9-(4-Chloro­phen­oxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate

Damian Trzybiński; Karol Krzymiński; Jerzy Błażejowski

doi:10.1107/S1600536810039541

. 2010 Oct 9;66(Pt 11):o2771–o2772. doi: 10.1107/S1600536810039541

9-(4-Chlorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

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

PMCID: PMC3009014 PMID: 21588972

Abstract

In the crystal of the title compound, C₂₁H₁₅ClNO₂ ⁺·CF₃SO₃ ⁻, adjacent cations are linked through C—H⋯π and π–π interactions [centroid–centroid distance = 3.987 (2) Å], and neighboring cations and anions via C—H⋯O and C—F⋯π interactions. The acridine ring system and benzene ring are oriented at a dihedral angle of 1.0 (1)° while the carboxyl group is twisted at an angle of 85.0 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are either parallel or inclined at an angle of 78.2 (1)° in the crystal structure.

Related literature

For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: 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. (2005 ▶); Trzybiński et al. (2010 ▶). For intermolecular interactions, see: Dorn et al. (2005 ▶); Hunter et al. (2001 ▶); Novoa et al. (2006 ▶); Takahashi et al. (2001 ▶). For the synthesis, see: Sato (1996 ▶); Trzybiński et al. (2010 ▶).

Experimental

Crystal data

C₂₁H₁₅ClNO₂ ⁺·CF₃SO₃ ⁻
M _r = 497.87
Monoclinic,
a = 13.3025 (11) Å
b = 8.6750 (9) Å
c = 19.6191 (18) Å
β = 106.577 (10)°
V = 2169.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 295 K
0.35 × 0.28 × 0.06 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
11162 measured reflections
3777 independent reflections
2679 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.112
S = 1.08
3777 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 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 datablocks global, I. DOI: 10.1107/S1600536810039541/xu5039sup1.cif

e-66-o2771-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039541/xu5039Isup2.hkl

e-66-o2771-Isup2.hkl^{(185.2KB, hkl)}

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

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

Cg4 is the centroid of the C18–C23 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O28ⁱ	0.93	2.59	3.328 (5)	136
C4—H4⋯O28	0.93	2.45	3.370 (4)	171
C5—H5⋯O27ⁱⁱ	0.93	2.39	3.258 (4)	154
C6—H6⋯O29ⁱⁱ	0.93	2.54	3.304 (5)	140
C8—H8⋯O29ⁱⁱⁱ	0.93	2.59	3.332 (4)	137
C19—H19⋯O29ⁱⁱⁱ	0.93	2.44	3.349 (4)	165
C25—H25C⋯O27	0.96	2.51	3.387 (4)	152
C25—H25B⋯Cg4^iv	0.96	2.65	3.519 (4)	151

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

Table 2. C–F⋯π interactions (Å,°).

Cg1 and Cg3 are the centroids of the C9/N10/C11–C14 and C5–C8/C13/C14 rings, respectively.

X	I	J	I⋯J	X⋯J	X–I⋯J
C30	F31	Cg1ⁱⁱ	3.570 (3)	3.916 (4)	94.4 (2)
C30	F32	Cg1ⁱⁱ	3.337 (3)	3.916 (4)	105.8 (2)
C30	F33	Cg3ⁱⁱ	3.387 (3)	4.073 (4)	111.9 (2)

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Symmetry code: (ii) Inline graphic .

Acknowledgments

This study was financed by the State Funds for Scientific Research (grant DS/8220-4-0087-0).

supplementary crystallographic information

Comment

The long-known chemiluminescence of 9-(phenoxycarbonyl)-10-methylacridinium salts has been used as chemiluminescent indicators and labels that are widely applied 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). 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 (Rak et al., 1999). The efficiency of chemiluminescence – crucial for analytical applications – is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). In continuing our investigations on the latter aspect, we synthesized 9-(4-chlorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate, whose crystal structure is presented here.

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., 2005; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0412 (3) Å and 0.0034 (3) Å, the acridine and benzene ring systems are almost parallel (are oriented at a dihedral angle of 1.0 (1)°). The carboxyl group is twisted at an angle of 85.0 (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 78.2 (1)° in the crystal lattice.

In the crystal structure, the adjacent cations are linked by C–H···π (Table 1, Fig. 2) and π-π (Table 3, Fig.2) contacts, and the cations and neighboring anions via C–H···O (Table 1, Figs. 1 and 2) and C–F···π (Table 2, Fig. 2) interactions. The C–H···O interactions are of the hydrogen bond type (Novoa et al. 2006). The C–H···π (Takahashi et al., 2001), C–F···π (Dorn et al., 2005) and 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.

Experimental

4-Chlorophenylacridine-9-carboxylate was synthesized by esterification of 9-(chlorocarbonyl)acridine (obtained by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride) with 4-chlorophenol 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). 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-(4-chlorophenoxycarbonyl)-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 absolute ethanol solution (m.p. 488–489 K).