10-Methyl-9-[2-(propan-2-yl)phenoxy­carbonyl]­acridinium trifluoro­methane­sulfonate

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

doi:10.1107/S160053681003953X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2773-o2774

https://doi.org/10.1107/S160053681003953X

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10-Methyl-9-[2-(propan-2-yl)phenoxycarbonyl]acridinium 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 30 September 2010; accepted 4 October 2010; online 9 October 2010)

In the crystal of the title compound, C₂₄H₂₂NO₂⁺·CF₃SO₃⁻, adjacent cations and anions are connected through C—H⋯O, C—H⋯F and S–O⋯π interactions, while neighboring cations via π–π interactions [centroid–centroid distance = 3.962 (2) Å]. The acridine and benzene ring systems are oriented at a dihedral angle of 14.6 (1)°. The carboxyl group is twisted at an angle of 87.6 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel or inclined at an angle of 13.4 (1)° in the crystal structure.

Related literature

For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Natrajan et al. (2010 ); 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. (2006 , 2007 ); Trzybiński et al. (2010 ). For intermolecular interactions, see: Bianchi et al. (2004 ); Dorn et al. (2005 ); Hunter et al. (2001 ); Lyssenko & Antipin (2004 ); Novoa et al. (2006 ). For the synthesis, see: Sato (1996 ); Trzybiński et al. (2010).

Experimental

Crystal data

C₂₄H₂₂NO₂⁺·CF₃SO₃⁻
M_r = 505.51
Monoclinic, P 2₁ /c
a = 14.4346 (7) Å
b = 12.9677 (5) Å
c = 13.0862 (5) Å
β = 107.160 (5)°
V = 2340.47 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 295 K
0.32 × 0.20 × 0.05 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.955, T_max = 1.000
17556 measured reflections
4169 independent reflections
2436 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.116
S = 0.93
4169 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O29ⁱ	0.93	2.48	3.363 (3)	159
C27—H27C⋯F35ⁱ	0.96	2.51	3.250 (4)	134
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
S–O⋯π interactions (Å,°)

Cg2 is the centroids of the C1–C4/C11/C12 ring.

X	I	J	I⋯J	X⋯J	X–I⋯J
S28	O31	Cg2ⁱⁱ	3.208 (2)	4.128 (2)	120.3 (2)
Symmetry code: (ii) -x+2, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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/S160053681003953X/ng5040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681003953X/ng5040Isup2.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; Natrajan et al., 2010). The cations of these salts are oxidized with H₂O₂ in alkaline media, a reaction that produces light. The latter 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 structure of the phenyl fragment (Zomer & Jacquemijns, 2001; Natrajan et al., 2010). In the search for efficient chemiluminogens we synthesized 9-(phenoxycarbonyl)-10-methylacridinium derivatives alkyl substituted in the ortho position of the phenyl fragment. Here we present the structure of 9-(2-i-propylphenoxycarbonyl)-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., 2006; Sikorski et al., 2007; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0127 (3) Å and 0.0030 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 14.6 (1)°. The carboxyl group is twisted at an angle of 87.6 (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 87.6 (1)° in the lattice. In the series of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates substituted in the ortho position of the phenyl fragment with Me (Sikorski et al., 2006), Et (Trzybiński et al., 2010), i-Pr (this work) and t-Bu (Sikorski et al., 2007), the dihedral angle between acridine and the benzene ring, and that between the carboxyl group and the acridine skeleton, increase in the order 2-Et < 2-i-Pr < 2-Me < 2-t-Bu, and 2-t-Bu < 2-Et < 2-i-Pr < 2-Me, respectively. This implies that increasing size of the alkyl substituent in the ortho position does not systematically influence the mutual arrangement of the above mentioned fragments of the molecules.

In the crystal structure, each anion is connected to the adjacent cations through C–H···O (Table 1, Fig. 2), C–H···F (Table 1, Fig. 2) and S–O···π (Table 2, Fig. 2) interactions. Neighboring cations contact each other via π–π (Table 3, Fig. 2) interactions. The C–H···O (Novoa et al. 2006) and C–H··· F (Bianchi et al., 2004; Lyssenko & Antipin, 2004) interactions are of the hydrogen bond type. The 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: Natrajan et al. (2010); 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. (2006, 2007); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Lyssenko & Antipin (2004); Novoa et al. (2006). For the synthesis, see: Sato (1996); Trzybiński et al. (2010).

Experimental top

9-(Chlorocarbonyl)acridine, obtained by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride, was first esterified with 2-i-propylphenol 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) to obtain 2-i-propylphenylacridine-9-carboxylate (purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 1/1 v/v)). The latter compound was then quaternarized with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane (Trzybiński et al., 2010). The crude 9-(i-propylphenoxycarbonyl)-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. 464–466 K).

Structure description top

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, and Cg3 denote the ring centroids.
	Fig. 2. The arrangement of the ions in the crystal structure. The C–H···O and C–H···F interactions are represented by dashed lines, the S–O···π and π–π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) –x + 2, y + 1/2, –z + 1/2; (ii) –x + 2, –y + 1, –z + 1; (iii) –x + 1, –y + 2, –z + 1.]

10-Methyl-9-[2-(propan-2-yl)phenoxycarbonyl]acridinium trifluoromethanesulfonate top

Crystal data top

C₂₄H₂₂NO₂⁺·CF₃SO₃⁻	F(000) = 1048
M_r = 505.51	D_x = 1.435 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5919 reflections
a = 14.4346 (7) Å	θ = 3.0–29.2°
b = 12.9677 (5) Å	µ = 0.20 mm⁻¹
c = 13.0862 (5) Å	T = 295 K
β = 107.160 (5)°	Prism, yellow
V = 2340.47 (17) Å³	0.32 × 0.20 × 0.05 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	4169 independent reflections
Radiation source: Enhanced (Mo) X-ray Source	2436 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 10.4002 pixels mm^-1	θ_max = 25.1°, θ_min = 3.0°
ω scans	h = −17→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −15→15
T_min = 0.955, T_max = 1.000	l = −15→14
17556 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0687P)²] where P = (F_o² + 2F_c²)/3
4169 reflections	(Δ/σ)_max = 0.002
319 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₄H₂₂NO₂⁺·CF₃SO₃⁻	V = 2340.47 (17) Å³
M_r = 505.51	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.4346 (7) Å	µ = 0.20 mm⁻¹
b = 12.9677 (5) Å	T = 295 K
c = 13.0862 (5) Å	0.32 × 0.20 × 0.05 mm
β = 107.160 (5)°

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	4169 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	2436 reflections with I > 2σ(I)
T_min = 0.955, T_max = 1.000	R_int = 0.043
17556 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 0.93	Δρ_max = 0.34 e Å⁻³
4169 reflections	Δρ_min = −0.26 e Å⁻³
319 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	0.79663 (19)	0.93471 (19)	0.23882 (19)	0.0538 (6)
H1	0.7585	0.9653	0.2766	0.065*
C2	0.83868 (19)	0.9943 (2)	0.1808 (2)	0.0597 (7)
H2	0.8295	1.0653	0.1783	0.072*
C3	0.89659 (19)	0.9483 (2)	0.12396 (19)	0.0611 (7)
H3	0.9250	0.9899	0.0836	0.073*
C4	0.91234 (18)	0.8453 (2)	0.12618 (18)	0.0543 (7)
H4	0.9516	0.8173	0.0883	0.065*
C5	0.85827 (19)	0.50582 (19)	0.25407 (18)	0.0529 (6)
H5	0.8967	0.4761	0.2162	0.064*
C6	0.8169 (2)	0.4459 (2)	0.3131 (2)	0.0630 (7)
H6	0.8270	0.3750	0.3146	0.076*
C7	0.7591 (2)	0.4880 (2)	0.3722 (2)	0.0615 (7)
H7	0.7319	0.4452	0.4127	0.074*
C8	0.74323 (19)	0.58985 (19)	0.37013 (18)	0.0511 (6)
H8	0.7052	0.6173	0.4098	0.061*
C9	0.76717 (16)	0.76264 (17)	0.30277 (17)	0.0416 (6)
N10	0.88297 (13)	0.67612 (15)	0.18987 (14)	0.0445 (5)
C11	0.80948 (17)	0.82595 (17)	0.24349 (17)	0.0429 (6)
C12	0.86933 (16)	0.78034 (18)	0.18595 (17)	0.0429 (6)
C13	0.78353 (16)	0.65678 (17)	0.30837 (16)	0.0415 (6)
C14	0.84322 (17)	0.61298 (17)	0.24995 (17)	0.0433 (6)
C15	0.70287 (18)	0.80997 (17)	0.3623 (2)	0.0450 (6)
O16	0.61194 (12)	0.81571 (14)	0.29809 (12)	0.0569 (5)
O17	0.72938 (13)	0.83794 (15)	0.45268 (14)	0.0667 (5)
C18	0.54272 (18)	0.8721 (2)	0.33483 (17)	0.0516 (6)
C19	0.48032 (18)	0.8207 (2)	0.37892 (18)	0.0529 (7)
C20	0.4108 (2)	0.8824 (2)	0.4042 (2)	0.0648 (8)
H20	0.3666	0.8514	0.4338	0.078*
C21	0.4053 (2)	0.9861 (3)	0.3872 (2)	0.0688 (8)
H21	0.3582	1.0245	0.4057	0.083*
C22	0.4685 (2)	1.0341 (2)	0.3430 (2)	0.0718 (8)
H22	0.4648	1.1049	0.3313	0.086*
C23	0.5384 (2)	0.9758 (2)	0.3157 (2)	0.0652 (8)
H23	0.5817	1.0070	0.2849	0.078*
C24	0.4878 (2)	0.7061 (2)	0.4025 (2)	0.0665 (8)
H24	0.5264	0.6755	0.3599	0.080*
C25	0.5415 (3)	0.6867 (3)	0.5193 (3)	0.1123 (14)
H25A	0.6038	0.7197	0.5370	0.168*
H25B	0.5500	0.6138	0.5315	0.168*
H25C	0.5047	0.7143	0.5632	0.168*
C26	0.3890 (3)	0.6532 (3)	0.3699 (3)	0.1142 (14)
H26A	0.3566	0.6672	0.2959	0.171*
H26B	0.3506	0.6789	0.4130	0.171*
H26C	0.3976	0.5801	0.3803	0.171*
C27	0.9445 (2)	0.6310 (2)	0.1287 (2)	0.0645 (7)
H27A	0.9342	0.6677	0.0625	0.097*
H27B	0.9277	0.5597	0.1139	0.097*
H27C	1.0114	0.6362	0.1698	0.097*
S28	0.91241 (5)	0.22174 (5)	0.57658 (5)	0.0556 (2)
O29	0.94541 (16)	0.30956 (14)	0.53324 (15)	0.0809 (6)
O30	0.87168 (17)	0.23980 (15)	0.66093 (15)	0.0838 (7)
O31	0.97784 (15)	0.13502 (16)	0.59437 (16)	0.0819 (6)
C32	0.8122 (2)	0.1755 (2)	0.4689 (2)	0.0603 (7)
F33	0.73755 (14)	0.24221 (15)	0.44537 (15)	0.0955 (6)
F34	0.77668 (13)	0.08743 (12)	0.49175 (13)	0.0840 (5)
F35	0.83430 (13)	0.16316 (15)	0.37865 (11)	0.0895 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0500 (17)	0.0489 (16)	0.0643 (15)	0.0028 (13)	0.0195 (14)	−0.0015 (12)
C2	0.0544 (18)	0.0509 (16)	0.0716 (17)	−0.0002 (13)	0.0151 (15)	0.0075 (14)
C3	0.0533 (19)	0.069 (2)	0.0583 (16)	−0.0096 (14)	0.0130 (14)	0.0150 (14)
C4	0.0429 (16)	0.0720 (19)	0.0499 (14)	−0.0010 (13)	0.0166 (12)	0.0044 (13)
C5	0.0505 (17)	0.0518 (16)	0.0532 (14)	0.0114 (13)	0.0101 (13)	−0.0025 (12)
C6	0.073 (2)	0.0457 (16)	0.0642 (16)	0.0109 (14)	0.0110 (15)	0.0028 (13)
C7	0.073 (2)	0.0538 (17)	0.0577 (15)	0.0001 (15)	0.0192 (15)	0.0078 (13)
C8	0.0516 (17)	0.0532 (16)	0.0500 (13)	0.0041 (12)	0.0175 (12)	0.0016 (12)
C9	0.0353 (15)	0.0456 (14)	0.0421 (12)	0.0012 (11)	0.0088 (11)	−0.0043 (10)
N10	0.0327 (12)	0.0512 (13)	0.0496 (11)	0.0048 (9)	0.0122 (10)	−0.0056 (9)
C11	0.0354 (14)	0.0459 (14)	0.0451 (12)	−0.0009 (11)	0.0079 (11)	−0.0033 (10)
C12	0.0313 (14)	0.0520 (16)	0.0419 (12)	0.0005 (11)	0.0057 (11)	−0.0020 (11)
C13	0.0350 (14)	0.0469 (14)	0.0400 (12)	0.0022 (11)	0.0072 (11)	−0.0027 (10)
C14	0.0352 (15)	0.0474 (15)	0.0433 (12)	0.0038 (11)	0.0053 (11)	−0.0011 (10)
C15	0.0448 (17)	0.0431 (14)	0.0491 (14)	0.0012 (11)	0.0168 (13)	−0.0002 (11)
O16	0.0371 (11)	0.0851 (13)	0.0496 (9)	0.0067 (9)	0.0144 (9)	−0.0141 (8)
O17	0.0565 (12)	0.0881 (14)	0.0508 (10)	0.0133 (10)	0.0083 (9)	−0.0208 (9)
C18	0.0415 (16)	0.0713 (18)	0.0416 (13)	0.0115 (13)	0.0117 (12)	−0.0051 (12)
C19	0.0424 (16)	0.0733 (18)	0.0438 (13)	0.0045 (13)	0.0141 (12)	−0.0088 (12)
C20	0.0462 (19)	0.088 (2)	0.0656 (16)	0.0073 (16)	0.0254 (14)	−0.0050 (15)
C21	0.053 (2)	0.092 (2)	0.0599 (17)	0.0258 (17)	0.0146 (15)	−0.0015 (16)
C22	0.073 (2)	0.075 (2)	0.0639 (17)	0.0230 (17)	0.0137 (16)	0.0102 (14)
C23	0.062 (2)	0.081 (2)	0.0571 (16)	0.0124 (16)	0.0234 (15)	0.0095 (14)
C24	0.062 (2)	0.0676 (19)	0.0780 (19)	−0.0062 (15)	0.0340 (16)	−0.0155 (15)
C25	0.169 (4)	0.072 (2)	0.092 (2)	−0.007 (2)	0.032 (3)	0.0148 (18)
C26	0.084 (3)	0.097 (3)	0.177 (4)	−0.025 (2)	0.062 (3)	−0.056 (3)
C27	0.0563 (19)	0.0703 (18)	0.0781 (17)	0.0122 (14)	0.0374 (15)	−0.0050 (14)
S28	0.0708 (5)	0.0511 (4)	0.0508 (4)	−0.0092 (4)	0.0269 (3)	−0.0037 (3)
O29	0.1012 (17)	0.0671 (12)	0.0837 (13)	−0.0311 (11)	0.0416 (13)	0.0000 (10)
O30	0.128 (2)	0.0756 (13)	0.0675 (11)	−0.0128 (12)	0.0596 (13)	−0.0138 (9)
O31	0.0703 (15)	0.0821 (14)	0.0873 (13)	0.0193 (12)	0.0142 (11)	0.0035 (11)
C32	0.061 (2)	0.0637 (18)	0.0655 (17)	0.0012 (15)	0.0326 (16)	0.0020 (13)
F33	0.0703 (13)	0.1043 (14)	0.1154 (14)	0.0249 (11)	0.0328 (11)	0.0228 (11)
F34	0.0793 (13)	0.0644 (11)	0.1129 (13)	−0.0209 (9)	0.0354 (11)	−0.0061 (9)
F35	0.0815 (13)	0.1338 (16)	0.0590 (9)	−0.0108 (11)	0.0300 (9)	−0.0252 (9)

Geometric parameters (Å, º) top

C1—C2	1.347 (3)	C18—C19	1.377 (3)
C1—C11	1.422 (3)	C19—C20	1.397 (3)
C1—H1	0.9300	C19—C24	1.515 (4)
C2—C3	1.405 (3)	C20—C21	1.362 (4)
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.354 (4)	C21—C22	1.365 (4)
C3—H3	0.9300	C21—H21	0.9300
C4—C12	1.412 (3)	C22—C23	1.389 (4)
C4—H4	0.9300	C22—H22	0.9300
C5—C6	1.353 (3)	C23—H23	0.9300
C5—C14	1.405 (3)	C24—C25	1.516 (4)
C5—H5	0.9300	C24—C26	1.527 (4)
C6—C7	1.405 (4)	C24—H24	0.9800
C6—H6	0.9300	C25—H25A	0.9600
C7—C8	1.340 (3)	C25—H25B	0.9600
C7—H7	0.9300	C25—H25C	0.9600
C8—C13	1.422 (3)	C26—H26A	0.9600
C8—H8	0.9300	C26—H26B	0.9600
C9—C11	1.389 (3)	C26—H26C	0.9600
C9—C13	1.391 (3)	C27—H27A	0.9600
C9—C15	1.507 (3)	C27—H27B	0.9600
N10—C12	1.365 (3)	C27—H27C	0.9600
N10—C14	1.373 (3)	S28—O30	1.4148 (17)
N10—C27	1.481 (3)	S28—O29	1.4161 (18)
C11—C12	1.431 (3)	S28—O31	1.443 (2)
C13—C14	1.428 (3)	S28—C32	1.799 (3)
C15—O17	1.188 (3)	C32—F35	1.321 (3)
C15—O16	1.335 (3)	C32—F34	1.322 (3)
O16—C18	1.431 (3)	C32—F33	1.344 (3)
C18—C23	1.366 (4)

C2—C1—C11	121.2 (2)	C18—C19—C24	123.0 (2)
C2—C1—H1	119.4	C20—C19—C24	121.8 (2)
C11—C1—H1	119.4	C21—C20—C19	122.6 (3)
C1—C2—C3	119.5 (2)	C21—C20—H20	118.7
C1—C2—H2	120.2	C19—C20—H20	118.7
C3—C2—H2	120.2	C20—C21—C22	120.3 (3)
C4—C3—C2	122.0 (2)	C20—C21—H21	119.9
C4—C3—H3	119.0	C22—C21—H21	119.9
C2—C3—H3	119.0	C21—C22—C23	119.2 (3)
C3—C4—C12	120.1 (2)	C21—C22—H22	120.4
C3—C4—H4	119.9	C23—C22—H22	120.4
C12—C4—H4	119.9	C18—C23—C22	119.0 (3)
C6—C5—C14	120.1 (2)	C18—C23—H23	120.5
C6—C5—H5	120.0	C22—C23—H23	120.5
C14—C5—H5	120.0	C19—C24—C25	110.7 (2)
C5—C6—C7	121.7 (2)	C19—C24—C26	112.3 (3)
C5—C6—H6	119.2	C25—C24—C26	111.4 (3)
C7—C6—H6	119.2	C19—C24—H24	107.4
C8—C7—C6	119.9 (2)	C25—C24—H24	107.4
C8—C7—H7	120.1	C26—C24—H24	107.4
C6—C7—H7	120.1	C24—C25—H25A	109.5
C7—C8—C13	121.1 (2)	C24—C25—H25B	109.5
C7—C8—H8	119.4	H25A—C25—H25B	109.5
C13—C8—H8	119.4	C24—C25—H25C	109.5
C11—C9—C13	121.1 (2)	H25A—C25—H25C	109.5
C11—C9—C15	119.2 (2)	H25B—C25—H25C	109.5
C13—C9—C15	119.70 (19)	C24—C26—H26A	109.5
C12—N10—C14	122.16 (18)	C24—C26—H26B	109.5
C12—N10—C27	118.31 (19)	H26A—C26—H26B	109.5
C14—N10—C27	119.5 (2)	C24—C26—H26C	109.5
C9—C11—C1	122.5 (2)	H26A—C26—H26C	109.5
C9—C11—C12	118.9 (2)	H26B—C26—H26C	109.5
C1—C11—C12	118.6 (2)	N10—C27—H27A	109.5
N10—C12—C4	122.0 (2)	N10—C27—H27B	109.5
N10—C12—C11	119.5 (2)	H27A—C27—H27B	109.5
C4—C12—C11	118.5 (2)	N10—C27—H27C	109.5
C9—C13—C8	122.7 (2)	H27A—C27—H27C	109.5
C9—C13—C14	119.0 (2)	H27B—C27—H27C	109.5
C8—C13—C14	118.3 (2)	O30—S28—O29	116.47 (12)
N10—C14—C5	121.7 (2)	O30—S28—O31	113.97 (13)
N10—C14—C13	119.3 (2)	O29—S28—O31	114.20 (13)
C5—C14—C13	118.9 (2)	O30—S28—C32	104.08 (13)
O17—C15—O16	125.3 (2)	O29—S28—C32	104.00 (12)
O17—C15—C9	124.9 (2)	O31—S28—C32	101.75 (13)
O16—C15—C9	109.79 (19)	F35—C32—F34	108.1 (2)
C15—O16—C18	118.12 (17)	F35—C32—F33	105.2 (2)
C23—C18—C19	123.6 (2)	F34—C32—F33	105.7 (2)
C23—C18—O16	116.1 (2)	F35—C32—S28	112.96 (19)
C19—C18—O16	120.1 (2)	F34—C32—S28	112.72 (19)
C18—C19—C20	115.2 (2)	F33—C32—S28	111.7 (2)

C11—C1—C2—C3	−0.2 (4)	C8—C13—C14—N10	−179.9 (2)
C1—C2—C3—C4	−0.5 (4)	C9—C13—C14—C5	−178.8 (2)
C2—C3—C4—C12	0.6 (4)	C8—C13—C14—C5	1.2 (3)
C14—C5—C6—C7	−0.6 (4)	C11—C9—C15—O17	−92.5 (3)
C5—C6—C7—C8	0.5 (4)	C13—C9—C15—O17	87.2 (3)
C6—C7—C8—C13	0.4 (4)	C11—C9—C15—O16	87.4 (2)
C13—C9—C11—C1	−178.0 (2)	C13—C9—C15—O16	−92.8 (2)
C15—C9—C11—C1	1.7 (3)	O17—C15—O16—C18	8.9 (3)
C13—C9—C11—C12	1.2 (3)	C9—C15—O16—C18	−171.01 (19)
C15—C9—C11—C12	−179.1 (2)	C15—O16—C18—C23	86.1 (3)
C2—C1—C11—C9	179.9 (2)	C15—O16—C18—C19	−98.8 (3)
C2—C1—C11—C12	0.7 (4)	C23—C18—C19—C20	−0.3 (4)
C14—N10—C12—C4	178.4 (2)	O16—C18—C19—C20	−175.1 (2)
C27—N10—C12—C4	−0.4 (3)	C23—C18—C19—C24	−178.2 (2)
C14—N10—C12—C11	−1.9 (3)	O16—C18—C19—C24	7.0 (4)
C27—N10—C12—C11	179.4 (2)	C18—C19—C20—C21	−0.4 (4)
C3—C4—C12—N10	179.7 (2)	C24—C19—C20—C21	177.5 (3)
C3—C4—C12—C11	−0.1 (3)	C19—C20—C21—C22	0.6 (4)
C9—C11—C12—N10	0.5 (3)	C20—C21—C22—C23	0.0 (4)
C1—C11—C12—N10	179.7 (2)	C19—C18—C23—C22	0.8 (4)
C9—C11—C12—C4	−179.8 (2)	O16—C18—C23—C22	175.8 (2)
C1—C11—C12—C4	−0.6 (3)	C21—C22—C23—C18	−0.6 (4)
C11—C9—C13—C8	178.6 (2)	C18—C19—C24—C25	97.9 (3)
C15—C9—C13—C8	−1.2 (3)	C20—C19—C24—C25	−79.8 (3)
C11—C9—C13—C14	−1.4 (3)	C18—C19—C24—C26	−137.0 (3)
C15—C9—C13—C14	178.9 (2)	C20—C19—C24—C26	45.3 (3)
C7—C8—C13—C9	178.8 (2)	O30—S28—C32—F35	174.13 (19)
C7—C8—C13—C14	−1.2 (3)	O29—S28—C32—F35	51.7 (2)
C12—N10—C14—C5	−179.5 (2)	O31—S28—C32—F35	−67.2 (2)
C27—N10—C14—C5	−0.8 (3)	O30—S28—C32—F34	−63.0 (2)
C12—N10—C14—C13	1.6 (3)	O29—S28—C32—F34	174.54 (18)
C27—N10—C14—C13	−179.6 (2)	O31—S28—C32—F34	55.6 (2)
C6—C5—C14—N10	−179.2 (2)	O30—S28—C32—F33	55.7 (2)
C6—C5—C14—C13	−0.3 (3)	O29—S28—C32—F33	−66.7 (2)
C9—C13—C14—N10	0.0 (3)	O31—S28—C32—F33	174.42 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O29ⁱ	0.93	2.48	3.363 (3)	159
C27—H27C···F35ⁱ	0.96	2.51	3.250 (4)	134

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₂NO₂⁺·CF₃SO₃⁻
M_r	505.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	14.4346 (7), 12.9677 (5), 13.0862 (5)
β (°)	107.160 (5)
V (Å³)	2340.47 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.32 × 0.20 × 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	0.955, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17556, 4169, 2436
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.116, 0.93
No. of reflections	4169
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.26

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
C4—H4···O29ⁱ	0.93	2.48	3.363 (3)	159
C27—H27C···F35ⁱ	0.96	2.51	3.250 (4)	134

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

S–O···π interactions (Å,°). top

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
S28	O29	Cg1ⁱⁱ	3.703 (2)	3.879 (2)	86.3 (1)
S28	O31	Cg1ⁱⁱ	3.528 (2)	3.879 (2)	92.9 (1)
S28	O31	Cg2ⁱⁱ	3.208 (2)	4.128 (2)	120.3 (2)

Symmetry code: (ii) –x + 2, –y + 1, –z + 1.

π–π interactions (Å,°). top

I	J	CgI···CgJ	Dihedral angle	CgI_Perp	CgI_Offset
3	3ⁱⁱⁱ	3.962 (2)	0	3.340 (1)	2.131 (1)

Symmetry code: (iii) –x + 1, –y + 2, –z + 1.

Notes: Cg3 is the centroid of the C18–C23 ring. 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.

Footnotes

‡to whom correspondence should be addressed

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 – and DS/8820–4-0087–0).

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