Crystal structure of the possible sulindac impurity 2-(5-fluoro-2-methyl-1H-inden-3-yl)aceto­nitrile

Yun-Deng, W.; Hui, W.; Yun, X.; Jie, N.; Jian, L.; Hui, Z.; Xiang-Yang, X.; Jun, X.

doi:10.1107/S2056989025002622

research communications

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ISSN: 2056-9890

Volume 81| Part 4| April 2025| Pages 341-344

https://doi.org/10.1107/S2056989025002622

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Crystal structure of the possible sulindac impurity 2-(5-fluoro-2-methyl-1H-inden-3-yl)acetonitrile

Wu Yun-Deng,^a ^* Wan Hui,^a Xia Yun,^a Ni Jie,^a Li Jian,^a Zhang Hui,^a Xu Xiang-Yang ^a and Xie Jun ^a

^aTechnique Center, Jinling Pharmaceutical Company Limited, 58 Xingang Road Qixia, district, Nanjing, Jiangsu 210046, People's Republic of China
^*Correspondence e-mail: 2351897844@qq.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 12 January 2025; accepted 22 March 2025; online 27 March 2025)

The title compound,C₁₂H₁₀FN, was identified as a possible critical degradation impurity of sulindac, a therapeutic COX-2 inhibitor for rheumatoid arthritis. Single-crystal X-ray analysis revealed two conformationally slightly different molecules in the asymmetric unit (Z′ = 2), each containing an indene ring system. In the crystal structure, [100] chains formed through C—H⋯N interactions are connected into a tri-periodic supramolecular structure by further C—H⋯F and C—H⋯π interactions through P2₁/n symmetry operations.

Keywords: sulindac; impurity; 2-(5-fluoro-2-methyl-1H-inden-3-yl)acetonitrile; synthesis; crystal structure.

CCDC reference: 2219596

1. Chemical context

Sulindac {systematic name [(Z)-2-methyl-1-[(4-methylsulfinylphenyl)methylene]-5-fluoro-1H-inden-3-acetic acid]} is a nonsteroidal anti-inflammatory drug (NSAID) that exhibits selective cyclooxygenase-2 (COX-2) inhibitory activity, effectively suppressing COX-2 overexpression through competitive inhibition. It is applied for clinical management of rheumatoid arthritis and degenerative joint disorders (Boolbol, 1996 ).

While impurity profiling represents a critical component of pharmaceutical development, the present investigation focuses on the characterization of a key process-related impurity compound in sulindac synthesis, namely 2-(5-fluoro-2-methyl-1H-inden-3-yl)acetonitrile (1). Based on single-crystal X-ray diffraction analysis, we have now unambiguously determined its configuration, representing novel structural data in pharmaceutical crystallography and report the results here.

2. Structural commentary

The asymmetric unit of (1) comprises two molecules and is illustrated in Fig. 1a; an overlay plot of the two molecules (one of which is inverted relative to the other) is shown in Fig. 1b. The root-mean-square-deviation between the two molecules is only 0.009 Å, with d_max of 0.020 Å between N1 and N2. The angles C7—C10—C11 and C19—C22—C23 are 112.47 (10) and 112.65 (10)°, respectively (Fig. 2a), and the torsion angles between the cyanide group and its corresponding indene ring plane is 64.09 (16) and 64.72 (14)° in the two independent molecules (Fig. 2b). The bond lengths in the two molecules are all within normal range.

Figure 1
(a) The asymmetric unit of (1) with displacement ellipsoids drawn at the 50% probability level; (b) overlay plot of the two independent molecules.

Figure 2
(a) The angle between the cyanide group and adjacent atoms in each of the two independent molecules; (b) the cyanide group and its dihedral angle with the corresponding indene ring plane in each of the two independent molecules.

3. Supramolecular features

As shown in Fig. 3, the methylene groups (C10, C22) attached to the —C≡N moiety act as hydrogen-bond donors to the cyanide N atoms (N2, N1) of adjacent molecules. These interactions (Table 1) link the molecules into an infinite supramolecular chain extending parallel to [100]. Other interactions shown in Fig. 3 include C—H⋯F interactions (Table 1) as well as C—H⋯π interactions [C22–H22A⋯π (2.780 Å) and C12—H12B⋯π (2.958 Å)], which connect the molecules into a tri-periodic supramolecular structure. A packing plot of (1) is shown in Fig. 4.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯N2ⁱ	0.99	2.65	3.3978 (18)	132
C22—H22A⋯N1ⁱⁱ	0.99	2.61	3.4010 (16)	137
C24—H24C⋯F2ⁱⁱⁱ	0.98	2.76	3.227 (2)	110
C24—H24B⋯F2ⁱⁱⁱ	0.98	2.83	3.227 (2)	105
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
Intermolecular interactions (C—H⋯N, C—H⋯F and C—H⋯π) between adjacent molecules shown as red dashed lines. Color codes: C (gray), N (blue), F(green) and H (white).

Figure 4
Packing plot of (1) approximately along [100]. C—H⋯N and C—H⋯F interactions are shown as red dotted lines.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 2024.1.0; Groom et al., 2016 ) was conducted using the keyword methylindene, which retrieved eleven relevant entries: BANNUA (Tsuno et al., 2003 ), CIRMIA (Santi et al., 2007 ), DOBVIZ (Biali & Rappoport, 1986 ), FUNPAG (Xu et al., 2010 ), HEXRAD (Bonifaci et al., 1994 ), ICEXOD (Halterman et al., 2000 ), SUZYER (Stenzel et al., 2001 ), MIJKIZ (Enders et al., 2002 ), NOYTOK (Brase et al., 1998 ), XAWFEG (Shapiro et al., 1999 ), and RESZEU (Herrmann et al., 1997 ). The primary distinction among these compounds lies in the substitution patterns of the methyl group on the indene ring. Notably, an indene derivative bearing both fluorine and cyano substituents has been obtained and reported exclusively in the present work. This comparative analysis underscores the structural novelty of the title compound, particularly its unique combination of hydrogen-bonding patterns (C—H⋯N and C—H⋯F).

5. Synthesis and crystallization

Compound (1) was prepared according to a literature method (Xu et al., 2020 ; Dai et al., 2009 ). The preparation procedure is schematically shown in Fig. 5. A 100 ml round-bottomed flask equipped with a magnetic stirring bar was charged with a mixture of 6-fluoro-2-methyl-2,3-dihydro-1H-inden-1-one, (2), (20.35 g, 124 mmol), cyanoacetic acid (13.65 g, 160.4 mmol), acetic acid (7.8 g, 129.9 mmol) and ammonium acetate (3.1 g, 40.2 mmol) in toluene (50 ml). The mixture was refluxed for 24 h and then cooled to room temperature. The solvent was removed in vacuo, and the residue (3) was dissolved in ethanol without further purification. The resulting solution was added to a potassium hydroxide solution (165 g, 25%_wt, w/w, 735.2 mmol) and heated to reflux for 13 h. Then, the ethanol was removed in vacuo, followed by the addition of 300 ml of water. The pH value was adjusted to 8 using concentrated hydrochloric acid, and the mixture was then extracted with dichloromethane (150 ml). The aqueous layer was collected and further adjusted to a pH value of 2 with concentrated hydrochloric acid, resulting in the precipitation of a significant amount of a yellow solid of (1). The solid was then filtered off, washed with water, and dried in air. Yield: 17.25 g, 85.2%. ¹H NMR spectrum (Varian Unity Inova 500 MHz, DMSO-d₆, ppm): δ: 7.38 (dd, 1H, J₁ = 5.55 Hz, J₂ = 7.85 Hz), 7.23 (dd, 1H, J₁ = 2.2 Hz, J₂ = 9.5 Hz), 6.94 (m, 1H), 3.87 (s, 2H), 3.35 (s, 2H), 2.13 (s, 3H). Single crystals were obtained by slow evaporation of a saturated solution of (1) in a dichloromethane–ethanol mixture (4:1, v/v) at room temperature over 20 d.

Figure 5
Synthesis scheme of the title compound (1).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms attached to carbon atoms were placed in calculated positions and constrained with AFIX instructions.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀FN
M_r	187.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	170
a, b, c (Å)	7.5248 (5), 15.1897 (10), 17.1823 (9)
β (°)	99.176 (2)
V (Å³)	1938.8 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.29 × 0.23

Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.654, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	28954, 4137, 3530
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.03
No. of reflections	4137
No. of parameters	256
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

7. Authorship contribution statement

The submitted manuscript includes contributions from eight authors. Yun-Deng Wu conceptualized and designed the research framework, conducted comprehensive data analysis, and drafted the manuscript. Yun-Deng Wu, Hui Wan, Yun Xia and Jie Ni performed the synthesis, isolation, purification, and characterization of the title compound. Jian Li, Hui Zhang, Xiangyang Xu and Jun Xie contributed to the single-crystal cultivation and associated experimental evaluations. All co-authors participated in the critical revision and final approval of the manuscript for publication.

Supporting information

CCDC reference: 2219596

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002622/wm5750sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002622/wm5750Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002622/wm5750Isup3.cml

checkCIF report

Computing details top

2-(5-Fluoro-2-methyl-1H-inden-3-yl)acetonitrile top

Crystal data top

C₁₂H₁₀FN	F(000) = 784
M_r = 187.21	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.5248 (5) Å	Cell parameters from 9932 reflections
b = 15.1897 (10) Å	θ = 2.7–26.7°
c = 17.1823 (9) Å	µ = 0.09 mm⁻¹
β = 99.176 (2)°	T = 170 K
V = 1938.8 (2) Å³	Block, colourless
Z = 8	0.42 × 0.29 × 0.23 mm

Data collection top

Bruker SMART APEX CCD area detector diffractometer	4137 independent reflections
Radiation source: sealed tube	3530 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 8 pixels mm^-1	θ_max = 26.8°, θ_min = 2.4°
ω and φ scans	h = −9→9
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −19→19
T_min = 0.654, T_max = 0.745	l = −21→21
28954 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0464P)² + 0.5292P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.105	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.21 e Å⁻³
4137 reflections	Δρ_min = −0.21 e Å⁻³
256 parameters	Extinction correction: SHELXL (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0048 (7)
Primary atom site location: dual

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
F1	0.08006 (14)	0.18981 (6)	0.05253 (6)	0.0683 (3)
N1	0.46276 (16)	0.13422 (7)	0.35764 (7)	0.0451 (3)
C1	0.16171 (16)	0.24962 (8)	0.17953 (8)	0.0373 (3)
H1	0.142597	0.194447	0.202895	0.045*
C2	0.13519 (18)	0.26100 (9)	0.09871 (8)	0.0446 (3)
C3	0.16163 (18)	0.33907 (10)	0.06189 (8)	0.0468 (3)
H3	0.141755	0.343036	0.006001	0.056*
C4	0.21793 (17)	0.41208 (9)	0.10788 (7)	0.0403 (3)
H4	0.236765	0.466889	0.083839	0.048*
C5	0.24625 (15)	0.40411 (8)	0.18899 (7)	0.0314 (3)
C6	0.21782 (14)	0.32325 (7)	0.22468 (7)	0.0296 (2)
C7	0.25771 (15)	0.33531 (8)	0.31024 (7)	0.0308 (3)
C8	0.30813 (16)	0.41860 (8)	0.32741 (7)	0.0343 (3)
C9	0.30565 (16)	0.47028 (8)	0.25250 (7)	0.0356 (3)
H9A	0.219788	0.519996	0.249653	0.043*
H9B	0.426803	0.493474	0.248492	0.043*
C10	0.23961 (19)	0.26298 (8)	0.36817 (8)	0.0410 (3)
H10A	0.262345	0.287413	0.422263	0.049*
H10B	0.114754	0.240222	0.358457	0.049*
C11	0.36465 (16)	0.19013 (8)	0.36265 (7)	0.0340 (3)
C12	0.3611 (2)	0.46070 (10)	0.40633 (8)	0.0503 (4)
H12A	0.282934	0.511371	0.411000	0.075*
H12B	0.486549	0.480414	0.411934	0.075*
H12C	0.348725	0.417899	0.447807	0.075*
F2	0.92640 (14)	0.55350 (6)	0.40592 (5)	0.0692 (3)
N2	0.52928 (17)	0.59111 (8)	0.10051 (8)	0.0555 (3)
C13	0.83947 (16)	0.48567 (8)	0.28300 (7)	0.0366 (3)
H13	0.857248	0.539097	0.256548	0.044*
C14	0.86929 (19)	0.47951 (9)	0.36423 (8)	0.0450 (3)
C15	0.84553 (19)	0.40399 (10)	0.40560 (8)	0.0465 (3)
H15	0.868240	0.403684	0.461595	0.056*
C16	0.78762 (17)	0.32816 (9)	0.36380 (7)	0.0394 (3)
H16	0.769749	0.275137	0.390833	0.047*
C17	0.75646 (15)	0.33098 (7)	0.28246 (7)	0.0310 (3)
C18	0.78197 (14)	0.40920 (7)	0.24219 (7)	0.0292 (2)
C19	0.73809 (14)	0.39234 (7)	0.15742 (6)	0.0280 (2)
C20	0.68786 (15)	0.30797 (7)	0.14500 (7)	0.0302 (2)
C21	0.69555 (16)	0.26085 (7)	0.22262 (7)	0.0328 (3)
H21A	0.575673	0.237782	0.229008	0.039*
H21B	0.782483	0.211482	0.227027	0.039*
C22	0.75293 (16)	0.46131 (7)	0.09589 (7)	0.0336 (3)
H22A	0.877380	0.484612	0.103829	0.040*
H22B	0.729198	0.433713	0.043056	0.040*
C23	0.62711 (17)	0.53441 (8)	0.09855 (7)	0.0370 (3)
C24	0.63087 (19)	0.26147 (8)	0.06865 (8)	0.0416 (3)
H24A	0.626613	0.303465	0.025088	0.062*
H24B	0.511239	0.235723	0.068025	0.062*
H24C	0.717319	0.214674	0.062657	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0791 (7)	0.0627 (6)	0.0581 (6)	0.0011 (5)	−0.0044 (5)	−0.0283 (5)
N1	0.0494 (6)	0.0335 (6)	0.0496 (7)	0.0066 (5)	−0.0003 (5)	0.0027 (5)
C1	0.0356 (6)	0.0331 (6)	0.0431 (7)	0.0031 (5)	0.0060 (5)	−0.0015 (5)
C2	0.0405 (7)	0.0498 (8)	0.0415 (7)	0.0044 (6)	0.0007 (5)	−0.0147 (6)
C3	0.0435 (7)	0.0669 (9)	0.0291 (6)	0.0092 (6)	0.0035 (5)	0.0015 (6)
C4	0.0367 (6)	0.0489 (7)	0.0356 (6)	0.0039 (5)	0.0066 (5)	0.0114 (5)
C5	0.0265 (5)	0.0343 (6)	0.0335 (6)	0.0033 (4)	0.0055 (4)	0.0064 (5)
C6	0.0259 (5)	0.0309 (6)	0.0323 (6)	0.0046 (4)	0.0059 (4)	0.0026 (4)
C7	0.0315 (6)	0.0314 (6)	0.0306 (6)	0.0080 (4)	0.0078 (4)	0.0047 (4)
C8	0.0336 (6)	0.0342 (6)	0.0342 (6)	0.0071 (5)	0.0025 (5)	0.0010 (5)
C9	0.0348 (6)	0.0300 (6)	0.0410 (7)	0.0001 (5)	0.0034 (5)	0.0050 (5)
C10	0.0522 (8)	0.0365 (7)	0.0376 (7)	0.0112 (6)	0.0172 (6)	0.0102 (5)
C11	0.0418 (6)	0.0298 (6)	0.0284 (6)	−0.0004 (5)	−0.0001 (5)	0.0046 (4)
C12	0.0586 (9)	0.0478 (8)	0.0411 (7)	0.0075 (7)	−0.0023 (6)	−0.0091 (6)
F2	0.0937 (7)	0.0482 (5)	0.0558 (5)	0.0070 (5)	−0.0178 (5)	−0.0238 (4)
N2	0.0527 (7)	0.0394 (6)	0.0758 (9)	0.0120 (6)	0.0146 (6)	0.0182 (6)
C13	0.0369 (6)	0.0294 (6)	0.0410 (7)	0.0045 (5)	−0.0011 (5)	−0.0025 (5)
C14	0.0485 (8)	0.0396 (7)	0.0426 (7)	0.0086 (6)	−0.0061 (6)	−0.0145 (6)
C15	0.0524 (8)	0.0559 (8)	0.0294 (6)	0.0127 (6)	0.0012 (6)	−0.0034 (6)
C16	0.0413 (7)	0.0441 (7)	0.0334 (6)	0.0068 (5)	0.0079 (5)	0.0059 (5)
C17	0.0291 (5)	0.0316 (6)	0.0330 (6)	0.0046 (4)	0.0067 (4)	0.0021 (5)
C18	0.0257 (5)	0.0289 (6)	0.0325 (6)	0.0048 (4)	0.0033 (4)	0.0001 (4)
C19	0.0267 (5)	0.0268 (5)	0.0305 (6)	0.0035 (4)	0.0051 (4)	0.0015 (4)
C20	0.0302 (5)	0.0282 (6)	0.0328 (6)	0.0022 (4)	0.0066 (4)	0.0000 (4)
C21	0.0356 (6)	0.0273 (6)	0.0363 (6)	−0.0003 (4)	0.0083 (5)	0.0032 (5)
C22	0.0369 (6)	0.0295 (6)	0.0349 (6)	0.0014 (5)	0.0069 (5)	0.0043 (5)
C23	0.0374 (6)	0.0312 (6)	0.0416 (7)	−0.0018 (5)	0.0040 (5)	0.0100 (5)
C24	0.0536 (8)	0.0328 (6)	0.0378 (7)	0.0006 (5)	0.0052 (6)	−0.0049 (5)

Geometric parameters (Å, º) top

F1—C2	1.3660 (15)	F2—C14	1.3648 (15)
N1—C11	1.1375 (16)	N2—C23	1.1370 (17)
C1—H1	0.9500	C13—H13	0.9500
C1—C2	1.3820 (19)	C13—C14	1.3810 (18)
C1—C6	1.3880 (17)	C13—C18	1.3898 (16)
C2—C3	1.373 (2)	C14—C15	1.376 (2)
C3—H3	0.9500	C15—H15	0.9500
C3—C4	1.388 (2)	C15—C16	1.3903 (19)
C4—H4	0.9500	C16—H16	0.9500
C4—C5	1.3813 (17)	C16—C17	1.3804 (17)
C5—C6	1.4044 (16)	C17—C18	1.4035 (16)
C5—C9	1.4983 (17)	C17—C21	1.5006 (16)
C6—C7	1.4643 (16)	C18—C19	1.4639 (15)
C7—C8	1.3402 (17)	C19—C20	1.3434 (16)
C7—C10	1.5032 (16)	C19—C22	1.5051 (15)
C8—C9	1.5051 (16)	C20—C21	1.5065 (16)
C8—C12	1.4947 (17)	C20—C24	1.4916 (17)
C9—H9A	0.9900	C21—H21A	0.9900
C9—H9B	0.9900	C21—H21B	0.9900
C10—H10A	0.9900	C22—H22A	0.9900
C10—H10B	0.9900	C22—H22B	0.9900
C10—C11	1.4654 (17)	C22—C23	1.4646 (17)
C12—H12A	0.9800	C24—H24A	0.9800
C12—H12B	0.9800	C24—H24B	0.9800
C12—H12C	0.9800	C24—H24C	0.9800

C2—C1—H1	121.8	C14—C13—H13	121.9
C2—C1—C6	116.30 (12)	C14—C13—C18	116.15 (12)
C6—C1—H1	121.8	C18—C13—H13	121.9
F1—C2—C1	117.80 (13)	F2—C14—C13	117.48 (13)
F1—C2—C3	117.96 (12)	F2—C14—C15	118.12 (12)
C3—C2—C1	124.24 (12)	C15—C14—C13	124.40 (12)
C2—C3—H3	120.6	C14—C15—H15	120.7
C2—C3—C4	118.76 (12)	C14—C15—C16	118.66 (12)
C4—C3—H3	120.6	C16—C15—H15	120.7
C3—C4—H4	120.4	C15—C16—H16	120.5
C5—C4—C3	119.23 (12)	C17—C16—C15	119.08 (12)
C5—C4—H4	120.4	C17—C16—H16	120.5
C4—C5—C6	120.50 (12)	C16—C17—C18	120.72 (11)
C4—C5—C9	131.01 (11)	C16—C17—C21	130.98 (11)
C6—C5—C9	108.49 (10)	C18—C17—C21	108.30 (10)
C1—C6—C5	120.97 (11)	C13—C18—C17	120.99 (11)
C1—C6—C7	131.10 (11)	C13—C18—C19	130.62 (11)
C5—C6—C7	107.93 (10)	C17—C18—C19	108.40 (10)
C6—C7—C10	123.20 (11)	C18—C19—C22	123.15 (10)
C8—C7—C6	110.16 (10)	C20—C19—C18	109.75 (10)
C8—C7—C10	126.63 (11)	C20—C19—C22	127.09 (10)
C7—C8—C9	109.85 (10)	C19—C20—C21	110.04 (10)
C7—C8—C12	128.96 (12)	C19—C20—C24	128.72 (11)
C12—C8—C9	121.19 (11)	C24—C20—C21	121.24 (10)
C5—C9—C8	103.57 (9)	C17—C21—C20	103.51 (9)
C5—C9—H9A	111.0	C17—C21—H21A	111.1
C5—C9—H9B	111.0	C17—C21—H21B	111.1
C8—C9—H9A	111.0	C20—C21—H21A	111.1
C8—C9—H9B	111.0	C20—C21—H21B	111.1
H9A—C9—H9B	109.0	H21A—C21—H21B	109.0
C7—C10—H10A	109.1	C19—C22—H22A	109.1
C7—C10—H10B	109.1	C19—C22—H22B	109.1
H10A—C10—H10B	107.8	H22A—C22—H22B	107.8
C11—C10—C7	112.47 (10)	C23—C22—C19	112.65 (10)
C11—C10—H10A	109.1	C23—C22—H22A	109.1
C11—C10—H10B	109.1	C23—C22—H22B	109.1
N1—C11—C10	179.06 (14)	N2—C23—C22	179.90 (19)
C8—C12—H12A	109.5	C20—C24—H24A	109.5
C8—C12—H12B	109.5	C20—C24—H24B	109.5
C8—C12—H12C	109.5	C20—C24—H24C	109.5
H12A—C12—H12B	109.5	H24A—C24—H24B	109.5
H12A—C12—H12C	109.5	H24A—C24—H24C	109.5
H12B—C12—H12C	109.5	H24B—C24—H24C	109.5

F1—C2—C3—C4	−179.90 (11)	F2—C14—C15—C16	−179.92 (12)
C1—C2—C3—C4	−0.3 (2)	C13—C14—C15—C16	0.0 (2)
C1—C6—C7—C8	179.91 (12)	C13—C18—C19—C20	−179.93 (12)
C1—C6—C7—C10	−1.04 (19)	C13—C18—C19—C22	1.14 (18)
C2—C1—C6—C5	−0.34 (17)	C14—C13—C18—C17	0.04 (17)
C2—C1—C6—C7	179.76 (11)	C14—C13—C18—C19	179.88 (11)
C2—C3—C4—C5	0.22 (19)	C14—C15—C16—C17	0.2 (2)
C3—C4—C5—C6	−0.25 (18)	C15—C16—C17—C18	−0.24 (18)
C3—C4—C5—C9	−179.87 (12)	C15—C16—C17—C21	179.58 (12)
C4—C5—C6—C1	0.32 (17)	C16—C17—C18—C13	0.13 (17)
C4—C5—C6—C7	−179.76 (10)	C16—C17—C18—C19	−179.75 (10)
C4—C5—C9—C8	179.75 (12)	C16—C17—C21—C20	179.62 (12)
C5—C6—C7—C8	0.00 (13)	C17—C18—C19—C20	−0.07 (13)
C5—C6—C7—C10	179.05 (10)	C17—C18—C19—C22	−179.00 (10)
C6—C1—C2—F1	179.96 (11)	C18—C13—C14—F2	179.80 (11)
C6—C1—C2—C3	0.3 (2)	C18—C13—C14—C15	−0.1 (2)
C6—C5—C9—C8	0.10 (12)	C18—C17—C21—C20	−0.54 (12)
C6—C7—C8—C9	0.06 (13)	C18—C19—C20—C21	−0.29 (13)
C6—C7—C8—C12	179.99 (12)	C18—C19—C20—C24	179.74 (11)
C6—C7—C10—C11	64.09 (16)	C18—C19—C22—C23	−64.72 (14)
C7—C8—C9—C5	−0.10 (13)	C19—C20—C21—C17	0.51 (12)
C8—C7—C10—C11	−117.02 (13)	C20—C19—C22—C23	116.54 (13)
C9—C5—C6—C1	−179.98 (10)	C21—C17—C18—C13	−179.73 (10)
C9—C5—C6—C7	−0.06 (12)	C21—C17—C18—C19	0.40 (12)
C10—C7—C8—C9	−178.95 (11)	C22—C19—C20—C21	178.59 (11)
C10—C7—C8—C12	1.0 (2)	C22—C19—C20—C24	−1.4 (2)
C12—C8—C9—C5	179.97 (11)	C24—C20—C21—C17	−179.52 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···N2ⁱ	0.99	2.65	3.3978 (18)	132
C22—H22A···N1ⁱⁱ	0.99	2.61	3.4010 (16)	137
C24—H24C···F2ⁱⁱⁱ	0.98	2.76	3.227 (2)	110
C24—H24B···F2ⁱⁱⁱ	0.98	2.83	3.227 (2)	105

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

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