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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o689.
Published online 2008 March 12. doi:  10.1107/S1600536808006156
PMCID: PMC2961049

6-Amino-3-methyl-4-(4-nitro­phen­yl)-1-phenyl­pyrazolo[3,4-b]pyridine-5-carbonitrile

Abstract

The title compound, C20H14N6O2, contains four rings. The dihedral angle between the pyridine ring and the pyrazole ring is 1.9 (1)°, i.e. almost coplanar, which gives rise to a conjugated structure. The dihedral angle between the nitro-substituted phenyl ring and the pyridine ring is 76.3 (1)° and that between the pyrazole ring and the non-substituted phenyl ring is 40.5 (1)°. In the crystal structure, symmetry-related mol­ecules are linked by N—H(...)O and C—H(...)N hydrogen bonds.

Related literature

For related structures, see: Quiroga et al. (1999 [triangle]); Zhu et al. (2005 [triangle]). For the biological and pharmacological activities, see: Kamal et al. (1991 [triangle]); Straub et al. (2001 [triangle]); Sekikawa et al. (1973 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o689-scheme1.jpg

Experimental

Crystal data

  • C20H14N6O2
  • M r = 370.37
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o689-efi1.jpg
  • a = 16.470 (11) Å
  • b = 9.742 (7) Å
  • c = 23.46 (2) Å
  • β = 105.857 (8)°
  • V = 3621 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 294 (2) K
  • 0.39 × 0.25 × 0.15 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.945, T max = 0.986
  • 13443 measured reflections
  • 3374 independent reflections
  • 2287 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.121
  • S = 1.02
  • 3374 reflections
  • 254 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [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/S1600536808006156/su2046sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006156/su2046Isup2.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) and the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 2008 HASTIT006).

supplementary crystallographic information

Comment

The structure of the title compound, (I), is shown below. Dimensions are available in the archived CIF.

For related literature, see Quiroga et al. (1999); Zhu et al. (2005). For the biological and pharmacological activities, see Kamal et al. (1991); Straub et al. (2001); Sekikawa et al. (1973).

Experimental

The title compound was prepared by the following procedure: To 1 ml of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) were added 4-nitrobenzaldehyde (1 mmol), malononitrile (1 mmol) and 5-amino-3-methyl-1-phenylpyrazole (1 mmol). The reaction mixture was stirred at 80°C for 10 hrs. The yellow solid product that was obtained was collected by suction and rinsed with water and ethanol (yield 93%). Single crystals of the title compound were obtained by slow evaporation from ethanol.

Refinement

H-atoms were included in calculated positions and treated as riding atoms: N—H = 0.86 Å and C—H = 0.93 - 0.96 Å with Uiso(H) = 1.5Ueq(CH3) and 1.2Ueq(NH2,CH).

Figures

Fig. 1.
Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Crystal data

C20H14N6O2F000 = 1536
Mr = 370.37Dx = 1.359 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2825 reflections
a = 16.470 (11) Åθ = 2.5–21.6º
b = 9.742 (7) ŵ = 0.09 mm1
c = 23.46 (2) ÅT = 294 (2) K
β = 105.857 (8)ºBlock, yellow
V = 3621 (5) Å30.39 × 0.25 × 0.15 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer3374 independent reflections
Radiation source: fine-focus sealed tube2287 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 294(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −19→19
Tmin = 0.945, Tmax = 0.986k = −11→11
13443 measured reflectionsl = −28→28

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.122  w = 1/[σ2(Fo2) + (0.0546P)2 + 1.3917P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3374 reflectionsΔρmax = 0.18 e Å3
254 parametersΔρmin = −0.16 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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*/Ueq
C10.14291 (11)0.3249 (2)0.22385 (8)0.0539 (5)
C20.13161 (11)0.17956 (19)0.22657 (8)0.0508 (4)
C30.12907 (11)0.06720 (19)0.18900 (8)0.0514 (5)
C40.11731 (12)−0.0608 (2)0.21136 (8)0.0579 (5)
C50.10829 (12)−0.0751 (2)0.27046 (8)0.0586 (5)
C60.11882 (11)0.1536 (2)0.28254 (8)0.0515 (5)
C70.16473 (14)0.4076 (2)0.17675 (9)0.0675 (6)
H7A0.11710.41090.14240.101*
H7B0.21170.36630.16650.101*
H7C0.17950.49920.19100.101*
C80.11094 (16)−0.1792 (2)0.17454 (10)0.0771 (7)
C90.13676 (11)0.08314 (19)0.12762 (8)0.0516 (5)
C100.06928 (13)0.1307 (3)0.08327 (9)0.0750 (7)
H100.01870.15100.09190.090*
C110.07559 (14)0.1485 (2)0.02644 (9)0.0749 (7)
H110.03000.1808−0.00340.090*
C120.15017 (13)0.11769 (19)0.01483 (8)0.0573 (5)
C130.21832 (13)0.0685 (2)0.05755 (9)0.0656 (6)
H130.26840.04710.04840.079*
C140.21111 (12)0.0516 (2)0.11416 (8)0.0617 (5)
H140.25680.01840.14370.074*
C150.11107 (11)0.3128 (2)0.36614 (8)0.0539 (5)
C160.14851 (12)0.2328 (2)0.41484 (9)0.0610 (5)
H160.17920.15500.41070.073*
C170.13988 (13)0.2697 (2)0.47001 (9)0.0674 (6)
H170.16400.21550.50290.081*
C180.09585 (14)0.3862 (3)0.47639 (10)0.0732 (7)
H180.09100.41110.51360.088*
C190.05918 (14)0.4654 (2)0.42781 (11)0.0722 (6)
H190.02940.54400.43220.087*
C200.06610 (12)0.4293 (2)0.37226 (10)0.0636 (5)
H200.04080.48280.33940.076*
N10.12015 (10)0.27857 (17)0.30914 (7)0.0569 (4)
N20.13518 (10)0.38354 (17)0.27275 (7)0.0592 (4)
N30.10738 (10)0.03211 (17)0.30563 (6)0.0575 (4)
N40.1045 (2)−0.2721 (2)0.14393 (10)0.1197 (9)
N50.10113 (12)−0.20117 (18)0.29226 (8)0.0784 (6)
H5A0.0962−0.21020.32760.094*
H5B0.1015−0.27260.27080.094*
N60.15858 (14)0.14160 (19)−0.04520 (8)0.0750 (5)
O10.22406 (12)0.1080 (2)−0.05634 (7)0.0962 (6)
O20.09960 (14)0.1956 (2)−0.08097 (7)0.1125 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0489 (10)0.0631 (12)0.0496 (11)0.0009 (9)0.0132 (8)0.0005 (9)
C20.0476 (10)0.0611 (12)0.0439 (10)0.0024 (8)0.0128 (8)−0.0009 (9)
C30.0479 (10)0.0626 (12)0.0425 (10)0.0093 (9)0.0102 (8)0.0001 (9)
C40.0672 (13)0.0611 (12)0.0430 (10)0.0062 (9)0.0111 (9)−0.0021 (9)
C50.0655 (12)0.0633 (13)0.0455 (11)−0.0049 (10)0.0128 (9)−0.0017 (9)
C60.0499 (11)0.0610 (12)0.0439 (10)−0.0028 (9)0.0135 (8)−0.0063 (9)
C70.0721 (13)0.0687 (13)0.0632 (13)−0.0008 (11)0.0210 (10)0.0070 (11)
C80.1150 (19)0.0602 (14)0.0533 (13)0.0113 (13)0.0184 (12)0.0015 (11)
C90.0545 (11)0.0572 (11)0.0428 (10)0.0114 (9)0.0128 (8)−0.0004 (8)
C100.0606 (13)0.1155 (19)0.0501 (11)0.0348 (12)0.0173 (10)0.0073 (12)
C110.0726 (14)0.1049 (18)0.0449 (11)0.0368 (13)0.0120 (10)0.0089 (11)
C120.0760 (13)0.0552 (11)0.0441 (10)0.0137 (10)0.0221 (9)−0.0006 (9)
C130.0623 (12)0.0805 (14)0.0601 (13)0.0194 (11)0.0267 (10)0.0038 (10)
C140.0560 (12)0.0791 (14)0.0490 (11)0.0208 (10)0.0130 (9)0.0070 (10)
C150.0470 (10)0.0664 (12)0.0498 (11)−0.0113 (9)0.0157 (8)−0.0135 (9)
C160.0535 (11)0.0732 (13)0.0557 (12)−0.0040 (10)0.0141 (9)−0.0105 (10)
C170.0603 (12)0.0911 (16)0.0513 (11)−0.0140 (11)0.0161 (9)−0.0092 (11)
C180.0684 (14)0.0973 (18)0.0617 (14)−0.0247 (13)0.0310 (11)−0.0278 (13)
C190.0646 (13)0.0787 (15)0.0832 (17)−0.0096 (11)0.0370 (12)−0.0239 (13)
C200.0565 (12)0.0698 (13)0.0672 (13)−0.0063 (10)0.0216 (10)−0.0086 (11)
N10.0641 (10)0.0628 (10)0.0464 (9)−0.0078 (8)0.0193 (7)−0.0086 (8)
N20.0627 (10)0.0615 (10)0.0540 (10)−0.0048 (8)0.0171 (8)−0.0040 (8)
N30.0638 (10)0.0638 (11)0.0449 (9)−0.0083 (8)0.0151 (7)−0.0043 (8)
N40.206 (3)0.0672 (14)0.0819 (15)0.0173 (16)0.0322 (16)−0.0113 (13)
N50.1225 (16)0.0619 (11)0.0510 (10)−0.0128 (10)0.0238 (10)−0.0003 (8)
N60.1076 (16)0.0713 (12)0.0516 (10)0.0168 (11)0.0311 (11)0.0007 (9)
O10.1160 (14)0.1135 (14)0.0769 (11)0.0135 (11)0.0567 (11)0.0013 (10)
O20.1504 (18)0.1383 (16)0.0511 (9)0.0640 (14)0.0312 (10)0.0233 (10)

Geometric parameters (Å, °)

C1—N21.318 (3)C12—C131.371 (3)
C1—C21.431 (3)C12—N61.471 (3)
C1—C71.489 (3)C13—C141.375 (3)
C2—C31.399 (3)C13—H130.9300
C2—C61.408 (3)C14—H140.9300
C3—C41.386 (3)C15—C161.381 (3)
C3—C91.488 (3)C15—C201.384 (3)
C4—C81.428 (3)C15—N11.425 (2)
C4—C51.441 (3)C16—C171.387 (3)
C5—N31.333 (2)C16—H160.9300
C5—N51.348 (3)C17—C181.376 (3)
C6—N31.336 (2)C17—H170.9300
C6—N11.365 (2)C18—C191.372 (3)
C7—H7A0.9600C18—H180.9300
C7—H7B0.9600C19—C201.384 (3)
C7—H7C0.9600C19—H190.9300
C8—N41.142 (3)C20—H200.9300
C9—C101.378 (3)N1—N21.397 (2)
C9—C141.380 (3)N5—H5A0.8600
C10—C111.376 (3)N5—H5B0.8600
C10—H100.9300N6—O21.216 (2)
C11—C121.362 (3)N6—O11.222 (2)
C11—H110.9300
N2—C1—C2110.21 (17)C13—C12—N6118.86 (19)
N2—C1—C7120.72 (18)C12—C13—C14118.58 (18)
C2—C1—C7129.00 (18)C12—C13—H13120.7
C3—C2—C6117.42 (18)C14—C13—H13120.7
C3—C2—C1136.70 (18)C13—C14—C9120.68 (17)
C6—C2—C1105.87 (16)C13—C14—H14119.7
C4—C3—C2116.66 (17)C9—C14—H14119.7
C4—C3—C9121.18 (17)C16—C15—C20120.50 (19)
C2—C3—C9122.16 (17)C16—C15—N1120.44 (18)
C3—C4—C8119.51 (18)C20—C15—N1119.04 (18)
C3—C4—C5120.85 (17)C15—C16—C17119.3 (2)
C8—C4—C5119.60 (19)C15—C16—H16120.4
N3—C5—N5117.52 (18)C17—C16—H16120.4
N3—C5—C4122.75 (19)C18—C17—C16120.4 (2)
N5—C5—C4119.73 (18)C18—C17—H17119.8
N3—C6—N1126.23 (17)C16—C17—H17119.8
N3—C6—C2127.62 (17)C19—C18—C17119.9 (2)
N1—C6—C2106.15 (17)C19—C18—H18120.0
C1—C7—H7A109.5C17—C18—H18120.0
C1—C7—H7B109.5C18—C19—C20120.5 (2)
H7A—C7—H7B109.5C18—C19—H19119.7
C1—C7—H7C109.5C20—C19—H19119.7
H7A—C7—H7C109.5C19—C20—C15119.4 (2)
H7B—C7—H7C109.5C19—C20—H20120.3
N4—C8—C4178.2 (3)C15—C20—H20120.3
C10—C9—C14119.01 (18)C6—N1—N2110.91 (15)
C10—C9—C3120.08 (17)C6—N1—C15130.13 (16)
C14—C9—C3120.91 (16)N2—N1—C15118.94 (16)
C11—C10—C9120.98 (19)C1—N2—N1106.83 (16)
C11—C10—H10119.5C5—N3—C6114.61 (17)
C9—C10—H10119.5C5—N5—H5A120.0
C12—C11—C10118.46 (18)C5—N5—H5B120.0
C12—C11—H11120.8H5A—N5—H5B120.0
C10—C11—H11120.8O2—N6—O1123.6 (2)
C11—C12—C13122.28 (18)O2—N6—C12117.6 (2)
C11—C12—N6118.84 (18)O1—N6—C12118.81 (19)
N2—C1—C2—C3176.8 (2)N6—C12—C13—C14177.45 (19)
C7—C1—C2—C3−6.2 (4)C12—C13—C14—C90.1 (3)
N2—C1—C2—C6−1.8 (2)C10—C9—C14—C130.7 (3)
C7—C1—C2—C6175.12 (18)C3—C9—C14—C13−178.96 (19)
C6—C2—C3—C4−2.4 (2)C20—C15—C16—C170.6 (3)
C1—C2—C3—C4179.1 (2)N1—C15—C16—C17178.90 (17)
C6—C2—C3—C9176.39 (16)C15—C16—C17—C18−1.2 (3)
C1—C2—C3—C9−2.1 (3)C16—C17—C18—C190.9 (3)
C2—C3—C4—C8177.67 (19)C17—C18—C19—C200.0 (3)
C9—C3—C4—C8−1.1 (3)C18—C19—C20—C15−0.5 (3)
C2—C3—C4—C50.0 (3)C16—C15—C20—C190.2 (3)
C9—C3—C4—C5−178.80 (17)N1—C15—C20—C19−178.06 (17)
C3—C4—C5—N32.7 (3)N3—C6—N1—N2178.85 (17)
C8—C4—C5—N3−174.99 (19)C2—C6—N1—N2−1.3 (2)
C3—C4—C5—N5−176.71 (18)N3—C6—N1—C150.7 (3)
C8—C4—C5—N55.6 (3)C2—C6—N1—C15−179.46 (17)
C3—C2—C6—N32.7 (3)C16—C15—N1—C640.1 (3)
C1—C2—C6—N3−178.33 (18)C20—C15—N1—C6−141.6 (2)
C3—C2—C6—N1−177.13 (15)C16—C15—N1—N2−137.89 (18)
C1—C2—C6—N11.82 (19)C20—C15—N1—N240.4 (2)
C3—C4—C8—N4−45 (11)C2—C1—N2—N11.0 (2)
C5—C4—C8—N4132 (10)C7—C1—N2—N1−176.20 (16)
C4—C3—C9—C10102.6 (2)C6—N1—N2—C10.2 (2)
C2—C3—C9—C10−76.2 (3)C15—N1—N2—C1178.58 (15)
C4—C3—C9—C14−77.8 (3)N5—C5—N3—C6176.90 (17)
C2—C3—C9—C14103.5 (2)C4—C5—N3—C6−2.5 (3)
C14—C9—C10—C11−0.9 (3)N1—C6—N3—C5179.64 (18)
C3—C9—C10—C11178.8 (2)C2—C6—N3—C5−0.2 (3)
C9—C10—C11—C120.2 (4)C11—C12—N6—O24.2 (3)
C10—C11—C12—C130.7 (4)C13—C12—N6—O2−174.2 (2)
C10—C11—C12—N6−177.6 (2)C11—C12—N6—O1−176.6 (2)
C11—C12—C13—C14−0.8 (3)C13—C12—N6—O15.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N5—H5A···O2i0.862.132.981 (3)168
C14—H14···N2ii0.932.613.529 (3)168

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2046).

References

  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kamal, A. M., Atalla, A. A., Mohamed, T. A. A. & Geies, A. (1991). Z. Naturforsch. Teil B, 46, 541–544.
  • Quiroga, J., Alvarado, M., Insuasty, B., Moreno, R., Ravina, E., Estevez, I. & de Almedia, R. H. (1999). J. Heterocycl. Chem.36, 1311–1316.
  • Sekikawa, I., Nishie, J., Tono-oka, S., Tanaka, Y. & Kakimoto, S. (1973). J. Heterocycl. Chem.10, 931–932.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Straub, A., Stasch, J.-P., Alonso-Alija, C., Benet-Buchholz, J., Ducke, B., Feurer, A. & Furstner, C. (2001). Bioorg. Med. Chem. Lett.11, 781–784. [PubMed]
  • Zhu, S.-L., Tu, S.-J., Li, T.-J., Zhang, X.-J., Ji, S.-J. & Zhang, Y. (2005). Chin. J. Org. Chem 25, 987–990.

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