2,6-Dimethyl­phenyl acridine-9-carboxyl­ate

Damian Trzybiński; Michał Wera; Karol Krzymiński; Jerzy Błażejowski

doi:10.1107/S160053681205129X

. 2013 Jan 4;69(Pt 2):o166. doi: 10.1107/S160053681205129X

2,6-Dimethylphenyl acridine-9-carboxylate

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

PMCID: PMC3569231 PMID: 23424454

Abstract

In the title compound, C₂₂H₁₇NO₂, the acridine ring system and the benzene ring are oriented at a dihedral angle of 37.7 (1)°. The carboxyl group is twisted at an angle of 67.7 (1)° relative to the acridine skeleton. In the crystal, molecules are arranged in stacks along the b axis, with all of the acridine rings involved in multiple π–π interactions [centroid–centroid distances in the range 3.632 (2)–4.101 (2) Å]. The acridine moieties are parallel within the stacks, but inclined at an angle of 52.7 (1)° in adjacent stacks.

Related literature

For general background, see: Krzymiński et al. (2011 ▶); Natrajan et al. (2012 ▶). For related structures, see: Sikorski et al. (2005 ▶); Sikorski et al. (2006 ▶). For intermolecular interactions, see: Hunter et al. (2001 ▶). For the synthesis, see: Sato (1996 ▶); Sikorski et al. (2005 ▶).

Experimental

Crystal data

C₂₂H₁₇NO₂
M _r = 327.37
Monoclinic,
a = 12.8617 (10) Å
b = 7.5352 (5) Å
c = 17.5950 (15) Å
β = 103.143 (8)°
V = 1660.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 K
0.45 × 0.12 × 0.05 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.349, T _max = 1.000
10387 measured reflections
2913 independent reflections
1908 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.151
S = 0.97
2913 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.24 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

Click here for additional data file.^{(25.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681205129X/ng5313sup1.cif

e-69-0o166-sup1.cif^{(25.4KB, cif)}

Click here for additional data file.^{(143KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681205129X/ng5313Isup2.hkl

e-69-0o166-Isup2.hkl^{(143KB, hkl)}

Click here for additional data file.^{(6.6KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681205129X/ng5313Isup3.cml

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

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).

supplementary crystallographic information

Comment

Phenyl acridine-9-carboxylates are the precursors of 9-(phenoxycarbonyl)-10-methylacridinium salts, whose cations exhibit a chemiluminogenic ability that can be utilized analytically (Natrajan et al., 2012). Here we present the structure of the precursor of one of the chemiluminogens that we have recently investigated (Krzymiński et al., 2011).

The bond lengths and angles characterizing the geometry of the acridine and phenyl moieties of the title compound (Fig. 1) are similar to those found in earlier investigated phenyl acridine-9-carboxylates alkyl-substituted at the benzene ring (Sikorski et al., 2005; Sikorski et al., 2006). With respective average deviations from planarity of 0.0245 (3) Å and 0.0084 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 37.7 (1)° (this angle is equal to 30.0 (2)° in 2-methylphenyl acridine-9-carboxylate (Sikorski et al., 2006) and 35.7 (2)° in 2,5-dimethylphenyl acridine-9-carboxylate (Sikorski et al., 2005)). The carboxyl group is twisted at an angle of 67.7 (1)° relative to the acridine skeleton (this angle is equal to 58.0 (2)° in 2-methylphenyl acridine-9-carboxylate (Sikorski et al., 2006) and 68.1 (2)° in 2,5-dimethylphenyl acridine-9-carboxylate (Sikorski et al., 2005)).

The search for intermolecular interactions in the crystal using PLATON (Spek, 2009) has shown that the inversely related molecules of the title compound (Fig. 2) are arranged in stacks along the b axis (Fig. 3) in which all acridine rings are involved in multiple π–π interactions (Table 1, Fig. 2) of an attractive nature (Hunter et al., 2001). The acridine moieties are parallel in stacks but inclined at an angle of 52.7 (1)° in adjacent stacks. The crystal structure is stabilized by dispersive interactions between neighboring stacks. This interesting crystal architecture is unique among the structures of phenyl acridine-9-carboxylates determined to date.

Experimental

2,6-Dimethylphenyl acridine-9-carboxylate was synthesized by the esterification of 9-(chlorocarbonyl)acridine (obtained in the reaction of acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride) with 2,6-dimethylphenol in anhydrous dichloromethane in the presence of N,N-diethylethanamine and a catalytic amount of N,N-dimethyl-4-pyridinamine (308–313 K, 25 h) (Sato, 1996; Sikorski et al., 2005). The product was purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 1/1 v/v). Light-yellow crystals suitable for X-ray investigations were grown from cyclohexane (m.p. 434.5–435.5 K).