Phenyl acridine-9-carboxyl­ate

Michał Wera; Damian Trzybiński; Karol Krzymiński; Jerzy Błażejowski

doi:10.1107/S1600536813002055

. 2013 Jan 31;69(Pt 2):o305. doi: 10.1107/S1600536813002055

Phenyl acridine-9-carboxylate

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

PMCID: PMC3569824 PMID: 23424570

Abstract

The acridine ring system and the benzene ring in the title compound, C₂₀H₁₃NO₂, are oriented at a dihedral angle of 6.4 (2)°. The carboxyl group is twisted at an angle of 83.6 (2)° relative to the acridine skeleton. The molecules in the crystal are arranged in stacks along the b axis, with two of the acridine rings involved in multiple π–π interactions [centroid–centroid distances in the range 3.536 (2)–3.894 (2) Å]. Stacks arranged parallel are linked via C—H⋯π interactions, forming layers in the ac plane that are in contact with adjacent, inversely oriented layers via other C—H⋯π interactions, giving rise to double layers. The inversely oriented double layers interact dispersively. The acridine units are parallel within the parallel-oriented stacks, but inclined at an angle of 79.6 (2)° in the inversely oriented stacks.

Related literature

For general background to the applications of the title compound, see: Krzymiński et al. (2011 ▶); Natrajan et al. (2012 ▶); Trzybiński et al. (2010 ▶). For related structures, see: Trzybiński et al. (2013 ▶). For intermolecular interactions, see: Hunter et al. (2001 ▶); Takahashi et al. (2001 ▶). For the synthesis, see: Sato (1996 ▶); Trzybiński et al. (2010 ▶).

Experimental

Crystal data

C₂₀H₁₃NO₂
M _r = 299.31
Monoclinic,
a = 17.094 (2) Å
b = 5.4175 (7) Å
c = 16.310 (2) Å
β = 95.545 (11)°
V = 1503.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.6 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.354, T _max = 0.986
9221 measured reflections
2651 independent reflections
1560 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.073
wR(F ²) = 0.203
S = 1.04
2651 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 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, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(24.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813002055/xu5671sup1.cif

e-69-0o305-sup1.cif^{(24.6KB, cif)}

Click here for additional data file.^{(130.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002055/xu5671Isup2.hkl

e-69-0o305-Isup2.hkl^{(130.2KB, hkl)}

Click here for additional data file.^{(5.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813002055/xu5671Isup3.cml

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

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

Cg2 and Cg4 denote the centroids of the C1–C4/C11/C12 and C18–C23 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg2ⁱ	0.93	2.98	3.712 (3)	137
C7—H7⋯Cg4ⁱⁱ	0.93	2.84	3.646 (3)	145

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

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 phenyl acridine-9-carboxylate, the precursor of a basic chemiluminogen in this group of compounds, whose structure (Trzybiński et al., 2010) and chemiluminogenic features (Krzymiński et al., 2011) have recently been investigated.

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 phenyl acridine-9-carboxylates alkyl-substituted at the benzene ring, investigated earlier (Trzybiński et al., 2013, and references cited therein). With respective average deviations from planarity of 0.0143 (3) Å and 0.0037 (3) Å, the acridine ring system and the benzene ring are oriented at a dihedral angle of 6.4 (2)° [this angle varies between 30.0 (2)° – 37.7 (1)°, as indicated by the data for phenyl acridine-9-carboxylates alkyl-substituted at the benzene ring, investigated earlier (Trzybiński et al., 2013, and the references cited therein)]. The carboxyl group is twisted at an angle of 83.6 (2)° relative to the acridine skeleton [this angle varies between 58.0 (2)° – 68.1 (2)° as indicated by the data for phenyl acridine-9-carboxylates alkyl-substituted at the benzene ring, investigated earlier (Trzybiński et al., 2013, and the references cited therein)].

The search for intermolecular interactions in the crystal using PLATON (Spek, 2009) has shown that the parallel oriented molecules of the title compound (Fig. 2) are arranged in stacks along the b axis (Fig. 3) in which two of the acridine rings are involved in multiple π–π interactions (Table 2, Fig. 2) of an attractive nature (Hunter et al., 2001). The stacks arranged parallel linked via C–H···π interactions, of an attractive nature (Takahashi et al., 2001), form layers in the ac plane that are in contact with adjacent, inversely-oriented such layers via other C–H···π interactons giving rise to double layers (Table 1, Figs. 2 and 3). The inversely oriented double layers interact dispersively. The acridine moieties are parallel within the stacks oriented in parallel, but inclined at an angle of 79.6 (2)° in the inversely oriented stacks. This interesting crystal architecture to some extent resembles the crystal structure of 2,6-dimethylphenyl acridine-9-carboxylate (Trzybiński et al., 2013).

Experimental

Phenyl 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 phenol 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; Trzybiński et al., 2010). The product was purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 3/2 v/v). Pale-yellow crystals suitable for X-ray investigations were grown from cyclohexane (m.p. 463–464 K).