Å^−3
466 parameters	Δρmin = −1.60 e Å^−3
17 restraints	Absolute structure: Flack (1983), with 1024 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.50 (3)

Special details

Experimental. Absorption correction: multi-scan from symmetry-related measurements (SORTAV; Blessing, 1995)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
C1	0.3142 (11)	0.7551 (8)	0.8804 (7)	0.030 (3)
C2	0.3588 (10)	0.8204 (9)	0.9302 (7)	0.025 (3)
H2	0.4209	0.8489	0.9282	0.031*
C3	0.3084 (11)	0.8424 (8)	0.9836 (7)	0.032 (3)
H3	0.3361	0.8864	1.0189	0.039*
C4	0.2187 (13)	0.7995 (9)	0.9838 (8)	0.027 (3)
C5	0.1753 (10)	0.7338 (8)	0.9348 (7)	0.027 (3)
H5	0.1137	0.7047	0.937	0.032*
C6	0.2252 (11)	0.7126 (9)	0.8827 (8)	0.031 (3)
H6	0.1978	0.668	0.848	0.038*
C7	0.4100 (10)	0.6170 (8)	0.8284 (8)	0.028 (3)
C8	0.4407 (11)	0.5863 (8)	0.9016 (7)	0.032 (3)
H8	0.4397	0.6225	0.942	0.039*
C9	0.4732 (11)	0.5034 (9)	0.9179 (7)	0.034 (3)
H9	0.4959	0.4825	0.9686	0.041*
C10	0.4707 (11)	0.4537 (9)	0.8576 (8)	0.034 (3)
C11	0.4369 (11)	0.4790 (8)	0.7835 (7)	0.031 (3)
H11	0.4333	0.4407	0.7436	0.037*
C12	0.4079 (10)	0.5624 (8)	0.7679 (7)	0.031 (3)
H12	0.3869	0.5825	0.7171	0.037*
C13	0.3018 (10)	0.7437 (9)	0.7165 (7)	0.028 (3)
C14	0.3257 (11)	0.8104 (8)	0.6791 (7)	0.032 (3)
H14	0.3836	0.8462	0.7046	0.039*
C15	0.2660 (12)	0.8264 (10)	0.6039 (8)	0.039 (3)
H15	0.2829	0.8723	0.5774	0.046*
C16	0.1829 (12)	0.7751 (10)	0.5689 (7)	0.036 (3)
C17	0.1550 (11)	0.7058 (10)	0.6046 (8)	0.040 (4)
H17	0.0975	0.67	0.5784	0.048*
C18	0.2146 (11)	0.6920 (9)	0.6796 (7)	0.032 (3)
H18	0.1964	0.647	0.7065	0.038*
C19	0.7064 (11)	0.6438 (9)	0.7811 (7)	0.033 (3)
C20	0.6955 (10)	0.5990 (8)	0.7131 (8)	0.029 (3)
H20	0.6979	0.6289	0.6695	0.035*
C21	0.6815 (10)	0.5141 (9)	0.7085 (7)	0.029 (3)
H21	0.6698	0.4856	0.6616	0.035*
C22	0.6848 (11)	0.4710 (8)	0.7731 (8)	0.034 (3)
C23	0.6986 (10)	0.5093 (8)	0.8425 (7)	0.026 (3)
H23	0.7016	0.4775	0.8863	0.032*
C24	0.7078 (10)	0.5954 (8)	0.8456 (7)	0.030 (3)
H24	0.7153	0.6232	0.8923	0.036*
C25	0.7782 (11)	0.7850 (9)	0.7181 (8)	0.027 (3)
C26	0.7317 (11)	0.8453 (8)	0.6630 (6)	0.029 (3)
H26	0.664	0.8686	0.659	0.035*
C27	0.7857 (12)	0.8707 (9)	0.6141 (7)	0.034 (3)
H27	0.7563	0.9121	0.5765	0.041*
C28	0.8820 (12)	0.8348 (10)	0.6211 (8)	0.038 (3)
C29	0.9322 (11)	0.7784 (8)	0.6766 (7)	0.028 (3)
H29	1.0021	0.7586	0.6819	0.034*
C30	0.8775 (11)	0.7511 (9)	0.7247 (8)	0.034 (3)
H30	0.9078	0.7095	0.7619	0.041*
C31	0.7746 (10)	0.7894 (8)	0.8764 (7)	0.026 (3)
C32	0.7293 (11)	0.8604 (9)	0.9013 (8)	0.034 (3)
H32	0.667	0.8862	0.8679	0.041*
C33	0.7752 (12)	0.8914 (10)	0.9732 (8)	0.038 (3)
H33	0.7455	0.9384	0.9905	0.046*
C34	0.8651 (11)	0.8527 (9)	1.0196 (8)	0.038 (3)
C35	0.9097 (11)	0.7790 (9)	0.9989 (8)	0.037 (3)
H35	0.969	0.7512	1.0336	0.045*
C36	0.8633 (10)	0.7510 (9)	0.9276 (7)	0.031 (3)
H36	0.8924	0.703	0.9115	0.038*
F1	0.1701 (6)	0.8209 (5)	1.0367 (5)	0.0405 (19)
F2	0.5024 (7)	0.3720 (5)	0.8725 (4)	0.044 (2)
F3	0.1250 (7)	0.7886 (6)	0.4947 (5)	0.053 (2)
F4	0.6695 (7)	0.3867 (5)	0.7683 (5)	0.045 (2)
F5	0.9367 (7)	0.8619 (6)	0.5733 (5)	0.047 (2)
F6	0.9122 (8)	0.8825 (6)	1.0919 (5)	0.059 (3)
O1	0.4837 (7)	0.7793 (5)	0.8323 (5)	0.029 (2)
O2	0.5949 (7)	0.7899 (6)	0.7509 (5)	0.032 (2)
P1	0.3826 (3)	0.7261 (2)	0.81384 (19)	0.0272 (7)
P2	0.7075 (3)	0.7527 (2)	0.7815 (2)	0.0288 (8)
I1	−0.00204 (10)	0.53170 (5)	0.84472 (7)	0.02541 (19)
I2	0.00364 (5)	0.53424 (6)	1.00457 (4)	0.0319 (3)	0.979 (4)
I3	−0.00631 (6)	0.52672 (7)	0.68753 (4)	0.0317 (3)	0.970 (4)
I2B	−0.013 (5)	0.531 (3)	0.527 (3)	0.028 (2)	0.021 (4)
I3B	0.009 (4)	0.522 (3)	1.167 (3)	0.028 (2)	0.030 (4)
H12P	0.5381	0.7843	0.7915	0.10 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.033 (7)	0.022 (7)	0.022 (6)	−0.003 (6)	−0.008 (6)	0.003 (5)
C2	0.025 (7)	0.035 (8)	0.017 (6)	−0.003 (6)	0.009 (5)	−0.004 (6)
C3	0.042 (8)	0.023 (7)	0.026 (7)	−0.008 (6)	0.004 (6)	0.002 (5)
C4	0.041 (9)	0.021 (7)	0.017 (6)	0.003 (7)	0.006 (6)	0.005 (6)
C5	0.018 (6)	0.024 (7)	0.037 (7)	−0.004 (5)	0.009 (6)	0.002 (6)
C6	0.029 (7)	0.027 (7)	0.040 (7)	0.001 (6)	0.015 (6)	−0.011 (6)
C7	0.025 (7)	0.026 (7)	0.036 (7)	0.000 (6)	0.014 (6)	0.001 (6)
C8	0.046 (8)	0.022 (7)	0.033 (7)	0.000 (6)	0.019 (6)	−0.001 (6)
C9	0.035 (8)	0.042 (8)	0.028 (6)	0.000 (6)	0.013 (6)	0.007 (7)
C10	0.029 (8)	0.036 (8)	0.038 (8)	0.000 (6)	0.013 (6)	0.012 (6)
C11	0.041 (8)	0.028 (7)	0.028 (6)	0.006 (6)	0.017 (6)	−0.009 (6)
C12	0.032 (7)	0.030 (7)	0.027 (6)	0.005 (6)	0.006 (5)	−0.002 (6)
C13	0.025 (7)	0.039 (8)	0.015 (5)	−0.011 (6)	0.000 (5)	0.000 (6)
C14	0.038 (8)	0.026 (7)	0.031 (7)	0.002 (6)	0.009 (6)	−0.003 (6)
C15	0.040 (8)	0.040 (8)	0.049 (9)	0.008 (7)	0.031 (7)	0.011 (7)
C16	0.042 (9)	0.045 (9)	0.020 (6)	0.009 (7)	0.008 (6)	0.002 (6)
C17	0.031 (8)	0.051 (10)	0.032 (7)	−0.002 (7)	0.002 (6)	−0.014 (7)
C18	0.042 (8)	0.029 (8)	0.028 (6)	−0.007 (6)	0.016 (6)	−0.007 (6)
C19	0.034 (7)	0.043 (8)	0.026 (6)	0.005 (7)	0.016 (6)	0.000 (6)
C20	0.030 (7)	0.019 (7)	0.044 (8)	0.001 (6)	0.017 (6)	0.010 (6)
C21	0.030 (7)	0.037 (8)	0.030 (6)	−0.002 (6)	0.021 (6)	0.001 (6)
C22	0.030 (7)	0.034 (8)	0.042 (8)	−0.009 (6)	0.018 (6)	0.001 (7)
C23	0.027 (7)	0.033 (7)	0.021 (6)	−0.004 (6)	0.010 (5)	0.007 (6)
C24	0.031 (7)	0.029 (8)	0.028 (6)	−0.005 (6)	0.006 (5)	0.004 (6)
C25	0.016 (6)	0.041 (8)	0.027 (7)	−0.003 (6)	0.011 (6)	−0.005 (6)
C26	0.032 (7)	0.030 (7)	0.019 (6)	0.001 (6)	−0.001 (5)	0.002 (5)
C27	0.045 (9)	0.029 (8)	0.024 (6)	0.001 (7)	0.004 (6)	0.010 (6)
C28	0.040 (8)	0.045 (9)	0.029 (7)	−0.008 (7)	0.011 (6)	−0.007 (7)
C29	0.030 (7)	0.033 (7)	0.024 (6)	−0.002 (6)	0.012 (5)	−0.004 (6)
C30	0.038 (8)	0.025 (7)	0.047 (8)	0.000 (6)	0.024 (7)	0.008 (6)
C31	0.022 (7)	0.024 (7)	0.036 (7)	0.006 (5)	0.015 (6)	0.005 (6)
C32	0.027 (7)	0.029 (8)	0.049 (8)	0.000 (6)	0.017 (7)	0.002 (7)
C33	0.046 (9)	0.039 (9)	0.033 (7)	0.000 (7)	0.018 (7)	0.003 (7)
C34	0.036 (8)	0.044 (9)	0.042 (8)	−0.015 (7)	0.026 (7)	−0.017 (7)
C35	0.030 (8)	0.037 (8)	0.043 (8)	0.004 (6)	0.009 (6)	0.004 (7)
C36	0.029 (7)	0.037 (8)	0.028 (6)	0.005 (6)	0.009 (6)	−0.005 (6)
F1	0.038 (5)	0.048 (5)	0.042 (4)	0.005 (4)	0.021 (4)	−0.003 (4)
F2	0.052 (5)	0.022 (4)	0.055 (5)	0.001 (4)	0.015 (5)	0.012 (3)
F3	0.048 (5)	0.068 (6)	0.038 (4)	0.015 (5)	0.007 (4)	0.010 (5)
F4	0.054 (5)	0.027 (5)	0.059 (5)	−0.001 (4)	0.026 (4)	0.000 (4)
F5	0.054 (5)	0.055 (6)	0.039 (5)	−0.006 (4)	0.025 (4)	0.002 (4)
F6	0.070 (6)	0.068 (6)	0.042 (5)	−0.027 (5)	0.019 (5)	−0.027 (5)
O1	0.027 (5)	0.029 (5)	0.035 (6)	−0.003 (4)	0.014 (5)	0.001 (4)
O2	0.035 (5)	0.034 (5)	0.029 (5)	0.004 (4)	0.014 (4)	−0.002 (4)
P1	0.0282 (17)	0.0293 (18)	0.0248 (15)	−0.0032 (15)	0.0093 (13)	−0.0032 (14)
P2	0.0305 (19)	0.0276 (18)	0.0290 (17)	0.0033 (16)	0.0108 (15)	0.0030 (16)
I1	0.0263 (3)	0.0264 (4)	0.0240 (3)	−0.0005 (4)	0.0087 (3)	0.0009 (4)
I2	0.0395 (6)	0.0333 (6)	0.0216 (5)	−0.0057 (4)	0.0079 (5)	−0.0004 (4)
I3	0.0426 (7)	0.0296 (7)	0.0273 (5)	−0.0021 (5)	0.0174 (5)	−0.0020 (5)
I2B	0.038 (4)	0.023 (4)	0.028 (2)	0.000 (4)	0.019 (4)	−0.003 (4)
I3B	0.034 (4)	0.028 (4)	0.021 (2)	0.000 (4)	0.008 (3)	−0.010 (4)

Geometric parameters (Å, º)

C1—C6	1.370 (19)	C21—C22	1.371 (18)
C1—C2	1.392 (18)	C21—H21	0.95
C1—P1	1.811 (15)	C22—F4	1.360 (15)
C2—C3	1.405 (18)	C22—C23	1.384 (18)
C2—H2	0.95	C23—C24	1.380 (18)
C3—C4	1.37 (2)	C23—H23	0.95
C3—H3	0.95	C24—H24	0.95
C4—F1	1.379 (16)	C25—C30	1.388 (19)
C4—C5	1.387 (19)	C25—C26	1.396 (19)
C5—C6	1.378 (18)	C25—P2	1.799 (14)
C5—H5	0.95	C26—C27	1.383 (19)
C6—H6	0.95	C26—H26	0.95
C7—C8	1.378 (18)	C27—C28	1.36 (2)
C7—C12	1.416 (18)	C27—H27	0.95
C7—P1	1.783 (13)	C28—C29	1.368 (19)
C8—C9	1.395 (19)	C28—F5	1.382 (16)
C8—H8	0.95	C29—C30	1.389 (18)
C9—C10	1.37 (2)	C29—H29	0.95
C9—H9	0.95	C30—H30	0.95
C10—C11	1.364 (18)	C31—C36	1.391 (18)
C10—F2	1.370 (15)	C31—C32	1.427 (18)
C11—C12	1.390 (19)	C31—P2	1.797 (14)
C11—H11	0.95	C32—C33	1.37 (2)
C12—H12	0.95	C32—H32	0.95
C13—C14	1.366 (18)	C33—C34	1.37 (2)
C13—C18	1.403 (18)	C33—H33	0.95
C13—P1	1.799 (12)	C34—F6	1.371 (16)
C14—C15	1.388 (19)	C34—C35	1.42 (2)
C14—H14	0.95	C35—C36	1.343 (19)
C15—C16	1.36 (2)	C35—H35	0.95
C15—H15	0.95	C36—H36	0.95
C16—F3	1.361 (15)	O1—P1	1.526 (10)
C16—C17	1.40 (2)	O1—H12P	1.203
C17—C18	1.378 (18)	O2—P2	1.530 (10)
C17—H17	0.95	O2—H12P	1.228
C18—H18	0.95	I1—I3	2.9023 (15)
C19—C20	1.416 (18)	I1—I2	2.9452 (14)
C19—C24	1.420 (18)	I2—I3B	2.99 (5)
C19—P2	1.740 (15)	I2—I3^i	3.5774 (11)
C20—C21	1.368 (18)	I3—I2B	2.95 (6)
C20—H20	0.95	I3—I2^ii	3.5774 (11)
C6—C1—C2	122.3 (14)	F4—C22—C21	118.5 (13)
C6—C1—P1	121.1 (10)	F4—C22—C23	118.1 (12)
C2—C1—P1	116.6 (11)	C21—C22—C23	123.3 (13)
C1—C2—C3	117.5 (13)	C24—C23—C22	117.6 (11)
C1—C2—H2	121.3	C24—C23—H23	121.2
C3—C2—H2	121.3	C22—C23—H23	121.2
C4—C3—C2	118.9 (13)	C23—C24—C19	122.0 (12)
C4—C3—H3	120.5	C23—C24—H24	119
C2—C3—H3	120.5	C19—C24—H24	119
C3—C4—F1	118.7 (12)	C30—C25—C26	120.9 (13)
C3—C4—C5	123.4 (13)	C30—C25—P2	120.4 (11)
F1—C4—C5	117.8 (13)	C26—C25—P2	118.7 (10)
C6—C5—C4	117.2 (12)	C27—C26—C25	119.0 (13)
C6—C5—H5	121.4	C27—C26—H26	120.5
C4—C5—H5	121.4	C25—C26—H26	120.5
C1—C6—C5	120.6 (13)	C28—C27—C26	118.5 (13)
C1—C6—H6	119.7	C28—C27—H27	120.7
C5—C6—H6	119.7	C26—C27—H27	120.7
C8—C7—C12	119.2 (12)	C27—C28—C29	124.1 (13)
C8—C7—P1	118.6 (10)	C27—C28—F5	118.2 (13)
C12—C7—P1	122.1 (10)	C29—C28—F5	117.5 (12)
C7—C8—C9	121.6 (12)	C28—C29—C30	117.6 (13)
C7—C8—H8	119.2	C28—C29—H29	121.2
C9—C8—H8	119.2	C30—C29—H29	121.2
C10—C9—C8	116.7 (12)	C25—C30—C29	119.6 (13)
C10—C9—H9	121.6	C25—C30—H30	120.2
C8—C9—H9	121.6	C29—C30—H30	120.2
C11—C10—C9	124.7 (13)	C36—C31—C32	118.6 (12)
C11—C10—F2	117.8 (12)	C36—C31—P2	124.5 (10)
C9—C10—F2	117.6 (12)	C32—C31—P2	116.8 (9)
C10—C11—C12	118.2 (12)	C33—C32—C31	120.2 (13)
C10—C11—H11	120.9	C33—C32—H32	119.9
C12—C11—H11	120.9	C31—C32—H32	119.9
C11—C12—C7	119.5 (12)	C32—C33—C34	118.1 (14)
C11—C12—H12	120.3	C32—C33—H33	120.9
C7—C12—H12	120.3	C34—C33—H33	120.9
C14—C13—C18	119.9 (12)	C33—C34—F6	119.1 (13)
C14—C13—P1	118.3 (10)	C33—C34—C35	123.7 (13)
C18—C13—P1	121.8 (10)	F6—C34—C35	117.1 (13)
C13—C14—C15	120.4 (13)	C36—C35—C34	116.4 (13)
C13—C14—H14	119.8	C36—C35—H35	121.8
C15—C14—H14	119.8	C34—C35—H35	121.8
C16—C15—C14	118.7 (14)	C35—C36—C31	122.9 (13)
C16—C15—H15	120.6	C35—C36—H36	118.6
C14—C15—H15	120.6	C31—C36—H36	118.6
C15—C16—F3	119.5 (14)	P1—O1—H12P	123.6
C15—C16—C17	123.2 (13)	P2—O2—H12P	117.2
F3—C16—C17	117.2 (13)	O1—P1—C7	112.9 (6)
C18—C17—C16	116.9 (13)	O1—P1—C13	109.4 (6)
C18—C17—H17	121.5	C7—P1—C13	109.3 (6)
C16—C17—H17	121.5	O1—P1—C1	107.4 (6)
C17—C18—C13	120.8 (13)	C7—P1—C1	105.5 (6)
C17—C18—H18	119.6	C13—P1—C1	112.4 (6)
C13—C18—H18	119.6	O2—P2—C19	112.4 (6)
C20—C19—C24	116.5 (12)	O2—P2—C31	110.5 (5)
C20—C19—P2	120.5 (10)	C19—P2—C31	109.4 (6)
C24—C19—P2	122.8 (10)	O2—P2—C25	107.0 (6)
C21—C20—C19	122.0 (12)	C19—P2—C25	106.8 (7)
C21—C20—H20	119	C31—P2—C25	110.6 (6)
C19—C20—H20	119	I3—I1—I2	179.15 (5)
C20—C21—C22	118.5 (13)	I1—I3—I2B	177.0 (8)
C20—C21—H21	120.7	I1—I2—I3B	175.5 (8)
C22—C21—H21	120.7
C6—C1—C2—C3	−1 (2)	P2—C25—C30—C29	−178.3 (10)
P1—C1—C2—C3	−178.4 (10)	C28—C29—C30—C25	−4 (2)
C1—C2—C3—C4	−0.3 (19)	C36—C31—C32—C33	2 (2)
C2—C3—C4—F1	179.4 (12)	P2—C31—C32—C33	179.3 (11)
C2—C3—C4—C5	1 (2)	C31—C32—C33—C34	0 (2)
C3—C4—C5—C6	−1 (2)	C32—C33—C34—F6	−179.8 (13)
F1—C4—C5—C6	−179.4 (12)	C32—C33—C34—C35	−4 (2)
C2—C1—C6—C5	1 (2)	C33—C34—C35—C36	5 (2)
P1—C1—C6—C5	178.4 (10)	F6—C34—C35—C36	−179.4 (12)
C4—C5—C6—C1	0 (2)	C34—C35—C36—C31	−2 (2)
C12—C7—C8—C9	2 (2)	C32—C31—C36—C35	−2 (2)
P1—C7—C8—C9	−173.8 (11)	P2—C31—C36—C35	−178.2 (11)
C7—C8—C9—C10	−1 (2)	C8—C7—P1—O1	78.0 (12)
C8—C9—C10—C11	−1 (2)	C12—C7—P1—O1	−97.7 (12)
C8—C9—C10—F2	180.0 (12)	C8—C7—P1—C13	−160.0 (11)
C9—C10—C11—C12	4 (2)	C12—C7—P1—C13	24.2 (13)
F2—C10—C11—C12	−177.9 (12)	C8—C7—P1—C1	−39.0 (12)
C10—C11—C12—C7	−3 (2)	C12—C7—P1—C1	145.3 (11)
C8—C7—C12—C11	0 (2)	C14—C13—P1—O1	−13.7 (13)
P1—C7—C12—C11	175.7 (10)	C18—C13—P1—O1	167.8 (11)
C18—C13—C14—C15	−2 (2)	C14—C13—P1—C7	−137.8 (11)
P1—C13—C14—C15	179.8 (11)	C18—C13—P1—C7	43.7 (14)
C13—C14—C15—C16	1 (2)	C14—C13—P1—C1	105.4 (12)
C14—C15—C16—F3	−178.5 (12)	C18—C13—P1—C1	−73.1 (13)
C14—C15—C16—C17	−1 (2)	C6—C1—P1—O1	−173.9 (10)
C15—C16—C17—C18	2 (2)	C2—C1—P1—O1	3.9 (11)
F3—C16—C17—C18	179.4 (12)	C6—C1—P1—C7	−53.2 (12)
C16—C17—C18—C13	−3 (2)	C2—C1—P1—C7	124.6 (10)
C14—C13—C18—C17	3 (2)	C6—C1—P1—C13	65.8 (13)
P1—C13—C18—C17	−178.9 (11)	C2—C1—P1—C13	−116.4 (10)
C24—C19—C20—C21	3.2 (19)	C20—C19—P2—O2	80.2 (12)
P2—C19—C20—C21	−172.0 (11)	C24—C19—P2—O2	−94.8 (12)
C19—C20—C21—C22	−4 (2)	C20—C19—P2—C31	−156.7 (10)
C20—C21—C22—F4	179.1 (12)	C24—C19—P2—C31	28.4 (13)
C20—C21—C22—C23	2 (2)	C20—C19—P2—C25	−37.0 (13)
F4—C22—C23—C24	−176.3 (11)	C24—C19—P2—C25	148.1 (11)
C21—C22—C23—C24	1 (2)	C36—C31—P2—O2	161.1 (11)
C22—C23—C24—C19	−1.7 (19)	C32—C31—P2—O2	−15.5 (12)
C20—C19—C24—C23	−0.2 (19)	C36—C31—P2—C19	36.9 (13)
P2—C19—C24—C23	174.9 (10)	C32—C31—P2—C19	−139.8 (10)
C30—C25—C26—C27	1 (2)	C36—C31—P2—C25	−80.5 (13)
P2—C25—C26—C27	179.8 (10)	C32—C31—P2—C25	102.9 (11)
C25—C26—C27—C28	1 (2)	C30—C25—P2—O2	−170.6 (11)
C26—C27—C28—C29	−4 (2)	C26—C25—P2—O2	10.1 (13)
C26—C27—C28—F5	−178.5 (11)	C30—C25—P2—C19	−50.0 (13)
C27—C28—C29—C30	5 (2)	C26—C25—P2—C19	130.7 (11)
F5—C28—C29—C30	180.0 (12)	C30—C25—P2—C31	68.9 (13)
C26—C25—C30—C29	1 (2)	C26—C25—P2—C31	−110.4 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H12P···O2	1.203	1.228	2.431 (13)	179.0