3-Meth­oxy-2-[2-({[6-(trifluoro­meth­yl)pyridin-2-yl]­oxy}meth­yl)phen­yl]prop-2-enoic acid

Rajni Kant; Vivek K Gupta; Kamini Kapoor; Chetan S Shripanavar; Madhukar B Deshmukh; Kaushik Banerjee

doi:10.1107/S1600536812042316

. 2012 Oct 20;68(Pt 11):o3163. doi: 10.1107/S1600536812042316

3-Methoxy-2-[2-({[6-(trifluoromethyl)pyridin-2-yl]oxy}methyl)phenyl]prop-2-enoic acid

Rajni Kant ^a,^*, Vivek K Gupta ^a, Kamini Kapoor ^a, Chetan S Shripanavar ^b, Madhukar B Deshmukh ^c, Kaushik Banerjee ^b

PMCID: PMC3515258 PMID: 23284478

Abstract

The title molecule, C₁₇H₁₄F₃NO₄, consists of two nearly planar fragments, viz. the 2-benzyloxypyridine (r.m.s. deviation 0.016 Å) and (E)-3-methoxyprop2-enoic (r.m.s. deviation 0.004 Å) units, which form a dihedral angle of 84.19 (7)°. In the crystal, pairs of O—H⋯O hydrogen bonds link molecules into dimers that are further connected by C—H⋯O and C—H⋯F interactions into (001) layers. In addition, π–π stacking interactions are observed within a layer between the pyridine and benzene rings [centroid–centroid distance = 3.768 (2) Å]. The F atoms of the trifluoromethyl group are disordered over two sets of sites in a 0.53 (4):0.47 (4) ratio.

Related literature

The title compound is the acid metabolite of picoxystrobin [systematic name: methyl (E)-3-methoxy-2-{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate], a systemic fungicide with broad-spectrum bio-efficacy against various diseases of agricultural crops, see: Balba (2007 ▶); Ammermann et al. (2000 ▶). For a related structure, see: Kant et al. (2012 ▶).

Experimental

Crystal data

C₁₇H₁₄F₃NO₄
M _r = 353.29
Triclinic,
a = 7.4701 (4) Å
b = 10.1619 (5) Å
c = 11.8219 (5) Å
α = 94.721 (4)°
β = 100.079 (4)°
γ = 110.685 (5)°
V = 816.42 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.821, T _max = 1.000
19533 measured reflections
3214 independent reflections
1988 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.154
S = 1.04
3214 reflections
253 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(25.5KB, cif)}

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536812042316/gk2523sup1.cif

e-68-o3163-sup1.cif^{(25.5KB, cif)}

Click here for additional data file.^{(154.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042316/gk2523Isup2.hkl

e-68-o3163-Isup2.hkl^{(154.4KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812042316/gk2523Isup3.cml

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
O4—H41⋯O3ⁱ	0.85 (4)	1.78 (4)	2.626 (3)	174 (4)
C15—H15⋯O3ⁱⁱ	0.93	2.58	3.392 (3)	146
C17—H17A⋯F11A ⁱⁱⁱ	0.96	2.41	3.135 (14)	132

Open in a new tab

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

Acknowledgments

RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003.

supplementary crystallographic information

Comment

The above compound is the acid metabolite of picoxystrobin, which is a systemic fungicide of strobilurin group with broad spectrum bio-efficacy against various diseases of economically important agricultural crops (Balba, 2007; Ammermann et al., 2000).

In (I) (Fig.1), all bond lengths and angles are normal and correspond to those observed in the related structure (Kant et al., 2012). The dihedral angle between the two aromatic rings is 1.93 (9)°. The propenoic acid fragment is nearly perpendicular to the attached benzene ring [dihedral angle 82.6 (1)°]. The two nearly planar fragments, 2-(benzyloxy)-3-(trifluoromethyl)pyridine unit (r.m.s. deviation 0.016Å) and (E)-3-methoxyprop2-enoic unit (r.m.s. deviation 0.004Å) form dihedral angle of 84.19 (7)°. The F atoms of the trifluoromethyl group were refined as disordered over two sets of sites with occupancies of 0.53 (4)/0.47 (4). In the crystal, O—H···O hydrogen bonds link molecules to form dimers (Table 1). Dimers are further connected by C—H···O and C—H···F hydrogen bonds into (001) layers (Fig. 2). The crystal structure is further stabilized by π–π interactions between the pyridine ring (C11—C15/N1) of the molecule at (x, y, z) and the benzene ring of an inversion related molecule at(1 - x, 1 - y, - z) [centroid separation = 3.768 (2) Å, interplanar spacing = 3.437 Å and centroid shift = 1.54 Å].

Experimental

Picoxystrobin (0.353 g, 0.001 mol) was dissolved in 5 ml of acetone and to it 5 ml of 1 N NaOH solution was added. The reaction mixture was refluxed at 343 K for 6 h, and then cooled. The compound was precipitated by neutralizing with 1 N HCl solution. The precipitated compound was dissolved in methanol and crystallized by the process of slow evaporation.(m.p. 415 K).