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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2356.
Published online 2008 November 13. doi:  10.1107/S1600536808037240
PMCID: PMC2959918

1-Methyl-7-(4-nitro­phen­yl)-3-phenyl­pyrazolo[3,4-b]pyrrolo[3,4-d]pyridine-6,8(3H,7H)-dione

Abstract

In the title compound, C21H13N5O4, the dihedral angles formed between the planes of the phenyl and nitro­phenyl rings and that of the heterotricyclic plane are 41.29 (7) and 61.35 (6)°, respectively. In the crystal, weak C—H(...)O interactions help to establish the packing.

Related literature

For background, see: Carneiro et al. (2005 [triangle]); Menegatti et al. (2006 [triangle]); Barreiro et al. (2006 [triangle]).

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Object name is e-64-o2356-scheme1.jpg

Experimental

Crystal data

  • C21H13N5O4
  • M r = 399.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2356-efi1.jpg
  • a = 9.677 (2) Å
  • b = 12.141 (3) Å
  • c = 17.438 (4) Å
  • β = 119.451 (16)°
  • V = 1784.0 (8) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 0.89 mm−1
  • T = 297 (2) K
  • 0.3 × 0.1 × 0.08 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 3813 measured reflections
  • 3259 independent reflections
  • 2578 reflections with I > 2σ(I)
  • R int = 0.023
  • 2 standard reflections frequency: 120 min intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.198
  • S = 1.07
  • 3259 reflections
  • 273 parameters
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: CAD-4-PC (Enraf–Nonius, 1993 [triangle]); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037240/tk2318sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037240/tk2318Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge the financial support of Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq, Pró-Reitoria de Pesquisa e Pós Graduação-PRPPG/UFG.

supplementary crystallographic information

Comment

The title compound (I) (Carneiro et al., 2005; Menegatti et al., 2006; Barreiro et al., 2006) features a novel functionalized three-fused rings skeleton, Fig. 1. The bond distances within the pyridine ring are consistent with aromatic delocalization but the pyrazole ring presents a double bond, Table 1. The C8—C9 and C11—C12 bond lengths are elongated from the expected distances by 0.025 and 0.03 Å, respectively.

The pyrazolo[3,4-b]pyrrolo[3,4-d]pyridine moiety is planar (plane α, with r.m.s. deviation of about 0.01 Å). Relative to plane α, the phenyl rings C21/C26 and C13/C18 form dihedral angles of 41.29 (7)° and 61.35 (6)°, respectively. The latter ring is slanted from the plane α so that the C21 and C24 atoms are shifted by 0.118 (3) and 0.436 (4) Å from the plane α, respectively. This might be in part due to the participation of the oxygen atom O30 in two C-H···O contacts, C7—H7···O30i and C18—H18···O30ii; see Table 2 for details. The former interaction connects molecules into a linear chain along the b-axis and the latter connects parallel chains to form sheets in the plane of approximate indices (-1 0 2). The molecules in the linear chains interact with centrosymmetrically related chains via π···π stacking [closest distance for C25···C25iv: 3.380 (5) Å; (iv): 1 - x, 1 - y, 1 - z]. In addition, molecules participate in a C—H···π interaction: C25—H25···C15iii [2.74 Å, 3.539 (4) Å, 144°; (iii) 1 -x, -y, 1 -z] to consolidate the crystal packing, Fig. 2.

Experimental

Compound (I) was synthesized as described previously (Menegatti et al., 2006). A colourless needle for crystallography was obtained by slow evaporation of a MeOH solution of (I) at room temperature.

Refinement

All H atoms were positioned in idealized positions in the riding model approximation with C—H = 0.93 - 0.96 Å, and with Uiso(H) = 1.2-1.5 Ueq(C).

Figures

Fig. 1.
View of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Fig. 2.
Packing diagram of (I). Intermolecular interactions are shown as dashed lines. Only the H atoms involved in intermolecular contacts are shown.

Crystal data

C21H13N5O4F000 = 824
Mr = 399.36Dx = 1.487 Mg m3
Monoclinic, P21/cCu Kα radiation λ = 1.5418 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 9.677 (2) Åθ = 14.8–40.8º
b = 12.141 (3) ŵ = 0.89 mm1
c = 17.438 (4) ÅT = 297 (2) K
β = 119.451 (16)ºPrism, colourless
V = 1784.0 (8) Å30.3 × 0.1 × 0.08 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerθmax = 67.9º
T = 297(2) Kθmin = 4.7º
Non–profiled ω/2ω scansh = 0→11
Absorption correction: nonek = −14→1
3813 measured reflectionsl = −20→18
3259 independent reflections2 standard reflections
2578 reflections with I > 2σ(I) every 120 min
Rint = 0.023 intensity decay: 1%

Refinement

Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.152P)2 + 0.0892P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.049(Δ/σ)max < 0.001
wR(F2) = 0.198Δρmax = 0.48 e Å3
S = 1.07Δρmin = −0.38 e Å3
3259 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
273 parametersExtinction coefficient: 0.0114 (15)

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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C3−0.0408 (3)0.00360 (19)0.37884 (14)0.0446 (5)
C40.1214 (3)0.00403 (18)0.44674 (14)0.0425 (5)
C50.1708 (3)−0.10707 (19)0.45566 (14)0.0431 (5)
C70.4230 (3)−0.07508 (19)0.56234 (16)0.0500 (6)
H70.5254−0.09870.60160.06*
C80.3874 (3)0.03680 (18)0.55955 (14)0.0452 (5)
C90.4917 (3)0.13014 (18)0.61003 (15)0.0455 (5)
C110.2390 (3)0.19832 (18)0.51522 (14)0.0442 (5)
C120.2381 (3)0.07694 (18)0.50241 (14)0.0427 (5)
C130.0263 (3)−0.28159 (19)0.37880 (16)0.0462 (5)
C140.0917 (3)−0.3569 (2)0.44682 (16)0.0514 (6)
H140.1508−0.33320.50490.062*
C150.0681 (3)−0.4684 (2)0.42733 (19)0.0584 (7)
H150.1132−0.51980.47260.07*
C16−0.0219 (3)−0.5039 (2)0.3414 (2)0.0606 (7)
H16−0.0394−0.57870.32890.073*
C17−0.0852 (3)−0.4279 (2)0.27450 (19)0.0616 (7)
H17−0.1454−0.45160.21650.074*
C18−0.0604 (3)−0.3157 (2)0.29235 (16)0.0542 (6)
H18−0.1016−0.26450.24680.065*
C19−0.1519 (3)0.0984 (2)0.34157 (17)0.0549 (6)
H19A−0.25920.07270.31720.082*
H19B−0.13830.13290.29620.082*
H19C−0.130.15090.38740.082*
C210.4456 (3)0.33472 (18)0.60655 (14)0.0426 (5)
C220.3722 (3)0.3988 (2)0.64181 (16)0.0489 (5)
H220.29480.36850.65230.059*
C230.4150 (3)0.5083 (2)0.66135 (16)0.0507 (6)
H230.36820.55250.68590.061*
C240.5284 (3)0.55016 (18)0.64357 (14)0.0461 (5)
C250.6055 (3)0.4867 (2)0.61069 (15)0.0496 (6)
H250.68420.51690.60120.06*
C260.5631 (3)0.37726 (19)0.59215 (15)0.0480 (5)
H260.61340.33250.57010.058*
O200.6301 (2)0.12980 (14)0.66441 (12)0.0587 (5)
O270.1327 (2)0.26369 (14)0.47771 (13)0.0592 (5)
O300.6424 (2)0.70822 (16)0.62526 (14)0.0675 (6)
N10.0428 (2)−0.16562 (16)0.39668 (12)0.0469 (5)
N2−0.0858 (2)−0.09733 (17)0.34974 (13)0.0497 (5)
N60.3155 (2)−0.14946 (16)0.51075 (13)0.0489 (5)
N100.3932 (2)0.22413 (15)0.58107 (12)0.0453 (5)
N280.5686 (3)0.66741 (18)0.65876 (13)0.0561 (6)
O290.5258 (3)0.71978 (17)0.70287 (16)0.0830 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C30.0414 (11)0.0460 (11)0.0430 (11)0.0022 (9)0.0181 (9)0.0009 (9)
C40.0394 (11)0.0436 (11)0.0430 (11)0.0017 (9)0.0190 (9)0.0022 (9)
C50.0401 (11)0.0427 (11)0.0459 (11)0.0016 (9)0.0207 (9)0.0017 (9)
C70.0398 (11)0.0408 (11)0.0580 (13)0.0049 (9)0.0152 (10)0.0057 (9)
C80.0418 (11)0.0406 (11)0.0479 (11)0.0017 (9)0.0180 (10)0.0039 (9)
C90.0436 (12)0.0393 (12)0.0490 (12)0.0048 (9)0.0192 (10)0.0033 (9)
C110.0407 (11)0.0425 (12)0.0464 (11)0.0035 (9)0.0191 (9)0.0036 (9)
C120.0410 (11)0.0411 (11)0.0444 (11)0.0046 (9)0.0196 (9)0.0045 (8)
C130.0411 (11)0.0424 (12)0.0567 (12)−0.0020 (9)0.0252 (10)−0.0056 (9)
C140.0511 (13)0.0476 (13)0.0544 (13)−0.0011 (10)0.0250 (11)−0.0023 (10)
C150.0586 (15)0.0462 (13)0.0755 (17)0.0040 (11)0.0368 (13)0.0043 (12)
C160.0550 (14)0.0457 (13)0.0872 (19)−0.0057 (11)0.0397 (14)−0.0145 (12)
C170.0524 (14)0.0661 (17)0.0650 (15)−0.0068 (12)0.0280 (12)−0.0226 (13)
C180.0492 (13)0.0567 (14)0.0548 (13)−0.0003 (11)0.0241 (11)−0.0034 (11)
C190.0426 (12)0.0534 (14)0.0545 (13)0.0090 (10)0.0130 (11)0.0022 (10)
C210.0389 (11)0.0386 (11)0.0436 (10)0.0011 (8)0.0152 (9)0.0014 (8)
C220.0469 (12)0.0464 (12)0.0550 (12)−0.0016 (10)0.0264 (11)−0.0028 (10)
C230.0475 (12)0.0483 (12)0.0530 (12)0.0023 (10)0.0222 (10)−0.0079 (10)
C240.0420 (11)0.0390 (11)0.0441 (11)−0.0020 (9)0.0109 (9)−0.0046 (9)
C250.0441 (12)0.0463 (12)0.0581 (13)−0.0018 (9)0.0248 (11)0.0008 (10)
C260.0454 (12)0.0457 (12)0.0528 (12)0.0029 (10)0.0241 (10)−0.0026 (10)
O200.0414 (9)0.0510 (10)0.0623 (11)0.0035 (7)0.0089 (8)0.0036 (7)
O270.0457 (9)0.0434 (9)0.0709 (11)0.0100 (7)0.0152 (8)0.0002 (8)
O300.0607 (11)0.0490 (10)0.0811 (13)−0.0093 (9)0.0258 (10)0.0001 (9)
N10.0415 (10)0.0421 (10)0.0497 (10)−0.0009 (8)0.0167 (8)−0.0029 (8)
N20.0411 (10)0.0498 (11)0.0498 (10)0.0019 (8)0.0159 (9)−0.0013 (8)
N60.0420 (10)0.0395 (9)0.0568 (11)0.0039 (8)0.0178 (9)0.0014 (8)
N100.0408 (10)0.0379 (10)0.0493 (10)0.0013 (8)0.0161 (8)0.0012 (7)
N280.0528 (12)0.0460 (11)0.0535 (11)−0.0040 (9)0.0139 (10)−0.0058 (9)
O290.1122 (19)0.0534 (11)0.0905 (15)−0.0043 (12)0.0553 (15)−0.0207 (10)

Geometric parameters (Å, °)

C3—N21.316 (3)C16—C171.373 (4)
C3—C41.428 (3)C16—H160.93
C3—C191.489 (3)C17—C181.392 (4)
C4—C121.387 (3)C17—H170.93
C4—C51.414 (3)C18—H180.93
C5—N61.351 (3)C19—H19A0.96
C5—N11.358 (3)C19—H19B0.96
C7—N61.337 (3)C19—H19C0.96
C7—C81.396 (3)C21—C261.380 (3)
C7—H70.93C21—C221.385 (3)
C8—C121.379 (3)C21—N101.427 (3)
C8—C91.484 (3)C22—C231.384 (3)
C9—O201.202 (3)C22—H220.93
C9—N101.411 (3)C23—C241.376 (4)
C11—O271.206 (3)C23—H230.93
C11—N101.400 (3)C24—C251.378 (3)
C11—C121.490 (3)C24—N281.465 (3)
C13—C181.380 (3)C25—C261.382 (3)
C13—C141.380 (3)C25—H250.93
C13—N11.434 (3)C26—H260.93
C14—C151.387 (3)O30—N281.228 (3)
C14—H140.93N1—N21.380 (3)
C15—C161.381 (4)N28—O291.216 (3)
C15—H150.93
N2—C3—C4110.1 (2)C13—C18—C17118.9 (2)
N2—C3—C19121.4 (2)C13—C18—H18120.6
C4—C3—C19128.5 (2)C17—C18—H18120.6
C12—C4—C5114.68 (19)C3—C19—H19A109.5
C12—C4—C3140.1 (2)C3—C19—H19B109.5
C5—C4—C3105.19 (19)H19A—C19—H19B109.5
N6—C5—N1125.4 (2)C3—C19—H19C109.5
N6—C5—C4128.1 (2)H19A—C19—H19C109.5
N1—C5—C4106.44 (19)H19B—C19—H19C109.5
N6—C7—C8122.5 (2)C26—C21—C22121.3 (2)
N6—C7—H7118.8C26—C21—N10119.6 (2)
C8—C7—H7118.8C22—C21—N10119.1 (2)
C12—C8—C7121.5 (2)C23—C22—C21119.5 (2)
C12—C8—C9108.9 (2)C23—C22—H22120.2
C7—C8—C9129.6 (2)C21—C22—H22120.2
O20—C9—N10125.4 (2)C24—C23—C22118.3 (2)
O20—C9—C8129.4 (2)C24—C23—H23120.8
N10—C9—C8105.23 (18)C22—C23—H23120.8
O27—C11—N10125.4 (2)C23—C24—C25122.8 (2)
O27—C11—C12129.0 (2)C23—C24—N28119.2 (2)
N10—C11—C12105.65 (18)C25—C24—N28117.9 (2)
C8—C12—C4118.9 (2)C24—C25—C26118.4 (2)
C8—C12—C11108.3 (2)C24—C25—H25120.8
C4—C12—C11132.8 (2)C26—C25—H25120.8
C18—C13—C14121.1 (2)C21—C26—C25119.6 (2)
C18—C13—N1118.3 (2)C21—C26—H26120.2
C14—C13—N1120.6 (2)C25—C26—H26120.2
C13—C14—C15119.0 (2)C5—N1—N2110.82 (18)
C13—C14—H14120.5C5—N1—C13129.86 (19)
C15—C14—H14120.5N2—N1—C13119.32 (18)
C16—C15—C14120.7 (2)C3—N2—N1107.44 (18)
C16—C15—H15119.6C7—N6—C5114.4 (2)
C14—C15—H15119.6C11—N10—C9111.87 (18)
C17—C16—C15119.4 (2)C11—N10—C21122.56 (18)
C17—C16—H16120.3C9—N10—C21125.15 (19)
C15—C16—H16120.3O29—N28—O30123.2 (2)
C16—C17—C18120.8 (3)O29—N28—C24118.7 (2)
C16—C17—H17119.6O30—N28—C24118.1 (2)
C18—C17—H17119.6
N2—C3—C4—C12179.4 (3)C22—C23—C24—N28176.4 (2)
C19—C3—C4—C12−0.2 (5)C23—C24—C25—C262.2 (4)
N2—C3—C4—C50.3 (3)N28—C24—C25—C26−177.0 (2)
C19—C3—C4—C5−179.4 (2)C22—C21—C26—C25−2.0 (3)
C12—C4—C5—N6−0.3 (3)N10—C21—C26—C25175.2 (2)
C3—C4—C5—N6179.1 (2)C24—C25—C26—C210.2 (3)
C12—C4—C5—N1−179.93 (19)N6—C5—N1—N2−179.1 (2)
C3—C4—C5—N1−0.5 (2)C4—C5—N1—N20.6 (2)
N6—C7—C8—C12−0.4 (4)N6—C5—N1—C131.1 (4)
N6—C7—C8—C9−178.5 (2)C4—C5—N1—C13−179.2 (2)
C12—C8—C9—O20−178.1 (3)C18—C13—N1—C5−140.1 (2)
C7—C8—C9—O200.2 (4)C14—C13—N1—C541.9 (4)
C12—C8—C9—N102.0 (3)C18—C13—N1—N240.1 (3)
C7—C8—C9—N10−179.7 (2)C14—C13—N1—N2−137.9 (2)
C7—C8—C12—C40.0 (3)C4—C3—N2—N10.1 (3)
C9—C8—C12—C4178.5 (2)C19—C3—N2—N1179.8 (2)
C7—C8—C12—C11−179.7 (2)C5—N1—N2—C3−0.4 (3)
C9—C8—C12—C11−1.2 (2)C13—N1—N2—C3179.4 (2)
C5—C4—C12—C80.3 (3)C8—C7—N6—C50.4 (4)
C3—C4—C12—C8−178.8 (3)N1—C5—N6—C7179.5 (2)
C5—C4—C12—C11179.9 (2)C4—C5—N6—C7−0.1 (4)
C3—C4—C12—C110.9 (5)O27—C11—N10—C9−178.1 (2)
O27—C11—C12—C8179.4 (2)C12—C11—N10—C91.3 (2)
N10—C11—C12—C80.0 (2)O27—C11—N10—C21−5.2 (4)
O27—C11—C12—C4−0.3 (4)C12—C11—N10—C21174.2 (2)
N10—C11—C12—C4−179.6 (2)O20—C9—N10—C11178.1 (2)
C18—C13—C14—C15−0.5 (4)C8—C9—N10—C11−2.0 (3)
N1—C13—C14—C15177.4 (2)O20—C9—N10—C215.4 (4)
C13—C14—C15—C16−1.1 (4)C8—C9—N10—C21−174.7 (2)
C14—C15—C16—C171.5 (4)C26—C21—N10—C11−115.1 (2)
C15—C16—C17—C18−0.3 (4)C22—C21—N10—C1162.1 (3)
C14—C13—C18—C171.8 (4)C26—C21—N10—C956.9 (3)
N1—C13—C18—C17−176.2 (2)C22—C21—N10—C9−125.9 (2)
C16—C17—C18—C13−1.4 (4)C23—C24—N28—O2914.8 (3)
C26—C21—C22—C231.4 (4)C25—C24—N28—O29−166.1 (2)
N10—C21—C22—C23−175.8 (2)C23—C24—N28—O30−164.4 (2)
C21—C22—C23—C241.0 (4)C25—C24—N28—O3014.8 (3)
C22—C23—C24—C25−2.8 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7···O30i0.932.553.216 (3)129
C18—H18···O30ii0.932.443.197 (3)139

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2318).

References

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