1,3-Dimethyl-5-(3-methyl­phen­oxy)-1H-pyrazole-4-carbaldehyde

Dai, H.; Zhang, H.-J.; Shi, L.; Sun, H.-Q.; Shi, Y.-J.

doi:10.1107/S1600536811050926

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3510

https://doi.org/10.1107/S1600536811050926

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1,3-Dimethyl-5-(3-methylphenoxy)-1H-pyrazole-4-carbaldehyde

Hong Dai,^a Hai-Jun Zhang,^a Lei Shi,^a Hai-Qin Sun ^a and Yu-Jun Shi ^a ^*

^aCollege of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, People's Republic of China
^*Correspondence e-mail: nankaidx228@yahoo.com.cn

(Received 4 November 2011; accepted 26 November 2011; online 30 November 2011)

There are two independent molecules in the asymmetric unit of the title compound, C₁₃H₁₄N₂O₂, in which the dihedral angles between the substituted phenyl ring and the pyrazole ring are 86.5 (2) and 82.3 (3)°. The crystal packing features weak intermolecular C—H⋯O interactions.

Related literature

For the biological activity of pyrazole derivatives, see: Drabek (1992 ); Haga et al. (1990 ); Motoba et al. (1992 ); Watanabe et al. (2001 ).

Experimental

Crystal data

C₁₃H₁₄N₂O₂
M_r = 230.26
Triclinic, $[P \overline 1]$
a = 7.9444 (16) Å
b = 10.643 (3) Å
c = 15.053 (3) Å
α = 107.732 (3)°
β = 102.473 (5)°
γ = 93.225 (7)°
V = 1173.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 113 K
0.20 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.982, T_max = 0.989
12386 measured reflections
5529 independent reflections
2226 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.100
S = 1.02
5529 reflections
313 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O4ⁱ	0.98	2.57	3.488 (3)	157
C15—H15⋯O2ⁱⁱ	0.95	2.58	3.315 (3)	134
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y-1, z.

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/S1600536811050926/ds2155sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050926/ds2155Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811050926/ds2155Isup3.cml

checkCIF report

Comment top

It is well known that compounds containing pyrazole ring have good bioactivities such as fungicidal, insecticidal, and herbicidal activities (Haga et al., 1990; Motoba et al., 1992; Watanabe et al., 2001). They are widely applied in the field of plant protection (Drabek, 1992). In order to discover more biologically active pyrazole compounds, the title compound, (I), was synthesized and its crystal structure was determined (Fig.1). The dihedral angles between substituted phenyl ring and pyrazole ring in the two independent molecules are 86.5 (2) ° and 82.3 (3) °, respectively. The crystal packing displays weak intermolecular C—H···O interactions (Table 1).

Related literature top

For the biological activity of pyrazole derivatives, see: Drabek (1992); Haga et al. (1990); Motoba et al. (1992); Watanabe et al. (2001).

Experimental top

To a stirred solution of 1-methyl-3-methyl-5-chloro-1H-pyrazole- 4-carbaldehyde(30 mmol) and 3-methylphenol(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 x 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

For the biological activity of pyrazole derivatives, see: Drabek (1992); Haga et al. (1990); Motoba et al. (1992); Watanabe et al. (2001).

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. View of the title compound (I), with displacement ellipsoids drawn at the 30% probability level.

1,3-Dimethyl-5-(3-methylphenoxy)-1H-pyrazole-4-carbaldehyde top

Crystal data top

C₁₃H₁₄N₂O₂	Z = 4
M_r = 230.27	F(000) = 488
Triclinic, P1	D_x = 1.303 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9444 (16) Å	Cell parameters from 4226 reflections
b = 10.643 (3) Å	θ = 2.0–28.1°
c = 15.053 (3) Å	µ = 0.09 mm⁻¹
α = 107.732 (3)°	T = 113 K
β = 102.473 (5)°	Prism, colourless
γ = 93.225 (7)°	0.20 × 0.16 × 0.12 mm
V = 1173.4 (5) Å³

Data collection top

Rigaku Saturn724 CCD diffractometer	5529 independent reflections
Radiation source: rotating anode	2226 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.064
Detector resolution: 14.22 pixels mm^-1	θ_max = 28.0°, θ_min = 2.0°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −14→14
T_min = 0.982, T_max = 0.989	l = −19→19
12386 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.010P)²] where P = (F_o² + 2F_c²)/3
5529 reflections	(Δ/σ)_max = 0.004
313 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₃H₁₄N₂O₂	γ = 93.225 (7)°
M_r = 230.27	V = 1173.4 (5) Å³
Triclinic, P1	Z = 4
a = 7.9444 (16) Å	Mo Kα radiation
b = 10.643 (3) Å	µ = 0.09 mm⁻¹
c = 15.053 (3) Å	T = 113 K
α = 107.732 (3)°	0.20 × 0.16 × 0.12 mm
β = 102.473 (5)°

Data collection top

Rigaku Saturn724 CCD diffractometer	5529 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	2226 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.989	R_int = 0.064
12386 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.02	Δρ_max = 0.25 e Å⁻³
5529 reflections	Δρ_min = −0.40 e Å⁻³
313 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
O1	0.8036 (2)	0.24450 (16)	0.10860 (11)	0.0294 (5)
O2	0.7737 (2)	0.60698 (17)	0.33053 (12)	0.0382 (5)
O3	0.0347 (2)	0.00932 (17)	0.28476 (11)	0.0328 (5)
O4	0.2005 (2)	0.11940 (17)	0.05903 (12)	0.0425 (5)
N1	0.6563 (3)	0.1553 (2)	0.19874 (14)	0.0278 (6)
N2	0.5999 (3)	0.1925 (2)	0.28185 (14)	0.0294 (6)
N3	0.0942 (3)	0.2408 (2)	0.35725 (15)	0.0303 (6)
N4	0.1457 (3)	0.3542 (2)	0.33896 (14)	0.0297 (6)
C1	0.7095 (3)	0.2757 (2)	0.02854 (17)	0.0241 (6)
C2	0.8041 (3)	0.2834 (2)	−0.03652 (16)	0.0274 (7)
H2	0.9235	0.2712	−0.0258	0.033*
C3	0.7187 (3)	0.3095 (2)	−0.11844 (17)	0.0321 (7)
H3	0.7797	0.3156	−0.1651	0.038*
C4	0.5444 (3)	0.3268 (2)	−0.13217 (17)	0.0301 (7)
H4	0.4875	0.3453	−0.1883	0.036*
C5	0.4513 (3)	0.3177 (2)	−0.06618 (17)	0.0255 (6)
C6	0.5371 (3)	0.2912 (2)	0.01631 (16)	0.0256 (6)
H6	0.4767	0.2840	0.0630	0.031*
C7	0.2610 (3)	0.3341 (2)	−0.08065 (16)	0.0341 (7)
H7A	0.2039	0.2766	−0.0529	0.051*
H7B	0.2067	0.3093	−0.1496	0.051*
H7C	0.2488	0.4271	−0.0488	0.051*
C8	0.7308 (3)	0.2600 (3)	0.18420 (17)	0.0256 (7)
C9	0.7234 (3)	0.3731 (2)	0.25874 (17)	0.0223 (6)
C10	0.6415 (3)	0.3234 (3)	0.31759 (17)	0.0255 (6)
C11	0.5998 (3)	0.4000 (2)	0.40987 (15)	0.0320 (7)
H11A	0.5401	0.3387	0.4337	0.048*
H11B	0.5243	0.4661	0.3986	0.048*
H11C	0.7077	0.4452	0.4577	0.048*
C12	0.6303 (3)	0.0156 (2)	0.13985 (17)	0.0377 (8)
H12A	0.6849	0.0053	0.0860	0.056*
H12B	0.5054	−0.0155	0.1149	0.056*
H12C	0.6830	−0.0372	0.1791	0.056*
C13	0.7929 (3)	0.5060 (3)	0.26952 (18)	0.0313 (7)
H13	0.8587	0.5164	0.2259	0.038*
C14	0.1617 (3)	−0.0619 (3)	0.32283 (16)	0.0274 (7)
C15	0.0930 (3)	−0.1703 (2)	0.34139 (16)	0.0294 (7)
H15	−0.0289	−0.1912	0.3313	0.035*
C16	0.2095 (3)	−0.2481 (2)	0.37553 (16)	0.0298 (7)
H16	0.1670	−0.3246	0.3881	0.036*
C17	0.3865 (3)	−0.2146 (2)	0.39111 (16)	0.0296 (7)
H17	0.4643	−0.2684	0.4145	0.035*
C18	0.4526 (3)	−0.1037 (2)	0.37326 (16)	0.0252 (6)
C19	0.3373 (3)	−0.0259 (2)	0.33883 (15)	0.0249 (6)
H19	0.3792	0.0510	0.3266	0.030*
C20	0.6461 (3)	−0.0664 (2)	0.39066 (16)	0.0320 (7)
H20A	0.6958	−0.0195	0.4593	0.048*
H20B	0.6672	−0.0084	0.3535	0.048*
H20C	0.7009	−0.1472	0.3704	0.048*
C21	0.0920 (3)	0.1315 (3)	0.28273 (19)	0.0287 (7)
C22	0.1413 (3)	0.1701 (3)	0.21237 (18)	0.0250 (6)
C23	0.1758 (3)	0.3107 (3)	0.25212 (18)	0.0268 (7)
C24	0.2314 (3)	0.4080 (2)	0.20729 (17)	0.0327 (7)
H24A	0.2286	0.4987	0.2485	0.049*
H24B	0.1522	0.3915	0.1440	0.049*
H24C	0.3499	0.3978	0.1999	0.049*
C25	0.0481 (3)	0.2495 (3)	0.44694 (16)	0.0417 (8)
H25A	−0.0006	0.1613	0.4440	0.063*
H25B	−0.0385	0.3111	0.4571	0.063*
H25C	0.1521	0.2821	0.5003	0.063*
C26	0.1513 (3)	0.0825 (3)	0.11980 (19)	0.0350 (7)
H26	0.1175	−0.0100	0.1050	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0228 (11)	0.0443 (12)	0.0271 (10)	0.0118 (9)	0.0112 (8)	0.0153 (9)
O2	0.0450 (13)	0.0302 (12)	0.0371 (11)	0.0036 (10)	0.0104 (10)	0.0076 (10)
O3	0.0224 (11)	0.0375 (12)	0.0437 (12)	0.0048 (9)	0.0077 (9)	0.0208 (10)
O4	0.0511 (14)	0.0431 (13)	0.0393 (12)	0.0058 (10)	0.0263 (10)	0.0116 (10)
N1	0.0281 (14)	0.0296 (14)	0.0244 (12)	0.0053 (11)	0.0086 (11)	0.0055 (11)
N2	0.0295 (14)	0.0351 (14)	0.0256 (13)	0.0052 (11)	0.0107 (11)	0.0100 (11)
N3	0.0255 (14)	0.0421 (15)	0.0279 (13)	0.0077 (12)	0.0114 (11)	0.0140 (12)
N4	0.0258 (14)	0.0330 (14)	0.0307 (13)	0.0028 (11)	0.0083 (11)	0.0100 (12)
C1	0.0238 (17)	0.0238 (15)	0.0240 (14)	0.0034 (12)	0.0067 (12)	0.0063 (12)
C2	0.0215 (16)	0.0336 (17)	0.0306 (15)	0.0078 (13)	0.0135 (12)	0.0099 (13)
C3	0.0399 (19)	0.0322 (17)	0.0311 (15)	0.0071 (14)	0.0191 (13)	0.0126 (14)
C4	0.0325 (18)	0.0335 (17)	0.0271 (15)	0.0107 (14)	0.0082 (13)	0.0122 (13)
C5	0.0249 (17)	0.0253 (15)	0.0266 (15)	0.0062 (12)	0.0077 (12)	0.0074 (13)
C6	0.0268 (17)	0.0283 (16)	0.0229 (14)	0.0044 (13)	0.0108 (12)	0.0066 (12)
C7	0.0307 (18)	0.0389 (18)	0.0353 (16)	0.0066 (14)	0.0093 (13)	0.0143 (14)
C8	0.0182 (16)	0.0387 (18)	0.0262 (15)	0.0080 (13)	0.0074 (13)	0.0172 (14)
C9	0.0176 (15)	0.0266 (15)	0.0226 (14)	0.0014 (12)	0.0045 (12)	0.0086 (12)
C10	0.0200 (16)	0.0331 (16)	0.0229 (14)	0.0057 (13)	0.0042 (12)	0.0089 (13)
C11	0.0333 (17)	0.0374 (18)	0.0274 (15)	0.0030 (14)	0.0147 (13)	0.0086 (14)
C12	0.0386 (19)	0.0305 (17)	0.0364 (16)	0.0054 (14)	0.0074 (14)	0.0014 (14)
C13	0.0240 (17)	0.0394 (18)	0.0343 (17)	0.0042 (14)	0.0048 (13)	0.0190 (15)
C14	0.0274 (18)	0.0315 (17)	0.0240 (15)	0.0078 (13)	0.0080 (13)	0.0079 (13)
C15	0.0255 (17)	0.0360 (17)	0.0284 (15)	0.0030 (14)	0.0138 (13)	0.0083 (13)
C16	0.0387 (19)	0.0278 (16)	0.0275 (15)	0.0036 (14)	0.0160 (13)	0.0103 (13)
C17	0.0342 (18)	0.0299 (16)	0.0302 (15)	0.0112 (14)	0.0129 (14)	0.0131 (13)
C18	0.0238 (16)	0.0290 (16)	0.0224 (14)	0.0073 (13)	0.0088 (12)	0.0052 (13)
C19	0.0223 (16)	0.0290 (16)	0.0272 (14)	0.0047 (12)	0.0087 (12)	0.0126 (13)
C20	0.0308 (18)	0.0351 (17)	0.0356 (16)	0.0095 (13)	0.0132 (13)	0.0150 (14)
C21	0.0162 (16)	0.0374 (18)	0.0376 (17)	0.0087 (13)	0.0064 (13)	0.0188 (15)
C22	0.0214 (16)	0.0289 (16)	0.0281 (15)	0.0073 (13)	0.0097 (12)	0.0107 (13)
C23	0.0166 (16)	0.0350 (17)	0.0305 (15)	0.0082 (13)	0.0049 (12)	0.0130 (14)
C24	0.0309 (17)	0.0314 (17)	0.0380 (16)	0.0083 (14)	0.0116 (13)	0.0116 (14)
C25	0.046 (2)	0.057 (2)	0.0274 (16)	0.0085 (16)	0.0162 (14)	0.0173 (15)
C26	0.0320 (18)	0.0327 (18)	0.0411 (18)	0.0060 (14)	0.0140 (15)	0.0092 (15)

Geometric parameters (Å, º) top

O1—C8	1.356 (3)	C11—H11A	0.9800
O1—C1	1.415 (2)	C11—H11B	0.9800
O2—C13	1.224 (3)	C11—H11C	0.9800
O3—C21	1.364 (3)	C12—H12A	0.9800
O3—C14	1.422 (3)	C12—H12B	0.9800
O4—C26	1.224 (3)	C12—H12C	0.9800
N1—C8	1.330 (3)	C13—H13	0.9500
N1—N2	1.372 (3)	C14—C19	1.374 (3)
N1—C12	1.458 (3)	C14—C15	1.378 (3)
N2—C10	1.325 (3)	C15—C16	1.395 (3)
N3—C21	1.344 (3)	C15—H15	0.9500
N3—N4	1.377 (3)	C16—C17	1.382 (3)
N3—C25	1.451 (3)	C16—H16	0.9500
N4—C23	1.326 (3)	C17—C18	1.387 (3)
C1—C6	1.369 (3)	C17—H17	0.9500
C1—C2	1.375 (3)	C18—C19	1.392 (3)
C2—C3	1.388 (3)	C18—C20	1.511 (3)
C2—H2	0.9500	C19—H19	0.9500
C3—C4	1.386 (3)	C20—H20A	0.9800
C3—H3	0.9500	C20—H20B	0.9800
C4—C5	1.382 (3)	C20—H20C	0.9800
C4—H4	0.9500	C21—C22	1.367 (3)
C5—C6	1.398 (3)	C22—C23	1.418 (3)
C5—C7	1.508 (3)	C22—C26	1.443 (3)
C6—H6	0.9500	C23—C24	1.492 (3)
C7—H7A	0.9800	C24—H24A	0.9800
C7—H7B	0.9800	C24—H24B	0.9800
C7—H7C	0.9800	C24—H24C	0.9800
C8—C9	1.388 (3)	C25—H25A	0.9800
C9—C10	1.408 (3)	C25—H25B	0.9800
C9—C13	1.437 (3)	C25—H25C	0.9800
C10—C11	1.498 (3)	C26—H26	0.9500

C8—O1—C1	117.58 (19)	H12A—C12—H12C	109.5
C21—O3—C14	117.0 (2)	H12B—C12—H12C	109.5
C8—N1—N2	111.3 (2)	O2—C13—C9	125.1 (3)
C8—N1—C12	128.9 (2)	O2—C13—H13	117.5
N2—N1—C12	119.8 (2)	C9—C13—H13	117.5
C10—N2—N1	105.0 (2)	C19—C14—C15	123.2 (2)
C21—N3—N4	110.9 (2)	C19—C14—O3	122.7 (2)
C21—N3—C25	128.5 (2)	C15—C14—O3	114.0 (2)
N4—N3—C25	120.6 (2)	C14—C15—C16	117.4 (2)
C23—N4—N3	104.8 (2)	C14—C15—H15	121.3
C6—C1—C2	123.6 (2)	C16—C15—H15	121.3
C6—C1—O1	122.0 (2)	C17—C16—C15	120.3 (2)
C2—C1—O1	114.3 (2)	C17—C16—H16	119.9
C1—C2—C3	117.5 (2)	C15—C16—H16	119.9
C1—C2—H2	121.2	C16—C17—C18	121.2 (2)
C3—C2—H2	121.2	C16—C17—H17	119.4
C4—C3—C2	120.0 (2)	C18—C17—H17	119.4
C4—C3—H3	120.0	C17—C18—C19	118.8 (2)
C2—C3—H3	120.0	C17—C18—C20	121.3 (2)
C5—C4—C3	121.6 (2)	C19—C18—C20	119.8 (2)
C5—C4—H4	119.2	C14—C19—C18	119.0 (2)
C3—C4—H4	119.2	C14—C19—H19	120.5
C4—C5—C6	118.5 (2)	C18—C19—H19	120.5
C4—C5—C7	122.3 (2)	C18—C20—H20A	109.5
C6—C5—C7	119.2 (2)	C18—C20—H20B	109.5
C1—C6—C5	118.7 (2)	H20A—C20—H20B	109.5
C1—C6—H6	120.6	C18—C20—H20C	109.5
C5—C6—H6	120.6	H20A—C20—H20C	109.5
C5—C7—H7A	109.5	H20B—C20—H20C	109.5
C5—C7—H7B	109.5	N3—C21—O3	119.8 (2)
H7A—C7—H7B	109.5	N3—C21—C22	108.6 (2)
C5—C7—H7C	109.5	O3—C21—C22	131.5 (3)
H7A—C7—H7C	109.5	C21—C22—C23	104.0 (2)
H7B—C7—H7C	109.5	C21—C22—C26	125.8 (3)
N1—C8—O1	120.9 (2)	C23—C22—C26	130.2 (3)
N1—C8—C9	108.3 (2)	N4—C23—C22	111.7 (2)
O1—C8—C9	130.8 (3)	N4—C23—C24	119.8 (2)
C8—C9—C10	103.7 (2)	C22—C23—C24	128.5 (2)
C8—C9—C13	125.1 (3)	C23—C24—H24A	109.5
C10—C9—C13	131.2 (2)	C23—C24—H24B	109.5
N2—C10—C9	111.8 (2)	H24A—C24—H24B	109.5
N2—C10—C11	120.3 (2)	C23—C24—H24C	109.5
C9—C10—C11	128.0 (2)	H24A—C24—H24C	109.5
C10—C11—H11A	109.5	H24B—C24—H24C	109.5
C10—C11—H11B	109.5	N3—C25—H25A	109.5
H11A—C11—H11B	109.5	N3—C25—H25B	109.5
C10—C11—H11C	109.5	H25A—C25—H25B	109.5
H11A—C11—H11C	109.5	N3—C25—H25C	109.5
H11B—C11—H11C	109.5	H25A—C25—H25C	109.5
N1—C12—H12A	109.5	H25B—C25—H25C	109.5
N1—C12—H12B	109.5	O4—C26—C22	124.5 (3)
H12A—C12—H12B	109.5	O4—C26—H26	117.8
N1—C12—H12C	109.5	C22—C26—H26	117.8

C8—N1—N2—C10	0.3 (3)	C8—C9—C13—O2	173.5 (2)
C12—N1—N2—C10	−179.72 (19)	C10—C9—C13—O2	−9.2 (4)
C21—N3—N4—C23	−0.5 (3)	C21—O3—C14—C19	−13.2 (3)
C25—N3—N4—C23	−179.5 (2)	C21—O3—C14—C15	167.3 (2)
C8—O1—C1—C6	−14.8 (3)	C19—C14—C15—C16	−1.9 (4)
C8—O1—C1—C2	167.7 (2)	O3—C14—C15—C16	177.68 (19)
C6—C1—C2—C3	0.6 (4)	C14—C15—C16—C17	1.1 (4)
O1—C1—C2—C3	178.1 (2)	C15—C16—C17—C18	−0.1 (4)
C1—C2—C3—C4	0.0 (4)	C16—C17—C18—C19	−0.1 (4)
C2—C3—C4—C5	−0.4 (4)	C16—C17—C18—C20	179.7 (2)
C3—C4—C5—C6	0.3 (4)	C15—C14—C19—C18	1.6 (4)
C3—C4—C5—C7	−179.1 (2)	O3—C14—C19—C18	−177.9 (2)
C2—C1—C6—C5	−0.7 (4)	C17—C18—C19—C14	−0.6 (4)
O1—C1—C6—C5	−178.0 (2)	C20—C18—C19—C14	179.6 (2)
C4—C5—C6—C1	0.2 (4)	N4—N3—C21—O3	−176.2 (2)
C7—C5—C6—C1	179.6 (2)	C25—N3—C21—O3	2.7 (4)
N2—N1—C8—O1	176.58 (19)	N4—N3—C21—C22	−0.4 (3)
C12—N1—C8—O1	−3.4 (4)	C25—N3—C21—C22	178.5 (2)
N2—N1—C8—C9	−0.9 (3)	C14—O3—C21—N3	−91.8 (3)
C12—N1—C8—C9	179.1 (2)	C14—O3—C21—C22	93.5 (3)
C1—O1—C8—N1	103.3 (3)	N3—C21—C22—C23	1.0 (3)
C1—O1—C8—C9	−79.9 (3)	O3—C21—C22—C23	176.2 (2)
N1—C8—C9—C10	1.1 (3)	N3—C21—C22—C26	−178.3 (2)
O1—C8—C9—C10	−176.1 (2)	O3—C21—C22—C26	−3.2 (5)
N1—C8—C9—C13	179.0 (2)	N3—N4—C23—C22	1.2 (3)
O1—C8—C9—C13	1.8 (4)	N3—N4—C23—C24	178.74 (19)
N1—N2—C10—C9	0.4 (3)	C21—C22—C23—N4	−1.4 (3)
N1—N2—C10—C11	−179.8 (2)	C26—C22—C23—N4	177.9 (2)
C8—C9—C10—N2	−0.9 (3)	C21—C22—C23—C24	−178.7 (2)
C13—C9—C10—N2	−178.7 (2)	C26—C22—C23—C24	0.6 (4)
C8—C9—C10—C11	179.3 (2)	C21—C22—C26—O4	−177.9 (3)
C13—C9—C10—C11	1.6 (4)	C23—C22—C26—O4	2.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O4ⁱ	0.98	2.57	3.488 (3)	157
C15—H15···O2ⁱⁱ	0.95	2.58	3.315 (3)	134

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂O₂
M_r	230.27
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	7.9444 (16), 10.643 (3), 15.053 (3)
α, β, γ (°)	107.732 (3), 102.473 (5), 93.225 (7)
V (Å³)	1173.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.16 × 0.12

Data collection
Diffractometer	Rigaku Saturn724 CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.982, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	12386, 5529, 2226
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.100, 1.02
No. of reflections	5529
No. of parameters	313
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.40

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
C12—H12A···O4ⁱ	0.98	2.57	3.488 (3)	157
C15—H15···O2ⁱⁱ	0.95	2.58	3.315 (3)	134

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NNSFC) (grant No. 20772068), the Science and Technology Projects Fund of Nantong City (grant Nos. K2010016, AS2010005), the Science Foundation of Nantong University (grant Nos. 09Z010, 09 C001) and the Scientific Research Foundation for Talent Introduction of Nantong University.

References

Drabek, J. (1992). DE Patent No. 4200742. Google Scholar
Haga, T., Toki, T., Koyanaqi, T., Okada, H., Imai, O. & Morita, M. (1990). Jpn Patent No. 02096568. Google Scholar
Motoba, K., Suzuki, T. & Uchida, M. (1992). Pestic. Biochem. Physiol. 43, 37–44. CrossRef CAS 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
Watanabe, M., Kuwata, T., Okada, T., Ohita, S., Asahara, T., Noritake, T. & Fukuda, Y. (2001). Jpn Patent No. 2001233861. Google Scholar