9-(3-Fluoro­phen­oxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate monohydrate

Damian Trzybiński; Agnieszka Ożóg; Karol Krzymiński; Jerzy Błażejowski

doi:10.1107/S1600536812003054

. 2012 Feb 4;68(Pt 3):o625–o626. doi: 10.1107/S1600536812003054

9-(3-Fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate monohydrate

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

PMCID: PMC3295421 PMID: 22412532

Abstract

In the crystal structure of the title molecular salt, C₂₁H₁₅FNO₂ ⁺·CF₃SO₃ ⁻·H₂O, the cations form inversion dimers through π–π interactions between the acridine ring systems. These dimers are linked via C—H⋯O and C—F⋯π interactions to adjacent anions, and by C—H⋯π and C—F⋯π interactions to neighbouring cations. The water molecule links two sites of the cation by C—H⋯O interactions and two adjacent anions by O—H⋯O hydrogen bonds. The mean planes of the acridine and benzene ring systems are oriented at a dihedral angle of 15.1 (1)°. The carboxyl group is twisted at an angle of 84.5 (1)° relative to the acridine skeleton. The mean planes of the acridine ring systems are parallel in the crystal.

Related literature

For general background to the chemiluminogenic features of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: King et al. (2007 ▶); Krzymiński et al. (2011 ▶); Roda et al. (2003 ▶). For related structures, see: Trzybiński et al. (2010 ▶). For intermolecular interactions, see: Aakeröy et al. (1992 ▶); 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

C₂₁H₁₅FNO₂ ⁺·CF₃O₃S⁻·H₂O
M _r = 499.44
Triclinic,
a = 9.5144 (10) Å
b = 11.5654 (11) Å
c = 11.9680 (12) Å
α = 109.975 (9)°
β = 97.838 (8)°
γ = 113.197 (9)°
V = 1080.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.40 × 0.15 × 0.10 mm

Data collection

Oxford Gemini R Ultra Ruby CCD diffractometer
9148 measured reflections
3769 independent reflections
1647 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.129
S = 0.81
3769 reflections
314 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 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/S1600536812003054/xu5452sup1.cif

e-68-0o625-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003054/xu5452Isup2.hkl

e-68-0o625-Isup2.hkl^{(184.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812003054/xu5452Isup3.cml

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
O1W—H1W⋯O29ⁱ	0.85 (3)	2.24 (3)	3.071 (5)	172 (4)
O1W—H2W⋯O28	0.89 (3)	1.99 (3)	2.873 (5)	176 (8)
C1—H1⋯O1W	0.93	2.51	3.365 (7)	152
C3—H3⋯O29ⁱⁱ	0.93	2.60	3.298 (5)	133
C19—H19⋯O1W	0.93	2.60	3.415 (7)	145
C25—H25A⋯O27ⁱⁱⁱ	0.96	2.53	3.424 (5)	155
C25—H25C⋯Cg4ⁱⁱ	0.96	2.64	3.527 (4)	154

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

Table 2. C—F⋯π interactions (Å,°).

Cg1, Cg2 and Cg3 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C5–C8/C13/C14 rings, respectively.

X	I	J	I⋯J	X⋯J	X—I⋯J
C20	F24	Cg2^iv	3.743 (3)	4.139 (5)	97.6 (2)
C20	F24	Cg2^v	3.854 (4)	4.188 (5)	94.9 (3)
C30	F31	Cg1^v	3.665 (4)	4.519 (6)	123.6 (3)
C30	F31	Cg3^v	3.910 (4)	4.049 (6)	86.7 (3)
C30	F33	Cg3^v	3.654 (4)	4.049 (6)	97.7 (3)

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Symmetry codes: (iv) x − 1, y, z; (v) −x + 1, −y + 2, −z + 1.

Table 3. π–π interactions (Å,°).

Cg1, Cg2 and Cg3 are as defined in Table 2. 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 the perpendicular projection of CgJ on ring I.

I	J	CgI⋯CgJ	Dihedral angle	CgI_Perp	CgI_Offset
1	1^vi	3.990 (2)		3.591 (2)	1.739 (2)
1	3^vi	3.645 (2)	2.08 (17)	3.557 (2)	0.796 (2)
2	3^vi	3.907 (2)	3.85 (19)	3.431 (2)	1.863 (2)
3	1^vi	3.645 (2)	2.08 (17)	3.546 (2)	0.844 (2)
3	2^vi	3.907 (2)	3.85 (19)	3.548 (2)	1.629 (2)

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Symmetry code: (vi) −x + 1, −y + 1, −z.

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 authors: the sponsors cannot be held responsible for any use which may be made of the information contained therein.

supplementary crystallographic information

Comment

9-Phenoxycarbonyl-10-methylacridinium cations react with oxidants (e.g. H₂O₂) in alkaline media, as a result of which electronically excited 10-methyl-9-acridinone molecules are generated (Krzymiński et al., 2011). This phenomenon forms the basis for the use of these entities as chemiluminogenic indicators or fragments of chemiluminescent labels (Roda et al., 2003; King et al., 2007; Krzymiński et al., 2011). It has been noted that the conversion efficiency of the above-mentioned cations to 10-methyl-9-acridinone molecules, and consequently the chemiluminescence quantum yield, crucial in analytical applications, depends on the structure of the phenoxycarbonyl fragment (Krzymiński et al., 2011). For these reasons we have been synthesizing 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates variously substituted in the phenyl fragment in order to select derivatives optimal for analytical applications. Here we present the structure of one of the compounds of this series.

In the cation of the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the acridinium and phenyl moieties are typical of 9-phenoxycarbonyl-10-methylacridinium derivatives (Trzybiński et al., 2010). With respective average deviations from planarity of 0.0397 (3) Å and 0.0066 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 15.1 (1)° [in 9-(4-fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate this angle is equal to 74.1 (1)° (Trzybiński et al., 2010)]. The carboxyl group is twisted at an angle of 84.5 (1)° relative to the acridine skeleton [in 9-(4-fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate this angle is 4.4 (1)° (Trzybiński et al., 2010)]. The mean planes of the adjacent acridine moieties are parallel [remain at an angle of 0.0 (1)°)] in the lattice.

In the crystal structure, the inversely oriented cations form dimers through π–π contacts involving all three rings of the acridine aromatic system (Table 3, Fig. 2). These dimers are linked by C—H···O (Table 1, Fig. 2) and C—F···π (Table 2, Fig. 2) interactions to adjacent anions and by C—H···π (Table 1, Fig. 2) and C—F···π (Table 2, Fig. 2) interactions to neighbouring cations. Each cation is involved in two C—H···O interactions with a water molecule, which in turn is engaged in O—H···O hydrogen bonds involving O atoms of two adjacent anions (Table 1, Figs. 1 and 2). The O—H···O (Aakeröy et al., 1992) and C—H···O (Novoa et al., 2006) interactions are of the hydrogen bond type. 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 the 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

3-Fluorophenylacridine-9-carboxylate was obtained by esterification of 9-(chlorocarbonyl)acridine (synthesized in the reaction of acridine-9-carboxylic acid with a tenfold excess of thionyl chloride) with 3-fluorophenol 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). 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 3-(fluorophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with a 20 v/v excess of diethyl ether (Trzybiński et al., 2010). Light-yellow crystals suitable for X-ray investigations were grown from methanol/water solution (1/1 v/v) (m.p. 497–498 K).