3-Amino-1-phenyl-4-(propan-2-yl­idene)pyrazol-5(4H)-one

Zhao, R.-G.; Lu, J.; Li, J.-K.

doi:10.1107/S1600536807063234

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o84

https://doi.org/10.1107/S1600536807063234

Open

access

3-Amino-1-phenyl-4-(propan-2-ylidene)pyrazol-5(4H)-one

Ren-Gao Zhao,^a Jie Lu ^b and Ji-Kun Li ^a ^*

^aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China, and ^bDepartment of Applied Science and Technology, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: imlijikun@163.com

(Received 23 November 2007; accepted 26 November 2007; online 6 December 2007)

In the title molecule, C₁₂H₁₃N₃O, the phenyl and the pyrazole rings make a dihedral angle of 7.5 (2)°. Intermolecular N—H⋯O hydrogen bonds involving the amino group link the molecules into a three-dimensional framework.

Related literature

For a related structure, see: Wang et al. (2003 ). For applications of pyrazolone derivatives, see: Hodnett et al. (1972 ).

Experimental

Crystal data

C₁₂H₁₃N₃O
M_r = 215.25
Orthorhombic, F d d 2
a = 22.557 (8) Å
b = 26.291 (9) Å
c = 7.528 (3) Å
V = 4465 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 273 (2) K
0.15 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.987, T_max = 0.993
7064 measured reflections
1448 independent reflections
960 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.138
S = 1.03
1448 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.25	3.105 (3)	174
N3—H3B⋯O1ⁱⁱ	0.86	2.32	3.054 (3)	144
C5—H5A⋯O1	0.96	2.20	2.935 (5)	131
C12—H12⋯O1	0.93	2.26	2.882 (4)	124
Symmetry codes: (i) -x+1, -y, z; (ii) $[-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063234/ci2526sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063234/ci2526Isup2.hkl

checkCIF report

Comment top

Pyrazolone derivatives are well known for their applications as analgesics, antipyretics, anti-inflammatory and insecticides (Hodnett & Paul, 1972). Therefore, the study on the derivatives of pyrazolone is the focus of many research groups working in the fields of coordination chemistry, biomedicine and pharmaceutical chemistry. We report here the crystal structure of the title compound.

All geometric parameters in the title molecule (Fig. 1) are in good agreement with those found in N-(1,5-dihydro-1-phenyl-3-methyl-4-benzoyl)-3-chloroaniline (Wang et al., 2003). The benzene and the pyrazole rings make a dihedral angle of 7.5 (2)°. Intermolecular N—H···O hydrogen bonds involving the amino group link the molecules into a three-dimensional framework (Fig. 2).

Related literature top

For a related structure, see: Wang et al. (2003). For applications of pyrazolone derivatives, see: Hodnett et al. (1972).

Experimental top

3-Amino-1-phenyl-5-pyrazolone (0.175 g, 1 mmol) was added to acetone (20 ml), and the mixture was stirred under reflux at 343 K for 6 h. The solution was allowed to cool to room temperature and filtered. Orange crystals suitable for X-ray diffraction study were obtained after 7 d (yield 0.172 g, 80%; m.p. 370–372 K). Analysis found: C 66.90, H 7.02, N 19.48%; C₁₂H₁₃N₃O requires: C 66.96, H 6.09, N 19.52%.

Structure description top

For a related structure, see: Wang et al. (2003). For applications of pyrazolone derivatives, see: Hodnett et al. (1972).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing of the title compound.

3-Amino-1-phenyl-4-(propan-2-ylidene)pyrazol-5(4H)-one top

Crystal data top

C₁₂H₁₃N₃O	F(000) = 1824
M_r = 215.25	D_x = 1.281 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1182 reflections
a = 22.557 (8) Å	θ = 3.0–21.1°
b = 26.291 (9) Å	µ = 0.09 mm⁻¹
c = 7.528 (3) Å	T = 273 K
V = 4465 (3) Å³	Block, orange
Z = 16	0.15 × 0.12 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1448 independent reflections
Radiation source: sealed tube	960 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
φ and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −30→30
T_min = 0.987, T_max = 0.993	k = −35→35
7064 measured reflections	l = −10→10

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0788P)²] where P = (F_o² + 2F_c²)/3
1448 reflections	(Δ/σ)_max = 0.001
147 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₂H₁₃N₃O	V = 4465 (3) Å³
M_r = 215.25	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 22.557 (8) Å	µ = 0.09 mm⁻¹
b = 26.291 (9) Å	T = 273 K
c = 7.528 (3) Å	0.15 × 0.12 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1448 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	960 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.993	R_int = 0.049
7064 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.03	Δρ_max = 0.15 e Å⁻³
1448 reflections	Δρ_min = −0.17 e Å⁻³
147 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	0.42250 (10)	0.19174 (8)	0.4851 (4)	0.0682 (8)
N1	0.48595 (11)	0.12402 (8)	0.4474 (4)	0.0491 (7)
N2	0.48444 (12)	0.07007 (8)	0.4631 (4)	0.0527 (7)
N3	0.41722 (12)	0.00919 (9)	0.5431 (5)	0.0677 (9)
H3A	0.4432	−0.0143	0.5262	0.081*
H3B	0.3821	0.0013	0.5779	0.081*
C1	0.43317 (14)	0.14594 (11)	0.4913 (5)	0.0493 (8)
C2	0.39362 (13)	0.10311 (10)	0.5399 (5)	0.0461 (8)
C3	0.43167 (14)	0.05839 (10)	0.5153 (5)	0.0484 (8)
C4	0.33718 (14)	0.10759 (11)	0.5946 (5)	0.0496 (8)
C5	0.30732 (16)	0.15770 (12)	0.6224 (6)	0.0622 (10)
H5A	0.3365	0.1842	0.6240	0.093*
H5B	0.2865	0.1573	0.7335	0.093*
H5C	0.2798	0.1637	0.5275	0.093*
C6	0.29806 (16)	0.06265 (13)	0.6325 (7)	0.0685 (12)
H6A	0.2930	0.0431	0.5260	0.103*
H6B	0.2601	0.0743	0.6733	0.103*
H6C	0.3161	0.0419	0.7224	0.103*
C7	0.53990 (13)	0.14704 (11)	0.3951 (5)	0.0471 (7)
C8	0.58725 (15)	0.11694 (14)	0.3435 (5)	0.0605 (9)
H8	0.5833	0.0817	0.3398	0.073*
C9	0.64021 (17)	0.13950 (15)	0.2978 (6)	0.0740 (12)
H9	0.6719	0.1192	0.2633	0.089*
C10	0.64711 (18)	0.19102 (16)	0.3021 (7)	0.0776 (12)
H10	0.6831	0.2058	0.2707	0.093*
C11	0.60048 (16)	0.22050 (14)	0.3530 (7)	0.0731 (12)
H11	0.6049	0.2557	0.3554	0.088*
C12	0.54684 (16)	0.19944 (13)	0.4011 (6)	0.0605 (10)
H12	0.5156	0.2201	0.4371	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0507 (13)	0.0357 (12)	0.118 (2)	0.0070 (9)	0.0051 (14)	0.0085 (12)
N1	0.0397 (14)	0.0350 (12)	0.0728 (19)	0.0038 (10)	−0.0001 (12)	0.0076 (13)
N2	0.0485 (15)	0.0354 (12)	0.074 (2)	0.0030 (11)	0.0015 (14)	0.0035 (13)
N3	0.0574 (17)	0.0351 (14)	0.111 (3)	0.0070 (12)	0.0143 (18)	0.0088 (15)
C1	0.0438 (17)	0.0390 (16)	0.065 (2)	0.0028 (12)	−0.0009 (16)	0.0060 (14)
C2	0.0464 (17)	0.0345 (14)	0.057 (2)	0.0027 (13)	−0.0045 (15)	0.0042 (14)
C3	0.0477 (18)	0.0341 (15)	0.063 (2)	0.0035 (12)	0.0000 (16)	0.0032 (14)
C4	0.0442 (18)	0.0455 (17)	0.059 (2)	0.0041 (13)	0.0001 (15)	0.0060 (14)
C5	0.053 (2)	0.053 (2)	0.081 (3)	0.0102 (15)	0.006 (2)	0.0052 (18)
C6	0.051 (2)	0.055 (2)	0.099 (3)	−0.0012 (15)	0.012 (2)	0.012 (2)
C7	0.0413 (17)	0.0493 (17)	0.0508 (19)	0.0001 (13)	−0.0011 (15)	0.0080 (16)
C8	0.056 (2)	0.0558 (19)	0.070 (3)	0.0046 (16)	0.0082 (19)	0.0041 (17)
C9	0.052 (2)	0.081 (3)	0.090 (3)	0.004 (2)	0.023 (2)	0.008 (2)
C10	0.053 (2)	0.082 (3)	0.098 (3)	−0.0153 (19)	0.016 (2)	0.009 (2)
C11	0.061 (2)	0.057 (2)	0.101 (3)	−0.0129 (17)	0.006 (2)	0.009 (2)
C12	0.052 (2)	0.0498 (19)	0.080 (3)	0.0001 (14)	0.0046 (18)	0.0082 (18)

Geometric parameters (Å, º) top

O1—C1	1.229 (3)	C5—H5C	0.96
N1—C1	1.363 (4)	C6—H6A	0.96
N1—C7	1.415 (4)	C6—H6B	0.96
N1—N2	1.424 (3)	C6—H6C	0.96
N2—C3	1.290 (4)	C7—C8	1.385 (5)
N3—C3	1.350 (4)	C7—C12	1.387 (4)
N3—H3A	0.86	C8—C9	1.377 (5)
N3—H3B	0.86	C8—H8	0.93
C1—C2	1.482 (4)	C9—C10	1.364 (5)
C2—C4	1.343 (4)	C9—H9	0.93
C2—C3	1.468 (4)	C10—C11	1.362 (6)
C4—C5	1.494 (4)	C10—H10	0.93
C4—C6	1.502 (5)	C11—C12	1.379 (5)
C5—H5A	0.96	C11—H11	0.93
C5—H5B	0.96	C12—H12	0.93

C1—N1—C7	129.6 (2)	C4—C6—H6A	109.5
C1—N1—N2	112.3 (2)	C4—C6—H6B	109.5
C7—N1—N2	118.0 (2)	H6A—C6—H6B	109.5
C3—N2—N1	106.5 (2)	C4—C6—H6C	109.5
C3—N3—H3A	120.0	H6A—C6—H6C	109.5
C3—N3—H3B	120.0	H6B—C6—H6C	109.5
H3A—N3—H3B	120.0	C8—C7—C12	119.3 (3)
O1—C1—N1	125.2 (3)	C8—C7—N1	119.8 (3)
O1—C1—C2	129.5 (3)	C12—C7—N1	120.8 (3)
N1—C1—C2	105.3 (2)	C9—C8—C7	119.5 (3)
C4—C2—C3	131.6 (3)	C9—C8—H8	120.2
C4—C2—C1	125.4 (3)	C7—C8—H8	120.2
C3—C2—C1	103.0 (3)	C10—C9—C8	121.4 (3)
N2—C3—N3	119.9 (3)	C10—C9—H9	119.3
N2—C3—C2	112.8 (2)	C8—C9—H9	119.3
N3—C3—C2	127.3 (3)	C11—C10—C9	118.9 (3)
C2—C4—C5	123.2 (3)	C11—C10—H10	120.5
C2—C4—C6	123.1 (3)	C9—C10—H10	120.5
C5—C4—C6	113.7 (3)	C10—C11—C12	121.5 (4)
C4—C5—H5A	109.5	C10—C11—H11	119.2
C4—C5—H5B	109.5	C12—C11—H11	119.2
H5A—C5—H5B	109.5	C11—C12—C7	119.3 (3)
C4—C5—H5C	109.5	C11—C12—H12	120.4
H5A—C5—H5C	109.5	C7—C12—H12	120.4
H5B—C5—H5C	109.5

C1—N1—N2—C3	0.2 (4)	C3—C2—C4—C5	175.8 (4)
C7—N1—N2—C3	178.7 (3)	C1—C2—C4—C5	−3.1 (5)
C7—N1—C1—O1	3.4 (6)	C3—C2—C4—C6	−4.6 (6)
N2—N1—C1—O1	−178.3 (3)	C1—C2—C4—C6	176.5 (4)
C7—N1—C1—C2	−178.3 (3)	C1—N1—C7—C8	−175.2 (4)
N2—N1—C1—C2	0.0 (4)	N2—N1—C7—C8	6.5 (5)
O1—C1—C2—C4	−2.8 (6)	C1—N1—C7—C12	7.3 (6)
N1—C1—C2—C4	179.0 (3)	N2—N1—C7—C12	−171.0 (3)
O1—C1—C2—C3	178.0 (4)	C12—C7—C8—C9	−0.5 (6)
N1—C1—C2—C3	−0.2 (4)	N1—C7—C8—C9	−178.1 (4)
N1—N2—C3—N3	−179.5 (3)	C7—C8—C9—C10	0.0 (7)
N1—N2—C3—C2	−0.3 (4)	C8—C9—C10—C11	0.1 (8)
C4—C2—C3—N2	−178.8 (4)	C9—C10—C11—C12	0.4 (8)
C1—C2—C3—N2	0.3 (4)	C10—C11—C12—C7	−0.9 (7)
C4—C2—C3—N3	0.3 (6)	C8—C7—C12—C11	1.0 (6)
C1—C2—C3—N3	179.4 (3)	N1—C7—C12—C11	178.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.25	3.105 (3)	174
N3—H3B···O1ⁱⁱ	0.86	2.32	3.054 (3)	144
C5—H5A···O1	0.96	2.20	2.935 (5)	131
C12—H12···O1	0.93	2.26	2.882 (4)	124

Symmetry codes: (i) −x+1, −y, z; (ii) −x+3/4, y−1/4, z+1/4.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃N₃O
M_r	215.25
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	273
a, b, c (Å)	22.557 (8), 26.291 (9), 7.528 (3)
V (Å³)	4465 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.15 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.987, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	7064, 1448, 960
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.138, 1.03
No. of reflections	1448
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.25	3.105 (3)	174
N3—H3B···O1ⁱⁱ	0.86	2.32	3.054 (3)	144
C5—H5A···O1	0.96	2.20	2.935 (5)	131
C12—H12···O1	0.93	2.26	2.882 (4)	124

Symmetry codes: (i) −x+1, −y, z; (ii) −x+3/4, y−1/4, z+1/4.

Acknowledgements

The authors thank the Postgraduate Foundation of Taishan University (grant No. Y06–2–12) for financial support.

References

Hodnett, E. M. & Paul, D. M. (1972). J. Med. Chem. 15, 339–341. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Wang, J. L., Yang, Y., Zhang, X. & Miao, F. M. (2003). Chin. J. Struct. Chem. 22, 677–680. CAS Google Scholar