9-Chloro-2,4-dimethoxy­acridinium trifluoro­methane­sulfonate

Zadykowicz, B.; Krzymiński, K.; Trzybiński, D.; Sikorski, A.; Błażejowski, J.

doi:10.1107/S1600536809008551

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o768-o769

doi:10.1107/S1600536809008551

Open

access

9-Chloro-2,4-dimethoxyacridinium trifluoromethanesulfonate

Beata Zadykowicz,^a Karol Krzymiński,^a Damian Trzybiński,^a Artur Sikorski ^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 28 January 2009; accepted 9 March 2009; online 14 March 2009)

In the molecular structure of the title compound, C₁₅H₁₃ClNO₂⁺·CF₃SO₃⁻, the methoxy groups are nearly coplanar with the acridine ring system, making dihedral angles of 0.4 (2) and 5.1 (2)°. Multidirectional π–π contacts between acridine units are observed in the crystal structure. N—H⋯O and C—H⋯O hydrogen bonds link cations and anions, forming a layer structure.

Related literature

For general background, see: Acheson (1973 ); Demeunynck et al. (2001 ); Wróblewska et al. (2004 ); Zomer & Jacquemijns (2001 ). For related structures, see: Achari & Neidle (1977 ); Neidle (1982 ); Ning et al. (1976 ); Ojida et al. (2006 ); Rimmer et al. (2000 ); Toma et al. (1993 ). For intermolecular interactions, see: Aakeröy et al. (1992 ); Bianchi et al. (2004 ); Hunter et al. (2001 ); Steiner (1999 ). For the synthesis, see: Acheson (1973); Sato (1996 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₅H₁₃ClNO₂⁺·CF₃SO₃⁻
M_r = 423.79
Monoclinic, P 2₁ /c
a = 11.0502 (9) Å
b = 23.110 (2) Å
c = 7.1435 (8) Å
β = 108.214 (11)°
V = 1732.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 295 K
0.60 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.782, T_max = 0.959
12548 measured reflections
3072 independent reflections
1932 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.179
S = 1.06
3072 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10⋯O23	0.86	2.01	2.826 (4)	159
C5—H5⋯O23	0.93	2.42	3.151 (5)	136
C8—H8⋯O22ⁱ	0.93	2.53	3.348 (6)	147
C18—H18A⋯O22	0.96	2.56	3.326 (5)	137
C18—H18C⋯O22ⁱⁱ	0.96	2.55	3.462 (5)	158
Symmetry codes: (i) x+1, y, z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Table 2
π–π Interactions (Å,°)

CgI	CgJ	Cg⋯Cg	Dihedral angle	Interplanar distance
1	1ⁱⁱⁱ	3.817 (2)	0.33	3.506 (2)
1	1ⁱⁱ	3.817 (2)	0.33	3.499 (2)
1	2ⁱⁱⁱ	3.984 (2)	1.19	3.484 (2)
1	2ⁱⁱ	3.616 (2)	1.19	3.493 (2)
2	3ⁱⁱⁱ	3.919 (2)	1.95	3.490 (2)
3	2ⁱⁱ	3.919 (2)	1.95	3.509 (2)
Symmetry codes: (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}.]$ Cg1, Cg2 and Cg3 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C5–C8/C13/C14 rings, respectively. Cg⋯Cg is the distance between ring centroids. The dihedral angle is that between the planes of the rings. The interplanar distance is the perpendicular distance of CgI from ring J.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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: 10.1107/S1600536809008551/xu2477sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008551/xu2477Isup2.hkl

checkCIF report

Comment top

Acridinium cations containing various substituents at position 9 and alkyl-substituted at the endocyclic N atom (position 10) undergo oxidation by H₂O₂ or other peroxides in alkaline media, which leads to the formation of electronically excited 10-alkyl-9-acridinones capable of emitting light with a quantum yield of several percent (Zomer & Jacquemijns, 2001; Wróblewska et al., 2004). This chemiluminescence is affected by the features of the substituent at position 9 and by the constitution of the acridine fragment. In the search for derivatives that could exhibit an enhanced chemiluminogenic ability we turned our attention to compounds in which the C atom at position 9 is bound to a Cl atom. One of the compounds synthesized was 9-chloro-2,4-dimethoxyacridinium trifluoromethanesulfonate. This compound was obtained by the reaction of 9-chloro-2,4-dimethoxyacridine with methyl trifluoromethanesulfonate, which usually leads to quarternarization of the endocyclic N atom (Sato, 1996). Since this did not happen, it is possible that traces of water caused the transformation of methyl trifluoromethanesulfonate to trifluoromethanesulfonic acid and methanol, and the reaction of the former entity with 9-chloro-2,4-dimethoxyacridine to yield 9-chloro-2,4-dimethoxyacridinium trifluoromethanesulfonate. The cation of the title compound has a protonated endocyclic N-atom, which makes its reaction with oxidants possible. On the other hand, substitution in the acridine moiety by two methoxy groups should cause a red shift of the chemiluminescence emission, advantageous in analytical applications. 9-Chloroacridines have been precursors of numerous 9-substitued acridine derivatives (Acheson, 1973; Wróblewska et al., 2004), including drugs (Acheson, 1973; Demeunynck et al., 2001). This paper presents the crystal structure of the title compound.

The acridine units, with an average deviation from planarity of 0.025 (5) Å, are parallel in the crystal lattice. In the cation of the title compound (Fig. 1) the bond lengths and angles characterizing the geometry of the 9-chloroacridine skeleton are similar to those in 9-chloroacridine itself (Achari & Neidle, 1977), a 9-chloroacridine derivative (Neidle, 1982), a 9-chloroacridine iodine complex (Rimmer et al., 2000), two solvates of 9-chloroacridine derivatives (Toma et al., 1993; Ojida et al., 2006) and the salt-type compound containing the 9-chloroacridinium cation (Ning et al., 1976). The crystal structures of these six compounds were found in the Cambridge Structural Database (Version 5.29; Allen, 2002). The C(9)–Cl, N(10)–C(12) and N(10)–C(14) bond lengths (in Å) in them vary from 1.719 to 1.748, from 1.332 to 1.375 and from 1.349 to 1.383, respectively. The corresponding values for the compound investigated (1.723, 1.346 and 1.351) thus fall well within the ranges found for other 9-chloroacridines.

In the crystal structure, N–H···O (Aakeröy et. al., 1992) and C–H···O (Steiner, 1999; Bianchi et al., 2004) hydrogen bonds link cations and anions in ion pairs (Table 1, Fig. 1). Inversely oriented ion pairs form stacks via π-π contacts of an attractive nature (Hunter et al., 2001), involving the central ring (Cg1) and the aromatic rings (Cg2 and Cg3) (Table 2), as well as C–H···O interactions between adjacent ions (Fig. 2). Stacks arranged in parallel are linked through intermolecular C–H···O interactions (Figs 2 and 3) to form layers (Fig. 3). The crystal structure is stabilized by short-range non-specific dispersive interactions between inversely oriented layers (Fig. 3) as well as by long-range electrostatic interactions between ions.

Related literature top

For general background, see: Acheson (1973); Demeunynck et al. (2001); Wróblewska et al. (2004); Zomer & Jacquemijns (2001). For related structures, see: Achari & Neidle (1977); Neidle (1982); Ning et al. (1976); Ojida et al. (2006); Rimmer et al. (2000); Toma et al. (1993). For intermolecular interactions, see: Aakeröy et al. (1992); Bianchi et al. (2004); Hunter et al. (2001); Steiner (1999). For the synthesis, see: Acheson (1973); Sato (1996). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

9-Chloro-2,4-dimethoxyacridine was prepared by heating 2-[(2,4-dimethoxyphenyl)amino]benzoic acid, obtained as described elsewhere (Acheson, 1973), with a sevenfold molar excess of POCl₃ (400 K, 3 h). The excess POCl₃ was subsequently removed under reduced pressure. The residue was dispersed in CHCl₃, stirred in the presence of a mixture of ice and aqueous ammonia, separated by filtration and dried. The crude product was purified chromatographically (neutral Al₂O₃, CHCl₃/toluene, 1/1 v/v, R_f=0.29). The 9-chloro-2,4-dimethoxyacridine was dissolved in CH₂Cl₂, then treated with a fivefold molal excess of methyl trifluoromethanesulfonate dissolved in the same solvent (under an Ar atmosphere at room temperature for 3 h) (Sato, 1996). The crude salt was dissolved in a small amount of ethanol, filtered and precipitated with a 25 v/v excess of diethyl ether (yield: 71%). Purple crystals suitable for X-ray investigations were grown from 2-propanol solution (m.p. 493–496 K).

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. The C5–H5···O23, N10–H10···O23 and C18–H18A···O22 hydrogen bonds are represented by dashed lines. Cg1, Cg2 and Cg3 denote the ring centroids.
	Fig. 2. The arrangement of the ions in the crystal structure, viewed along the a axis. The N–H···O and C–H···O hydrogen bonds are represented by dashed lines, the π-π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) x + 1, y, z + 1; (ii) x, -y + 3/2, z + 1/2; (iii) x, -y + 3/2, z - 1/2.]
	Fig. 3. Ion pair stacks in the crystal structure, viewed along the c axis. The N–H···O and C–H···O interactions are represented by dashed lines. H atoms not involved in interactions have been omitted.

9-Chloro-2,4-dimethoxyacridinium trifluoromethanesulfonate top

Crystal data top

C₁₅H₁₃ClNO₂⁺·CF₃SO₃⁻	F(000) = 864
M_r = 423.79	D_x = 1.625 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5776 reflections
a = 11.0502 (9) Å	θ = 3.0–29.2°
b = 23.110 (2) Å	µ = 0.40 mm⁻¹
c = 7.1435 (8) Å	T = 295 K
β = 108.214 (11)°	Plate, purple
V = 1732.8 (3) Å³	0.60 × 0.20 × 0.10 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3072 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1932 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
Detector resolution: 10.4002 pixels mm^-1	θ_max = 25.1°, θ_min = 3.1°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −25→27
T_min = 0.782, T_max = 0.959	l = −8→8
12548 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1062P)²P] where P = (F_o² + 2F_c²)/3
3072 reflections	(Δ/σ)_max < 0.001
246 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₅H₁₃ClNO₂⁺·CF₃SO₃⁻	V = 1732.8 (3) Å³
M_r = 423.79	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.0502 (9) Å	µ = 0.40 mm⁻¹
b = 23.110 (2) Å	T = 295 K
c = 7.1435 (8) Å	0.60 × 0.20 × 0.10 mm
β = 108.214 (11)°

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3072 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	1932 reflections with I > 2σ(I)
T_min = 0.782, T_max = 0.959	R_int = 0.063
12548 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
3072 reflections	Δρ_min = −0.28 e Å⁻³
246 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	1.1372 (3)	0.84277 (15)	0.6837 (5)	0.0588 (9)
H1	1.2152	0.8604	0.7447	0.071*
C2	1.0316 (3)	0.87560 (16)	0.6029 (5)	0.0630 (9)
C3	0.9120 (3)	0.85005 (15)	0.5039 (5)	0.0606 (9)
H3	0.8414	0.8734	0.4478	0.073*
C4	0.9004 (3)	0.79165 (14)	0.4907 (5)	0.0539 (8)
C5	1.0717 (4)	0.60054 (16)	0.6391 (5)	0.0672 (9)
H5	0.9905	0.5857	0.5802	0.081*
C6	1.1712 (4)	0.56449 (18)	0.7170 (6)	0.0774 (11)
H6	1.1578	0.5247	0.7103	0.093*
C7	1.2939 (4)	0.5859 (2)	0.8075 (6)	0.0824 (12)
H7	1.3608	0.5603	0.8595	0.099*
C8	1.3169 (4)	0.64432 (19)	0.8204 (6)	0.0740 (10)
H8	1.3990	0.6579	0.8812	0.089*
C9	1.2292 (3)	0.74378 (17)	0.7518 (5)	0.0586 (9)
N10	0.9955 (2)	0.69822 (11)	0.5708 (4)	0.0525 (7)
H10	0.9213	0.6840	0.5128	0.063*
C11	1.1281 (3)	0.78210 (15)	0.6748 (4)	0.0532 (8)
C12	1.0075 (3)	0.75623 (14)	0.5787 (4)	0.0507 (8)
C13	1.2163 (3)	0.68400 (16)	0.7418 (5)	0.0606 (9)
C14	1.0924 (3)	0.66091 (15)	0.6481 (4)	0.0552 (8)
O15	1.0275 (2)	0.93401 (11)	0.6023 (4)	0.0789 (8)
C16	1.1437 (4)	0.96502 (17)	0.6957 (6)	0.0822 (11)
H16A	1.1261	1.0057	0.6933	0.123*
H16B	1.2038	0.9577	0.6263	0.123*
H16C	1.1787	0.9523	0.8298	0.123*
O17	0.7946 (2)	0.76076 (10)	0.3978 (4)	0.0661 (7)
C18	0.6815 (3)	0.79154 (16)	0.2905 (6)	0.0708 (10)
H18A	0.6146	0.7644	0.2313	0.106*
H18B	0.6985	0.8145	0.1894	0.106*
H18C	0.6557	0.8164	0.3789	0.106*
Cl19	1.37790 (8)	0.77318 (5)	0.86037 (16)	0.0835 (4)
S20	0.67506 (9)	0.60826 (4)	0.27655 (15)	0.0686 (4)
O21	0.7046 (4)	0.56795 (15)	0.1495 (6)	0.1301 (14)
O22	0.5948 (3)	0.65462 (13)	0.1825 (5)	0.1074 (11)
O23	0.7793 (2)	0.62580 (14)	0.4408 (5)	0.0967 (9)
C24	0.5785 (4)	0.56702 (17)	0.3904 (6)	0.0738 (10)
F25	0.6355 (3)	0.52276 (13)	0.4837 (5)	0.1314 (12)
F26	0.5357 (4)	0.59810 (14)	0.5057 (6)	0.1486 (14)
F27	0.4759 (3)	0.54695 (15)	0.2592 (5)	0.1493 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.054 (2)	0.065 (2)	0.0553 (19)	−0.0088 (16)	0.0140 (17)	−0.0015 (16)
C2	0.063 (2)	0.063 (2)	0.065 (2)	−0.0052 (18)	0.0233 (19)	0.0038 (17)
C3	0.052 (2)	0.060 (2)	0.069 (2)	0.0021 (16)	0.0174 (17)	0.0038 (16)
C4	0.0440 (19)	0.060 (2)	0.0566 (19)	0.0002 (15)	0.0145 (16)	0.0040 (15)
C5	0.063 (2)	0.068 (2)	0.066 (2)	0.0039 (18)	0.0139 (18)	0.0018 (18)
C6	0.085 (3)	0.068 (2)	0.075 (2)	0.021 (2)	0.019 (2)	0.004 (2)
C7	0.069 (3)	0.091 (3)	0.078 (3)	0.027 (2)	0.010 (2)	0.001 (2)
C8	0.054 (2)	0.092 (3)	0.068 (2)	0.016 (2)	0.0068 (18)	0.002 (2)
C9	0.0459 (19)	0.079 (2)	0.0499 (19)	−0.0051 (17)	0.0143 (16)	−0.0011 (16)
N10	0.0432 (15)	0.0611 (17)	0.0512 (15)	−0.0001 (12)	0.0117 (12)	0.0015 (12)
C11	0.0461 (19)	0.070 (2)	0.0451 (17)	0.0013 (16)	0.0166 (15)	0.0014 (15)
C12	0.048 (2)	0.061 (2)	0.0460 (17)	0.0001 (15)	0.0194 (15)	−0.0001 (14)
C13	0.047 (2)	0.083 (3)	0.0505 (19)	0.0091 (17)	0.0132 (16)	0.0031 (17)
C14	0.052 (2)	0.065 (2)	0.0497 (18)	0.0068 (16)	0.0174 (16)	0.0027 (16)
O15	0.0707 (17)	0.0567 (15)	0.1022 (19)	−0.0073 (13)	0.0168 (15)	−0.0006 (13)
C16	0.082 (3)	0.067 (2)	0.087 (3)	−0.022 (2)	0.011 (2)	−0.002 (2)
O17	0.0444 (14)	0.0601 (14)	0.0823 (17)	−0.0032 (11)	0.0030 (12)	0.0067 (12)
C18	0.045 (2)	0.071 (2)	0.086 (3)	0.0088 (17)	0.0050 (19)	0.0042 (19)
Cl19	0.0457 (6)	0.1037 (8)	0.0908 (7)	−0.0074 (5)	0.0067 (5)	−0.0076 (6)
S20	0.0630 (6)	0.0553 (6)	0.0846 (7)	−0.0041 (4)	0.0190 (5)	0.0067 (5)
O21	0.186 (4)	0.090 (2)	0.156 (3)	−0.022 (2)	0.114 (3)	−0.022 (2)
O22	0.082 (2)	0.0794 (19)	0.138 (3)	−0.0040 (16)	0.0005 (19)	0.0429 (18)
O23	0.0595 (16)	0.099 (2)	0.115 (2)	−0.0209 (16)	0.0038 (16)	0.0111 (18)
C24	0.063 (2)	0.066 (2)	0.089 (3)	−0.001 (2)	0.021 (2)	0.005 (2)
F25	0.112 (2)	0.109 (2)	0.178 (3)	0.0179 (17)	0.052 (2)	0.080 (2)
F26	0.165 (3)	0.122 (2)	0.210 (4)	−0.025 (2)	0.132 (3)	−0.023 (2)
F27	0.111 (2)	0.174 (3)	0.136 (3)	−0.081 (2)	−0.001 (2)	0.033 (2)

Geometric parameters (Å, º) top

C1—C2	1.360 (5)	N10—C12	1.346 (4)
C1—C11	1.405 (5)	N10—C14	1.351 (4)
C1—H1	0.9300	N10—H10	0.8600
C2—O15	1.351 (4)	C11—C12	1.426 (4)
C2—C3	1.418 (5)	C13—C14	1.427 (5)
C3—C4	1.356 (5)	O15—C16	1.439 (4)
C3—H3	0.9300	C16—H16A	0.9600
C4—O17	1.354 (4)	C16—H16B	0.9600
C4—C12	1.414 (4)	C16—H16C	0.9600
C5—C6	1.353 (5)	O17—C18	1.434 (4)
C5—C14	1.412 (5)	C18—H18A	0.9600
C5—H5	0.9300	C18—H18B	0.9600
C6—C7	1.398 (6)	C18—H18C	0.9600
C6—H6	0.9300	S20—O21	1.408 (3)
C7—C8	1.370 (6)	S20—O22	1.419 (3)
C7—H7	0.9300	S20—O23	1.422 (3)
C8—C13	1.415 (5)	S20—C24	1.803 (4)
C8—H8	0.9300	C24—F25	1.275 (4)
C9—C13	1.388 (5)	C24—F26	1.289 (4)
C9—C11	1.396 (5)	C24—F27	1.310 (5)
C9—Cl19	1.723 (3)

C2—C1—C11	119.9 (3)	N10—C12—C11	120.2 (3)
C2—C1—H1	120.1	C4—C12—C11	119.8 (3)
C11—C1—H1	120.1	C9—C13—C8	124.7 (3)
O15—C2—C1	125.6 (3)	C9—C13—C14	117.7 (3)
O15—C2—C3	112.9 (3)	C8—C13—C14	117.6 (4)
C1—C2—C3	121.4 (3)	N10—C14—C5	121.1 (3)
C4—C3—C2	120.1 (3)	N10—C14—C13	118.3 (3)
C4—C3—H3	119.9	C5—C14—C13	120.6 (3)
C2—C3—H3	119.9	C2—O15—C16	118.2 (3)
O17—C4—C3	127.4 (3)	O15—C16—H16A	109.5
O17—C4—C12	112.8 (3)	O15—C16—H16B	109.5
C3—C4—C12	119.9 (3)	H16A—C16—H16B	109.5
C6—C5—C14	119.4 (4)	O15—C16—H16C	109.5
C6—C5—H5	120.3	H16A—C16—H16C	109.5
C14—C5—H5	120.3	H16B—C16—H16C	109.5
C5—C6—C7	121.2 (4)	C4—O17—C18	118.4 (3)
C5—C6—H6	119.4	O17—C18—H18A	109.5
C7—C6—H6	119.4	O17—C18—H18B	109.5
C8—C7—C6	120.9 (4)	H18A—C18—H18B	109.5
C8—C7—H7	119.6	O17—C18—H18C	109.5
C6—C7—H7	119.6	H18A—C18—H18C	109.5
C7—C8—C13	120.4 (4)	H18B—C18—H18C	109.5
C7—C8—H8	119.8	O21—S20—O22	115.5 (2)
C13—C8—H8	119.8	O21—S20—O23	115.4 (2)
C13—C9—C11	123.7 (3)	O22—S20—O23	113.59 (19)
C13—C9—Cl19	118.9 (3)	O21—S20—C24	103.3 (2)
C11—C9—Cl19	117.4 (3)	O22—S20—C24	104.03 (19)
C12—N10—C14	124.3 (3)	O23—S20—C24	102.66 (19)
C12—N10—H10	117.9	F25—C24—F26	109.4 (4)
C14—N10—H10	117.9	F25—C24—F27	105.4 (4)
C9—C11—C1	125.3 (3)	F26—C24—F27	104.2 (4)
C9—C11—C12	115.8 (3)	F25—C24—S20	113.3 (3)
C1—C11—C12	118.8 (3)	F26—C24—S20	112.4 (3)
N10—C12—C4	120.0 (3)	F27—C24—S20	111.5 (3)

C11—C1—C2—O15	179.7 (3)	Cl19—C9—C13—C8	2.0 (5)
C11—C1—C2—C3	−1.8 (5)	C11—C9—C13—C14	−0.3 (5)
O15—C2—C3—C4	179.7 (3)	Cl19—C9—C13—C14	−179.0 (2)
C1—C2—C3—C4	1.1 (5)	C7—C8—C13—C9	178.3 (3)
C2—C3—C4—O17	−178.2 (3)	C7—C8—C13—C14	−0.7 (5)
C2—C3—C4—C12	1.0 (5)	C12—N10—C14—C5	178.1 (3)
C14—C5—C6—C7	0.5 (6)	C12—N10—C14—C13	−1.1 (4)
C5—C6—C7—C8	0.2 (6)	C6—C5—C14—N10	179.6 (3)
C6—C7—C8—C13	−0.1 (6)	C6—C5—C14—C13	−1.2 (5)
C13—C9—C11—C1	179.4 (3)	C9—C13—C14—N10	1.5 (4)
Cl19—C9—C11—C1	−2.0 (4)	C8—C13—C14—N10	−179.5 (3)
C13—C9—C11—C12	−1.2 (4)	C9—C13—C14—C5	−177.7 (3)
Cl19—C9—C11—C12	177.4 (2)	C8—C13—C14—C5	1.3 (5)
C2—C1—C11—C9	180.0 (3)	C1—C2—O15—C16	−0.5 (5)
C2—C1—C11—C12	0.6 (5)	C3—C2—O15—C16	−179.0 (3)
C14—N10—C12—C4	179.1 (3)	C3—C4—O17—C18	3.6 (5)
C14—N10—C12—C11	−0.6 (4)	C12—C4—O17—C18	−175.7 (3)
O17—C4—C12—N10	−2.6 (4)	O21—S20—C24—F25	59.0 (4)
C3—C4—C12—N10	178.1 (3)	O22—S20—C24—F25	−180.0 (3)
O17—C4—C12—C11	177.1 (3)	O23—S20—C24—F25	−61.4 (4)
C3—C4—C12—C11	−2.2 (4)	O21—S20—C24—F26	−176.3 (4)
C9—C11—C12—N10	1.7 (4)	O22—S20—C24—F26	−55.3 (4)
C1—C11—C12—N10	−178.9 (3)	O23—S20—C24—F26	63.3 (4)
C9—C11—C12—C4	−178.0 (3)	O21—S20—C24—F27	−59.7 (4)
C1—C11—C12—C4	1.4 (4)	O22—S20—C24—F27	61.3 (4)
C11—C9—C13—C8	−179.3 (3)	O23—S20—C24—F27	179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···O23	0.86	2.01	2.826 (4)	159
C5—H5···O23	0.93	2.42	3.151 (5)	136
C8—H8···O22ⁱ	0.93	2.53	3.348 (6)	147
C18—H18A···O22	0.96	2.56	3.326 (5)	137
C18—H18C···O22ⁱⁱ	0.96	2.55	3.462 (5)	158

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃ClNO₂⁺·CF₃SO₃⁻
M_r	423.79
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	11.0502 (9), 23.110 (2), 7.1435 (8)
β (°)	108.214 (11)
V (Å³)	1732.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.60 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.782, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	12548, 3072, 1932
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.179, 1.06
No. of reflections	3072
No. of parameters	246
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.28

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
N10—H10···O23	0.86	2.01	2.826 (4)	159
C5—H5···O23	0.93	2.42	3.151 (5)	136
C8—H8···O22ⁱ	0.93	2.53	3.348 (6)	147
C18—H18A···O22	0.96	2.56	3.326 (5)	137
C18—H18C···O22ⁱⁱ	0.96	2.55	3.462 (5)	158

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

π–π Interactions (Å,°). top

CgI	CgJ	Cg···Cg	Dihedral angle	Interplanar distance
1	1ⁱⁱⁱ	3.817 (2)	0.33	3.506 (2)
1	1ⁱⁱ	3.817 (2)	0.33	3.499 (2)
1	2ⁱⁱⁱ	3.984 (2)	1.19	3.484 (2)
1	2ⁱⁱ	3.616 (2)	1.19	3.493 (2)
2	3ⁱⁱⁱ	3.919 (2)	1.95	3.490 (2)
3	2ⁱⁱ	3.919 (2)	1.95	3.509 (2)

Symmetry codes: (ii) x, -y+3/2, z+1/2; (iii) x, -y+3/2, z-1/2. Cg1, Cg2 and Cg3 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C5–C8/C13/C14 rings, respectively. Cg···Cg is the distance between ring centroids. The dihedral angle is that between the planes of the rings. The interplanar distance is the perpendicular distance of CgI from ring J.

Acknowledgements

The financing of this work from 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) is acknowledged. BZ is grateful for a fellowship from the European Social Fund, the Polish State Budget and the Budget of the Province of Pomerania within the framework of the "Priority VIII Human Capital Operational Programme, action 8.2, subaction 8.2.2 `Regional Innovation Strategy'", of the `InnoDoktorant' project of the Province of Pomerania - fellowships for PhD students, 1^st edition.

References

Aakeröy, C. B., Seddon, K. R. & Leslie, M. (1992). Struct. Chem. 3, 63–65. Google Scholar
Achari, A. & Neidle, S. (1977). Acta Cryst. B33, 3269–3270. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Acheson, R. M. (1973). Acridines, 2nd ed. New York: Interscience. Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bianchi, R., Forni, A. & Pilati, T. (2004). Acta Cryst. B60, 559–568. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Demeunynck, M., Charmantray, F. & Martelli, A. (2001). Curr. Pharm. Des. 7, 1703–1724. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hunter, C. A., Lawson, K. R., Perkins, J. & Urch, C. J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 651–669. Web of Science CrossRef Google Scholar
Neidle, S. (1982). Acta Cryst. B38, 159–162. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ning, R. Y., Madan, P. B., Blount, J. F. & Frayer, R. I. (1976). J. Org. Chem. 41, 3406–3409. CSD CrossRef CAS Web of Science Google Scholar
Ojida, A., Miyahara, Y., Wongkongkapet, J., Tamaru, S., Sada, K. & Hamachi, I. (2006). Chem. Asia. J. 1, 555–563. Web of Science CSD CrossRef CAS Google Scholar
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Rimmer, E. L., Bailey, R. D., Hanks, T. W. & Pennington, W. T. (2000). Chem. Eur. J. 6, 4071–4081. CrossRef PubMed CAS Google Scholar
Sato, N. (1996). Tetrahedron Lett. 37, 8519–8522. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steiner, T. (1999). Chem. Commun. pp. 313–314. Web of Science CrossRef Google Scholar
Toma, P. H., Nguyen, D. N. & Byrn, S. R. (1993). Acta Cryst. C49, 914–916. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Wróblewska, A., Huta, O. M., Midyanyj, S. V., Patsay, I. O., Rak, J. & Błażejowski, J. (2004). J. Org. Chem. 69, 1607–1614. Web of Science CrossRef PubMed CAS Google Scholar
Zomer, G. & Jacquemijns, M. (2001). Chemiluminescence in Analytical Chemistry, edited by A. M. Garcia-Campana & W. R. G. Baeyens, pp. 529–549. New York: Marcel Dekker. Google Scholar