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Acta Cryst. (2008). E64, o689    [ doi:10.1107/S1600536808006156 ]

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

X.-Y. Zhang, X.-Y. Li, X. Wang, X.-S. Fan and G.-R. Qu

Abstract top

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.

Comment top

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).

Related literature top

For related structures, 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 top

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 top

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).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
6-Amino-3-methyl-4-(4-nitrophenyl)-1-phenylpyrazolo[3,4-b]pyridine- 5-carbonitrile top
Crystal data top
C20H14N6O2F000 = 1536
Mr = 370.37Dx = 1.359 Mg m−3
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 mm−1
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 top
Bruker SMART CCD area-detector
diffractometer		3374 independent reflections
Radiation source: fine-focus sealed tube2287 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 294(2) Kθmax = 25.5º
φ 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 top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-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 Å−3
254 parametersΔρmin = −0.16 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C20H14N6O2V = 3621 (5) Å3
Mr = 370.37Z = 8
Monoclinic, C2/cMo Kα
a = 16.470 (11) ŵ = 0.09 mm−1
b = 9.742 (7) ÅT = 294 (2) K
c = 23.46 (2) Å0.39 × 0.25 × 0.15 mm
β = 105.857 (8)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3374 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2287 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.986Rint = 0.027
13443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042254 parameters
wR(F2) = 0.122H-atom parameters constrained
S = 1.02Δρmax = 0.18 e Å−3
3374 reflectionsΔρmin = −0.16 e Å−3
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
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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).

references
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