Diclomezine: 6-(3,5-dichloro-4-methyl­phen­yl)pyridazin-3(2H)-one

Kim, H.; Kim, T.H.; Kim, J.; Park, K.-M.

doi:10.1107/S1600536810047409

organic compounds

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Volume 66| Part 12| December 2010| Page o3257

https://doi.org/10.1107/S1600536810047409

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Diclomezine: 6-(3,5-dichloro-4-methylphenyl)pyridazin-3(2H)-one

Hyunjee Kim,^a Tae Ho Kim,^a ^* Jineun Kim ^a and Ki-Min Park ^a ^*

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

(Received 12 November 2010; accepted 16 November 2010; online 20 November 2010)

In the title compound, C₁₁H₈Cl₂N₂O, the benzene and pyridazine rings are tilted by 8.6 (1)° relative to each other. In the crystal, pairs of intermolecular N—H⋯O hydrogen bonds form centrosymmetric dimers. π–π contacts with centroid–centroid distances of 3.698 (2) and 3.751 (1) Å and halogen–halogen interactions [3.379 (1) Å] also stabilize the structure.

Related literature

For information on the toxicity and fungicidal properties of the title compound, see: Sankyo (1998 ). For a related structure, see: Prout et al. (1994 ).

Experimental

Crystal data

C₁₁H₈Cl₂N₂O
M_r = 255.09
Monoclinic, P 2₁ /c
a = 9.745 (4) Å
b = 13.850 (5) Å
c = 8.481 (3) Å
β = 111.557 (6)°
V = 1064.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 173 K
0.19 × 0.09 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.897, T_max = 0.955
10410 measured reflections
2657 independent reflections
2038 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.091
S = 1.07
2657 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	1.90	2.771 (2)	172
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); 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: SHELXTL and DIAMOND (Brandenburg, 1998 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810047409/sj5054sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047409/sj5054Isup2.hkl

checkCIF report

Comment top

Declomezine (systematic name: 6-(3,5-dichloro-4-methylphenyl)- 3(2H)-pyridazinone), is a well known fungicide (Sankyo 1998). In this paper, the structure of the title pyridazinone derivative is reported.

In the molecular structure of the title compound (Scheme 1, Fig. 1), the dihedral angle between the phenyl ring and the pyridazine ring is 8.6 (1) °, compared to the value of 18.0 ° in the similar compound 6-phenyl-3(2H)-pyridazinone (Prout et al., 1994). Bond lengths and angles observed here are also similar to those in 6-phenyl-3(2H)-pyridazinone.

In the crystal structure, as shown in Fig. 2, there are pair-wise intermolecular N—H···O hydrogen bonds (Table 1; symmetry code as in Fig. 2). Weak intermolecular π—π and halogen···halogen interactions also exist [Cg1···Cg2^iv 3.75 Å, Cg2···Cg2^v 3.70 Å and Cl1···Cl2ⁱⁱⁱ 3.379 (1) Å; Cg1 and Cg2 are the centroids of the phenyl and pyridazine rings, respectively.]. These intermolecular interactions contribute to the stabilization of the packing.

Related literature top

For information on the toxicity and fungicidal properties of the title compound, see: Sankyo (1998). For a related structure, see: Prout et al. (1994).

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: Sankyo (1998). For a related structure, see: Prout et al. (1994).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998).

Figures top

Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Fig. 2. Crystal packing of the title compound with intermolecular N—H···O hydrogen bonds, π—π and halogen—halogen interactions shown as dashed lines. H atoms not involved in intermolecular interactions have been omitted for clarity. Cg1 and Cg2 are the centroids of the phenyl and pyridazine rings, respectively. (Symmetry codes: i) 1 - x, 1 - y, -z; ii) x, 0.5 - y, 1/2 + z; iii) -x, -1/2 + y, 1.5 - z; iv) 1 - x, 1 - y, 1 - z; v) -x, 1 - y, 1 - z; vi) -x, 1/2 + y, 1.5 - z; vii) x, 1.5 - y, 1/2 + z; viii) 1 - x, 1/2 + y, 0.5 - z; ix) 1 - x, -1/2 + y, 0.5 - z) .

6-(3,5-dichloro-4-methylphenyl)pyridazin-3(2H)-one top

Crystal data top

C₁₁H₈Cl₂N₂O	F(000) = 520
M_r = 255.09	D_x = 1.591 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3791 reflections
a = 9.745 (4) Å	θ = 2.9–28.2°
b = 13.850 (5) Å	µ = 0.59 mm⁻¹
c = 8.481 (3) Å	T = 173 K
β = 111.557 (6)°	Block, colourless
V = 1064.7 (7) Å³	0.19 × 0.09 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2657 independent reflections
Radiation source: fine-focus sealed tube	2038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
φ and ω scans	θ_max = 28.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.897, T_max = 0.955	k = −18→17
10410 measured reflections	l = −11→11

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0323P)² + 0.5573P] where P = (F_o² + 2F_c²)/3
2657 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₈Cl₂N₂O	V = 1064.7 (7) Å³
M_r = 255.09	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.745 (4) Å	µ = 0.59 mm⁻¹
b = 13.850 (5) Å	T = 173 K
c = 8.481 (3) Å	0.19 × 0.09 × 0.08 mm
β = 111.557 (6)°

Data collection top

Bruker APEXII CCD diffractometer	2657 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2038 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.955	R_int = 0.042
10410 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.07	Δρ_max = 0.30 e Å⁻³
2657 reflections	Δρ_min = −0.26 e Å⁻³
146 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	0.11909 (5)	0.35378 (4)	0.82090 (6)	0.03367 (14)
Cl2	0.15267 (6)	0.72198 (3)	0.62638 (7)	0.03884 (15)
O1	0.52503 (15)	0.37232 (9)	0.02888 (17)	0.0290 (3)
N1	0.42007 (16)	0.47759 (11)	0.15589 (18)	0.0240 (3)
H1	0.4313	0.5229	0.0888	0.029*
N2	0.35554 (16)	0.50487 (11)	0.26436 (18)	0.0239 (3)
C1	0.47026 (19)	0.38769 (13)	0.1379 (2)	0.0234 (4)
C2	0.45389 (19)	0.31751 (13)	0.2541 (2)	0.0258 (4)
H2	0.4893	0.2536	0.2543	0.031*
C3	0.38829 (19)	0.34224 (13)	0.3631 (2)	0.0246 (4)
H3	0.3760	0.2954	0.4387	0.029*
C4	0.33735 (18)	0.43848 (12)	0.3652 (2)	0.0214 (3)
C5	0.26737 (18)	0.47099 (12)	0.4848 (2)	0.0218 (3)
C6	0.22820 (18)	0.40586 (13)	0.5865 (2)	0.0239 (4)
H6	0.2436	0.3386	0.5781	0.029*
C7	0.16682 (18)	0.43931 (13)	0.6996 (2)	0.0243 (4)
C8	0.13991 (18)	0.53629 (13)	0.7192 (2)	0.0241 (4)
C9	0.17893 (19)	0.59892 (13)	0.6130 (2)	0.0254 (4)
C10	0.23982 (18)	0.56857 (13)	0.4983 (2)	0.0238 (4)
H10	0.2630	0.6143	0.4284	0.029*
C11	0.0760 (2)	0.57125 (15)	0.8451 (2)	0.0332 (4)
H11C	0.1557	0.5816	0.9551	0.050*
H11A	0.0072	0.5229	0.8573	0.050*
H11B	0.0235	0.6321	0.8053	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0373 (3)	0.0338 (3)	0.0379 (3)	−0.00164 (19)	0.0233 (2)	0.0084 (2)
Cl2	0.0529 (3)	0.0248 (2)	0.0479 (3)	0.0092 (2)	0.0292 (3)	0.0019 (2)
O1	0.0396 (7)	0.0248 (7)	0.0304 (7)	0.0001 (5)	0.0220 (6)	−0.0012 (5)
N1	0.0319 (8)	0.0224 (7)	0.0227 (8)	0.0001 (6)	0.0157 (6)	0.0023 (6)
N2	0.0283 (7)	0.0235 (7)	0.0240 (8)	0.0003 (6)	0.0147 (6)	0.0006 (6)
C1	0.0247 (8)	0.0223 (8)	0.0242 (9)	−0.0025 (6)	0.0101 (7)	−0.0022 (7)
C2	0.0304 (9)	0.0192 (8)	0.0292 (10)	−0.0006 (7)	0.0127 (8)	0.0000 (7)
C3	0.0286 (9)	0.0219 (9)	0.0250 (9)	−0.0022 (7)	0.0120 (7)	0.0017 (7)
C4	0.0222 (8)	0.0216 (8)	0.0210 (8)	−0.0020 (6)	0.0087 (7)	−0.0003 (7)
C5	0.0202 (8)	0.0243 (9)	0.0203 (8)	−0.0014 (6)	0.0068 (6)	0.0003 (7)
C6	0.0239 (8)	0.0230 (9)	0.0265 (9)	−0.0003 (7)	0.0112 (7)	0.0009 (7)
C7	0.0226 (8)	0.0285 (9)	0.0231 (9)	−0.0019 (7)	0.0099 (7)	0.0037 (7)
C8	0.0197 (8)	0.0303 (9)	0.0220 (9)	0.0008 (7)	0.0072 (7)	−0.0012 (7)
C9	0.0261 (9)	0.0233 (9)	0.0266 (9)	0.0038 (7)	0.0096 (7)	0.0002 (7)
C10	0.0241 (8)	0.0244 (9)	0.0246 (9)	0.0010 (7)	0.0109 (7)	0.0037 (7)
C11	0.0374 (10)	0.0373 (11)	0.0296 (10)	0.0043 (8)	0.0178 (8)	−0.0001 (9)

Geometric parameters (Å, º) top

Cl1—C7	1.7404 (18)	C5—C10	1.391 (3)
Cl2—C9	1.733 (2)	C5—C6	1.395 (2)
O1—C1	1.244 (2)	C6—C7	1.384 (2)
N1—N2	1.345 (2)	C6—H6	0.9500
N1—C1	1.367 (2)	C7—C8	1.390 (3)
N1—H1	0.8800	C8—C9	1.400 (3)
N2—C4	1.311 (2)	C8—C11	1.500 (2)
C1—C2	1.435 (3)	C9—C10	1.378 (2)
C2—C3	1.347 (3)	C10—H10	0.9500
C2—H2	0.9500	C11—H11C	0.9800
C3—C4	1.425 (2)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C4—C5	1.485 (2)

N2—N1—C1	127.50 (15)	C7—C6—H6	120.1
N2—N1—H1	116.2	C5—C6—H6	120.1
C1—N1—H1	116.2	C6—C7—C8	123.71 (16)
C4—N2—N1	117.27 (15)	C6—C7—Cl1	117.35 (14)
O1—C1—N1	120.54 (16)	C8—C7—Cl1	118.93 (14)
O1—C1—C2	125.54 (17)	C7—C8—C9	114.45 (16)
N1—C1—C2	113.92 (16)	C7—C8—C11	122.88 (17)
C3—C2—C1	120.00 (17)	C9—C8—C11	122.67 (17)
C3—C2—H2	120.0	C10—C9—C8	123.67 (17)
C1—C2—H2	120.0	C10—C9—Cl2	117.27 (14)
C2—C3—C4	120.11 (16)	C8—C9—Cl2	119.06 (14)
C2—C3—H3	119.9	C9—C10—C5	120.05 (16)
C4—C3—H3	119.9	C9—C10—H10	120.0
N2—C4—C3	121.12 (16)	C5—C10—H10	120.0
N2—C4—C5	116.03 (15)	C8—C11—H11C	109.5
C3—C4—C5	122.79 (15)	C8—C11—H11A	109.5
C10—C5—C6	118.21 (16)	H11C—C11—H11A	109.5
C10—C5—C4	120.12 (15)	C8—C11—H11B	109.5
C6—C5—C4	121.67 (16)	H11C—C11—H11B	109.5
C7—C6—C5	119.90 (17)	H11A—C11—H11B	109.5

C1—N1—N2—C4	−0.2 (3)	C4—C5—C6—C7	178.27 (15)
N2—N1—C1—O1	178.37 (16)	C5—C6—C7—C8	0.3 (3)
N2—N1—C1—C2	−2.0 (3)	C5—C6—C7—Cl1	179.41 (13)
O1—C1—C2—C3	−177.86 (17)	C6—C7—C8—C9	0.6 (3)
N1—C1—C2—C3	2.6 (2)	Cl1—C7—C8—C9	−178.51 (13)
C1—C2—C3—C4	−1.1 (3)	C6—C7—C8—C11	−178.75 (17)
N1—N2—C4—C3	1.9 (2)	Cl1—C7—C8—C11	2.2 (2)
N1—N2—C4—C5	179.33 (14)	C7—C8—C9—C10	−0.3 (3)
C2—C3—C4—N2	−1.3 (3)	C11—C8—C9—C10	178.98 (17)
C2—C3—C4—C5	−178.51 (16)	C7—C8—C9—Cl2	−179.37 (13)
N2—C4—C5—C10	−6.9 (2)	C11—C8—C9—Cl2	−0.1 (2)
C3—C4—C5—C10	170.44 (16)	C8—C9—C10—C5	−0.8 (3)
N2—C4—C5—C6	173.38 (16)	Cl2—C9—C10—C5	178.26 (13)
C3—C4—C5—C6	−9.3 (3)	C6—C5—C10—C9	1.7 (3)
C10—C5—C6—C7	−1.5 (3)	C4—C5—C10—C9	−178.06 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	1.90	2.771 (2)	172

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₈Cl₂N₂O
M_r	255.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.745 (4), 13.850 (5), 8.481 (3)
β (°)	111.557 (6)
V (Å³)	1064.7 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.19 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.897, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	10410, 2657, 2038
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.07
No. of reflections	2657
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.26

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), 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
N1—H1···O1ⁱ	0.88	1.90	2.771 (2)	172.2

Symmetry code: (i) −x+1, −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. 2010–0009089).

References

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