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

Damian Trzybiński; Karol Krzymiński; Artur Sikorski; Jerzy Błażejowski

doi:10.1107/S1600536810016302

. 2010 May 12;66(Pt 6):o1311–o1312. doi: 10.1107/S1600536810016302

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

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

PMCID: PMC2979660 PMID: 21579406

Abstract

In the crystal structure of the title compound, C₂₂H₁₈NO₂ ⁺·CF₃SO₃ ⁻, adjacent cations are linked through C—H⋯π and π–π interactions, and the cations and anions are connected by C—H⋯O and C—F⋯π interactions. The acridine and benzene ring systems are oriented at a dihedral angle of 3.0 (1)°. The carboxyl group is twisted at an angle of 83.1 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel or inclined at an angle of 75.2 (1)° in the crystal structure.

Related literature

For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009 ▶); Rak et al. (1999 ▶); Roda et al. (2003 ▶); Zomer & Jacquemijns (2001 ▶). For related structures, see: Sikorski et al. (2006 ▶); Trzybiński et al. (2010 ▶). For intermolecular interactions, see: Bianchi et al. (2004 ▶); Dorn et al. (2005 ▶); Hunter et al. (2001 ▶); Novoa et al. (2006 ▶); Takahashi et al. (2001 ▶). For the synthesis, see: Sato (1996 ▶); Sikorski et al. (2006 ▶); Trzybiński et al. (2010 ▶).

Experimental

Crystal data

C₂₂H₁₈NO₂ ⁺·CF₃O₃S⁻
M _r = 477.45
Monoclinic,
a = 13.2686 (6) Å
b = 8.4788 (4) Å
c = 20.4078 (10) Å
β = 106.749 (5)°
V = 2198.51 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 295 K
0.50 × 0.40 × 0.10 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.869, T _max = 1.000
12172 measured reflections
3892 independent reflections
2096 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.137
S = 0.95
3892 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED; 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/S1600536810016302/ng2760sup1.cif

e-66-o1311-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016302/ng2760Isup2.hkl

e-66-o1311-Isup2.hkl^{(190.8KB, 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⋯O27ⁱ	0.93	2.57	3.314 (5)	137
C4—H4⋯O29ⁱ	0.93	2.44	3.319 (4)	159
C5—H5⋯O28	0.93	2.44	3.364 (5)	171
C6—H6⋯O28ⁱⁱ	0.93	2.56	3.342 (5)	142
C23—H23⋯O27ⁱⁱⁱ	0.93	2.53	3.448 (4)	169
C25—H25A⋯O29	0.96	2.56	3.415 (5)	149
C25—H25B⋯Cg4^iv	0.96	2.62	3.487 (4)	151

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

Table 2. C–F⋯π interactions (Å,°).

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
C30	F31	Cg2ⁱ	3.420 (3)	4.044 (4)	108.9 (2)
C30	F32	Cg1ⁱ	3.441 (3)	4.032 (4)	107.1 (2)
C30	F32	Cg2ⁱ	3.788 (4)	4.044 (4)	91.5 (2)
C30	F33	Cg1ⁱ	3.669 (3)	4.032 (4)	96.2 (2)

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Symmetry code: (i) Inline graphic .

Table 3. π–π interactions (Å,°).

Cg3 and Cg4 are the centroids of the C5–C8/C13/C14 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 is the perpendicular distance of CgI from ring J. CgI_Offset is the distance between CgI and perpendicular projection of CgJ on ring I.

I	J	CgI⋯CgJ	Dihedral angle	CgI_Perp	CgI_Offset
3	4^v	3.913 (2)	4.80 (17)	3.472 (2)	1.805 (2)
4	3^v	3.913 (2)	4.80 (17)	3.565 (2)	1.613 (2)

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Symmetry code: (v) Inline graphic .

Acknowledgments

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.

supplementary crystallographic information

Comment

9-(Phenoxycarbonyl)-10-methylacridinium salts appear to be convenient chemiluminescent indicators or the chemiluminogenic fragments of chemiluminescent labels (Zomer & Jacquemijns, 2001), which are widely applied in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Roda et al., 2003; Brown et al., 2009). Oxidation of the cations of these salts with hydrogen peroxide in alkaline media is accompanied by the removal of the phenoxycarbonyl fragment and the conversion of the remaining part of the molecule to electronically excited, light emitting 10-methyl-9-acridinone (Rak et al., 1999; Zomer & Jacquemijns, 2001). The efficiency of chemiluminescence – crucial for analytical applications – is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). This prompted us to undertake investigations on derivatives substituted in this fragment. Here we present the structure of 9-(4-methylphenoxy)carbonyl-10-methylacridinium trifluoromethanesulfonate, a structural isomer of the 2-methyl substituted salt, whose structure has already been refined (Sikorski et al., 2006).

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; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0386 (3) Å and 0.0017 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 3.0 (1)°. The carboxyl group is twisted at an angle of 83.1 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (remain at an angle of 0.0 (1)°) or inclined at an angle of 75.2 (1)° in the lattice.

In the crystal structure, the adjacent cations are linked through C–H···π (Table 1, Fig. 2) and π–π (involving acridine and phenyl moieties) (Table 3, Fig. 2) interactions, and cations and anions are connected by multidirectional 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 (Bianchi et al. 2004; Novoa et al., 2006). The C–H···π interactions should be of an attractive nature (Takahashi et al., 2001), like the C–F···π (Dorn et al., 2005) and π–π (Hunter et al., 2001) interactions. The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.

Experimental

The compound was synthesized as described elsewhere (Sikorski et al., 2006; Trzybiński et al., 2010), i.e., 9-(chlorocarbonyl)acridine obtained by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride was esterified with 4-methylphenol 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 – 4-methylphenyl acridine-9-carboxylate, purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 3/2 v/v) – was quaternarized with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane. The crude 9-(4-methylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with 25 v/v excess of diethyl ether. Light-orange crystals suitable for X-ray investigations were grown from absolute ethanol solution (m.p. 445 - 447 K).