9-[(2,6-Dimethoxy­phen­oxy)carbon­yl]-10-methyl­acridinium trifluoro­methane­sulfonate

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

doi:10.1107/S1600536809007570

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o789-o790

doi:10.1107/S1600536809007570

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9-[(2,6-Dimethoxyphenoxy)carbonyl]-10-methylacridinium trifluoromethanesulfonate

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 11 February 2009; accepted 2 March 2009; online 19 March 2009)

In the crystal structure of the title compound, C₂₃H₂₀NO₄⁺·CF₃SO₃⁻, the cations are linked through C—H⋯O, C—H⋯π and π–π interactions [centroid-centroid distances = 3.641 (2) and 3.885 (2) Å]. The cation and the anion are held together by C—H⋯O and S—O⋯π interactions. The acridine ring system and the benzene ring in the cation are oriented at a dihedral angle of 8.7 (1)°. The carboxy group is twisted at an angle of 83.2 (1)° relative to the acridine skeleton.

Related literature

For general background, see: Adamczyk et al. (2004 ); Becker et al. (1999 ); Rak et al. (1999 ); Zomer & Jacquemijns (2001 ). For related structures, see: Sikorski et al. (2008 ). For molecular interactions, see: Bianchi et al. (2004 ); Dorn et al. (2005 ); Hunter et al. (2001 ); Steiner (1999 ); Takahashi et al. (2001 ). For the synthesis, see: Sato (1996 ).

Experimental

Crystal data

C₂₃H₂₀NO₄⁺·CF₃SO₃⁻
M_r = 523.48
Monoclinic, P 2₁ /c
a = 11.6803 (4) Å
b = 14.7434 (5) Å
c = 13.6286 (5) Å
β = 93.462 (4)°
V = 2342.66 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 295 K
0.55 × 0.30 × 0.02 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 = 0.911, T_max = 0.995
20680 measured reflections
4160 independent reflections
2274 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 0.87
4160 reflections
328 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O30ⁱ	0.93	2.57	3.449 (3)	158
C4—H4⋯O31ⁱ	0.93	2.58	3.352 (3)	141
C7—H7⋯O32ⁱⁱ	0.93	2.54	3.427 (3)	159
C27—H27C⋯O17ⁱⁱⁱ	0.96	2.46	3.371 (3)	159
C25—H25C⋯Cg4^iv	0.96	2.98	3.845 (3)	150
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+2, -y, -z+1. Cg4 is the centroid of the C18–C23 ring.

Table 2
S—O⋯π Interactions (Å,°)

X	I	J	I⋯J	X⋯J	X—I⋯J
S29	O32	Cg1^v	3.178 (2)	3.757 (2)	103
Symmetry codes: (v) –x+1, –y+1, –z+1. Cg1 is the centroid of the C9/N10/C11–C14 ring.

Table 3
π–π Interactions (Å,°)

I	J	CgI⋯CgJ	Dihedral angle	CgI_Perp	CgJ_Perp	CgI_Offset	CgJ_Offset
1	4ⁱⁱ	3.641 (2)	5.31 (10)	3.416 (2)	3.492 (2)	0.767 (2)	1.031 (2)
2	4ⁱⁱ	3.885 (2)	6.74 (11)	3.666 (2)	3.491 (2)	1.286 (2)	1.705 (2)
Symmetry code: (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Notes: Cg1, Cg2 and Cg4 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 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 and CgJ_Perp are the perpendicular distances of CgI from ring J and of CgJ from ring I, respectively. CgI_Offset and CgJ_Offset are the distances between CgI and the perpendicular projection of CgJ on ring I, and between CgJ and the perpendicular projection of CgI on ring J, respectively.

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/S1600536809007570/is2390sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007570/is2390Isup2.hkl

checkCIF report

Comment top

Phenyl 10-alkylacridinium-9-carboxylates have long been known as chemiluminescent indicators or the chemiluminogenic fragments of chemiluminescent labels (Zomer & Jacquemijns, 2001). These compounds are widely applied in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Becker et al., 1999; Adamczyk et al., 2004). The reaction of the cations of these salts with hydrogen peroxide in alkaline media produces light. Our own investigations (Rak et al., 1999) and those of others (Zomer & Jacquemijns, 2001) have revealed that oxidation of acridinium chemiluminogens is accompanied by the removal of the phenoxycarbonyl fragment and the convertion of the rest of molecules to electronically excited, light-emitting 10-alkyl-9-acridinones. It has been found that the efficiency of chemiluminescence is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). Continuing our investigations onto the above mentioned effect, we synthesized the compound containing two methoxy groups in the phenyl fragment. Here, we present its structure. Methoxy groups, which possess electron-attractive features, may influence the stability and chemiluminogenic ability of the compound investigated.

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., 2008). With respective average deviations from planarity of 0.037 (3) Å and 0.010 (3) Å, the acridine and benzene ring systems in the cation are oriented at 8.7 (1)°. The carboxy group is twisted at an angle of 83.2 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are either parallel or inclined at an angle of 10.9 (1)° in the lattice.

In the crystal structure, the cations are linked through C—H···O (Table 1, Fig. 2), C—H···π (Table 1, Fig. 2) and π–π (Table 3, Fig. 2) interactions, and the cations and anions by C—H···O (Table 1, Fig. 2) and S—O···π (Table 2, Fig. 2) interactions. The C—H···O (Steiner, 1999; Bianchi et al., 2004) interactions are of the hydrogen-bond type. The C—H···π (Takahashi et al., 2001) and S—O···π (Dorn et al., 2005) interactions should be of an attractive nature, like the π–π contacts (Hunter et al., 2001). The crystal structure is stabilized by a network of the aforementioned short-range specific interactions and by long-range electrostatic interactions between ions.

Related literature top

For general background, see: Adamczyk et al. (2004); Becker et al. (1999); Rak et al. (1999); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2008). For molecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Steiner (1999); Takahashi et al. (2001). For the synthesis, see: Sato (1996). Cg4 is the centroid of the C18–C23 ring.

Experimental top

2,6-Dimethoxyphenylacridine-9-carboxylate was prepared by heating anhydrous acridine-9-carboxylic acid with thionyl chloride, followed by esterification of the resulting acid chloride with an equimolar quantity of 2,6-dimethoxyphenol (Sato, 1996). The reaction was carried out in anhydrous dichloromethane in the presence of N,N-diethylethanamine (1.5 molar excess) and a catalytic amount of N,N-dimethyl-4-pyridinamine (room temperature, 15 - 25 h). The crude product was purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 3/2 v/v). The 2,6-dimethoxyphenylacridine-9-carboxylate thus obtained was subsequently dissolved in anhydrous dichloromethane and treated with a fivefold molar excess of methyl triluoromethanesulfonate dissolved in the same solvent (under an Ar atmosphere at room temperature for 4 h). The crude salt was dissolved in a small amount of ethanol, filtered and precipitated with a 25 v/v excess of diethyl ether (yield 42%). Yellow crystals suitable for X-ray investigations were grown from absolute ethanol solution (m.p. 243–245 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. Cg1, Cg2 and Cg4 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 C—H···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 + 3/2, z - 1/2; (ii) x, -y + 1/2, z - 1/2; (iii) x, -y + 1/2, z + 1/2; (iv) -x + 2, -y, -z + 1; (v) -x + 1, -y + 1, -z + 1.]

9-[(2,6-Dimethoxyphenoxy)carbonyl]-10-methylacridinium trifluoromethanesulfonate top

Crystal data top

C₂₃H₂₀NO₄⁺·CF₃SO₃⁻	F(000) = 1080
M_r = 523.48	D_x = 1.484 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 6747 reflections
a = 11.6803 (4) Å	θ = 3.1–29.2°
b = 14.7434 (5) Å	µ = 0.21 mm⁻¹
c = 13.6286 (5) Å	T = 295 K
β = 93.462 (4)°	Plate, yellow
V = 2342.66 (14) Å³	0.55 × 0.30 × 0.02 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	4160 independent reflections
Radiation source: Enhanced (Mo) X-ray Source	2274 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 = −13→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −17→17
T_min = 0.911, T_max = 0.995	l = −15→16
20680 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 0.87	w = 1/[σ²(F_o²) + (0.0672P)²] where P = (F_o² + 2F_c²)/3
4160 reflections	(Δ/σ)_max = 0.001
328 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂₃H₂₀NO₄⁺·CF₃SO₃⁻	V = 2342.66 (14) Å³
M_r = 523.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6803 (4) Å	µ = 0.21 mm⁻¹
b = 14.7434 (5) Å	T = 295 K
c = 13.6286 (5) Å	0.55 × 0.30 × 0.02 mm
β = 93.462 (4)°

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	4160 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	2274 reflections with I > 2σ(I)
T_min = 0.911, T_max = 0.995	R_int = 0.045
20680 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 0.87	Δρ_max = 0.24 e Å⁻³
4160 reflections	Δρ_min = −0.29 e Å⁻³
328 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	0.7814 (2)	0.40388 (17)	0.39746 (18)	0.0638 (6)
H1	0.8256	0.3737	0.4462	0.077*
C2	0.7685 (2)	0.49461 (18)	0.4029 (2)	0.0758 (8)
H2	0.8031	0.5265	0.4556	0.091*
C3	0.7034 (2)	0.54073 (18)	0.3296 (2)	0.0732 (8)
H3	0.6953	0.6033	0.3341	0.088*
C4	0.6517 (2)	0.49643 (17)	0.2521 (2)	0.0651 (7)
H4	0.6096	0.5289	0.2038	0.078*
C5	0.5619 (2)	0.2128 (2)	0.08150 (18)	0.0665 (7)
H5	0.5216	0.2437	0.0310	0.080*
C6	0.5684 (2)	0.1217 (2)	0.0792 (2)	0.0759 (8)
H6	0.5322	0.0908	0.0265	0.091*
C7	0.6277 (2)	0.07213 (19)	0.1532 (2)	0.0748 (7)
H7	0.6284	0.0091	0.1505	0.090*
C8	0.6843 (2)	0.11584 (17)	0.22920 (18)	0.0622 (6)
H8	0.7255	0.0828	0.2776	0.075*
C9	0.73852 (17)	0.26032 (15)	0.31071 (15)	0.0471 (6)
N10	0.61009 (14)	0.35392 (13)	0.16713 (13)	0.0508 (5)
C11	0.72823 (17)	0.35398 (15)	0.31827 (15)	0.0497 (6)
C12	0.66127 (18)	0.40128 (15)	0.24392 (16)	0.0503 (6)
C13	0.68078 (18)	0.21248 (15)	0.23483 (16)	0.0495 (6)
C14	0.61625 (18)	0.26140 (16)	0.16052 (16)	0.0514 (6)
C15	0.8199 (2)	0.21059 (14)	0.38169 (16)	0.0523 (6)
O16	0.77183 (12)	0.18961 (10)	0.46502 (11)	0.0556 (4)
O17	0.91548 (15)	0.19252 (14)	0.36460 (13)	0.0862 (6)
C18	0.84322 (18)	0.14411 (16)	0.53585 (15)	0.0512 (6)
C19	0.84232 (19)	0.05032 (16)	0.53766 (17)	0.0548 (6)
C20	0.9070 (2)	0.00594 (18)	0.61157 (19)	0.0657 (7)
H20	0.9073	−0.0570	0.6151	0.079*
C21	0.9708 (2)	0.0567 (2)	0.67943 (19)	0.0742 (8)
H21	1.0134	0.0270	0.7296	0.089*
C22	0.9739 (2)	0.1498 (2)	0.67584 (17)	0.0700 (7)
H22	1.0185	0.1823	0.7224	0.084*
C23	0.9101 (2)	0.19452 (17)	0.60234 (16)	0.0569 (6)
O24	0.77711 (14)	0.01014 (11)	0.46366 (12)	0.0674 (5)
C25	0.7774 (2)	−0.08702 (17)	0.4597 (2)	0.0771 (8)
H25A	0.7387	−0.1068	0.3993	0.116*
H25B	0.7386	−0.1108	0.5143	0.116*
H25C	0.8551	−0.1086	0.4629	0.116*
O26	0.90647 (16)	0.28607 (12)	0.58923 (12)	0.0754 (5)
C27	0.9977 (3)	0.3383 (2)	0.6341 (2)	0.0978 (10)
H27A	0.9918	0.3998	0.6111	0.147*
H27B	1.0698	0.3132	0.6172	0.147*
H27C	0.9932	0.3372	0.7042	0.147*
C28	0.5417 (2)	0.40504 (19)	0.09069 (19)	0.0798 (8)
H28A	0.5904	0.4472	0.0593	0.120*
H28B	0.4816	0.4376	0.1205	0.120*
H28C	0.5086	0.3635	0.0426	0.120*
S29	0.62429 (6)	0.72700 (4)	0.67537 (5)	0.0605 (2)
O30	0.6575 (2)	0.73286 (15)	0.77722 (13)	0.1141 (8)
O31	0.59056 (15)	0.81084 (11)	0.62945 (13)	0.0719 (5)
O32	0.55268 (15)	0.65261 (13)	0.64848 (15)	0.0913 (6)
C33	0.7559 (2)	0.70003 (18)	0.6202 (2)	0.0687 (7)
F34	0.79921 (14)	0.62064 (11)	0.65070 (14)	0.1050 (6)
F35	0.83549 (13)	0.76166 (12)	0.64108 (16)	0.1158 (6)
F36	0.74067 (16)	0.69624 (13)	0.52297 (12)	0.1107 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0710 (16)	0.0497 (17)	0.0707 (15)	−0.0017 (13)	0.0038 (13)	0.0012 (13)
C2	0.095 (2)	0.0490 (18)	0.0841 (19)	−0.0063 (15)	0.0125 (16)	−0.0089 (14)
C3	0.0845 (19)	0.0378 (15)	0.099 (2)	0.0033 (14)	0.0219 (17)	0.0021 (16)
C4	0.0616 (16)	0.0456 (17)	0.0894 (19)	0.0057 (12)	0.0156 (14)	0.0186 (14)
C5	0.0560 (15)	0.071 (2)	0.0721 (17)	−0.0045 (14)	−0.0009 (12)	0.0024 (15)
C6	0.0752 (18)	0.065 (2)	0.0870 (19)	−0.0106 (15)	−0.0002 (15)	−0.0110 (16)
C7	0.0789 (18)	0.0448 (16)	0.101 (2)	−0.0049 (14)	0.0100 (16)	−0.0090 (16)
C8	0.0645 (15)	0.0417 (16)	0.0806 (17)	0.0021 (12)	0.0055 (13)	0.0037 (13)
C9	0.0448 (12)	0.0396 (14)	0.0578 (13)	0.0018 (10)	0.0112 (11)	0.0103 (11)
N10	0.0406 (10)	0.0473 (13)	0.0649 (12)	0.0041 (9)	0.0070 (9)	0.0127 (10)
C11	0.0483 (13)	0.0400 (14)	0.0616 (14)	−0.0005 (11)	0.0109 (11)	0.0071 (12)
C12	0.0464 (13)	0.0385 (15)	0.0675 (15)	0.0019 (11)	0.0170 (12)	0.0087 (12)
C13	0.0456 (12)	0.0412 (15)	0.0628 (14)	−0.0006 (11)	0.0114 (11)	0.0057 (11)
C14	0.0410 (12)	0.0483 (15)	0.0658 (15)	0.0006 (11)	0.0104 (11)	0.0082 (12)
C15	0.0512 (15)	0.0434 (15)	0.0634 (15)	0.0005 (11)	0.0114 (12)	0.0072 (11)
O16	0.0543 (9)	0.0517 (10)	0.0617 (9)	0.0094 (7)	0.0104 (8)	0.0111 (8)
O17	0.0573 (11)	0.1193 (17)	0.0841 (12)	0.0260 (10)	0.0210 (9)	0.0410 (11)
C18	0.0500 (13)	0.0538 (16)	0.0505 (13)	0.0100 (12)	0.0085 (11)	0.0076 (12)
C19	0.0551 (14)	0.0506 (16)	0.0596 (15)	0.0053 (12)	0.0115 (12)	0.0081 (13)
C20	0.0700 (16)	0.0562 (17)	0.0721 (17)	0.0092 (14)	0.0144 (14)	0.0178 (14)
C21	0.0784 (19)	0.081 (2)	0.0628 (16)	0.0142 (16)	0.0023 (14)	0.0194 (16)
C22	0.0726 (17)	0.081 (2)	0.0564 (15)	0.0022 (15)	0.0027 (13)	−0.0005 (14)
C23	0.0622 (15)	0.0554 (17)	0.0542 (14)	0.0075 (13)	0.0131 (13)	0.0059 (13)
O24	0.0732 (11)	0.0490 (11)	0.0794 (11)	−0.0003 (9)	−0.0007 (9)	0.0070 (9)
C25	0.0817 (19)	0.0502 (18)	0.1008 (19)	−0.0032 (14)	0.0178 (15)	−0.0019 (15)
O26	0.0934 (13)	0.0544 (12)	0.0776 (11)	−0.0019 (10)	−0.0010 (10)	−0.0035 (9)
C27	0.126 (3)	0.083 (2)	0.0849 (19)	−0.028 (2)	0.0082 (18)	−0.0061 (17)
C28	0.0725 (18)	0.074 (2)	0.0911 (18)	0.0139 (15)	−0.0125 (14)	0.0230 (16)
S29	0.0693 (4)	0.0491 (4)	0.0639 (4)	−0.0018 (3)	0.0105 (3)	0.0018 (3)
O30	0.183 (2)	0.1048 (17)	0.0545 (11)	0.0155 (16)	0.0050 (12)	0.0030 (11)
O31	0.0811 (12)	0.0492 (11)	0.0853 (11)	0.0124 (9)	0.0036 (9)	0.0049 (9)
O32	0.0713 (12)	0.0602 (13)	0.1427 (16)	−0.0205 (10)	0.0087 (11)	0.0027 (12)
C33	0.0625 (17)	0.0533 (17)	0.089 (2)	−0.0042 (14)	−0.0076 (14)	0.0083 (14)
F34	0.0808 (11)	0.0678 (11)	0.1654 (16)	0.0192 (9)	−0.0016 (10)	0.0175 (11)
F35	0.0617 (10)	0.0977 (13)	0.1853 (18)	−0.0272 (10)	−0.0152 (10)	0.0345 (12)
F36	0.1302 (15)	0.1217 (16)	0.0842 (12)	0.0248 (11)	0.0384 (11)	−0.0103 (10)

Geometric parameters (Å, º) top

C1—C2	1.349 (3)	C18—C23	1.377 (3)
C1—C11	1.418 (3)	C18—C19	1.383 (3)
C1—H1	0.9300	C19—O24	1.362 (3)
C2—C3	1.396 (4)	C19—C20	1.387 (3)
C2—H2	0.9300	C20—C21	1.374 (3)
C3—C4	1.353 (3)	C20—H20	0.9300
C3—H3	0.9300	C21—C22	1.374 (4)
C4—C12	1.412 (3)	C21—H21	0.9300
C4—H4	0.9300	C22—C23	1.380 (3)
C5—C6	1.345 (4)	C22—H22	0.9300
C5—C14	1.412 (3)	C23—O26	1.362 (3)
C5—H5	0.9300	O24—C25	1.433 (3)
C6—C7	1.396 (4)	C25—H25A	0.9600
C6—H6	0.9300	C25—H25B	0.9600
C7—C8	1.357 (3)	C25—H25C	0.9600
C7—H7	0.9300	O26—C27	1.423 (3)
C8—C13	1.428 (3)	C27—H27A	0.9600
C8—H8	0.9300	C27—H27B	0.9600
C9—C11	1.390 (3)	C27—H27C	0.9600
C9—C13	1.392 (3)	C28—H28A	0.9600
C9—C15	1.506 (3)	C28—H28B	0.9600
N10—C12	1.366 (3)	C28—H28C	0.9600
N10—C14	1.369 (3)	S29—O32	1.4142 (19)
N10—C28	1.480 (3)	S29—O30	1.421 (2)
C11—C12	1.424 (3)	S29—O31	1.4300 (17)
C13—C14	1.422 (3)	S29—C33	1.796 (3)
C15—O17	1.184 (2)	C33—F35	1.319 (3)
C15—O16	1.334 (2)	C33—F36	1.327 (3)
O16—C18	1.407 (2)	C33—F34	1.332 (3)

C2—C1—C11	120.8 (2)	C19—C18—O16	118.9 (2)
C2—C1—H1	119.6	O24—C19—C18	115.2 (2)
C11—C1—H1	119.6	O24—C19—C20	126.1 (2)
C1—C2—C3	120.1 (3)	C18—C19—C20	118.7 (2)
C1—C2—H2	120.0	C21—C20—C19	118.8 (2)
C3—C2—H2	120.0	C21—C20—H20	120.6
C4—C3—C2	121.5 (2)	C19—C20—H20	120.6
C4—C3—H3	119.3	C20—C21—C22	122.3 (2)
C2—C3—H3	119.3	C20—C21—H21	118.8
C3—C4—C12	120.5 (2)	C22—C21—H21	118.8
C3—C4—H4	119.7	C21—C22—C23	119.3 (3)
C12—C4—H4	119.7	C21—C22—H22	120.4
C6—C5—C14	120.1 (2)	C23—C22—H22	120.4
C6—C5—H5	119.9	O26—C23—C18	115.9 (2)
C14—C5—H5	119.9	O26—C23—C22	125.5 (2)
C5—C6—C7	122.1 (3)	C18—C23—C22	118.7 (2)
C5—C6—H6	118.9	C19—O24—C25	117.39 (19)
C7—C6—H6	118.9	O24—C25—H25A	109.5
C8—C7—C6	120.0 (2)	O24—C25—H25B	109.5
C8—C7—H7	120.0	H25A—C25—H25B	109.5
C6—C7—H7	120.0	O24—C25—H25C	109.5
C7—C8—C13	120.0 (2)	H25A—C25—H25C	109.5
C7—C8—H8	120.0	H25B—C25—H25C	109.5
C13—C8—H8	120.0	C23—O26—C27	117.6 (2)
C11—C9—C13	121.2 (2)	O26—C27—H27A	109.5
C11—C9—C15	119.3 (2)	O26—C27—H27B	109.5
C13—C9—C15	119.3 (2)	H27A—C27—H27B	109.5
C12—N10—C14	122.52 (18)	O26—C27—H27C	109.5
C12—N10—C28	118.1 (2)	H27A—C27—H27C	109.5
C14—N10—C28	119.28 (19)	H27B—C27—H27C	109.5
C9—C11—C1	122.4 (2)	N10—C28—H28A	109.5
C9—C11—C12	118.7 (2)	N10—C28—H28B	109.5
C1—C11—C12	118.9 (2)	H28A—C28—H28B	109.5
N10—C12—C4	122.4 (2)	N10—C28—H28C	109.5
N10—C12—C11	119.4 (2)	H28A—C28—H28C	109.5
C4—C12—C11	118.2 (2)	H28B—C28—H28C	109.5
C9—C13—C14	119.0 (2)	O32—S29—O30	115.00 (13)
C9—C13—C8	122.1 (2)	O32—S29—O31	114.45 (12)
C14—C13—C8	118.9 (2)	O30—S29—O31	115.25 (12)
N10—C14—C5	122.2 (2)	O32—S29—C33	103.15 (12)
N10—C14—C13	119.1 (2)	O30—S29—C33	103.43 (14)
C5—C14—C13	118.7 (2)	O31—S29—C33	103.20 (11)
O17—C15—O16	124.5 (2)	F35—C33—F36	107.1 (2)
O17—C15—C9	123.3 (2)	F35—C33—F34	106.8 (2)
O16—C15—C9	112.20 (19)	F36—C33—F34	107.5 (2)
C15—O16—C18	115.60 (16)	F35—C33—S29	111.5 (2)
C23—C18—C19	122.2 (2)	F36—C33—S29	111.15 (18)
C23—C18—O16	118.9 (2)	F34—C33—S29	112.49 (19)

C11—C1—C2—C3	−0.7 (4)	C8—C13—C14—C5	−2.7 (3)
C1—C2—C3—C4	0.2 (4)	C11—C9—C15—O17	−94.4 (3)
C2—C3—C4—C12	0.8 (4)	C13—C9—C15—O17	81.4 (3)
C14—C5—C6—C7	0.1 (4)	C11—C9—C15—O16	85.7 (2)
C5—C6—C7—C8	−2.1 (4)	C13—C9—C15—O16	−98.5 (2)
C6—C7—C8—C13	1.7 (4)	O17—C15—O16—C18	1.0 (3)
C13—C9—C11—C1	176.74 (19)	C9—C15—O16—C18	−179.09 (18)
C15—C9—C11—C1	−7.6 (3)	C15—O16—C18—C23	88.2 (2)
C13—C9—C11—C12	−2.9 (3)	C15—O16—C18—C19	−93.1 (2)
C15—C9—C11—C12	172.79 (19)	C23—C18—C19—O24	−176.27 (18)
C2—C1—C11—C9	−179.3 (2)	O16—C18—C19—O24	5.0 (3)
C2—C1—C11—C12	0.3 (3)	C23—C18—C19—C20	2.9 (3)
C14—N10—C12—C4	−177.94 (19)	O16—C18—C19—C20	−175.80 (18)
C28—N10—C12—C4	−0.5 (3)	O24—C19—C20—C21	178.2 (2)
C14—N10—C12—C11	2.9 (3)	C18—C19—C20—C21	−0.9 (3)
C28—N10—C12—C11	−179.61 (19)	C19—C20—C21—C22	−0.9 (4)
C3—C4—C12—N10	179.7 (2)	C20—C21—C22—C23	0.7 (4)
C3—C4—C12—C11	−1.1 (3)	C19—C18—C23—O26	177.12 (18)
C9—C11—C12—N10	−0.6 (3)	O16—C18—C23—O26	−4.2 (3)
C1—C11—C12—N10	179.75 (18)	C19—C18—C23—C22	−3.1 (3)
C9—C11—C12—C4	−179.77 (18)	O16—C18—C23—C22	175.59 (18)
C1—C11—C12—C4	0.6 (3)	C21—C22—C23—O26	−179.0 (2)
C11—C9—C13—C14	4.1 (3)	C21—C22—C23—C18	1.3 (3)
C15—C9—C13—C14	−171.59 (19)	C18—C19—O24—C25	177.29 (18)
C11—C9—C13—C8	−175.94 (19)	C20—C19—O24—C25	−1.8 (3)
C15—C9—C13—C8	8.4 (3)	C18—C23—O26—C27	−160.7 (2)
C7—C8—C13—C9	−179.3 (2)	C22—C23—O26—C27	19.5 (3)
C7—C8—C13—C14	0.7 (3)	O32—S29—C33—F35	−177.69 (18)
C12—N10—C14—C5	179.21 (18)	O30—S29—C33—F35	−57.6 (2)
C28—N10—C14—C5	1.8 (3)	O31—S29—C33—F35	62.9 (2)
C12—N10—C14—C13	−1.7 (3)	O32—S29—C33—F36	62.8 (2)
C28—N10—C14—C13	−179.15 (19)	O30—S29—C33—F36	−177.05 (19)
C6—C5—C14—N10	−178.6 (2)	O31—S29—C33—F36	−56.6 (2)
C6—C5—C14—C13	2.3 (3)	O32—S29—C33—F34	−57.7 (2)
C9—C13—C14—N10	−1.8 (3)	O30—S29—C33—F34	62.4 (2)
C8—C13—C14—N10	178.23 (18)	O31—S29—C33—F34	−177.18 (18)
C9—C13—C14—C5	177.31 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O30ⁱ	0.93	2.57	3.449 (3)	158
C4—H4···O31ⁱ	0.93	2.58	3.352 (3)	141
C7—H7···O32ⁱⁱ	0.93	2.54	3.427 (3)	159
C27—H27C···O17ⁱⁱⁱ	0.96	2.46	3.371 (3)	159
C25—H25C···Cg4^iv	0.96	2.98	3.845 (3)	150

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

Experimental details

Crystal data
Chemical formula	C₂₃H₂₀NO₄⁺·CF₃SO₃⁻
M_r	523.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	11.6803 (4), 14.7434 (5), 13.6286 (5)
β (°)	93.462 (4)
V (Å³)	2342.66 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.55 × 0.30 × 0.02

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.911, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	20680, 4160, 2274
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 0.87
No. of reflections	4160
No. of parameters	328
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.29

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (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
C3—H3···O30ⁱ	0.93	2.57	3.449 (3)	158
C4—H4···O31ⁱ	0.93	2.58	3.352 (3)	141
C7—H7···O32ⁱⁱ	0.93	2.54	3.427 (3)	159
C27—H27C···O17ⁱⁱⁱ	0.96	2.46	3.371 (3)	159
C25—H25C···Cg4^iv	0.96	2.98	3.845 (3)	150

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

S–O···π Interactions (Å,°) top

X	I	J	I···J	X···J	X—I···J
S29	O31	Cg3^v	3.968 (2)	4.111 (2)	85
S29	O32	Cg1^v	3.178 (2)	3.757 (2)	103
S29	O32	Cg2^v	3.512 (2)	4.741 (2)	145

Symmetry codes: (v) –x+1, –y+1, –z+1.

Notes: Cg1, Cg2 and Cg3 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C5–C8/C13/C14 rings, respectively.

π–π Interactions (Å,°) top

I	J	CgI···CgJ	Dihedral angle	CgI_Perp	CgJ_Perp	CgI_Offset	CgJ_Offset
1	4ⁱⁱ	3.641 (2)	5.31 (10)	3.416 (2)	3.492 (2)	0.767 (2)	1.031 (2)
2	4ⁱⁱ	3.885 (2)	6.74 (11)	3.666 (2)	3.491 (2)	1.286 (2)	1.705 (2)

Symmetry code: (ii) x, –y+1/2, z–1/2.

Notes: Cg1, Cg2 and Cg4 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 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 and CgJ_Perp are the perpendicular distances of CgI from ring J and of CgJ from ring I, respectively. CgI_Offset and CgJ_Offset are the distances between CgI and the perpendicular projection of CgJ on ring I, and between CgJ and the perpendicular projection of CgI on ring J, respectively.

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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