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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809053641/hb5279sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536809053641/hb5279Isup2.hkl
Contains datablock I

CCDC reference: 766845

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.059
  • wR factor = 0.146
  • Data-to-parameter ratio = 11.1

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.94 PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.583 82
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 24.50 From the CIF: _diffrn_reflns_theta_full 24.50 From the CIF: _reflns_number_total 1357 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 1442 Completeness (_total/calc) 94.11% THETM01_ALERT_3_C The value of sine(theta_max)/wavelength is less than 0.590 Calculated sin(theta_max)/wavelength = 0.5835 PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.94 PLAT023_ALERT_3_C Resolution (too) Low [sin(theta)/Lambda < 0.6].. 24.50 Deg. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 6 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 3
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 8 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.

Refinement top

The O-bound H atom was located in a difference map and freely refined. The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.96 Å and with Uiso(H) = 1.2Ueq of the parent atoms.

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
[Figure 1] 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
C9H7ClN2OF(000) = 400
Mr = 194.62Dx = 1.494 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1171 reflections
a = 9.6461 (19) Åθ = 3.5–27.5°
b = 13.833 (3) ŵ = 0.40 mm1
c = 6.5045 (13) ÅT = 293 K
β = 94.33 (3)°Bar, colourless
V = 865.4 (3) Å30.11 × 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 tubeRint = 0.038
Graphite monochromatorθmax = 24.5°, θmin = 3.5°
ω scansh = 1111
5771 measured reflectionsk = 1616
1357 independent reflectionsl = 77
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146 w = 1/[σ2(Fo2) + (0.0166P)2 + 1.7755P]
where P = (Fo2 + 2Fc2)/3
S = 1.24(Δ/σ)max < 0.001
1357 reflectionsΔρmax = 0.23 e Å3
122 parametersΔρmin = 0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.049 (5)
Crystal data top
C9H7ClN2OV = 865.4 (3) Å3
Mr = 194.62Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.6461 (19) ŵ = 0.40 mm1
b = 13.833 (3) ÅT = 293 K
c = 6.5045 (13) Å0.11 × 0.09 × 0.08 mm
β = 94.33 (3)°
Data collection top
Bruker SMART CCD
diffractometer
1171 reflections with I > 2σ(I)
5771 measured reflectionsRint = 0.038
1357 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 1.24Δρmax = 0.23 e Å3
1357 reflectionsΔρmin = 0.32 e Å3
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
xyzUiso*/Ueq
Cl11.03021 (14)0.13637 (11)0.3127 (2)0.0771 (6)
O10.3291 (3)0.0636 (2)0.5246 (5)0.0508 (8)
H10.377 (5)0.019 (3)0.588 (7)0.061*
N10.5047 (3)0.1156 (2)0.1005 (5)0.0361 (8)
N20.5009 (3)0.0759 (2)0.2928 (5)0.0380 (8)
C10.3807 (4)0.1554 (3)0.0396 (7)0.0458 (10)
H1A0.35880.18680.08510.055*
C20.2936 (4)0.1420 (3)0.1900 (6)0.0443 (10)
H2B0.20150.16170.19080.053*
C30.3726 (4)0.0919 (3)0.3442 (6)0.0386 (9)
C40.6308 (4)0.1525 (3)0.1997 (6)0.0423 (10)
H4A0.54760.17070.27100.051*
C50.7541 (5)0.1583 (3)0.2943 (6)0.0467 (11)
H5A0.75390.18070.42920.056*
C60.8760 (5)0.1314 (3)0.1905 (7)0.0475 (11)
C70.8777 (4)0.0988 (3)0.0093 (7)0.0489 (11)
H7A0.96130.08080.07920.059*
C80.7556 (4)0.0929 (3)0.1066 (6)0.0414 (10)
H8A0.75700.07100.24190.050*
C90.6311 (4)0.1195 (2)0.0022 (6)0.0339 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0584 (9)0.1009 (11)0.0757 (10)0.0004 (7)0.0298 (7)0.0190 (7)
O10.0422 (17)0.065 (2)0.0469 (18)0.0123 (14)0.0141 (15)0.0138 (14)
N10.0355 (18)0.0400 (17)0.0322 (17)0.0012 (13)0.0011 (15)0.0040 (13)
N20.0361 (19)0.0440 (18)0.0338 (18)0.0036 (13)0.0011 (15)0.0065 (14)
C10.044 (2)0.051 (2)0.040 (2)0.0064 (18)0.009 (2)0.0060 (18)
C20.034 (2)0.051 (2)0.048 (3)0.0073 (17)0.000 (2)0.0012 (18)
C30.036 (2)0.038 (2)0.042 (2)0.0023 (16)0.0044 (19)0.0017 (16)
C40.045 (2)0.045 (2)0.035 (2)0.0016 (17)0.007 (2)0.0043 (16)
C50.058 (3)0.048 (2)0.035 (2)0.0062 (19)0.007 (2)0.0046 (17)
C60.048 (3)0.045 (2)0.052 (3)0.0038 (18)0.015 (2)0.0037 (19)
C70.039 (2)0.052 (2)0.055 (3)0.0012 (18)0.004 (2)0.008 (2)
C80.042 (2)0.047 (2)0.035 (2)0.0014 (17)0.0012 (19)0.0063 (17)
C90.039 (2)0.0323 (19)0.030 (2)0.0027 (15)0.0007 (17)0.0013 (14)
Geometric parameters (Å, º) top
Cl1—C61.740 (4)C4—C51.382 (6)
O1—C31.334 (5)C4—C91.390 (5)
O1—H10.86 (5)C4—H4A0.9300
N1—C11.349 (5)C5—C61.363 (6)
N1—N21.369 (4)C5—H5A0.9300
N1—C91.420 (5)C6—C71.374 (6)
N2—C31.325 (5)C7—C81.381 (6)
C1—C21.349 (6)C7—H7A0.9300
C1—H1A0.9300C8—C91.384 (5)
C2—C31.396 (5)C8—H8A0.9300
C2—H2B0.9300
C3—O1—H1116 (3)C9—C4—H4A120.0
C1—N1—N2110.4 (3)C6—C5—C4120.2 (4)
C1—N1—C9128.7 (3)C6—C5—H5A119.9
N2—N1—C9120.6 (3)C4—C5—H5A119.9
C3—N2—N1104.7 (3)C5—C6—C7120.4 (4)
N1—C1—C2108.5 (4)C5—C6—Cl1119.9 (3)
N1—C1—H1A125.7C7—C6—Cl1119.7 (4)
C2—C1—H1A125.7C6—C7—C8120.2 (4)
C1—C2—C3104.7 (4)C6—C7—H7A119.9
C1—C2—H2B127.7C8—C7—H7A119.9
C3—C2—H2B127.7C7—C8—C9119.9 (4)
N2—C3—O1122.3 (3)C7—C8—H8A120.1
N2—C3—C2111.8 (3)C9—C8—H8A120.1
O1—C3—C2125.9 (4)C8—C9—C4119.4 (4)
C5—C4—C9119.9 (4)C8—C9—N1120.8 (3)
C5—C4—H4A120.0C4—C9—N1119.8 (3)
C1—N1—N2—C30.5 (4)C5—C6—C7—C80.2 (6)
C9—N1—N2—C3174.5 (3)Cl1—C6—C7—C8178.8 (3)
N2—N1—C1—C20.3 (4)C6—C7—C8—C90.2 (6)
C9—N1—C1—C2173.7 (3)C7—C8—C9—C40.3 (6)
N1—C1—C2—C30.1 (5)C7—C8—C9—N1178.9 (3)
N1—N2—C3—O1179.6 (3)C5—C4—C9—C80.1 (6)
N1—N2—C3—C20.6 (4)C5—C4—C9—N1178.6 (3)
C1—C2—C3—N20.4 (5)C1—N1—C9—C8165.9 (4)
C1—C2—C3—O1179.4 (4)N2—N1—C9—C86.9 (5)
C9—C4—C5—C60.3 (6)C1—N1—C9—C412.7 (6)
C4—C5—C6—C70.4 (6)N2—N1—C9—C4174.5 (3)
C4—C5—C6—Cl1178.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N2i0.86 (4)1.89 (4)2.744 (4)173 (4)
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC9H7ClN2O
Mr194.62
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)9.6461 (19), 13.833 (3), 6.5045 (13)
β (°) 94.33 (3)
V3)865.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.40
Crystal size (mm)0.11 × 0.09 × 0.08
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5771, 1357, 1171
Rint0.038
(sin θ/λ)max1)0.583
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.146, 1.24
No. of reflections1357
No. of parameters122
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1···N2i0.86 (4)1.89 (4)2.744 (4)173 (4)
Symmetry code: (i) x+1, y, z+1.
 

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