(E)-2-[(4-Chloro-1,3-dimethyl-1H-pyrazol-5-yl)methyl­eneamino]benzamide

Cong, Y.; Yang, H.; Yu, H.; Li, B.

doi:10.1107/S1600536809050685

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3263

doi:10.1107/S1600536809050685

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(E)-2-[(4-Chloro-1,3-dimethyl-1H-pyrazol-5-yl)methyleneamino]benzamide

Yunbo Cong,^a Huibin Yang,^b Haibo Yu ^b and Bin Li ^b ^*

^aShenyang Institute of Chemical Technology, Shenyang 110142, People's Republic of China, and ^bAgrochemicals Division, Shenyang Research Institute of Chemical Industry, Shenyang 110021, People's Republic of China
^*Correspondence e-mail: libin1@sinochem.com

(Received 24 November 2009; accepted 25 November 2009; online 28 November 2009)

In the title compound, C₁₃H₁₃ClN₄O, the dihedral angle between the aromatic rings is 33.47 (9)° and an intramolecular N—H⋯N hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur, resulting in R₂²(8) loops.

Related literature

For catalytic studies on a related compound, see: Chen et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₃ClN₄O
M_r = 276.72
Monoclinic, C 2/c
a = 22.046 (3) Å
b = 8.6785 (10) Å
c = 14.1137 (16) Å
β = 96.005 (2)°
V = 2685.5 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.32 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.725, T_max = 1.000
6634 measured reflections
2375 independent reflections
2098 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.06
2375 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯N3	0.86	2.07	2.749 (2)	136
N4—H4A⋯O1ⁱ	0.86	2.10	2.930 (2)	161
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050685/hb5252sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050685/hb5252Isup2.hkl

checkCIF report

Related literature top

For catalytic studies on a related compound, see: Chen et al. (2008).

Experimental top

The title compound was synthesized by the reaction of 4-chloro-1,3-dimethyl-1H-pyrazole-5- carbaldehyde with 2-aminobenzamide in 1,2-dichloroethane. The crude product was purified by silica-gel column chromatography and then grown from methylene chloride to afford colourless blocks of (I).

Anal. Calcd for C₁₃H₁₃N₄O₁: C, 56.42; H, 4.74; N, 20.25; O, 5.78. Found: C, 56.57; H, 4.64; N, 20.66; O, 5.25. ¹H NMR(DMSO): 2.21(s,3H, CH₃), 4.12 (s,3H, N—CH₃), 7.33(s, 2H, CONH₂), 7.50–7.61 (m, 2H, Ph), 7.89 (t, 1H, Ph—H), 8.26 (s, 1H, Ph—H), 8.46 (s, 1H, CH=N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 30% probability displacement ellipsoids.

(E)-2-[(4-Chloro-1,3-dimethyl-1H-pyrazol-5- yl)methyleneamino]benzamide top

Crystal data top

C₁₃H₁₃ClN₄O	F(000) = 1152
M_r = 276.72	D_x = 1.369 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4144 reflections
a = 22.046 (3) Å	θ = 2.2–30.2°
b = 8.6785 (10) Å	µ = 0.28 mm⁻¹
c = 14.1137 (16) Å	T = 296 K
β = 96.005 (2)°	Block, colourless
V = 2685.5 (5) Å³	0.32 × 0.30 × 0.28 mm
Z = 8

Data collection top

Bruker SMART CCD diffractometer	2375 independent reflections
Radiation source: fine-focus sealed tube	2098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −25→26
T_min = 0.725, T_max = 1.000	k = −6→10
6634 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.052P)² + 1.4091P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2375 reflections	Δρ_max = 0.17 e Å⁻³
175 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0266 (12)

Crystal data top

C₁₃H₁₃ClN₄O	V = 2685.5 (5) Å³
M_r = 276.72	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.046 (3) Å	µ = 0.28 mm⁻¹
b = 8.6785 (10) Å	T = 296 K
c = 14.1137 (16) Å	0.32 × 0.30 × 0.28 mm
β = 96.005 (2)°

Data collection top

Bruker SMART CCD diffractometer	2375 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2098 reflections with I > 2σ(I)
T_min = 0.725, T_max = 1.000	R_int = 0.018
6634 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	Δρ_max = 0.17 e Å⁻³
2375 reflections	Δρ_min = −0.19 e Å⁻³
175 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.45129 (2)	0.49955 (4)	0.12551 (4)	0.0612 (2)
N4	0.29251 (6)	0.43146 (17)	0.04310 (11)	0.0531 (4)
H4A	0.3006	0.3480	0.0140	0.064*
H4B	0.3217	0.4899	0.0670	0.064*
O1	0.19254 (5)	0.38809 (14)	0.01737 (10)	0.0600 (4)
N1	0.52045 (6)	0.91074 (16)	0.12334 (10)	0.0486 (4)
N2	0.46079 (6)	0.94242 (16)	0.12143 (10)	0.0445 (3)
C6	0.36052 (7)	0.82150 (17)	0.12489 (11)	0.0397 (4)
H6	0.3417	0.9174	0.1202	0.048*
N3	0.32795 (6)	0.70280 (14)	0.13302 (9)	0.0376 (3)
C1	0.46698 (7)	0.69287 (17)	0.12368 (11)	0.0400 (4)
C2	0.52480 (7)	0.75722 (19)	0.12428 (11)	0.0430 (4)
C3	0.58468 (8)	0.6779 (2)	0.12766 (15)	0.0576 (5)
H3A	0.6159	0.7518	0.1181	0.086*
H3B	0.5831	0.6013	0.0784	0.086*
H3C	0.5938	0.6294	0.1886	0.086*
C4	0.44200 (9)	1.1028 (2)	0.12241 (16)	0.0614 (5)
H4C	0.4316	1.1292	0.1847	0.092*
H4D	0.4072	1.1179	0.0766	0.092*
H4E	0.4749	1.1672	0.1066	0.092*
C5	0.42578 (7)	0.81350 (17)	0.12263 (11)	0.0379 (4)
C7	0.26516 (7)	0.72357 (17)	0.14214 (10)	0.0364 (3)
C8	0.22185 (7)	0.61479 (17)	0.10333 (10)	0.0363 (3)
C9	0.16068 (7)	0.6395 (2)	0.11507 (12)	0.0445 (4)
H9	0.1317	0.5694	0.0890	0.053*
C10	0.14195 (8)	0.7653 (2)	0.16439 (13)	0.0541 (5)
H10	0.1007	0.7807	0.1701	0.065*
C11	0.18475 (8)	0.8675 (2)	0.20506 (14)	0.0577 (5)
H11	0.1726	0.9509	0.2398	0.069*
C12	0.24531 (8)	0.8468 (2)	0.19446 (13)	0.0504 (4)
H12	0.2738	0.9163	0.2227	0.060*
C13	0.23540 (7)	0.46978 (18)	0.05100 (11)	0.0401 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0557 (3)	0.0314 (3)	0.0956 (4)	−0.00049 (17)	0.0037 (2)	−0.0028 (2)
N4	0.0376 (7)	0.0445 (8)	0.0774 (10)	−0.0038 (6)	0.0064 (7)	−0.0244 (7)
O1	0.0391 (6)	0.0426 (7)	0.0960 (10)	−0.0043 (5)	−0.0039 (6)	−0.0204 (6)
N1	0.0387 (7)	0.0446 (8)	0.0618 (9)	−0.0076 (6)	0.0021 (6)	0.0017 (6)
N2	0.0407 (7)	0.0328 (7)	0.0589 (8)	−0.0046 (5)	−0.0004 (6)	0.0008 (6)
C6	0.0404 (8)	0.0316 (8)	0.0452 (8)	0.0002 (6)	−0.0044 (6)	0.0003 (6)
N3	0.0356 (7)	0.0345 (7)	0.0418 (7)	−0.0026 (5)	−0.0006 (5)	−0.0032 (5)
C1	0.0417 (8)	0.0332 (8)	0.0442 (8)	−0.0017 (6)	−0.0001 (6)	−0.0015 (6)
C2	0.0403 (8)	0.0434 (9)	0.0450 (9)	−0.0012 (7)	0.0025 (7)	−0.0004 (7)
C3	0.0447 (10)	0.0609 (12)	0.0674 (12)	0.0047 (8)	0.0066 (8)	0.0000 (9)
C4	0.0561 (11)	0.0322 (9)	0.0946 (15)	−0.0052 (8)	0.0017 (10)	−0.0010 (9)
C5	0.0389 (8)	0.0322 (8)	0.0414 (8)	−0.0043 (6)	−0.0018 (6)	−0.0007 (6)
C7	0.0374 (8)	0.0346 (8)	0.0364 (7)	0.0027 (6)	0.0004 (6)	0.0009 (6)
C8	0.0367 (8)	0.0338 (8)	0.0381 (8)	−0.0006 (6)	0.0018 (6)	0.0023 (6)
C9	0.0366 (8)	0.0452 (9)	0.0513 (9)	−0.0019 (7)	0.0024 (7)	0.0001 (7)
C10	0.0404 (9)	0.0613 (11)	0.0614 (11)	0.0102 (8)	0.0097 (8)	−0.0044 (9)
C11	0.0547 (11)	0.0574 (11)	0.0608 (11)	0.0142 (9)	0.0046 (8)	−0.0175 (9)
C12	0.0478 (10)	0.0461 (9)	0.0557 (10)	0.0014 (8)	−0.0012 (8)	−0.0145 (8)
C13	0.0379 (8)	0.0343 (8)	0.0472 (8)	−0.0027 (6)	0.0009 (6)	−0.0010 (6)

Geometric parameters (Å, º) top

Cl1—C1	1.7137 (16)	C3—H3B	0.9600
N4—C13	1.318 (2)	C3—H3C	0.9600
N4—H4A	0.8600	C4—H4C	0.9600
N4—H4B	0.8600	C4—H4D	0.9600
O1—C13	1.2356 (18)	C4—H4E	0.9600
N1—C2	1.336 (2)	C7—C12	1.396 (2)
N1—N2	1.3413 (19)	C7—C8	1.412 (2)
N2—C5	1.360 (2)	C8—C9	1.392 (2)
N2—C4	1.452 (2)	C8—C13	1.505 (2)
C6—N3	1.2677 (19)	C9—C10	1.381 (2)
C6—C5	1.444 (2)	C9—H9	0.9300
C6—H6	0.9300	C10—C11	1.376 (3)
N3—C7	1.4151 (19)	C10—H10	0.9300
C1—C5	1.385 (2)	C11—C12	1.371 (2)
C1—C2	1.391 (2)	C11—H11	0.9300
C2—C3	1.485 (2)	C12—H12	0.9300
C3—H3A	0.9600

C13—N4—H4A	120.0	H4C—C4—H4E	109.5
C13—N4—H4B	120.0	H4D—C4—H4E	109.5
H4A—N4—H4B	120.0	N2—C5—C1	104.45 (14)
C2—N1—N2	105.89 (13)	N2—C5—C6	121.91 (13)
N1—N2—C5	112.81 (13)	C1—C5—C6	133.62 (14)
N1—N2—C4	118.44 (13)	C12—C7—C8	118.74 (14)
C5—N2—C4	128.70 (14)	C12—C7—N3	120.63 (13)
N3—C6—C5	122.55 (14)	C8—C7—N3	120.52 (13)
N3—C6—H6	118.7	C9—C8—C7	118.35 (14)
C5—C6—H6	118.7	C9—C8—C13	115.57 (13)
C6—N3—C7	118.26 (13)	C7—C8—C13	126.07 (13)
C5—C1—C2	107.22 (14)	C10—C9—C8	121.76 (16)
C5—C1—Cl1	127.38 (12)	C10—C9—H9	119.1
C2—C1—Cl1	125.40 (13)	C8—C9—H9	119.1
N1—C2—C1	109.62 (14)	C11—C10—C9	119.45 (16)
N1—C2—C3	121.67 (15)	C11—C10—H10	120.3
C1—C2—C3	128.70 (16)	C9—C10—H10	120.3
C2—C3—H3A	109.5	C12—C11—C10	120.20 (16)
C2—C3—H3B	109.5	C12—C11—H11	119.9
H3A—C3—H3B	109.5	C10—C11—H11	119.9
C2—C3—H3C	109.5	C11—C12—C7	121.41 (16)
H3A—C3—H3C	109.5	C11—C12—H12	119.3
H3B—C3—H3C	109.5	C7—C12—H12	119.3
N2—C4—H4C	109.5	O1—C13—N4	121.44 (15)
N2—C4—H4D	109.5	O1—C13—C8	119.04 (14)
H4C—C4—H4D	109.5	N4—C13—C8	119.52 (13)
N2—C4—H4E	109.5

C2—N1—N2—C5	0.99 (18)	N3—C6—C5—C1	3.3 (3)
C2—N1—N2—C4	178.50 (16)	C6—N3—C7—C12	−37.2 (2)
C5—C6—N3—C7	175.07 (13)	C6—N3—C7—C8	146.70 (15)
N2—N1—C2—C1	−0.46 (18)	C12—C7—C8—C9	3.1 (2)
N2—N1—C2—C3	−179.23 (15)	N3—C7—C8—C9	179.31 (13)
C5—C1—C2—N1	−0.19 (18)	C12—C7—C8—C13	−175.57 (15)
Cl1—C1—C2—N1	−179.43 (12)	N3—C7—C8—C13	0.6 (2)
C5—C1—C2—C3	178.46 (17)	C7—C8—C9—C10	−0.9 (2)
Cl1—C1—C2—C3	−0.8 (3)	C13—C8—C9—C10	177.86 (15)
N1—N2—C5—C1	−1.09 (18)	C8—C9—C10—C11	−1.5 (3)
C4—N2—C5—C1	−178.29 (17)	C9—C10—C11—C12	1.7 (3)
N1—N2—C5—C6	177.42 (13)	C10—C11—C12—C7	0.5 (3)
C4—N2—C5—C6	0.2 (3)	C8—C7—C12—C11	−2.9 (3)
C2—C1—C5—N2	0.75 (17)	N3—C7—C12—C11	−179.15 (16)
Cl1—C1—C5—N2	179.96 (12)	C9—C8—C13—O1	4.2 (2)
C2—C1—C5—C6	−177.51 (16)	C7—C8—C13—O1	−177.06 (15)
Cl1—C1—C5—C6	1.7 (3)	C9—C8—C13—N4	−174.85 (15)
N3—C6—C5—N2	−174.72 (15)	C7—C8—C13—N4	3.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N3	0.86	2.07	2.749 (2)	136
N4—H4A···O1ⁱ	0.86	2.10	2.930 (2)	161

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃ClN₄O
M_r	276.72
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	22.046 (3), 8.6785 (10), 14.1137 (16)
β (°)	96.005 (2)
V (Å³)	2685.5 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.32 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.725, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6634, 2375, 2098
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.06
No. of reflections	2375
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
N4—H4B···N3	0.86	2.07	2.749 (2)	136
N4—H4A···O1ⁱ	0.86	2.10	2.930 (2)	161

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

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, J., Su, W., Wu, H., Liu, M. & Jin, C. (2008). Catal. Commun. 9, 785–788. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef IUCr Journals Google Scholar

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doi:10.1107/S1600536809050685

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