5-Amino-1-(4-nitro­phen­yl)-1H-pyrazole-3-carbonitrile

Jiang, Q.-H.; He, Q.; Zhang, J.-Q.; Yang, Y.; Wan, R.

doi:10.1107/S1600536811052147

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o65

doi:10.1107/S1600536811052147

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5-Amino-1-(4-nitrophenyl)-1H-pyrazole-3-carbonitrile

Qiang-Hua Jiang,^a Qiu He,^a Jian-Qiang Zhang,^a Yang Yang ^a and Rong Wan ^a ^*

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

(Received 23 November 2011; accepted 3 December 2011; online 10 December 2011)

The title compound, C₁₀H₇N₅O₂, was synthesized by the reaction of 4-nitroaniline and 2,3-dicyanopropionic acid ethyl ester. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds link the molecules, forming a three-dimensional network.

Related literature

N-pyrazole derivatives are of great interest because of their chemical and pharmaceutical properties, see: Cheng et al. (2008 ). They also exhibit diverse biological activity such as insecticidal (Zhao et al., 2010 ) and antifungal activities (Liu et al., 2010 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₇N₅O₂
M_r = 229.21
Monoclinic, C c
a = 3.7685 (2) Å
b = 27.3441 (17) Å
c = 10.1294 (8) Å
β = 96.20 (3)°
V = 1037.70 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.10 mm

Data collection

Enaf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.968, T_max = 0.989
2148 measured reflections
951 independent reflections
856 reflections with I > 2σ(I)
R_int = 0.071
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.123
S = 1.00
951 reflections
155 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O2ⁱ	0.86	2.53	3.335 (5)	156
C4—H4A⋯O1ⁱⁱ	0.93	2.52	3.216 (5)	132
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[x-1, -y, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811052147/hg5146sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052147/hg5146Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052147/hg5146Isup3.cml

checkCIF report

Comment top

In a variety of biological heterocyclic compounds, N-pyrazole derivatives are of great interest because of their chemical and pharmaceutical properties (Cheng et al., 2008). These compounds are known to exhibit diverse biological activities, such as insecticidal (Zhao et al., 2010) and antifungal activities (Liu et al., 2010).

Here we report the crystal structure of the title compound,(I). In the molecule of the title compound (Fig.1),the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A(C1—C6),B(N2/N3/C9/C8/C7) are, of course, planar. The dihedral angle between them is A/B = 34.3 (1) Å. In the crystal structure, intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) link the molecules to form a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

N-pyrazole derivatives are of great interest because of their chemical and pharmaceutical properties, see: Cheng et al. (2008). They also exhibit diverse biological activities, such as insecticidal (Zhao et al., 2010) and antifungal activities (Liu et al., 2010). For bond-length data, see: Allen et al. (1987).

Experimental top

Sodium nitrite(1.49 g) was dissolved 10 ml water, then the solution was added dropwise to a mixture of 4-nitrophenylamino (0.02 mol) and 36.5% aq. HCl(5 ml) at 0–5°C. After the addition, the above reaction mixture was stirred for 10 min at 0–5°C. 2,3-Dicyano-propionic acid ethyl ester (0.02 mol) was added dropwise and stirred for 2 hr at room temperature. The reaction mixture was extracted with dichloromethane and the pH was adjusted to 9 with ammonia. The aqueous layer was removed and the organic layer was dried over anhydrous Na₂SO₄, concentrated and precipitated. The pure compound (I) was obtained by recrystallization from ethanol. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram for (I). Hydrogen bonds are shown as dashed lines.

5-Amino-1-(4-nitrophenyl)-1H-pyrazole-3-carbonitrile top

Crystal data top

C₁₀H₇N₅O₂	F(000) = 472
M_r = 229.21	D_x = 1.467 Mg m⁻³
Monoclinic, Cc	Melting point = 498–501 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 3.7685 (2) Å	Cell parameters from 25 reflections
b = 27.3441 (17) Å	θ = 9–13°
c = 10.1294 (8) Å	µ = 0.11 mm⁻¹
β = 96.20 (3)°	T = 293 K
V = 1037.70 (12) Å³	Block, yellow
Z = 4	0.30 × 0.30 × 0.10 mm

Data collection top

Enaf–Nonius CAD-4 diffractometer	856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.071
Graphite monochromator	θ_max = 25.4°, θ_min = 2.5°
ω/2θ scans	h = 0→4
Absorption correction: ψ scan (North et al., 1968)	k = −32→32
T_min = 0.968, T_max = 0.989	l = −12→12
2148 measured reflections	3 standard reflections every 200 reflections
951 independent reflections	intensity decay: 1%

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.093P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
951 reflections	Δρ_max = 0.26 e Å⁻³
155 parameters	Δρ_min = −0.31 e Å⁻³
2 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: 0.017 (6)

Crystal data top

C₁₀H₇N₅O₂	V = 1037.70 (12) Å³
M_r = 229.21	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 3.7685 (2) Å	µ = 0.11 mm⁻¹
b = 27.3441 (17) Å	T = 293 K
c = 10.1294 (8) Å	0.30 × 0.30 × 0.10 mm
β = 96.20 (3)°

Data collection top

Enaf–Nonius CAD-4 diffractometer	856 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.071
T_min = 0.968, T_max = 0.989	3 standard reflections every 200 reflections
2148 measured reflections	intensity decay: 1%
951 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	2 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
951 reflections	Δρ_min = −0.31 e Å⁻³
155 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
C1	0.6000 (9)	0.14112 (13)	0.7685 (3)	0.0345 (8)
H1A	0.6497	0.1737	0.7890	0.041*
N1	0.7783 (9)	0.01800 (13)	0.9127 (4)	0.0495 (9)
O1	0.9593 (11)	0.02857 (14)	1.0134 (4)	0.0782 (13)
N2	0.2632 (8)	0.16762 (10)	0.5653 (3)	0.0343 (7)
C2	0.7254 (10)	0.10486 (14)	0.8562 (4)	0.0370 (8)
H2A	0.8616	0.1124	0.9357	0.044*
O2	0.6973 (13)	−0.02441 (11)	0.8819 (4)	0.0763 (12)
C3	0.6406 (9)	0.05648 (13)	0.8214 (3)	0.0347 (8)
N3	0.1670 (9)	0.21026 (11)	0.6233 (3)	0.0362 (7)
C4	0.4432 (9)	0.04433 (12)	0.7061 (4)	0.0361 (8)
H4A	0.3940	0.0117	0.6858	0.043*
N4	0.2620 (12)	0.13064 (12)	0.3498 (3)	0.0517 (9)
H4B	0.3581	0.1043	0.3834	0.062*
H4C	0.2109	0.1331	0.2652	0.062*
C5	0.3155 (9)	0.08073 (14)	0.6189 (3)	0.0353 (8)
H5A	0.1748	0.0731	0.5405	0.042*
N5	−0.2189 (12)	0.32149 (13)	0.5701 (4)	0.0571 (10)
C6	0.4020 (9)	0.12921 (12)	0.6510 (4)	0.0316 (7)
C7	0.1906 (10)	0.16856 (13)	0.4306 (4)	0.0367 (8)
C8	0.0411 (12)	0.21334 (14)	0.3985 (4)	0.0412 (8)
H8A	−0.0359	0.2255	0.3146	0.049*
C9	0.0310 (9)	0.23653 (12)	0.5213 (4)	0.0347 (8)
C10	−0.1059 (10)	0.28392 (14)	0.5470 (4)	0.0411 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0409 (17)	0.0288 (16)	0.0351 (16)	−0.0030 (14)	0.0102 (15)	−0.0032 (14)
N1	0.050 (2)	0.0475 (19)	0.053 (2)	0.0072 (16)	0.0127 (18)	0.0160 (16)
O1	0.094 (3)	0.070 (2)	0.065 (2)	0.005 (2)	−0.021 (2)	0.0227 (19)
N2	0.0461 (16)	0.0256 (14)	0.0317 (14)	0.0020 (13)	0.0072 (12)	0.0000 (12)
C2	0.0424 (18)	0.0389 (18)	0.0305 (16)	0.0005 (16)	0.0073 (14)	0.0026 (14)
O2	0.111 (3)	0.0379 (17)	0.079 (2)	0.0041 (19)	0.010 (2)	0.0194 (16)
C3	0.0330 (17)	0.0337 (17)	0.0394 (17)	0.0046 (15)	0.0129 (15)	0.0066 (15)
N3	0.0488 (17)	0.0255 (14)	0.0357 (15)	0.0032 (12)	0.0108 (13)	−0.0018 (10)
C4	0.0400 (19)	0.0275 (17)	0.0427 (18)	0.0031 (14)	0.0135 (16)	0.0008 (14)
N4	0.090 (3)	0.0352 (16)	0.0300 (14)	0.0101 (17)	0.0084 (16)	−0.0028 (12)
C5	0.0416 (19)	0.0306 (18)	0.0340 (17)	−0.0001 (14)	0.0053 (15)	−0.0029 (12)
N5	0.080 (3)	0.0384 (18)	0.055 (2)	0.0178 (19)	0.0208 (19)	0.0037 (16)
C6	0.0351 (16)	0.0261 (15)	0.0360 (17)	0.0022 (14)	0.0145 (14)	0.0033 (13)
C7	0.0441 (19)	0.0337 (17)	0.0332 (16)	−0.0010 (15)	0.0091 (15)	0.0011 (14)
C8	0.050 (2)	0.0407 (18)	0.0330 (17)	0.0015 (16)	0.0047 (15)	0.0086 (14)
C9	0.0379 (18)	0.0289 (17)	0.0383 (17)	0.0014 (15)	0.0090 (14)	0.0023 (13)
C10	0.049 (2)	0.036 (2)	0.0410 (19)	0.0059 (17)	0.0150 (17)	0.0075 (15)

Geometric parameters (Å, º) top

C1—C6	1.374 (5)	C4—C5	1.382 (5)
C1—C2	1.381 (5)	C4—H4A	0.9300
C1—H1A	0.9300	N4—C7	1.366 (5)
N1—O1	1.199 (5)	N4—H4B	0.8600
N1—O2	1.231 (5)	N4—H4C	0.8600
N1—C3	1.459 (5)	C5—C6	1.395 (5)
N2—C7	1.363 (5)	C5—H5A	0.9300
N2—N3	1.371 (4)	N5—C10	1.146 (5)
N2—C6	1.425 (4)	C7—C8	1.372 (5)
C2—C3	1.397 (5)	C8—C9	1.400 (5)
C2—H2A	0.9300	C8—H8A	0.9300
C3—C4	1.357 (5)	C9—C10	1.429 (5)
N3—C9	1.316 (5)

C6—C1—C2	120.2 (3)	C7—N4—H4B	120.0
C6—C1—H1A	119.9	C7—N4—H4C	120.0
C2—C1—H1A	119.9	H4B—N4—H4C	120.0
O1—N1—O2	123.1 (4)	C4—C5—C6	118.6 (3)
O1—N1—C3	119.7 (4)	C4—C5—H5A	120.7
O2—N1—C3	117.2 (4)	C6—C5—H5A	120.7
C7—N2—N3	112.3 (3)	C1—C6—C5	121.2 (3)
C7—N2—C6	130.1 (3)	C1—C6—N2	118.8 (3)
N3—N2—C6	117.6 (3)	C5—C6—N2	119.8 (3)
C1—C2—C3	117.7 (3)	N2—C7—N4	123.7 (3)
C1—C2—H2A	121.2	N2—C7—C8	106.7 (3)
C3—C2—H2A	121.2	N4—C7—C8	129.6 (4)
C4—C3—C2	122.6 (3)	C7—C8—C9	104.1 (3)
C4—C3—N1	119.6 (3)	C7—C8—H8A	128.0
C2—C3—N1	117.8 (3)	C9—C8—H8A	128.0
C9—N3—N2	103.1 (3)	N3—C9—C8	113.9 (3)
C3—C4—C5	119.6 (3)	N3—C9—C10	118.0 (3)
C3—C4—H4A	120.2	C8—C9—C10	128.2 (3)
C5—C4—H4A	120.2	N5—C10—C9	178.4 (4)

C6—C1—C2—C3	−0.6 (5)	C4—C5—C6—N2	−177.7 (3)
C1—C2—C3—C4	0.1 (5)	C7—N2—C6—C1	150.6 (4)
C1—C2—C3—N1	178.9 (3)	N3—N2—C6—C1	−33.0 (5)
O1—N1—C3—C4	178.4 (4)	C7—N2—C6—C5	−33.7 (6)
O2—N1—C3—C4	−2.3 (5)	N3—N2—C6—C5	142.6 (3)
O1—N1—C3—C2	−0.4 (5)	N3—N2—C7—N4	179.8 (4)
O2—N1—C3—C2	178.9 (4)	C6—N2—C7—N4	−3.7 (6)
C7—N2—N3—C9	0.8 (4)	N3—N2—C7—C8	−0.1 (4)
C6—N2—N3—C9	−176.1 (3)	C6—N2—C7—C8	176.4 (4)
C2—C3—C4—C5	−0.7 (5)	N2—C7—C8—C9	−0.7 (4)
N1—C3—C4—C5	−179.4 (3)	N4—C7—C8—C9	179.4 (4)
C3—C4—C5—C6	1.6 (5)	N2—N3—C9—C8	−1.3 (4)
C2—C1—C6—C5	1.6 (5)	N2—N3—C9—C10	178.7 (3)
C2—C1—C6—N2	177.2 (3)	C7—C8—C9—N3	1.3 (5)
C4—C5—C6—C1	−2.1 (5)	C7—C8—C9—C10	−178.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O2ⁱ	0.86	2.53	3.335 (5)	156
C4—H4A···O1ⁱⁱ	0.93	2.52	3.216 (5)	132

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

Experimental details

Crystal data
Chemical formula	C₁₀H₇N₅O₂
M_r	229.21
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	3.7685 (2), 27.3441 (17), 10.1294 (8)
β (°)	96.20 (3)
V (Å³)	1037.70 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Enaf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.968, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	2148, 951, 856
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.123, 1.00
No. of reflections	951
No. of parameters	155
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.31

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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···O2ⁱ	0.8600	2.5300	3.335 (5)	156.00
C4—H4A···O1ⁱⁱ	0.9300	2.5200	3.216 (5)	132.00

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

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for the use of the diffractometer for this research project.

References

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