9-(2-tert-Butyl­phenoxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate

Sikorski, A.; Krzymiński, K.; Malecha, P.; Lis, T.; Błażejowski, J.

doi:10.1107/S1600536807052002

9-(2-tert-Butylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

A. Sikorski, K. Krzymiński, P. Malecha, T. Lis and J. Błażejowski

The crystal structure of the title compound, C₂₅H₂₄NO₂⁺·CF₃SO₃⁻, is stabilized by C—H

O, C—H

F and C—H

π hydrogen bonds, and by O

F [2.94 (1) Å] and O

N [2.87 (1) Å] interactions. In the packing of the molecules, acridine groups are either parallel or inclined at an angle of 5.4 (1)°. Similarly, the benzene rings are either parallel or lie at an angle of 72.4 (1)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052002/om2169sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052002/om2169Isup2.hkl Contains datablock I

CCDC reference: 667479

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.047
wR factor = 0.102
Data-to-parameter ratio = 21.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT412_ALERT_2_B Short Intra XH3 .. XHn     H5     ..  H28C    ..       1.78 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O17    ..  N10     ..       2.87 Ang.

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.23 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.22 Ratio
PLAT431_ALERT_2_C Short Inter HL..A Contact  F34    ..  O32     ..       2.94 Ang.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Phenyl 10-alkylacridinium-9-carboxylates have been successfully applied as chemiluminescent indicators or chemiluminogenic fragments of chemiluminescent labels in assays of biologically and environmentally important entities (Yang et al., 2002; Adamczyk et al., 2004). The reactions of the above-mentioned cations with hydrogen peroxide in alkaline media produce light, and determination of its intensity enables labeled entities or entities present in the medium to be assayed quantitatively at the attomole level (Roda et al., 2003). Our own investigations (Rak et al., 1999) and those of others (Dodeigne et al., 2000; Razawi & McCapra, 2000; Zomer & Jacquemijns, 2001) have revealed that oxidation of these compounds is accompanied by the removal of the phenyl fragment and conversion of the rest of the molecule to electronically excited, light-emitting 10-alkyl-9-acridinones. It may thus be expected that the efficiency of chemiluminescence is affected by changes in the constitution of the phenyl ester fragment. In order to find out whether this is indeed the case investigations were undertaken on phenyl 10-methylacridinium-9-carboxylates differently substituted in the phenyl fragment. Alkyl-substituted representatives of this group of compounds were selected for these investigations principally because it is relatively easy to synthesize them and to influence their structure and features. The structure of 9-(2-methylphenoxycarbonyl-acridinium trifluoromethanesulfonate was described in an earlier report (Sikorski et al., 2006b). Here the crystal structure of the title compound is presented.

Parameters characterizing the geometries of the central acridine ring and the ester fragment are typical of acridine-based derivatives (Meszko et al., 2002; Sikorski et al., 2006a,b). With respective average deviations from planarity of 0.009 and 0.002 Å, the acridine and benzene ring systems in the cation are oriented at 53.7 (1)° to each other (Fig. 1). The carboxyl group is twisted at an angle of 60.6 (1)° relative to the acridine skeleton. The mean planes of the acridine moieties lie either parallel or are inclined at an angle of 5.4 (1)° in the lattice. The benzene rings are either parallel or inclined at an angle of 72.4 (1)°.

All the O atoms and two F atoms of the trifluoromethanesulfonate anions are respectively involved in weak C–H···O and C–H···F hydrogen bonds with cations (Fig. 3). Adjacent cations are linked through C—H···π (phenyl) interactions (Figs. 2 and 3) and N···O (carbonyl) contacts [N10···O17 = 2.87 (1) Å (symmetry code: (vii) x, 1/2 - y, z - 1/2); Fig. 3]. Adjacent anions are linked through O···F contacts [O32···F34 = 2.94 (1) Å (symmetry code: (viii) x, 3/2 - y, z - 1/2); Fig. 2].

All interactions demonstrated were found by PLATON (Spek, 2003). The C–H···O (Bianchi et al., 2004; Steiner, 1999), C–H···F (Bianchi et al., 2004; Lyssenko & Antipin, 2004) and C–H···π (Takahashi et al., 2001) interactions exhibit a hydrogen-bond-type nature. The C–F···O interactions between anions (Allen et al., 1997; Lyssenko & Antipin, 2004) identified as O···F contacts, and also the N···O (carbonyl) contacts between cations (Lee et al., 2003), should be of an attractive nature.

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 related literature, see: Adamczyk et al. (2004); Allen et al. (1997); Bianchi et al. (2004); Dodeigne et al. (2000); Lee et al. (2003); Lyssenko & Antipin (2004); Meszko et al. (2002); Rak et al. (1999); Razawi & McCapra (2000); Roda et al. (2003); Sikorski et al. (2006a,b); Steiner (1999); Takahashi et al. (2001); Yang et al. (2002); Zomer & Jacquemijns (2001).

Experimental top

9-(2-Tertbutylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was synthesized by treatment of 2-tertbutylphenyl acridine-9-carboxylate [obtained in the same way as described elsewhere (Sikorski et al., 2006a)], dissolved in anhydrous dichloromethane, with a fivefold molar excess of methyl trifluoromethanesulfonate, dissolved in the same solvent, under an Ar atmosphere at room temperature for 3 h. The crude salt was purified by repeated precipitation from ethanol-diethyl ether (1/20 v/v) solution (yield 63%). Pale-yellow crystals suitable for X-ray investigations were grown from absolute ethanol (m.p. = 502–504 K).

Structure description top

The crystal structure is stabilized by a network of the aforementioned short-range interactions, as well as by long-range electrostatic interactions between ions.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radii. Cg4 denotes the ring centroid.
	Fig. 2. The arrangement of the ions in the unit cell, viewed approximately along the a axis. The C—H···O and C—H···F interactions, as well as O···F contacts are represented by dashed lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (ii) x, y - 1, z; (iii) x, 1/2 - y, z + 1/2; (iv) x, 3/2 - y, z + 1/2; (viii) x, 3/2 - y, z - 1/2.]
	Fig. 3. The arrangement of the ions of in the unit cell, viewed approximately along the b axis. The C—H···O interactions and N···O contacts are represented by dashed lines, and C—H···π interactions by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) -x, 1 - y, -z; (v) -x, y - 1/2, 1/2 - z; (vi) 1 - x,1 - y,1 - z; (vii) x, 1/2 - y, z - 1/2.]

9-(2-tert-Butylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate top

Crystal data top

C₂₅H₂₄NO₂⁺·CF₃O₃S⁻	F(000) = 1080
M_r = 519.52	D_x = 1.397 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 29629 reflections
a = 15.307 (4) Å	θ = 3.1–30.0°
b = 13.480 (3) Å	µ = 0.19 mm⁻¹
c = 12.263 (3) Å	T = 100 K
β = 102.56 (3)°	Plate, pale-yellow
V = 2469.8 (10) Å³	0.50 × 0.40 × 0.07 mm
Z = 4

Data collection top

Kuma KM4 CCD κ-geometry diffractometer	4774 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 30.0°, θ_min = 3.1°
ω scans	h = −20→21
29629 measured reflections	k = −18→15
7120 independent reflections	l = −17→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0485P)²] where P = (F_o² + 2F_c²)/3
7120 reflections	(Δ/σ)_max = 0.001
329 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₂₅H₂₄NO₂⁺·CF₃O₃S⁻	V = 2469.8 (10) Å³
M_r = 519.52	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.307 (4) Å	µ = 0.19 mm⁻¹
b = 13.480 (3) Å	T = 100 K
c = 12.263 (3) Å	0.50 × 0.40 × 0.07 mm
β = 102.56 (3)°

Data collection top

Kuma KM4 CCD κ-geometry diffractometer	4774 reflections with I > 2σ(I)
29629 measured reflections	R_int = 0.056
7120 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.00	Δρ_max = 0.39 e Å⁻³
7120 reflections	Δρ_min = −0.36 e Å⁻³
329 parameters

Special details top

Experimental. no

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	0.18044 (10)	0.44204 (12)	0.37019 (13)	0.0225 (3)
H1	0.2153	0.4694	0.4371	0.027*
C2	0.14022 (10)	0.50362 (12)	0.28609 (14)	0.0257 (4)
H2	0.1476	0.5734	0.2937	0.031*
C3	0.08736 (11)	0.46260 (13)	0.18723 (14)	0.0263 (4)
H3	0.0602	0.5060	0.1286	0.032*
C4	0.07408 (10)	0.36328 (12)	0.17317 (13)	0.0240 (3)
H4	0.0373	0.3383	0.1063	0.029*
C5	0.13276 (11)	0.02677 (12)	0.31435 (15)	0.0275 (4)
H5	0.0960	0.0010	0.2479	0.033*
C6	0.17425 (12)	−0.03608 (13)	0.39641 (16)	0.0322 (4)
H6	0.1658	−0.1056	0.3863	0.039*
C7	0.22935 (12)	−0.00065 (13)	0.49580 (15)	0.0307 (4)
H7	0.2576	−0.0461	0.5516	0.037*
C8	0.24223 (11)	0.09821 (12)	0.51229 (14)	0.0254 (4)
H8	0.2796	0.1215	0.5796	0.030*
C9	0.21201 (9)	0.27061 (11)	0.44236 (12)	0.0180 (3)
N10	0.10445 (8)	0.19637 (9)	0.24688 (11)	0.0203 (3)
C11	0.17080 (10)	0.33657 (11)	0.35902 (12)	0.0190 (3)
C12	0.11555 (10)	0.29719 (11)	0.25893 (13)	0.0199 (3)
C13	0.20006 (10)	0.16768 (11)	0.42931 (13)	0.0190 (3)
C14	0.14451 (10)	0.13085 (11)	0.32812 (13)	0.0200 (3)
C15	0.26928 (9)	0.30738 (11)	0.55043 (13)	0.0184 (3)
O16	0.34079 (7)	0.35813 (7)	0.53231 (8)	0.0187 (2)
O17	0.25354 (7)	0.29088 (8)	0.64040 (9)	0.0262 (3)
C18	0.40531 (10)	0.39120 (11)	0.62741 (13)	0.0191 (3)
C19	0.49459 (10)	0.36474 (11)	0.63384 (13)	0.0228 (3)
C20	0.55491 (11)	0.40454 (13)	0.72586 (15)	0.0308 (4)
H20	0.6168	0.3898	0.7350	0.037*
C21	0.52788 (12)	0.46475 (13)	0.80441 (15)	0.0337 (4)
H21	0.5711	0.4899	0.8658	0.040*
C22	0.43907 (12)	0.48808 (12)	0.79388 (14)	0.0290 (4)
H22	0.4206	0.5291	0.8477	0.035*
C23	0.37686 (11)	0.45117 (11)	0.70407 (14)	0.0234 (3)
H23	0.3152	0.4669	0.6952	0.028*
C24	0.52464 (11)	0.29761 (12)	0.54776 (15)	0.0285 (4)
C25	0.62422 (13)	0.27135 (19)	0.5846 (2)	0.0582 (7)
H25C	0.6411	0.2266	0.5296	0.087*
H25B	0.6351	0.2385	0.6576	0.087*
H25A	0.6601	0.3321	0.5900	0.087*
C26	0.50849 (15)	0.34945 (15)	0.43347 (17)	0.0466 (5)
H26C	0.5263	0.3051	0.3788	0.070*
H26B	0.5440	0.4105	0.4398	0.070*
H26A	0.4448	0.3658	0.4090	0.070*
C27	0.47260 (12)	0.19901 (12)	0.53535 (16)	0.0303 (4)
H27C	0.5035	0.1502	0.4979	0.045*
H27B	0.4120	0.2098	0.4908	0.045*
H27A	0.4692	0.1742	0.6094	0.045*
C28	0.04879 (11)	0.15863 (13)	0.14064 (14)	0.0286 (4)
H28C	0.0551	0.0864	0.1374	0.043*
H28B	0.0686	0.1890	0.0775	0.043*
H28A	−0.0141	0.1755	0.1368	0.043*
S29	0.08377 (3)	0.77767 (3)	0.14174 (3)	0.02144 (10)
O30	0.04026 (8)	0.87134 (8)	0.11081 (9)	0.0279 (3)
O31	0.04331 (8)	0.69409 (9)	0.07621 (10)	0.0339 (3)
O32	0.11069 (8)	0.75903 (9)	0.26006 (9)	0.0312 (3)
C33	0.19027 (11)	0.79272 (12)	0.10050 (14)	0.0257 (4)
F34	0.17898 (7)	0.80771 (9)	−0.00912 (9)	0.0457 (3)
F35	0.24265 (7)	0.71301 (8)	0.12630 (9)	0.0428 (3)
F36	0.23632 (7)	0.86934 (8)	0.15244 (10)	0.0414 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0206 (8)	0.0202 (8)	0.0250 (8)	0.0011 (6)	0.0011 (6)	−0.0019 (6)
C2	0.0244 (8)	0.0203 (8)	0.0322 (9)	0.0024 (7)	0.0057 (7)	0.0031 (7)
C3	0.0228 (8)	0.0296 (9)	0.0262 (9)	0.0053 (7)	0.0051 (7)	0.0070 (7)
C4	0.0192 (8)	0.0330 (9)	0.0190 (8)	0.0018 (7)	0.0025 (6)	−0.0003 (7)
C5	0.0255 (9)	0.0235 (9)	0.0326 (10)	−0.0062 (7)	0.0047 (7)	−0.0090 (7)
C6	0.0364 (10)	0.0178 (8)	0.0422 (11)	−0.0036 (7)	0.0081 (8)	−0.0038 (8)
C7	0.0330 (10)	0.0200 (8)	0.0379 (10)	−0.0005 (7)	0.0046 (8)	0.0036 (8)
C8	0.0239 (8)	0.0218 (8)	0.0287 (9)	−0.0023 (7)	0.0018 (7)	0.0004 (7)
C9	0.0143 (7)	0.0209 (8)	0.0192 (7)	−0.0009 (6)	0.0044 (5)	−0.0016 (6)
N10	0.0160 (6)	0.0232 (7)	0.0212 (7)	−0.0008 (5)	0.0032 (5)	−0.0061 (5)
C11	0.0167 (7)	0.0202 (8)	0.0205 (8)	0.0010 (6)	0.0052 (6)	−0.0016 (6)
C12	0.0145 (7)	0.0244 (8)	0.0212 (8)	0.0014 (6)	0.0049 (6)	−0.0019 (6)
C13	0.0157 (7)	0.0194 (8)	0.0227 (8)	−0.0014 (6)	0.0057 (6)	−0.0013 (6)
C14	0.0152 (7)	0.0216 (8)	0.0244 (8)	−0.0017 (6)	0.0068 (6)	−0.0039 (7)
C15	0.0151 (7)	0.0159 (7)	0.0237 (8)	0.0006 (6)	0.0032 (6)	0.0001 (6)
O16	0.0175 (5)	0.0184 (5)	0.0193 (5)	−0.0034 (4)	0.0018 (4)	0.0000 (4)
O17	0.0259 (6)	0.0309 (6)	0.0227 (6)	−0.0077 (5)	0.0068 (5)	−0.0016 (5)
C18	0.0198 (8)	0.0140 (7)	0.0210 (8)	−0.0048 (6)	−0.0013 (6)	0.0024 (6)
C19	0.0208 (8)	0.0201 (8)	0.0271 (8)	−0.0020 (6)	0.0037 (6)	0.0032 (7)
C20	0.0207 (8)	0.0281 (9)	0.0396 (10)	−0.0019 (7)	−0.0023 (7)	0.0015 (8)
C21	0.0331 (10)	0.0282 (10)	0.0328 (10)	−0.0073 (8)	−0.0081 (8)	−0.0024 (8)
C22	0.0367 (10)	0.0216 (9)	0.0268 (9)	−0.0041 (7)	0.0029 (7)	−0.0042 (7)
C23	0.0224 (8)	0.0178 (8)	0.0294 (9)	−0.0008 (6)	0.0045 (7)	0.0004 (7)
C24	0.0239 (8)	0.0280 (9)	0.0354 (10)	−0.0007 (7)	0.0107 (7)	−0.0005 (7)
C25	0.0235 (10)	0.0716 (16)	0.0808 (17)	0.0045 (10)	0.0139 (10)	−0.0276 (14)
C26	0.0683 (15)	0.0342 (11)	0.0479 (13)	−0.0014 (10)	0.0361 (11)	0.0058 (9)
C27	0.0342 (10)	0.0215 (9)	0.0373 (10)	0.0054 (7)	0.0124 (8)	0.0002 (7)
C28	0.0270 (9)	0.0296 (9)	0.0258 (9)	−0.0018 (7)	−0.0014 (7)	−0.0090 (7)
S29	0.02347 (19)	0.0218 (2)	0.01792 (19)	−0.00431 (16)	0.00205 (14)	−0.00007 (16)
O30	0.0275 (6)	0.0292 (6)	0.0258 (6)	0.0059 (5)	0.0033 (5)	−0.0017 (5)
O31	0.0408 (7)	0.0270 (6)	0.0284 (7)	−0.0141 (5)	−0.0043 (5)	−0.0001 (5)
O32	0.0380 (7)	0.0351 (7)	0.0190 (6)	−0.0063 (5)	0.0028 (5)	0.0036 (5)
C33	0.0258 (8)	0.0270 (9)	0.0234 (8)	0.0018 (7)	0.0033 (6)	−0.0023 (7)
F34	0.0346 (6)	0.0779 (9)	0.0271 (6)	0.0028 (6)	0.0124 (5)	0.0057 (6)
F35	0.0349 (6)	0.0407 (6)	0.0488 (7)	0.0174 (5)	0.0001 (5)	−0.0094 (5)
F36	0.0302 (6)	0.0375 (6)	0.0564 (7)	−0.0148 (5)	0.0092 (5)	−0.0106 (5)

Geometric parameters (Å, º) top

C1—C2	1.362 (2)	C19—C20	1.400 (2)
C1—C11	1.433 (2)	C19—C24	1.535 (2)
C1—H1	0.9500	C20—C21	1.390 (3)
C2—C3	1.416 (2)	C20—H20	0.9500
C2—H2	0.9500	C21—C22	1.374 (3)
C3—C4	1.359 (2)	C21—H21	0.9500
C3—H3	0.9500	C22—C23	1.383 (2)
C4—C12	1.418 (2)	C22—H22	0.9500
C4—H4	0.9500	C23—H23	0.9500
C5—C6	1.362 (2)	C24—C25	1.534 (3)
C5—C14	1.420 (2)	C24—C26	1.537 (3)
C5—H5	0.9500	C24—C27	1.540 (2)
C6—C7	1.406 (3)	C25—H25C	0.9800
C6—H6	0.9500	C25—H25B	0.9800
C7—C8	1.356 (2)	C25—H25A	0.9800
C7—H7	0.9500	C26—H26C	0.9800
C8—C13	1.430 (2)	C26—H26B	0.9800
C8—H8	0.9500	C26—H26A	0.9800
C9—C11	1.397 (2)	C27—H27C	0.9800
C9—C13	1.404 (2)	C27—H27B	0.9800
C9—C15	1.505 (2)	C27—H27A	0.9800
N10—C14	1.372 (2)	C28—H28C	0.9800
N10—C12	1.374 (2)	C28—H28B	0.9800
N10—C28	1.483 (2)	C28—H28A	0.9800
C11—C12	1.433 (2)	S29—O30	1.4395 (12)
C13—C14	1.432 (2)	S29—O32	1.4416 (12)
C15—O16	1.3496 (18)	S29—O31	1.4431 (12)
C15—O17	1.2001 (18)	S29—C33	1.8202 (17)
O16—C18	1.4259 (18)	C33—F36	1.3319 (19)
C18—C23	1.380 (2)	C33—F34	1.3330 (19)
C18—C19	1.398 (2)	C33—F35	1.3369 (19)

C2—C1—C11	120.80 (15)	C21—C20—H20	118.7
C2—C1—H1	119.6	C19—C20—H20	118.7
C11—C1—H1	119.6	C22—C21—C20	120.42 (16)
C1—C2—C3	119.37 (15)	C22—C21—H21	119.8
C1—C2—H2	120.3	C20—C21—H21	119.8
C3—C2—H2	120.3	C21—C22—C23	119.25 (16)
C4—C3—C2	122.35 (15)	C21—C22—H22	120.4
C4—C3—H3	118.8	C23—C22—H22	120.4
C2—C3—H3	118.8	C18—C23—C22	119.25 (15)
C3—C4—C12	119.61 (15)	C18—C23—H23	120.4
C3—C4—H4	120.2	C22—C23—H23	120.4
C12—C4—H4	120.2	C25—C24—C19	111.16 (15)
C6—C5—C14	120.00 (16)	C25—C24—C26	109.00 (17)
C6—C5—H5	120.0	C19—C24—C26	110.26 (14)
C14—C5—H5	120.0	C25—C24—C27	106.82 (15)
C5—C6—C7	121.63 (16)	C19—C24—C27	110.54 (13)
C5—C6—H6	119.2	C26—C24—C27	108.97 (15)
C7—C6—H6	119.2	C24—C25—H25C	109.5
C8—C7—C6	120.23 (16)	C24—C25—H25B	109.5
C8—C7—H7	119.9	H25C—C25—H25B	109.5
C6—C7—H7	119.9	C24—C25—H25A	109.5
C7—C8—C13	120.61 (16)	H25C—C25—H25A	109.5
C7—C8—H8	119.7	H25B—C25—H25A	109.5
C13—C8—H8	119.7	C24—C26—H26C	109.5
C11—C9—C13	121.23 (14)	C24—C26—H26B	109.5
C11—C9—C15	121.22 (13)	H26C—C26—H26B	109.5
C13—C9—C15	117.54 (13)	C24—C26—H26A	109.5
C14—N10—C12	122.24 (13)	H26C—C26—H26A	109.5
C14—N10—C28	119.84 (13)	H26B—C26—H26A	109.5
C12—N10—C28	117.90 (13)	C24—C27—H27C	109.5
C9—C11—C12	118.65 (14)	C24—C27—H27B	109.5
C9—C11—C1	122.73 (14)	H27C—C27—H27B	109.5
C12—C11—C1	118.61 (14)	C24—C27—H27A	109.5
N10—C12—C4	121.11 (14)	H27C—C27—H27A	109.5
N10—C12—C11	119.66 (14)	H27B—C27—H27A	109.5
C4—C12—C11	119.22 (14)	N10—C28—H28C	109.5
C9—C13—C8	122.60 (14)	N10—C28—H28B	109.5
C9—C13—C14	118.65 (14)	H28C—C28—H28B	109.5
C8—C13—C14	118.74 (14)	N10—C28—H28A	109.5
N10—C14—C5	121.64 (14)	H28C—C28—H28A	109.5
N10—C14—C13	119.56 (13)	H28B—C28—H28A	109.5
C5—C14—C13	118.80 (14)	O30—S29—O32	115.64 (7)
O17—C15—O16	125.27 (14)	O30—S29—O31	114.84 (7)
C9—C15—O16	111.10 (13)	O32—S29—O31	114.74 (7)
C9—C15—O17	123.61 (13)	O30—S29—C33	102.71 (7)
C15—O16—C18	117.78 (11)	O32—S29—C33	102.82 (8)
C23—C18—C19	124.09 (14)	O31—S29—C33	103.54 (8)
C23—C18—O16	118.38 (13)	F36—C33—F34	107.68 (14)
C19—C18—O16	117.45 (14)	F36—C33—F35	106.40 (13)
C18—C19—C20	114.39 (15)	F34—C33—F35	107.46 (13)
C18—C19—C24	123.17 (14)	F36—C33—S29	111.49 (11)
C20—C19—C24	122.44 (15)	F34—C33—S29	111.69 (11)
C21—C20—C19	122.61 (16)	F35—C33—S29	111.84 (12)

C11—C1—C2—C3	0.8 (2)	C9—C13—C14—C5	179.59 (14)
C1—C2—C3—C4	0.8 (2)	C8—C13—C14—C5	0.5 (2)
C2—C3—C4—C12	−1.2 (2)	C11—C9—C15—O17	119.85 (17)
C14—C5—C6—C7	−0.1 (3)	C13—C9—C15—O17	−58.9 (2)
C5—C6—C7—C8	0.2 (3)	C11—C9—C15—O16	−61.87 (17)
C6—C7—C8—C13	0.1 (3)	C13—C9—C15—O16	119.39 (14)
C13—C9—C11—C12	0.0 (2)	O17—C15—O16—C18	3.0 (2)
C15—C9—C11—C12	−178.70 (13)	C9—C15—O16—C18	−175.23 (12)
C13—C9—C11—C1	179.05 (14)	C15—O16—C18—C23	−56.98 (18)
C15—C9—C11—C1	0.4 (2)	C15—O16—C18—C19	126.28 (15)
C2—C1—C11—C9	178.95 (15)	C23—C18—C19—C20	−0.1 (2)
C2—C1—C11—C12	−2.0 (2)	O16—C18—C19—C20	176.40 (13)
C14—N10—C12—C4	179.37 (14)	C23—C18—C19—C24	179.78 (15)
C28—N10—C12—C4	0.9 (2)	O16—C18—C19—C24	−3.7 (2)
C14—N10—C12—C11	0.2 (2)	C18—C19—C20—C21	0.4 (2)
C28—N10—C12—C11	−178.30 (13)	C24—C19—C20—C21	−179.52 (16)
C3—C4—C12—N10	−179.19 (14)	C19—C20—C21—C22	−0.3 (3)
C3—C4—C12—C11	0.0 (2)	C20—C21—C22—C23	−0.2 (3)
C9—C11—C12—N10	−0.1 (2)	C19—C18—C23—C22	−0.3 (2)
C1—C11—C12—N10	−179.23 (13)	O16—C18—C23—C22	−176.77 (13)
C9—C11—C12—C4	−179.34 (13)	C21—C22—C23—C18	0.4 (2)
C1—C11—C12—C4	1.6 (2)	C18—C19—C24—C25	−172.91 (17)
C11—C9—C13—C8	179.12 (14)	C20—C19—C24—C25	7.0 (2)
C15—C9—C13—C8	−2.1 (2)	C18—C19—C24—C26	66.1 (2)
C11—C9—C13—C14	0.1 (2)	C20—C19—C24—C26	−113.99 (19)
C15—C9—C13—C14	178.85 (13)	C18—C19—C24—C27	−54.5 (2)
C7—C8—C13—C9	−179.48 (15)	C20—C19—C24—C27	125.45 (17)
C7—C8—C13—C14	−0.5 (2)	O30—S29—C33—F36	58.93 (13)
C12—N10—C14—C5	−179.72 (14)	O32—S29—C33—F36	−61.49 (13)
C28—N10—C14—C5	−1.3 (2)	O31—S29—C33—F36	178.76 (11)
C12—N10—C14—C13	−0.1 (2)	O30—S29—C33—F34	−61.59 (13)
C28—N10—C14—C13	178.38 (13)	O32—S29—C33—F34	177.99 (12)
C6—C5—C14—N10	179.41 (15)	O31—S29—C33—F34	58.23 (13)
C6—C5—C14—C13	−0.2 (2)	O30—S29—C33—F35	177.92 (11)
C9—C13—C14—N10	−0.1 (2)	O32—S29—C33—F35	57.51 (12)
C8—C13—C14—N10	−179.12 (13)	O31—S29—C33—F35	−62.25 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O32	0.95	2.58	3.478 (2)	158
C4—H4···O31ⁱ	0.95	2.35	3.285 (2)	168
C5—H5···O30ⁱⁱ	0.95	2.45	3.330 (2)	155
C6—H6···O32ⁱⁱ	0.95	2.42	3.265 (2)	148
C7—H7···F35ⁱⁱⁱ	0.95	2.46	3.264 (2)	143
C23—H23···F36^iv	0.95	2.52	3.208 (2)	130
C28—H28A···O32^v	0.98	2.42	3.251 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₄NO₂⁺·CF₃O₃S⁻
M_r	519.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	15.307 (4), 13.480 (3), 12.263 (3)
β (°)	102.56 (3)
V (Å³)	2469.8 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.50 × 0.40 × 0.07

Data collection
Diffractometer	Kuma KM4 CCD κ-geometry
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	29629, 7120, 4774
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.102, 1.00
No. of reflections	7120
No. of parameters	329
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.36

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).