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

Abstract

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,

• a = 22.557 (8) Å

• b = 26.291 (9) Å

• c = 7.528 (3) Å

• V = 4465 (3) ų

• 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[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

H atoms were positioned geometrically (C—H = 0.93 - 0.96 Å and N—H = 0.86 Å) and refined as riding, with U_iso(H) = 1.5U_eq(C_methyl) and U_iso(H) = 1.2U_eq(N and C_aromatic). In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

Figures

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.

Crystal data

C12H13N3O	F000 = 1824
Mr = 215.25	Dx = 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 = 3.0–21.1º
b = 26.291 (9) Å	µ = 0.09 mm−1
c = 7.528 (3) Å	T = 273 (2) K
V = 4465 (3) Å3	Block, orange
Z = 16	0.15 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1448 independent reflections
Radiation source: sealed tube	960 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.049
T = 273(2) K	θmax = 28.3º
φ and ω scans	θmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −30→30
Tmin = 0.987, Tmax = 0.993	k = −35→35
7064 measured reflections	l = −10→10

Refinement

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)] = 0.049	H-atom parameters constrained
wR(F2) = 0.138	w = 1/[σ2(Fo2) + (0.0788P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
1448 reflections	Δρmax = 0.15 e Å−3
147 parameters	Δρmin = −0.17 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.