(2E)-N-(2-Iodo-4,6-dimethyl­phen­yl)-2-methyl­but-2-enamide

The title compound, C₁₄H₁₈INO, crystallizes as +sc/+sp/+sc 2-iodo­anilide mol­ecules (and racemic opposites) and shows significant inter­molecular I...O inter­actions in the solid state, forming dimeric pairs about centres of symmetry. Under asymmetric Heck conditions, the S enantio­mer of the dihydro­indol-2-one was obtained using (R)-(+)-2,2′-bis(di­phenylphosphino)-1,1′-binaphthyl [(R)-BINAP], suggesting a mechanism that proceeds by oxidative addition to give the title (P) enantio­mer of the compound and pro-S coordination of the Re face of the alkene in a conformation similar to that defined crystallographically, except that rotation about the C—C bond of the butenyl group is required.

S1. Comment

The (M) enantiomer of the title iodoanilide, (Ib), gives rise (Lapierre et al., 2007), predominantly, to the (R)-1,3-dihydroindol-2-one, (IIb), when cyclized (see scheme) using an intramolecular Heck reaction (Beletskaya & Cheprakov, 2000) under Hartwig's low-temperature conditions (Stambuli et al., 2001). The crystallographic study reported in that work (Lapierre et al., 2007) employed a 4-bromo-2-iodoaryl analogue, (Ic), not the 2,4-dimethyl substrate itself. Furthermore, the conformation adopted in the solid state for the 4-bromo case was different from that which we had described earlier (McDermott et al., 2006) for Overman's original substrate (Ia) (Ashimori & Overman, 1992; Mandin & Overman, 1992; Ashimori et al., 1998) and a symmetrized analogue.

The structure now defined for (Ib) (Fig. 1) resembles that needed (McDermott et al., 2006) for cyclization, except that rotation about C21—C22 is required. Our crystallographic results for (Ia) (McDermott et al., 2006) and (Ib), however, indicate that strong intermolecular I···O interactions (Messina et al., 2001) are present [3.071 (6) Å in (Ia) and 2.964 (3) Å in (Ib)], significantly shorter than the sum of the van der Waals radii (3.55 Å; Pauling, 1960). Unlike (Ia), however, which was characterized as homochiral crystals containing chains of ribbons of +ac/-sp/-sc 2-iodoanilides (Table 1 and Fig. 2) linked by a zigzag pattern of I···O interactions, the title compound crystallizes with the +sc/+sp/+sc conformation and is linked into dimer pairs about an inversion centre through short I···O interactions. The conformations adopted by 2-iodoanilide butenoyl amides of this type are best described (Curran & Heffner, 1990; McDermott et al., 2006) by consideration of three planes (see scheme), corresponding to the three roughly planar sections of the molecule (the aromatic ring, the amide and the alkene). Table 1 compares data for these key features of the molecule.

The 2-iodo-4,6-dimethyl substrate, (Ib), gave the racemic indol-2-one derivative in 86% yield. Reaction of (Ib) with Pd₂(dba)₃ and (R)-BINAP under Overman's silver phosphate conditions [silver phosphate (Aldrich) in DMA [Please define] (McDermott et al., 2007)] gave the same product, (IIb), with an e.e. [Please define] of 25%. This interconversion is thus consistent with oxidative addition to (P)-(Ib) and pro-(S) coordination of the Re face of the alkene, in the conformation shown in Fig. 1.

Related literature

For related literature, see: Ashimori & Overman (1992); Ashimori et al. (1998); Beletskaya & Cheprakov (2000); Berliner & Hann (1925); Curran & Heffner (1990); Fujikura et al. (1995); Lapierre et al. (2007); Mandin & Overman (1992); McDermott et al. (2006, 2007); Messina et al. (2001); Pauling (1960); Stambuli et al. (2001).

S2. Experimental

Compound (Ib) was synthesized from 2,4-dimethylaniline using procedures based on the iodination of anilines by Berliner & Hann (1925), and the Takahashi method for the methylation of anilides (Fujikura et al., 1995). Purification was achieved by column chromatography on silica using hexane–dichloromethane (1:1 v/v) as the eluent, and recrystallization from hexane. N-(2-Iodo-4,6-dimethylphenyl)-2-methyl-(2E)-butenamide was obtained as short pale-turquoise needles (8.27 g, 31%, m.p. 382–385 K). Additional details of the synthesis and spectroscopic data are given in the Supplementary material.

S3. Refinement

H atoms were included in idealized positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for the trigonal planar groups, and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for the methyl groups.

Two persistent difference peaks were assigned and refined as partial disordered I atoms, I2 and I3, with site occupancies of 0.0206 (12) and 0.015, respectively. The first of these atoms, I2, is close to C31 and represents a molecule with the phenyl group rotated by 180° about the C2···C5 axis, i.e. with atom I1 and the C31 methyl group interchanged. Consequently, the site occupation factors of atom I1 and the C31 methyl group were constrained to 0.9794 (12), but the minor disorder site for the C31 methyl group was not included in the model.

The second peak was also assigned as a low-occupancy site for an I atom, I3, which lies ca 2.2 Å from atom I1 and quite separate from any other atom. A data set collected from a second crystal showed the same residual electron-density peaks. Examination of reconstructed zero-layer precession images showed severe streaking of the reflections and possibly some satellite reflections. One explanation for these images could be that the crystals consist of stacked plates that are very slightly slipped relative to one another. Consequently, it is likely that the residual peak assigned as atom I3 is an artefact of the data.

In the final difference map, the highest residual peaks (to ca 0.7 e Å^-3) were close to the major-occupancy I atom, I1.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Projections down the C2—N2 bond of the (P) and (M) enantiomers for examples of sc/sp/sc and ac/sp/sc geometries of 2-iodoanilide butenoyl amides.
	Fig. 2. (a) The structure of (P)-(Ib), taken from a racemic crystal, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitary radii. (b) The proposed conformation after the oxidative addition step of the AHR [Please give in full. Asymmetric Heck reaction?] using (R)-BINAP, which retains the (P) relationship between N2—C21—O21 and C21—N2—C25 but requires rotation about C21—C22.
	Fig. 3. Principal planes of 2-iodoanilide, (I).

(2E)-N-(2-Iodo-4,6-dimethylphenyl)-2-methylbut-2-enamide

Crystal data

C14H18INO	V = 715.14 (8) Å^3
Mr = 343.19	Z = 2
Triclinic, P1	F(000) = 340
a = 8.8872 (6) Å	Dx = 1.594 Mg m^−3
b = 9.3897 (6) Å	Mo Kα radiation, λ = 0.71073 Å
c = 10.1875 (7) Å	µ = 2.23 mm^−1
α = 66.389 (4)°	T = 120 K
β = 67.135 (4)°	Slab, colourless
γ = 76.842 (5)°	0.45 × 0.3 × 0.14 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3278 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2812 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.612, Tmax = 1.00	l = −13→13
15106 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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 0.6769P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.007
3278 reflections	Δρmax = 0.73 e Å^−3
163 parameters	Δρmin = −1.12 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (2)

Special details

Experimental. The preparation of N-(2-iodo-4,6-dimethylphenyl)-2-methyl-(2E)-butenamide, (Ib), was carried out as follows. By the procedure of Hann (Berliner & Hann, 1925) a round-bottomed flask was charged with 2,4-dimethylaniline [Eguchi, S., Kimoto, H., Okano, T. & Tsuge, H. (1997). J. Chem. Soc., Perkin Trans. 1, pp. 1581–1587; Barluenga, J., Ezquerra, J., Lamas, C., Pedregal, C. & Perez, M. (1996). J. Org. Chem. 61, 5804–5812.] (5 g, 41.26 mmol) and diethyl ether (30 ml). Concentrated hydrochloric acid (10 ml) was added dropwise. The mixture was stirred at room temperature for 30 min and the precipitate which formed was collected by filtration. This aniline hydrogen chloride salt, iodine (11.50 g, 45.39 mmol) and calcium carbonate (6.30 g, 61.89 mmol) were stirred in water–diethyl ether (5:1 v/v, 180 ml) at room temperature for 16 h. Sodium thiosulfate was added directly to the reaction mixture and stirred until the brown colour faded. The product was extracted with ethyl acetate, washed with half brine, dried over magnesium sulfate, filtered, and the solvent removed in vacuo. The crude product was dissolved in dichloromethane (DCM) and filtered through a column containing 20 cm silica over 5 cm magnesium sulfate, using dichloromethane as the eluent. The product was obtained as a brown oil and crystallized from propan-2-ol–water. 4,6-Dimethyl-2-iodoaniline was isolated as brown needle-like crystals (6.64 g, 65%). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.27 (1H, s, H3), 6.74 (1H, s, H5), 3.82 (2H, br s, NH₂), 2.10 (6H, s, ArCH₃); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 141.6, 136.1, 130.6, 128.4, 121.6, 83.9 (C—I), 18.8 (ArCH₃), 17.8 (ArCH₃). The procedure was repeated twice. The product (20 g, 80.95 mmol) was dissolved in dry DCM (60 ml) and cooled to 273 K before a solution of 2-methylbut-2-enoyl chloride (9.54 g, 89.04 mmol) in dry DCM (60 ml) was added dropwise from a syringe. Potassium carbonate (16.78 g, 121.4 mmol) was added, and the suspension was allowed to warm to room temperature and stirred for 16 h. Aqueous sodium hydroxide (2 M) was added, and stirring continued for 1 h at room temperature. The organic layer was separated off and the aqueous layer was extracted with DCM. The organic extracts were combined, dried over magnesium sulfate, filtered and the solvent removed in vacuo. Purification was achieved by column chromatography on silica using hexane–DCM (1:1) as the eluent, and recrystallization from hexane.

N-(2-Iodo-4,6-dimethylphenyl)-2-methyl-(2E)-butenamide was obtained as pale-turquoise short needles (8.27 g, 31%; m.p. 382–385 K). IR (ν_max, thin film, cm^-1): 3286, 2981, 2918, 2855, 1662, 1627, 1599, 1557, 1387, 1334, 1284, 1261, 1230, 1150, 1123, 1074, 1041, 1017, 962, 896, 848, 813, 773, 738, 709, 648, 577, 552; ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.42 (1H, s, H3), 7.08 (1H, br s, NH), 6.93 (1H, s, H5), 6.58 (1H, q, J = 6.7 Hz, CH₃CH═CCH₃R), 2.18 (3H, s, ArCH₃), 2.14 (3H, s, ArCH₃), 1.89 (3H, d, J = 1.0 Hz, CH₃CH═CCH₃R), 1.74 (3H, dd, J = 6.9 Hz, 1.0, CH₃CH═CCH₃R); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 167.6 (C═ O), 138.9, 137.3, 137.0, 134.8, 132.0, 131.9, 99.3 (C—I), 20.3 (ArCH₃), 19.5 (ArCH₃), 14.0 (CCH₃), 12.5 (CCH₃); m/z (CI) 347 (45%), 330 (M + H⁺, 100), 221 (13), 204 (23), 202 (M - I, 6), 188 (8), 83 (3); m/z (EI) 329 (M, 1%), 246 (8), 202 (M - I, 67), 187 (2), 158 (2), 118 (22), 104 (12), 91 (39), 83 (C₅H₇O, 100), 77 (17), 55 (C₄H₇, 96); HRMS, found: 330.0355;; C₁₃H₁₇NOI (M + H⁺) requires: 330.0349. The product (3.50 g, 10.63 mmol) was methylated by the procedure of Takahashi (Fujikura et al., 1995) [which is almost identical to the method described by Curran (Lapierre et al., 2007)] to give N-(2-iodo-4,6-dimethylphenyl)-N,2-dimethyl-(2E)-butenamide, (Ib), as colourless crystals (3.51 g, 96%).

1,3,5,7-Tetramethyl-1-vinyl-1,3-dihydroindol-2-one, (IIb), was prepared as follows. N-(2-iodo-4,6-dimethylphenyl)-N,2-dimethyl-(2E)-butenamide, (Ib), was converted into 1,3,5,7-tetramethyl-1-vinyl-1,3-dihydroindol-2-one (IIb) [m.p. 323–325 K for racemic (IIb)], which corresponded to the product described by Curran (Lapierre et al., 2007). The asymmetric Heck reaction was conducted at 353 K. The enantiomeric excess of (IIb) formed using (R)-BINAP was measured by NMR using approximately 15 mg of (IIb) in CDCl₃ (0.75 ml) and a 1 M solution of tris[3-heptafluoropropylhydroxymethylene)-(+)-camphorato]europium(III) in CDCl₃, which was added in small portions (a few drops) until a suitable separation of the peaks representing the two enantiomers in the ¹H NMR spectrum was obtained. The e.e.s were calculated using the magnitude of the integration of the two peaks for the quaternary methyl group (C1—Me). The product from the reaction using (R)-BINAP had an e.e. of 25%, with the (S)-(-)-1,3,5,7-tetramethyl-1-vinyl-1,3-dihydroindol-2-one, (IIb), predominating [enantiomer ratio = 62.5:37.5 (S):(R)].

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	0.51658 (3)	0.05041 (2)	0.19658 (2)	0.02860 (12)	0.9794 (12)
N2	0.2797 (3)	0.3217 (3)	0.0346 (3)	0.0234 (6)
C1	0.3676 (4)	0.2376 (4)	0.2583 (4)	0.0241 (7)
C2	0.2815 (4)	0.3447 (4)	0.1653 (4)	0.0222 (6)
C3	0.2000 (4)	0.4805 (4)	0.1958 (4)	0.0244 (7)
C4	0.2000 (4)	0.4988 (4)	0.3250 (4)	0.0272 (7)
H4	0.1443	0.5875	0.3471	0.033*
C5	0.2796 (4)	0.3901 (4)	0.4220 (4)	0.0272 (7)
C6	0.3649 (4)	0.2590 (4)	0.3861 (4)	0.0260 (7)
H6	0.4205	0.1852	0.4486	0.031*
C21	0.2043 (4)	0.2062 (4)	0.0411 (4)	0.0239 (7)
O21	0.2347 (3)	0.1755 (3)	−0.0740 (3)	0.0280 (5)
C22	0.0769 (4)	0.1215 (4)	0.1856 (4)	0.0250 (7)
C221	0.0723 (5)	−0.0463 (4)	0.2082 (5)	0.0403 (9)
H22A	0.0116	−0.1003	0.3123	0.060*
H22B	0.1821	−0.0948	0.1834	0.060*
H22C	0.0202	−0.0507	0.1433	0.060*
C23	−0.0332 (4)	0.1963 (4)	0.2744 (4)	0.0282 (7)
H23	−0.0201	0.3007	0.2487	0.034*
C24	−0.1760 (5)	0.1288 (5)	0.4113 (5)	0.0420 (9)
H24A	−0.2761	0.1811	0.3934	0.063*
H24B	−0.1702	0.1423	0.4977	0.063*
H24C	−0.1732	0.0196	0.4305	0.063*
C25	0.3947 (5)	0.4040 (5)	−0.1129 (4)	0.0342 (8)
H25A	0.4823	0.3313	−0.1455	0.051*
H25B	0.4386	0.4829	−0.1041	0.051*
H25C	0.3386	0.4518	−0.1859	0.051*
C31	0.1170 (5)	0.6052 (4)	0.0891 (6)	0.0251 (7)	0.9794 (12)
H31A	0.1984	0.6653	0.0011	0.038*	0.9794 (12)
H31B	0.0414	0.6725	0.1403	0.038*	0.9794 (12)
H31C	0.0589	0.5565	0.0583	0.038*	0.9794 (12)
C51	0.2778 (5)	0.4138 (5)	0.5609 (4)	0.0365 (8)
H51A	0.3727	0.4646	0.5357	0.055*
H51B	0.2790	0.3145	0.6402	0.055*
H51C	0.1806	0.4774	0.5949	0.055*
I2	0.1355 (13)	0.6249 (7)	0.0334 (8)	0.034 (5)*	0.0206 (12)
I3	0.4489 (13)	−0.1553 (5)	0.4115 (7)	0.033 (3)*	0.015

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02867 (16)	0.02619 (16)	0.02963 (16)	0.00385 (9)	−0.00859 (10)	−0.01280 (10)
N2	0.0265 (14)	0.0258 (14)	0.0172 (13)	−0.0035 (11)	−0.0052 (11)	−0.0084 (11)
C1	0.0203 (15)	0.0234 (16)	0.0259 (16)	−0.0023 (12)	−0.0029 (13)	−0.0103 (13)
C2	0.0223 (15)	0.0233 (16)	0.0197 (15)	−0.0038 (12)	−0.0034 (12)	−0.0087 (13)
C3	0.0235 (15)	0.0248 (16)	0.0235 (16)	−0.0039 (12)	−0.0045 (13)	−0.0091 (13)
C4	0.0271 (16)	0.0263 (17)	0.0278 (17)	−0.0041 (13)	−0.0027 (14)	−0.0142 (14)
C5	0.0252 (16)	0.0333 (18)	0.0215 (16)	−0.0070 (14)	−0.0017 (13)	−0.0114 (14)
C6	0.0246 (16)	0.0300 (17)	0.0230 (16)	−0.0036 (13)	−0.0082 (13)	−0.0080 (14)
C21	0.0232 (15)	0.0221 (16)	0.0256 (16)	0.0047 (12)	−0.0081 (13)	−0.0111 (13)
O21	0.0330 (13)	0.0279 (12)	0.0269 (12)	0.0044 (10)	−0.0111 (10)	−0.0158 (10)
C22	0.0274 (16)	0.0221 (16)	0.0261 (16)	−0.0036 (13)	−0.0108 (13)	−0.0064 (13)
C221	0.048 (2)	0.0277 (19)	0.044 (2)	−0.0078 (16)	−0.0102 (19)	−0.0140 (17)
C23	0.0257 (16)	0.0284 (17)	0.0307 (18)	−0.0066 (13)	−0.0085 (14)	−0.0092 (14)
C24	0.033 (2)	0.051 (2)	0.039 (2)	−0.0127 (17)	−0.0001 (17)	−0.0185 (19)
C25	0.039 (2)	0.041 (2)	0.0227 (17)	−0.0126 (16)	−0.0043 (15)	−0.0115 (15)
C31	0.032 (2)	0.0188 (17)	0.030 (3)	0.0035 (14)	−0.0163 (17)	−0.0111 (15)
C51	0.039 (2)	0.047 (2)	0.0267 (18)	−0.0037 (17)	−0.0077 (16)	−0.0200 (17)

Geometric parameters (Å, º)

I1—C1	2.101 (3)	C22—C221	1.506 (5)
N2—C21	1.367 (4)	C221—H22A	0.9600
N2—C25	1.461 (4)	C221—H22B	0.9600
C1—C6	1.386 (5)	C221—H22C	0.9600
C1—C2	1.395 (5)	C23—C24	1.496 (5)
C2—C3	1.403 (4)	C23—H23	0.9300
C2—N2	1.438 (4)	C24—H24A	0.9600
C3—C4	1.394 (5)	C24—H24B	0.9600
C3—C31	1.519 (5)	C24—H24C	0.9600
C3—I2	1.868 (5)	C25—H25A	0.9600
C4—C5	1.387 (5)	C25—H25B	0.9600
C4—H4	0.9300	C25—H25C	0.9600
C5—C6	1.395 (5)	C31—H31A	0.9600
C5—C51	1.511 (5)	C31—H31B	0.9600
C6—H6	0.9300	C31—H31C	0.9600
C21—O21	1.233 (4)	C51—H51A	0.9600
C21—C22	1.503 (5)	C51—H51B	0.9600
C22—C23	1.334 (5)	C51—H51C	0.9600
C21—N2—C2	124.5 (3)	C21—C22—C221	114.1 (3)
C21—N2—C25	116.8 (3)	C22—C221—H22A	109.5
C2—N2—C25	117.3 (3)	C22—C221—H22B	109.5
C6—C1—C2	120.6 (3)	H22A—C221—H22B	109.5
C6—C1—I1	119.3 (2)	C22—C221—H22C	109.5
C2—C1—I1	120.0 (2)	H22A—C221—H22C	109.5
C1—C2—C3	119.7 (3)	H22B—C221—H22C	109.5
C1—C2—N2	121.2 (3)	C22—C23—C24	126.3 (3)
C3—C2—N2	119.1 (3)	C22—C23—H23	116.8
C4—C3—C2	118.2 (3)	C24—C23—H23	116.8
C4—C3—C31	121.1 (3)	C23—C24—H24A	109.5
C2—C3—C31	120.7 (3)	C23—C24—H24B	109.5
C4—C3—I2	129.6 (3)	C23—C24—H24C	109.5
C2—C3—I2	111.5 (3)	N2—C25—H25A	109.5
C5—C4—C3	122.7 (3)	N2—C25—H25B	109.5
C5—C4—H4	118.6	H25A—C25—H25B	109.5
C3—C4—H4	118.6	N2—C25—H25C	109.5
C4—C5—C6	118.0 (3)	H25A—C25—H25C	109.5
C4—C5—C51	121.4 (3)	H25B—C25—H25C	109.5
C6—C5—C51	120.6 (3)	C3—C31—H31A	109.5
C1—C6—C5	120.7 (3)	C3—C31—H31B	109.5
C1—C6—H6	119.7	C3—C31—H31C	109.5
C5—C6—H6	119.7	C5—C51—H51A	109.5
O21—C21—N2	120.1 (3)	C5—C51—H51B	109.5
O21—C21—C22	119.2 (3)	H51A—C51—H51B	109.5
N2—C21—C22	120.6 (3)	C5—C51—H51C	109.5
C23—C22—C21	121.5 (3)	H51A—C51—H51C	109.5
C23—C22—C221	124.0 (3)	H51B—C51—H51C	109.5
C6—C1—C2—C3	4.1 (5)	C4—C5—C6—C1	−0.9 (5)
I1—C1—C2—C3	−171.5 (2)	C51—C5—C6—C1	−179.5 (3)
C6—C1—C2—N2	−178.3 (3)	C1—C2—N2—C21	68.2 (4)
I1—C1—C2—N2	6.1 (4)	C3—C2—N2—C21	−114.1 (4)
C1—C2—C3—C4	−3.8 (5)	C1—C2—N2—C25	−97.7 (4)
N2—C2—C3—C4	178.5 (3)	C3—C2—N2—C25	79.9 (4)
C1—C2—C3—C31	175.0 (3)	C2—N2—C21—O21	−165.9 (3)
N2—C2—C3—C31	−2.7 (5)	C25—N2—C21—O21	0.1 (5)
C1—C2—C3—I2	167.0 (4)	C2—N2—C21—C22	17.6 (5)
N2—C2—C3—I2	−10.7 (5)	C25—N2—C21—C22	−176.4 (3)
C2—C3—C4—C5	1.3 (5)	O21—C21—C22—C23	−137.0 (3)
C31—C3—C4—C5	−177.5 (3)	N2—C21—C22—C23	39.6 (5)
I2—C3—C4—C5	−167.6 (5)	O21—C21—C22—C221	35.4 (4)
C3—C4—C5—C6	1.1 (5)	N2—C21—C22—C221	−148.0 (3)
C3—C4—C5—C51	179.7 (3)	C21—C22—C23—C24	173.1 (3)
C2—C1—C6—C5	−1.7 (5)	C221—C22—C23—C24	1.4 (6)
I1—C1—C6—C5	173.9 (2)