Imaza­lil: 1-[2-(2,4-dichloro­phen­yl)-2-(prop-2-en­yloxy)eth­yl]-1H-imidazole

Cheon, S.; Shin, Y.W.; Park, K.-M.; Kim, J.; Kim, T.H.

doi:10.1107/S1600536811018241

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1459

doi:10.1107/S1600536811018241

Open

access

Imazalil: 1-[2-(2,4-dichlorophenyl)-2-(prop-2-enyloxy)ethyl]-1H-imidazole

Sanghun Cheon,^a Yong Woon Shin,^b Ki-Min Park,^a ^* Jineun Kim ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea, and ^bTest & Analytical Laboratory, Korea Food & Drug Administration, 123-7 Yongdang-dong, Busan 608-829, Republic of Korea
^*Correspondence e-mail: kmpark@gnu.ac.kr, thkim@gnu.ac.kr

(Received 11 May 2011; accepted 13 May 2011; online 20 May 2011)

In the title compound, C₁₄H₁₄Cl₂N₂O, the imidazole ring is almost parallel to the benzene ring, the dihedral angle between them being 7.3 (2)°. In the crystal, there is an intermolecular C—Cl⋯π interaction (Cl⋯centroid = 3.36 Å and C—Cl⋯centroid = 89.2°). In addition, a Cl⋯Cl contact of 3.411 (1) Å and an intermolecular C—H⋯N hydrogen bond are observed. These interactions contribute to the stabilization of the crystal packing.

Related literature

For information on the toxicity of the title compound, see: Sisman & Türkez (2010 ). For related structures, see: Bisaha et al. (2005 ).

Experimental

Crystal data

C₁₄H₁₄Cl₂N₂O
M_r = 297.17
Monoclinic, P 2₁ /c
a = 7.9374 (6) Å
b = 13.4144 (12) Å
c = 13.479 (1) Å
β = 103.386 (5)°
V = 1396.19 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 173 K
0.20 × 0.09 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.914, T_max = 0.964
12201 measured reflections
3040 independent reflections
2282 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.119
S = 1.08
3040 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N2ⁱ	0.95	2.66	3.562 (3)	159
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018241/wn2433sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018241/wn2433Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018241/wn2433Isup3.cml

checkCIF report

Comment top

Imazalil (systematic name: 1-[2-(2,4-dichlorophenyl)-2- (2-propen-1-yloxy)ethyl]-1H-imidazole) is a fungicide widely used in agriculture, particularly in the growth of citrus fruits. It is also known as "enilconazole" (Sisman & Türkez, 2010). However,until now its crystal structure has not been reported.

In the title compound (Fig. 1), the imidazole ring is almost parallel to the benzene ring, the dihedral angle between them being 7.3 (2)°. All bond lengths and bond angles are normal and comparable to those observed in similar crystal structures (Bisaha et al. 2005).

In the crystal structure, as shown in Fig. 2, weak intermolecular C—H···N hydrogen bonds (Table 1) and a Cl···Cl contact of 3.411 (1) Å are observed. There are also C—Cl···π interactions involving chlorine Cl2 and benzene ring (C1–C6), with a Cl···centroid (Cgⁱⁱⁱ) distance of 3.36 Å and a C3—Cl2···Cgⁱⁱⁱ angle of 89.2° [symmetry code: (iii) -x + 1, -y + 2, -z + 1] (Fig. 2). These intermolecular interactions may contribute to the stabilization of the crystal packing.

Related literature top

For information on the toxicity of the title compound, see: Sisman & Türkez (2010). For related structures, see: Bisaha et al. (2005).

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.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); 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 intermolecular C—H···N hydrogen bonds, C—Cl···π interactions and Cl···Cl contacts shown as dashed lines. H atoms not involved in intermolecular interactions have been omitted for clarity. [Symmetry codes: (i) -x + 2, -y + 2, -z + 1; (ii) x + 1, -y + 1.5, z + 1/2; (iii) -x + 1, -y + 2, -z + 1; (iv) -x, y + 1/2, -z + 1/2; (v) x - 1, y, z.]

1-[2-(2,4-dichlorophenyl)-2-(prop-2-enyloxy)ethyl]-1H-imidazole top

Crystal data top

C₁₄H₁₄Cl₂N₂O	F(000) = 616
M_r = 297.17	D_x = 1.414 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2420 reflections
a = 7.9374 (6) Å	θ = 2.2–28.4°
b = 13.4144 (12) Å	µ = 0.46 mm⁻¹
c = 13.479 (1) Å	T = 173 K
β = 103.386 (5)°	Plate, colourless
V = 1396.19 (19) Å³	0.20 × 0.09 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3040 independent reflections
Radiation source: fine-focus sealed tube	2282 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.914, T_max = 0.964	k = −17→14
12201 measured reflections	l = −17→17

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0525P)² + 0.2498P] where P = (F_o² + 2F_c²)/3
3040 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₁₄Cl₂N₂O	V = 1396.19 (19) Å³
M_r = 297.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.9374 (6) Å	µ = 0.46 mm⁻¹
b = 13.4144 (12) Å	T = 173 K
c = 13.479 (1) Å	0.20 × 0.09 × 0.08 mm
β = 103.386 (5)°

Data collection top

Bruker APEXII CCD diffractometer	3040 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2282 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.964	R_int = 0.069
12201 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.08	Δρ_max = 0.37 e Å⁻³
3040 reflections	Δρ_min = −0.27 e Å⁻³
172 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	0.41595 (8)	0.69956 (5)	0.57733 (5)	0.0410 (2)
Cl2	0.77994 (7)	0.98990 (4)	0.47431 (5)	0.03569 (19)
O1	0.0431 (2)	0.71310 (11)	0.25901 (12)	0.0294 (4)
N1	−0.1440 (2)	0.69576 (14)	0.40437 (15)	0.0289 (4)
N2	−0.3936 (3)	0.60867 (17)	0.34432 (19)	0.0465 (6)
C1	0.4327 (3)	0.78309 (16)	0.48568 (17)	0.0282 (5)
C2	0.5822 (3)	0.84344 (16)	0.51200 (18)	0.0285 (5)
H2	0.6668	0.8363	0.5742	0.034*
C3	0.5937 (3)	0.91175 (16)	0.44116 (18)	0.0279 (5)
C4	0.4636 (3)	0.91953 (16)	0.34627 (18)	0.0297 (5)
H4	0.4775	0.9689	0.2982	0.036*
C5	0.3172 (3)	0.85669 (16)	0.32241 (18)	0.0277 (5)
H5	0.2343	0.8632	0.2594	0.033*
C6	0.2977 (3)	0.78727 (15)	0.39102 (17)	0.0255 (5)
C7	0.1325 (3)	0.72205 (16)	0.36550 (17)	0.0253 (5)
H7	0.1605	0.6540	0.3949	0.030*
C8	−0.0025 (3)	0.76633 (17)	0.40885 (19)	0.0311 (5)
H8A	0.0469	0.7854	0.4806	0.037*
H8B	−0.0474	0.8274	0.3704	0.037*
C9	−0.3009 (3)	0.68361 (19)	0.3287 (2)	0.0377 (6)
H9	−0.3345	0.7269	0.2718	0.045*
C10	−0.2883 (4)	0.5710 (2)	0.4355 (2)	0.0505 (7)
H10	−0.3197	0.5139	0.4688	0.061*
C11	−0.1353 (4)	0.6230 (2)	0.4733 (2)	0.0440 (6)
H11	−0.0471	0.6102	0.5328	0.053*
C12	0.1149 (3)	0.63442 (17)	0.21546 (18)	0.0312 (5)
H12A	0.2426	0.6410	0.2344	0.037*
H12B	0.0777	0.6401	0.1403	0.037*
C13	0.0682 (3)	0.53464 (18)	0.24568 (19)	0.0350 (6)
H13	−0.0508	0.5167	0.2311	0.042*
C14	0.1862 (4)	0.4672 (2)	0.2933 (2)	0.0451 (7)
H14B	0.3060	0.4833	0.3087	0.054*
H14A	0.1493	0.4037	0.3112	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0519 (4)	0.0404 (4)	0.0294 (3)	−0.0131 (3)	0.0066 (3)	0.0096 (3)
Cl2	0.0339 (3)	0.0338 (3)	0.0442 (4)	−0.0075 (2)	0.0189 (3)	−0.0031 (3)
O1	0.0340 (8)	0.0319 (8)	0.0244 (8)	0.0010 (7)	0.0111 (7)	−0.0023 (7)
N1	0.0320 (10)	0.0296 (10)	0.0285 (10)	0.0003 (8)	0.0139 (9)	−0.0005 (8)
N2	0.0390 (12)	0.0524 (14)	0.0515 (15)	−0.0104 (11)	0.0170 (11)	−0.0142 (12)
C1	0.0376 (12)	0.0253 (11)	0.0253 (12)	0.0009 (10)	0.0147 (10)	0.0020 (9)
C2	0.0310 (12)	0.0305 (12)	0.0256 (12)	0.0001 (10)	0.0098 (10)	−0.0012 (10)
C3	0.0286 (11)	0.0249 (11)	0.0347 (13)	−0.0021 (9)	0.0168 (10)	−0.0065 (10)
C4	0.0362 (12)	0.0251 (11)	0.0337 (13)	0.0022 (9)	0.0203 (11)	0.0035 (10)
C5	0.0305 (12)	0.0288 (12)	0.0256 (12)	0.0033 (9)	0.0104 (10)	0.0002 (10)
C6	0.0315 (12)	0.0233 (11)	0.0253 (11)	0.0030 (9)	0.0142 (10)	−0.0022 (9)
C7	0.0313 (11)	0.0236 (11)	0.0225 (11)	−0.0007 (9)	0.0090 (10)	−0.0019 (9)
C8	0.0399 (13)	0.0259 (12)	0.0324 (13)	−0.0017 (10)	0.0183 (11)	−0.0032 (10)
C9	0.0362 (13)	0.0440 (14)	0.0357 (14)	0.0031 (11)	0.0136 (12)	−0.0004 (12)
C10	0.0503 (16)	0.0398 (15)	0.066 (2)	−0.0085 (13)	0.0237 (16)	0.0085 (14)
C11	0.0441 (15)	0.0475 (15)	0.0410 (15)	−0.0023 (12)	0.0109 (13)	0.0163 (13)
C12	0.0367 (13)	0.0334 (12)	0.0277 (12)	−0.0062 (10)	0.0159 (11)	−0.0058 (10)
C13	0.0403 (13)	0.0357 (13)	0.0319 (13)	−0.0111 (11)	0.0143 (11)	−0.0077 (11)
C14	0.0631 (18)	0.0383 (14)	0.0387 (15)	−0.0040 (13)	0.0219 (14)	−0.0038 (12)

Geometric parameters (Å, º) top

Cl1—C1	1.696 (2)	C5—H5	0.9500
Cl2—C3	1.783 (2)	C6—C7	1.547 (3)
O1—C12	1.392 (3)	C7—C8	1.461 (3)
O1—C7	1.452 (3)	C7—H7	1.0000
N1—C11	1.338 (3)	C8—H8A	0.9900
N1—C9	1.425 (3)	C8—H8B	0.9900
N1—C8	1.459 (3)	C9—H9	0.9500
N2—C9	1.291 (3)	C10—C11	1.391 (4)
N2—C10	1.410 (4)	C10—H10	0.9500
C1—C2	1.412 (3)	C11—H11	0.9500
C1—C6	1.465 (3)	C12—C13	1.471 (3)
C2—C3	1.342 (3)	C12—H12A	0.9900
C2—H2	0.9500	C12—H12B	0.9900
C3—C4	1.450 (3)	C13—C14	1.353 (4)
C4—C5	1.411 (3)	C13—H13	0.9500
C4—H4	0.9500	C14—H14B	0.9500
C5—C6	1.346 (3)	C14—H14A	0.9500

C12—O1—C7	108.98 (17)	C6—C7—H7	109.2
C11—N1—C9	108.0 (2)	N1—C8—C7	110.39 (18)
C11—N1—C8	121.9 (2)	N1—C8—H8A	109.6
C9—N1—C8	129.8 (2)	C7—C8—H8A	109.6
C9—N2—C10	100.1 (2)	N1—C8—H8B	109.6
C2—C1—C6	126.8 (2)	C7—C8—H8B	109.6
C2—C1—Cl1	113.51 (18)	H8A—C8—H8B	108.1
C6—C1—Cl1	119.65 (16)	N2—C9—N1	114.1 (2)
C3—C2—C1	113.9 (2)	N2—C9—H9	122.9
C3—C2—H2	123.1	N1—C9—H9	122.9
C1—C2—H2	123.1	C11—C10—N2	115.5 (2)
C2—C3—C4	121.7 (2)	C11—C10—H10	122.2
C2—C3—Cl2	114.37 (18)	N2—C10—H10	122.2
C4—C3—Cl2	123.96 (17)	N1—C11—C10	102.2 (2)
C5—C4—C3	122.6 (2)	N1—C11—H11	128.9
C5—C4—H4	118.7	C10—C11—H11	128.9
C3—C4—H4	118.7	O1—C12—C13	114.76 (18)
C6—C5—C4	118.4 (2)	O1—C12—H12A	108.6
C6—C5—H5	120.8	C13—C12—H12A	108.6
C4—C5—H5	120.8	O1—C12—H12B	108.6
C5—C6—C1	116.6 (2)	C13—C12—H12B	108.6
C5—C6—C7	117.7 (2)	H12A—C12—H12B	107.6
C1—C6—C7	125.69 (19)	C14—C13—C12	123.3 (2)
O1—C7—C8	101.13 (18)	C14—C13—H13	118.4
O1—C7—C6	117.51 (17)	C12—C13—H13	118.4
C8—C7—C6	110.10 (17)	C13—C14—H14B	120.0
O1—C7—H7	109.2	C13—C14—H14A	120.0
C8—C7—H7	109.2	H14B—C14—H14A	120.0

C6—C1—C2—C3	1.4 (3)	C1—C6—C7—O1	−160.79 (18)
Cl1—C1—C2—C3	−178.10 (16)	C5—C6—C7—C8	−93.1 (2)
C1—C2—C3—C4	−1.0 (3)	C1—C6—C7—C8	84.2 (3)
C1—C2—C3—Cl2	179.00 (15)	C11—N1—C8—C7	80.7 (3)
C2—C3—C4—C5	0.3 (3)	C9—N1—C8—C7	−93.6 (3)
Cl2—C3—C4—C5	−179.78 (16)	O1—C7—C8—N1	67.1 (2)
C3—C4—C5—C6	0.4 (3)	C6—C7—C8—N1	−167.88 (18)
C4—C5—C6—C1	−0.1 (3)	C10—N2—C9—N1	−0.1 (3)
C4—C5—C6—C7	177.48 (18)	C11—N1—C9—N2	0.2 (3)
C2—C1—C6—C5	−0.8 (3)	C8—N1—C9—N2	175.2 (2)
Cl1—C1—C6—C5	178.64 (16)	C9—N2—C10—C11	0.0 (3)
C2—C1—C6—C7	−178.2 (2)	C9—N1—C11—C10	−0.2 (3)
Cl1—C1—C6—C7	1.3 (3)	C8—N1—C11—C10	−175.6 (2)
C12—O1—C7—C8	−152.67 (17)	N2—C10—C11—N1	0.2 (3)
C12—O1—C7—C6	87.5 (2)	C7—O1—C12—C13	73.9 (2)
C5—C6—C7—O1	21.8 (3)	O1—C12—C13—C14	−120.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2ⁱ	0.95	2.66	3.562 (3)	159

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄Cl₂N₂O
M_r	297.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	7.9374 (6), 13.4144 (12), 13.479 (1)
β (°)	103.386 (5)
V (Å³)	1396.19 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.20 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.914, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	12201, 3040, 2282
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.119, 1.08
No. of reflections	3040
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.27

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2ⁱ	0.95	2.66	3.562 (3)	159

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Korea government (MEST) (No. 2010–0018586).

References

Bisaha, S. N., Malley, M. F., Pudzianowski, A., Monshizadegan, H., Wang, P., Madsen, C. S., Gougoutas, J. Z. & Stein, P. (2005). Bioorg. Med. Chem. Lett. 15, 2749–2751. Web of Science CrossRef PubMed CAS Google Scholar
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sisman, T. & Türkez, H. (2010). Toxicol. Ind. Health, 26, 641–648. Web of Science CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1459

doi:10.1107/S1600536811018241

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Imaza­lil: 1-[2-(2,4-di­chloro­phen­yl)-2-(prop-2-en­yl­oxy)eth­yl]-1H-imidazole

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Imazalil: 1-[2-(2,4-dichlorophenyl)-2-(prop-2-enyloxy)ethyl]-1H-imidazole