Vinclozolin: 3-(3,5-di­chloro­phen­yl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione

Cho, S.; Kim, J.; Lee, S.; Kim, T.H.

doi:10.1107/S1600536814012781

organic compounds

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Volume 70| Part 7| July 2014| Page o754

https://doi.org/10.1107/S1600536814012781

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Vinclozolin: 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione

Seonghwa Cho,^a Jineun Kim,^a ^* Sangjin Lee ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
^*Correspondence e-mail: jekim@gnu.ac.kr, thkim@gnu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 30 May 2014; accepted 2 June 2014; online 7 June 2014)

In the title compound, C₁₂H₉Cl₂NO₃, which is the fungicide vinclozolin, the dihedral angle between the oxazolidine ring mean plane [r.m.s. deviation = 0.029 Å] and the benzene ring is 77.55 (8)°. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming chains along [010]. The chains are linked by short Cl⋯Cl contacts [3.4439 (3) and 3.5798 (3) Å], resulting in a three-dimensional architecture.

CCDC reference: 1006251

Related literature

For information on the toxicity and fungicidal properties of the title compound, see: van Ravenzwaay et al. (2013 ); Pothuluri et al. (2000 ). For a related crystal structure, see: Merino et al. (2010 ).

Experimental

Crystal data

C₁₂H₉Cl₂NO₃
M_r = 286.10
Monoclinic, P 2₁ /n
a = 15.0727 (12) Å
b = 5.2947 (5) Å
c = 15.5390 (12) Å
β = 100.916 (5)°
V = 1217.66 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 173 K
0.26 × 0.21 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.874, T_max = 0.974
7915 measured reflections
2103 independent reflections
1720 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.115
S = 1.06
2103 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.95	2.59	3.454 (3)	151
Symmetry code: (i) x, y-1, z.

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

Supporting information

CCDC reference: 1006251

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536814012781/sj5407sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012781/sj5407Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012781/sj5407Isup3.cml

checkCIF report

Comment top

The title compound vinclozolin, C₁₂H₉Cl₂NO₃, is a systemic dicarboximide fungicide used widely for the control of diseases in grapes, fruits, vegetables, ornamental plants, and turfgrass (Pothuluri et al., 2000; van Ravenzwaay et al., 2013), and its crystal structure is reported herein. In this compound (Fig. 1), the dihedral angle between the oxazolidine ring and the phenyl ring is 77.55 (8)°. All bond lengths and bond angles are normal and comparable to those observed in the crystal structure of a similar compound (Merino et al., 2010).

In the crystal structure (Fig. 2), an intermolecular C—H···O hydrogen bond is observed (Table 1). In addition, short Cl···Cl contacts [Cl1···Cl1ⁱⁱ, 3.4439 (3) Å and Cl2···Cl2ⁱⁱⁱ, 3.5798 (3) Å] are present. [symmetry codes: (ii), -x, y, -z + 1, and (iii), -x - 1/2, y - 1/2, -z + 1/2].

Related literature top

For information on the toxicity and fungicidal properties of the title compound, see: van Ravenzwaay et al. (2013); Pothuluri et al. (2000). For a related crystal structure, see: Merino et al. (2010).

Experimental top

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CH₂Cl₂ gave single crystals suitable for X-ray analysis.

Structure description top

For information on the toxicity and fungicidal properties of the title compound, see: van Ravenzwaay et al. (2013); Pothuluri et al. (2000). For a related crystal structure, see: Merino et al. (2010).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Crystal packing of the title compound with C—H···O hydrogen bonds and weak intermolecular Cl···Cl interactions shown as dashed lines.

3-(3,5-Dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione top

Crystal data top

C₁₂H₉Cl₂NO₃	F(000) = 584
M_r = 286.10	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4964 reflections
a = 15.0727 (12) Å	θ = 2.7–28.1°
b = 5.2947 (5) Å	µ = 0.53 mm⁻¹
c = 15.5390 (12) Å	T = 173 K
β = 100.916 (5)°	Plate, colourless
V = 1217.66 (18) Å³	0.26 × 0.21 × 0.05 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2103 independent reflections
Radiation source: fine-focus sealed tube	1720 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→17
T_min = 0.874, T_max = 0.974	k = −6→5
7915 measured reflections	l = −18→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0581P)² + 0.9965P] where P = (F_o² + 2F_c²)/3
2103 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₂H₉Cl₂NO₃	V = 1217.66 (18) Å³
M_r = 286.10	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.0727 (12) Å	µ = 0.53 mm⁻¹
b = 5.2947 (5) Å	T = 173 K
c = 15.5390 (12) Å	0.26 × 0.21 × 0.05 mm
β = 100.916 (5)°

Data collection top

Bruker APEXII CCD diffractometer	2103 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1720 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.974	R_int = 0.030
7915 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	Δρ_max = 0.87 e Å⁻³
2103 reflections	Δρ_min = −0.30 e Å⁻³
163 parameters

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
Cl1	0.01684 (5)	0.22311 (15)	0.42408 (5)	0.0385 (2)
Cl2	−0.16975 (5)	0.99394 (15)	0.25170 (5)	0.0376 (2)
O1	0.19649 (12)	0.9720 (4)	0.22124 (12)	0.0290 (5)
O2	0.06758 (13)	0.2867 (4)	0.06863 (13)	0.0359 (5)
O3	0.23229 (11)	0.7650 (3)	0.10675 (11)	0.0240 (4)
N1	0.11223 (13)	0.6312 (4)	0.15799 (13)	0.0229 (5)
C1	0.06127 (17)	0.4411 (5)	0.28171 (17)	0.0255 (6)
H1	0.1090	0.3216	0.2872	0.031*
C2	0.00147 (18)	0.4404 (5)	0.33904 (17)	0.0259 (6)
C3	−0.06989 (17)	0.6085 (6)	0.33076 (17)	0.0274 (6)
H3	−0.1110	0.6039	0.3702	0.033*
C4	−0.07979 (17)	0.7832 (5)	0.26364 (17)	0.0271 (6)
C5	−0.02013 (17)	0.7960 (5)	0.20586 (17)	0.0262 (6)
H5	−0.0268	0.9199	0.1609	0.031*
C6	0.04936 (16)	0.6214 (5)	0.21620 (16)	0.0233 (6)
C7	0.18216 (17)	0.8082 (5)	0.16778 (16)	0.0224 (6)
C8	0.11644 (17)	0.4631 (5)	0.09092 (17)	0.0259 (6)
C9	0.19567 (18)	0.5543 (5)	0.04975 (17)	0.0258 (6)
C10	0.1611 (2)	0.6600 (7)	−0.04096 (18)	0.0392 (8)
H10A	0.1145	0.7872	−0.0380	0.059*
H10B	0.1352	0.5231	−0.0803	0.059*
H10C	0.2111	0.7381	−0.0633	0.059*
C11	0.26703 (18)	0.3557 (6)	0.05662 (18)	0.0297 (7)
H11	0.2954	0.3018	0.1135	0.036*
C12	0.2928 (3)	0.2518 (8)	−0.0106 (2)	0.0583 (10)
H12A	0.2657	0.3016	−0.0683	0.070*
H12B	0.3386	0.1262	−0.0019	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0470 (5)	0.0333 (5)	0.0372 (4)	0.0032 (3)	0.0134 (3)	0.0124 (3)
Cl2	0.0288 (4)	0.0354 (5)	0.0501 (5)	0.0108 (3)	0.0113 (3)	0.0021 (3)
O1	0.0311 (10)	0.0223 (11)	0.0338 (10)	−0.0024 (8)	0.0068 (8)	−0.0051 (9)
O2	0.0336 (11)	0.0318 (13)	0.0446 (11)	−0.0144 (10)	0.0132 (9)	−0.0112 (10)
O3	0.0245 (9)	0.0209 (11)	0.0281 (9)	−0.0056 (8)	0.0090 (8)	−0.0028 (8)
N1	0.0200 (11)	0.0235 (13)	0.0260 (11)	−0.0028 (9)	0.0064 (9)	−0.0023 (9)
C1	0.0207 (13)	0.0237 (16)	0.0320 (14)	0.0007 (11)	0.0048 (11)	−0.0012 (12)
C2	0.0298 (14)	0.0213 (16)	0.0268 (13)	−0.0023 (12)	0.0056 (11)	0.0014 (11)
C3	0.0248 (14)	0.0273 (17)	0.0323 (14)	−0.0039 (12)	0.0109 (12)	−0.0039 (12)
C4	0.0219 (13)	0.0246 (16)	0.0349 (15)	0.0020 (11)	0.0055 (11)	−0.0032 (12)
C5	0.0256 (14)	0.0244 (16)	0.0284 (13)	−0.0020 (12)	0.0047 (11)	0.0026 (12)
C6	0.0209 (13)	0.0227 (15)	0.0271 (13)	−0.0012 (11)	0.0061 (11)	−0.0034 (11)
C7	0.0216 (13)	0.0190 (15)	0.0259 (13)	−0.0002 (11)	0.0023 (11)	0.0015 (12)
C8	0.0220 (13)	0.0269 (17)	0.0286 (14)	−0.0010 (12)	0.0044 (11)	−0.0016 (12)
C9	0.0286 (14)	0.0241 (16)	0.0265 (13)	−0.0092 (12)	0.0097 (11)	−0.0052 (11)
C10	0.0396 (17)	0.044 (2)	0.0324 (15)	−0.0095 (15)	0.0035 (13)	0.0032 (14)
C11	0.0310 (15)	0.0277 (17)	0.0342 (14)	−0.0048 (13)	0.0158 (12)	−0.0030 (12)
C12	0.060 (2)	0.058 (3)	0.062 (2)	0.006 (2)	0.0230 (19)	−0.006 (2)

Geometric parameters (Å, º) top

Cl1—C2	1.734 (3)	C3—H3	0.9500
Cl2—C4	1.739 (3)	C4—C5	1.388 (4)
O1—C7	1.192 (3)	C5—C6	1.383 (4)
O2—C8	1.199 (3)	C5—H5	0.9500
O3—C7	1.340 (3)	C8—C9	1.536 (4)
O3—C9	1.466 (3)	C9—C11	1.494 (4)
N1—C8	1.381 (3)	C9—C10	1.515 (4)
N1—C7	1.397 (3)	C10—H10A	0.9800
N1—C6	1.430 (3)	C10—H10B	0.9800
C1—C2	1.382 (4)	C10—H10C	0.9800
C1—C6	1.382 (4)	C11—C12	1.303 (4)
C1—H1	0.9500	C11—H11	0.9500
C2—C3	1.383 (4)	C12—H12A	0.9500
C3—C4	1.381 (4)	C12—H12B	0.9500

C7—O3—C9	111.06 (18)	O1—C7—N1	126.7 (2)
C8—N1—C7	111.9 (2)	O3—C7—N1	108.9 (2)
C8—N1—C6	125.8 (2)	O2—C8—N1	127.3 (2)
C7—N1—C6	122.2 (2)	O2—C8—C9	127.4 (2)
C2—C1—C6	117.9 (2)	N1—C8—C9	105.2 (2)
C2—C1—H1	121.1	O3—C9—C11	108.0 (2)
C6—C1—H1	121.1	O3—C9—C10	107.8 (2)
C1—C2—C3	121.9 (2)	C11—C9—C10	116.3 (2)
C1—C2—Cl1	118.9 (2)	O3—C9—C8	102.78 (19)
C3—C2—Cl1	119.2 (2)	C11—C9—C8	110.8 (2)
C4—C3—C2	118.2 (2)	C10—C9—C8	110.2 (2)
C4—C3—H3	120.9	C9—C10—H10A	109.5
C2—C3—H3	120.9	C9—C10—H10B	109.5
C3—C4—C5	122.1 (3)	H10A—C10—H10B	109.5
C3—C4—Cl2	118.8 (2)	C9—C10—H10C	109.5
C5—C4—Cl2	119.2 (2)	H10A—C10—H10C	109.5
C6—C5—C4	117.5 (3)	H10B—C10—H10C	109.5
C6—C5—H5	121.3	C12—C11—C9	124.0 (3)
C4—C5—H5	121.3	C12—C11—H11	118.0
C1—C6—C5	122.5 (2)	C9—C11—H11	118.0
C1—C6—N1	118.8 (2)	C11—C12—H12A	120.0
C5—C6—N1	118.7 (2)	C11—C12—H12B	120.0
O1—C7—O3	124.4 (2)	H12A—C12—H12B	120.0

C6—C1—C2—C3	1.8 (4)	C6—N1—C7—O1	−2.6 (4)
C6—C1—C2—Cl1	−177.9 (2)	C8—N1—C7—O3	1.4 (3)
C1—C2—C3—C4	−1.0 (4)	C6—N1—C7—O3	177.2 (2)
Cl1—C2—C3—C4	178.7 (2)	C7—N1—C8—O2	177.7 (3)
C2—C3—C4—C5	−0.8 (4)	C6—N1—C8—O2	2.1 (4)
C2—C3—C4—Cl2	179.4 (2)	C7—N1—C8—C9	−3.6 (3)
C3—C4—C5—C6	1.7 (4)	C6—N1—C8—C9	−179.2 (2)
Cl2—C4—C5—C6	−178.5 (2)	C7—O3—C9—C11	−120.7 (2)
C2—C1—C6—C5	−0.8 (4)	C7—O3—C9—C10	112.9 (2)
C2—C1—C6—N1	177.9 (2)	C7—O3—C9—C8	−3.6 (3)
C4—C5—C6—C1	−0.8 (4)	O2—C8—C9—O3	−177.1 (3)
C4—C5—C6—N1	−179.6 (2)	N1—C8—C9—O3	4.2 (3)
C8—N1—C6—C1	74.6 (3)	O2—C8—C9—C11	−61.9 (4)
C7—N1—C6—C1	−100.6 (3)	N1—C8—C9—C11	119.3 (2)
C8—N1—C6—C5	−106.7 (3)	O2—C8—C9—C10	68.3 (4)
C7—N1—C6—C5	78.2 (3)	N1—C8—C9—C10	−110.5 (3)
C9—O3—C7—O1	−178.6 (2)	O3—C9—C11—C12	−129.1 (3)
C9—O3—C7—N1	1.6 (3)	C10—C9—C11—C12	−7.9 (4)
C8—N1—C7—O1	−178.4 (3)	C8—C9—C11—C12	119.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.59	3.454 (3)	151

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.59	3.454 (3)	151

Symmetry code: (i) x, y−1, z.

Acknowledgements

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. 2012M2B2A4029305).

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Merino, O., Santoyo, B. M., Montiel, L. E., Jimenez-Vazquez, H. A., Zepeda, L. G. & Tamariz, J. (2010). Tetrahedron Lett. 51, 3738–3742. Web of Science CSD CrossRef CAS Google Scholar
Pothuluri, J. V., Freeman, J. P., Heinze, T. M., Beger, R. D. & Cerniglia, C. E. (2000). J. Agric. Food Chem. 48, 6138–6148. Web of Science CrossRef PubMed CAS Google Scholar
Ravenzwaay, B. van, Kolle, S. N., Ramirez, T. & Kamp, H. G. (2013). Toxicol. Lett. 223, 271–279. Web of Science CrossRef PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Vinclozolin: 3-(3,5-di­chloro­phen­yl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Vinclozolin: 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione