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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o908.
Published online 2008 April 26. doi:  10.1107/S1600536808011562
PMCID: PMC2961285

2-[(5-Amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-chloro­phen­yl)meth­yl]malononitrile

Abstract

In the crystal structure of the title compound, C20H16ClN5, the dihedral angle between the pyrazole ring and the phenyl ring is 54.7 (1)° and that between the pyrazole ring and the chloro-substituted phenyl ring is 72.4 (1)°. The methyl H atoms are disordered over two positions with site occupancy factors of ca 0.7 and 0.3. One amino H is disordered equally over two positions. In the crystal structure, the mol­ecules are linked via inter­molecular N—H(...)N hydrogen bonding.

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Object name is e-64-0o908-scheme1.jpg

Experimental

Crystal data

  • C20H16ClN5
  • M r = 361.83
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o908-efi1.jpg
  • a = 10.4700 (11) Å
  • b = 14.0482 (15) Å
  • c = 25.409 (3) Å
  • V = 3737.3 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 294 (2) K
  • 0.49 × 0.48 × 0.45 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.901, T max = 0.908
  • 32456 measured reflections
  • 4661 independent reflections
  • 3055 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.118
  • S = 1.03
  • 4661 reflections
  • 237 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808011562/nc2101sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011562/nc2101Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 20772025), the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 2008HASTIT006) and the Department of Education of Henan Province (No. 2008 A150013).

supplementary crystallographic information

Comment

The structure determination was undertaken as a part of a project on the synthesis of new pyrazole derivatives. In the title compound the dihedral angle between the pyrazole ring and the non-substituted phenyl ring which is directly connected to the pyrazole ring is 54.7 (1)° and that between the pyrazole ring and the chloro-substituted phenyl ring is 72.4 (1)°. The dihedral angle between the non-substituted and the chloro-substituted phenyl ring amount to 69.7 (1)° (Fig. 1).

In the crystal structure the molecules are connected via intermolecular N—H···N hydrogen bonding between the amino group at N3 and the N atoms N2 and N4 (Fig. 2 and Table 1).

Experimental

To 1 ml of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 4-chloroaldehyde (1 mmol), malononitrile (1 mmol) and 5-amino-3-methyl-1-phenylpyrazole (1 mmol) were added. The reaction mixture was stirred at room temperature for 4 h and afterwards extracted five times with 2 ml of diethylether. The ether extracts were combined and concentrated. The obtained residue was recrystallized with 95% ethanol to give the product in a yield of 95% as white solid. Single crystals of the title compound were obtained by slow evaporation of the solvent from a petroleum ether-ethyl ether (1:1 v/v) solution.

Refinement

All H atoms were placed in geometrically idealized positions (methyl H atoms are disordered in two orientations) and constrained to ride on their parent atoms, with C—H distances of 0.93 - 0.98 Å and with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms). The N-H H atoms were located in difference map, their bond lengths were set to ideal values and afterwards they were refined using a riding model with Uiso(H) = 1.2Ueq(C). One of the N-H H atoms is disordered and was refined using a split model.

Figures

Fig. 1.
Molecular structure of the title compound, with labelling displacement ellipsoids drawn at the 30% probability level. The disordering of the H atoms is not shown for clarity.
Fig. 2.
Crystal structure of the title compound with view along the a-axis. Intermolecular N—H···N hydrogen bonding is shown as dashed lines and the disordering of the H atoms is not shown for clarity.

Crystal data

C20H16ClN5Dx = 1.286 Mg m3
Mr = 361.83Mo Kα radiation λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 8329 reflections
a = 10.4700 (11) Åθ = 2.5–25.8º
b = 14.0482 (15) ŵ = 0.22 mm1
c = 25.409 (3) ÅT = 294 (2) K
V = 3737.3 (7) Å3Block, colourless
Z = 80.49 × 0.48 × 0.45 mm
F000 = 1504

Data collection

Bruker SMART CCD area-detector diffractometer4661 independent reflections
Radiation source: fine-focus sealed tube3055 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 294(2) Kθmax = 28.4º
[var phi] and ω scansθmin = 2.5º
Absorption correction: multi-scan(SADABS; Bruker, 1997)h = −14→13
Tmin = 0.901, Tmax = 0.909k = −18→18
32456 measured reflectionsl = −33→33

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041  w = 1/[σ2(Fo2) + (0.0404P)2 + 1.3457P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.118(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.18 e Å3
4661 reflectionsΔρmin = −0.32 e Å3
237 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0012 (3)
Secondary atom site location: difference Fourier map

Special details

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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*/UeqOcc. (<1)
Cl10.34596 (7)1.04230 (4)0.53076 (2)0.0837 (2)
N10.27144 (14)0.71251 (10)0.78626 (5)0.0509 (4)
N20.17726 (15)0.64522 (12)0.77803 (6)0.0605 (4)
N30.43568 (16)0.79533 (11)0.74011 (5)0.0623 (4)
N40.4155 (2)0.44105 (12)0.68772 (7)0.0751 (5)
N50.52582 (19)0.58634 (13)0.54493 (7)0.0748 (5)
C10.18531 (16)0.62494 (13)0.72710 (6)0.0512 (4)
C20.28333 (15)0.67629 (11)0.70228 (5)0.0414 (3)
C30.33723 (15)0.73171 (11)0.74145 (6)0.0429 (4)
C40.0940 (2)0.55545 (17)0.70288 (8)0.0772 (7)
H4A0.06130.58110.67060.116*0.73
H4B0.02450.54400.72670.116*0.73
H4C0.13760.49670.69580.116*0.73
H4D0.08760.50010.72490.116*0.27
H4E0.12440.53720.66870.116*0.27
H4F0.01140.58450.69960.116*0.27
C50.29537 (17)0.74496 (15)0.83845 (6)0.0579 (5)
C60.2963 (2)0.84064 (18)0.84956 (9)0.0847 (7)
H60.28120.88540.82330.102*
C70.3206 (3)0.8691 (3)0.90156 (14)0.1220 (14)
H70.32320.93350.90990.146*
C80.3407 (3)0.8023 (4)0.94005 (12)0.1401 (18)
H80.35670.82180.97440.168*
C90.3375 (3)0.7080 (3)0.92837 (10)0.1239 (13)
H90.35040.66320.95480.149*
C100.3151 (2)0.6782 (2)0.87746 (8)0.0846 (7)
H100.31330.61360.86950.102*
C110.33508 (15)0.76013 (11)0.61584 (5)0.0415 (3)
C120.22572 (17)0.79784 (13)0.59298 (6)0.0516 (4)
H120.14910.76470.59560.062*
C130.2283 (2)0.88387 (14)0.56630 (6)0.0588 (5)
H130.15450.90820.55100.071*
C140.3417 (2)0.93244 (12)0.56298 (6)0.0550 (5)
C150.45228 (19)0.89664 (13)0.58425 (7)0.0569 (5)
H150.52870.92990.58110.068*
C160.44836 (17)0.81010 (12)0.61058 (6)0.0510 (4)
H160.52300.78530.62490.061*
C170.32395 (14)0.66623 (11)0.64546 (5)0.0401 (3)
H170.25680.62960.62780.048*
C180.44800 (16)0.60557 (11)0.64192 (6)0.0444 (4)
H180.51530.63910.66130.053*
C190.42937 (18)0.51193 (13)0.66700 (6)0.0525 (4)
C200.49158 (17)0.59315 (12)0.58707 (7)0.0511 (4)
H1N30.46390.81730.76950.061*
H2N30.50270.76930.72700.061*0.50
H3N30.46470.81340.71010.061*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.1235 (5)0.0600 (3)0.0677 (3)0.0238 (3)0.0273 (3)0.0234 (2)
N10.0586 (9)0.0588 (8)0.0354 (7)−0.0138 (7)0.0064 (6)−0.0075 (6)
N20.0636 (9)0.0760 (11)0.0418 (8)−0.0252 (8)0.0098 (7)−0.0067 (7)
N30.0761 (11)0.0659 (9)0.0448 (8)−0.0308 (8)0.0096 (7)−0.0120 (7)
N40.1013 (14)0.0569 (10)0.0669 (11)0.0076 (9)−0.0131 (10)0.0121 (8)
N50.0918 (13)0.0807 (12)0.0518 (9)0.0059 (10)0.0158 (9)−0.0074 (8)
C10.0543 (10)0.0587 (10)0.0405 (8)−0.0137 (8)0.0015 (7)−0.0033 (7)
C20.0474 (8)0.0430 (8)0.0338 (7)−0.0020 (7)0.0003 (6)−0.0009 (6)
C30.0505 (9)0.0416 (8)0.0365 (7)−0.0045 (7)0.0040 (6)−0.0021 (6)
C40.0765 (14)0.0976 (16)0.0575 (11)−0.0416 (12)0.0044 (10)−0.0101 (11)
C50.0542 (10)0.0810 (13)0.0384 (8)−0.0124 (9)0.0110 (7)−0.0155 (8)
C60.0862 (16)0.0897 (16)0.0782 (14)−0.0306 (13)0.0300 (12)−0.0365 (12)
C70.102 (2)0.157 (3)0.107 (2)−0.063 (2)0.0500 (18)−0.088 (2)
C80.091 (2)0.268 (5)0.0613 (17)−0.046 (3)0.0176 (15)−0.071 (3)
C90.112 (2)0.220 (4)0.0398 (12)0.002 (3)0.0031 (13)−0.0061 (18)
C100.0911 (17)0.120 (2)0.0427 (10)0.0025 (15)0.0073 (10)−0.0001 (12)
C110.0507 (9)0.0458 (8)0.0281 (7)0.0033 (7)0.0007 (6)−0.0010 (6)
C120.0513 (10)0.0586 (10)0.0449 (9)0.0051 (8)−0.0033 (7)0.0022 (7)
C130.0670 (12)0.0632 (11)0.0461 (9)0.0200 (10)−0.0025 (8)0.0052 (8)
C140.0803 (13)0.0494 (9)0.0353 (8)0.0139 (9)0.0115 (8)0.0056 (7)
C150.0649 (11)0.0555 (10)0.0503 (10)−0.0040 (9)0.0091 (8)0.0076 (8)
C160.0514 (10)0.0555 (10)0.0462 (9)0.0005 (8)−0.0012 (7)0.0083 (7)
C170.0450 (8)0.0438 (8)0.0315 (7)−0.0024 (7)−0.0039 (6)−0.0020 (6)
C180.0516 (9)0.0471 (9)0.0345 (7)0.0018 (7)−0.0056 (6)−0.0022 (6)
C190.0623 (11)0.0530 (10)0.0421 (8)0.0088 (8)−0.0079 (8)−0.0005 (7)
C200.0560 (10)0.0515 (10)0.0457 (9)0.0062 (8)0.0001 (8)−0.0027 (7)

Geometric parameters (Å, °)

Cl1—C141.7477 (17)C6—H60.9300
N1—C31.3577 (19)C7—C81.371 (5)
N1—N21.3819 (19)C7—H70.9300
N1—C51.424 (2)C8—C91.359 (5)
N2—C11.328 (2)C8—H80.9300
N3—C31.365 (2)C9—C101.379 (3)
N3—H1N30.8602C9—H90.9300
N3—H2N30.8587C10—H100.9300
N3—H3N30.8595C11—C161.385 (2)
N4—C191.136 (2)C11—C121.389 (2)
N5—C201.133 (2)C11—C171.523 (2)
C1—C21.404 (2)C12—C131.386 (2)
C1—C41.499 (2)C12—H120.9300
C2—C31.384 (2)C13—C141.372 (3)
C2—C171.5117 (19)C13—H130.9300
C4—H4A0.9600C14—C151.373 (3)
C4—H4B0.9600C15—C161.388 (2)
C4—H4C0.9600C15—H150.9300
C4—H4D0.9600C16—H160.9300
C4—H4E0.9600C17—C181.556 (2)
C4—H4F0.9600C17—H170.9800
C5—C61.373 (3)C18—C191.475 (2)
C5—C101.380 (3)C18—C201.477 (2)
C6—C71.404 (4)C18—H180.9800
C3—N1—N2111.78 (12)C7—C6—H6120.9
C3—N1—C5128.89 (14)C8—C7—C6120.3 (3)
N2—N1—C5119.03 (13)C8—C7—H7119.8
C1—N2—N1104.41 (13)C6—C7—H7119.8
C3—N3—H1N3118.2C9—C8—C7120.5 (3)
C3—N3—H2N3110.3C9—C8—H8119.8
H1N3—N3—H2N3102.1C7—C8—H8119.8
C3—N3—H3N3118.9C8—C9—C10120.3 (3)
H1N3—N3—H3N3122.9C8—C9—H9119.8
H2N3—N3—H3N359.4C10—C9—H9119.8
N2—C1—C2111.96 (14)C9—C10—C5119.6 (3)
N2—C1—C4119.96 (16)C9—C10—H10120.2
C2—C1—C4128.07 (15)C5—C10—H10120.2
C3—C2—C1105.31 (13)C16—C11—C12118.19 (15)
C3—C2—C17128.66 (14)C16—C11—C17123.53 (14)
C1—C2—C17125.92 (14)C12—C11—C17118.29 (14)
N1—C3—N3122.28 (14)C13—C12—C11121.41 (17)
N1—C3—C2106.52 (13)C13—C12—H12119.3
N3—C3—C2131.19 (14)C11—C12—H12119.3
C1—C4—H4A109.5C14—C13—C12118.72 (17)
C1—C4—H4B109.5C14—C13—H13120.6
H4A—C4—H4B109.5C12—C13—H13120.6
C1—C4—H4C109.5C13—C14—C15121.56 (16)
H4A—C4—H4C109.5C13—C14—Cl1119.35 (15)
H4B—C4—H4C109.5C15—C14—Cl1119.09 (16)
C1—C4—H4D109.5C14—C15—C16119.04 (18)
H4A—C4—H4D141.1C14—C15—H15120.5
H4B—C4—H4D56.3C16—C15—H15120.5
H4C—C4—H4D56.3C11—C16—C15121.05 (16)
C1—C4—H4E109.5C11—C16—H16119.5
H4A—C4—H4E56.3C15—C16—H16119.5
H4B—C4—H4E141.1C2—C17—C11114.36 (12)
H4C—C4—H4E56.3C2—C17—C18109.95 (12)
H4D—C4—H4E109.5C11—C17—C18112.45 (12)
C1—C4—H4F109.5C2—C17—H17106.5
H4A—C4—H4F56.3C11—C17—H17106.5
H4B—C4—H4F56.3C18—C17—H17106.5
H4C—C4—H4F141.1C19—C18—C20110.08 (14)
H4D—C4—H4F109.5C19—C18—C17110.68 (14)
H4E—C4—H4F109.5C20—C18—C17112.15 (13)
C6—C5—C10121.1 (2)C19—C18—H18107.9
C6—C5—N1120.4 (2)C20—C18—H18107.9
C10—C5—N1118.53 (19)C17—C18—H18107.9
C5—C6—C7118.2 (3)N4—C19—C18177.99 (18)
C5—C6—H6120.9N5—C20—C18178.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H1N3···N4i0.862.413.159 (2)146
N3—H2N3···N2ii0.862.533.325 (2)155

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1/2, y, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2101).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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