2-[2-Hydr­oxy-4-(pyrrolidin-1-yl)benzo­yl]benzoic acid

Yun-Long Gao; Jian-Wu Wang

doi:10.1107/S1600536809011349

. 2009 Mar 31;65(Pt 4):o936. doi: 10.1107/S1600536809011349

2-[2-Hydroxy-4-(pyrrolidin-1-yl)benzoyl]benzoic acid

Yun-Long Gao ^a, Jian-Wu Wang ^a,^*

PMCID: PMC2968880 PMID: 21582636

Abstract

The title compound, C₁₈H₁₇NO₄, crystallizes with two independent molecules in the asymmetric unit. The pyrrolidine ring in one molecule is disordered over two positions, with refined site-occupancy factors of 0.853 (5) and 0.147 (5). The dihedral angles between the planes of the benzene rings in the two independent molecules are 56.8 (2) and 68.2 (5)°. The molecular conformations are stabilized by intramolecular O—H⋯O hydrogen bonds. In the crystal structure, molecules are linked by intermolecular O—H⋯O hydrogen bonds, forming dimers and generating rings of graph-set motif R ₂ ²(8).

Related literature

For the synthesis and applications of the title compound, see: Lee et al. (2005 ▶); Masakichi et al. (1974 ▶); Luo et al. (1994 ▶). For bond-length and angle data for pyrrolidines, see: Effenberger et al. (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₈H₁₇NO₄
M _r = 311.33
Triclinic,
a = 10.841 (2) Å
b = 11.878 (2) Å
c = 13.781 (3) Å
α = 71.70 (3)°
β = 82.05 (3)°
γ = 65.17 (3)°
V = 1529.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 113 K
0.18 × 0.16 × 0.12 mm

Data collection

Rigaku SATURN CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.983, T _max = 0.989
13535 measured reflections
6888 independent reflections
4673 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.136
S = 1.04
6888 reflections
437 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011349/rz2305sup1.cif

e-65-0o936-sup1.cif^{(31.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011349/rz2305Isup2.hkl

e-65-0o936-Isup2.hkl^{(337KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.956 (19)	1.66 (2)	2.547 (2)	151.8 (18)
O5—H5⋯O6	0.943 (19)	1.68 (2)	2.565 (2)	154.9 (19)
O7—H7A⋯O3ⁱ	0.86 (2)	1.784 (10)	2.6387 (17)	169.3 (19)
O4—H4⋯O8ⁱⁱ	0.879 (10)	1.785 (11)	2.6451 (19)	166 (2)

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

supplementary crystallographic information

Comment

2-[2-Hydroxy-4-(1-pyrrolidinyl)benzoyl)]benzoic acid is an intermediate in the synthesis of pyrrolidinylrhodamine (Lee et al., 2005) and its derivatives (Masakichi et al., 1974). It has been synthesized from 3-pyrrolidinylphenol and phthalic anhydride in toluene (Luo et al.,1994). Although its synthesis has been studied, the crystal structure of title compound has not been investigated. In this paper we reported its crystal structure.

The title compound crystallizes with two independent molecules in the asymmetric unit (Fig. 1). Bond lengths and angles within the pyrrolidine rings are normal and in good agreement with those reported previously for 2,4,6-tripyrrolidino-2',4',6'-trinitrobiphenyl (Effenberger et al., 1983). The dihedral angles between the planes of the benzene rings in the two independent molecules are 56.8 (2) and 68.2 (5)°. The molecular conformations are stabilized by intramolecular O—H···O hydrogen bonds (Table 1). In the crystal packing, the molecules are linked by intermolecular O—H···O hydrogen bonds to form dimers generating rings of graph-set motif R₂²(8) (Bernstein et al., 1995).

Experimental

A solution of 3-pyrrolidinylphenol (1.20 g, 7.36 mmol) and phthalic anhydride (1.31 g, 8.83 mmol) in toluene was refluxed under N₂ for 3 h. The mixture was cooled to 50–60°C. Then 7 ml of 35.0% aqueous NaOH (w/w) was added and heated at 90° C for 6 h. The resulting mixture was poured into 70 ml of H2O, acidified with hydrochloric acid, and allowed to stand at room temperature for 2 h. The suspension was then filtered. The solid was recrystallized from a mixture of water and methanol, and then dried to afford the desired product (1.63 g, 70.7%). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a CD₃OD/CDCl₃ (5:1 v/v) solution.