N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)formamide

Wang, H.-W.; Yang, M.-M.; Lu, Q.-S.; Li, F.-S.

doi:10.1107/S1600536811015558

organic compounds

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Volume 67| Part 6| June 2011| Page o1310

doi:10.1107/S1600536811015558

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N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)formamide

Hao-Wei Wang,^a Ming-Ming Yang,^a Qi-Sheng Lu ^a and Fang-Shi Li ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fangshi.li@njut.edu.cn

(Received 16 March 2011; accepted 25 April 2011; online 7 May 2011)

In the title compound, C₁₂H₁₃N₃O₂, the dihedral angle between the pyrazole and benzene rings is 50.0 (3)°. In the crystal, molecules are linked by intermolecular N—H⋯O hydrogen bonds to form a three-dimensional network. Two weak C—H⋯π interactions reinforce the crystal packing.

Related literature

For bond-length data, see: Allen et al. (1987 ). For the preparation, see: Hosseini-Sarvari & Sharghi (2006 ).

Experimental

Crystal data

C₁₂H₁₃N₃O₂
M_r = 231.25
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.4220 (17) Å
b = 9.2950 (19) Å
c = 14.501 (3) Å
V = 1135.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.981, T_max = 0.991
2320 measured reflections
2048 independent reflections
1327 reflections with I > 2σ(I)
R_int = 0.088
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.158
S = 1.01
2048 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱ	0.86	2.01	2.864 (5)	172
C10—H10B⋯Cg1ⁱⁱ	0.96	2.85	3.733 (5)	153
C12—H12A⋯Cg1ⁱⁱⁱ	0.93	3.03	3.647 (5)	125
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x-1, y+{\script{3\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x, y+{\script{3\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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/S1600536811015558/bq2288sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015558/bq2288Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015558/bq2288Isup3.cml

checkCIF report

Comment top

The title compound, N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)formamide is an important intermediate for the synthesis of many drugs with antipyretic and analgesic effects. We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. In the crystal, molecules are linked via intermolecular N—H···O hydrogen bond (Table 1) to form a three-dimensional network. The bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the rings C1—C6) and (N1/N2/C7-C9) is 50.0 (3)°.

In the crystal, there are one intermolecular N—H···O hydrogen bond and two C—H···π interactions, one is between the methyl hydrogen and the phenyl ring, and the other is between the aldehyde hydrogen and the phenyl ring. The molecules are linked to each other by the intermolecular hydrogen bonds to form a three-dimensional network, which seem to be very effective in the stabilization of the crystal structure (Fig. 2.).

Related literature top

For bond-length data, see: Allen et al. (1987). For the p reparation, see: Hosseini-Sarvari & Sharghi (2006).

Experimental top

The title compound, (I) was prepared by the reaction of aminoantipyrin and formic acid in the presence of zinc oxide reported in literature (Hosseini-Sarvari & Sharghi, 2006). The crystals were obtained by dissolving (I) (0.2 g) in acetone (25 ml) and evaporating the solvent slowly at room temperature for about 5 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4- yl)formamide top

Crystal data top

C₁₂H₁₃N₃O₂	F(000) = 488
M_r = 231.25	D_x = 1.353 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 8.4220 (17) Å	θ = 9–13°
b = 9.2950 (19) Å	µ = 0.10 mm⁻¹
c = 14.501 (3) Å	T = 293 K
V = 1135.2 (4) Å³	Block, colorless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1327 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.088
Graphite monochromator	θ_max = 25.3°, θ_min = 2.6°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.981, T_max = 0.991	l = −17→17
2320 measured reflections	3 standard reflections every 200 reflections
2048 independent reflections	intensity decay: 1%

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.050P)² + 0.950P] where P = (F_o² + 2F_c²)/3
2048 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₂H₁₃N₃O₂	V = 1135.2 (4) Å³
M_r = 231.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.4220 (17) Å	µ = 0.10 mm⁻¹
b = 9.2950 (19) Å	T = 293 K
c = 14.501 (3) Å	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1327 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.088
T_min = 0.981, T_max = 0.991	3 standard reflections every 200 reflections
2320 measured reflections	intensity decay: 1%
2048 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.01	Δρ_max = 0.19 e Å⁻³
2048 reflections	Δρ_min = −0.25 e Å⁻³
154 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	0.0661 (4)	0.6540 (3)	0.6577 (2)	0.0585 (9)
N1	−0.0044 (4)	0.7935 (4)	0.5315 (2)	0.0464 (9)
C1	−0.0412 (6)	0.5576 (5)	0.4655 (3)	0.0578 (12)
H1A	−0.1048	0.5335	0.5157	0.069*
O2	0.2871 (5)	0.8913 (4)	0.8637 (2)	0.0757 (11)
N2	−0.0004 (5)	0.9417 (4)	0.5102 (2)	0.0524 (10)
C2	−0.0105 (8)	0.4577 (5)	0.3988 (3)	0.0781 (18)
H2A	−0.0536	0.3659	0.4031	0.094*
N3	0.1224 (5)	0.9449 (4)	0.7471 (2)	0.0562 (10)
H3A	0.0730	1.0081	0.7796	0.067*
C3	0.0846 (8)	0.4939 (6)	0.3253 (4)	0.0777 (17)
H3B	0.1059	0.4252	0.2803	0.093*
C4	0.1490 (6)	0.6293 (6)	0.3167 (3)	0.0641 (14)
H4A	0.2137	0.6524	0.2669	0.077*
C5	0.1153 (6)	0.7298 (5)	0.3838 (3)	0.0593 (13)
H5A	0.1556	0.8226	0.3787	0.071*
C6	0.0215 (5)	0.6931 (5)	0.4588 (3)	0.0485 (11)
C7	0.0387 (5)	1.0119 (4)	0.5892 (3)	0.0478 (11)
C8	0.0694 (5)	0.9167 (4)	0.6560 (3)	0.0425 (10)
C9	0.0471 (5)	0.7744 (5)	0.6213 (3)	0.0480 (11)
C10	−0.1189 (6)	0.9958 (5)	0.4451 (3)	0.0610 (13)
H10A	−0.1081	1.0982	0.4393	0.091*
H10B	−0.2234	0.9731	0.4673	0.091*
H10C	−0.1030	0.9515	0.3860	0.091*
C11	0.0424 (7)	1.1725 (5)	0.5918 (3)	0.0712 (16)
H11A	0.0750	1.2039	0.6519	0.107*
H11B	−0.0615	1.2095	0.5785	0.107*
H11C	0.1163	1.2073	0.5465	0.107*
C12	0.2435 (6)	0.8781 (5)	0.7834 (3)	0.0592 (12)
H12A	0.3008	0.8160	0.7457	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.073 (2)	0.0519 (19)	0.0506 (18)	−0.0047 (16)	−0.0022 (16)	0.0143 (15)
N1	0.056 (2)	0.045 (2)	0.0383 (18)	−0.0037 (18)	0.0060 (16)	0.0059 (16)
C1	0.069 (3)	0.053 (3)	0.051 (3)	−0.012 (3)	−0.004 (2)	0.006 (2)
O2	0.087 (3)	0.080 (2)	0.060 (2)	−0.009 (2)	−0.0133 (19)	−0.0047 (19)
N2	0.071 (3)	0.0441 (19)	0.0423 (19)	0.011 (2)	−0.0070 (18)	0.0030 (17)
C2	0.127 (5)	0.051 (3)	0.057 (3)	−0.010 (3)	−0.021 (3)	0.000 (3)
N3	0.069 (3)	0.054 (2)	0.046 (2)	0.010 (2)	0.0007 (19)	−0.0117 (19)
C3	0.119 (5)	0.063 (3)	0.052 (3)	0.024 (4)	−0.016 (3)	−0.014 (3)
C4	0.060 (3)	0.087 (4)	0.045 (3)	0.006 (3)	0.007 (2)	−0.005 (3)
C5	0.067 (3)	0.064 (3)	0.047 (3)	−0.008 (3)	0.010 (2)	−0.001 (2)
C6	0.050 (3)	0.053 (3)	0.042 (2)	0.000 (2)	−0.004 (2)	−0.003 (2)
C7	0.050 (3)	0.046 (2)	0.047 (3)	0.003 (2)	−0.005 (2)	−0.001 (2)
C8	0.039 (2)	0.046 (2)	0.042 (2)	−0.0001 (19)	0.0031 (18)	−0.005 (2)
C9	0.044 (3)	0.061 (3)	0.039 (2)	−0.001 (2)	0.0013 (19)	0.004 (2)
C10	0.071 (3)	0.062 (3)	0.050 (3)	0.006 (3)	0.001 (2)	0.010 (2)
C11	0.101 (5)	0.048 (3)	0.065 (3)	0.000 (3)	−0.009 (3)	−0.007 (2)
C12	0.059 (3)	0.057 (3)	0.062 (3)	−0.004 (3)	−0.002 (3)	−0.003 (3)

Geometric parameters (Å, º) top

O1—C9	1.248 (5)	C3—H3B	0.9300
N1—C9	1.384 (5)	C4—C5	1.379 (6)
N1—N2	1.412 (5)	C4—H4A	0.9300
N1—C6	1.424 (5)	C5—C6	1.387 (6)
C1—C2	1.365 (6)	C5—H5A	0.9300
C1—C6	1.369 (6)	C7—C8	1.338 (5)
C1—H1A	0.9300	C7—C11	1.493 (6)
O2—C12	1.228 (5)	C8—C9	1.427 (6)
N2—C7	1.359 (5)	C10—H10A	0.9600
N2—C10	1.463 (5)	C10—H10B	0.9600
C2—C3	1.375 (8)	C10—H10C	0.9600
C2—H2A	0.9300	C11—H11A	0.9600
N3—C12	1.305 (6)	C11—H11B	0.9600
N3—C8	1.419 (5)	C11—H11C	0.9600
N3—H3A	0.8600	C12—H12A	0.9300
C3—C4	1.376 (7)

C9—N1—N2	108.9 (3)	C5—C6—N1	120.4 (4)
C9—N1—C6	124.3 (3)	C8—C7—N2	109.8 (4)
N2—N1—C6	118.3 (3)	C8—C7—C11	129.7 (4)
C2—C1—C6	120.1 (5)	N2—C7—C11	120.4 (4)
C2—C1—H1A	119.9	C7—C8—N3	127.8 (4)
C6—C1—H1A	119.9	C7—C8—C9	109.4 (4)
C7—N2—N1	106.9 (3)	N3—C8—C9	122.7 (4)
C7—N2—C10	123.0 (4)	O1—C9—N1	123.6 (4)
N1—N2—C10	117.4 (4)	O1—C9—C8	131.7 (4)
C1—C2—C3	119.6 (5)	N1—C9—C8	104.7 (4)
C1—C2—H2A	120.2	N2—C10—H10A	109.5
C3—C2—H2A	120.2	N2—C10—H10B	109.5
C12—N3—C8	122.2 (4)	H10A—C10—H10B	109.5
C12—N3—H3A	118.9	N2—C10—H10C	109.5
C8—N3—H3A	118.9	H10A—C10—H10C	109.5
C2—C3—C4	121.6 (5)	H10B—C10—H10C	109.5
C2—C3—H3B	119.2	C7—C11—H11A	109.5
C4—C3—H3B	119.2	C7—C11—H11B	109.5
C3—C4—C5	118.3 (5)	H11A—C11—H11B	109.5
C3—C4—H4A	120.8	C7—C11—H11C	109.5
C5—C4—H4A	120.8	H11A—C11—H11C	109.5
C4—C5—C6	120.3 (5)	H11B—C11—H11C	109.5
C4—C5—H5A	119.8	O2—C12—N3	124.7 (5)
C6—C5—H5A	119.8	O2—C12—H12A	117.7
C1—C6—C5	120.1 (4)	N3—C12—H12A	117.7
C1—C6—N1	119.4 (4)

C9—N1—N2—C7	−5.6 (5)	N1—N2—C7—C11	−175.9 (4)
C6—N1—N2—C7	−155.0 (4)	C10—N2—C7—C11	−35.6 (7)
C9—N1—N2—C10	−148.5 (4)	N2—C7—C8—N3	176.4 (4)
C6—N1—N2—C10	62.1 (5)	C11—C7—C8—N3	−3.6 (8)
C6—C1—C2—C3	0.5 (8)	N2—C7—C8—C9	−1.2 (5)
C1—C2—C3—C4	−0.5 (9)	C11—C7—C8—C9	178.8 (5)
C2—C3—C4—C5	−0.4 (8)	C12—N3—C8—C7	−130.2 (5)
C3—C4—C5—C6	1.4 (7)	C12—N3—C8—C9	47.1 (6)
C2—C1—C6—C5	0.5 (7)	N2—N1—C9—O1	−175.3 (4)
C2—C1—C6—N1	−176.6 (4)	C6—N1—C9—O1	−28.2 (6)
C4—C5—C6—C1	−1.5 (7)	N2—N1—C9—C8	4.8 (4)
C4—C5—C6—N1	175.6 (4)	C6—N1—C9—C8	151.9 (4)
C9—N1—C6—C1	61.7 (6)	C7—C8—C9—O1	177.7 (5)
N2—N1—C6—C1	−154.0 (4)	N3—C8—C9—O1	0.0 (7)
C9—N1—C6—C5	−115.4 (5)	C7—C8—C9—N1	−2.3 (5)
N2—N1—C6—C5	28.9 (6)	N3—C8—C9—N1	180.0 (4)
N1—N2—C7—C8	4.1 (5)	C8—N3—C12—O2	−174.8 (4)
C10—N2—C7—C8	144.5 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.86	2.01	2.864 (5)	172
C10—H10B···Cg1ⁱⁱ	0.96	2.85	3.733 (5)	153
C12—H12A···Cg1ⁱⁱⁱ	0.93	3.03	3.647 (5)	125

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x−1, y+3/2, −z+3/2; (iii) −x, y+3/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃N₃O₂
M_r	231.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.4220 (17), 9.2950 (19), 14.501 (3)
V (Å³)	1135.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.981, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2320, 2048, 1327
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.158, 1.01
No. of reflections	2048
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.86	2.01	2.864 (5)	172
C10—H10B···Cg1ⁱⁱ	0.96	2.85	3.733 (5)	153
C12—H12A···Cg1ⁱⁱⁱ	0.93	3.03	3.647 (5)	125

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x−1, y+3/2, −z+3/2; (iii) −x, y+3/2, −z+3/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Hosseini-Sarvari, M. & Sharghi, H. (2006). J. Org. Chem. 71, 6652–6654. Web of Science PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536811015558

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