5-Chloro-1-phenyl-1H-pyrazol-4-amine

Korzański, A.; Wagner, P.; Kubicki, M.

doi:10.1107/S1600536811032065

organic compounds

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Volume 67| Part 9| September 2011| Page o2320

doi:10.1107/S1600536811032065

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5-Chloro-1-phenyl-1H-pyrazol-4-amine

Artur Korzański,^a Pawel Wagner ^b and Maciej Kubicki ^a ^*

^aDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60–780 Poznań, Poland, and ^bThe ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Innovation Campus, Squires Way, Fairy Meadow, NSW 2519, Australia
^*Correspondence e-mail: mkubicki@amu.edu.pl

(Received 29 July 2011; accepted 8 August 2011; online 11 August 2011)

In the crystal structure of the title compound, C₉H₈ClN₃, amino–pyrazole N—H⋯N hydrogen bonds connect the molecules along the [010] direction; the chains interact with each other only by van der Waals-type interactions. The pyrazole and phenyl rings are inclined at a dihedral angle of 45.65 (6)°

Related literature

For the synthesis, see: Tallec et al. (2000 ). For other 4-aminopyrazoles, see: Infantes et al. (1998 , 1999 ); Schmidt et al. (2001 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₉H₈ClN₃
M_r = 193.63
Monoclinic, P 2₁ /c
a = 3.8926 (6) Å
b = 9.9679 (13) Å
c = 22.617 (2) Å
β = 92.795 (11)°
V = 876.52 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 295 K
0.4 × 0.07 × 0.06 mm

Data collection

Agilent Xcalibur Sapphire2 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.853, T_max = 1.000
5036 measured reflections
1879 independent reflections
1340 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.091
S = 1.02
1879 reflections
132 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯N2ⁱ	0.85 (3)	2.31 (3)	3.144 (3)	169 (3)
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811032065/rk2288sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032065/rk2288Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811032065/rk2288Isup3.cml

checkCIF report

Comment top

In the course of our studies on small heterocyclic ring derivatives we have determined the crystal structure of another member of 1–phenyl–4–amino–5–chloro–pyrazole, I, (Scheme 1). Some crystal structures of 4–aminopyrazoles were also reported, e.g. two polymorphic forms of 4–aminopyrazole (Infantes et al., 1998), 3,5–dimethyl–4–aminopyrazole (Infantes et al., 1999), and 4–amino–3,5–dinitropyrazole and it s dimethylsulfoxide solvate (Schmidt et al., 2001).

The Fig. 1 shows the perspective view of I. Two planar fragments, pyrazole (maximum deviation 0.0025 (12)Å) and phenyl (0.0082 (13)Å) rings are inclined by 45.65 (6)°. This is quite a typical value, for 241 compounds with similar structural fragment (5–substituted pyrazole, non–o–substituted phenyl) found in the Cambridge Structural Database (Allen, 2002; ver. 5.32 of Nov. 2010, last update May 2011) mean value of the twist angle is around 43°, and such is also the median value. The NH₂–group is quite significantly twisted with respect to the pyrazole ring plane, the dihedral angle between two planes is 48 (2)°.

In the crystal structure the relatively weak N4—H41···N2ⁱ hydrogen bonds join 2₁ screw–related molecules into the C(5) chains along y–direction. Symmetry code: (i) -x, y-1/2, -z+1/2. There are no other specific interactions, so apparently the chains are organized into three–dimensional structure by van der Waals forces.

Related literature top

For the synthesis, see: Tallec et al. (2000). For other 4-aminopyrazoles, see: Infantes et al. (1998, 1999); Schmidt et al. (2001). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The compound was synthesized by electrochemical reduction of 4–nitro–1–phenylpyrazole in diluted hydrochloric acid to corresponding hydroxylamine and its in situ nucleophilic transformation into 5–chloro derivative. The compound was separated from post–reaction mixture with low yield. (Tallec et al., 2000).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of title compound with the atom numbering scheme. The displacement ellipsoids are drawn at 50% probability level. Hydrogen atoms are depicted as spheres of arbitrary radius.
	Fig. 2. The crystal packing as seen along [1 0 0] direction; hydrogen bonds are shown as dashed lines.

5-Chloro-1-phenyl-1H-pyrazol-4-amine top

Crystal data top

C₉H₈ClN₃	F(000) = 400
M_r = 193.63	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1285 reflections
a = 3.8926 (6) Å	θ = 2.0–27.8°
b = 9.9679 (13) Å	µ = 0.39 mm⁻¹
c = 22.617 (2) Å	T = 295 K
β = 92.795 (11)°	Needle, colourless
V = 876.52 (19) Å³	0.4 × 0.07 × 0.06 mm
Z = 4

Data collection top

Agilent Xcalibur Sapphire2 diffractometer	1879 independent reflections
Radiation source: Enhance (Mo) X–ray Source	1340 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 8.1929 pixels mm^-1	θ_max = 27.0°, θ_min = 3.6°
ω scans	h = −4→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −12→12
T_min = 0.853, T_max = 1.000	l = −28→28
5036 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0382P)² + 0.093P] where P = (F_o² + 2F_c²)/3
1879 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₈ClN₃	V = 876.52 (19) Å³
M_r = 193.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8926 (6) Å	µ = 0.39 mm⁻¹
b = 9.9679 (13) Å	T = 295 K
c = 22.617 (2) Å	0.4 × 0.07 × 0.06 mm
β = 92.795 (11)°

Data collection top

Agilent Xcalibur Sapphire2 diffractometer	1879 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1340 reflections with I > 2σ(I)
T_min = 0.853, T_max = 1.000	R_int = 0.035
5036 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.17 e Å⁻³
1879 reflections	Δρ_min = −0.21 e Å⁻³
132 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.2024 (4)	1.05610 (15)	0.15336 (6)	0.0333 (4)
C11	0.2744 (4)	1.17917 (18)	0.12513 (8)	0.0323 (4)
C12	0.1587 (5)	1.2018 (2)	0.06707 (8)	0.0398 (5)
H12	0.0415	1.1350	0.0457	0.043 (6)*
C13	0.2187 (5)	1.3236 (2)	0.04152 (9)	0.0476 (5)
H13	0.1442	1.3391	0.0024	0.070 (7)*
C14	0.3879 (5)	1.4228 (2)	0.07319 (10)	0.0497 (6)
H14	0.4254	1.5056	0.0558	0.060 (7)*
C15	0.5023 (5)	1.3995 (2)	0.13093 (9)	0.0457 (5)
H15	0.6165	1.4670	0.1524	0.046 (6)*
C16	0.4486 (5)	1.27721 (19)	0.15698 (8)	0.0377 (4)
H16	0.5292	1.2610	0.1957	0.039 (5)*
N2	0.0761 (4)	1.05812 (17)	0.20821 (6)	0.0400 (4)
C3	0.0204 (5)	0.9308 (2)	0.22098 (8)	0.0414 (5)
H3	−0.0687	0.9022	0.2563	0.057 (6)*
C4	0.1090 (5)	0.8444 (2)	0.17613 (8)	0.0400 (5)
N4	0.0706 (7)	0.7062 (2)	0.17291 (11)	0.0673 (7)
H42	0.231 (7)	0.668 (3)	0.1551 (14)	0.096 (12)*
H41	0.059 (7)	0.670 (3)	0.2067 (13)	0.090 (10)*
C5	0.2237 (5)	0.92795 (19)	0.13352 (7)	0.0343 (4)
Cl5	0.39097 (13)	0.88538 (6)	0.06812 (2)	0.04946 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0408 (8)	0.0330 (9)	0.0265 (7)	0.0010 (7)	0.0052 (7)	−0.0009 (7)
C11	0.0326 (9)	0.0331 (10)	0.0316 (9)	0.0015 (8)	0.0051 (8)	0.0015 (8)
C12	0.0402 (10)	0.0455 (12)	0.0339 (10)	0.0005 (10)	0.0034 (8)	0.0001 (9)
C13	0.0519 (12)	0.0535 (14)	0.0378 (11)	0.0064 (11)	0.0082 (10)	0.0132 (10)
C14	0.0514 (12)	0.0404 (13)	0.0588 (14)	0.0034 (10)	0.0186 (11)	0.0133 (11)
C15	0.0459 (11)	0.0366 (12)	0.0552 (13)	−0.0017 (10)	0.0071 (10)	−0.0038 (10)
C16	0.0392 (10)	0.0368 (11)	0.0370 (10)	0.0032 (9)	0.0016 (8)	−0.0018 (9)
N2	0.0506 (9)	0.0423 (10)	0.0278 (8)	0.0028 (8)	0.0086 (7)	0.0006 (7)
C3	0.0526 (12)	0.0422 (12)	0.0300 (9)	0.0003 (10)	0.0078 (9)	0.0072 (9)
C4	0.0479 (11)	0.0361 (11)	0.0356 (10)	0.0021 (9)	−0.0021 (9)	0.0025 (9)
N4	0.113 (2)	0.0338 (11)	0.0560 (14)	−0.0017 (12)	0.0120 (14)	0.0028 (10)
C5	0.0367 (10)	0.0377 (11)	0.0283 (9)	0.0018 (8)	0.0007 (8)	−0.0021 (8)
Cl5	0.0591 (3)	0.0560 (4)	0.0338 (3)	0.0070 (3)	0.0076 (2)	−0.0094 (2)

Geometric parameters (Å, º) top

N1—N2	1.3566 (19)	C15—C16	1.375 (3)
N1—C5	1.358 (2)	C15—H15	0.9300
N1—C11	1.417 (2)	C16—H16	0.9300
C11—C16	1.373 (2)	N2—C3	1.322 (2)
C11—C12	1.386 (2)	C3—C4	1.387 (3)
C12—C13	1.369 (3)	C3—H3	0.9300
C12—H12	0.9300	C4—C5	1.365 (3)
C13—C14	1.371 (3)	C4—N4	1.387 (3)
C13—H13	0.9300	N4—H42	0.85 (3)
C14—C15	1.379 (3)	N4—H41	0.85 (3)
C14—H14	0.9300	C5—Cl5	1.6988 (18)

N2—N1—C5	110.30 (15)	C14—C15—H15	119.8
N2—N1—C11	119.19 (15)	C11—C16—C15	119.21 (18)
C5—N1—C11	130.45 (15)	C11—C16—H16	120.4
C16—C11—C12	120.69 (17)	C15—C16—H16	120.4
C16—C11—N1	118.89 (15)	C3—N2—N1	104.85 (15)
C12—C11—N1	120.37 (17)	N2—C3—C4	112.76 (17)
C13—C12—C11	119.35 (19)	N2—C3—H3	123.6
C13—C12—H12	120.3	C4—C3—H3	123.6
C11—C12—H12	120.3	C5—C4—C3	103.84 (18)
C12—C13—C14	120.42 (19)	C5—C4—N4	127.4 (2)
C12—C13—H13	119.8	C3—C4—N4	128.7 (2)
C14—C13—H13	119.8	C4—N4—H42	113 (2)
C13—C14—C15	119.9 (2)	C4—N4—H41	113 (2)
C13—C14—H14	120.0	H42—N4—H41	108 (3)
C15—C14—H14	120.0	N1—C5—C4	108.25 (16)
C16—C15—C14	120.4 (2)	N1—C5—Cl5	123.71 (14)
C16—C15—H15	119.8	C4—C5—Cl5	127.94 (16)

N2—N1—C11—C16	45.7 (2)	C11—N1—N2—C3	176.97 (15)
C5—N1—C11—C16	−137.71 (19)	N1—N2—C3—C4	0.4 (2)
N2—N1—C11—C12	−131.79 (18)	N2—C3—C4—C5	−0.4 (2)
C5—N1—C11—C12	44.8 (3)	N2—C3—C4—N4	−176.6 (2)
C16—C11—C12—C13	−0.2 (3)	N2—N1—C5—C4	0.1 (2)
N1—C11—C12—C13	177.24 (16)	C11—N1—C5—C4	−176.81 (17)
C11—C12—C13—C14	−0.8 (3)	N2—N1—C5—Cl5	−176.49 (12)
C12—C13—C14—C15	0.8 (3)	C11—N1—C5—Cl5	6.7 (3)
C13—C14—C15—C16	0.2 (3)	C3—C4—C5—N1	0.2 (2)
C12—C11—C16—C15	1.1 (3)	N4—C4—C5—N1	176.4 (2)
N1—C11—C16—C15	−176.34 (17)	C3—C4—C5—Cl5	176.55 (14)
C14—C15—C16—C11	−1.1 (3)	N4—C4—C5—Cl5	−7.2 (3)
C5—N1—N2—C3	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···N2ⁱ	0.85 (3)	2.31 (3)	3.144 (3)	169 (3)

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈ClN₃
M_r	193.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	3.8926 (6), 9.9679 (13), 22.617 (2)
β (°)	92.795 (11)
V (Å³)	876.52 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.4 × 0.07 × 0.06

Data collection
Diffractometer	Agilent Xcalibur Sapphire2 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.853, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5036, 1879, 1340
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.091, 1.02
No. of reflections	1879
No. of parameters	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.21

Computer programs: CrysAlis PRO (Agilent, 2010), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···N2ⁱ	0.85 (3)	2.31 (3)	3.144 (3)	169 (3)

Symmetry code: (i) −x, y−1/2, −z+1/2.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2320

doi:10.1107/S1600536811032065

Open

access