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

Zhang, H.-J.; Fan, C.-G.; Shi, L.

doi:10.1107/S1600536812026530

organic compounds

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Volume 68| Part 7| July 2012| Page o2129

https://doi.org/10.1107/S1600536812026530

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

Hai-Jun Zhang,^a Chong-Guang Fan ^a and Lei Shi ^a ^*

^aCollege of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, People's Republic of China
^*Correspondence e-mail: fz8566@yahoo.com.cn

(Received 6 June 2012; accepted 12 June 2012; online 16 June 2012)

In the title molecule, C₁₂H₁₂ClN₃O₂, the benzene and pyrazole rings are inclined to each other at a dihedral angle of 83.3 (3)°. In the crystal, molecules are linked into [010] chains via O—H⋯N hydrogen bonds with the unsubstituted pyrazole N atom acting as the acceptor.

Related literature

For a related structure, see: Dai et al. (2011 ).

Experimental

Crystal data

C₁₂H₁₂ClN₃O₂
M_r = 265.70
Monoclinic, P 2₁ /c
a = 11.108 (2) Å
b = 14.998 (3) Å
c = 8.0839 (16) Å
β = 104.94 (3)°
V = 1301.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 113 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.918, T_max = 0.944
10731 measured reflections
2288 independent reflections
1638 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.159
S = 0.99
2288 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N2ⁱ	0.82	1.97	2.787 (3)	171
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536812026530/cv5311sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026530/cv5311Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812026530/cv5311Isup3.cml

checkCIF report

Comment top

In a continuation of our search for new pyrazole oxime derivatives (Dai et al., 2011), we present here the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those observed in the related compound (Dai et al., 2011). The plane of substituted phenyl ring makes a dihedral angle of 83.3 (3)° with the pyrazole ring. In the crystal, intermolecular O—H···N hydrogen bonds (Table1) link molecules into chains in [010].

Related literature top

For a related structure, see: Dai et al. (2011).

Experimental top

To a stirred solution of hydroxylamine hydrochloride (6 mmol) and potassium hydroxide (8 mmol) in methanol (30 ml) was added 5-(2-chlorophenoxy)-1,3-dimethyl-1H-pyrazole-4-carbaldehyde (4 mmol). The resulting mixture was heated to reflux for 6 h. The reaction mixture was cooled and poured into cold water (80 ml). The resulting colourless solid was collected and then recrystallized from ethyl acetate to give colourless crystals.

Structure description top

In a continuation of our search for new pyrazole oxime derivatives (Dai et al., 2011), we present here the title compound, (I).

For a related structure, see: Dai 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-Chlorophenoxy)-1,3-dimethyl-1H-pyrazole-4-carbaldehyde oxime top

Crystal data top

C₁₂H₁₂ClN₃O₂	F(000) = 552
M_r = 265.70	D_x = 1.356 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10109 reflections
a = 11.108 (2) Å	θ = 3.1–27.7°
b = 14.998 (3) Å	µ = 0.29 mm⁻¹
c = 8.0839 (16) Å	T = 113 K
β = 104.94 (3)°	Prism, colourless
V = 1301.2 (4) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2288 independent reflections
Radiation source: fine-focus sealed tube	1638 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ω and φ scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −13→13
T_min = 0.918, T_max = 0.944	k = −17→17
10731 measured reflections	l = −9→9

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0775P)² + 0.5684P] where P = (F_o² + 2F_c²)/3
2288 reflections	(Δ/σ)_max = 0.096
166 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₂H₁₂ClN₃O₂	V = 1301.2 (4) Å³
M_r = 265.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.108 (2) Å	µ = 0.29 mm⁻¹
b = 14.998 (3) Å	T = 113 K
c = 8.0839 (16) Å	0.30 × 0.25 × 0.20 mm
β = 104.94 (3)°

Data collection top

Rigaku SCXmini diffractometer	2288 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	1638 reflections with I > 2σ(I)
T_min = 0.918, T_max = 0.944	R_int = 0.064
10731 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 0.99	Δρ_max = 0.21 e Å⁻³
2288 reflections	Δρ_min = −0.25 e Å⁻³
166 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	0.95727 (9)	0.11946 (8)	−0.10002 (12)	0.0797 (4)
O1	0.78065 (18)	0.08065 (15)	0.0915 (3)	0.0555 (6)
N2	0.5175 (2)	0.13782 (17)	0.2347 (3)	0.0504 (7)
N3	0.5840 (2)	−0.14771 (16)	0.2182 (4)	0.0526 (7)
N1	0.6218 (2)	0.15655 (17)	0.1805 (3)	0.0502 (7)
C7	0.6784 (3)	0.0805 (2)	0.1570 (4)	0.0459 (8)
C10	0.6468 (3)	−0.0833 (2)	0.1825 (4)	0.0489 (8)
H10	0.7180	−0.0960	0.1466	0.059*
O2	0.6382 (2)	−0.22945 (15)	0.1961 (4)	0.0742 (8)
H2	0.5990	−0.2700	0.2262	0.111*
C6	0.8951 (3)	0.10481 (19)	0.2006 (4)	0.0437 (7)
C1	0.9878 (3)	0.1260 (2)	0.1212 (4)	0.0488 (8)
C8	0.6126 (2)	0.0091 (2)	0.1949 (4)	0.0418 (7)
C9	0.5111 (3)	0.0494 (2)	0.2418 (4)	0.0421 (7)
C5	0.9187 (3)	0.1079 (2)	0.3747 (4)	0.0585 (9)
H5	0.8565	0.0936	0.4281	0.070*
C2	1.1039 (3)	0.1516 (2)	0.2186 (5)	0.0618 (10)
H2A	1.1660	0.1663	0.1651	0.074*
C4	1.0363 (3)	0.1327 (3)	0.4714 (5)	0.0685 (10)
H4	1.0533	0.1337	0.5903	0.082*
C11	0.4042 (3)	0.0054 (2)	0.2915 (4)	0.0527 (8)
H11A	0.3653	0.0475	0.3508	0.079*
H11B	0.4344	−0.0444	0.3650	0.079*
H11C	0.3444	−0.0150	0.1904	0.079*
C3	1.1281 (3)	0.1556 (2)	0.3924 (5)	0.0649 (10)
H3	1.2060	0.1737	0.4574	0.078*
C12	0.6535 (4)	0.2479 (2)	0.1475 (5)	0.0698 (11)
H12A	0.7002	0.2747	0.2523	0.105*
H12B	0.5785	0.2813	0.1026	0.105*
H12C	0.7027	0.2479	0.0658	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0725 (7)	0.1143 (9)	0.0598 (6)	−0.0115 (6)	0.0303 (5)	0.0005 (5)
O1	0.0435 (12)	0.0732 (15)	0.0515 (13)	−0.0175 (11)	0.0154 (10)	−0.0114 (12)
N2	0.0440 (15)	0.0478 (17)	0.0599 (17)	−0.0044 (12)	0.0146 (13)	−0.0034 (12)
N3	0.0401 (14)	0.0422 (15)	0.076 (2)	0.0033 (12)	0.0152 (13)	0.0009 (13)
N1	0.0462 (15)	0.0455 (16)	0.0596 (18)	−0.0065 (13)	0.0151 (13)	−0.0003 (13)
C7	0.0357 (15)	0.054 (2)	0.0471 (18)	−0.0056 (15)	0.0090 (13)	−0.0038 (15)
C10	0.0344 (15)	0.052 (2)	0.062 (2)	−0.0015 (15)	0.0148 (14)	−0.0025 (16)
O2	0.0556 (14)	0.0429 (14)	0.133 (2)	0.0071 (11)	0.0413 (15)	0.0007 (15)
C6	0.0377 (16)	0.0433 (18)	0.0497 (19)	−0.0055 (13)	0.0106 (14)	−0.0037 (14)
C1	0.0454 (18)	0.0468 (18)	0.056 (2)	−0.0005 (14)	0.0155 (15)	0.0048 (15)
C8	0.0326 (14)	0.0462 (18)	0.0449 (18)	−0.0034 (13)	0.0070 (13)	−0.0017 (14)
C9	0.0363 (15)	0.0460 (18)	0.0424 (17)	−0.0036 (13)	0.0072 (13)	−0.0028 (14)
C5	0.0478 (19)	0.076 (2)	0.056 (2)	−0.0112 (17)	0.0200 (16)	−0.0001 (18)
C2	0.0400 (18)	0.074 (2)	0.074 (3)	−0.0041 (17)	0.0190 (17)	0.009 (2)
C4	0.057 (2)	0.092 (3)	0.050 (2)	−0.005 (2)	0.0039 (17)	0.0002 (19)
C11	0.0390 (16)	0.063 (2)	0.057 (2)	−0.0041 (15)	0.0141 (14)	−0.0010 (17)
C3	0.0366 (18)	0.081 (3)	0.073 (3)	−0.0074 (17)	0.0067 (17)	0.002 (2)
C12	0.073 (2)	0.052 (2)	0.087 (3)	−0.0079 (18)	0.026 (2)	0.0095 (19)

Geometric parameters (Å, º) top

Cl1—C1	1.735 (3)	C8—C9	1.415 (4)
O1—C7	1.371 (3)	C9—C11	1.501 (4)
O1—C6	1.396 (3)	C5—C4	1.389 (5)
N2—C9	1.330 (4)	C5—H5	0.9300
N2—N1	1.369 (3)	C2—C3	1.362 (5)
N3—C10	1.267 (4)	C2—H2A	0.9300
N3—O2	1.397 (3)	C4—C3	1.379 (5)
N1—C7	1.339 (4)	C4—H4	0.9300
N1—C12	1.456 (4)	C11—H11A	0.9600
C7—C8	1.376 (4)	C11—H11B	0.9600
C10—C8	1.446 (4)	C11—H11C	0.9600
C10—H10	0.9300	C3—H3	0.9300
O2—H2	0.8200	C12—H12A	0.9600
C6—C5	1.364 (4)	C12—H12B	0.9600
C6—C1	1.383 (4)	C12—H12C	0.9600
C1—C2	1.381 (5)

C7—O1—C6	117.8 (2)	C6—C5—C4	119.5 (3)
C9—N2—N1	106.1 (2)	C6—C5—H5	120.2
C10—N3—O2	111.1 (3)	C4—C5—H5	120.2
C7—N1—N2	109.8 (2)	C3—C2—C1	120.5 (3)
C7—N1—C12	129.1 (3)	C3—C2—H2A	119.8
N2—N1—C12	121.1 (3)	C1—C2—H2A	119.8
N1—C7—O1	121.3 (3)	C3—C4—C5	120.4 (3)
N1—C7—C8	109.6 (3)	C3—C4—H4	119.8
O1—C7—C8	128.9 (3)	C5—C4—H4	119.8
N3—C10—C8	123.0 (3)	C9—C11—H11A	109.5
N3—C10—H10	118.5	C9—C11—H11B	109.5
C8—C10—H10	118.5	H11A—C11—H11B	109.5
N3—O2—H2	109.5	C9—C11—H11C	109.5
C5—C6—C1	120.2 (3)	H11A—C11—H11C	109.5
C5—C6—O1	124.2 (3)	H11B—C11—H11C	109.5
C1—C6—O1	115.6 (3)	C2—C3—C4	119.7 (3)
C6—C1—C2	119.8 (3)	C2—C3—H3	120.2
C6—C1—Cl1	119.7 (2)	C4—C3—H3	120.2
C2—C1—Cl1	120.6 (3)	N1—C12—H12A	109.5
C7—C8—C9	103.5 (3)	N1—C12—H12B	109.5
C7—C8—C10	124.5 (3)	H12A—C12—H12B	109.5
C9—C8—C10	132.0 (3)	N1—C12—H12C	109.5
N2—C9—C8	111.0 (3)	H12A—C12—H12C	109.5
N2—C9—C11	120.3 (3)	H12B—C12—H12C	109.5
C8—C9—C11	128.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2ⁱ	0.82	1.97	2.787 (3)	171

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClN₃O₂
M_r	265.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	11.108 (2), 14.998 (3), 8.0839 (16)
β (°)	104.94 (3)
V (Å³)	1301.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.918, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	10731, 2288, 1638
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.159, 0.99
No. of reflections	2288
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25

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
O2—H2···N2ⁱ	0.82	1.97	2.787 (3)	171

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the Science Foundation of Nantong University (grant No. 11Z046).

References

Dai, H., Miao, W.-K., Wu, S.-S., Qin, X. & Fang, J.-X. (2011). Acta Cryst. E67, o775. Web of Science CSD CrossRef IUCr Journals Google Scholar
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