9-(2,5-Dimethyl­phen­oxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate

Damian Trzybiński; Karol Krzymiński; Jerzy Błażejowski

doi:10.1107/S1600536811045090

. 2011 Nov 5;67(Pt 12):o3205–o3206. doi: 10.1107/S1600536811045090

9-(2,5-Dimethylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

Damian Trzybiński ^a, Karol Krzymiński ^a, Jerzy Błażejowski ^a,^*

PMCID: PMC3238871 PMID: 22199724

Abstract

In the title compound, C₂₃H₂₀NO₂ ⁺·CF₃SO₃ ⁻, the acridine ring system is oriented at a dihedral angle of 23.1 (1)° with respect to the benzene ring and the carboxyl group is twisted at an angle of 74.1 (1)° relative to the acridine skeleton. In the crystal, adjacent cations are linked through C—H⋯π interactions and neighboring cations and anions via weak C—H⋯O hydrogen bonds. The mean planes of adjacent acridine units are either parallel or inclined at angles of 15.0 (1), 26.9 (1) and 48.1 (1)° in the crystal structure.

Related literature

For general background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009 ▶); King et al. (2007 ▶); Krzymiński et al. (2011 ▶); Roda et al. (2003 ▶). For related structures, see: Krzymiński et al. (2009 ▶). For intermolecular interactions, see: Novoa et al. (2006 ▶); Takahashi et al. (2001 ▶). For the synthesis, see: Sato (1996 ▶); Krzymiński et al. (2011 ▶).

Experimental

Crystal data

C₂₃H₂₀NO₂ ⁺·CF₃SO₃ ⁻
M _r = 491.48
Orthorhombic,
a = 12.3604 (17) Å
b = 17.341 (3) Å
c = 21.101 (3) Å
V = 4522.8 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 295 K
0.60 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.960, T _max = 0.985
32535 measured reflections
4000 independent reflections
2050 reflections with I > 2σ(I)
R _int = 0.106

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.185
S = 1.01
4000 reflections
310 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); 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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811045090/xu5358sup1.cif

e-67-o3205-sup1.cif^{(30.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045090/xu5358Isup2.hkl

e-67-o3205-Isup2.hkl^{(196.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811045090/xu5358Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O29ⁱ	0.93	2.59	3.257 (5)	129
C5—H5⋯O30	0.93	2.58	3.466 (5)	160
C6—H6⋯O28	0.93	2.52	3.303 (5)	142
C7—H7⋯O29ⁱⁱ	0.93	2.39	3.188 (5)	144
C20—H20⋯Cg2ⁱⁱⁱ	0.93	2.81	3.439 (4)	126
C25—H25B⋯O28ⁱⁱ	0.96	2.49	3.289 (5)	141
C26—H26A⋯O30ⁱ	0.96	2.47	3.314 (5)	146

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This study was financed by the State Funds for Scientific Research through National Center for Science grant No. N N204 375 740 (contract No. 3757/B/H03/2011/40). DT acknowledges financial support from the European Social Fund within the project "Educators for the elite – integrated training program for PhD students, post-docs and professors as academic teachers at the University of Gdansk" and the Human Capital Operational Program Action 4.1.1, Improving the quality on offer at tertiary educational institutions. This publication reflects the views only of the author: the sponsor cannot be held responsible for any use which may be made of the information contained therein.

supplementary crystallographic information

Comment

Chemiluminescing 9-(phenoxycarbonyl)-10-methylacridinium cations are widely applied as indicators or fragments of labels in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Roda et al., 2003; King et al., 2007; Brown et al., 2009). The cations of these salts are oxidized by H₂O₂ in alkaline media, a reaction that 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 (Krzymiński et al., 2011). The efficiency of chemiluminescence – crucial to analytical applications – is affected by the constitution of the phenyl fragment. Here we present the crystal structure of 9-(2,5-dimethylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate, whose chemiluminogenic features we have thoroughly investigated (Krzymiński et al., 2011).

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 (Krzymiński et al., 2009). With respective average deviations from planarity of 0.022 (3) Å and 0.006 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 23.1 (1)°. The carboxyl group is twisted at an angle of 74.1 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (at an angle 0.0 (1)°) or inclined at angles of 15.0 (1), 26.9 (1) and 48.1 (1)° in the crystal lattice.

In the crystal structure, the adjacent cations are linked by C–H···π (Table 1, Fig. 2) contacts and the neighboring cations and anions via C–H···O (Table 1, Figs. 1 and 2) interactions. The C–H···O interactions are of the hydrogen bond type (Novoa et al. 2006), while the C–H···π (Takahashi et al., 2001) contacts should be of an attractive nature. The crystal structure is stabilized by a network of these specific short-range interactions and by long-range electrostatic interactions between ions.

Experimental

2,5-Dimethylphenylacridine-9-carboxylate was synthesized by esterification of 9-(chlorocarbonyl)acridine (obtained in the reaction of acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride) with 2,5-dimethylphenol in anhydrous dichloromethane in the presence of N,N-diethylethanamine and a catalytic amount of N,N-dimethyl-4-pyridinamine (room temperature, 15 h) (Sato, 1996; Krzymiński et al., 2011). The product was purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 1/1 v/v) and subsequently quaternarized with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane. The crude 9-(2,5-dimethylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with a 20 v/v excess of diethyl ether. Yellow crystals suitable for X-ray investigations were grown from ethanol/water solution (1:1 v/v) (m.p. 509–511 K).