Crystal structure of the enol form of mesotrione: a benzoyl­cyclo­hexa­nedione herbicide

Gihaeng Kang; Jineun Kim; Hyunjin Park; Tae Ho Kim

doi:10.1107/S2056989015012803

. 2015 Jul 8;71(Pt 8):o548–o549. doi: 10.1107/S2056989015012803

Crystal structure of the enol form of mesotrione: a benzoylcyclohexanedione herbicide

Gihaeng Kang ^a, Jineun Kim ^a,^*, Hyunjin Park ^a, Tae Ho Kim ^a,^*

PMCID: PMC4571390 PMID: 26396790

Abstract

The title compound [systematic name: 3-hydroxy-2-(4-methylsulfonyl-2-nitrobenzoyl)cyclohex-2-enone], C₁₄H₁₃NO₇S, is the enol form of a benzoylcyclohexanedione herbicide. As a result of this tautomerization, there is intramolecular O—H⋯O hydrogen bond enclosing an S(6) ring motif. The cyclohexene ring has an envelope conformation, with the central CH₂ C atom as the flap. Its mean plane is inclined to the benzene ring by 87.46 (8)°. In the crystal, molecules are linked by a series of C—H⋯O hydrogen bonds, forming a three-dimensional framework.

Keywords: crystal structure, tautomerization, enol form, intramolecular O—H⋯O hydrogen bond.

Related literature

For information on the herbicidal properties of the title compound, see: Mitchell et al. (2001 ▸). For related crystal structures, see: Eftekhari-Sis et al. (2012 ▸); Liu & Tang (2012 ▸). graphic file with name e-71-0o548-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₃NO₇S
M _r = 339.31
Monoclinic,
a = 10.4208 (2) Å
b = 11.2525 (3) Å
c = 12.3550 (3) Å
β = 95.370 (1)°
V = 1442.39 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 K
0.43 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.895, T _max = 0.949
12093 measured reflections
2828 independent reflections
2572 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.04
2828 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg, 2010 ▸); software used to prepare material for publication: SHELXTL (Sheldrick 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015012803/su5166sup1.cif

e-71-0o548-sup1.cif^{(410.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012803/su5166Isup2.hkl

e-71-0o548-Isup2.hkl^{(155.4KB, hkl)}

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

Supporting information file. DOI: 10.1107/S2056989015012803/su5166Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015012803/su5166fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular O—H⋯O hydrogen bond is shown as a dashed line (see Table 1 for details).

Click here for additional data file.^{(1.5MB, tif)}

a . DOI: 10.1107/S2056989015012803/su5166fig2.tif

Crystal packing of the title compound viewed along the a axis. The intermolecular C—H⋯O hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1410192

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O6H6OO5	0.91(3)	1.71(3)	2.524(2)	148(2)
C1H1BO4ⁱ	0.98	2.58	3.393(2)	140
C1H1BO7ⁱⁱ	0.98	2.58	3.265(2)	127
C11H11AO3ⁱⁱⁱ	0.99	2.40	3.135(2)	131

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

Acknowledgments

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2014R1A1A4A01009105).

supplementary crystallographic information

S1. Comment

Mesotrione, [keto form systematic name: 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione], is a benzoylcyclohexanedione herbicide and it has been developed for the selective pre- and post-emergence control of a wide range of broad-leaved and grass weeds in maize (Mitchell et al., 2001). However, until now its crystal structure has not been reported.

The title compound crystallized in the enol form (Fig. 1 and Table 1), with an intramolecular O6—H6O···O5 hydrogen bond embedded in an S(6) ring. The cyclohexene ring has an envelope conformation with the central CH₂ C-atom, C12, as the flap. Its mean plane is inclined to the benzene ring by 87.46 (8) °.

All bond lengths and bond angles are normal and comparable to those observed in the crystal structures of similar compounds (Eftekhari-Sis et al., 2012; Liu et al., 2012).

In the crystal, molecules are linked by a series of C—H···O hydrogen bonds forming a three-dimensional framework (Fig. 2 and Table 1).

S2. Experimental

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CH₃CN gave single crystals suitable for X-ray analysis.