5-Fluoro-1-(prop-2-en-1-yl)-2,3-di­hydro-1H-indole-2,3-dione

Qachchachi, F.-Z.; Mague, J.T.; Kandri Rodi, Y.; Haoudi, A.; Ouzidan, Y.; Essassi, E.M.

doi:10.1107/S2414314617000281

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x170028

https://doi.org/10.1107/S2414314617000281

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access

5-Fluoro-1-(prop-2-en-1-yl)-2,3-dihydro-1H-indole-2,3-dione

Fatim-Zahrae Qachchachi,^a Joel T. Mague,^b Youssef Kandri Rodi,^a Amal Haoudi,^a Younes Ouzidan ^a ^* and El Mokhtar Essassi ^c

^aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Imouzzer, BP 2202, Fez, Morocco, ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and ^cLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco
^*Correspondence e-mail: younes.ouzidan@usmba.ac.ma

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 23 December 2016; accepted 6 January 2017; online 13 January 2017)

The asymmetric unit of the title compound, C₁₁H₈FNO₂, consists of two independent molecules having different conformations and associated through pairwise C—H⋯F hydrogen bonds. These units form `stairstep' stacks along the b-axis direction via π–π stacking interactions between dihydroindole moieties, with interplanar spacings of 3.578 (3) and 3.627 (3) Å. The stacks are tied together by weak C—H⋯O hydrogen bonds.

Keywords: crystal structure; hydrogen bonding; π–π stacking; dihydroindole.

CCDC reference: 1526011

Structure description

Isatin (1H-indole-2,3- dione) derivatives are synthetically versatile substrates, which can be used for the synthesis of a large variety of heterocyclic compounds and as raw material for drug synthesis. Compounds containing an isatin moiety are most widely used as anti-Parkinsonian (Knölker & Reddy, 2002 ), antifungal (Granik et al., 1978 ) and anticancer agents (Marko et al., 2001 ). Additionally, isatin derivatives find applications in chemistry of transition metal catalysts for uniform polymerization and in luminescence chemistry (Grandberg et al., 1968 ). It has been shown that isatins exhibit antitumor activity due to the formation of stable complexes with DNA (Aravinda et al., 2009 ). For the biological activity of isatin derivatives, see: Ramachandran (2011 ); Smitha et al. (2008 ).

As a continuation of our research devoted to the synthesis of isatin derivatives (Qachchachi et al., 2014 ), we report here the synthesis and structure of 1-allyl-5-fluoroindoline-2,3-dione. The asymmetric unit consists of two independent molecules forming pseudo-centrosymmetric dimers associated through pairwise C5—H5⋯F2 and C16—H16⋯F1 hydrogen bonds (Table 1 and Fig. 1). These units form `stairstep' stacks parallel to the b axis via π–π stacking interactions in which the N1,C1,C6–C8 ring associates with the C1–C6 ring of the corresponding molecule at x, 1 + y, z while the C1–C6 ring associates with the N1,C1,C6–C8 ring of the corresponding molecule at x, −1 + y, z (Fig. 2). In both instances, the interplanar spacing is 3.578 (3) Å and the dihedral angle between the planes is 1.5 (2)°. Concurrently, the other half of the asymmetric unit forms analogous stacking interactions with its counterparts generated by the same symmetry operations with the interplanar spacing being 3.627 (3) Å and the dihedral angle 2.0 (2)°. Fig. 3 shows the packing of the complete unit cell. For the structure of 1-octylindoline-2,3-dione, see: Qachchachi et al. (2013 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯F2	0.95	2.64	3.477 (6)	148
C9—H9B⋯O1ⁱ	0.99	2.45	3.408 (7)	163
C16—H16⋯F1	0.95	2.50	3.353 (5)	150
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of the title compound, showing the atom-labeling scheme and 50% probability displacement ellipsoids. The C—H⋯F hydrogen bonds are shown as dotted lines.

Figure 2
Detail of the π–π stacking in the crystal packing of the title compound (purple dotted lines). [Symmetry codes: (i) x, 1 + y, z; (ii) x, −1 + y, z.]

Figure 3
Crystal packing of the title compound viewed along the b axis. The C—H⋯F and C—H⋯O hydrogen bonds are shown, respectively, by orange and black dotted lines.

Synthesis and crystallization

To a solution of 5-fluoro-2,3-indoledione (0.5 g, 3.5 mmol) dissolved in DMF (20 ml) was added potassium carbonate (0.61 g, 4.4 mmol), a catalytic quantity of tetra-n-butylammonium (0.1 g, 0.4 mmol) and 3-bromo-1-propene (0.2 ml, 3.6 mmol). The mixture was stirred for 48 h; the reaction was monitored by thin layer chromatography. The mixture was filtered and the solvent removed under vacuum. The solid obtained was recrystallized from ethanol solution to afford the title compound as red crystals in 86% yield (m.p.: 450 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₈FNO₂
M_r	205.18
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	31.531 (3), 4.2752 (4), 14.1080 (13)
V (Å³)	1901.8 (3)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	0.96
Crystal size (mm)	0.27 × 0.07 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.76, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	13399, 3201, 2813
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.189, 1.10
No. of reflections	3201
No. of parameters	272
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.32
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.5 (4)
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and DIAMOND (Brandenburg & Putz, 2012 ).

Structural data

CCDC reference: 1526011

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617000281/vm4020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000281/vm4020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000281/vm4020Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000281/vm4020Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

5-Fluoro-1-(prop-2-en-1-yl)-2,3-dihydro-1H-indole-2,3-dione top

Crystal data top

C₁₁H₈FNO₂	D_x = 1.433 Mg m⁻³
M_r = 205.18	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pna2₁	Cell parameters from 9630 reflections
a = 31.531 (3) Å	θ = 3.4–72.5°
b = 4.2752 (4) Å	µ = 0.96 mm⁻¹
c = 14.1080 (13) Å	T = 150 K
V = 1901.8 (3) Å³	Column, orange
Z = 8	0.27 × 0.07 × 0.06 mm
F(000) = 848

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3201 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2813 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.047
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.6°, θ_min = 2.8°
ω scans	h = −35→38
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −5→5
T_min = 0.76, T_max = 0.94	l = −17→14
13399 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.073	H-atom parameters constrained
wR(F²) = 0.189	w = 1/[σ²(F_o²) + (0.1367P)² + 0.156P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3201 reflections	Δρ_max = 0.86 e Å⁻³
272 parameters	Δρ_min = −0.32 e Å⁻³
1 restraint	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.5 (4)

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.

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 > 2sigma(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. The model was refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
F1	0.36220 (9)	0.5663 (7)	0.6091 (3)	0.0471 (8)
O1	0.28379 (13)	1.1914 (11)	0.3187 (3)	0.0519 (10)
O2	0.21272 (12)	1.5827 (9)	0.3844 (3)	0.0466 (9)
N1	0.23084 (11)	1.3640 (9)	0.5286 (3)	0.0296 (8)
C1	0.26289 (13)	1.1603 (10)	0.5611 (3)	0.0268 (9)
C2	0.27104 (14)	1.0662 (10)	0.6529 (3)	0.0308 (9)
H2	0.2540	1.1363	0.7041	0.037*
C3	0.30516 (14)	0.8649 (10)	0.6680 (3)	0.0344 (10)
H3	0.3119	0.7975	0.7304	0.041*
C4	0.32926 (12)	0.7631 (10)	0.5915 (4)	0.0320 (9)
C5	0.32217 (13)	0.8575 (10)	0.4997 (3)	0.0323 (9)
H5	0.3396	0.7889	0.4489	0.039*
C6	0.28839 (13)	1.0576 (10)	0.4855 (3)	0.0291 (9)
C7	0.27201 (14)	1.2069 (11)	0.4003 (3)	0.0320 (9)
C8	0.23410 (14)	1.4111 (11)	0.4335 (4)	0.0348 (10)
C9	0.19819 (13)	1.5140 (9)	0.5867 (4)	0.0323 (9)
H9A	0.1905	1.7172	0.5578	0.039*
H9B	0.2099	1.5561	0.6505	0.039*
C10	0.15888 (13)	1.3173 (10)	0.5963 (4)	0.0371 (10)
H10	0.1456	1.2464	0.5398	0.044*
C11	0.14177 (16)	1.2374 (14)	0.6771 (5)	0.0514 (14)
H11A	0.1542	1.3042	0.7349	0.062*
H11B	0.1169	1.1123	0.6779	0.062*
F2	0.38964 (10)	0.3522 (8)	0.3790 (3)	0.0540 (9)
O3	0.46219 (11)	−0.2464 (9)	0.6830 (3)	0.0463 (9)
O4	0.53563 (12)	−0.6362 (10)	0.6272 (3)	0.0541 (10)
N2	0.52058 (11)	−0.4257 (8)	0.4808 (3)	0.0313 (8)
C12	0.48881 (13)	−0.2282 (9)	0.4430 (3)	0.0255 (8)
C13	0.48270 (14)	−0.1402 (10)	0.3493 (3)	0.0321 (9)
H13	0.5010	−0.2114	0.3003	0.039*
C14	0.44864 (15)	0.0568 (10)	0.3302 (4)	0.0373 (10)
H14	0.4433	0.1198	0.2667	0.045*
C15	0.42247 (13)	0.1622 (10)	0.4021 (4)	0.0353 (10)
C16	0.42799 (13)	0.0785 (10)	0.4950 (4)	0.0343 (10)
H16	0.4096	0.1516	0.5435	0.041*
C17	0.46198 (13)	−0.1195 (10)	0.5149 (3)	0.0320 (9)
C18	0.47587 (13)	−0.2635 (10)	0.6037 (4)	0.0325 (10)
C19	0.51490 (15)	−0.4685 (11)	0.5751 (3)	0.0361 (10)
C20	0.55462 (13)	−0.5753 (10)	0.4267 (4)	0.0351 (10)
H20A	0.5436	−0.6369	0.3637	0.042*
H20B	0.5636	−0.7680	0.4600	0.042*
C21	0.59237 (14)	−0.3680 (10)	0.4134 (4)	0.0377 (11)
H21	0.6048	−0.2783	0.4683	0.045*
C22	0.60947 (17)	−0.3015 (16)	0.3314 (5)	0.0569 (16)
H22A	0.5979	−0.3870	0.2749	0.068*
H22B	0.6335	−0.1677	0.3283	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0423 (15)	0.0477 (15)	0.0515 (19)	0.0148 (12)	−0.0090 (14)	0.0057 (13)
O1	0.055 (2)	0.079 (3)	0.022 (2)	0.018 (2)	0.0040 (16)	0.0009 (17)
O2	0.050 (2)	0.056 (2)	0.033 (2)	0.0138 (17)	−0.0089 (17)	0.0035 (16)
N1	0.0287 (16)	0.0353 (18)	0.025 (2)	0.0031 (14)	0.0008 (14)	−0.0018 (14)
C1	0.0263 (19)	0.0320 (19)	0.022 (2)	−0.0063 (15)	−0.0031 (16)	−0.0022 (16)
C2	0.031 (2)	0.0341 (19)	0.027 (2)	−0.0034 (16)	0.0029 (17)	−0.0009 (17)
C3	0.037 (2)	0.036 (2)	0.030 (3)	−0.0063 (17)	−0.0061 (19)	0.0079 (18)
C4	0.0248 (19)	0.038 (2)	0.033 (3)	0.0034 (16)	−0.0020 (18)	0.0000 (18)
C5	0.031 (2)	0.0353 (19)	0.031 (2)	−0.0015 (16)	0.0010 (18)	0.0005 (17)
C6	0.0294 (19)	0.0333 (19)	0.024 (2)	−0.0012 (16)	0.0004 (17)	−0.0032 (16)
C7	0.035 (2)	0.040 (2)	0.021 (2)	0.0041 (17)	−0.0011 (19)	−0.0005 (18)
C8	0.035 (2)	0.042 (2)	0.028 (2)	0.0022 (18)	−0.0030 (18)	0.0015 (18)
C9	0.0276 (19)	0.0323 (19)	0.037 (3)	0.0016 (16)	0.0012 (18)	−0.0080 (18)
C10	0.0266 (19)	0.037 (2)	0.047 (3)	0.0012 (16)	−0.004 (2)	−0.007 (2)
C11	0.035 (3)	0.062 (3)	0.057 (4)	−0.006 (2)	0.015 (3)	0.000 (3)
F2	0.0416 (15)	0.0552 (17)	0.065 (2)	0.0140 (13)	−0.0024 (16)	0.0120 (16)
O3	0.043 (2)	0.071 (2)	0.0246 (19)	−0.0072 (17)	0.0022 (15)	−0.0020 (16)
O4	0.047 (2)	0.065 (2)	0.050 (3)	0.0056 (18)	−0.0079 (18)	0.020 (2)
N2	0.0299 (17)	0.0325 (17)	0.031 (2)	0.0008 (14)	−0.0008 (15)	0.0043 (15)
C12	0.0266 (19)	0.0279 (18)	0.022 (2)	−0.0018 (15)	0.0007 (16)	0.0006 (14)
C13	0.033 (2)	0.0325 (19)	0.031 (2)	−0.0047 (16)	0.0009 (18)	0.0009 (18)
C14	0.038 (2)	0.039 (2)	0.035 (2)	−0.0023 (18)	−0.001 (2)	0.0113 (19)
C15	0.026 (2)	0.038 (2)	0.042 (3)	−0.0021 (16)	−0.0081 (19)	0.005 (2)
C16	0.0306 (19)	0.0346 (19)	0.038 (3)	−0.0020 (17)	0.0015 (19)	−0.0027 (17)
C17	0.031 (2)	0.0333 (19)	0.031 (2)	−0.0041 (16)	0.0012 (18)	−0.0031 (17)
C18	0.029 (2)	0.044 (2)	0.025 (2)	−0.0069 (16)	−0.0004 (19)	0.0019 (18)
C19	0.037 (2)	0.043 (2)	0.029 (2)	−0.0033 (18)	−0.0045 (17)	0.0037 (19)
C20	0.031 (2)	0.0313 (19)	0.043 (3)	0.0017 (16)	0.0002 (19)	−0.0058 (18)
C21	0.027 (2)	0.033 (2)	0.053 (3)	0.0015 (17)	−0.003 (2)	−0.003 (2)
C22	0.039 (3)	0.068 (4)	0.063 (4)	−0.009 (2)	0.009 (3)	−0.005 (3)

Geometric parameters (Å, º) top

F1—C4	1.360 (5)	F2—C15	1.355 (5)
O1—C7	1.212 (6)	O3—C18	1.202 (6)
O2—C8	1.213 (6)	O4—C19	1.217 (6)
N1—C8	1.362 (6)	N2—C19	1.356 (6)
N1—C1	1.411 (5)	N2—C12	1.414 (5)
N1—C9	1.463 (5)	N2—C20	1.464 (6)
C1—C2	1.380 (6)	C12—C13	1.388 (7)
C1—C6	1.406 (6)	C12—C17	1.400 (6)
C2—C3	1.394 (6)	C13—C14	1.391 (6)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.389 (7)	C14—C15	1.383 (7)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.375 (7)	C15—C16	1.370 (7)
C5—C6	1.381 (6)	C16—C17	1.394 (6)
C5—H5	0.9500	C16—H16	0.9500
C6—C7	1.456 (6)	C17—C18	1.463 (7)
C7—C8	1.552 (6)	C18—C19	1.564 (6)
C9—C10	1.504 (6)	C20—C21	1.496 (6)
C9—H9A	0.9900	C20—H20A	0.9900
C9—H9B	0.9900	C20—H20B	0.9900
C10—C11	1.306 (8)	C21—C22	1.307 (8)
C10—H10	0.9500	C21—H21	0.9500
C11—H11A	0.9500	C22—H22A	0.9500
C11—H11B	0.9500	C22—H22B	0.9500

C8—N1—C1	110.9 (4)	C19—N2—C12	110.9 (4)
C8—N1—C9	122.7 (4)	C19—N2—C20	123.4 (4)
C1—N1—C9	126.4 (4)	C12—N2—C20	125.7 (4)
C2—C1—C6	120.9 (4)	C13—C12—C17	121.1 (4)
C2—C1—N1	128.2 (4)	C13—C12—N2	128.2 (4)
C6—C1—N1	110.9 (4)	C17—C12—N2	110.7 (4)
C1—C2—C3	117.9 (4)	C12—C13—C14	117.1 (4)
C1—C2—H2	121.1	C12—C13—H13	121.4
C3—C2—H2	121.1	C14—C13—H13	121.4
C4—C3—C2	119.8 (4)	C15—C14—C13	121.0 (5)
C4—C3—H3	120.1	C15—C14—H14	119.5
C2—C3—H3	120.1	C13—C14—H14	119.5
F1—C4—C5	118.5 (4)	F2—C15—C16	118.9 (4)
F1—C4—C3	118.0 (4)	F2—C15—C14	118.3 (5)
C5—C4—C3	123.4 (4)	C16—C15—C14	122.7 (4)
C4—C5—C6	116.4 (4)	C15—C16—C17	116.7 (4)
C4—C5—H5	121.8	C15—C16—H16	121.7
C6—C5—H5	121.8	C17—C16—H16	121.7
C5—C6—C1	121.6 (4)	C16—C17—C12	121.4 (4)
C5—C6—C7	131.7 (4)	C16—C17—C18	131.1 (4)
C1—C6—C7	106.7 (4)	C12—C17—C18	107.4 (4)
O1—C7—C6	130.7 (4)	O3—C18—C17	131.6 (4)
O1—C7—C8	123.6 (4)	O3—C18—C19	123.8 (4)
C6—C7—C8	105.7 (4)	C17—C18—C19	104.5 (4)
O2—C8—N1	127.6 (5)	O4—C19—N2	126.9 (5)
O2—C8—C7	126.6 (5)	O4—C19—C18	126.7 (5)
N1—C8—C7	105.8 (4)	N2—C19—C18	106.3 (4)
N1—C9—C10	112.7 (3)	N2—C20—C21	113.0 (3)
N1—C9—H9A	109.1	N2—C20—H20A	109.0
C10—C9—H9A	109.1	C21—C20—H20A	109.0
N1—C9—H9B	109.1	N2—C20—H20B	109.0
C10—C9—H9B	109.1	C21—C20—H20B	109.0
H9A—C9—H9B	107.8	H20A—C20—H20B	107.8
C11—C10—C9	124.5 (5)	C22—C21—C20	124.6 (5)
C11—C10—H10	117.8	C22—C21—H21	117.7
C9—C10—H10	117.8	C20—C21—H21	117.7
C10—C11—H11A	120.0	C21—C22—H22A	120.0
C10—C11—H11B	120.0	C21—C22—H22B	120.0
H11A—C11—H11B	120.0	H22A—C22—H22B	120.0

C8—N1—C1—C2	177.3 (4)	C19—N2—C12—C13	−177.0 (4)
C9—N1—C1—C2	−1.9 (7)	C20—N2—C12—C13	1.2 (7)
C8—N1—C1—C6	−1.5 (5)	C19—N2—C12—C17	3.3 (5)
C9—N1—C1—C6	179.3 (4)	C20—N2—C12—C17	−178.5 (4)
C6—C1—C2—C3	−0.4 (6)	C17—C12—C13—C14	−0.7 (6)
N1—C1—C2—C3	−179.1 (4)	N2—C12—C13—C14	179.6 (4)
C1—C2—C3—C4	−0.8 (6)	C12—C13—C14—C15	0.8 (6)
C2—C3—C4—F1	−179.8 (4)	C13—C14—C15—F2	−179.6 (4)
C2—C3—C4—C5	1.9 (7)	C13—C14—C15—C16	−0.7 (7)
F1—C4—C5—C6	−179.9 (4)	F2—C15—C16—C17	179.4 (4)
C3—C4—C5—C6	−1.7 (6)	C14—C15—C16—C17	0.5 (6)
C4—C5—C6—C1	0.4 (6)	C15—C16—C17—C12	−0.5 (6)
C4—C5—C6—C7	178.9 (4)	C15—C16—C17—C18	−177.0 (4)
C2—C1—C6—C5	0.6 (6)	C13—C12—C17—C16	0.6 (6)
N1—C1—C6—C5	179.5 (4)	N2—C12—C17—C16	−179.7 (4)
C2—C1—C6—C7	−178.2 (4)	C13—C12—C17—C18	177.9 (4)
N1—C1—C6—C7	0.7 (5)	N2—C12—C17—C18	−2.4 (5)
C5—C6—C7—O1	0.8 (9)	C16—C17—C18—O3	−1.3 (8)
C1—C6—C7—O1	179.4 (5)	C12—C17—C18—O3	−178.2 (5)
C5—C6—C7—C8	−178.4 (4)	C16—C17—C18—C19	177.7 (4)
C1—C6—C7—C8	0.3 (5)	C12—C17—C18—C19	0.8 (4)
C1—N1—C8—O2	−176.7 (5)	C12—N2—C19—O4	176.5 (5)
C9—N1—C8—O2	2.5 (8)	C20—N2—C19—O4	−1.8 (7)
C1—N1—C8—C7	1.6 (5)	C12—N2—C19—C18	−2.6 (5)
C9—N1—C8—C7	−179.2 (4)	C20—N2—C19—C18	179.1 (4)
O1—C7—C8—O2	−2.1 (8)	O3—C18—C19—O4	1.1 (8)
C6—C7—C8—O2	177.1 (5)	C17—C18—C19—O4	−178.0 (5)
O1—C7—C8—N1	179.6 (5)	O3—C18—C19—N2	−179.8 (4)
C6—C7—C8—N1	−1.1 (5)	C17—C18—C19—N2	1.1 (5)
C8—N1—C9—C10	91.9 (5)	C19—N2—C20—C21	−97.0 (5)
C1—N1—C9—C10	−89.0 (5)	C12—N2—C20—C21	85.0 (5)
N1—C9—C10—C11	125.9 (5)	N2—C20—C21—C22	−126.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F2	0.95	2.64	3.477 (6)	148
C9—H9B···O1ⁱ	0.99	2.45	3.408 (7)	163
C16—H16···F1	0.95	2.50	3.353 (5)	150

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

Acknowledgements

The support of NSF-MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

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