5-(2,4-Dichloro­phen­oxy)-1,3-dimethyl-1H-pyrazole-4-carbaldehyde

Shen, Y.-J.; Xu, M.; Fan, C.-G.

doi:10.1107/S1600536811045831

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3194

https://doi.org/10.1107/S1600536811045831

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5-(2,4-Dichlorophenoxy)-1,3-dimethyl-1H-pyrazole-4-carbaldehyde

Yong-Jun Shen,^a Mei Xu ^b and Chong-Guang Fan ^a ^*

^aCollege of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, People's Republic of China, and ^bDepartment of Chemistry and Environmental Science, Cangzhou Normal University, Cangzhou 061001, People's Republic of China
^*Correspondence e-mail: gaofz2005@yahoo.com.cn

(Received 28 October 2011; accepted 31 October 2011; online 5 November 2011)

In the title molecule, C₁₂H₁₀Cl₂N₂O₂, the benzene and pyrazole rings form a dihedral angle of 72.8 (3)°. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into chains along [01 $[\overline{1}]$ ].

Related literature

For the crystal structure of a related pyrazole derivative studied recently by our group, see: Shen et al. (2011 ).

Experimental

Crystal data

C₁₂H₁₀Cl₂N₂O₂
M_r = 285.12
Triclinic, $[P \overline 1]$
a = 8.018 (3) Å
b = 8.505 (3) Å
c = 10.365 (5) Å
α = 74.56 (2)°
β = 83.96 (3)°
γ = 67.30 (2)°
V = 628.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 113 K
0.24 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.887, T_max = 0.905
6391 measured reflections
2948 independent reflections
2766 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.146
S = 1.06
2948 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.95	2.45	3.284 (3)	147
C10—H10C⋯O2ⁱⁱ	0.98	2.46	3.391 (3)	158
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y, -z+2.

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811045831/cv5188sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045831/cv5188Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045831/cv5188Isup3.cml

checkCIF report

Comment top

As a continuation of our structural study of pyrazole derivatives (Shen et al., 2011), we present here the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related compound (Shen et al., 2011). The dihedral angle between the substituted benzene ring and pyrazole ring is 72.8 (3) °. The crystal packing exhibits weak intermolecular C—H···O interactions (Table 1), which link molecules into chains along [01-1].

Related literature top

For the crystal structure of a related pyrazole derivative studied recently by our group, see: Shen et al. (2011).

Experimental top

To a stirred solution of 1-methyl-3-methyl-5-chloro-1H-pyrazole- 4-carbaldehyde(30 mmol) and 2,4-dichlorophenol(48 mmol) in DMF(30 ml) was added potassium hydroxide(60 mmol) at room temperature. The resulting mixture was heated to 388 k for 6 h. Then the reaction solution was poured into cold water(100 ml) and extracted with ethyl acetate (3 * 60 ml). The organic layer was dried over anhydrous magnesium sulfate. After removal of the solvent, the residue was recrystallized from ethyl acetate/petroleum ether to give colourless crystals.

Structure description top

As a continuation of our structural study of pyrazole derivatives (Shen et al., 2011), we present here the title compound (I).

For the crystal structure of a related pyrazole derivative studied recently by our group, see: Shen et al. (2011).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.

5-(2,4-Dichlorophenoxy)-1,3-dimethyl-1H-pyrazole-4-carbaldehyde top

Crystal data top

C₁₂H₁₀Cl₂N₂O₂	Z = 2
M_r = 285.12	F(000) = 292
Triclinic, P1	D_x = 1.507 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.018 (3) Å	Cell parameters from 2204 reflections
b = 8.505 (3) Å	θ = 2.0–27.9°
c = 10.365 (5) Å	µ = 0.51 mm⁻¹
α = 74.56 (2)°	T = 113 K
β = 83.96 (3)°	Prism, colourless
γ = 67.30 (2)°	0.24 × 0.22 × 0.20 mm
V = 628.5 (5) Å³

Data collection top

Rigaku Saturn724 CCD diffractometer	2948 independent reflections
Radiation source: rotating anode	2766 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.059
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 2.0°
ω and φ scans	h = −10→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −11→11
T_min = 0.887, T_max = 0.905	l = −13→13
6391 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0863P)² + 0.4717P] where P = (F_o² + 2F_c²)/3
2948 reflections	(Δ/σ)_max = 0.002
165 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₂H₁₀Cl₂N₂O₂	γ = 67.30 (2)°
M_r = 285.12	V = 628.5 (5) Å³
Triclinic, P1	Z = 2
a = 8.018 (3) Å	Mo Kα radiation
b = 8.505 (3) Å	µ = 0.51 mm⁻¹
c = 10.365 (5) Å	T = 113 K
α = 74.56 (2)°	0.24 × 0.22 × 0.20 mm
β = 83.96 (3)°

Data collection top

Rigaku Saturn724 CCD diffractometer	2948 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	2766 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.905	R_int = 0.059
6391 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.06	Δρ_max = 0.40 e Å⁻³
2948 reflections	Δρ_min = −0.59 e Å⁻³
165 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	0.32121 (7)	0.81388 (7)	0.29679 (5)	0.03004 (17)
Cl2	0.90839 (7)	0.84252 (7)	0.48228 (5)	0.02853 (17)
O1	0.7986 (2)	0.68007 (19)	0.73949 (13)	0.0229 (3)
O2	1.1787 (2)	0.15447 (19)	0.88478 (15)	0.0268 (3)
N1	0.6770 (2)	0.6174 (2)	0.95613 (15)	0.0200 (3)
N2	0.7105 (2)	0.4841 (2)	1.07097 (15)	0.0203 (3)
C1	0.5338 (3)	0.6535 (3)	0.66259 (18)	0.0220 (4)
H1	0.5090	0.5963	0.7502	0.026*
C2	0.4222 (3)	0.6874 (3)	0.55656 (19)	0.0233 (4)
H2	0.3203	0.6540	0.5711	0.028*
C3	0.4611 (3)	0.7702 (3)	0.42976 (19)	0.0225 (4)
C4	0.6096 (3)	0.8200 (2)	0.40452 (19)	0.0220 (4)
H4	0.6347	0.8762	0.3167	0.026*
C5	0.7201 (3)	0.7854 (2)	0.51096 (18)	0.0201 (4)
C6	0.6823 (3)	0.7040 (2)	0.63958 (18)	0.0194 (4)
C7	0.7948 (3)	0.5673 (2)	0.85978 (17)	0.0186 (4)
C8	0.9135 (3)	0.3965 (2)	0.90937 (18)	0.0194 (4)
C9	0.8528 (3)	0.3516 (2)	1.04350 (18)	0.0188 (4)
C10	0.9292 (3)	0.1822 (3)	1.1457 (2)	0.0249 (4)
H10A	0.8626	0.1912	1.2300	0.037*
H10B	1.0569	0.1563	1.1602	0.037*
H10C	0.9185	0.0875	1.1143	0.037*
C11	0.5330 (3)	0.7878 (3)	0.9522 (2)	0.0245 (4)
H11A	0.5564	0.8774	0.8794	0.037*
H11B	0.5286	0.8182	1.0376	0.037*
H11C	0.4170	0.7822	0.9369	0.037*
C12	1.0679 (3)	0.3008 (3)	0.8386 (2)	0.0226 (4)
H12	1.0848	0.3566	0.7485	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0258 (3)	0.0415 (3)	0.0194 (3)	−0.0095 (2)	−0.00688 (19)	−0.0039 (2)
Cl2	0.0265 (3)	0.0386 (3)	0.0221 (3)	−0.0183 (2)	0.00085 (19)	−0.0012 (2)
O1	0.0273 (7)	0.0298 (7)	0.0143 (6)	−0.0164 (6)	−0.0027 (5)	0.0001 (5)
O2	0.0248 (7)	0.0256 (7)	0.0293 (7)	−0.0064 (6)	0.0004 (6)	−0.0104 (6)
N1	0.0201 (8)	0.0219 (8)	0.0159 (7)	−0.0060 (6)	−0.0012 (6)	−0.0034 (6)
N2	0.0240 (8)	0.0236 (8)	0.0142 (7)	−0.0107 (7)	−0.0025 (6)	−0.0022 (6)
C1	0.0255 (10)	0.0260 (9)	0.0141 (8)	−0.0108 (8)	0.0007 (7)	−0.0030 (7)
C2	0.0218 (9)	0.0284 (10)	0.0206 (9)	−0.0108 (8)	−0.0001 (7)	−0.0051 (7)
C3	0.0226 (9)	0.0262 (9)	0.0149 (8)	−0.0045 (8)	−0.0027 (7)	−0.0049 (7)
C4	0.0207 (9)	0.0216 (9)	0.0175 (8)	−0.0027 (7)	0.0014 (7)	−0.0032 (7)
C5	0.0199 (9)	0.0215 (9)	0.0169 (8)	−0.0069 (7)	0.0029 (7)	−0.0039 (7)
C6	0.0207 (9)	0.0202 (8)	0.0151 (8)	−0.0048 (7)	−0.0024 (7)	−0.0041 (6)
C7	0.0218 (9)	0.0231 (9)	0.0131 (7)	−0.0110 (7)	−0.0026 (6)	−0.0030 (6)
C8	0.0204 (9)	0.0232 (9)	0.0165 (8)	−0.0100 (7)	−0.0016 (7)	−0.0049 (7)
C9	0.0207 (9)	0.0210 (8)	0.0165 (8)	−0.0094 (7)	−0.0026 (6)	−0.0041 (6)
C10	0.0272 (10)	0.0230 (9)	0.0216 (9)	−0.0087 (8)	−0.0062 (7)	0.0005 (7)
C11	0.0232 (10)	0.0215 (9)	0.0254 (9)	−0.0038 (8)	−0.0032 (7)	−0.0061 (7)
C12	0.0235 (9)	0.0251 (9)	0.0222 (9)	−0.0101 (8)	0.0001 (7)	−0.0092 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.740 (2)	C4—C5	1.386 (3)
Cl2—C5	1.731 (2)	C4—H4	0.9500
O1—C7	1.361 (2)	C5—C6	1.391 (3)
O1—C6	1.388 (2)	C7—C8	1.385 (3)
O2—C12	1.219 (3)	C8—C9	1.426 (3)
N1—C7	1.338 (2)	C8—C12	1.443 (3)
N1—N2	1.374 (2)	C9—C10	1.489 (3)
N1—C11	1.456 (3)	C10—H10A	0.9800
N2—C9	1.328 (3)	C10—H10B	0.9800
C1—C2	1.390 (3)	C10—H10C	0.9800
C1—C6	1.392 (3)	C11—H11A	0.9800
C1—H1	0.9500	C11—H11B	0.9800
C2—C3	1.382 (3)	C11—H11C	0.9800
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.389 (3)

C7—O1—C6	118.55 (15)	N1—C7—C8	108.81 (16)
C7—N1—N2	110.80 (16)	O1—C7—C8	128.76 (17)
C7—N1—C11	128.50 (17)	C7—C8—C9	103.53 (16)
N2—N1—C11	120.66 (16)	C7—C8—C12	125.35 (17)
C9—N2—N1	105.68 (15)	C9—C8—C12	130.95 (18)
C2—C1—C6	119.56 (17)	N2—C9—C8	111.17 (17)
C2—C1—H1	120.2	N2—C9—C10	121.08 (17)
C6—C1—H1	120.2	C8—C9—C10	127.74 (18)
C3—C2—C1	119.33 (19)	C9—C10—H10A	109.5
C3—C2—H2	120.3	C9—C10—H10B	109.5
C1—C2—H2	120.3	H10A—C10—H10B	109.5
C2—C3—C4	121.98 (18)	C9—C10—H10C	109.5
C2—C3—Cl1	119.51 (16)	H10A—C10—H10C	109.5
C4—C3—Cl1	118.50 (15)	H10B—C10—H10C	109.5
C5—C4—C3	118.21 (17)	N1—C11—H11A	109.5
C5—C4—H4	120.9	N1—C11—H11B	109.5
C3—C4—H4	120.9	H11A—C11—H11B	109.5
C4—C5—C6	120.74 (18)	N1—C11—H11C	109.5
C4—C5—Cl2	119.32 (14)	H11A—C11—H11C	109.5
C6—C5—Cl2	119.94 (15)	H11B—C11—H11C	109.5
O1—C6—C5	116.08 (17)	O2—C12—C8	125.49 (19)
O1—C6—C1	123.75 (16)	O2—C12—H12	117.3
C5—C6—C1	120.17 (17)	C8—C12—H12	117.3
N1—C7—O1	122.15 (17)

C7—N1—N2—C9	0.7 (2)	C11—N1—C7—O1	2.7 (3)
C11—N1—N2—C9	−177.30 (16)	N2—N1—C7—C8	−0.6 (2)
C6—C1—C2—C3	0.2 (3)	C11—N1—C7—C8	177.13 (18)
C1—C2—C3—C4	0.4 (3)	C6—O1—C7—N1	−85.0 (2)
C1—C2—C3—Cl1	−179.69 (15)	C6—O1—C7—C8	101.7 (2)
C2—C3—C4—C5	−0.3 (3)	N1—C7—C8—C9	0.3 (2)
Cl1—C3—C4—C5	179.75 (14)	O1—C7—C8—C9	174.29 (17)
C3—C4—C5—C6	−0.4 (3)	N1—C7—C8—C12	−175.30 (17)
C3—C4—C5—Cl2	178.92 (14)	O1—C7—C8—C12	−1.3 (3)
C7—O1—C6—C5	−165.15 (17)	N1—N2—C9—C8	−0.4 (2)
C7—O1—C6—C1	15.6 (3)	N1—N2—C9—C10	179.92 (16)
C4—C5—C6—O1	−178.22 (16)	C7—C8—C9—N2	0.1 (2)
Cl2—C5—C6—O1	2.5 (2)	C12—C8—C9—N2	175.37 (19)
C4—C5—C6—C1	1.0 (3)	C7—C8—C9—C10	179.69 (18)
Cl2—C5—C6—C1	−178.27 (15)	C12—C8—C9—C10	−5.0 (3)
C2—C1—C6—O1	178.23 (17)	C7—C8—C12—O2	175.37 (19)
C2—C1—C6—C5	−0.9 (3)	C9—C8—C12—O2	1.0 (3)
N2—N1—C7—O1	−175.06 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.95	2.45	3.284 (3)	147
C10—H10C···O2ⁱⁱ	0.98	2.46	3.391 (3)	158

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀Cl₂N₂O₂
M_r	285.12
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	8.018 (3), 8.505 (3), 10.365 (5)
α, β, γ (°)	74.56 (2), 83.96 (3), 67.30 (2)
V (Å³)	628.5 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku Saturn724 CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.887, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	6391, 2948, 2766
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.146, 1.06
No. of reflections	2948
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.59

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.95	2.45	3.284 (3)	147
C10—H10C···O2ⁱⁱ	0.98	2.46	3.391 (3)	158

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+2.

Acknowledgements

This work was supported by the Scientific Research Foundation for Talent Introduction of Nantong University (grant No. 03080226).

References

Rigaku (2008). CrystalClear. Rigaku Corporation, Toyko, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, Y.-J., Xu, M. & Fan, C.-G. (2011). Acta Cryst. E67, o2936. Web of Science CSD CrossRef IUCr Journals Google Scholar