(2S)-2-[1-(2,4-Di­fluoro-5-iodo­phenyl)-2-deoxy-[beta]-D-ribo­furanos-5-yloxy]-8-methyl-4H-1,3,2-benzodioxa­phosphole 2-oxide

The title compound, C₁₉H₁₈F₂IO₆P, prepared as a potential antiviral and anticancer agent from 3-methyl­salicyl­chloro­phosphane and 1-(2,4-di­fluoro-5-iodo­phenyl)-2-deoxy-[beta]-D-ribo­furan­ose, is one of a 1:1 mixture of two diastereomers. The diastereomers differ in their configuration, S or R, at the asymmetric phosphorus center. X-Ray crystallographic analysis of the title compound has determined the absolute configuration at the asymmetric P center to be S.

S1. Comment

A group of synthetic 3-substituted (H, Me, OMe) cyclosaligenyl derivatives of 1-(2-deoxy-β-D-ribofuranosyl)-2,4-difluoro-5-iodo- (or -trifluoromethyl-) benzene, previously evaluated as antiviral and anticancer agents (Wang et al., 2001), have been synthesized. These cyclosaligenyl derivatives were designed to act as thymidine kinase-bypass pronucleotides that would give rise to the intracellular release of the monophosphate derivative of 1-(2-deoxy-β-D-ribofuranosyl)-2,4-difluoro-5-iodo- (or trifluoromethyl-) benzene (Meier De Clercq & Balzarini, 1998; Meier et al., 1999). The configuration of the phosphorus center in cyclosaligenyl phosphate has so far been assigned only by comparison with the known stereochemistry of the model compound using CD Please define spectroscopy (Meier Lorey et al., 1998). We now report the results of the X-ray crystal structure analysis for the title compound, (I), one of the two diastereomers of iodinated cyclosaligenyl phosphate produced in the reaction, in order to establish the absolute configuration at the asymmetric P center. \sch

Compound (I) was synthesized by the oxidation reaction of the coupled product of 1-(2-deoxy-β-D-ribofuranosyl)-2,4-difluoro-5-iodobenzene with 3-methylsaligenylchlorophosphane. Removal of the solvent in vacuo gave a residue which was purified by flash silica-gel column chromatography using CH₂Cl₂-EtOAc (1:1, v/v) as eluent, to give a 1:1 mixture of the respective S– and R-diastereomeric products. Optically pure (I) was obtained by fractional crystallization of an ether solution of the diastereomeric mixture. Single crystals for X-ray crystallographic analysis were prepared by the following procedure. Subsequent flash silica-gel column chromatography of the 1:1 mixture of S– [(I)] and R-diastereomeric isomers with CH₂Cl₂-EtOAc (3:2, v/v) as eluent gave the fast-eluting isomer, (I), and the slow-eluting isomer, respectively. The fast-eluting isomer, (I), was recrystallized from ether to afford optically pure crystals. Characterization of (I) by ¹H and ³¹P NMR spectroscopy showed that the ³¹P resonance was more shielded (higher field), but in the¹H NMR spectra, the benzylic-CH₂ H atoms were less shielded than those of the slow-eluting isomer. Thus, the less polar diastereisomer, (I), was successfully crystallized from ether as colorless needles, which were subsequently subjected to X-ray crystallographic analysis. The crystallographic analysis afforded the assignment of the absolute configuration of the compound at the asymmetric P center in the cyclosaligenyl ring as S.

The molecular structure of (I) is shown in Fig. 1 and selected geometric parameters are listed in Table 1. The P1═O1 bond [1.454 (4) Å] indicates double-bond character and is shorter than P1—O2, P1—O3 and P1—O4 [1.565 (4), 1.557 (4) and 1.565 (4) Å, respectively]. The torsion angles at the phosphate, O1—P1—O2—C11, O1—P1—O3—C12 and O1—P1—O4—C18, are −48.3 (3), −170.6 (3) and 136.5 (4)°, respectively. The absolute stereochemistry of the iodinated molecule, (I), is confirmed by the value of the Flack (1983) parameter [0.02 (2)].

Our labeling of the deoxyribose ring differs from the standard labeling and therefore, in our description of its conformation, we use standard labels for the atoms followed by our labeling in parentheses. The O4' (O5)-endo conformation of the deoxyribose ring present in (I) is different from the C2'-endo conformation found in the structurally related compounds (E)-1-(2-deoxy-β-D-ribofuranosyl)-2,4-difluoro-5-(2-iodovinyl)benzene (Mark et al., 2001) and 1-(2-deoxy-β-D-ribofuranosyl)-2,4-difluoro-5-methylbenzene (Guckian & Kool, 1997). This O4' (O5)-endo conformation is consistent with the larger C3'-C4'-O4'-C1' (C9—C10—O5—C7) torsion angle of 32.4 (5)° relative to the smaller C1'-C2'-C3'-C4' (C7—C8—C9—C10) torsion angle of −13.3 (5)°. The 2,4-difluoro-5-iodobenzene ring in (I) is anti with respect to the deoxyribose, as measured by the O4'-C1'-C1—C2 (O5—C7—C1—C2) torsion angle of −171.2 (5)°.

Inspection of the packing structure of (I) reveals that intermolecular interactions are formed through hydrogen-bonding between a hydroxyl group (O6—H18) of the sugar ring and a phosphate O atom (P1═O1) (Fig. 2, Table 2), and also through π–π interactions between the methylsaligenyl aromatic ring, represented by the short intermolecular distance [3.011 (8) Å] between atoms O3 and C18 of the cyclosaligenyl rings and the molecules related by unit-cell translations along the crystallographic b axis·(Fig. 3) Intermolecular C—H—F—C hydrogen-bonding interactions have been observed in the crystal structure of 1-deoxy-1-(2,4-difluorophenyl)-β-D-ribofuranose (Bats et al., 2000). The crystal structure of (I), however, shows no intermolecular hydrogen bonding involving the F atoms of the aryl ring.

S2. Experimental

The title compound was prepared from the coupling reaction of methylsalicylchlorophosphane and 1-(2,4-difluoro-5-iodophenyl)-2-deoxy-β-D-ribofuranose, followed by oxidation using tert-butyl hydroperoxide (Sun et al., 2003) (m.p. 408–409 K; yield 20%). Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 7.86 (t, J = 7.6 Hz, 1H, difluorophenyl H), 7.19 (d, J = 6.9 Hz, 1H, saligenyl H4), 7.05 (dd, J = 7.3 and 6.9 Hz, 1H, saligenyl H5), 6.94 (d, J = 7.3 Hz, 1H, saligenyl H6), 6.82 (dd, J = 9.8 and 7.6 Hz, 1H, difluorophenyl H), 5.38 (d, J = 16.5 Hz, 2H, benzyl-CH₂), 5.33 (dd, J = 10.4 and 6.1 Hz, 1H, H1'), 4.51 (ddd, J = 6.5, 3.4 and 3.1 Hz, 1H, H3'), 4.26–4.47 (m, 2H, H5'), 4.10–4.18 (m, 1H, H4'), 2.40 (ddt, J = 12.8, 5.8 and 1.8 Hz, 1H, H2'α), 2.30 (s, 3H, CH₃), 1.89–2.00 (m, 1H, H2'β), 1.82 (br s, 1H, OH); ³¹P NMR (CDCl₃, δ, p.p.m.): −8.69.

S3. Refinement

H atoms were treated as riding, with C—H = 0.95 and O—H = 0.93 Å, and with U_iso(H) = 1.3U_eq(C,O). Please check added text. In particular, please clarify the treatment of atom H18 - the CIF bond table gives no s.u.s, but Table 2 does. Please also check the symmetry operator in Table 2 - the CIF originally gave 3_656, but no symmetry code 3 was defined, nor is one possible for this space group, and symmetry code 2 was assumed.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A molecular view of (I), showing the hydrogen-bonding pattern. The two molecules are related by the crystallographic 21 screw axis, with atom O6 of the left-hand molecule hydrogen-bonding to atom O1 of a molecule related to the right-hand molecule by a translation along the b axis, leading to the formation of an infinite spiral arrangement along the twofold screw axis.
	Fig. 3. A packing diagram for (I), showing the π–π interactions between atoms O3 and C18 (dashed lines). The molecules shown are related by translations along the b axis.

(2S)-2-[1-(2,4-Difluoro-5-iodophenyl)-2-deoxy-β-D-ribofuranos-5-yl]-8- methyl-4H-1,3,2-benzodioxaphosphole 2-oxide

Crystal data

C19H18F2IO6P	F(000) = 532.00
Mr = 538.22	Dx = 1.772 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2yb	Cell parameters from 9501 reflections
a = 14.552 (5) Å	θ = 3.3–27.5°
b = 4.610 (2) Å	µ = 1.72 mm^−1
c = 15.989 (5) Å	T = 123 K
β = 109.86 (3)°	Needle, colorless
V = 1008.9 (6) Å^3	0.10 × 0.10 × 0.05 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	3621 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.053
ω scans	θmax = 27.5°
Absorption correction: numerical (ABSCOR; Higashi, 1999)	h = −18→18
Tmin = 0.641, Tmax = 0.800	k = −5→5
9720 measured reflections	l = −20→20
4063 independent reflections

Refinement

Refinement on F^2	(Δ/σ)max < 0.001
R[F^2 > 2σ(F^2)] = 0.037	Δρmax = 2.12 e Å^−3
wR(F^2) = 0.096	Δρmin = −2.03 e Å^−3
S = 1.06	Extinction correction: Larson (1970), eq. 22
4063 reflections	Extinction coefficient: 61 (6)
282 parameters	Absolute structure: Flack (1983), with 1493 Friedel pairs
H-atom parameters constrained	Absolute structure parameter: 0.02 (2)
w = 1/[0.0002Fo^2 + 0.6σ(Fo^2)]/(4Fo^2)

Special details

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.50272 (2)	−0.0311 (2)	0.60024 (2)	0.03475 (9)
P1	0.94755 (9)	0.6546 (3)	0.81250 (8)	0.0262 (3)
F1	0.4394 (2)	0.6480 (8)	0.9091 (2)	0.0413 (9)
F2	0.3197 (2)	0.0298 (8)	0.6639 (2)	0.044 (1)
O1	1.0313 (2)	0.483 (1)	0.8646 (2)	0.0363 (9)
O2	0.9008 (2)	0.8397 (7)	0.8697 (2)	0.0262 (9)
O3	0.8640 (2)	0.469 (1)	0.7479 (2)	0.0297 (8)
O4	0.9737 (2)	0.8855 (7)	0.7524 (2)	0.0293 (9)
O5	0.7089 (2)	0.6939 (8)	0.8730 (2)	0.0298 (9)
O6	0.7742 (3)	0.8890 (8)	1.0968 (2)	0.034 (1)
C1	0.5455 (3)	0.503 (2)	0.8349 (3)	0.028 (1)
C2	0.4527 (3)	0.498 (1)	0.8422 (3)	0.028 (1)
C3	0.3778 (4)	0.335 (1)	0.7887 (3)	0.033 (1)
C4	0.3942 (4)	0.188 (1)	0.7202 (3)	0.033 (1)
C5	0.4841 (4)	0.187 (1)	0.7077 (3)	0.028 (1)
C6	0.5591 (4)	0.352 (1)	0.7659 (3)	0.030 (1)
C7	0.6247 (3)	0.684 (1)	0.9001 (3)	0.028 (1)
C8	0.6633 (4)	0.556 (1)	0.9942 (3)	0.030 (1)
C9	0.7680 (4)	0.669 (1)	1.0327 (3)	0.028 (1)
C10	0.7877 (3)	0.789 (1)	0.9496 (3)	0.025 (1)
C11	0.8816 (3)	0.686 (1)	0.9421 (3)	0.027 (1)
C12	0.7835 (4)	0.628 (1)	0.6828 (3)	0.032 (1)
C13	0.8225 (4)	0.821 (1)	0.6290 (3)	0.031 (1)
C14	0.7676 (4)	0.889 (1)	0.5406 (3)	0.042 (2)
C15	0.8051 (5)	1.077 (1)	0.4926 (4)	0.048 (2)
C16	0.8988 (5)	1.187 (1)	0.5296 (4)	0.045 (2)
C17	0.9561 (4)	1.121 (1)	0.6161 (3)	0.031 (1)
C18	0.9150 (3)	0.937 (1)	0.6634 (3)	0.028 (1)
C19	1.0580 (5)	1.236 (2)	0.6572 (4)	0.050 (2)
H1	0.3170	0.3227	0.7983	0.043*
H2	0.6206	0.3611	0.7575	0.038*
H3	0.6011	0.8748	0.9022	0.035*
H4	0.6625	0.3502	0.9923	0.038*
H5	0.6254	0.6216	1.0285	0.038*
H6	0.8117	0.5153	1.0586	0.036*
H7	0.7880	0.9948	0.9515	0.032*
H8	0.8775	0.4837	0.9302	0.034*
H9	0.9332	0.7225	0.9964	0.034*
H10	0.7503	0.7405	0.7134	0.038*
H11	0.7392	0.4931	0.6449	0.038*
H12	0.7046	0.8067	0.5136	0.049*
H13	0.7663	1.1299	0.4338	0.057*
H14	0.9242	1.3107	0.4951	0.059*
H15	1.0738	1.3540	0.6152	0.068*
H16	1.1025	1.0785	0.6743	0.068*
H17	1.0619	1.3485	0.7081	0.068*
H18	0.8353	0.9770	1.1197	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0441 (2)	0.0384 (2)	0.0269 (2)	0.0037 (2)	0.0187 (1)	−0.0005 (2)
P1	0.0234 (6)	0.0353 (8)	0.0245 (6)	0.0018 (5)	0.0141 (5)	0.0009 (6)
F1	0.032 (2)	0.055 (2)	0.046 (2)	−0.005 (2)	0.026 (1)	−0.018 (2)
F2	0.037 (2)	0.057 (3)	0.041 (1)	−0.017 (2)	0.016 (1)	−0.015 (2)
O1	0.030 (2)	0.052 (2)	0.033 (1)	0.009 (2)	0.018 (1)	0.010 (3)
O2	0.028 (2)	0.031 (2)	0.027 (2)	−0.003 (1)	0.018 (1)	−0.004 (1)
O3	0.032 (2)	0.032 (2)	0.028 (1)	0.005 (2)	0.014 (1)	0.007 (2)
O4	0.030 (2)	0.037 (2)	0.025 (1)	−0.001 (1)	0.015 (1)	0.004 (1)
O5	0.023 (2)	0.041 (2)	0.030 (2)	−0.005 (2)	0.015 (1)	0.002 (2)
O6	0.028 (2)	0.049 (3)	0.032 (2)	−0.005 (1)	0.018 (1)	−0.010 (2)
C1	0.028 (2)	0.028 (3)	0.034 (2)	0.001 (3)	0.019 (2)	0.008 (3)
C2	0.034 (2)	0.028 (3)	0.029 (2)	−0.011 (3)	0.018 (2)	−0.010 (3)
C3	0.023 (3)	0.042 (3)	0.043 (3)	−0.003 (2)	0.021 (2)	−0.004 (3)
C4	0.031 (3)	0.039 (3)	0.029 (2)	−0.010 (2)	0.011 (2)	−0.002 (2)
C5	0.034 (3)	0.029 (3)	0.026 (2)	0.004 (2)	0.016 (2)	0.007 (2)
C6	0.026 (3)	0.035 (3)	0.035 (2)	0.000 (2)	0.017 (2)	0.008 (2)
C7	0.021 (2)	0.036 (3)	0.032 (2)	−0.002 (2)	0.017 (2)	−0.002 (2)
C8	0.034 (3)	0.037 (3)	0.025 (2)	−0.008 (2)	0.018 (2)	−0.003 (2)
C9	0.028 (3)	0.035 (3)	0.027 (2)	0.001 (2)	0.019 (2)	0.004 (2)
C10	0.026 (2)	0.029 (3)	0.026 (2)	−0.006 (2)	0.015 (2)	−0.005 (2)
C11	0.025 (2)	0.034 (3)	0.027 (2)	−0.001 (2)	0.016 (2)	−0.001 (2)
C12	0.027 (3)	0.038 (3)	0.030 (2)	0.000 (2)	0.007 (2)	−0.003 (2)
C13	0.034 (3)	0.031 (3)	0.031 (2)	0.009 (2)	0.016 (2)	−0.002 (2)
C14	0.039 (3)	0.055 (4)	0.030 (2)	0.014 (3)	0.008 (2)	−0.002 (2)
C15	0.062 (4)	0.057 (4)	0.025 (2)	0.026 (3)	0.014 (3)	0.009 (3)
C16	0.074 (5)	0.041 (3)	0.031 (3)	0.014 (3)	0.032 (3)	0.012 (3)
C17	0.046 (3)	0.029 (3)	0.028 (2)	0.003 (2)	0.024 (2)	0.000 (2)
C18	0.035 (2)	0.028 (3)	0.024 (2)	0.009 (2)	0.016 (2)	0.005 (3)
C19	0.069 (4)	0.055 (4)	0.045 (3)	−0.012 (4)	0.044 (3)	−0.003 (3)

Geometric parameters (Å, º)

I1—C5	2.088 (5)	C13—C14	1.403 (7)
P1—O1	1.454 (4)	C13—C18	1.378 (7)
P1—O2	1.565 (4)	C14—C15	1.39 (1)
P1—O3	1.557 (4)	C15—C16	1.386 (9)
P1—O4	1.565 (4)	C16—C17	1.385 (7)
F1—C2	1.341 (7)	C17—C18	1.399 (8)
F2—C4	1.362 (6)	C17—C19	1.500 (9)
O2—C11	1.463 (6)	O6—H18	0.9314
O3—C12	1.470 (6)	C3—H1	0.9500
O4—C18	1.410 (5)	C6—H2	0.9500
O5—C7	1.433 (7)	C7—H3	0.9500
O5—C10	1.433 (5)	C8—H4	0.9500
O6—C9	1.421 (6)	C8—H5	0.9501
C1—C2	1.395 (7)	C9—H6	0.9500
C1—C6	1.373 (8)	C10—H7	0.9500
C1—C7	1.515 (7)	C11—H8	0.9500
C2—C3	1.360 (7)	C11—H9	0.9500
C3—C4	1.375 (8)	C12—H10	0.9500
C4—C5	1.389 (8)	C12—H11	0.9500
C5—C6	1.394 (6)	C14—H12	0.9500
C7—C8	1.533 (6)	C15—H13	0.9499
C8—C9	1.528 (7)	C16—H14	0.9500
C9—C10	1.552 (7)	C19—H15	0.9500
C10—C11	1.488 (7)	C19—H16	0.9500
C12—C13	1.479 (8)	C19—H17	0.9500
I1···F2	3.170 (4)	O5···H7	1.9603
I1···C4	3.043 (6)	O5···H8	2.5036
I1···C6	3.055 (5)	O5···H9	3.1916
P1···C11	2.567 (6)	O5···H10	2.8228
P1···C12	2.579 (4)	O6···H3	3.2720
P1···C13	2.980 (5)	O6···H4	3.1240
P1···C18	2.615 (5)	O6···H4^iv	2.8477
F1···C1	2.343 (7)	O6···H5	2.4075
F1···C3	2.327 (6)	O6···H6	1.9658
F1···C4	3.562 (6)	O6···H6^iv	3.0384
F1···C6	3.584 (7)	O6···H7	2.4476
F1···C7	2.754 (6)	O6···H9	3.3226
F1···C8	3.105 (6)	C1···H1	3.2816
F2···C2	3.575 (6)	C1···H2	2.0170
F2···C3	2.352 (6)	C1···H3^iii	3.0975
F2···C5	2.367 (6)	C1···H3	2.0413
F2···C14^i	3.497 (6)	C1···H4	2.6103
F2···C15^ii	3.292 (7)	C1···H5	2.9650
F2···C15^i	3.582 (7)	C2···H1	2.0259
O1···O2^iii	3.539 (6)	C2···H2	3.2330
O1···O2	2.534 (6)	C2···H3^iii	3.5269
O1···O3	2.515 (4)	C2···H3	2.6818
O1···O4^iii	3.239 (6)	C2···H4	3.2517
O1···O4	2.517 (6)	C2···H5	3.2295
O1···C11	2.999 (7)	C4···H1	2.0389
O2···O1^iv	3.539 (6)	C4···H2	3.2422
O2···O3	2.508 (5)	C4···H12^i	3.5623
O2···O3^iv	3.433 (6)	C4···H13^i	3.4285
O2···O4	2.457 (5)	C5···H1	3.2855
O2···O5	2.890 (5)	C5···H2	2.0362
O2···C10	2.413 (7)	C5···H3^iii	3.3243
O2···C12	3.054 (5)	C6···H3^iii	3.0111
O2···C18	3.404 (6)	C6···H3	3.1661
O3···O2^iii	3.433 (6)	C6···H4	3.4161
O3···O4^iii	3.116 (6)	C7···H2	2.7064
O3···O4	2.481 (6)	C7···H4	2.0708
O3···C11	3.190 (6)	C7···H4^iv	3.3706
O3···C13^iii	3.482 (7)	C7···H5	2.0693
O3···C13	2.414 (6)	C7···H6	3.1223
O3···C17^iii	3.275 (7)	C7···H7	2.6555
O3···C18^iii	3.011 (8)	C8···H3^iii	3.4559
O3···C18	2.777 (7)	C8···H3	2.0583
O4···O1^iv	3.239 (6)	C8···H6	2.0610
O4···O3^iv	3.116 (6)	C8···H7^iii	3.3605
O4···C12	2.867 (6)	C8···H7	2.9472
O4···C13	2.424 (5)	C8···H18	3.2623
O4···C17	2.370 (6)	C9···H3	2.7759
O4···C19	2.776 (8)	C9···H4	2.0657
O5···O6	3.494 (5)	C9···H4^iv	3.4564
O5···C1	2.412 (6)	C9···H5	2.0658
O5···C6	2.762 (6)	C9···H7^iii	3.4202
O5···C8	2.339 (6)	C9···H7	2.0673
O5···C9	2.404 (6)	C9···H8	2.7801
O5···C11	2.377 (5)	C9···H9	2.6683
O5···C12	3.572 (7)	C9···H18^iii	3.4871
O6···C7	3.297 (5)	C9···H18	1.9950
O6···C8	2.419 (6)	C10···H3	2.5898
O6···C8^iv	3.599 (6)	C10···H4	2.9524
O6···C10	2.471 (6)	C10···H4^iv	3.3650
O6···C11	3.472 (7)	C10···H5	3.1287
C1···C3	2.424 (7)	C10···H6	2.0825
C1···C4	2.751 (7)	C10···H8	2.0142
C1···C5	2.410 (7)	C10···H8^iv	3.5131
C1···C8	2.554 (6)	C10···H9	2.0147
C2···C4	2.332 (7)	C10···H18	2.7114
C2···C5	2.748 (8)	C11···H6	2.5317
C2···C6	2.371 (8)	C11···H7^iii	3.4889
C2···C7	2.506 (7)	C11···H7	2.0104
C2···C8	3.212 (6)	C11···H10	3.5132
C3···C5	2.428 (9)	C11···H18	3.4081
C3···C6	2.784 (8)	C12···H2	3.2370
C4···C6	2.382 (7)	C12···H12	2.6855
C6···C7	2.542 (7)	C13···H10	2.0056
C6···C8	3.571 (6)	C13···H11	2.0057
C7···C9	2.418 (6)	C13···H11^iv	3.3680
C7···C10	2.283 (6)	C13···H12	2.0496
C7···C11	3.567 (7)	C13···H13	3.2719
C8···O6^iii	3.599 (6)	C14···H10	2.9387
C8···C10	2.411 (8)	C14···H11	2.5981
C8···C11	3.596 (8)	C14···H11^iv	3.3418
C9···C11	2.541 (8)	C14···H13	2.0315
C12···C14	2.514 (8)	C14···H14	3.2599
C12···C18	2.489 (8)	C15···H11^iv	3.4813
C13···O3^iv	3.482 (7)	C15···H12	2.0338
C13···C15	2.416 (8)	C15···H14	2.0301
C13···C16	2.795 (9)	C16···H12	3.2624
C13···C17	2.452 (8)	C16···H13	2.0316
C14···F2^v	3.497 (6)	C16···H15	2.5653
C14···C16	2.41 (1)	C16···H16	3.1194
C14···C17	2.807 (8)	C16···H17	3.1195
C14···C18	2.375 (6)	C17···H13	3.2643
C15···F2^v	3.582 (7)	C17···H14	2.0278
C15···F2^vi	3.292 (7)	C17···H15	2.0254
C15···C17	2.413 (7)	C17···H16	2.0241
C15···C18	2.731 (7)	C17···H17	2.0237
C16···C18	2.370 (8)	C18···H10	2.9158
C16···C19	2.523 (8)	C18···H11	3.2095
C17···O3^iv	3.275 (7)	C18···H11^iv	3.5609
C18···O3^iv	3.011 (8)	C18···H12	3.2383
C18···C19	2.527 (9)	C18···H14	3.2354
I1···H2	3.0989	C18···H15	3.2921
I1···H10^iii	3.5967	C18···H16	2.7535
I1···H12^i	3.3331	C18···H17^iii	3.3783
P1···H8	2.5506	C18···H17	2.7647
P1···H9	3.0341	C19···H14	2.6827
P1···H10	2.7956	H2···O5^iii	3.5932
P1···H11	3.3774	H3···C1^iv	3.0975
P1···H17^iii	3.0719	H3···C2^iv	3.5269
F1···H1	2.5322	H3···C5^iv	3.3243
F1···H3	2.6116	H3···C6^iv	3.0111
F1···H4	3.3565	H3···C8^iv	3.4559
F1···H5	2.7345	H4···O6^iii	2.8477
F2···H1	2.5497	H4···C7^iii	3.3706
F2···H12^i	3.0215	H4···C9^iii	3.4564
F2···H13^ii	2.4654	H4···C10^iii	3.3650
F2···H13^i	3.2145	H6···O6^iii	3.0384
F2···H16^vii	3.2285	H7···O5^iv	3.5076
O1···H8	2.7762	H7···C8^iv	3.3605
O1···H9	3.1212	H7···C9^iv	3.4202
O1···H17^iii	2.7575	H7···C11^iv	3.4889
O2···H7	2.5252	H8···O2^iii	3.1761
O2···H8	1.9917	H8···C10^iii	3.5131
O2···H8^iv	3.1761	H10···I1^iv	3.5967
O2···H9	1.9926	H11···C13^iii	3.3680
O2···H10	2.7442	H11···C14^iii	3.3418
O3···H8	2.8555	H11···C15^iii	3.4813
O3···H10	1.9971	H11···C18^iii	3.5609
O3···H11	1.9978	H12···I1^v	3.3331
O3···H17^iii	3.2018	H12···F2^v	3.0215
O4···H10	3.1658	H12···C4^v	3.5623
O4···H16	2.7312	H13···F2^v	3.2145
O4···H17^iii	2.9832	H13···F2^vi	2.4654
O4···H17	2.7064	H13···C4^v	3.4285
O5···H2	2.4091	H16···F2^viii	3.2285
O5···H2^iv	3.5932	H17···P1^iv	3.0719
O5···H3	1.9682	H17···O1^iv	2.7575
O5···H4	2.7345	H17···O3^iv	3.2018
O5···H5	3.1343	H17···O4^iv	2.9832
O5···H6	2.9509	H17···C18^iv	3.3783
O5···H7^iii	3.5076	H18···C9^iv	3.4871
I1—C5—C4	120.8 (3)	C16—C17—C18	116.8 (5)
I1—C5—C6	121.4 (4)	C16—C17—C19	122.0 (6)
O2—P1—O1	114.1 (2)	C19—C17—C18	121.3 (4)
O3—P1—O1	113.3 (3)	O2—C11—H8	109.3906
O4—P1—O1	113.0 (2)	O2—C11—H9	109.4650
O3—P1—O2	106.9 (2)	O3—C12—H10	109.3402
O4—P1—O2	103.4 (2)	O3—C12—H11	109.4004
P1—O2—C11	115.9 (3)	O5—C7—H3	109.6849
O4—P1—O3	105.3 (2)	O5—C10—H7	109.0370
P1—O3—C12	116.8 (4)	O6—C9—H6	110.4086
P1—O4—C18	123.0 (3)	H18—O6—C9	114.3573
F1—C2—C1	117.7 (4)	C1—C6—H2	119.4290
F1—C2—C3	118.9 (5)	C1—C7—H3	109.6671
F2—C4—C5	118.7 (5)	C2—C3—H1	121.5308
F2—C4—C3	118.4 (5)	H1—C3—C4	121.4657
O2—C11—C10	109.7 (4)	C5—C6—H2	119.3931
O3—C12—C13	109.9 (4)	H3—C7—C8	109.7221
O4—C18—C13	120.8 (5)	C7—C8—H4	110.8091
O4—C18—C17	115.1 (4)	C7—C8—H5	110.6725
O5—C7—C1	109.8 (4)	H4—C8—C9	110.7524
O5—C7—C8	104.0 (4)	H5—C8—C9	110.7578
C10—O5—C7	105.6 (4)	C8—C9—H6	110.3483
O5—C10—C11	108.9 (4)	H5—C8—H4	109.4610
O5—C10—C9	107.3 (4)	C9—C10—H7	109.0865
O6—C9—C8	110.1 (4)	H6—C9—C10	110.3851
O6—C9—C10	112.3 (4)	C10—C11—H8	109.3943
C6—C1—C2	117.9 (5)	C10—C11—H9	109.4351
C1—C2—C3	123.2 (5)	H7—C10—C11	109.0632
C7—C1—C2	118.8 (5)	H9—C11—H8	109.4572
C1—C6—C5	121.2 (5)	H10—C12—C13	109.3617
C7—C1—C6	123.3 (5)	H11—C12—C13	109.3709
C1—C7—C8	113.8 (5)	H11—C12—H10	109.4646
C2—C3—C4	117.0 (5)	C13—C14—H12	119.9537
C3—C4—C5	122.9 (5)	H12—C14—C15	119.9574
C4—C5—C6	117.7 (5)	C14—C15—H13	119.7218
C7—C8—C9	104.3 (4)	H13—C15—C16	119.6723
C8—C9—C10	103.0 (3)	C15—C16—H14	119.5128
C9—C10—C11	113.4 (4)	H14—C16—C17	119.4041
C12—C13—C18	121.2 (4)	C17—C19—H16	109.3666
C12—C13—C14	121.5 (5)	C17—C19—H17	109.3295
C18—C13—C14	117.3 (5)	C17—C19—H15	109.4787
C13—C14—C15	120.1 (5)	H16—C19—H15	109.5921
C13—C18—C17	124.1 (4)	H17—C19—H15	109.5883
C14—C15—C16	120.6 (5)	H17—C19—H16	109.4715
C15—C16—C17	121.1 (6)
O1—P1—O2—C11	−48.3 (3)	F2—C4—C5—C6	179.7 (5)
O3—P1—O2—C11	77.7 (3)	C3—C4—C5—I1	−178.4 (4)
O4—P1—O2—C11	−171.4 (2)	C3—C4—C5—C6	−2.5 (8)
O1—P1—O3—C12	−170.6 (3)	I1—C5—C6—C1	178.1 (4)
O2—P1—O3—C12	62.8 (4)	C4—C5—C6—C1	2.2 (8)
O4—P1—O3—C12	−46.7 (4)	O5—C7—C8—C9	33.1 (5)
O1—P1—O4—C18	136.5 (4)	C1—C7—C8—C9	152.5 (4)
O2—P1—O4—C18	−99.6 (4)	C7—C8—C9—O6	106.7 (4)
O3—P1—O4—C18	12.4 (4)	C7—C8—C9—C10	−13.3 (5)
P1—O2—C11—C10	−141.9 (3)	O6—C9—C10—O5	−129.2 (4)
P1—O3—C12—C13	56.3 (5)	O6—C9—C10—C11	110.6 (5)
P1—O4—C18—C13	11.2 (8)	C8—C9—C10—O5	−10.7 (5)
P1—O4—C18—C17	−171.4 (4)	C8—C9—C10—C11	−130.9 (4)
C10—O5—C7—C1	−162.9 (4)	O5—C10—C11—O2	68.6 (5)
C10—O5—C7—C8	−40.8 (5)	C9—C10—C11—O2	−172.1 (3)
C7—O5—C10—C9	32.4 (5)	O3—C12—C13—C14	149.5 (5)
C7—O5—C10—C11	155.5 (4)	O3—C12—C13—C18	−29.4 (7)
C6—C1—C2—F1	−179.2 (5)	C12—C13—C14—C15	178.4 (6)
C6—C1—C2—C3	5.4 (9)	C18—C13—C14—C15	−2.7 (9)
C7—C1—C2—F1	−2.4 (8)	C12—C13—C18—O4	−2.9 (9)
C7—C1—C2—C3	−177.7 (5)	C12—C13—C18—C17	−180.0 (5)
C2—C1—C6—C5	−3.5 (8)	C14—C13—C18—O4	178.2 (5)
C7—C1—C6—C5	179.8 (5)	C14—C13—C18—C17	1.1 (9)
C2—C1—C7—O5	−171.2 (5)	C13—C14—C15—C16	3 (1)
C2—C1—C7—C8	72.7 (7)	C14—C15—C16—C17	−2 (1)
C6—C1—C7—O5	5.5 (8)	C15—C16—C17—C18	0.4 (9)
C6—C1—C7—C8	−110.6 (6)	C15—C16—C17—C19	179.4 (6)
F1—C2—C3—C4	179.1 (5)	C16—C17—C18—O4	−177.2 (5)
C1—C2—C3—C4	−5.6 (8)	C16—C17—C18—C13	0.0 (8)
C2—C3—C4—F2	−178.1 (5)	C19—C17—C18—O4	3.8 (8)
C2—C3—C4—C5	4.1 (8)	C19—C17—C18—C13	−179.0 (6)
F2—C4—C5—I1	3.8 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H18···O1^ix	0.93 (1)	1.87 (1)	2.719 (5)	150 (4)

Symmetry code: (ix) −x+2, y+1/2, −z+2.