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Acta Cryst. (2009). E65, o510    [ doi:10.1107/S1600536809004243 ]

4-[(2-Benzoyl-4-chlorophenyl)diazenyl]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Z. Bahreni, H. Rahmani and S. W. Ng

Abstract top

In the title compound, C23H17ClN4O2, the amino H atom forms an intramolecular hydrogen bond to the exocyclic carbonyl O atom as well as to the O atom of the benzoyl group.

Related literature top

For the crystal structure of 1-phenyl-3-methyl-4-(-4'-chlorophenyazo)-pyrazol-5-one, whose amino H atom is intramolecularly hydrogen-bonded to the carbonyl O atom, see: Golinski et al. (1983).

Experimental top

2-Amino-5-chlorobenzophenone (2.32 g, 0.01 mol) was suspended in strong hydrochloric acid (20 ml, pH ca. 5) at 273 K. A solution of sodium nitrite (0.69 g in 15 ml water) was added. Following the diazotization, an aqueous solution of 3-methyl-1-phenyl-2-pyrazoline-5-one (1.75 g, 0.01 mol) was added. The compound that separated was collected and recrystallized from ethanol.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.85±0.01 Å; its temperature factors was freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2009).

Figures top
[Figure 1] Fig. 1. Thermal displacement plot (Barbour, 2001) of C23H17ClN4O2; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.
4-[(2-Benzoyl-4-chlorophenyl)diazenyl]-3-methyl-1-phenyl-1H-pyrazol- 5(4H)-one top
Crystal data top
C23H17ClN4O2F(000) = 1728
Mr = 416.86Dx = 1.452 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2643 reflections
a = 25.800 (3) Åθ = 2.2–26.9°
b = 12.124 (1) ŵ = 0.23 mm−1
c = 13.966 (1) ÅT = 120 K
β = 119.179 (1)°Block, orange
V = 3813.9 (7) Å30.35 × 0.25 × 0.10 mm
Z = 8
Data collection top
Bruker SMART APEX
diffractometer		4346 independent reflections
Radiation source: fine-focus sealed tube3309 reflections with I > 2σ(I)
graphiteRint = 0.032
ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −33→33
Tmin = 0.791, Tmax = 0.862k = −15→12
10753 measured reflectionsl = −18→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.05P)2 + 2.1067P]
where P = (Fo2 + 2Fc2)/3
4346 reflections(Δ/σ)max = 0.001
276 parametersΔρmax = 0.30 e Å−3
1 restraintΔρmin = −0.30 e Å−3
Crystal data top
C23H17ClN4O2V = 3813.9 (7) Å3
Mr = 416.86Z = 8
Monoclinic, C2/cMo Kα radiation
a = 25.800 (3) ŵ = 0.23 mm−1
b = 12.124 (1) ÅT = 120 K
c = 13.966 (1) Å0.35 × 0.25 × 0.10 mm
β = 119.179 (1)°
Data collection top
Bruker SMART APEX
diffractometer		4346 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3309 reflections with I > 2σ(I)
Tmin = 0.791, Tmax = 0.862Rint = 0.032
10753 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105Δρmax = 0.30 e Å−3
S = 1.00Δρmin = −0.30 e Å−3
4346 reflectionsAbsolute structure: ?
276 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.176742 (18)0.72052 (4)0.10069 (4)0.03104 (13)
O10.51920 (5)0.65437 (10)0.64529 (9)0.0270 (3)
O20.42743 (6)0.81878 (10)0.49190 (10)0.0301 (3)
N10.56804 (6)0.48796 (11)0.72365 (11)0.0209 (3)
N20.55349 (6)0.37433 (11)0.70777 (11)0.0208 (3)
N30.42128 (6)0.49431 (11)0.50462 (11)0.0200 (3)
N40.40777 (6)0.59936 (12)0.47918 (11)0.0204 (3)
H40.4336 (7)0.6518 (13)0.5167 (15)0.037 (6)*
C10.62606 (7)0.51899 (15)0.80413 (13)0.0214 (4)
C20.66295 (7)0.44153 (15)0.88027 (13)0.0239 (4)
H20.64890.36910.87990.029*
C30.72042 (8)0.47068 (16)0.95664 (14)0.0279 (4)
H30.74580.41751.00820.034*
C40.74136 (8)0.57598 (16)0.95878 (15)0.0307 (4)
H4A0.78100.59511.01080.037*
C50.70394 (8)0.65311 (16)0.88431 (15)0.0310 (4)
H50.71790.72610.88660.037*
C60.64650 (8)0.62588 (15)0.80647 (14)0.0270 (4)
H60.62130.67940.75520.032*
C70.52131 (7)0.55349 (14)0.65290 (13)0.0204 (3)
C80.47428 (7)0.47380 (14)0.58702 (13)0.0195 (3)
C90.49904 (7)0.36666 (14)0.62833 (13)0.0201 (3)
C100.46871 (7)0.25862 (14)0.59029 (15)0.0246 (4)
H10A0.49620.19920.63230.037*
H10B0.45590.24920.51220.037*
H10C0.43400.25620.60120.037*
C110.35288 (7)0.62787 (14)0.38933 (13)0.0198 (3)
C120.30754 (7)0.55002 (14)0.34178 (13)0.0226 (4)
H120.31400.47700.37000.027*
C130.25322 (7)0.57835 (15)0.25382 (14)0.0241 (4)
H130.22210.52550.22240.029*
C140.24456 (7)0.68414 (15)0.21197 (13)0.0221 (4)
C150.28903 (7)0.76156 (14)0.25581 (13)0.0213 (3)
H150.28220.83360.22520.026*
C160.34421 (7)0.73499 (14)0.34516 (13)0.0200 (3)
C170.39169 (7)0.82058 (14)0.39359 (13)0.0210 (3)
C180.39651 (7)0.90830 (14)0.32340 (13)0.0205 (3)
C190.42522 (7)1.00593 (14)0.37423 (14)0.0251 (4)
H190.43771.01720.44970.030*
C200.43574 (8)1.08644 (15)0.31600 (15)0.0298 (4)
H200.45491.15310.35130.036*
C210.41840 (8)1.07047 (15)0.20623 (15)0.0299 (4)
H210.42571.12590.16620.036*
C220.39037 (8)0.97341 (15)0.15512 (14)0.0273 (4)
H220.37870.96230.07990.033*
C230.37924 (7)0.89228 (14)0.21274 (13)0.0230 (4)
H230.35990.82590.17710.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0196 (2)0.0284 (3)0.0321 (2)0.00060 (17)0.00242 (17)0.00243 (19)
O10.0295 (7)0.0183 (7)0.0261 (6)−0.0014 (5)0.0080 (5)0.0012 (5)
O20.0339 (7)0.0233 (7)0.0217 (6)−0.0045 (5)0.0045 (5)−0.0012 (5)
N10.0219 (7)0.0173 (7)0.0210 (7)−0.0018 (6)0.0086 (6)0.0006 (5)
N20.0209 (7)0.0177 (7)0.0238 (7)−0.0010 (6)0.0109 (6)0.0014 (6)
N30.0219 (7)0.0200 (8)0.0204 (7)0.0008 (6)0.0121 (6)0.0028 (6)
N40.0210 (7)0.0181 (8)0.0195 (7)−0.0015 (6)0.0079 (6)0.0013 (6)
C10.0192 (8)0.0252 (9)0.0193 (8)−0.0022 (7)0.0089 (7)−0.0021 (7)
C20.0247 (9)0.0248 (10)0.0229 (8)−0.0011 (7)0.0121 (7)−0.0003 (7)
C30.0263 (9)0.0311 (10)0.0233 (9)0.0028 (8)0.0097 (7)0.0006 (8)
C40.0226 (9)0.0373 (11)0.0264 (9)−0.0057 (8)0.0073 (7)−0.0078 (8)
C50.0309 (10)0.0271 (10)0.0325 (10)−0.0085 (8)0.0133 (8)−0.0061 (8)
C60.0272 (9)0.0239 (10)0.0270 (9)−0.0015 (7)0.0109 (7)0.0012 (7)
C70.0229 (8)0.0209 (9)0.0180 (8)0.0010 (7)0.0105 (7)0.0024 (6)
C80.0209 (8)0.0204 (9)0.0184 (8)−0.0010 (6)0.0106 (7)0.0017 (6)
C90.0193 (8)0.0224 (9)0.0205 (8)0.0006 (7)0.0111 (7)0.0029 (7)
C100.0216 (8)0.0198 (9)0.0295 (9)−0.0019 (7)0.0102 (7)−0.0006 (7)
C110.0184 (8)0.0223 (9)0.0185 (8)0.0008 (6)0.0090 (7)−0.0007 (6)
C120.0245 (8)0.0191 (9)0.0251 (9)−0.0001 (7)0.0129 (7)0.0036 (7)
C130.0211 (8)0.0218 (9)0.0276 (9)−0.0047 (7)0.0106 (7)−0.0006 (7)
C140.0157 (8)0.0261 (9)0.0208 (8)0.0021 (7)0.0062 (6)0.0000 (7)
C150.0214 (8)0.0180 (9)0.0233 (8)0.0026 (6)0.0100 (7)0.0007 (7)
C160.0211 (8)0.0193 (9)0.0205 (8)0.0003 (7)0.0107 (7)−0.0011 (6)
C170.0204 (8)0.0178 (8)0.0212 (8)0.0024 (6)0.0074 (7)−0.0016 (7)
C180.0168 (7)0.0180 (9)0.0229 (8)0.0016 (6)0.0067 (6)0.0008 (7)
C190.0231 (8)0.0214 (9)0.0248 (9)−0.0009 (7)0.0070 (7)−0.0036 (7)
C200.0294 (9)0.0188 (9)0.0353 (10)−0.0049 (7)0.0110 (8)−0.0018 (8)
C210.0300 (10)0.0241 (10)0.0348 (10)−0.0013 (8)0.0151 (8)0.0053 (8)
C220.0266 (9)0.0275 (10)0.0247 (9)0.0021 (7)0.0099 (7)0.0021 (7)
C230.0207 (8)0.0192 (9)0.0247 (9)−0.0007 (7)0.0076 (7)−0.0019 (7)
Geometric parameters (Å, °) top
Cl1—C141.738 (2)C10—H10A0.9800
O1—C71.227 (2)C10—H10B0.9800
O2—C171.225 (2)C10—H10C0.9800
N1—C71.378 (2)C11—C121.394 (2)
N1—C11.416 (2)C11—C161.408 (2)
N1—N21.417 (2)C12—C131.383 (2)
N2—C91.301 (2)C12—H120.9500
N3—C81.312 (2)C13—C141.382 (2)
N3—N41.323 (2)C13—H130.9500
N4—C111.402 (2)C14—C151.374 (2)
N4—H40.885 (9)C15—C161.398 (2)
C1—C21.390 (2)C15—H150.9500
C1—C61.393 (2)C16—C171.492 (2)
C2—C31.385 (2)C17—C181.492 (2)
C2—H20.9500C18—C191.393 (2)
C3—C41.381 (3)C18—C231.397 (2)
C3—H30.9500C19—C201.380 (3)
C4—C51.382 (3)C19—H190.9500
C4—H4A0.9500C20—C211.385 (3)
C5—C61.384 (3)C20—H200.9500
C5—H50.9500C21—C221.383 (3)
C6—H60.9500C21—H210.9500
C7—C81.471 (2)C22—C231.387 (2)
C8—C91.438 (2)C22—H220.9500
C9—C101.485 (2)C23—H230.9500
C7—N1—C1129.3 (2)H10B—C10—H10C109.5
C7—N1—N2112.1 (1)C12—C11—N4120.4 (2)
C1—N1—N2118.7 (1)C12—C11—C16119.9 (2)
C9—N2—N1107.2 (1)N4—C11—C16119.7 (1)
C8—N3—N4116.3 (1)C13—C12—C11120.4 (2)
N3—N4—C11119.8 (1)C13—C12—H12119.8
N3—N4—H4121 (1)C11—C12—H12119.8
C11—N4—H4120 (1)C12—C13—C14119.4 (2)
C2—C1—C6120.0 (2)C12—C13—H13120.3
C2—C1—N1119.5 (2)C14—C13—H13120.3
C6—C1—N1120.5 (2)C15—C14—C13121.2 (2)
C3—C2—C1119.6 (2)C15—C14—Cl1118.9 (1)
C3—C2—H2120.2C13—C14—Cl1119.9 (1)
C1—C2—H2120.2C14—C15—C16120.4 (2)
C4—C3—C2120.9 (2)C14—C15—H15119.8
C4—C3—H3119.6C16—C15—H15119.8
C2—C3—H3119.6C15—C16—C11118.6 (2)
C3—C4—C5119.2 (2)C15—C16—C17119.9 (2)
C3—C4—H4A120.4C11—C16—C17121.5 (2)
C5—C4—H4A120.4O2—C17—C18119.4 (2)
C4—C5—C6121.2 (2)O2—C17—C16119.9 (2)
C4—C5—H5119.4C18—C17—C16120.7 (1)
C6—C5—H5119.4C19—C18—C23119.0 (2)
C5—C6—C1119.2 (2)C19—C18—C17117.7 (2)
C5—C6—H6120.4C23—C18—C17122.9 (2)
C1—C6—H6120.4C20—C19—C18120.6 (2)
O1—C7—N1128.6 (2)C20—C19—H19119.7
O1—C7—C8127.8 (2)C18—C19—H19119.7
N1—C7—C8103.7 (1)C19—C20—C21120.2 (2)
N3—C8—C9126.3 (2)C19—C20—H20119.9
N3—C8—C7127.8 (2)C21—C20—H20119.9
C9—C8—C7105.8 (1)C20—C21—C22119.7 (2)
N2—C9—C8111.2 (2)C20—C21—H21120.1
N2—C9—C10122.0 (2)C22—C21—H21120.1
C8—C9—C10126.8 (2)C21—C22—C23120.5 (2)
C9—C10—H10A109.5C21—C22—H22119.7
C9—C10—H10B109.5C23—C22—H22119.7
H10A—C10—H10B109.5C22—C23—C18119.9 (2)
C9—C10—H10C109.5C22—C23—H23120.0
H10A—C10—H10C109.5C18—C23—H23120.0
C7—N1—N2—C90.5 (2)N3—N4—C11—C1214.3 (2)
C1—N1—N2—C9−178.1 (1)N3—N4—C11—C16−164.0 (1)
C8—N3—N4—C11177.4 (1)N4—C11—C12—C13179.4 (2)
C7—N1—C1—C2168.3 (2)C16—C11—C12—C13−2.4 (2)
N2—N1—C1—C2−13.4 (2)C11—C12—C13—C141.2 (3)
C7—N1—C1—C6−12.6 (3)C12—C13—C14—C150.3 (3)
N2—N1—C1—C6165.8 (2)C12—C13—C14—Cl1179.4 (1)
C6—C1—C2—C3−1.4 (3)C13—C14—C15—C16−0.7 (3)
N1—C1—C2—C3177.8 (2)Cl1—C14—C15—C16−179.8 (1)
C1—C2—C3—C40.6 (3)C14—C15—C16—C11−0.5 (2)
C2—C3—C4—C50.8 (3)C14—C15—C16—C17−178.6 (2)
C3—C4—C5—C6−1.4 (3)C12—C11—C16—C152.0 (2)
C4—C5—C6—C10.6 (3)N4—C11—C16—C15−179.8 (1)
C2—C1—C6—C50.8 (3)C12—C11—C16—C17−179.9 (2)
N1—C1—C6—C5−178.4 (2)N4—C11—C16—C17−1.6 (2)
C1—N1—C7—O1−1.6 (3)C15—C16—C17—O2148.1 (2)
N2—N1—C7—O1180.0 (2)C11—C16—C17—O2−30.0 (2)
C1—N1—C7—C8177.7 (2)C15—C16—C17—C18−32.3 (2)
N2—N1—C7—C8−0.7 (2)C11—C16—C17—C18149.6 (2)
N4—N3—C8—C9−179.0 (2)O2—C17—C18—C19−23.7 (2)
N4—N3—C8—C7−1.8 (2)C16—C17—C18—C19156.7 (2)
O1—C7—C8—N32.3 (3)O2—C17—C18—C23149.5 (2)
N1—C7—C8—N3−177.0 (2)C16—C17—C18—C23−30.1 (2)
O1—C7—C8—C9180.0 (2)C23—C18—C19—C200.9 (3)
N1—C7—C8—C90.6 (2)C17—C18—C19—C20174.4 (2)
N1—N2—C9—C8−0.1 (2)C18—C19—C20—C21−0.7 (3)
N1—N2—C9—C10−179.3 (1)C19—C20—C21—C220.1 (3)
N3—C8—C9—N2177.3 (2)C20—C21—C22—C230.3 (3)
C7—C8—C9—N2−0.4 (2)C21—C22—C23—C18−0.1 (3)
N3—C8—C9—C10−3.5 (3)C19—C18—C23—C22−0.5 (2)
C7—C8—C9—C10178.8 (2)C17—C18—C23—C22−173.6 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···O10.89 (1)2.06 (2)2.755 (2)135 (2)
N4—H4···O20.89 (1)2.05 (2)2.698 (2)130 (2)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···O10.89 (1)2.06 (2)2.755 (2)135 (2)
N4—H4···O20.89 (1)2.05 (2)2.698 (2)130 (2)
Acknowledgements top

We thank the Iranian Research Organization for Science and Technology and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Golinski, B., Reck, G. & Kutschabsky, L. (1983). Z. Kristallogr. 158, 271–278.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.