9-(4-Fluoro­phen­oxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate

Trzybiński, D.; Krzymiński, K.; Błażejowski, J.

doi:10.1107/S1600536810039231

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2769-o2770

https://doi.org/10.1107/S1600536810039231

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9-(4-Fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

Damian Trzybiński,^a Karol Krzymiński ^a and Jerzy Błażejowski ^a ^*

^aFaculty of Chemistry, University of Gdańsk, J. Sobieskiego 18, 80-952 Gdańsk, Poland
^*Correspondence e-mail: bla@chem.univ.gda.pl

(Received 27 September 2010; accepted 30 September 2010; online 9 October 2010)

In the crystal structure of the title compound, C₂₁H₁₅FNO₂⁺·CF₃SO₃⁻, the cations form inversion dimers through C—H⋯O, C—F⋯π and π–π interactions. These dimers are further linked by π–π interactions. The cations and anions are connected through C—H⋯O, C—F⋯π and S—O⋯π interactions. The acridine and benzene ring systems are oriented at a dihedral angle of 74.1 (1)°. The carboxylate group is twisted at an angle of 4.4 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel or inclined at an angle of 55.4 (1)° in the crystal structure.

Related literature

For general background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009 ); King et al. (2007 ); Rak et al. (1999 ); Roda et al. (2003 ); Zomer & Jacquemijns (2001 ). For related structures, see: Sikorski et al. (2005 ); Trzybiński et al. (2010 ). For intermolecular interactions, see: Bianchi et al. (2004 ); Dorn et al. (2005 ); Hunter et al. (2001 ); Novoa et al. (2006 ). For the synthesis, see: Sato (1996 ); Sikorski et al. (2005).

Experimental

Crystal data

C₂₁H₁₅FNO₂⁺·CF₃SO₃⁻
M_r = 481.41
Monoclinic, C 2/c
a = 20.854 (3) Å
b = 7.8092 (12) Å
c = 25.690 (4) Å
β = 100.893 (15)°
V = 4108.2 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.38 × 0.29 × 0.05 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.676, T_max = 0.985
15588 measured reflections
3634 independent reflections
1978 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.117
S = 0.91
3634 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O17ⁱ	0.93	2.49	3.299 (3)	146
C4—H4⋯O27	0.93	2.46	3.185 (3)	134
C5—H5⋯O27ⁱⁱ	0.93	2.53	3.200 (4)	130
C22—H22⋯O29ⁱⁱⁱ	0.93	2.54	3.399 (3)	153
Symmetry codes: (i) -x, -y, -z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
C—F⋯π and S—O⋯π interactions (Å,°)

Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 rings, respectively.

X	I	J	I⋯J	X⋯J	X—I⋯J
C21	F24	Cg2ⁱ	3.870 (2)	3.616 (3)	69.12 (12)
C30	F33	Cg2^iv	3.835 (2)	4.951 (4)	143.41 (19)
S26	O29	Cg1ⁱⁱ	3.646 (2)	5.055 (15)	170.66 (13)
Symmetry codes: (i) −x, −y, −z; (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) −x, y, −z + $[{1\over 2}]$ .

Table 3
π–π interactions (Å,°)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12, C5–C8/C13/C14 and C18–C23 rings, respectively. CgI⋯CgJ is the distance between ring centroids. The dihedral angle is that between the planes of the rings I and J. CgI_Perp is the perpendicular distance of CgI from ring J. CgI_Offset is the distance between CgI and perpendicular projection of CgJ on ring I.

I	J	CgI⋯CgJ	Dihedral angle	CgI_Perp	CgI_Offset
1	4^v	3.572 (2)	5.04 (11)	3.408 (1)	1.089 (2)
2	4ⁱ	3.856 (2)	4.29 (13)	3.596 (2)	1.392 (2)
3	4^v	3.898 (2)	4.66 (12)	3.380 (2)	1.942 (2)
4	1^v	3.572 (2)	5.04 (11)	3.472 (1)	0.839 (2)
4	2ⁱ	3.856 (2)	4.29 (13)	3.502 (1)	1.614 (2)
4	3^v	3.898 (2)	4.66 (12)	3.483 (1)	1.750 (2)
Symmetry codes: (i) −x, −y, −z; (v) −x, −y + 1, −z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810039231/ng5037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039231/ng5037Isup2.hkl

checkCIF report

Comment top

9-(Phenoxycarbonyl)-10-methylacridinium salts have long been known as chemiluminescent indicators or the chemiluminogenic fragments of chemiluminescent labels widely used in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Zomer & Jacquemijns, 2001; Roda et al., 2003; King et al., 2007; Brown et al., 2009). The cations of these salts are oxidized with hydrogen peroxide in alkaline media, which produces light. It has been found that this process is accompanied by the removal of the phenoxycarbonyl fragment and the conversion of the remaining part of the molecules to electronically excited, light-emitting 10-methyl-9-acridinone (Rak et al., 1999). The efficiency of chemiluminescence - crucial for analytical applications - is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). In the search for efficient chemiluminogens we undertook investigations on 9-(phenoxycarbonyl)-10-methylacridinium derivatives substituted in the phenyl fragment. Here we present the structure of 9-(4-fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate.

In the cation of the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the acridinium moiety are typical of acridine-based derivatives (Sikorski et al., 2005; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0288 (3) Å and 0.0081 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 74.1 (1)°. The carboxyl group is twisted at an angle of 4.4 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (remain at an angle 0.0 (1)°) or inclined at an angle of 55.4 (1)° in the lattice.

In the crystal structure, the inversely oriented cations form dimers through multidirectional C-H···O (Table 1, Fig. 2), C-F···π (Table 2, Fig. 2) and π-π (Table 3, Fig. 2) interactions. These dimers are further linked by π-π (Table 3, Fig. 2) interactions. The adjacent cations (dimers) and anions are connected through C-H···O (Table 1, Fig. 2), C-F···π (Table 2, Fig. 2) and S-O···π (Table 2, Fig. 2) interactions. The C-H···O interactions are of the hydrogen bond type (Bianchi et al. 2004; Novoa et al. 2006). C-F···π (Dorn et al., 2005), S-O···π (Dorn et al., 2005) and the π-π (Hunter et al., 2001) interactions should be of an attractive nature. The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.

Related literature top

For general background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009); King et al. (2007); Rak et al. (1999); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2005); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006). For the synthesis, see: Sato (1996); Sikorski et al. (2005).

Experimental top

The compound was synthesized in two steps (Sikorski et al., 2005). First, 9-(chlorocarbonyl)acridine, obtained by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride, was esterified with 4-fluorophenol in anhydrous dichloromethane in the presence of N,N-diethylethanamine and a catalytic amount of N,N-dimethyl-4-pyridinamine (room temperature, 15h) (Sato, 1996). Second, the product - 4-fluorophenylacridine-9-carboxylate, purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 1/1 v/v) - was quaternarized with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane. The crude 9-(4-fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with 20 v/v excess of diethyl ether. Yellow crystals suitable for X-ray investigations were grown from absolute ethanol solution (m.p. 474-475 K).

Structure description top

For general background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009); King et al. (2007); Rak et al. (1999); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2005); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006). For the synthesis, see: Sato (1996); Sikorski et al. (2005).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radius. Cg1, Cg2, Cg3 and Cg4 denote the ring centroids. The C-H···O interaction is represented by dashed lines.
	Fig. 2. The arrangement of the ions in the crystal structure. The C-H···O interactions are represented by dashed lines, the C-F···π, S-O···π and π-π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) -x, -y, -z; (ii) -x + 1/2, y + 1/2, -z + 1/2; (iii) x - 1/2, -y + 1/2, z - 1/2; (iv) -x, y, -z + 1/2; (v) -x, -y + 1, -z.]

9-(4-Fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate top

Crystal data top

C₂₁H₁₅FNO₂⁺·CF₃SO₃⁻	F(000) = 1968
M_r = 481.41	D_x = 1.557 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3994 reflections
a = 20.854 (3) Å	θ = 3.0–24.9°
b = 7.8092 (12) Å	µ = 0.23 mm⁻¹
c = 25.690 (4) Å	T = 295 K
β = 100.893 (15)°	Plate, yellow
V = 4108.2 (11) Å³	0.38 × 0.29 × 0.05 mm
Z = 8

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3634 independent reflections
Radiation source: Enhanced (Mo) X-ray Source	1978 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 10.4002 pixels mm^-1	θ_max = 25.1°, θ_min = 3.1°
ω scans	h = −23→24
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −9→9
T_min = 0.676, T_max = 0.985	l = −30→30
15588 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.068P)²] where P = (F_o² + 2F_c²)/3
3634 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₁H₁₅FNO₂⁺·CF₃SO₃⁻	V = 4108.2 (11) Å³
M_r = 481.41	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.854 (3) Å	µ = 0.23 mm⁻¹
b = 7.8092 (12) Å	T = 295 K
c = 25.690 (4) Å	0.38 × 0.29 × 0.05 mm
β = 100.893 (15)°

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3634 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	1978 reflections with I > 2σ(I)
T_min = 0.676, T_max = 0.985	R_int = 0.045
15588 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 0.91	Δρ_max = 0.17 e Å⁻³
3634 reflections	Δρ_min = −0.25 e Å⁻³
299 parameters

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
C1	0.03283 (13)	0.1193 (3)	0.11048 (10)	0.0600 (7)
H1	0.0011	0.1023	0.0802	0.072*
C2	0.02112 (15)	0.0689 (4)	0.15766 (12)	0.0797 (9)
H2	−0.0186	0.0186	0.1602	0.096*
C3	0.06910 (18)	0.0924 (5)	0.20305 (12)	0.0860 (10)
H3	0.0608	0.0560	0.2356	0.103*
C4	0.12683 (16)	0.1660 (4)	0.20108 (10)	0.0707 (8)
H4	0.1578	0.1792	0.2320	0.085*
C5	0.27041 (13)	0.4437 (4)	0.09888 (12)	0.0660 (7)
H5	0.3020	0.4586	0.1293	0.079*
C6	0.28130 (13)	0.5020 (4)	0.05259 (13)	0.0733 (8)
H6	0.3205	0.5572	0.0514	0.088*
C7	0.23522 (14)	0.4824 (4)	0.00556 (11)	0.0698 (8)
H7	0.2435	0.5262	−0.0262	0.084*
C8	0.17902 (13)	0.3997 (3)	0.00688 (9)	0.0568 (7)
H8	0.1488	0.3852	−0.0244	0.068*
C9	0.10650 (12)	0.2530 (3)	0.05781 (9)	0.0441 (6)
N10	0.19775 (10)	0.3032 (3)	0.14935 (8)	0.0539 (6)
C11	0.09265 (12)	0.1981 (3)	0.10599 (9)	0.0471 (6)
C12	0.14047 (13)	0.2230 (3)	0.15271 (9)	0.0508 (6)
C13	0.16483 (12)	0.3344 (3)	0.05474 (9)	0.0475 (6)
C14	0.21142 (11)	0.3595 (3)	0.10230 (9)	0.0503 (6)
C15	0.05947 (12)	0.2166 (3)	0.00717 (9)	0.0465 (6)
O16	0.00735 (8)	0.3201 (2)	0.00150 (6)	0.0547 (5)
O17	0.06869 (8)	0.1103 (2)	−0.02370 (6)	0.0632 (5)
C18	−0.03879 (12)	0.3069 (3)	−0.04620 (9)	0.0463 (6)
C19	−0.02424 (12)	0.3744 (3)	−0.09170 (9)	0.0544 (6)
H19	0.0161	0.4252	−0.0917	0.065*
C20	−0.07040 (12)	0.3656 (3)	−0.13730 (9)	0.0584 (7)
H20	−0.0619	0.4093	−0.1690	0.070*
C21	−0.12898 (12)	0.2915 (3)	−0.13526 (10)	0.0573 (7)
C22	−0.14428 (12)	0.2281 (3)	−0.09000 (10)	0.0589 (7)
H22	−0.1851	0.1800	−0.0900	0.071*
C23	−0.09828 (12)	0.2366 (3)	−0.04435 (10)	0.0541 (6)
H23	−0.1074	0.1952	−0.0126	0.065*
F24	−0.17440 (7)	0.2840 (2)	−0.18049 (6)	0.0861 (5)
C25	0.24602 (14)	0.3310 (4)	0.19848 (10)	0.0818 (9)
H25A	0.2755	0.4207	0.1930	0.123*
H25B	0.2702	0.2273	0.2079	0.123*
H25C	0.2238	0.3629	0.2265	0.123*
S26	0.15240 (4)	0.38413 (11)	0.35642 (3)	0.0719 (3)
O27	0.15245 (13)	0.2321 (3)	0.32563 (8)	0.1034 (8)
O28	0.11971 (11)	0.3678 (3)	0.40094 (7)	0.0928 (7)
O29	0.21189 (9)	0.4779 (3)	0.36698 (9)	0.1031 (8)
C30	0.09881 (15)	0.5223 (5)	0.31287 (13)	0.0770 (9)
F31	0.11978 (10)	0.5488 (3)	0.26795 (7)	0.1135 (7)
F32	0.09350 (10)	0.6752 (3)	0.33429 (9)	0.1138 (7)
F33	0.03935 (9)	0.4604 (3)	0.30042 (8)	0.1163 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0610 (18)	0.0645 (16)	0.0525 (16)	−0.0065 (14)	0.0053 (13)	−0.0087 (14)
C2	0.078 (2)	0.095 (2)	0.071 (2)	−0.0137 (17)	0.0241 (18)	−0.0010 (17)
C3	0.098 (3)	0.112 (3)	0.0518 (18)	−0.003 (2)	0.0229 (18)	0.0057 (17)
C4	0.077 (2)	0.092 (2)	0.0400 (16)	0.0092 (18)	0.0029 (14)	−0.0005 (15)
C5	0.0481 (16)	0.0763 (19)	0.0671 (19)	−0.0031 (14)	−0.0056 (14)	−0.0100 (16)
C6	0.0557 (18)	0.079 (2)	0.086 (2)	−0.0064 (16)	0.0130 (17)	−0.0049 (18)
C7	0.0716 (19)	0.0736 (19)	0.0665 (18)	−0.0049 (16)	0.0190 (16)	0.0019 (15)
C8	0.0601 (17)	0.0600 (16)	0.0462 (15)	−0.0010 (14)	0.0000 (12)	0.0017 (12)
C9	0.0509 (15)	0.0377 (12)	0.0391 (14)	0.0074 (11)	−0.0028 (11)	−0.0044 (10)
N10	0.0524 (14)	0.0609 (13)	0.0419 (13)	0.0078 (11)	−0.0074 (10)	−0.0062 (10)
C11	0.0519 (15)	0.0430 (13)	0.0439 (15)	0.0066 (12)	0.0026 (12)	−0.0042 (11)
C12	0.0584 (17)	0.0512 (15)	0.0398 (15)	0.0114 (13)	0.0017 (12)	−0.0043 (11)
C13	0.0466 (15)	0.0447 (14)	0.0469 (15)	0.0063 (12)	−0.0016 (12)	−0.0054 (11)
C14	0.0462 (15)	0.0529 (15)	0.0466 (15)	0.0067 (12)	−0.0045 (12)	−0.0038 (12)
C15	0.0499 (15)	0.0449 (14)	0.0409 (14)	0.0005 (12)	−0.0011 (12)	0.0005 (11)
O16	0.0563 (10)	0.0565 (10)	0.0448 (9)	0.0131 (9)	−0.0070 (8)	−0.0087 (8)
O17	0.0652 (12)	0.0623 (11)	0.0540 (11)	0.0152 (9)	−0.0090 (9)	−0.0200 (9)
C18	0.0475 (15)	0.0457 (13)	0.0406 (14)	0.0093 (12)	−0.0047 (11)	−0.0024 (11)
C19	0.0432 (14)	0.0631 (16)	0.0541 (16)	−0.0029 (12)	0.0016 (12)	−0.0018 (13)
C20	0.0553 (17)	0.0742 (17)	0.0432 (14)	0.0011 (14)	0.0027 (13)	0.0031 (13)
C21	0.0463 (16)	0.0646 (17)	0.0527 (16)	0.0050 (13)	−0.0116 (13)	−0.0039 (13)
C22	0.0426 (15)	0.0630 (17)	0.0661 (19)	−0.0024 (13)	−0.0027 (14)	0.0048 (14)
C23	0.0532 (16)	0.0524 (15)	0.0571 (16)	0.0047 (13)	0.0111 (13)	0.0099 (12)
F24	0.0617 (10)	0.1201 (13)	0.0636 (10)	−0.0034 (9)	−0.0210 (8)	0.0016 (9)
C25	0.0658 (19)	0.120 (3)	0.0491 (16)	−0.0003 (18)	−0.0162 (14)	−0.0050 (16)
S26	0.0683 (5)	0.0884 (5)	0.0517 (4)	0.0159 (4)	−0.0074 (4)	−0.0033 (4)
O27	0.145 (2)	0.0928 (16)	0.0634 (13)	0.0384 (15)	−0.0047 (13)	−0.0118 (12)
O28	0.1093 (17)	0.1221 (18)	0.0467 (11)	0.0021 (14)	0.0142 (11)	0.0038 (11)
O29	0.0523 (12)	0.138 (2)	0.1089 (17)	0.0033 (13)	−0.0110 (11)	0.0050 (15)
C30	0.069 (2)	0.095 (3)	0.068 (2)	0.0111 (18)	0.0138 (17)	0.0039 (19)
F31	0.1171 (15)	0.1541 (19)	0.0703 (12)	0.0225 (13)	0.0202 (11)	0.0343 (12)
F32	0.1120 (16)	0.0935 (15)	0.1339 (17)	0.0282 (12)	0.0182 (13)	0.0020 (13)
F33	0.0566 (11)	0.164 (2)	0.1149 (15)	0.0014 (12)	−0.0169 (10)	0.0110 (14)

Geometric parameters (Å, º) top

C1—C2	1.340 (4)	C13—C14	1.423 (3)
C1—C11	1.415 (3)	C15—O17	1.188 (3)
C1—H1	0.9300	C15—O16	1.340 (3)
C2—C3	1.398 (4)	O16—C18	1.412 (3)
C2—H2	0.9300	C18—C23	1.366 (3)
C3—C4	1.344 (4)	C18—C19	1.368 (3)
C3—H3	0.9300	C19—C20	1.370 (3)
C4—C12	1.399 (4)	C19—H19	0.9300
C4—H4	0.9300	C20—C21	1.362 (4)
C5—C6	1.332 (4)	C20—H20	0.9300
C5—C14	1.412 (4)	C21—F24	1.355 (3)
C5—H5	0.9300	C21—C22	1.356 (3)
C6—C7	1.403 (4)	C22—C23	1.369 (3)
C6—H6	0.9300	C22—H22	0.9300
C7—C8	1.344 (3)	C23—H23	0.9300
C7—H7	0.9300	C25—H25A	0.9600
C8—C13	1.413 (3)	C25—H25B	0.9600
C8—H8	0.9300	C25—H25C	0.9600
C9—C13	1.388 (3)	S26—O29	1.422 (2)
C9—C11	1.391 (3)	S26—O27	1.427 (2)
C9—C15	1.501 (3)	S26—O28	1.444 (2)
N10—C14	1.366 (3)	S26—C30	1.787 (3)
N10—C12	1.366 (3)	C30—F33	1.313 (3)
N10—C25	1.474 (3)	C30—F31	1.325 (3)
C11—C12	1.421 (3)	C30—F32	1.328 (4)

C2—C1—C11	121.0 (2)	C5—C14—C13	118.1 (2)
C2—C1—H1	119.5	O17—C15—O16	125.4 (2)
C11—C1—H1	119.5	O17—C15—C9	123.3 (2)
C1—C2—C3	119.5 (3)	O16—C15—C9	111.3 (2)
C1—C2—H2	120.3	C15—O16—C18	117.11 (17)
C3—C2—H2	120.3	C23—C18—C19	122.3 (2)
C4—C3—C2	122.0 (3)	C23—C18—O16	118.3 (2)
C4—C3—H3	119.0	C19—C18—O16	119.3 (2)
C2—C3—H3	119.0	C18—C19—C20	118.5 (2)
C3—C4—C12	120.2 (3)	C18—C19—H19	120.7
C3—C4—H4	119.9	C20—C19—H19	120.7
C12—C4—H4	119.9	C21—C20—C19	118.6 (2)
C6—C5—C14	120.8 (2)	C21—C20—H20	120.7
C6—C5—H5	119.6	C19—C20—H20	120.7
C14—C5—H5	119.6	F24—C21—C22	118.7 (2)
C5—C6—C7	121.8 (3)	F24—C21—C20	118.2 (2)
C5—C6—H6	119.1	C22—C21—C20	123.1 (2)
C7—C6—H6	119.1	C21—C22—C23	118.4 (2)
C8—C7—C6	119.3 (3)	C21—C22—H22	120.8
C8—C7—H7	120.3	C23—C22—H22	120.8
C6—C7—H7	120.3	C18—C23—C22	118.9 (2)
C7—C8—C13	121.5 (2)	C18—C23—H23	120.5
C7—C8—H8	119.3	C22—C23—H23	120.5
C13—C8—H8	119.3	N10—C25—H25A	109.5
C13—C9—C11	121.6 (2)	N10—C25—H25B	109.5
C13—C9—C15	118.3 (2)	H25A—C25—H25B	109.5
C11—C9—C15	120.1 (2)	N10—C25—H25C	109.5
C14—N10—C12	122.33 (19)	H25A—C25—H25C	109.5
C14—N10—C25	119.2 (2)	H25B—C25—H25C	109.5
C12—N10—C25	118.5 (2)	O29—S26—O27	116.26 (16)
C9—C11—C1	122.8 (2)	O29—S26—O28	114.84 (13)
C9—C11—C12	118.6 (2)	O27—S26—O28	114.55 (15)
C1—C11—C12	118.6 (2)	O29—S26—C30	103.21 (15)
N10—C12—C4	121.9 (2)	O27—S26—C30	102.78 (15)
N10—C12—C11	119.5 (2)	O28—S26—C30	102.50 (14)
C4—C12—C11	118.6 (3)	F33—C30—F31	107.3 (2)
C9—C13—C8	123.0 (2)	F33—C30—F32	106.4 (3)
C9—C13—C14	118.5 (2)	F31—C30—F32	106.7 (3)
C8—C13—C14	118.4 (2)	F33—C30—S26	112.4 (2)
N10—C14—C5	122.3 (2)	F31—C30—S26	111.7 (2)
N10—C14—C13	119.5 (2)	F32—C30—S26	112.0 (2)

C11—C1—C2—C3	−0.9 (4)	C6—C5—C14—C13	1.7 (4)
C1—C2—C3—C4	0.7 (5)	C9—C13—C14—N10	0.1 (3)
C2—C3—C4—C12	0.4 (5)	C8—C13—C14—N10	177.6 (2)
C14—C5—C6—C7	−0.1 (4)	C9—C13—C14—C5	−179.5 (2)
C5—C6—C7—C8	−1.3 (4)	C8—C13—C14—C5	−2.0 (3)
C6—C7—C8—C13	1.1 (4)	C13—C9—C15—O17	71.6 (3)
C13—C9—C11—C1	178.1 (2)	C11—C9—C15—O17	−105.2 (3)
C15—C9—C11—C1	−5.2 (3)	C13—C9—C15—O16	−107.5 (2)
C13—C9—C11—C12	−1.5 (3)	C11—C9—C15—O16	75.7 (3)
C15—C9—C11—C12	175.2 (2)	O17—C15—O16—C18	−3.1 (4)
C2—C1—C11—C9	−179.6 (2)	C9—C15—O16—C18	175.98 (19)
C2—C1—C11—C12	0.0 (4)	C15—O16—C18—C23	109.5 (2)
C14—N10—C12—C4	−179.9 (2)	C15—O16—C18—C19	−74.8 (3)
C25—N10—C12—C4	−0.5 (4)	C23—C18—C19—C20	−2.3 (4)
C14—N10—C12—C11	−0.7 (3)	O16—C18—C19—C20	−177.8 (2)
C25—N10—C12—C11	178.7 (2)	C18—C19—C20—C21	0.6 (4)
C3—C4—C12—N10	177.9 (3)	C19—C20—C21—F24	179.8 (2)
C3—C4—C12—C11	−1.3 (4)	C19—C20—C21—C22	1.0 (4)
C9—C11—C12—N10	1.5 (3)	F24—C21—C22—C23	−179.8 (2)
C1—C11—C12—N10	−178.2 (2)	C20—C21—C22—C23	−1.1 (4)
C9—C11—C12—C4	−179.3 (2)	C19—C18—C23—C22	2.3 (4)
C1—C11—C12—C4	1.1 (3)	O16—C18—C23—C22	177.9 (2)
C11—C9—C13—C8	−176.6 (2)	C21—C22—C23—C18	−0.6 (4)
C15—C9—C13—C8	6.6 (3)	O29—S26—C30—F33	−176.9 (2)
C11—C9—C13—C14	0.8 (3)	O27—S26—C30—F33	61.8 (3)
C15—C9—C13—C14	−176.0 (2)	O28—S26—C30—F33	−57.3 (3)
C7—C8—C13—C9	178.0 (2)	O29—S26—C30—F31	62.5 (3)
C7—C8—C13—C14	0.6 (4)	O27—S26—C30—F31	−58.8 (3)
C12—N10—C14—C5	179.4 (2)	O28—S26—C30—F31	−177.9 (2)
C25—N10—C14—C5	0.1 (4)	O29—S26—C30—F32	−57.1 (3)
C12—N10—C14—C13	−0.1 (3)	O27—S26—C30—F32	−178.4 (2)
C25—N10—C14—C13	−179.5 (2)	O28—S26—C30—F32	62.5 (3)
C6—C5—C14—N10	−177.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O17ⁱ	0.93	2.49	3.299 (3)	146
C4—H4···O27	0.93	2.46	3.185 (3)	134
C5—H5···O27ⁱⁱ	0.93	2.53	3.200 (4)	130
C22—H22···O29ⁱⁱⁱ	0.93	2.54	3.399 (3)	153

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

Experimental details

Crystal data
Chemical formula	C₂₁H₁₅FNO₂⁺·CF₃SO₃⁻
M_r	481.41
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	20.854 (3), 7.8092 (12), 25.690 (4)
β (°)	100.893 (15)
V (Å³)	4108.2 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.38 × 0.29 × 0.05

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra Ruby CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.676, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	15588, 3634, 1978
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.117, 0.91
No. of reflections	3634
No. of parameters	299
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O17ⁱ	0.93	2.49	3.299 (3)	146
C4—H4···O27	0.93	2.46	3.185 (3)	134
C5—H5···O27ⁱⁱ	0.93	2.53	3.200 (4)	130
C22—H22···O29ⁱⁱⁱ	0.93	2.54	3.399 (3)	153

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

C-F···π and S-O···π interactions (Å,°). top

X	I	J	I···J	X···J	X-I···J
C21	F24	Cg2ⁱ	3.870 (2)	3.616 (3)	69.12 (12)
C30	F33	Cg2^iv	3.835 (2)	4.951 (4)	143.41 (19)
S26	O29	Cg1ⁱⁱ	3.646 (2)	5.055 (15)	170.66 (13)

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

Notes: Cg1 and Cg2 are the centroids of the C9/N10/C11-C14 and C1-C4/C11/C12 rings, respectively.

π-π interactions (Å,°). top

I	J	CgI···CgJ	Dihedral angle	CgI_Perp	CgI_Offset
1	4^v	3.572 (2)	5.04 (11)	3.408 (1)	1.089 (2)
2	4ⁱ	3.856 (2)	4.29 (13)	3.596 (2)	1.392 (2)
3	4^v	3.898 (2)	4.66 (12)	3.380 (2)	1.942 (2)
4	1^v	3.572 (2)	5.04 (11)	3.472 (1)	0.839 (2)
4	2ⁱ	3.856 (2)	4.29 (13)	3.502 (1)	1.614 (2)
4	3^v	3.898 (2)	4.66 (12)	3.483 (1)	1.750 (2)

Symmetry codes: (i) -x, -y, -z; (v) -x, -y + 1, -z.

Notes: Cg1, Cg2, Cg3 and Cg4 are the centroids of the C9/N10/C11-C14, C1-C4/C11/C12, C5-C8/C13/C14 and C18-C23 rings, respectively. CgI···CgJ is the distance between ring centroids. The dihedral angle is that between the planes of the rings I and J. CgI_Perp is the perpendicular distance of CgI from ring J. CgI_Offset is the distance between CgI and perpendicular projection of CgJ on ring I.

Acknowledgements

This study was financed by the State Funds for Scientific Research (grant No. DS/8820-4-0087-0).

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