Ethyl 5-meth­oxy-2-trifluoro­methyl-1H-indole-3-carboxyl­ate

Crochet, A.; Alimi, I.; Bochet, C.G.; Fromm, K.M.

doi:10.1107/S1600536813002614

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o339

doi:10.1107/S1600536813002614

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Ethyl 5-methoxy-2-trifluoromethyl-1H-indole-3-carboxylate

Aurelien Crochet,^a ^* Isak Alimi,^b Christian G. Bochet ^b and Katharina M. Fromm ^b

^aFribourg Center for Nanomaterials, FriMat, University of Fribourg, Chemin du Musee 3, CH-1700 Fribourg, Switzerland, and ^bChemistry Department, University of Fribourg, Chemin du Musee 9, CH-1700 Fribourg, Switzerland
^*Correspondence e-mail: aurelien.crochet@unifr.ch

(Received 16 January 2013; accepted 25 January 2013; online 2 February 2013)

The title compound, C₁₃H₁₂F₃NO₃, is almost planar if one excludes the F atoms of the –CF₃ group [maximum deviation for the other hetero atoms = 0.069 (1) Å], and the dihedral angle between the pyrrole and benzene ring of the indole system is 2.54 (8)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating along the a-axis direction. These chains are linked via C—H⋯O and C—H⋯F hydrogen bonds, forming a three-dimensional network.

Related literature

For indoles, see: Kochanowska-Karamyan & Hamann (2010 ); Debieux & Bochet (2009 ); Helgen & Bochet (2003 ); Oppolzer et al. (1994 ), and for their synthesis, see: Chen et al. (2008 ); Barton et al. (1977 ). For photochemical methods for the synthesis of substituted indoles, see: Bochet & Blanc (2010 ); Bochet & Mercier (2009 ); Debieux & Bochet (2012 ); Streit & Bochet (2011 ); Alimi & Bochet (2013 ).

Experimental

Crystal data

C₁₃H₁₂F₃NO₃
M_r = 287.24
Orthorhombic, P b c a
a = 13.9211 (8) Å
b = 8.6383 (4) Å
c = 21.5316 (7) Å
V = 2589.3 (2) Å³
Z = 8
Cu Kα radiation
μ = 1.16 mm⁻¹
T = 200 K
0.74 × 0.39 × 0.14 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2001 ) T_min = 0.610, T_max = 0.850
15525 measured reflections
2130 independent reflections
1894 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.097
S = 1.09
2130 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.835 (19)	2.109 (19)	2.8623 (16)	149.8 (16)
C6—H6⋯O3ⁱⁱ	0.95	2.53	3.460 (2)	168
C11—H11B⋯F2ⁱⁱⁱ	0.99	2.50	3.336 (2)	142
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+2, -z+1; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813002614/su2553sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813002614/su2553Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813002614/su2553Isup3.cml

checkCIF report

Comment top

Indoles exhibit a plethora of biological applications (Kochanowska-Karamyan & Hamann, 2010), and a wide range of synthetic methods have been developed to synthesize them (Chen et al., 2008; Barton et al., 1977). Recently an efficient photochemical method for the synthesis of substituted indoles, based on a [3 + 2] cycloaddition of azide and alcynes, has been developed (Alimi & Bochet, 2013). During this work the title compound was synthesized and we report herein on its crystal structure.

The molecular structure of the title molecule is illustrated in Fig. 1. The molecule is almost planar [mean deviation for atoms (O1-O3,N1,C1-C8,C10-C13) is 0.069 (1) Å] with small deviations for the C9, CF₃ group. The dihedral angle between the pyrrole (N1/C1-C3/C8) and the benzene (C3-C8) ring is only 2.54 (8)°.

In the crystal, N-H···O hydrogen bonds link the molecules to form chains propagating along the a axis direction (Table 1 and Fig. 2). These chains are linked via C-H···O and C-H···F hydrogen bonds forming a three-dimensional network (Table 1 and Fig. 3).

Related literature top

For indoles, see: Kochanowska-Karamyan & Hamann (2010); Debieux & Bochet (2009); Helgen & Bochet (2003); Oppolzer et al. (1994), and for their synthesis, see: Chen et al. (2008); Barton et al. (1977). For photochemical methods for the synthesis of substituted indoles, see: Bochet & Blanc (2010); Bochet & Mercier (2009); Debieux & Bochet (2012); Streit & Bochet (2011); Alimi & Bochet (2013).

Experimental top

Ethyl 1-(4-methoxyphenyl)-5-(trifluoromethyl)-1H-1,2,3-triazole-4-carboxylate (101.7 g, 323 mmol) was dissolved in MeCN (15 ml) and irradiated during 10 h at 254 nm. The solution was concentrated in vacuo and purified with flash chromatography (Pentane: EtOAc, 4:1) to afford the title compound as a white solid [60.5 g, 211 mmol, 65.3% yield; M.p. 416 - 419 K; HRMS 310.0662 (C₁₃H₁₂F₃NO₃ + Na⁺; calcd. 310.0661]. The compound was recrystallized from chloroform to afford colourless block-like crystals suitable for X-ray analysis. Spectroscopic and other analytical data for the title compound are available in the archived CIF.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the molecular structure of the title molecule, with atom labelling. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view normal to the ac plane showing the N-H···O hydrogen bonded (dashed lines) chains propagating along the a axis direction in the crystal structure of the title compound [symmetry code: (i) x+1/2, y, -z+1/2; see Table 1 for details].
	Fig. 3. A view along the a axis of the crystal packing of the title compound. H atoms not involved in the C-H···O and C-H···F hydrogen bonds (dashed lines; see Table 1 for details) have been omitted for clarity.

Ethyl 5-methoxy-2-trifluoromethyl-1H-indole-3-carboxylate top

Crystal data top

C₁₃H₁₂F₃NO₃	D_x = 1.474 Mg m⁻³
M_r = 287.24	Melting point: 416 K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54186 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 35241 reflections
a = 13.9211 (8) Å	θ = 3.2–67.3°
b = 8.6383 (4) Å	µ = 1.16 mm⁻¹
c = 21.5316 (7) Å	T = 200 K
V = 2589.3 (2) Å³	Block, colourless
Z = 8	0.74 × 0.39 × 0.14 mm
F(000) = 1184

Data collection top

Stoe IPDS 2T diffractometer	2130 independent reflections
Radiation source: fine-focus sealed tube	1894 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 6.67 pixels mm^-1	θ_max = 65.0°, θ_min = 6.4°
rotation method scans	h = −16→16
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2001)	k = −9→9
T_min = 0.610, T_max = 0.850	l = −25→25
15525 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0488P)² + 1.0298P] where P = (F_o² + 2F_c²)/3
2130 reflections	(Δ/σ)_max < 0.001
186 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₁₂F₃NO₃	V = 2589.3 (2) Å³
M_r = 287.24	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 13.9211 (8) Å	µ = 1.16 mm⁻¹
b = 8.6383 (4) Å	T = 200 K
c = 21.5316 (7) Å	0.74 × 0.39 × 0.14 mm

Data collection top

Stoe IPDS 2T diffractometer	2130 independent reflections
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2001)	1894 reflections with I > 2σ(I)
T_min = 0.610, T_max = 0.850	R_int = 0.051
15525 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.19 e Å⁻³
2130 reflections	Δρ_min = −0.19 e Å⁻³
186 parameters

Special details top

Experimental. Spectroscopic data for the title compound: ¹H NMR (360 MHz, CDCl₃) δ p.p.m. 8.88 (br. s., 1 H) 7.74 (s, 1 H) 7.36 (d, J = 8.63 Hz, 1 H) 7.05 (d, J = 9.08 Hz, 1 H) 4.44 (q, J = 6.96 Hz, 2 H) 3.90 (s, 3 H) 1.44 (t, J = 7.04 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃) d p.p.m. 163.48, 156.43, 129.48, 128.97, 128.84, 128.45, 127.94, 127.62, 125.75, 122.17, 118.60, 116.85, 115.03, 112.92, 107.77 (d, J=2.20 Hz, 1 C) 102.90, 60.57, 55.58, 14.05. IR (neat, cm^-1) 3280, 2995, 2833, 1681, 1550, 1467, 1439, 1309, 1209, 1166, 1154, 1112, 1032, 845, 824, 713, 637. Rf 0.42 (Pentane: EtOAc 4:1).

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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.

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

	x	y	z	U_iso*/U_eq
F1	0.83489 (7)	0.47973 (13)	0.17707 (5)	0.0429 (3)
F2	0.69256 (7)	0.43215 (11)	0.21010 (5)	0.0352 (3)
F3	0.72136 (8)	0.64436 (11)	0.16278 (4)	0.0399 (3)
O1	0.57084 (7)	0.64000 (15)	0.27202 (5)	0.0348 (4)
O2	0.59337 (7)	0.76352 (14)	0.36252 (5)	0.0342 (4)
O3	0.86605 (9)	0.98158 (18)	0.49087 (5)	0.0471 (5)
N1	0.87955 (9)	0.64042 (15)	0.27672 (6)	0.0241 (4)
C1	0.78495 (10)	0.61930 (17)	0.26378 (7)	0.0209 (4)
C2	0.72915 (10)	0.68707 (17)	0.30968 (6)	0.0210 (4)
C3	0.79547 (10)	0.75592 (18)	0.35320 (6)	0.0223 (4)
C4	0.78425 (11)	0.8434 (2)	0.40791 (7)	0.0281 (5)
C5	0.86630 (12)	0.8946 (2)	0.43723 (7)	0.0327 (5)
C6	0.95870 (12)	0.8613 (2)	0.41420 (8)	0.0377 (6)
C7	0.97083 (11)	0.7768 (2)	0.36098 (7)	0.0329 (5)
C8	0.88812 (10)	0.72466 (18)	0.33081 (7)	0.0240 (4)
C9	0.75746 (11)	0.54400 (17)	0.20418 (7)	0.0249 (4)
C10	0.62433 (10)	0.69181 (18)	0.31147 (7)	0.0243 (4)
C11	0.49061 (12)	0.7820 (3)	0.36956 (9)	0.0467 (7)
C12	0.47534 (15)	0.8662 (3)	0.42942 (11)	0.0636 (9)
C13	0.77531 (14)	1.0206 (3)	0.51655 (8)	0.0439 (6)
H1	0.9254 (14)	0.616 (2)	0.2537 (8)	0.0290*
H4	0.72230	0.86620	0.42400	0.0340*
H6	1.01350	0.89810	0.43590	0.0450*
H7	1.03300	0.75450	0.34520	0.0390*
H11A	0.45860	0.67970	0.37070	0.0560*
H11B	0.46390	0.84220	0.33450	0.0560*
H12A	0.50170	0.80480	0.46370	0.0950*
H12B	0.40640	0.88220	0.43600	0.0950*
H12C	0.50790	0.96660	0.42770	0.0950*
H13A	0.73750	1.07770	0.48570	0.0660*
H13B	0.78460	1.08520	0.55350	0.0660*
H13C	0.74110	0.92570	0.52820	0.0660*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0257 (5)	0.0536 (7)	0.0493 (6)	0.0019 (5)	0.0055 (4)	−0.0246 (5)
F2	0.0295 (5)	0.0287 (5)	0.0473 (6)	−0.0098 (4)	−0.0046 (4)	−0.0037 (4)
F3	0.0607 (7)	0.0331 (6)	0.0260 (5)	0.0016 (5)	−0.0127 (4)	0.0004 (4)
O1	0.0156 (5)	0.0566 (8)	0.0322 (6)	0.0001 (5)	−0.0052 (4)	−0.0080 (5)
O2	0.0154 (6)	0.0534 (7)	0.0339 (6)	0.0031 (5)	0.0021 (4)	−0.0119 (5)
O3	0.0381 (7)	0.0734 (10)	0.0299 (6)	−0.0043 (7)	−0.0059 (5)	−0.0191 (6)
N1	0.0140 (6)	0.0334 (7)	0.0249 (6)	0.0002 (5)	0.0015 (5)	−0.0004 (5)
C1	0.0145 (7)	0.0239 (8)	0.0242 (7)	−0.0004 (5)	−0.0021 (5)	0.0027 (6)
C2	0.0136 (7)	0.0270 (8)	0.0225 (7)	−0.0008 (6)	−0.0015 (5)	0.0030 (6)
C3	0.0176 (7)	0.0288 (8)	0.0204 (7)	−0.0012 (6)	−0.0018 (5)	0.0039 (6)
C4	0.0224 (8)	0.0403 (9)	0.0217 (7)	−0.0007 (7)	−0.0007 (6)	0.0009 (7)
C5	0.0294 (9)	0.0460 (10)	0.0227 (8)	−0.0045 (7)	−0.0047 (6)	−0.0033 (7)
C6	0.0233 (8)	0.0581 (12)	0.0318 (9)	−0.0098 (8)	−0.0086 (7)	−0.0034 (8)
C7	0.0167 (8)	0.0507 (11)	0.0313 (8)	−0.0062 (7)	−0.0029 (6)	0.0010 (7)
C8	0.0152 (7)	0.0338 (9)	0.0230 (7)	−0.0020 (6)	−0.0007 (6)	0.0025 (6)
C9	0.0197 (7)	0.0239 (8)	0.0310 (8)	0.0006 (6)	−0.0004 (6)	−0.0006 (6)
C10	0.0165 (7)	0.0326 (9)	0.0237 (7)	0.0008 (6)	−0.0002 (6)	0.0016 (6)
C11	0.0165 (8)	0.0685 (14)	0.0552 (12)	0.0071 (8)	0.0061 (7)	−0.0133 (10)
C12	0.0418 (12)	0.0882 (18)	0.0607 (14)	0.0105 (11)	0.0208 (10)	−0.0212 (12)
C13	0.0476 (11)	0.0566 (12)	0.0274 (9)	0.0025 (9)	0.0004 (7)	−0.0096 (8)

Geometric parameters (Å, º) top

F1—C9	1.3457 (18)	C4—C5	1.378 (2)
F2—C9	1.3289 (18)	C5—C6	1.408 (2)
F3—C9	1.3412 (18)	C6—C7	1.369 (2)
O1—C10	1.2150 (18)	C7—C8	1.397 (2)
O2—C10	1.3333 (19)	C11—C12	1.495 (3)
O2—C11	1.447 (2)	C4—H4	0.9500
O3—C5	1.378 (2)	C6—H6	0.9500
O3—C13	1.420 (2)	C7—H7	0.9500
N1—C1	1.3584 (19)	C11—H11A	0.9900
N1—C8	1.379 (2)	C11—H11B	0.9900
N1—H1	0.835 (19)	C12—H12A	0.9800
C1—C2	1.387 (2)	C12—H12B	0.9800
C1—C9	1.489 (2)	C12—H12C	0.9800
C2—C3	1.4437 (19)	C13—H13A	0.9800
C2—C10	1.460 (2)	C13—H13B	0.9800
C3—C8	1.403 (2)	C13—H13C	0.9800
C3—C4	1.408 (2)

C10—O2—C11	117.20 (13)	F2—C9—C1	114.19 (13)
C5—O3—C13	117.27 (14)	O1—C10—O2	123.32 (13)
C1—N1—C8	109.15 (12)	O1—C10—C2	125.71 (14)
C8—N1—H1	124.7 (13)	O2—C10—C2	110.97 (12)
C1—N1—H1	125.8 (13)	O2—C11—C12	106.53 (15)
N1—C1—C9	118.99 (13)	C3—C4—H4	121.00
C2—C1—C9	130.91 (13)	C5—C4—H4	121.00
N1—C1—C2	109.89 (13)	C5—C6—H6	119.00
C3—C2—C10	127.62 (13)	C7—C6—H6	119.00
C1—C2—C3	106.16 (12)	C6—C7—H7	121.00
C1—C2—C10	126.19 (13)	C8—C7—H7	121.00
C4—C3—C8	119.51 (13)	O2—C11—H11A	110.00
C2—C3—C4	133.88 (13)	O2—C11—H11B	110.00
C2—C3—C8	106.59 (12)	C12—C11—H11A	110.00
C3—C4—C5	117.62 (14)	C12—C11—H11B	110.00
C4—C5—C6	122.02 (15)	H11A—C11—H11B	109.00
O3—C5—C4	123.85 (15)	C11—C12—H12A	109.00
O3—C5—C6	114.13 (14)	C11—C12—H12B	109.00
C5—C6—C7	121.08 (15)	C11—C12—H12C	109.00
C6—C7—C8	117.36 (14)	H12A—C12—H12B	110.00
N1—C8—C7	129.39 (13)	H12A—C12—H12C	110.00
C3—C8—C7	122.41 (14)	H12B—C12—H12C	110.00
N1—C8—C3	108.20 (12)	O3—C13—H13A	109.00
F1—C9—C1	110.38 (12)	O3—C13—H13B	110.00
F1—C9—F2	106.63 (12)	O3—C13—H13C	109.00
F1—C9—F3	106.17 (12)	H13A—C13—H13B	110.00
F3—C9—C1	112.76 (12)	H13A—C13—H13C	109.00
F2—C9—F3	106.20 (12)	H13B—C13—H13C	109.00

C11—O2—C10—O1	−1.4 (2)	C1—C2—C3—C8	−0.23 (16)
C11—O2—C10—C2	177.83 (15)	C10—C2—C3—C4	0.3 (3)
C10—O2—C11—C12	−179.41 (16)	C10—C2—C3—C8	−178.02 (14)
C13—O3—C5—C4	−0.5 (3)	C1—C2—C10—O1	−1.9 (3)
C13—O3—C5—C6	179.56 (16)	C1—C2—C10—O2	178.96 (14)
C8—N1—C1—C2	−0.98 (17)	C3—C2—C10—O1	175.48 (15)
C8—N1—C1—C9	174.28 (13)	C3—C2—C10—O2	−3.7 (2)
C1—N1—C8—C3	0.82 (17)	C2—C3—C4—C5	−178.23 (16)
C1—N1—C8—C7	−178.31 (16)	C8—C3—C4—C5	−0.1 (2)
N1—C1—C2—C3	0.74 (17)	C2—C3—C8—N1	−0.35 (17)
N1—C1—C2—C10	178.57 (14)	C2—C3—C8—C7	178.85 (14)
C9—C1—C2—C3	−173.78 (15)	C4—C3—C8—N1	−178.96 (14)
C9—C1—C2—C10	4.1 (3)	C4—C3—C8—C7	0.2 (2)
N1—C1—C9—F1	12.34 (19)	C3—C4—C5—O3	179.75 (15)
N1—C1—C9—F2	132.45 (14)	C3—C4—C5—C6	−0.3 (2)
N1—C1—C9—F3	−106.22 (16)	O3—C5—C6—C7	−179.55 (16)
C2—C1—C9—F1	−173.56 (15)	C4—C5—C6—C7	0.5 (3)
C2—C1—C9—F2	−53.5 (2)	C5—C6—C7—C8	−0.3 (2)
C2—C1—C9—F3	67.9 (2)	C6—C7—C8—N1	178.97 (16)
C1—C2—C3—C4	178.10 (17)	C6—C7—C8—C3	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.835 (19)	2.109 (19)	2.8623 (16)	149.8 (16)
C6—H6···O3ⁱⁱ	0.95	2.53	3.460 (2)	168
C11—H11B···F2ⁱⁱⁱ	0.99	2.50	3.336 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂F₃NO₃
M_r	287.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	200
a, b, c (Å)	13.9211 (8), 8.6383 (4), 21.5316 (7)
V (Å³)	2589.3 (2)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	1.16
Crystal size (mm)	0.74 × 0.39 × 0.14

Data collection
Diffractometer	Stoe IPDS 2T diffractometer
Absorption correction	Integration (X-SHAPE; Stoe & Cie, 2001)
T_min, T_max	0.610, 0.850
No. of measured, independent and observed [I > 2σ(I)] reflections	15525, 2130, 1894
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.097, 1.09
No. of reflections	2130
No. of parameters	186
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: X-AREA (Stoe & Cie, 2001), X-RED32 (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.835 (19)	2.109 (19)	2.8623 (16)	149.8 (16)
C6—H6···O3ⁱⁱ	0.95	2.53	3.460 (2)	168
C11—H11B···F2ⁱⁱⁱ	0.99	2.50	3.336 (2)	142

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

Acknowledgements

The authors thank the Swiss National Science Foundation and the Fribourg Center for Nanomaterials (FriMat) for generous support.

References

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