4-(4-Chloro­phen­yl)-1-methyl-3-trifluoro­methyl-1H-pyrazol-5-amine

Jiang, X.-P.; Ng, S.W.

doi:10.1107/S1600536810032435

organic compounds

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Volume 66| Part 9| September 2010| Page o2336

https://doi.org/10.1107/S1600536810032435

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4-(4-Chlorophenyl)-1-methyl-3-trifluoromethyl-1H-pyrazol-5-amine

Xiao-Ping Jiang ^a and Seik Weng Ng ^b ^*

^aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou, Hunan 425100, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 12 August 2010; accepted 12 August 2010; online 18 August 2010)

The five-membered ring of the title compound, C₁₁H₉ClF₃N₃, is almost planar (r.m.s. deviation = 0.002 Å) and the phenylene ring is aligned at 44.8 (1)°. The N atom of the amino substituent shows a pyramidal geometry and is a hydrogen-bond donor to a Cl atom and to a ring N atom, which together generate a layer motif.

Related literature

For the synthesis of the title compound, see: Coispeau (1977 ); Nishiwaki et al. (1995 ).

Experimental

Crystal data

C₁₁H₉ClF₃N₃
M_r = 275.66
Monoclinic, P 2₁ /c
a = 5.8958 (5) Å
b = 16.8618 (13) Å
c = 12.1087 (10) Å
β = 98.459 (1)°
V = 1190.68 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.40 × 0.40 × 0.20 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.864, T_max = 1.000
5716 measured reflections
2581 independent reflections
1769 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.119
S = 1.02
2581 reflections
172 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯Cl1ⁱ	0.88 (1)	2.65 (2)	3.413 (2)	146 (2)
N3—H2⋯N2ⁱⁱ	0.88 (1)	2.54 (2)	3.180 (3)	130 (2)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810032435/hg2700sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032435/hg2700Isup2.hkl

checkCIF report

Comment top

The title compound (Scheme I) is first mentioned in a synthesis by the cyclocondensation of hydrazines with 4,4,4-trifluoro-2-arylacetoacetonitriles in the context of colorants for polyacrylonitriles (Coispeau, 1977). The structure has been eluciated by carbon-13 NMR spectroscopy (Nishiwaki et al., 1995). We have used a modification of the published procedure to synthesize the compound, which is intended for further study on its pharmaceutical activity. There are no other reports on this compound aside from these studies.

Related literature top

For the synthesis of the title compound, see: Coispeau (1977); Nishiwaki et al. (1995).

Experimental top

Sodium metal (0.35 g, 15 mmol) was dissolved in absolute ethanol (50 ml). To this solution was added 2-(4-chlorophenyl)acetonitrile (1.52 g, 10 mmol) followed by ethyl trifluoroacetate (1.42 g, 10 mmol). The solution was heated for 3 h. The solution was concentrated under vacuum. To the residue was added acetic acid (20 ml) followed by methylhydrazine (0.55 g, 12 mmol). The mixture was stirred for 12 h. The solution was again concentrated under vacuum. The residue was treated with water (30 ml) and the organic compound was extracted with ethyl acetate. The organic phase was washed with saturated sodium bicarbonate (230 ml) and then dried over sodium sulfate. The solvent was removed and the residue was chromatographed on a silica gel column with ethyl acetate:petroleum ether (1:10) as eluant. This gave 2 g (70%) of product as a yellow solid, which was recrystallized from ethyl acetate.

Structure description top

For the synthesis of the title compound, see: Coispeau (1977); Nishiwaki et al. (1995).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₁H₉ClF₃N₃ showing displacement ellipsoids at the 50% probability level. H-atoms are drawn as spheres of arbitrary radius.

4-(4-Chlorophenyl)-1-methyl-3-trifluoromethyl-1H-pyrazol-5-amine top

Crystal data top

C₁₁H₉ClF₃N₃	F(000) = 560
M_r = 275.66	D_x = 1.538 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2152 reflections
a = 5.8958 (5) Å	θ = 2.5–26.6°
b = 16.8618 (13) Å	µ = 0.34 mm⁻¹
c = 12.1087 (10) Å	T = 293 K
β = 98.459 (1)°	Block, yellow
V = 1190.68 (17) Å³	0.40 × 0.40 × 0.20 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	2581 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.864, T_max = 1.000	k = −21→10
5716 measured reflections	l = −15→12

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0629P)² + 0.1525P] where P = (F_o² + 2F_c²)/3
2581 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.32 e Å⁻³
2 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₉ClF₃N₃	V = 1190.68 (17) Å³
M_r = 275.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8958 (5) Å	µ = 0.34 mm⁻¹
b = 16.8618 (13) Å	T = 293 K
c = 12.1087 (10) Å	0.40 × 0.40 × 0.20 mm
β = 98.459 (1)°

Data collection top

Bruker SMART area-detector diffractometer	2581 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1769 reflections with I > 2σ(I)
T_min = 0.864, T_max = 1.000	R_int = 0.029
5716 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.32 e Å⁻³
2581 reflections	Δρ_min = −0.26 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.24293 (10)	0.63048 (3)	0.86611 (5)	0.03743 (19)
F1	0.9033 (3)	0.36727 (9)	0.43732 (12)	0.0619 (5)
F2	0.7674 (3)	0.46344 (8)	0.52371 (12)	0.0503 (4)
F3	0.5700 (3)	0.35880 (11)	0.48636 (14)	0.0685 (5)
N1	1.1139 (3)	0.27925 (10)	0.73828 (14)	0.0272 (4)
N2	1.0499 (3)	0.29559 (10)	0.62838 (14)	0.0292 (4)
N3	1.0445 (3)	0.31883 (12)	0.91929 (16)	0.0314 (4)
H1	0.929 (3)	0.3386 (15)	0.948 (2)	0.054 (8)*
H2	1.087 (4)	0.2714 (8)	0.944 (2)	0.044 (7)*
C1	0.6890 (4)	0.43079 (11)	0.77159 (17)	0.0238 (5)
C2	0.4645 (4)	0.43995 (12)	0.71925 (18)	0.0283 (5)
H2A	0.4060	0.4049	0.6629	0.034*
C3	0.3258 (4)	0.50032 (13)	0.74945 (19)	0.0293 (5)
H3	0.1767	0.5063	0.7129	0.035*
C4	0.4114 (4)	0.55085 (12)	0.83380 (19)	0.0271 (5)
C5	0.6307 (4)	0.54242 (12)	0.89124 (18)	0.0282 (5)
H5	0.6846	0.5763	0.9499	0.034*
C6	0.7681 (4)	0.48252 (12)	0.85957 (18)	0.0266 (5)
H6	0.9161	0.4764	0.8975	0.032*
C7	0.8443 (4)	0.37063 (11)	0.73603 (18)	0.0239 (4)
C8	0.9973 (3)	0.32257 (12)	0.80477 (18)	0.0253 (5)
C9	0.8878 (4)	0.35046 (12)	0.62864 (18)	0.0267 (5)
C10	0.7831 (4)	0.38467 (14)	0.5202 (2)	0.0377 (6)
C11	1.2992 (4)	0.22382 (14)	0.7729 (2)	0.0398 (6)
H11A	1.4002	0.2456	0.8349	0.060*
H11B	1.3831	0.2146	0.7119	0.060*
H11C	1.2369	0.1746	0.7948	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0397 (3)	0.0332 (3)	0.0428 (4)	0.0094 (2)	0.0172 (3)	0.0028 (2)
F1	0.0999 (14)	0.0632 (11)	0.0261 (8)	0.0360 (9)	0.0205 (8)	0.0060 (7)
F2	0.0765 (11)	0.0380 (8)	0.0359 (9)	0.0191 (7)	0.0067 (7)	0.0071 (6)
F3	0.0630 (11)	0.0885 (13)	0.0445 (10)	−0.0080 (9)	−0.0238 (9)	−0.0024 (9)
N1	0.0322 (10)	0.0243 (9)	0.0245 (10)	0.0041 (8)	0.0025 (8)	−0.0016 (7)
N2	0.0370 (11)	0.0260 (9)	0.0242 (10)	−0.0007 (8)	0.0037 (8)	−0.0031 (7)
N3	0.0414 (12)	0.0300 (11)	0.0223 (10)	0.0046 (9)	0.0023 (9)	0.0029 (8)
C1	0.0276 (11)	0.0209 (10)	0.0230 (11)	−0.0014 (8)	0.0040 (9)	0.0029 (8)
C2	0.0305 (12)	0.0269 (11)	0.0273 (12)	−0.0045 (9)	0.0036 (9)	−0.0009 (9)
C3	0.0244 (11)	0.0300 (11)	0.0334 (13)	−0.0007 (9)	0.0039 (9)	0.0074 (9)
C4	0.0304 (12)	0.0221 (10)	0.0316 (12)	0.0037 (9)	0.0139 (10)	0.0055 (9)
C5	0.0333 (12)	0.0274 (11)	0.0243 (11)	−0.0033 (9)	0.0057 (9)	−0.0041 (9)
C6	0.0272 (11)	0.0258 (11)	0.0259 (12)	−0.0005 (9)	0.0007 (9)	−0.0002 (9)
C7	0.0272 (11)	0.0212 (10)	0.0232 (11)	−0.0017 (8)	0.0030 (9)	−0.0003 (8)
C8	0.0283 (11)	0.0205 (10)	0.0271 (12)	−0.0035 (8)	0.0034 (9)	−0.0004 (9)
C9	0.0312 (11)	0.0228 (10)	0.0257 (12)	−0.0028 (9)	0.0026 (9)	−0.0028 (9)
C10	0.0496 (15)	0.0362 (13)	0.0260 (13)	0.0060 (11)	0.0014 (11)	−0.0025 (10)
C11	0.0408 (14)	0.0353 (13)	0.0425 (15)	0.0127 (11)	0.0038 (11)	−0.0030 (11)

Geometric parameters (Å, º) top

Cl1—C4	1.749 (2)	C2—C3	1.388 (3)
F1—C10	1.344 (3)	C2—H2A	0.9300
F2—C10	1.333 (3)	C3—C4	1.368 (3)
F3—C10	1.336 (3)	C3—H3	0.9300
N1—C8	1.348 (3)	C4—C5	1.382 (3)
N1—N2	1.357 (2)	C5—C6	1.384 (3)
N1—C11	1.452 (3)	C5—H5	0.9300
N2—C9	1.331 (3)	C6—H6	0.9300
N3—C8	1.375 (3)	C7—C8	1.394 (3)
N3—H1	0.88 (1)	C7—C9	1.404 (3)
N3—H2	0.88 (1)	C9—C10	1.483 (3)
C1—C2	1.389 (3)	C11—H11A	0.9600
C1—C6	1.402 (3)	C11—H11B	0.9600
C1—C7	1.473 (3)	C11—H11C	0.9600

C8—N1—N2	112.53 (17)	C5—C6—H6	119.3
C8—N1—C11	127.18 (19)	C1—C6—H6	119.3
N2—N1—C11	120.18 (18)	C8—C7—C9	102.82 (18)
C9—N2—N1	103.59 (17)	C8—C7—C1	126.98 (19)
C8—N3—H1	109.5 (19)	C9—C7—C1	130.08 (19)
C8—N3—H2	113.0 (17)	N1—C8—N3	122.16 (19)
H1—N3—H2	114 (2)	N1—C8—C7	107.49 (19)
C2—C1—C6	117.73 (19)	N3—C8—C7	130.2 (2)
C2—C1—C7	122.32 (18)	N2—C9—C7	113.57 (19)
C6—C1—C7	119.94 (19)	N2—C9—C10	118.3 (2)
C3—C2—C1	121.3 (2)	C7—C9—C10	128.1 (2)
C3—C2—H2A	119.3	F2—C10—F3	105.6 (2)
C1—C2—H2A	119.3	F2—C10—F1	106.7 (2)
C4—C3—C2	119.1 (2)	F3—C10—F1	105.95 (19)
C4—C3—H3	120.5	F2—C10—C9	112.43 (19)
C2—C3—H3	120.5	F3—C10—C9	113.2 (2)
C3—C4—C5	121.79 (19)	F1—C10—C9	112.3 (2)
C3—C4—Cl1	119.06 (17)	N1—C11—H11A	109.5
C5—C4—Cl1	119.10 (17)	N1—C11—H11B	109.5
C4—C5—C6	118.5 (2)	H11A—C11—H11B	109.5
C4—C5—H5	120.7	N1—C11—H11C	109.5
C6—C5—H5	120.7	H11A—C11—H11C	109.5
C5—C6—C1	121.4 (2)	H11B—C11—H11C	109.5

C8—N1—N2—C9	−0.4 (2)	N2—N1—C8—C7	0.5 (2)
C11—N1—N2—C9	−176.89 (19)	C11—N1—C8—C7	176.7 (2)
C6—C1—C2—C3	2.8 (3)	C9—C7—C8—N1	−0.3 (2)
C7—C1—C2—C3	−175.81 (19)	C1—C7—C8—N1	−176.80 (19)
C1—C2—C3—C4	−1.1 (3)	C9—C7—C8—N3	175.8 (2)
C2—C3—C4—C5	−1.3 (3)	C1—C7—C8—N3	−0.6 (4)
C2—C3—C4—Cl1	176.15 (16)	N1—N2—C9—C7	0.2 (2)
C3—C4—C5—C6	2.0 (3)	N1—N2—C9—C10	177.86 (18)
Cl1—C4—C5—C6	−175.48 (16)	C8—C7—C9—N2	0.1 (2)
C4—C5—C6—C1	−0.2 (3)	C1—C7—C9—N2	176.4 (2)
C2—C1—C6—C5	−2.1 (3)	C8—C7—C9—C10	−177.3 (2)
C7—C1—C6—C5	176.54 (19)	C1—C7—C9—C10	−1.0 (4)
C2—C1—C7—C8	−138.4 (2)	N2—C9—C10—F2	−134.0 (2)
C6—C1—C7—C8	43.0 (3)	C7—C9—C10—F2	43.3 (3)
C2—C1—C7—C9	46.1 (3)	N2—C9—C10—F3	106.4 (2)
C6—C1—C7—C9	−132.4 (2)	C7—C9—C10—F3	−76.3 (3)
N2—N1—C8—N3	−176.08 (18)	N2—C9—C10—F1	−13.6 (3)
C11—N1—C8—N3	0.1 (3)	C7—C9—C10—F1	163.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···Cl1ⁱ	0.88 (1)	2.65 (2)	3.413 (2)	146 (2)
N3—H2···N2ⁱⁱ	0.88 (1)	2.54 (2)	3.180 (3)	130 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₉ClF₃N₃
M_r	275.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.8958 (5), 16.8618 (13), 12.1087 (10)
β (°)	98.459 (1)
V (Å³)	1190.68 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.40 × 0.40 × 0.20

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.864, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5716, 2581, 1769
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 1.02
No. of reflections	2581
No. of parameters	172
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.26

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···Cl1ⁱ	0.88 (1)	2.65 (2)	3.413 (2)	146 (2)
N3—H2···N2ⁱⁱ	0.88 (1)	2.54 (2)	3.180 (3)	130 (2)

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

Acknowledgements

The authors thank Hunan University of Science and Engineering and the University of Malaya for supporting this study.

References

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