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

Damian Trzybiński; Karol Krzymiński; Artur Sikorski; Jerzy Błażejowski

doi:10.1107/S1600536810016296

. 2010 May 12;66(Pt 6):o1313–o1314. doi: 10.1107/S1600536810016296

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

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

PMCID: PMC2979630 PMID: 21579407

Abstract

In the crystal structure of the title compound, C₂₁H₁₅BrNO₂ ⁺·CF₃SO₃ ⁻, the cations form inversion dimers through π–π interactions between the acridine ring systems. These dimers are further linked by C—H⋯π and C—Br⋯π interactions. The cations and anions are connected by multidirectional C—H⋯O and C—F⋯π interactions. The acridine and benzene ring systems are oriented at 10.8 (1)°. The carboxyl group is twisted at an angle of 85.2 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel or almost parallel [inclined at an angle of 1.4 (1)°] in the crystal structure.

Related literature

For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Adamczyk & Mattingly (2002 ▶); King et al. (2007 ▶); Rak et al. (1999 ▶); Roda et al. (2003 ▶); Zomer & Jacquemijns (2001 ▶). For related structures, see: Sikorski et al. (2005a ▶,b ▶). For intermolecular interactions, see: Bianchi et al. (2004 ▶); Dorn et al. (2005 ▶); Hunter et al. (2001 ▶); Novoa et al. (2006 ▶); Seo et al. (2009 ▶); Takahashi et al. (2001 ▶). For the synthesis, see: Sato (1996 ▶); Sikorski et al. (2005a ▶,b ▶).

Experimental

Crystal data

C₂₁H₁₅BrNO₂ ⁺·CF₃O₃S⁻
M _r = 542.32
Monoclinic,
a = 9.5755 (2) Å
b = 20.4912 (7) Å
c = 11.6241 (5) Å
β = 104.011 (3)°
V = 2212.95 (13) Å³
Z = 4
Mo Kα radiation
μ = 2.01 mm⁻¹
T = 295 K
0.37 × 0.15 × 0.05 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.77, T _max = 0.92
50472 measured reflections
3910 independent reflections
2200 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.112
S = 0.98
3910 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.62 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/S1600536810016296/om2334sup1.cif

e-66-o1313-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016296/om2334Isup2.hkl

e-66-o1313-Isup2.hkl^{(191.7KB, 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
C2—H2⋯O27ⁱ	0.93	2.59	3.361 (5)	141
C4—H4⋯O28ⁱⁱ	0.93	2.50	3.365 (4)	155
C20—H20⋯O27	0.93	2.50	3.176 (4)	130
C25—H25A⋯Cg4ⁱⁱⁱ	0.96	2.81	3.569 (4)	136
C25—H25B⋯O28ⁱⁱ	0.96	2.53	3.472 (5)	167

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

Table 2. C–Br⋯π and C–F⋯π interactions (Å,°).

Cg1, Cg3 and Cg4 are the centroids of the C9/N10/C11–C14, C5–C8/C13/C14 and C18–C23 rings, respectively.

X	I	J	I⋯J	X⋯J	X–I⋯J
C21	Br24	Cg1^iv	3.958 (2)	4.158 (3)	82.3 (1)
C21	Br24	Cg3^iv	3.937 (2)	4.235 (4)	85.4 (2)
C30	F31	Cg4^v	3.212 (4)	4.305 (5)	137.5 (3)

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Symmetry codes: (iv) Inline graphic ; (v) .

Table 3. π–π interactions (Å,°).

Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 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
1	2^vi	3.650 (2)	2.82 (16)	3.623 (2)	0.444 (2)

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Symmetry code: (vi) 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

The cations of 9-(phenoxycarbonyl)-10-methylacridinium salts react efficiently with H₂O₂ in alkaline media producing light (Zomer & Jacquemijns, 2001; Adamczyk & Mattingly, 2002). This effect means that the compounds can serve as chemiluminescent indicators or as chemiluminogenic fragments of chemiluminescent labels in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Zomer & Jacquemijns, 2001; Adamczyk & Mattingly, 2002; Roda et al. , 2003; King et al., 2007). The chemiluminogenic features of the compounds depend on the structure of the cations, particularly the phenoxycarbonyl fragment which is removed during their oxidation leading to electronically excited 10-methyl-9-acridinone molecules (Rak et al., 1999; Zomer & Jacquemijns, 2001). It has been found that the efficiency of chemiluminescence – crucial for analytical applications – is influenced by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). This prompted us to synthesize and investigate derivatives substituted in this latter fragment. In this paper, a continuation of a series on bromo-substituted derivatives (Sikorski et al., 2005a), we present the structure of the title compound.

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., 2005a,b). With respective average deviations from planarity of 0.0442 (3) Å and 0.0046 (3) Å, the acridine and benzene ring systems are oriented at 10.8 (1)°. The carboxyl group is twisted at an angle of 85.2 (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 almost parallel (remain at an angle of 1.4 (1)°) in the lattice.

In the crystal structure, the inversely oriented cations form dimers through π–π interactions involving acridine moieties (Table 3, Fig. 2). These dimers are further linked by C–H···π (Table 1, Fig. 2) and C–Br···π (Table 2, Fig. 2) interactions. The cations and anions are connected by multidirectional C–H···O (Table 1, Fig. 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 C–Br···π interactions have been reported by others (Seo et al., 2009). The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.

Experimental

The title compound was obtained by treating 4-bromophenyl acridine-9-carboxylate [synthesized by heating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride and reacting the product thus obtained with an equimolar amount of 4-bromophenol (Sato, 1996; Sikorski et al., 2005b)] with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in dichloromethane (Sikorski et al., 2005a). The crude 9-(4-bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with a 25 v/v excess of diethyl ether. Yellow crystals suitable for X-ray investigations were grown from anhydrous ethanol (m.p. 504 - 505 K).