9-Ethyl-10-methyl­acridinium trifluoro­methane­sulfonate

Zadykowicz, B.; Wera, M.; Sikorski, A.; Błażejowski, J.

doi:10.1107/S1600536808039676

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages o30-o31

doi:10.1107/S1600536808039676

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9-Ethyl-10-methylacridinium trifluoromethanesulfonate

Beata Zadykowicz,^a Michał Wera,^a Artur Sikorski ^a and Jerzy Błażejowski ^a ^*

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

(Received 14 November 2008; accepted 25 November 2008; online 6 December 2008)

In the molecule of the title compound, C₁₆H₁₆N⁺·CF₃SO₃⁻, the central ring adopts a flattened-boat conformation, and the two aromatic rings are oriented at a dihedral angle of 3.94 (2)°. In the crystal structure, weak intermolecular hydrogen bonds link the molecules. There are π–π contacts between the aromatic rings and the central ring and one of the aromatic rings [centroid–centroid distances = 3.874 (2), 3.945 (2) and 3.814 (2) Å]. There is also an S—O⋯π contact between the central ring and one of the O atoms of the anion.

Related literature

For general background, see: Bianchi et al. (2004 ); Dorn et al. (2005 ); Hunter & Sanders (1990 ); Steiner (1991 ); Suzuki & Tanaka (2001 ); Zomer & Jacquemijns (2001 ). For related structures, see: Huta et al. (2002 ); Krzymiński et al. (2007 ); Meszko et al. (2002 ); Sikorski et al. (2005a ,b ,c , 2006 , 2008 ); Storoniak et al. (2000 ); Tsuge et al. (1965 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₆H₁₆N⁺·CF₃SO₃⁻
M_r = 371.37
Triclinic, $[P \overline 1]$
a = 7.771 (2) Å
b = 9.440 (2) Å
c = 11.898 (2) Å
α = 76.76 (3)°
β = 74.04 (3)°
γ = 82.14 (3)°
V = 814.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 295 (2) K
0.5 × 0.5 × 0.05 mm

Data collection

Oxford Diffraction GEMINI R ULTRA Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.870, T_max = 0.988
7781 measured reflections
2857 independent reflections
2078 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.102
S = 1.08
2857 reflections
229 parameters
H-atom parameters constrained
Δρ_max = 0.21 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
C2—H2⋯O23ⁱ	0.93	2.47	3.369 (3)	164
C15—H15C⋯O24ⁱⁱ	0.96	2.40	3.276 (3)	151
C16—H16B⋯O25ⁱⁱⁱ	0.97	2.58	3.377 (3)	140
Symmetry codes: (i) x, y, z+1; (ii) x, y-1, z+1; (iii) -x+1, -y+2, -z+1.

Table 2
π–π Interactions (Å, °)

CgI	CgJ	Cg⋯Cg	Dihedral angle	Interplanar distance	Offset
1	2^iv	3.814 (2)	3.88	3.517 (2)	5.188
2	1^iv	3.814 (2)	3.88	3.542 (2)	5.205
2	2^iv	3.945 (2)	0.02	3.578 (2)	5.326
2	2^v	3.874 (2)	0.02	3.440 (2)	5.181
Symmetry codes: (iv) -x, -y+1, -z+2; (v) -x+1, -y+1, -z+2. Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 rings, respectively. Cg⋯Cg is the distance between ring centroids. The dihedral angle is that between the planes of the rings CgI and CgJ. The interplanar distance is the perpendicular distance of CgI from ring J. The offset is the perpendicular distance of ring I from ring J.

Table 3
S—O⋯π Interactions (Å, °)

X	I	J	I⋯J	X⋯J	X—I⋯J
S22	O23	Cg1^vi	3.255 (2)	3.072 (2)	146
Symmetry codes: (vi) -x+1, -y+1, -z+1. Cg1 is the centroid of the C9/N10/C11–C14 ring.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039676/hk2577sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039676/hk2577Isup2.hkl

checkCIF report

Comment top

Acridinium cations substituted in positions 9 and 10 are susceptible to attack by OOH^- or other oxidants at C9, which initiates conversion of these cations to electronically excited-light emitting 9-acridinones (Zomer & Jacquemijns, 2001). We investigated the above described chemiluminescence in the case of 9-(phenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonates, the several structures of which we recently determined (Sikorski et al., 2005a, b, c; Sikorski et al., 2006; Krzymiński et al., 2007; Sikorski et al., 2008). Chemiluminogenic features are also exhibited by the 9-cyano-10-methylacridinium and 9,10-dimethylacridinium cations respectively present as counterpart ions in hydrogen dinitrate and methylsulfate salts, the crystal structures of which were also refined (Huta et al., 2002; Meszko et al., 2002). We report herein the crystal structure of the title compound, which was selected for investigations as a potential chemiluminogen. The 9-ethyl-10-methylacridinium cation may also be interesting as a model compound in investigations of C-acidic features of organic molecules, since such properties are exhibited by the 9,10-dimethylacridinium cation (Suzuki & Tanaka, 2001).

In the molecule of the title compound (Fig. 1) the bond lengths and angles, characterizing the geometry of the acridine ring, are typical of acridine-based derivatives (Storoniak et al., 2000; Meszko et al., 2002). Rings A (C1-C4/C11/C12) and C (C5-C8/C13/C14) are planar and are oriented at a dihedral angle of 3.94 (2)°. Ring B (C9/N10/C11-C14) is not planar, having total puckering amplitude, Q_T, of 1.990 (5) and flattened-boat conformation [ϕ = 31.52 (5)° and θ = 21.87 (4)°] (Cremer & Pople, 1975).

In the crystal structure, weak intermolecular hydrogen bonds (Table 1) link the molecules. The central ring B and the aromatic ring A are involved in multidirectional π-π interactions (Table 2, Fig. 2). One of the O atoms of the anion is involved in weak S—O···π interactions directed toward the center of the acridine ring system (Table 3, Fig. 2). The C—H···O (Bianchi et al., 2004; Steiner, 1999) interactions are of the hydrogen-bond type. The S—O···π interactions (Dorn et al., 2005) should be of an attractive nature, such as is also exhibited by π-π interactions (Hunter & Sanders, 1990). The crystal structure is stabilized by a network of the aforementioned short-range interactions, as well as by long-range electrostatic interactions between ions.

Related literature top

For general background, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter & Sanders (1990); Steiner (1991); Suzuki & Tanaka (2001); Zomer & Jacquemijns (2001). For related structures, see: Huta et al. (2002); Krzymiński et al. (2007); Meszko et al. (2002); Sikorski et al. (2005a,b,c, 2006, 2008); Storoniak et al. (2000); Tsuge et al. (1965). For ring puckering parameters, see: Cremer & Pople (1975).

Experimental top

9-Ethylacridine was synthesized by heating a mixture of N-phenylaniline with an equimolar amount of propanoic acid, both dispersed in molten zinc chloride (493 K, 26 h) (Tsuge et al., 1965). The crude product was purified by gravitational column chromatography (SiO₂, n-hexane-ethyl acetate, 5:1 v/v). 9-Ethyl-10-methylacridinium trifluoromethanesulfonate was obtained by dissolving 9-ethylacridine with a fivefold molar excess of methyl trifluoromethanesulfonate in anhydrous dichloromethane and leaving the mixture for 3 h (Ar atmosphere, room temperature). The crude salt that precipitated was dissolved in a small amount of ethanol, filtered, and again precipitated with a 25 v/v excess of diethyl ether (yield; 89%). Pale-yellow crystals suitable for X-ray analysis were grown from absolute ethanol solution.

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: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

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 and Cg2 denote the ring centroids.

Fig. 2. The arrangement of the ions in the crystal structure. The C—H···O interactions are represented by dashed lines, the π-π and S—O···π interactions by dotted lines. H atoms not involved in the interactions have been omitted. [Symmetry codes: (i) x, y, z + 1; (ii) x, y - 1, z + 1; (iii) -x, -y + 2, -z + 1; (iv) -x, -y + 1, -z + 2; (v) -x + 1, -y + 1, -z + 2; (vi) -x + 1, -y + 1, -z + 1.]

9-Ethyl-10-methylacridinium trifluoromethanesulfonate top

Crystal data top

C₁₆H₁₆N⁺·CF₃SO₃⁻	Z = 2
M_r = 371.37	F(000) = 384
Triclinic, P1	D_x = 1.515 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.771 (2) Å	Cell parameters from 2857 reflections
b = 9.440 (2) Å	θ = 3.1–25.0°
c = 11.898 (2) Å	µ = 0.25 mm⁻¹
α = 76.76 (3)°	T = 295 K
β = 74.04 (3)°	Plate, pale-yellow
γ = 82.14 (3)°	0.5 × 0.5 × 0.05 mm
V = 814.3 (3) Å³

Data collection top

Oxford Diffraction GEMINI R ULTRA Ruby CCD diffractometer	2857 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2078 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 10.4002 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −8→11
T_min = 0.870, T_max = 0.988	l = −13→14
7781 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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0604P)² + 0.0136P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2857 reflections	Δρ_max = 0.22 e Å⁻³
229 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (3)

Crystal data top

C₁₆H₁₆N⁺·CF₃SO₃⁻	γ = 82.14 (3)°
M_r = 371.37	V = 814.3 (3) Å³
Triclinic, P1	Z = 2
a = 7.771 (2) Å	Mo Kα radiation
b = 9.440 (2) Å	µ = 0.25 mm⁻¹
c = 11.898 (2) Å	T = 295 K
α = 76.76 (3)°	0.5 × 0.5 × 0.05 mm
β = 74.04 (3)°

Data collection top

Oxford Diffraction GEMINI R ULTRA Ruby CCD diffractometer	2857 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	2078 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.988	R_int = 0.020
7781 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.08	Δρ_max = 0.22 e Å⁻³
2857 reflections	Δρ_min = −0.25 e Å⁻³
229 parameters

Special details top

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
C1	0.3057 (2)	0.6242 (2)	0.97192 (18)	0.0479 (5)
H1	0.3455	0.7172	0.9413	0.057*
C2	0.2727 (3)	0.5708 (2)	1.09064 (19)	0.0541 (5)
H2	0.2876	0.6276	1.1411	0.065*
C3	0.2161 (3)	0.4299 (2)	1.13769 (19)	0.0551 (5)
H3	0.1946	0.3940	1.2195	0.066*
C4	0.1918 (3)	0.3445 (2)	1.06641 (18)	0.0490 (5)
H4	0.1571	0.2503	1.0993	0.059*
C5	0.1504 (3)	0.2917 (2)	0.68005 (19)	0.0526 (5)
H5	0.1046	0.2013	0.7141	0.063*
C6	0.1686 (3)	0.3478 (2)	0.5618 (2)	0.0616 (6)
H6	0.1340	0.2947	0.5159	0.074*
C7	0.2377 (3)	0.4825 (2)	0.50750 (19)	0.0594 (6)
H7	0.2505	0.5175	0.4262	0.071*
C8	0.2859 (3)	0.5621 (2)	0.57323 (17)	0.0509 (5)
H8	0.3312	0.6522	0.5364	0.061*
C9	0.3131 (2)	0.59454 (18)	0.76881 (17)	0.0397 (4)
N10	0.18592 (19)	0.31700 (15)	0.86993 (13)	0.0387 (4)
C11	0.2806 (2)	0.54049 (18)	0.89252 (17)	0.0394 (4)
C12	0.2190 (2)	0.39871 (18)	0.94283 (16)	0.0388 (4)
C13	0.2688 (2)	0.51098 (19)	0.69798 (16)	0.0398 (4)
C14	0.2018 (2)	0.37195 (19)	0.75118 (17)	0.0397 (4)
C15	0.1358 (3)	0.1658 (2)	0.92047 (19)	0.0548 (5)
H15A	0.1862	0.1064	0.8619	0.082*
H15B	0.0074	0.1650	0.9426	0.082*
H15C	0.1813	0.1277	0.9897	0.082*
C16	0.3835 (3)	0.7413 (2)	0.71458 (19)	0.0492 (5)
H16A	0.4536	0.7416	0.6333	0.059*
H16B	0.4621	0.7601	0.7594	0.059*
C17	0.2316 (3)	0.8623 (2)	0.7141 (2)	0.0590 (6)
H17A	0.2808	0.9541	0.6753	0.088*
H17B	0.1670	0.8665	0.7948	0.088*
H17C	0.1515	0.8423	0.6720	0.088*
C18	0.2605 (3)	0.9709 (2)	0.36020 (18)	0.0563 (5)
F19	0.12725 (18)	0.89034 (15)	0.42780 (11)	0.0835 (4)
F20	0.19886 (19)	1.11050 (15)	0.35499 (12)	0.0838 (4)
F21	0.3880 (2)	0.94796 (18)	0.41894 (12)	0.0913 (5)
S22	0.34301 (7)	0.92827 (5)	0.21309 (4)	0.0488 (2)
O23	0.4120 (2)	0.77973 (17)	0.23799 (17)	0.0817 (5)
O24	0.18424 (19)	0.95139 (17)	0.17045 (13)	0.0650 (4)
O25	0.47217 (19)	1.03268 (17)	0.15403 (13)	0.0688 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0441 (11)	0.0382 (11)	0.0692 (14)	−0.0014 (8)	−0.0219 (10)	−0.0183 (10)
C2	0.0527 (13)	0.0543 (13)	0.0663 (14)	0.0040 (10)	−0.0248 (11)	−0.0271 (11)
C3	0.0548 (13)	0.0607 (14)	0.0535 (12)	0.0015 (10)	−0.0206 (10)	−0.0138 (10)
C4	0.0473 (12)	0.0422 (11)	0.0587 (13)	−0.0025 (9)	−0.0182 (9)	−0.0072 (9)
C5	0.0559 (13)	0.0417 (12)	0.0660 (14)	−0.0073 (9)	−0.0171 (10)	−0.0182 (10)
C6	0.0667 (15)	0.0633 (15)	0.0669 (15)	−0.0079 (12)	−0.0235 (12)	−0.0275 (12)
C7	0.0609 (14)	0.0682 (15)	0.0523 (12)	−0.0046 (11)	−0.0177 (11)	−0.0147 (11)
C8	0.0478 (12)	0.0491 (12)	0.0555 (13)	−0.0064 (9)	−0.0130 (10)	−0.0083 (10)
C9	0.0296 (10)	0.0320 (10)	0.0584 (12)	−0.0004 (7)	−0.0121 (8)	−0.0107 (8)
N10	0.0355 (8)	0.0285 (8)	0.0541 (10)	−0.0026 (6)	−0.0129 (7)	−0.0103 (7)
C11	0.0288 (9)	0.0336 (10)	0.0600 (12)	0.0019 (7)	−0.0154 (8)	−0.0155 (8)
C12	0.0305 (9)	0.0329 (10)	0.0557 (12)	0.0018 (7)	−0.0145 (8)	−0.0124 (8)
C13	0.0318 (10)	0.0346 (10)	0.0540 (11)	−0.0005 (7)	−0.0108 (8)	−0.0124 (8)
C14	0.0330 (10)	0.0340 (10)	0.0547 (12)	0.0009 (7)	−0.0125 (8)	−0.0146 (8)
C15	0.0676 (14)	0.0329 (11)	0.0676 (13)	−0.0116 (10)	−0.0219 (11)	−0.0070 (9)
C16	0.0468 (12)	0.0394 (11)	0.0621 (12)	−0.0107 (9)	−0.0124 (9)	−0.0093 (9)
C17	0.0638 (14)	0.0367 (12)	0.0740 (14)	−0.0036 (10)	−0.0152 (11)	−0.0091 (10)
C18	0.0564 (13)	0.0557 (14)	0.0565 (13)	−0.0210 (11)	−0.0115 (11)	−0.0041 (10)
F19	0.0803 (10)	0.0913 (11)	0.0695 (9)	−0.0423 (8)	0.0020 (7)	−0.0019 (7)
F20	0.0990 (11)	0.0619 (9)	0.0841 (9)	−0.0101 (8)	0.0033 (8)	−0.0317 (7)
F21	0.0951 (11)	0.1268 (13)	0.0649 (9)	−0.0367 (10)	−0.0363 (8)	−0.0091 (8)
S22	0.0461 (3)	0.0466 (3)	0.0603 (3)	−0.0064 (2)	−0.0172 (2)	−0.0179 (2)
O23	0.0841 (12)	0.0528 (10)	0.1235 (14)	0.0168 (8)	−0.0476 (11)	−0.0355 (9)
O24	0.0598 (9)	0.0738 (10)	0.0708 (9)	−0.0122 (8)	−0.0342 (8)	−0.0078 (8)
O25	0.0612 (10)	0.0840 (11)	0.0630 (9)	−0.0324 (8)	0.0022 (7)	−0.0248 (8)

Geometric parameters (Å, º) top

C1—C2	1.351 (3)	N10—C14	1.366 (2)
C1—C11	1.428 (2)	N10—C12	1.377 (2)
C1—H1	0.9300	N10—C15	1.477 (2)
C2—C3	1.399 (3)	C11—C12	1.424 (2)
C2—H2	0.9300	C13—C14	1.421 (3)
C3—C4	1.359 (3)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C12	1.408 (3)	C15—H15C	0.9600
C4—H4	0.9300	C16—C17	1.526 (3)
C5—C6	1.360 (3)	C16—H16A	0.9700
C5—C14	1.418 (3)	C16—H16B	0.9700
C5—H5	0.9300	C17—H17A	0.9600
C6—C7	1.394 (3)	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C7—C8	1.351 (3)	F19—C18	1.332 (2)
C7—H7	0.9300	F20—C18	1.333 (3)
C8—C13	1.426 (3)	F21—C18	1.331 (2)
C8—H8	0.9300	S22—O25	1.4276 (15)
C9—C11	1.406 (3)	S22—O24	1.4308 (14)
C9—C13	1.411 (2)	S22—C18	1.809 (2)
C9—C16	1.496 (3)	O23—S22	1.4257 (16)

C2—C1—C11	121.23 (19)	C9—C13—C14	119.89 (17)
C2—C1—H1	119.4	C9—C13—C8	122.18 (17)
C11—C1—H1	119.4	C14—C13—C8	117.92 (16)
C1—C2—C3	120.02 (18)	N10—C14—C5	120.50 (17)
C1—C2—H2	120.0	N10—C14—C13	120.14 (15)
C3—C2—H2	120.0	C5—C14—C13	119.36 (18)
C4—C3—C2	121.4 (2)	N10—C15—H15A	109.5
C4—C3—H3	119.3	N10—C15—H15B	109.5
C2—C3—H3	119.3	H15A—C15—H15B	109.5
C3—C4—C12	120.01 (19)	N10—C15—H15C	109.5
C3—C4—H4	120.0	H15A—C15—H15C	109.5
C12—C4—H4	120.0	H15B—C15—H15C	109.5
C6—C5—C14	119.59 (19)	C9—C16—C17	111.60 (16)
C6—C5—H5	120.2	C9—C16—H16A	109.3
C14—C5—H5	120.2	C17—C16—H16A	109.3
C5—C6—C7	121.87 (18)	C9—C16—H16B	109.3
C5—C6—H6	119.1	C17—C16—H16B	109.3
C7—C6—H6	119.1	H16A—C16—H16B	108.0
C8—C7—C6	119.9 (2)	C16—C17—H17A	109.5
C8—C7—H7	120.1	C16—C17—H17B	109.5
C6—C7—H7	120.1	H17A—C17—H17B	109.5
C7—C8—C13	121.37 (19)	C16—C17—H17C	109.5
C7—C8—H8	119.3	H17A—C17—H17C	109.5
C13—C8—H8	119.3	H17B—C17—H17C	109.5
C11—C9—C13	118.54 (16)	F21—C18—F19	106.83 (16)
C11—C9—C16	120.65 (16)	F21—C18—F20	106.57 (17)
C13—C9—C16	120.72 (17)	F19—C18—F20	107.29 (19)
C14—N10—C12	121.38 (15)	F21—C18—S22	112.10 (16)
C14—N10—C15	119.21 (14)	F19—C18—S22	112.04 (14)
C12—N10—C15	119.40 (16)	F20—C18—S22	111.67 (14)
C9—C11—C12	120.23 (15)	O23—S22—O25	116.29 (11)
C9—C11—C1	122.06 (17)	O23—S22—O24	115.01 (10)
C12—C11—C1	117.71 (18)	O25—S22—O24	114.73 (10)
N10—C12—C4	120.96 (17)	O23—S22—C18	102.68 (11)
N10—C12—C11	119.48 (17)	O25—S22—C18	102.77 (9)
C4—C12—C11	119.55 (16)	O24—S22—C18	102.49 (10)

C11—C1—C2—C3	1.2 (3)	C16—C9—C13—C8	−0.9 (3)
C1—C2—C3—C4	−0.5 (3)	C7—C8—C13—C9	−177.97 (18)
C2—C3—C4—C12	−1.7 (3)	C7—C8—C13—C14	1.0 (3)
C14—C5—C6—C7	0.3 (3)	C12—N10—C14—C5	−173.83 (16)
C5—C6—C7—C8	−1.1 (3)	C15—N10—C14—C5	7.4 (3)
C6—C7—C8—C13	0.4 (3)	C12—N10—C14—C13	5.7 (2)
C13—C9—C11—C12	5.4 (2)	C15—N10—C14—C13	−173.07 (16)
C16—C9—C11—C12	−178.00 (15)	C6—C5—C14—N10	−179.46 (17)
C13—C9—C11—C1	−174.00 (16)	C6—C5—C14—C13	1.0 (3)
C16—C9—C11—C1	2.6 (3)	C9—C13—C14—N10	−2.2 (3)
C2—C1—C11—C9	179.61 (16)	C8—C13—C14—N10	178.83 (16)
C2—C1—C11—C12	0.2 (3)	C9—C13—C14—C5	177.31 (17)
C14—N10—C12—C4	176.08 (16)	C8—C13—C14—C5	−1.7 (3)
C15—N10—C12—C4	−5.2 (2)	C11—C9—C16—C17	−87.9 (2)
C14—N10—C12—C11	−3.5 (2)	C13—C9—C16—C17	88.5 (2)
C15—N10—C12—C11	175.24 (16)	O23—S22—C18—F21	56.86 (17)
C3—C4—C12—N10	−176.51 (16)	O25—S22—C18—F21	−64.24 (17)
C3—C4—C12—C11	3.1 (3)	O24—S22—C18—F21	176.45 (14)
C9—C11—C12—N10	−2.2 (2)	O23—S22—C18—F19	−63.24 (18)
C1—C11—C12—N10	177.29 (15)	O25—S22—C18—F19	175.66 (15)
C9—C11—C12—C4	178.25 (16)	O24—S22—C18—F19	56.35 (18)
C1—C11—C12—C4	−2.3 (2)	O23—S22—C18—F20	176.37 (14)
C11—C9—C13—C14	−3.3 (3)	O25—S22—C18—F20	55.27 (17)
C16—C9—C13—C14	−179.86 (15)	O24—S22—C18—F20	−64.04 (16)
C11—C9—C13—C8	175.63 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O23ⁱ	0.93	2.47	3.369 (3)	164
C15—H15C···O24ⁱⁱ	0.96	2.40	3.276 (3)	151
C16—H16B···O25ⁱⁱⁱ	0.97	2.58	3.377 (3)	140

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N⁺·CF₃SO₃⁻
M_r	371.37
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.771 (2), 9.440 (2), 11.898 (2)
α, β, γ (°)	76.76 (3), 74.04 (3), 82.14 (3)
V (Å³)	814.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.5 × 0.5 × 0.05

Data collection
Diffractometer	Oxford Diffraction GEMINI R ULTRA Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.870, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7781, 2857, 2078
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.102, 1.08
No. of reflections	2857
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O23ⁱ	0.93	2.47	3.369 (3)	164
C15—H15C···O24ⁱⁱ	0.96	2.40	3.276 (3)	151
C16—H16B···O25ⁱⁱⁱ	0.97	2.58	3.377 (3)	140

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

π–π Interactions (Å, °). top

CgI	CgJ	Cg···Cg	Dihedral angle	Interplanar distance	Offset
1	2^iv	3.814 (2)	3.88	3.517 (2)	5.188
2	1^iv	3.814 (2)	3.88	3.542 (2)	5.205
2	2^iv	3.945 (2)	0.02	3.578 (2)	5.326
2	2^v	3.874 (2)	0.02	3.440 (2)	5.181

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

Notes: Cg1 is the centroid of ring B (C9/N10/C11-C14), Cg2 is the centroid of ring A (C1-C4/C11/C12). Cg···Cg is the distance between ring centroids. The dihedral angle is that between the planes of the rings CgI and CgJ. The interplanar distance is the perpendicular distance of CgI from ring J. The offset is the perpendicular distance of ring I from ring J.

S—O···π Interactions (Å, °). top

X	I	J	I···J	X···J	X-I···J
S22	O23	1^vi	3.255 (2)	3.072 (2)	146

Symmetry codes: (vi) -x+1, -y+1, -z+1.

Notes: Cg1 is the centroid of ring B (C9/N10/C11-C14).

Acknowledgements

This study was financed by the State Funds for Scientific Research (grant No. N204 123 32/3143, contract No. 3143/H03/ 2007/32 of the Polish Ministry of Research and Higher Education) for the period 2007–2010.

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