1-(4-Chloro­phen­yl)-1H-pyrazol-3-ol

Ren, X.-Y.; Wang, J.-G.; Li, Y.-Y.

doi:10.1107/S1600536809053641

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o186

doi:10.1107/S1600536809053641

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1-(4-Chlorophenyl)-1H-pyrazol-3-ol

Xiao-Yan Ren,^a ^* Jian-Gang Wang ^b and Yun-Ying Li ^c

^aChemical Engineering Department, Weifang Vocational College, Weifang 261000, People's Republic of China, ^bBioengineering School, Weifang University, Weifang 261061, People's Republic of China, and ^cThe 7th Middle School, Weifang 261000, People's Republic of China
^*Correspondence e-mail: rxy718@126.com

(Received 11 December 2009; accepted 13 December 2009; online 19 December 2009)

In the title compound, C₉H₇ClN₂O, the dihedral angle between the aromatic ring planes is 11.0 (2)°. In the crystal, inversion dimers linked by pairs of O—H⋯N hydrogen bonds generate R₂²(8) loops.

Related literature

For a related structure, see: Jian et al. (2005 ). For background to herbicides and plant-growth promoters related to the title compound, see: Shi et al. (1995 ); Xu et al. (2002 ).

Experimental

Crystal data

C₉H₇ClN₂O
M_r = 194.62
Monoclinic, P 2₁ /c
a = 9.6461 (19) Å
b = 13.833 (3) Å
c = 6.5045 (13) Å
β = 94.33 (3)°
V = 865.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.11 × 0.09 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
5771 measured reflections
1357 independent reflections
1171 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.146
S = 1.24
1357 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.86 (4)	1.89 (4)	2.744 (4)	173 (4)
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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: SHELXTL .

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053641/hb5279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053641/hb5279Isup2.hkl

checkCIF report

Comment top

p-Chlorophenyl hydrazine hydrochloride is an important biologically active compound used in herbicides and plant growth substances (Shi et al.,1995; Xu, et al.,2002). Here we report the crystal structure of the title compound (I).

In the title compound (I) (Fig. 1), the The dihedral angle between the pheny ring (C4,C5,C6,C7,C8 and C9) and ring 1(N1,N2,C1,C2 and C3) is 11.0 (2)°. The C—N bonds length in the range of (1.321 (5) Å-1.416 (5) Å) are in agreement with that observed before (Jian et al., 2005).

Related literature top

For a related structure, see: Jian et al. (2005). For background to herbicides and plant-growth promoters related to the title compound, see: Shi et al. (1995); Xu et al. (2002).

Experimental top

A mixture of p-Chlorophenylhydrazing hydrochloride (0.02 mol) and methyl acrylate (0.02 mol) was stirred in ethanol (30 ml) at 353 K for 2 h to afford the title compound (yield 50%). Colourless bars of (I) were obtained by recrystallization from acetone at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level.

1-(4-Chlorophenyl)-1H-pyrazol-3-ol top

Crystal data top

C₉H₇ClN₂O	F(000) = 400
M_r = 194.62	D_x = 1.494 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1171 reflections
a = 9.6461 (19) Å	θ = 3.5–27.5°
b = 13.833 (3) Å	µ = 0.40 mm⁻¹
c = 6.5045 (13) Å	T = 293 K
β = 94.33 (3)°	Bar, colourless
V = 865.4 (3) Å³	0.11 × 0.09 × 0.08 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1171 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 24.5°, θ_min = 3.5°
ω scans	h = −11→11
5771 measured reflections	k = −16→16
1357 independent reflections	l = −7→7

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)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0166P)² + 1.7755P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
1357 reflections	Δρ_max = 0.23 e Å⁻³
122 parameters	Δρ_min = −0.32 e Å⁻³
0 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: 0.049 (5)

Crystal data top

C₉H₇ClN₂O	V = 865.4 (3) Å³
M_r = 194.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6461 (19) Å	µ = 0.40 mm⁻¹
b = 13.833 (3) Å	T = 293 K
c = 6.5045 (13) Å	0.11 × 0.09 × 0.08 mm
β = 94.33 (3)°

Data collection top

Bruker SMART CCD diffractometer	1171 reflections with I > 2σ(I)
5771 measured reflections	R_int = 0.038
1357 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	Δρ_max = 0.23 e Å⁻³
1357 reflections	Δρ_min = −0.32 e Å⁻³
122 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
Cl1	1.03021 (14)	0.13637 (11)	−0.3127 (2)	0.0771 (6)
O1	0.3291 (3)	0.0636 (2)	0.5246 (5)	0.0508 (8)
H1	0.377 (5)	0.019 (3)	0.588 (7)	0.061*
N1	0.5047 (3)	0.1156 (2)	0.1005 (5)	0.0361 (8)
N2	0.5009 (3)	0.0759 (2)	0.2928 (5)	0.0380 (8)
C1	0.3807 (4)	0.1554 (3)	0.0396 (7)	0.0458 (10)
H1A	0.3588	0.1868	−0.0851	0.055*
C2	0.2936 (4)	0.1420 (3)	0.1900 (6)	0.0443 (10)
H2B	0.2015	0.1617	0.1908	0.053*
C3	0.3726 (4)	0.0919 (3)	0.3442 (6)	0.0386 (9)
C4	0.6308 (4)	0.1525 (3)	−0.1997 (6)	0.0423 (10)
H4A	0.5476	0.1707	−0.2710	0.051*
C5	0.7541 (5)	0.1583 (3)	−0.2943 (6)	0.0467 (11)
H5A	0.7539	0.1807	−0.4292	0.056*
C6	0.8760 (5)	0.1314 (3)	−0.1905 (7)	0.0475 (11)
C7	0.8777 (4)	0.0988 (3)	0.0093 (7)	0.0489 (11)
H7A	0.9613	0.0808	0.0792	0.059*
C8	0.7556 (4)	0.0929 (3)	0.1066 (6)	0.0414 (10)
H8A	0.7570	0.0710	0.2419	0.050*
C9	0.6311 (4)	0.1195 (2)	0.0022 (6)	0.0339 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0584 (9)	0.1009 (11)	0.0757 (10)	−0.0004 (7)	0.0298 (7)	0.0190 (7)
O1	0.0422 (17)	0.065 (2)	0.0469 (18)	0.0123 (14)	0.0141 (15)	0.0138 (14)
N1	0.0355 (18)	0.0400 (17)	0.0322 (17)	0.0012 (13)	−0.0011 (15)	0.0040 (13)
N2	0.0361 (19)	0.0440 (18)	0.0338 (18)	0.0036 (13)	0.0011 (15)	0.0065 (14)
C1	0.044 (2)	0.051 (2)	0.040 (2)	0.0064 (18)	−0.009 (2)	0.0060 (18)
C2	0.034 (2)	0.051 (2)	0.048 (3)	0.0073 (17)	0.000 (2)	−0.0012 (18)
C3	0.036 (2)	0.038 (2)	0.042 (2)	0.0023 (16)	0.0044 (19)	−0.0017 (16)
C4	0.045 (2)	0.045 (2)	0.035 (2)	−0.0016 (17)	−0.007 (2)	0.0043 (16)
C5	0.058 (3)	0.048 (2)	0.035 (2)	−0.0062 (19)	0.007 (2)	0.0046 (17)
C6	0.048 (3)	0.045 (2)	0.052 (3)	−0.0038 (18)	0.015 (2)	0.0037 (19)
C7	0.039 (2)	0.052 (2)	0.055 (3)	0.0012 (18)	0.004 (2)	0.008 (2)
C8	0.042 (2)	0.047 (2)	0.035 (2)	0.0014 (17)	0.0012 (19)	0.0063 (17)
C9	0.039 (2)	0.0323 (19)	0.030 (2)	−0.0027 (15)	−0.0007 (17)	−0.0013 (14)

Geometric parameters (Å, º) top

Cl1—C6	1.740 (4)	C4—C5	1.382 (6)
O1—C3	1.334 (5)	C4—C9	1.390 (5)
O1—H1	0.86 (5)	C4—H4A	0.9300
N1—C1	1.349 (5)	C5—C6	1.363 (6)
N1—N2	1.369 (4)	C5—H5A	0.9300
N1—C9	1.420 (5)	C6—C7	1.374 (6)
N2—C3	1.325 (5)	C7—C8	1.381 (6)
C1—C2	1.349 (6)	C7—H7A	0.9300
C1—H1A	0.9300	C8—C9	1.384 (5)
C2—C3	1.396 (5)	C8—H8A	0.9300
C2—H2B	0.9300

C3—O1—H1	116 (3)	C9—C4—H4A	120.0
C1—N1—N2	110.4 (3)	C6—C5—C4	120.2 (4)
C1—N1—C9	128.7 (3)	C6—C5—H5A	119.9
N2—N1—C9	120.6 (3)	C4—C5—H5A	119.9
C3—N2—N1	104.7 (3)	C5—C6—C7	120.4 (4)
N1—C1—C2	108.5 (4)	C5—C6—Cl1	119.9 (3)
N1—C1—H1A	125.7	C7—C6—Cl1	119.7 (4)
C2—C1—H1A	125.7	C6—C7—C8	120.2 (4)
C1—C2—C3	104.7 (4)	C6—C7—H7A	119.9
C1—C2—H2B	127.7	C8—C7—H7A	119.9
C3—C2—H2B	127.7	C7—C8—C9	119.9 (4)
N2—C3—O1	122.3 (3)	C7—C8—H8A	120.1
N2—C3—C2	111.8 (3)	C9—C8—H8A	120.1
O1—C3—C2	125.9 (4)	C8—C9—C4	119.4 (4)
C5—C4—C9	119.9 (4)	C8—C9—N1	120.8 (3)
C5—C4—H4A	120.0	C4—C9—N1	119.8 (3)

C1—N1—N2—C3	0.5 (4)	C5—C6—C7—C8	0.2 (6)
C9—N1—N2—C3	174.5 (3)	Cl1—C6—C7—C8	−178.8 (3)
N2—N1—C1—C2	−0.3 (4)	C6—C7—C8—C9	0.2 (6)
C9—N1—C1—C2	−173.7 (3)	C7—C8—C9—C4	−0.3 (6)
N1—C1—C2—C3	−0.1 (5)	C7—C8—C9—N1	−178.9 (3)
N1—N2—C3—O1	−179.6 (3)	C5—C4—C9—C8	0.1 (6)
N1—N2—C3—C2	−0.6 (4)	C5—C4—C9—N1	178.6 (3)
C1—C2—C3—N2	0.4 (5)	C1—N1—C9—C8	165.9 (4)
C1—C2—C3—O1	179.4 (4)	N2—N1—C9—C8	−6.9 (5)
C9—C4—C5—C6	0.3 (6)	C1—N1—C9—C4	−12.7 (6)
C4—C5—C6—C7	−0.4 (6)	N2—N1—C9—C4	174.5 (3)
C4—C5—C6—Cl1	178.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.86 (4)	1.89 (4)	2.744 (4)	173 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₇ClN₂O
M_r	194.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.6461 (19), 13.833 (3), 6.5045 (13)
β (°)	94.33 (3)
V (Å³)	865.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.11 × 0.09 × 0.08

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5771, 1357, 1171
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.583

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.146, 1.24
No. of reflections	1357
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.32

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
O1—H1···N2ⁱ	0.86 (4)	1.89 (4)	2.744 (4)	173 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The author thanks for the Scientific and Technological Foundation of Weifang Vacational College (No. WZKJ200907).

References

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