Synthesis and crystal structure of (E)-N-[(2-bromo­phen­yl)methyl­idene]-3,5-bis­(tri­fluoro­meth­yl)aniline

Kingsley, N.B.; Doyon, T.J.; Janzen, D.E.

doi:10.1107/S2056989025007650

research communications

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ISSN: 2056-9890

Volume 81| Part 10| October 2025| Pages 916-919

https://doi.org/10.1107/S2056989025007650

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Synthesis and crystal structure of (E)-N-[(2-bromophenyl)methylidene]-3,5-bis(trifluoromethyl)aniline

Nicholas B. Kingsley,^a ^* Tyler J. Doyon ^b and Daron E. Janzen ^c

^aDepartment of Green Chemistry and Biochemistry, University of Michigan-Flint, 303 E. Kearsley St, Flint, MI 48502, USA, ^bDepartment of Chemistry and Biochemistry, University of Wisconsin-Eau Claire, Phillips Science Hall, 101 Roosevelt Ave., Eau Claire, WI 54701, USA, and ^cDept. of Chemistry & Biochemistry, St. Catherine University, 2004 Randolph Avenue, St. Paul, MN 55105, USA
^*Correspondence e-mail: [email protected]

Edited by G. Ferrence, Illinois State University, USA (Received 9 June 2025; accepted 27 August 2025; online 5 September 2025)

The title compound C₁₅H₈BrF₆N, was prepared by a condensation reaction of 2-bromobenzaldehyde and 3,5-bis(trifluoromethyl)aniline in the presence of anhydrous magnesium sulfate. The compound readily crystallizes from a concentrated hexanes solution in high yield. The imine bond is nearly planar with the 2-bromophenyl group, while the N-(3,5-bis(trifluoromethyl)phenyl moiety is significantly twisted from the imine group [49.61 (5)°]. The crystal packing involves short intermolecular C—H⋯Br contacts linking zigzag ribbons flanked by fluorous layers.

Keywords: crystal structure; trifluoromethyl; aryl imine ligands.

CCDC reference: 2483197

1. Chemical context

Arylimine-type ligands have increasingly been used as ancillary ligands for a variety of metal complexes. (Dostál et al., 2011 ; Hejda et al., 2012 ; Hejda et al., 2013 , 2017 ; Joseph et al., 2018 ; Kingsley et al., 2016 ; Kořenková et al., 2016 ; Kremláček et al., 2018 ; Mungwe et al., 2011 ; Novák et al., 2014 , 2016 ; Šimon et al., 2013 ; Urbanová et al., 2013 , 2014 ; Vrána et al., 2013 ; Zhao et al., 2010 , 2011 ) Synthesis of these ligands is typically performed with alkyl-substituted anilines or alkyl amines reacting with 2-brombenzaldehyde. There is interest in modifying the electronic structure of the ligands but this has been limited to substitutions on the aromatic ring of the benzaldehyde starting material. (Chen et al., 2004 ; Li et al., 2019 ). Our group is interested in developing arylimine ligands with electron-withdrawing groups on the aromatic ring of the N-imine portion of the ligand. Herein we report the synthesis and crystal structure of (E)-N-[(2-bromophenyl)methylidene]-3,5-bis(trifluoromethyl)aniline (I).

2. Structural commentary

A displacement ellipsoid plot of compound I is shown in Fig. 1. The imine bond length C7—N1 [1.280 (4) Å] and C7—N1—C8 bond angle [119.1 (2)°] are consistent with atom N1 being sp² hybridized. The imine bond is oriented nearly coplanar with the C1–C6 phenyl ring [angle between least squares planes formed by C1–C6 and N1,C7,C1 = 5.9 (3)°]. Torsion angles (Table 1) near the imine bond demonstrate this as well as the twist of the C8–C13 phenyl ring relative to the imine bond plane formed by C8/N1/C7 is 42.0 (3)°). The angle between the least-squares planes formed by C1–C8/N1/Br1 and C8–C15/N1 of 49.61 (5)° is consistent with steric limitations influenced by atom positions of H7 and H9. Short intramolecular interactions involving C—H bonds with acceptors are also present. A short C7—H7⋯Br1 contact (2.82 Å, length − vdW radii sums = −0.244 Å) and another contact involving C6—H6⋯N1 (2.52 Å, length − vdW sums = −0.342 Å) help define the observed conformation of I (Table 2).

Table 1
Selected torsion angles (°)

C2—C1—C7—N1	174.5 (2)	C7—N1—C8—C13	139.5 (3)
C6—C1—C7—N1	−5.9 (4)	C8—N1—C7—C1	176.7 (2)
C7—N1—C8—C9	−43.7 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F2Aⁱ	0.95	2.46	3.365 (7)	160
C3—H3⋯F7Aⁱ	0.95	2.25	3.063 (7)	143
C4—H4⋯F1Aⁱⁱ	0.95	2.54	3.411 (6)	153
C4—H4⋯F9Aⁱⁱ	0.95	2.36	3.152 (9)	140
C6—H6⋯N1	0.95	2.52	2.828 (4)	99
C7—H7⋯Br1	0.95	2.82	3.233 (3)	108
C13—H13⋯Br1ⁱⁱⁱ	0.95	2.97	3.851 (3)	155
Symmetry codes: (i) ; (ii) ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of I. Only one of the three CF₃ disorder model conformations shown. Thermal displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

While no conventional hydrogen-bonding interactions are present, several short C—H⋯F contacts with fluorine atoms of the disordered CF₃ group and hydrogen atoms H3 and H4 are present (Table 2, Fig. 2). A contact involving C13—H13⋯Br1 is also present, forming zigzag infinite ribbons of molecules along (001) as shown in Fig. 3. The packing diagram of I (Fig. 4) demonstrates how the CF₃ groups associate in fluorous layers in the bc plane at x = 0.5 with the ribbons of C—H⋯Br interactions between the CF₃-rich layers. Weak π–π dimer intermolecular interactions between a neighboring brominated phenyl ring (less electron poor) and the trifluoromethylated phenyl ring (more electron poor) are evident, with a 3.730 (2) Å centroid-to-centroid distance.

Figure 2
Intermolecular interactions of I including centroids of the weak π–π dimer.

Figure 3
Packing diagram of I in a view along the a-axis direction. C—H⋯Br interactions are shown as dashed lines.

Figure 4
Packing diagram of I in a view along the c-axis direction. C—H⋯Br interactions are shown as dashed lines.

4. Database survey

A recent search in the CSD (version 6.00, last update April 2025; Groom et al., 2016 ) using ConQuest (Bruno et al., 2002 ) revealed the most closely related structures to I include a single meta-fluoro substitution (in place of a bis-trifluoromethyl-substituted phenyl ring). The structure of 1-(2-bromophenyl)-N-(3-fluorophenyl)methanimine (FOBLUF; Kaur & Choudhury, 2014 ) demonstrates similar intramolecular features to I, including the imine C—H⋯Br and phenyl ortho C—H⋯N distances (2.76 and 2.53 Å, respectively) as well as the twist angle between phenyl least-squares planes [40.97 (8)°]. Another related structure reported with a single electron-withdrawing meta substituent on the N-imine ring is N-(2-iodobenzylidene)-3-nitroaniline (MOPPOW; Wardell et al., 2002 ). Similar to I, this mono-nitro-substituted structure also demonstrates analogous phenyl ortho C—H⋯N distances (2.58 Å) but the twist angle between phenyl least-squares planes (64.2°) is significantly different and may be related to the presence of the intermolecular halogen bonding that is present (I⋯N distance = 3.487 Å, C8—I1⋯N1 = 160.1°). The structure of 2-({[3,5-bis(trifluoromethyl)phenyl]imino}methyl)-5-(dimethylamino)phenol (BIDCUQ; Zhao et al., 2023 ) possesses the same 3,5-bis(trifluoromethyl)phenyl moiety as I, but the imine-linked 2-hydroxy phenyl group engages an intramolecular interaction (O1—H1⋯N2 = 1.84 Å), inducing a coplanar orientation of the phenyl rings. Also, the CF₃ groups of BIDCUQ associate in fluorous layers (similar to I) between infinite single-distance π–π stacked aromatic regions (3.47 Å).

5. Synthesis and crystallization

2-Bromobenzaldehyde (4.50 g, 24.3 mmol) was stirred in hexanes (250 mL) in the presence of anhydrous MgSO₄ (1.0 g). 3,5-Bis(trifluoromethyl)aniline (5.575 g, 24.3 mmol) was slowly added and the solution was allowed to stir for 2 h. MgSO₄ was then removed via vacuum filtration and the filtrate cooled to 243 K for 48 h. The yellow precipitate was collected via vacuum filtration and purified through recrystallization from hexanes. The resulting material was light-yellow and crystalline. Yield: 7.62 g, 79%. ¹H NMR (CDCl₃, 400 MHz): δ 8.86 (s, 1H, CH=N), 8.22 (dd, ³J_HH = 7.7 Hz, ⁴J_HH = 1.9 Hz 1H, aryl H6), 7.76 (br s, 1H, aryl H11), 7.66 (dd, ³J_HH = 7.7 Hz, ⁴J_HH = 1.9 Hz 1H, aryl H3), 7.63 (br s, 2H, aryl H9, H13), 7.44 (m, 1H, aryl H5), 7.38 (m, 1H, aryl H4). ¹³C NMR {¹H} (CDCl₃, 100 MHz): δ 162.30 (s, C7), 153.15 (s, aryl C8), 133.81 (s, aryl C1), 133.62 (s, aryl C4), 133.58 (s, aryl C3), 132.79 (q, ²J_CF = 33.6 Hz, aryl C10, C12), 129.41 (s, aryl C6), 128.05 (s, aryl C5), 126.71 (s, aryl C2), 123.32 (q, ¹J_CF = 272.8 Hz, C14, C15), 121.40 (q, ³J_CF = 2.7 Hz, aryl C9, C13), 119.71 (sept, ³J_CF = 3.8 Hz, aryl C11). M.p.: 361–363 K. X-ray quality crystals were grown from a concentrated solution in warm hexanes followed by slow cooling to room temperature and storage at 243 K for 96 h.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were refined with riding coordinates with fixed U_iso(H) at 1.2 times of the riding C atom. Several restraints and constraints were used to model disorder in one of the CF₃ groups. Distance restraints were employed for C14—F1A, C14—F2A, C14—F3A, C14—F4A, C14—F5A, C14—F6A, C14—F7A, C14—F8A, and C14—F9A with sigma of 0.02; F1A—F2A, F2A—F3A, F3A—F1A, F4A—F5A, F5A—F6A, F6A—F4A, F7A—F8A, F8A—F9A, and F9A—F7A with sigma of 0.04; and C10—F1A, C10—F2A, C10—F3A, C10—F4A, C10—F5A, C10—F6A, C10—F7A, C10—F8A, and C10—F9A with sigma of 0.1. U_aniso restraints were applied to C10, C14, F1A, F2A, F3A, F4A, F5A, F6A, F7A, F8A, and F9A within 2 Å with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2 Å. Rigid body (RIGU) restraints were applied to C10, C14, F1A, F2A, F3A, F4A, F5A, F6A, F7A, F8A, F9A with sigma for 1–2 distances of 0.004 and sigma for 1–3 distances of 0.004. The three orientations of the CF₃ group were fixed at sof values of 0.37 (F1A, F2A, F3A), 0.38 (F4A, F5A, F6A), and 0.25 (F7A, F8A, F9A).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₅H₈BrF₆N
M_r	396.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.261 (2), 7.7224 (12), 14.176 (2)
β (°)	93.394 (2)
V (Å³)	1449.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.90
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.575, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	23866, 5193, 3166
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.766

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.137, 1.06
No. of reflections	5193
No. of parameters	217
No. of restraints	189
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.68
Computer programs: APEX2 and SAINT (Bruker 2017 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2019/2 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2483197

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025007650/ej2015sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025007650/ej2015Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025007650/ej2015Isup3.cml

checkCIF report

Computing details top

(E)-N-[(2-Bromophenyl)methylidene]-3,5-bis(trifluoromethyl)aniline top

Crystal data top

C₁₅H₈BrF₆N	F(000) = 776
M_r = 396.13	D_x = 1.816 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.261 (2) Å	Cell parameters from 6800 reflections
b = 7.7224 (12) Å	θ = 2.9–31.3°
c = 14.176 (2) Å	µ = 2.90 mm⁻¹
β = 93.394 (2)°	T = 100 K
V = 1449.2 (4) Å³	Irregular brick, yellow
Z = 4	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	3166 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.053
φ and ω scans	θ_max = 33.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→19
T_min = 0.575, T_max = 0.747	k = −11→11
23866 measured reflections	l = −21→21
5193 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.137	w = 1/[σ²(F_o²) + (0.0521P)² + 1.1524P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
5193 reflections	Δρ_max = 0.89 e Å⁻³
217 parameters	Δρ_min = −0.68 e Å⁻³
189 restraints

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	Occ. (<1)
Br1	−0.04663 (2)	0.75027 (4)	−0.00485 (2)	0.03627 (10)
N1	0.05952 (17)	0.5457 (3)	0.28171 (18)	0.0335 (5)
C1	−0.08432 (19)	0.5863 (3)	0.1738 (2)	0.0288 (5)
C2	−0.12674 (19)	0.6484 (3)	0.08793 (19)	0.0293 (5)
C3	−0.2302 (2)	0.6421 (4)	0.0656 (2)	0.0363 (6)
H3	−0.257428	0.686307	0.006931	0.044*
C4	−0.2931 (2)	0.5709 (4)	0.1295 (2)	0.0409 (7)
H4	−0.363907	0.565656	0.114812	0.049*
C5	−0.2530 (2)	0.5069 (4)	0.2152 (3)	0.0415 (7)
H5	−0.296289	0.457257	0.258939	0.050*
C6	−0.1504 (2)	0.5155 (3)	0.2369 (2)	0.0349 (6)
H6	−0.123955	0.472455	0.296075	0.042*
C7	0.02492 (19)	0.5917 (3)	0.1993 (2)	0.0289 (5)
H7	0.070172	0.629651	0.154103	0.035*
C8	0.16523 (19)	0.5438 (3)	0.3021 (2)	0.0297 (5)
C9	0.23302 (19)	0.4776 (3)	0.2399 (2)	0.0288 (5)
H9	0.209397	0.434980	0.179772	0.035*
C10	0.33567 (19)	0.4746 (3)	0.26672 (19)	0.0290 (5)
C11	0.3715 (2)	0.5378 (3)	0.35389 (19)	0.0317 (5)
H11	0.441795	0.536850	0.371320	0.038*
C12	0.3035 (2)	0.6022 (4)	0.41483 (19)	0.0346 (6)
C13	0.2009 (2)	0.6037 (4)	0.3903 (2)	0.0350 (6)
H13	0.154798	0.645660	0.433828	0.042*
C14	0.4097 (2)	0.4018 (4)	0.2017 (2)	0.0355 (6)
F1A	0.4543 (5)	0.5294 (7)	0.1579 (5)	0.0421 (12)*	0.37
F2A	0.3653 (4)	0.2903 (8)	0.1396 (4)	0.0366 (12)*	0.37
F3A	0.4837 (4)	0.3151 (8)	0.2533 (3)	0.0359 (11)*	0.37
F4A	0.4225 (4)	0.4969 (7)	0.1218 (4)	0.0469 (12)*	0.38
F5A	0.3808 (4)	0.2437 (6)	0.1641 (4)	0.0375 (11)*	0.38
F6A	0.5052 (4)	0.3815 (7)	0.2361 (4)	0.0438 (12)*	0.38
F7A	0.3694 (5)	0.3701 (10)	0.1145 (4)	0.0354 (14)*	0.25
F8A	0.4543 (7)	0.2606 (11)	0.2394 (6)	0.049 (2)*	0.25
F9A	0.4841 (7)	0.5119 (11)	0.1888 (7)	0.055 (2)*	0.25
C15	0.3438 (3)	0.6664 (6)	0.5095 (2)	0.0547 (9)
F4	0.27725 (19)	0.7607 (3)	0.55397 (15)	0.0614 (6)
F5	0.4281 (2)	0.7610 (4)	0.50321 (19)	0.0861 (10)
F6	0.3718 (2)	0.5370 (4)	0.56638 (16)	0.0989 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03181 (15)	0.04145 (16)	0.03619 (15)	0.00118 (12)	0.00736 (10)	0.00104 (12)
N1	0.0269 (11)	0.0333 (12)	0.0412 (12)	0.0038 (9)	0.0078 (9)	0.0063 (10)
C1	0.0238 (11)	0.0230 (11)	0.0405 (14)	−0.0009 (9)	0.0086 (10)	−0.0062 (10)
C2	0.0259 (12)	0.0251 (11)	0.0377 (14)	0.0000 (9)	0.0088 (10)	−0.0087 (10)
C3	0.0284 (13)	0.0351 (13)	0.0452 (16)	0.0030 (11)	0.0011 (11)	−0.0102 (12)
C4	0.0215 (12)	0.0402 (15)	0.062 (2)	−0.0021 (11)	0.0078 (12)	−0.0148 (14)
C5	0.0310 (15)	0.0332 (14)	0.063 (2)	−0.0032 (11)	0.0217 (14)	−0.0041 (14)
C6	0.0315 (14)	0.0265 (12)	0.0479 (16)	−0.0001 (10)	0.0120 (12)	−0.0021 (11)
C7	0.0257 (11)	0.0238 (11)	0.0380 (14)	−0.0006 (9)	0.0086 (10)	−0.0016 (10)
C8	0.0265 (12)	0.0274 (12)	0.0357 (13)	0.0010 (9)	0.0049 (10)	0.0085 (10)
C9	0.0253 (12)	0.0276 (12)	0.0339 (13)	−0.0014 (9)	0.0041 (10)	0.0035 (10)
C10	0.0269 (12)	0.0269 (11)	0.0336 (13)	−0.0008 (9)	0.0042 (10)	0.0052 (10)
C11	0.0309 (13)	0.0309 (13)	0.0329 (13)	−0.0003 (10)	−0.0005 (10)	0.0104 (10)
C12	0.0421 (15)	0.0353 (14)	0.0262 (12)	0.0044 (11)	0.0008 (11)	0.0072 (10)
C13	0.0380 (15)	0.0351 (14)	0.0324 (13)	0.0082 (11)	0.0074 (11)	0.0085 (11)
C14	0.0257 (12)	0.0401 (15)	0.0406 (15)	−0.0003 (10)	0.0004 (11)	0.0021 (12)
C15	0.059 (2)	0.072 (2)	0.0316 (16)	0.0147 (19)	−0.0048 (15)	0.0031 (16)
F4	0.0617 (14)	0.0846 (17)	0.0374 (10)	0.0156 (11)	−0.0001 (9)	−0.0144 (10)
F5	0.0564 (14)	0.144 (3)	0.0563 (15)	−0.0185 (15)	−0.0079 (11)	−0.0325 (15)
F6	0.139 (3)	0.119 (2)	0.0364 (12)	0.058 (2)	−0.0165 (14)	0.0149 (13)

Geometric parameters (Å, º) top

Br1—C2	1.908 (3)	C10—C11	1.386 (4)
N1—C7	1.280 (4)	C10—C14	1.496 (4)
N1—C8	1.414 (3)	C11—H11	0.9500
C1—C2	1.396 (4)	C11—C12	1.378 (4)
C1—C6	1.400 (4)	C12—C13	1.384 (4)
C1—C7	1.473 (4)	C12—C15	1.499 (4)
C2—C3	1.391 (4)	C13—H13	0.9500
C3—H3	0.9500	C14—F1A	1.323 (6)
C3—C4	1.382 (4)	C14—F2A	1.342 (5)
C4—H4	0.9500	C14—F3A	1.364 (5)
C4—C5	1.388 (5)	C14—F4A	1.369 (5)
C5—H5	0.9500	C14—F5A	1.377 (5)
C5—C6	1.379 (4)	C14—F6A	1.338 (5)
C6—H6	0.9500	C14—F7A	1.339 (6)
C7—H7	0.9500	C14—F8A	1.336 (7)
C8—C9	1.392 (4)	C14—F9A	1.323 (8)
C8—C13	1.390 (4)	C15—F4	1.331 (4)
C9—H9	0.9500	C15—F5	1.343 (5)
C9—C10	1.392 (3)	C15—F6	1.324 (4)

C7—N1—C8	119.1 (2)	C12—C11—C10	118.9 (3)
C2—C1—C6	117.2 (2)	C12—C11—H11	120.5
C2—C1—C7	122.9 (2)	C11—C12—C13	121.1 (3)
C6—C1—C7	119.9 (3)	C11—C12—C15	117.9 (3)
C1—C2—Br1	122.07 (19)	C13—C12—C15	121.0 (3)
C3—C2—Br1	116.1 (2)	C8—C13—H13	120.0
C3—C2—C1	121.8 (3)	C12—C13—C8	120.0 (3)
C2—C3—H3	120.3	C12—C13—H13	120.0
C4—C3—C2	119.4 (3)	F1A—C14—C10	109.7 (3)
C4—C3—H3	120.3	F1A—C14—F2A	111.2 (4)
C3—C4—H4	120.0	F1A—C14—F3A	106.9 (4)
C3—C4—C5	120.1 (3)	F2A—C14—C10	111.5 (3)
C5—C4—H4	120.0	F2A—C14—F3A	108.1 (4)
C4—C5—H5	120.0	F3A—C14—C10	109.3 (3)
C6—C5—C4	120.0 (3)	F4A—C14—C10	115.2 (3)
C6—C5—H5	120.0	F4A—C14—F5A	101.6 (4)
C1—C6—H6	119.2	F5A—C14—C10	113.2 (3)
C5—C6—C1	121.6 (3)	F6A—C14—C10	117.4 (3)
C5—C6—H6	119.2	F6A—C14—F4A	101.7 (4)
N1—C7—C1	120.7 (2)	F6A—C14—F5A	105.9 (4)
N1—C7—H7	119.7	F7A—C14—C10	113.4 (3)
C1—C7—H7	119.7	F8A—C14—C10	110.5 (4)
C9—C8—N1	123.0 (3)	F8A—C14—F7A	111.3 (5)
C13—C8—N1	117.4 (2)	F9A—C14—C10	111.4 (4)
C13—C8—C9	119.6 (2)	F9A—C14—F7A	104.5 (6)
C8—C9—H9	120.3	F9A—C14—F8A	105.3 (6)
C10—C9—C8	119.4 (3)	F4—C15—C12	113.2 (3)
C10—C9—H9	120.3	F4—C15—F5	108.2 (3)
C9—C10—C14	120.4 (2)	F5—C15—C12	112.0 (3)
C11—C10—C9	121.0 (2)	F6—C15—C12	111.6 (3)
C11—C10—C14	118.6 (2)	F6—C15—F4	107.1 (3)
C10—C11—H11	120.6	F6—C15—F5	104.3 (3)

Br1—C2—C3—C4	−179.7 (2)	C9—C10—C14—F5A	−47.6 (4)
N1—C8—C9—C10	−177.6 (2)	C9—C10—C14—F6A	−171.5 (4)
N1—C8—C13—C12	178.9 (2)	C9—C10—C14—F7A	10.2 (5)
C1—C2—C3—C4	−0.6 (4)	C9—C10—C14—F8A	−115.5 (5)
C2—C1—C6—C5	0.2 (4)	C9—C10—C14—F9A	127.7 (5)
C2—C1—C7—N1	174.5 (2)	C10—C11—C12—C13	0.3 (4)
C2—C3—C4—C5	0.2 (4)	C10—C11—C12—C15	178.7 (3)
C3—C4—C5—C6	0.4 (4)	C11—C10—C14—F1A	−79.9 (4)
C4—C5—C6—C1	−0.7 (4)	C11—C10—C14—F2A	156.5 (4)
C6—C1—C2—Br1	179.45 (19)	C11—C10—C14—F3A	37.0 (4)
C6—C1—C2—C3	0.4 (4)	C11—C10—C14—F4A	−111.5 (4)
C6—C1—C7—N1	−5.9 (4)	C11—C10—C14—F5A	132.2 (3)
C7—N1—C8—C9	−43.7 (4)	C11—C10—C14—F6A	8.3 (5)
C7—N1—C8—C13	139.5 (3)	C11—C10—C14—F7A	−170.0 (4)
C7—C1—C2—Br1	−0.9 (3)	C11—C10—C14—F8A	64.3 (5)
C7—C1—C2—C3	−179.9 (2)	C11—C10—C14—F9A	−52.5 (6)
C7—C1—C6—C5	−179.5 (3)	C11—C12—C13—C8	−1.7 (4)
C8—N1—C7—C1	176.7 (2)	C11—C12—C15—F4	165.6 (3)
C8—C9—C10—C11	−0.6 (4)	C11—C12—C15—F5	43.0 (4)
C8—C9—C10—C14	179.1 (2)	C11—C12—C15—F6	−73.5 (4)
C9—C8—C13—C12	2.0 (4)	C13—C8—C9—C10	−0.8 (4)
C9—C10—C11—C12	0.9 (4)	C13—C12—C15—F4	−16.0 (5)
C9—C10—C14—F1A	100.3 (4)	C13—C12—C15—F5	−138.6 (3)
C9—C10—C14—F2A	−23.2 (5)	C13—C12—C15—F6	104.9 (4)
C9—C10—C14—F3A	−142.7 (4)	C14—C10—C11—C12	−178.9 (2)
C9—C10—C14—F4A	68.7 (4)	C15—C12—C13—C8	179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F2Aⁱ	0.95	2.46	3.365 (7)	160
C3—H3···F7Aⁱ	0.95	2.25	3.063 (7)	143
C4—H4···F1Aⁱⁱ	0.95	2.54	3.411 (6)	153
C4—H4···F9Aⁱⁱ	0.95	2.36	3.152 (9)	140
C6—H6···N1	0.95	2.52	2.828 (4)	99
C7—H7···Br1	0.95	2.82	3.233 (3)	108
C13—H13···Br1ⁱⁱⁱ	0.95	2.97	3.851 (3)	155

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

Acknowledgements

Special acknowledgement is given to Dr. Chris Gianopoulos for assistance in data collection and structure refinement, Elizabeth Grabowski at the University of Michigan-Flint for assistance in characterization and to the University of Toledo Instrumentation Center for the use of their Bruker APEXII diffractometer.

Funding information

Funding for this research was provided by: University of Michigan-Flint Office of Research and Economic Development.

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