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Acta Crystallogr Sect E Struct Rep Online. 2012 April 1; 68(Pt 4): o975.
Published online 2012 March 7. doi:  10.1107/S1600536812009105
PMCID: PMC3343949

1-[3-(4-Chloro­phen­yl)-5-(4-meth­oxy­phen­yl)-4,5-dihydro-1H-pyrazol-1-yl]butan-1-one

Abstract

In the title compound, C20H21ClN2O2, the benzene rings form dihedral angles of 6.35 (5) and 81.82 (5)° with the mean plane of the 4,5-dihydro-1H-pyrazole ring (r.m.s. deviation = 0.145 Å). This latter ring adopts an envelope conformation with the CH grouping as the flap. The dihedral angle between the benzene rings is 75.63 (4)°. In the crystal, mol­ecules are linked by C—H(...)Cl and C—H(...)O hydrogen bonds into chains along [-201]. The crystal structure also features C—H(...)π inter­actions.

Related literature  

For a related structure, see: Fun et al. (2010 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]). For standard bond lengths, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-0o975-scheme1.jpg

Experimental  

Crystal data  

  • C20H21ClN2O2
  • M r = 356.84
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-0o975-efi1.jpg
  • a = 6.7918 (3) Å
  • b = 10.8822 (4) Å
  • c = 13.2576 (5) Å
  • α = 109.202 (1)°
  • β = 91.396 (1)°
  • γ = 105.087 (1)°
  • V = 886.93 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 100 K
  • 0.43 × 0.17 × 0.14 mm

Data collection  

  • Bruker SMART APEXII DUO CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.908, T max = 0.968
  • 17324 measured reflections
  • 6403 independent reflections
  • 5492 reflections with I > 2σ(I)
  • R int = 0.021

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.104
  • S = 1.04
  • 6403 reflections
  • 228 parameters
  • H-atom parameters constrained
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812009105/hb6658sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009105/hb6658Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812009105/hb6658Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). BN thanks the UGC for financial assistance through an SAP and BSR one-time grant for the purchase of chemicals. SS thanks Mangalore University for the research facilities.

supplementary crystallographic information

Comment

In continuation of our work on the synthesis and sturctures of pyrazoline derivatives (Fun et al., 2010), the title compound (I) is prepared and its crystal structure is reported.

In the title molecule (Fig. 1), the two benzene rings (C1-C6 and C10-C15) form dihedral angles of 6.35 (5) and 81.82 (5)°, respectively, with the mean plane of 4,5-dihydro-1H-pyrazole ring (N1/N2/C7-C9, r.m.s. deviation = 0.145 Å). The dihedral angle between the two benzene rings is 75.63 (4)°. Bond lengths are comparable with a related structure (Fun et al., 2010).

In the crystal structure, Fig. 2, molecules are linked via C11–H11A···Cl1 and C14–H14A···O2 hydrogen bonds (Table 1) into chains along [-201]. The crystal structure is further consolidated by C18–H18A···Cg1iii (Table 1) interactions, where Cg1 is the centroid of C1-C6 benzene ring.

Experimental

A mixture of (2E)-1-(4-chlorophenyl)-3-(4-methoxyphenyl)prop-2-en-1-one (2.72 g, 0.01 mol) and hydrazine hydrate (0.5 ml, 0.01 mol) in 25 ml butyric acid was refluxed for 8 h. The reaction mixture was cooled and poured into 50 ml ice-cold water. The precipitate was collected by filtration and purified by recrystallization from ethanol. Colourless blocks of (I) were grown from a DMF solution by slow evaporation and yield of the compound was 76% (m.p. : 369 K).

Refinement

All H atoms were positioned geometrically and refined using a riding model with C–H = 0.93 or 0.98 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating group model was applied to the methyl groups.

Figures

Fig. 1.
The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
Fig. 2.
The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

Crystal data

C20H21ClN2O2Z = 2
Mr = 356.84F(000) = 376
Triclinic, P1Dx = 1.336 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7918 (3) ÅCell parameters from 8526 reflections
b = 10.8822 (4) Åθ = 3.1–32.7°
c = 13.2576 (5) ŵ = 0.23 mm1
α = 109.202 (1)°T = 100 K
β = 91.396 (1)°Block, colourless
γ = 105.087 (1)°0.43 × 0.17 × 0.14 mm
V = 886.93 (6) Å3

Data collection

Bruker SMART APEXII DUO CCD diffractometer6403 independent reflections
Radiation source: fine-focus sealed tube5492 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
[var phi] and ω scansθmax = 32.7°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −10→9
Tmin = 0.908, Tmax = 0.968k = −16→16
17324 measured reflectionsl = −20→20

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0556P)2 + 0.2279P] where P = (Fo2 + 2Fc2)/3
6403 reflections(Δ/σ)max = 0.001
228 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = −0.30 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
Cl10.89607 (4)0.72819 (3)0.48730 (2)0.02770 (7)
O1−0.64280 (11)0.12922 (7)0.66911 (6)0.02244 (14)
O2−0.24411 (10)0.75836 (7)0.97896 (5)0.01753 (13)
N10.11361 (11)0.74489 (7)0.79068 (6)0.01296 (12)
N2−0.00821 (11)0.71541 (7)0.86691 (6)0.01292 (12)
C10.42153 (13)0.77985 (9)0.65141 (7)0.01642 (15)
H1A0.33540.83580.66290.020*
C20.57466 (14)0.79372 (10)0.58516 (7)0.01864 (16)
H2A0.59300.85940.55300.022*
C30.70038 (13)0.70779 (10)0.56759 (7)0.01822 (16)
C40.67516 (13)0.60834 (9)0.61348 (7)0.01807 (16)
H4A0.75850.55050.59950.022*
C50.52253 (13)0.59623 (9)0.68109 (7)0.01569 (15)
H5A0.50510.53040.71300.019*
C60.39554 (12)0.68211 (8)0.70129 (6)0.01347 (14)
C70.24252 (12)0.67322 (8)0.77666 (6)0.01296 (14)
C80.22791 (12)0.59223 (8)0.85087 (7)0.01436 (14)
H8A0.33900.63420.90950.017*
H8B0.22930.49980.81230.017*
C90.01915 (12)0.59689 (8)0.89181 (6)0.01294 (14)
H9A0.02970.61610.96960.016*
C10−0.15764 (12)0.47169 (8)0.83447 (6)0.01292 (14)
C11−0.15456 (14)0.38856 (9)0.72900 (7)0.01689 (15)
H11A−0.04030.40900.69390.020*
C12−0.31873 (14)0.27611 (9)0.67577 (7)0.01846 (16)
H12A−0.31350.22180.60570.022*
C13−0.49209 (13)0.24412 (9)0.72721 (7)0.01629 (15)
C14−0.49940 (13)0.32638 (9)0.83207 (7)0.01572 (15)
H14A−0.61460.30670.86680.019*
C15−0.33179 (13)0.43875 (8)0.88443 (7)0.01423 (14)
H15A−0.33660.49300.95460.017*
C16−0.82621 (16)0.09749 (11)0.71737 (10)0.0288 (2)
H16A−0.92110.01600.66900.043*
H16B−0.88730.17090.73240.043*
H16C−0.79350.08430.78320.043*
C17−0.14102 (12)0.78735 (8)0.91064 (6)0.01265 (14)
C18−0.14900 (12)0.90227 (8)0.87211 (6)0.01306 (14)
H18A−0.18000.86720.79440.016*
H18B−0.01510.96880.89050.016*
C19−0.30931 (13)0.97135 (8)0.92125 (7)0.01505 (14)
H19A−0.27821.00690.99900.018*
H19B−0.44340.90500.90300.018*
C20−0.31538 (16)1.08654 (9)0.88125 (8)0.02108 (17)
H20A−0.41381.13020.91600.032*
H20B−0.35411.05080.80480.032*
H20C−0.18201.15130.89770.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.02295 (12)0.03579 (14)0.02385 (12)0.00841 (9)0.01502 (9)0.00879 (9)
O10.0177 (3)0.0192 (3)0.0253 (3)−0.0002 (2)0.0032 (2)0.0053 (3)
O20.0185 (3)0.0192 (3)0.0194 (3)0.0091 (2)0.0097 (2)0.0092 (2)
N10.0110 (3)0.0152 (3)0.0140 (3)0.0049 (2)0.0047 (2)0.0057 (2)
N20.0127 (3)0.0142 (3)0.0155 (3)0.0067 (2)0.0061 (2)0.0074 (2)
C10.0142 (3)0.0208 (4)0.0165 (3)0.0072 (3)0.0039 (3)0.0075 (3)
C20.0175 (4)0.0238 (4)0.0162 (4)0.0058 (3)0.0050 (3)0.0088 (3)
C30.0136 (3)0.0243 (4)0.0136 (3)0.0046 (3)0.0052 (3)0.0030 (3)
C40.0143 (4)0.0214 (4)0.0175 (4)0.0078 (3)0.0053 (3)0.0031 (3)
C50.0133 (3)0.0176 (3)0.0163 (3)0.0064 (3)0.0041 (3)0.0043 (3)
C60.0105 (3)0.0168 (3)0.0130 (3)0.0049 (3)0.0027 (2)0.0042 (3)
C70.0103 (3)0.0150 (3)0.0140 (3)0.0044 (3)0.0025 (2)0.0050 (3)
C80.0120 (3)0.0169 (3)0.0178 (3)0.0069 (3)0.0042 (3)0.0083 (3)
C90.0130 (3)0.0143 (3)0.0144 (3)0.0065 (3)0.0041 (3)0.0065 (3)
C100.0130 (3)0.0142 (3)0.0144 (3)0.0062 (3)0.0047 (3)0.0066 (3)
C110.0159 (4)0.0189 (4)0.0159 (3)0.0053 (3)0.0071 (3)0.0055 (3)
C120.0185 (4)0.0191 (4)0.0160 (3)0.0048 (3)0.0054 (3)0.0038 (3)
C130.0151 (3)0.0153 (3)0.0192 (4)0.0039 (3)0.0028 (3)0.0071 (3)
C140.0144 (3)0.0170 (3)0.0197 (4)0.0060 (3)0.0070 (3)0.0098 (3)
C150.0157 (3)0.0156 (3)0.0150 (3)0.0074 (3)0.0061 (3)0.0074 (3)
C160.0190 (4)0.0264 (5)0.0360 (5)−0.0015 (4)0.0059 (4)0.0101 (4)
C170.0113 (3)0.0130 (3)0.0137 (3)0.0050 (2)0.0024 (2)0.0035 (3)
C180.0122 (3)0.0136 (3)0.0150 (3)0.0056 (3)0.0033 (3)0.0054 (3)
C190.0141 (3)0.0148 (3)0.0174 (3)0.0073 (3)0.0025 (3)0.0045 (3)
C200.0252 (4)0.0186 (4)0.0230 (4)0.0121 (3)0.0016 (3)0.0073 (3)

Geometric parameters (Å, º)

Cl1—C31.7377 (9)C9—H9A0.9800
O1—C131.3661 (11)C10—C151.3928 (11)
O1—C161.4285 (13)C10—C111.3976 (11)
O2—C171.2305 (10)C11—C121.3864 (12)
N1—C71.2952 (10)C11—H11A0.9300
N1—N21.3874 (9)C12—C131.3981 (12)
N2—C171.3628 (10)C12—H12A0.9300
N2—C91.4862 (10)C13—C141.3944 (12)
C1—C21.3878 (12)C14—C151.3970 (12)
C1—C61.4036 (12)C14—H14A0.9300
C1—H1A0.9300C15—H15A0.9300
C2—C31.3928 (13)C16—H16A0.9600
C2—H2A0.9300C16—H16B0.9600
C3—C41.3829 (13)C16—H16C0.9600
C4—C51.3955 (12)C17—C181.5106 (11)
C4—H4A0.9300C18—C191.5210 (11)
C5—C61.3983 (11)C18—H18A0.9700
C5—H5A0.9300C18—H18B0.9700
C6—C71.4662 (11)C19—C201.5222 (12)
C7—C81.5114 (11)C19—H19A0.9700
C8—C91.5376 (11)C19—H19B0.9700
C8—H8A0.9700C20—H20A0.9600
C8—H8B0.9700C20—H20B0.9600
C9—C101.5161 (11)C20—H20C0.9600
C13—O1—C16116.96 (8)C12—C11—H11A119.4
C7—N1—N2107.57 (7)C10—C11—H11A119.4
C17—N2—N1122.26 (7)C11—C12—C13120.15 (8)
C17—N2—C9124.98 (7)C11—C12—H12A119.9
N1—N2—C9112.74 (6)C13—C12—H12A119.9
C2—C1—C6120.57 (8)O1—C13—C14124.71 (8)
C2—C1—H1A119.7O1—C13—C12115.63 (8)
C6—C1—H1A119.7C14—C13—C12119.63 (8)
C1—C2—C3118.99 (8)C13—C14—C15119.28 (8)
C1—C2—H2A120.5C13—C14—H14A120.4
C3—C2—H2A120.5C15—C14—H14A120.4
C4—C3—C2121.74 (8)C10—C15—C14121.80 (8)
C4—C3—Cl1119.37 (7)C10—C15—H15A119.1
C2—C3—Cl1118.87 (7)C14—C15—H15A119.1
C3—C4—C5118.89 (8)O1—C16—H16A109.5
C3—C4—H4A120.6O1—C16—H16B109.5
C5—C4—H4A120.6H16A—C16—H16B109.5
C4—C5—C6120.66 (8)O1—C16—H16C109.5
C4—C5—H5A119.7H16A—C16—H16C109.5
C6—C5—H5A119.7H16B—C16—H16C109.5
C5—C6—C1119.12 (8)O2—C17—N2119.86 (7)
C5—C6—C7120.28 (7)O2—C17—C18123.61 (7)
C1—C6—C7120.57 (7)N2—C17—C18116.52 (7)
N1—C7—C6121.23 (7)C17—C18—C19112.44 (7)
N1—C7—C8113.34 (7)C17—C18—H18A109.1
C6—C7—C8125.25 (7)C19—C18—H18A109.1
C7—C8—C9101.98 (6)C17—C18—H18B109.1
C7—C8—H8A111.4C19—C18—H18B109.1
C9—C8—H8A111.4H18A—C18—H18B107.8
C7—C8—H8B111.4C18—C19—C20111.65 (7)
C9—C8—H8B111.4C18—C19—H19A109.3
H8A—C8—H8B109.2C20—C19—H19A109.3
N2—C9—C10110.38 (6)C18—C19—H19B109.3
N2—C9—C899.94 (6)C20—C19—H19B109.3
C10—C9—C8114.84 (7)H19A—C19—H19B108.0
N2—C9—H9A110.4C19—C20—H20A109.5
C10—C9—H9A110.4C19—C20—H20B109.5
C8—C9—H9A110.4H20A—C20—H20B109.5
C15—C10—C11117.92 (8)C19—C20—H20C109.5
C15—C10—C9120.71 (7)H20A—C20—H20C109.5
C11—C10—C9121.33 (7)H20B—C20—H20C109.5
C12—C11—C10121.22 (8)
C7—N1—N2—C17170.91 (8)C7—C8—C9—C1098.74 (7)
C7—N1—N2—C9−10.65 (9)N2—C9—C10—C15−91.37 (9)
C6—C1—C2—C30.94 (13)C8—C9—C10—C15156.62 (7)
C1—C2—C3—C40.68 (14)N2—C9—C10—C1186.38 (9)
C1—C2—C3—Cl1−178.41 (7)C8—C9—C10—C11−25.64 (11)
C2—C3—C4—C5−1.50 (14)C15—C10—C11—C12−0.50 (13)
Cl1—C3—C4—C5177.60 (7)C9—C10—C11—C12−178.30 (8)
C3—C4—C5—C60.70 (13)C10—C11—C12—C130.25 (14)
C4—C5—C6—C10.87 (13)C16—O1—C13—C144.58 (13)
C4—C5—C6—C7−176.92 (8)C16—O1—C13—C12−176.96 (8)
C2—C1—C6—C5−1.70 (13)C11—C12—C13—O1−178.16 (8)
C2—C1—C6—C7176.08 (8)C11—C12—C13—C140.38 (13)
N2—N1—C7—C6−179.36 (7)O1—C13—C14—C15177.66 (8)
N2—N1—C7—C8−4.00 (9)C12—C13—C14—C15−0.74 (13)
C5—C6—C7—N1−174.99 (8)C11—C10—C15—C140.12 (12)
C1—C6—C7—N17.25 (12)C9—C10—C15—C14177.94 (7)
C5—C6—C7—C810.22 (12)C13—C14—C15—C100.49 (12)
C1—C6—C7—C8−167.54 (8)N1—N2—C17—O2−179.14 (7)
N1—C7—C8—C915.87 (9)C9—N2—C17—O22.62 (12)
C6—C7—C8—C9−168.98 (7)N1—N2—C17—C18−0.20 (11)
C17—N2—C9—C1076.57 (10)C9—N2—C17—C18−178.45 (7)
N1—N2—C9—C10−101.82 (8)O2—C17—C18—C19−4.07 (11)
C17—N2—C9—C8−162.10 (8)N2—C17—C18—C19177.04 (7)
N1—N2—C9—C819.52 (8)C17—C18—C19—C20−179.85 (7)
C7—C8—C9—N2−19.34 (8)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···AD—HH···AD···AD—H···A
C11—H11A···Cl1i0.932.733.4539 (10)135
C14—H14A···O2ii0.932.513.3253 (12)147
C18—H18A···Cg1iii0.972.623.4514 (9)144

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6658).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2009). APEX2, SAINT and SADABSBruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.
  • Fun, H.-K., Hemamalini, M., Samshuddin, S., Narayana, B. & Yathirajan, H. S. (2010). Acta Cryst. E66, o582–o583. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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