(S)-[5-Methyl-3-(3-methyl­thio­phen-2-yl)-4,5-dihydro­isoxazol-5-yl]methanol

Ko, Y.K.; Ryu, J.W.; Koo, D.W.; Woo, J.C.; Kim, C.-H.

doi:10.1107/S1600536811011639

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1040

doi:10.1107/S1600536811011639

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(S)-[5-Methyl-3-(3-methylthiophen-2-yl)-4,5-dihydroisoxazol-5-yl]methanol

Young Kwan Ko,^a ^* Jae Wook Ryu,^a Dong Wan Koo,^a Jae Choon Woo ^b and Chong-Hyeak Kim ^c

^aBiomaterials Research Center, Korea Research Institute of Chemical Technology, PO Box 107, Yuseong, Daejeon 305-600, Republic of Korea, ^bDrug Discovery Platform Technology Team, Korea Research Institute of Chemical Technology, PO Box 107, Yuseong, Daejeon 305-600, Republic of Korea, and ^cCenter for Chemical Analysis, Korea Research Institute of Chemical Technology, PO Box 107, Yuseong, Daejeon 305-600, Republic of Korea
^*Correspondence e-mail: ykko@krict.re.kr

(Received 24 March 2011; accepted 29 March 2011; online 7 April 2011)

In the title compound, C₁₀H₁₃NO₂S, the thiophene and isoxazoline rings are almost coplanar, the dihedral angle between their least-squares planes being 2.08 (1)°. The O—H atoms of the methyl hydroxy group and the N atom of the isoxazole ring are orientated in the same direction to allow for the formation of intermolecular O—H⋯N hydrogen bonds that lead to a supramolecular chain along the a axis.

Related literature

For the synthesis, biological activity and mode of action of herbicides, see; Ryu et al. (2005 ); Hwang et al. (2005 ); Koo et al. (2007 ); Koo & Hwang (2008 ). For relevant reviews of herbicides, see; Boger et al. (2002 ); Bryant & Bite (2010 ).

Experimental

Crystal data

C₁₀H₁₃NO₂S
M_r = 211.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.3672 (9) Å
b = 8.8534 (11) Å
c = 16.0632 (19) Å
V = 1047.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.39 × 0.20 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.898, T_max = 0.970
11038 measured reflections
2619 independent reflections
2096 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.149
S = 1.08
2619 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 1087 Friedel pairs
Flack parameter: 0.02 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13⋯N7ⁱ	0.82	2.17	2.905 (3)	150
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ .

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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011639/tk2733sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011639/tk2733Isup2.hkl

checkCIF report

Comment top

Weed control is very important for the improvment of agricultural efficiency Boger et al., 2002; Bryant et al., 2010). A number of herbicides have been used for the purpose of weed killing. Recently a new isoxazoline herbicide MRC-01 has been developed (Ryu et al., 2005; Hwang et al., 2005; Koo et al., 2007; Koo & Hwang, 2008; Bryant & Bite, 2010). MRC-01 was synthesized by the reaction of [5-methyl-3-(3-methylthiophen -2-yl)-4,5-dihydroisoxazol-5-yl]methanol and 2,6-difluorobenzylbromide in the presence of base. The key intermediate [5-methyl-3-(3-methylthiophen-2-yl)-4,5-dihydroisoxazol-5-yl]methanol was used as racemic compound but could be separated into enantiomers by employing chiral HPLC column technology. Herein, we report the crystal structure of title compound (Fig. 1). The thiophene ring and the isoxazole ring are almost coplanar with the dihedral angle being 2.08 (1) °. The conformation of the O—H of the methyl hydroxy group and the N atom of the isoxazole ring are in the same direction to allow intermolecular hydrogen bonds to form. In the crystal structure (Fig. 2), the molecules are linked by these O—H···N hydrogen bonds into a one-dimensional chain running along the a axis.

Related literature top

For the synthesis, biological activity and mode of action of herbicides, see; Ryu et al. (2005); Hwang et al. (2005); Koo et al. (2007); Koo & Hwang (2008). For relevant reviews of herbicides, see; Boger et al. (2002); Bryant & Bite (2010).

Experimental top

The title compound was obtained by a chiral separation of racemic [5-methyl-3-(3-methylthiophen-2-yl)-4,5-dihydroisoxazol-5-yl]methanol employing chiral prep-HPLC under the condition shown below. HPLC conditions: Column: (R,R) WHELK-01 (25 cm x 10.0 mm). Regis.Co.; Eluent: 25% 2-propanol + 75% n-hexane; Flow Rate 4.0 ml/min; Detection: 254 nm; Injection volume: 0.1 ml. The first eluting fraction was concentrated under reduced pressure to provide the title compound [α]_D (+) 59.96 (c = 1, dichloromethane). Single crystals suitable for X-ray diffraction were prepared by recrystallization from its ethyl acetate solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. The molecular packing structure of the title compound, viewed down the c axis showing the O—H···N hydrogen bonds as dashed lines.

(S)-[5-Methyl-3-(3-methylthiophen-2-yl)-4,5-dihydroisoxazol-5-yl]methanol top

Crystal data top

C₁₀H₁₃NO₂S	F(000) = 448
M_r = 211.27	D_x = 1.339 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4205 reflections
a = 7.3672 (9) Å	θ = 2.5–26.1°
b = 8.8534 (11) Å	µ = 0.28 mm⁻¹
c = 16.0632 (19) Å	T = 296 K
V = 1047.7 (2) Å³	Block, silver
Z = 4	0.39 × 0.20 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2619 independent reflections
Radiation source: fine-focus sealed tube	2096 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→9
T_min = 0.898, T_max = 0.970	k = −11→11
11038 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.086P)² + 0.1644P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2619 reflections	Δρ_max = 0.47 e Å⁻³
127 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1087 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (14)

Crystal data top

C₁₀H₁₃NO₂S	V = 1047.7 (2) Å³
M_r = 211.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.3672 (9) Å	µ = 0.28 mm⁻¹
b = 8.8534 (11) Å	T = 296 K
c = 16.0632 (19) Å	0.39 × 0.20 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2619 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2096 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.970	R_int = 0.025
11038 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.149	Δρ_max = 0.47 e Å⁻³
S = 1.08	Δρ_min = −0.36 e Å⁻³
2619 reflections	Absolute structure: Flack (1983), 1087 Friedel pairs
127 parameters	Absolute structure parameter: 0.02 (14)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	−0.00757 (12)	0.90745 (7)	0.64150 (4)	0.0503 (2)
C2	−0.0074 (4)	0.8815 (3)	0.53306 (13)	0.0390 (4)
C3	−0.0070 (5)	0.7321 (3)	0.51314 (15)	0.0446 (5)
C4	−0.0075 (4)	0.6395 (3)	0.58618 (17)	0.0525 (6)
H4A	−0.0080	0.5345	0.5841	0.063*
C5	−0.0071 (5)	0.7169 (3)	0.65749 (17)	0.0568 (6)
H5	−0.0067	0.6721	0.7099	0.068*
C6	−0.0104 (4)	1.0139 (2)	0.47984 (12)	0.0368 (4)
N7	−0.0045 (4)	1.1462 (2)	0.51234 (11)	0.0448 (4)
O8	−0.0178 (4)	1.25711 (18)	0.45051 (10)	0.0490 (5)
C9	−0.0104 (4)	1.1857 (3)	0.36792 (13)	0.0405 (5)
C10	−0.0244 (4)	1.0174 (3)	0.38670 (13)	0.0423 (6)
H10A	−0.1394	0.9763	0.3679	0.051*
H10B	0.0740	0.9615	0.3610	0.051*
C11	0.1691 (4)	1.2299 (4)	0.3280 (2)	0.0630 (9)
H11A	0.1707	1.3369	0.3182	0.094*
H11B	0.1828	1.1774	0.2760	0.094*
H11C	0.2672	1.2033	0.3645	0.094*
C12	−0.1672 (4)	1.2500 (4)	0.31872 (17)	0.0452 (6)
H12A	−0.1627	1.3593	0.3219	0.054*
H12B	−0.1527	1.2219	0.2607	0.054*
O13	−0.3406 (2)	1.2007 (2)	0.34646 (11)	0.0489 (5)
H13	−0.3554	1.2261	0.3951	0.073*
C14	−0.0073 (5)	0.6707 (3)	0.42966 (17)	0.0507 (6)
H14A	−0.0080	0.7518	0.3900	0.076*
H14B	−0.1134	0.6093	0.4220	0.076*
H14C	0.0994	0.6101	0.4216	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0500 (4)	0.0629 (4)	0.0381 (3)	0.0022 (4)	−0.0002 (4)	0.0035 (2)
C2	0.0289 (10)	0.0484 (11)	0.0399 (9)	0.0021 (13)	−0.0002 (12)	0.0035 (8)
C3	0.0314 (11)	0.0483 (12)	0.0540 (13)	0.0039 (14)	0.0010 (14)	0.0021 (9)
C4	0.0406 (12)	0.0495 (13)	0.0673 (16)	0.0052 (15)	−0.0003 (17)	0.0198 (11)
C5	0.0458 (13)	0.0715 (17)	0.0529 (13)	0.0036 (18)	0.0057 (16)	0.0222 (12)
C6	0.0320 (10)	0.0401 (10)	0.0383 (10)	−0.0011 (13)	−0.0029 (12)	−0.0017 (8)
N7	0.0555 (12)	0.0430 (9)	0.0361 (8)	0.0010 (14)	−0.0045 (13)	0.0004 (7)
O8	0.0711 (14)	0.0379 (8)	0.0380 (8)	0.0026 (11)	−0.0086 (11)	−0.0009 (6)
C9	0.0412 (11)	0.0465 (11)	0.0340 (9)	−0.0041 (14)	−0.0004 (13)	0.0005 (8)
C10	0.0525 (15)	0.0389 (10)	0.0355 (9)	0.0021 (12)	−0.0024 (12)	−0.0035 (8)
C11	0.0416 (15)	0.079 (2)	0.069 (2)	−0.0069 (16)	0.0063 (15)	0.0075 (18)
C12	0.0408 (14)	0.0556 (15)	0.0391 (12)	0.0012 (13)	0.0003 (12)	0.0045 (11)
O13	0.0397 (9)	0.0606 (11)	0.0462 (10)	−0.0008 (9)	0.0025 (8)	−0.0063 (9)
C14	0.0455 (12)	0.0429 (12)	0.0637 (14)	0.0026 (15)	0.0004 (16)	0.0016 (10)

Geometric parameters (Å, º) top

S1—C5	1.706 (3)	C9—C11	1.522 (4)
S1—C2	1.757 (2)	C9—C10	1.524 (3)
C2—C3	1.361 (3)	C10—H10A	0.9700
C2—C6	1.451 (3)	C10—H10B	0.9700
C3—C4	1.431 (3)	C11—H11A	0.9600
C3—C14	1.447 (3)	C11—H11B	0.9600
C4—C5	1.335 (4)	C11—H11C	0.9600
C4—H4A	0.9300	C12—O13	1.422 (3)
C5—H5	0.9300	C12—H12A	0.9700
C6—N7	1.283 (3)	C12—H12B	0.9700
C6—C10	1.500 (3)	O13—H13	0.8200
N7—O8	1.400 (2)	C14—H14A	0.9600
O8—C9	1.470 (3)	C14—H14B	0.9600
C9—C12	1.511 (4)	C14—H14C	0.9600

C5—S1—C2	91.14 (12)	C6—C10—H10A	111.3
C3—C2—C6	130.3 (2)	C9—C10—H10A	111.3
C3—C2—S1	111.12 (17)	C6—C10—H10B	111.3
C6—C2—S1	118.57 (17)	C9—C10—H10B	111.3
C2—C3—C4	111.4 (2)	H10A—C10—H10B	109.2
C2—C3—C14	125.7 (2)	C9—C11—H11A	109.5
C4—C3—C14	123.0 (2)	C9—C11—H11B	109.5
C5—C4—C3	114.1 (2)	H11A—C11—H11B	109.5
C5—C4—H4A	122.9	C9—C11—H11C	109.5
C3—C4—H4A	122.9	H11A—C11—H11C	109.5
C4—C5—S1	112.24 (19)	H11B—C11—H11C	109.5
C4—C5—H5	123.9	O13—C12—C9	114.0 (2)
S1—C5—H5	123.9	O13—C12—H12A	108.7
N7—C6—C2	119.83 (19)	C9—C12—H12A	108.7
N7—C6—C10	112.94 (18)	O13—C12—H12B	108.7
C2—C6—C10	127.22 (19)	C9—C12—H12B	108.7
C6—N7—O8	110.42 (17)	H12A—C12—H12B	107.6
N7—O8—C9	109.65 (16)	C12—O13—H13	109.5
O8—C9—C12	106.4 (2)	C3—C14—H14A	109.5
O8—C9—C11	107.6 (2)	C3—C14—H14B	109.5
C12—C9—C11	110.33 (19)	H14A—C14—H14B	109.5
O8—C9—C10	103.84 (16)	C3—C14—H14C	109.5
C12—C9—C10	114.8 (2)	H14A—C14—H14C	109.5
C11—C9—C10	113.2 (3)	H14B—C14—H14C	109.5
C6—C10—C9	102.27 (17)

C5—S1—C2—C3	0.0 (3)	C2—C6—N7—O8	−177.1 (3)
C5—S1—C2—C6	179.1 (2)	C10—C6—N7—O8	1.6 (4)
C6—C2—C3—C4	−178.8 (3)	C6—N7—O8—C9	−7.3 (3)
S1—C2—C3—C4	0.2 (4)	N7—O8—C9—C12	131.1 (2)
C6—C2—C3—C14	0.8 (6)	N7—O8—C9—C11	−110.7 (3)
S1—C2—C3—C14	179.8 (3)	N7—O8—C9—C10	9.5 (3)
C2—C3—C4—C5	−0.4 (4)	N7—C6—C10—C9	4.4 (4)
C14—C3—C4—C5	−180.0 (3)	C2—C6—C10—C9	−177.1 (3)
C3—C4—C5—S1	0.4 (4)	O8—C9—C10—C6	−8.0 (3)
C2—S1—C5—C4	−0.2 (3)	C12—C9—C10—C6	−123.7 (2)
C3—C2—C6—N7	−177.8 (4)	C11—C9—C10—C6	108.3 (3)
S1—C2—C6—N7	3.3 (4)	O8—C9—C12—O13	−70.1 (3)
C3—C2—C6—C10	3.7 (5)	C11—C9—C12—O13	173.5 (3)
S1—C2—C6—C10	−175.2 (3)	C10—C9—C12—O13	44.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N7ⁱ	0.82	2.17	2.905 (3)	150

Symmetry code: (i) x−1/2, −y+5/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃NO₂S
M_r	211.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	7.3672 (9), 8.8534 (11), 16.0632 (19)
V (Å³)	1047.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.39 × 0.20 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.898, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	11038, 2619, 2096
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.149, 1.08
No. of reflections	2619
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.36
Absolute structure	Flack (1983), 1087 Friedel pairs
Absolute structure parameter	0.02 (14)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N7ⁱ	0.82	2.17	2.905 (3)	150

Symmetry code: (i) x−1/2, −y+5/2, −z+1.

Acknowledgements

This work was supported by the R&D Program of MKE/KEIT [10035240, Development of new herbicides for resistant weeds with mutated genes].

References

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