(E)-(2,4-Dichloro-phen-yl)[2-hydr-oxy-6-(methoxy-imino)cyclo-hex-1-en-yl]methanone.

The title compound, C(14)H(13)Cl(2)NO(3), was obtained as the product of an attempted synthesis of herbicidally active compounds containing oxime ether and cyclo-hexenone groups. In the crystal structure, the mol-ecule adopts an endocyclic enol tautomeric form and the cyclo-hexene ring adopts a distorted envelope form. The oxime ether group has an E configuration, with the meth-oxy group anti to the ortho-chloro substitutent. Intra-molecular O-H⋯O and inter-molecular C-H⋯O hydrogen bonds are found in the crystal structure.

Related literature

For the structure of 5-chloro-2-methyl­thio-3H-indole-3-one 3-oxime O-methyl ether, see: Beddoes et al. (1992 ▶). For theoretical studies on the tautomerism of benzoyl­cyclo­hexane-1,3-dione and its derivatives, see: Huang et al. (2002 ▶). For the potential herbicidal property of the title compound and related compounds, see: Knudsen (1988 ▶). For the chemistry of 2-acyl­cyclo­alkane-1,3-diones, see: Rubinov et al. (1999 ▶).

Experimental

Crystal data

C14H13Cl2NO3

M = 314.15

Triclinic,

a = 8.4096 (17) Å

b = 8.9944 (18) Å

c = 11.740 (2) Å

α = 68.38 (3)°

β = 74.50 (3)°

γ = 62.32 (3)°

V = 726.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.45 mm−1

T = 298 (2) K

0.68 × 0.34 × 0.23 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.748, T max = 0.903

6630 measured reflections

3247 independent reflections

2162 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.144

S = 1.08

3247 reflections

233 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.40 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001883/si2144sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001883/si2144Isup2.hkl

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

C14H13Cl2NO3	Z = 2
Mr = 314.15	F(000) = 324
Triclinic, P1	Dx = 1.437 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4096 (17) Å	Cell parameters from 3247 reflections
b = 8.9944 (18) Å	θ = 3.2–27.5°
c = 11.740 (2) Å	µ = 0.45 mm−1
α = 68.38 (3)°	T = 298 K
β = 74.50 (3)°	Block, green
γ = 62.32 (3)°	0.68 × 0.34 × 0.23 mm
V = 726.0 (3) Å3

Bruker APEXII CCD diffractometer	3247 independent reflections
Radiation source: fine-focus sealed tube	2162 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 8.40 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −11→10
Tmin = 0.748, Tmax = 0.903	l = −15→15
6630 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0701P)2 + 0.0941P] where P = (Fo2 + 2Fc2)/3
3247 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.20742 (14)	0.71882 (10)	0.43507 (6)	0.0984 (3)
Cl2	0.28869 (13)	1.27753 (12)	0.43224 (9)	0.1098 (3)
O1	0.4465 (2)	0.7560 (2)	0.09971 (15)	0.0676 (4)
O2	0.3124 (2)	0.5952 (2)	0.05046 (15)	0.0658 (4)
H10	0.389 (4)	0.641 (4)	0.050 (3)	0.099 (10)*
O3	−0.25125 (19)	1.1694 (2)	0.24393 (17)	0.0686 (5)
N1	−0.0704 (2)	1.0779 (2)	0.19908 (16)	0.0551 (4)
C1	0.2934 (3)	1.1452 (3)	0.3538 (3)	0.0689 (6)
C2	0.3365 (3)	1.1861 (3)	0.2287 (3)	0.0677 (7)
H3	0.361 (4)	1.281 (4)	0.184 (3)	0.087 (9)*
C3	0.2551 (4)	1.0015 (3)	0.4191 (3)	0.0702 (7)
H6	0.231 (4)	0.968 (4)	0.507 (3)	0.089 (9)*
C4	0.3381 (3)	1.0831 (3)	0.1661 (2)	0.0583 (5)
H1	0.370 (3)	1.110 (3)	0.076 (2)	0.064 (7)*
C5	0.2563 (3)	0.9004 (3)	0.3541 (2)	0.0604 (5)
C6	−0.0470 (3)	0.9302 (3)	0.19137 (19)	0.0511 (5)
C7	0.2943 (2)	0.9405 (3)	0.22713 (19)	0.0510 (5)
C8	0.1559 (3)	0.6921 (3)	0.09904 (19)	0.0539 (5)
C9	0.2954 (3)	0.8347 (3)	0.15450 (19)	0.0518 (5)
C10	0.0020 (3)	0.6524 (4)	0.1021 (3)	0.0688 (7)
H8	−0.056 (4)	0.718 (4)	0.021 (3)	0.113 (11)*
H11	0.041 (4)	0.528 (4)	0.105 (3)	0.108 (10)*
C11	0.1366 (3)	0.8193 (3)	0.14735 (18)	0.0485 (5)
C12	−0.1359 (4)	0.6906 (4)	0.2117 (3)	0.0826 (8)
H7	−0.244 (4)	0.675 (4)	0.210 (3)	0.100 (9)*
H14	−0.080 (5)	0.606 (5)	0.301 (4)	0.139 (13)*
C13	−0.1984 (3)	0.8748 (4)	0.2142 (3)	0.0746 (7)
H2	−0.259 (4)	0.888 (4)	0.289 (3)	0.086 (9)*
H15	−0.275 (5)	0.953 (5)	0.131 (4)	0.143 (14)*
C14	−0.2681 (4)	1.3347 (3)	0.2447 (3)	0.0700 (7)
H4	−0.178 (4)	1.311 (4)	0.295 (3)	0.101 (10)*
H5	−0.386 (4)	1.389 (4)	0.281 (3)	0.085 (8)*
H9	−0.252 (4)	1.405 (4)	0.157 (3)	0.096 (9)*

	U11	U22	U33	U12	U13	U23
Cl1	0.1770 (9)	0.0882 (5)	0.0587 (4)	−0.0887 (6)	−0.0179 (4)	−0.0028 (3)
Cl2	0.1302 (7)	0.1061 (6)	0.1376 (8)	−0.0655 (6)	−0.0103 (6)	−0.0629 (6)
O1	0.0478 (9)	0.0763 (11)	0.0799 (11)	−0.0253 (8)	0.0041 (8)	−0.0315 (9)
O2	0.0621 (10)	0.0652 (10)	0.0717 (10)	−0.0211 (9)	−0.0022 (8)	−0.0318 (9)
O3	0.0475 (8)	0.0587 (9)	0.1003 (12)	−0.0155 (7)	−0.0036 (8)	−0.0352 (9)
N1	0.0437 (9)	0.0536 (10)	0.0654 (11)	−0.0154 (8)	−0.0069 (8)	−0.0198 (9)
C1	0.0621 (14)	0.0655 (14)	0.0918 (19)	−0.0265 (12)	−0.0169 (13)	−0.0299 (14)
C2	0.0538 (13)	0.0547 (13)	0.098 (2)	−0.0278 (11)	−0.0148 (12)	−0.0138 (13)
C3	0.0854 (18)	0.0705 (16)	0.0681 (16)	−0.0395 (14)	−0.0169 (13)	−0.0183 (13)
C4	0.0441 (11)	0.0593 (13)	0.0698 (14)	−0.0252 (10)	−0.0098 (10)	−0.0090 (11)
C5	0.0694 (14)	0.0562 (12)	0.0603 (13)	−0.0317 (11)	−0.0142 (10)	−0.0090 (10)
C6	0.0455 (11)	0.0521 (11)	0.0573 (11)	−0.0198 (9)	−0.0103 (9)	−0.0146 (9)
C7	0.0388 (10)	0.0511 (11)	0.0605 (12)	−0.0163 (9)	−0.0125 (9)	−0.0113 (10)
C8	0.0528 (12)	0.0514 (12)	0.0548 (11)	−0.0165 (10)	−0.0091 (9)	−0.0167 (10)
C9	0.0475 (11)	0.0495 (11)	0.0516 (11)	−0.0183 (9)	−0.0069 (9)	−0.0085 (9)
C10	0.0619 (14)	0.0684 (15)	0.0903 (18)	−0.0237 (12)	−0.0170 (13)	−0.0361 (15)
C11	0.0457 (11)	0.0484 (11)	0.0490 (10)	−0.0169 (9)	−0.0096 (8)	−0.0117 (9)
C12	0.0660 (16)	0.0835 (19)	0.121 (3)	−0.0422 (15)	0.0002 (16)	−0.0455 (19)
C13	0.0544 (14)	0.0774 (17)	0.108 (2)	−0.0333 (13)	0.0044 (15)	−0.0450 (17)
C14	0.0738 (17)	0.0558 (14)	0.0770 (17)	−0.0174 (13)	−0.0090 (15)	−0.0272 (14)

Cl1—C5	1.735 (2)	C6—C11	1.473 (3)
Cl2—C1	1.735 (3)	C6—C13	1.500 (3)
O1—C9	1.262 (2)	C7—C9	1.490 (3)
O2—C8	1.310 (3)	C8—C11	1.383 (3)
O2—H10	0.91 (3)	C8—C10	1.483 (3)
O3—N1	1.413 (2)	C9—C11	1.432 (3)
O3—C14	1.429 (3)	C10—C12	1.509 (4)
N1—C6	1.284 (3)	C10—H8	1.03 (3)
C1—C2	1.366 (4)	C10—H11	1.00 (3)
C1—C3	1.373 (4)	C12—C13	1.497 (4)
C2—C4	1.373 (3)	C12—H7	0.99 (3)
C2—H3	0.90 (3)	C12—H14	1.12 (4)
C3—C5	1.381 (3)	C13—H2	0.91 (3)
C3—H6	0.96 (3)	C13—H15	1.13 (4)
C4—C7	1.384 (3)	C14—H4	0.99 (3)
C4—H1	0.99 (2)	C14—H5	0.94 (3)
C5—C7	1.382 (3)	C14—H9	1.00 (3)
C8—O2—H10	104.4 (19)	C11—C9—C7	122.91 (18)
N1—O3—C14	107.48 (18)	C8—C10—C12	110.6 (2)
C6—N1—O3	110.89 (17)	C8—C10—H8	112.0 (19)
C2—C1—C3	121.8 (2)	C12—C10—H8	111.5 (18)
C2—C1—Cl2	119.0 (2)	C8—C10—H11	112.8 (19)
C3—C1—Cl2	119.2 (2)	C12—C10—H11	108.9 (18)
C1—C2—C4	119.2 (2)	H8—C10—H11	101 (2)
C1—C2—H3	122.8 (18)	C8—C11—C9	118.71 (18)
C4—C2—H3	118.0 (18)	C8—C11—C6	118.12 (18)
C1—C3—C5	118.0 (2)	C9—C11—C6	123.15 (18)
C1—C3—H6	122.7 (17)	C13—C12—C10	111.8 (3)
C5—C3—H6	119.3 (17)	C13—C12—H7	107.1 (18)
C2—C4—C7	121.2 (2)	C10—C12—H7	111.0 (17)
C2—C4—H1	120.3 (14)	C13—C12—H14	105 (2)
C7—C4—H1	118.5 (14)	C10—C12—H14	112 (2)
C3—C5—C7	121.9 (2)	H7—C12—H14	109 (3)
C3—C5—Cl1	118.64 (19)	C12—C13—C6	113.5 (2)
C7—C5—Cl1	119.48 (17)	C12—C13—H2	110.8 (19)
N1—C6—C11	116.84 (18)	C6—C13—H2	106.2 (18)
N1—C6—C13	123.33 (19)	C12—C13—H15	102.1 (19)
C11—C6—C13	119.61 (19)	C6—C13—H15	106 (2)
C5—C7—C4	117.9 (2)	H2—C13—H15	118 (3)
C5—C7—C9	123.08 (19)	O3—C14—H4	107.5 (19)
C4—C7—C9	119.0 (2)	O3—C14—H5	105.9 (18)
O2—C8—C11	122.27 (19)	H4—C14—H5	111 (2)
O2—C8—C10	115.41 (19)	O3—C14—H9	108.2 (16)
C11—C8—C10	122.29 (19)	H4—C14—H9	114 (3)
O1—C9—C11	121.04 (19)	H5—C14—H9	110 (2)
O1—C9—C7	116.05 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H10···O1	0.91 (3)	1.64 (3)	2.485 (2)	152 (3)
C4—H1···O1i	0.99 (2)	2.51 (2)	3.347 (3)	143 (2)
C2—H3···O2ii	0.91 (4)	2.57 (3)	3.438 (3)	160 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H10⋯O1	0.91 (3)	1.64 (3)	2.485 (2)	152 (3)
C4—H1⋯O1i	0.99 (2)	2.51 (2)	3.347 (3)	143 (2)
C2—H3⋯O2ii	0.91 (4)	2.57 (3)	3.438 (3)	160 (3)

Symmetry codes: (i) ; (ii) .