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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1851.
Published online 2010 June 26. doi:  10.1107/S1600536810024748
PMCID: PMC3007069

1,3-Diallyl-1H-anthra[1,2-d]imidazole-2,6,11(3H)-trione

Abstract

In the title compound, C21H16N2O3, the fused-ring system (r.m.s. deviation = 0.067 Å) is slightly buckled at the carbonyl C atom of the anthracenyl ring system [deviation = 0.177 (1) Å] that is closer to an allyl substituent. The two allyl units lie on the same side of the fused-ring plane but are oriented in opposite directions, with N—C—C—C torsion angles of 126.9 (2) and 116.7 (2)°. In the crystal, the mol­ecules are linked into chains propagating along the b axis by C—H(...)O hydrogen bonds.

Related literature

For a related structure, see: Guimarães et al. (2009 [triangle]).

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Object name is e-66-o1851-scheme1.jpg

Experimental

Crystal data

  • C21H16N2O3
  • M r = 344.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1851-efi1.jpg
  • a = 7.8539 (2) Å
  • b = 11.5822 (3) Å
  • c = 18.1455 (4) Å
  • β = 93.537 (1)°
  • V = 1647.47 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.40 × 0.35 × 0.20 mm

Data collection

  • Bruker X8 APEXII area-detector diffractometer
  • 22612 measured reflections
  • 4806 independent reflections 4805 in Refinement?
  • 3053 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.153
  • S = 1.02
  • 4805 reflections
  • 236 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [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: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024748/ci5112sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024748/ci5112Isup2.hkl

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

Acknowledgments

The authors thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

An imidazol-one such as 1H-anthra[2,1-d]imidazole-2,6,11(3H)-trione, in which the five-membered ring is fused with an anthraquinone system, alkyl halides under catalytic conditions to yield di-N,N'-substituted derivatives that serve as starting reagents for the synthesis of other drugs. The anthraquinone system itself is found in a large number of pigments and dyes. The title compound (Scheme I, Fig. 1) is a deep orange material that may be useful as an organic fluorophone.

The title molecule features four rings that are fused together (r.m.s. deviation 0.067 Å). The fused-ring system is slightly buckled at that carbonyl C-atom, C3, of the anthracenyl system [0.177 (1) Å] that is closer to an allyl substituent. The pendant allyl units lie on the same side of the fused-ring plane but are oriented in opposite directions. The crystal packing is stabilized by C—H···O hydrogen bonds (Table 1).

Experimental

To a solution of 1H-anthra[2,1-d]imidazole-2,6,11(3H)-trione (1.00 g, 0.38 mmol), potassium carbonate (1.56 g,11 mmol) and tetra n-butyl ammonium bromide (0.12 g, 0.38 mmol) in DMF (20 ml)) was added allyl bromide (0.77 ml, 11 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue was extracted with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate-hexane (1/1) as eluent. Orange crystals were isolated when the solvent was allowed to evaporate.

Refinement

H atoms were placed in calculated positions (C–H = 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C).

Figures

Fig. 1.
Displacement ellipsoid plot (Barbour, 2001) of C21H16N2O3 at the 50% probability leve. H atoms are drawn as spheres of arbitrary radii.

Crystal data

C21H16N2O3F(000) = 720
Mr = 344.36Dx = 1.388 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4815 reflections
a = 7.8539 (2) Åθ = 2.2–29.4°
b = 11.5822 (3) ŵ = 0.09 mm1
c = 18.1455 (4) ÅT = 293 K
β = 93.537 (1)°Block, orange
V = 1647.47 (7) Å30.40 × 0.35 × 0.20 mm
Z = 4

Data collection

Bruker X8 APEXII area-detector diffractometer3053 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
graphiteθmax = 30.0°, θmin = 2.1°
[var phi] and ω scansh = −11→11
22612 measured reflectionsk = −16→16
4806 independent reflectionsl = −25→25

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.153w = 1/[σ2(Fo2) + (0.0755P)2 + 0.2066P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
4805 reflectionsΔρmax = 0.31 e Å3
236 parametersΔρmin = −0.22 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0033 (11)

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

xyzUiso*/Ueq
O10.14067 (16)0.31774 (10)0.53905 (6)0.0588 (3)
O20.23915 (17)0.77316 (10)0.53322 (7)0.0623 (3)
O30.44816 (18)0.19062 (10)0.30395 (6)0.0633 (4)
N10.35081 (16)0.29295 (10)0.40381 (6)0.0405 (3)
N20.42897 (16)0.38962 (10)0.30579 (6)0.0422 (3)
C10.32994 (17)0.40923 (11)0.41903 (7)0.0342 (3)
C20.27111 (16)0.47213 (11)0.47863 (7)0.0342 (3)
C30.18650 (18)0.41799 (12)0.54058 (7)0.0387 (3)
C40.14672 (17)0.49192 (13)0.60472 (8)0.0408 (3)
C50.0848 (2)0.43992 (15)0.66656 (9)0.0532 (4)
H50.07290.36010.66830.064*
C60.0408 (2)0.50686 (19)0.72553 (9)0.0635 (5)
H6−0.00010.47190.76710.076*
C70.0572 (2)0.62479 (19)0.72301 (10)0.0649 (5)
H70.02650.66930.76270.078*
C80.1187 (2)0.67763 (16)0.66225 (10)0.0557 (4)
H80.13010.75750.66100.067*
C90.16416 (18)0.61104 (13)0.60235 (8)0.0427 (3)
C100.22782 (18)0.66824 (13)0.53631 (8)0.0428 (3)
C110.27960 (17)0.59389 (12)0.47464 (7)0.0372 (3)
C120.3362 (2)0.64983 (13)0.41289 (8)0.0443 (3)
H120.34030.73010.41220.053*
C130.38660 (19)0.58851 (12)0.35255 (8)0.0437 (3)
H130.42190.62610.31080.052*
C140.38263 (17)0.47023 (12)0.35652 (7)0.0368 (3)
C150.4124 (2)0.28065 (13)0.33395 (8)0.0451 (4)
C160.4861 (2)0.40982 (14)0.23155 (7)0.0462 (4)
H16A0.58290.36030.22370.055*
H16B0.52340.48930.22770.055*
C170.3483 (2)0.38657 (17)0.17310 (9)0.0595 (5)
H170.30700.31140.16880.071*
C180.2826 (3)0.4620 (2)0.12858 (11)0.0851 (7)
H18A0.32060.53800.13120.102*
H18B0.19690.44090.09350.102*
C190.3537 (2)0.18926 (12)0.45100 (8)0.0431 (3)
H19A0.36150.21330.50230.052*
H19B0.45520.14480.44240.052*
C200.2018 (2)0.11366 (14)0.43818 (8)0.0498 (4)
H200.09390.14610.44030.060*
C210.2140 (3)0.00335 (17)0.42404 (11)0.0695 (5)
H21A0.3207−0.03070.42170.083*
H21B0.1158−0.04110.41630.083*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0796 (8)0.0408 (6)0.0591 (7)−0.0081 (6)0.0298 (6)−0.0009 (5)
O20.0821 (9)0.0354 (6)0.0711 (8)−0.0067 (6)0.0191 (6)−0.0114 (5)
O30.1046 (10)0.0388 (6)0.0494 (7)0.0101 (6)0.0285 (6)−0.0027 (5)
N10.0577 (7)0.0304 (6)0.0343 (6)0.0046 (5)0.0110 (5)0.0026 (4)
N20.0573 (7)0.0374 (6)0.0330 (6)0.0023 (5)0.0113 (5)0.0013 (5)
C10.0386 (7)0.0309 (6)0.0332 (6)0.0013 (5)0.0033 (5)0.0014 (5)
C20.0356 (7)0.0342 (7)0.0327 (6)0.0008 (5)0.0021 (5)0.0006 (5)
C30.0418 (7)0.0374 (7)0.0373 (7)0.0022 (6)0.0067 (6)0.0014 (6)
C40.0381 (7)0.0484 (8)0.0363 (7)0.0042 (6)0.0048 (6)−0.0015 (6)
C50.0589 (10)0.0575 (10)0.0447 (8)0.0056 (8)0.0151 (7)0.0033 (7)
C60.0697 (11)0.0793 (13)0.0434 (9)0.0053 (10)0.0189 (8)−0.0030 (9)
C70.0712 (12)0.0783 (14)0.0465 (9)0.0071 (10)0.0143 (8)−0.0192 (9)
C80.0608 (10)0.0552 (10)0.0518 (9)0.0046 (8)0.0077 (8)−0.0152 (8)
C90.0399 (7)0.0472 (8)0.0409 (7)0.0030 (6)0.0024 (6)−0.0077 (6)
C100.0443 (8)0.0376 (8)0.0466 (8)−0.0008 (6)0.0034 (6)−0.0079 (6)
C110.0395 (7)0.0330 (7)0.0392 (7)0.0004 (5)0.0028 (6)−0.0015 (5)
C120.0560 (9)0.0311 (7)0.0462 (8)−0.0028 (6)0.0064 (7)0.0023 (6)
C130.0548 (9)0.0366 (7)0.0404 (7)−0.0025 (6)0.0087 (6)0.0061 (6)
C140.0408 (7)0.0361 (7)0.0339 (7)0.0010 (6)0.0052 (5)0.0013 (5)
C150.0618 (9)0.0382 (8)0.0365 (7)0.0053 (7)0.0123 (7)0.0003 (6)
C160.0564 (9)0.0479 (8)0.0360 (7)−0.0006 (7)0.0158 (6)0.0019 (6)
C170.0686 (11)0.0708 (12)0.0406 (8)−0.0083 (9)0.0168 (8)−0.0026 (8)
C180.0780 (14)0.131 (2)0.0468 (10)0.0076 (13)0.0107 (9)0.0108 (12)
C190.0573 (9)0.0331 (7)0.0394 (7)0.0057 (6)0.0076 (6)0.0057 (6)
C200.0611 (10)0.0430 (8)0.0458 (8)0.0004 (7)0.0067 (7)0.0062 (7)
C210.0869 (13)0.0486 (10)0.0739 (13)−0.0104 (10)0.0114 (10)−0.0024 (9)

Geometric parameters (Å, °)

O1—C31.2154 (18)C8—H80.93
O2—C101.2200 (18)C9—C101.483 (2)
O3—C151.2170 (17)C10—C111.4884 (19)
N1—C11.3867 (16)C11—C121.3908 (19)
N1—C151.3918 (18)C12—C131.383 (2)
N1—C191.4742 (17)C12—H120.93
N2—C151.3708 (19)C13—C141.372 (2)
N2—C141.3757 (17)C13—H130.93
N2—C161.4647 (17)C16—C171.493 (2)
C1—C21.4056 (18)C16—H16A0.97
C1—C141.4194 (18)C16—H16B0.97
C2—C111.4139 (19)C17—C181.277 (3)
C2—C31.4800 (18)C17—H170.93
C3—C41.4934 (19)C18—H18A0.93
C4—C91.387 (2)C18—H18B0.93
C4—C51.388 (2)C19—C201.486 (2)
C5—C61.382 (2)C19—H19A0.97
C5—H50.93C19—H19B0.97
C6—C71.373 (3)C20—C211.308 (2)
C6—H60.93C20—H200.93
C7—C81.375 (3)C21—H21A0.93
C7—H70.93C21—H21B0.93
C8—C91.397 (2)
C1—N1—C15109.44 (11)C2—C11—C10121.50 (12)
C1—N1—C19132.32 (11)C13—C12—C11121.32 (13)
C15—N1—C19116.86 (11)C13—C12—H12119.3
C15—N2—C14109.90 (11)C11—C12—H12119.3
C15—N2—C16122.09 (12)C14—C13—C12117.55 (13)
C14—N2—C16128.00 (12)C14—C13—H13121.2
N1—C1—C2134.84 (12)C12—C13—H13121.2
N1—C1—C14106.28 (11)C13—C14—N2129.39 (13)
C2—C1—C14118.87 (12)C13—C14—C1123.19 (13)
C1—C2—C11117.30 (12)N2—C14—C1107.40 (12)
C1—C2—C3123.31 (12)O3—C15—N2126.33 (14)
C11—C2—C3119.10 (12)O3—C15—N1126.71 (14)
O1—C3—C2122.25 (13)N2—C15—N1106.95 (12)
O1—C3—C4119.32 (13)N2—C16—C17112.01 (13)
C2—C3—C4118.31 (12)N2—C16—H16A109.2
C9—C4—C5119.78 (14)C17—C16—H16A109.2
C9—C4—C3121.35 (13)N2—C16—H16B109.2
C5—C4—C3118.81 (14)C17—C16—H16B109.2
C6—C5—C4119.96 (17)H16A—C16—H16B107.9
C6—C5—H5120.0C18—C17—C16125.0 (2)
C4—C5—H5120.0C18—C17—H17117.5
C7—C6—C5120.24 (17)C16—C17—H17117.5
C7—C6—H6119.9C17—C18—H18A120.0
C5—C6—H6119.9C17—C18—H18B120.0
C6—C7—C8120.54 (16)H18A—C18—H18B120.0
C6—C7—H7119.7N1—C19—C20113.92 (13)
C8—C7—H7119.7N1—C19—H19A108.8
C7—C8—C9119.83 (18)C20—C19—H19A108.8
C7—C8—H8120.1N1—C19—H19B108.8
C9—C8—H8120.1C20—C19—H19B108.8
C4—C9—C8119.64 (15)H19A—C19—H19B107.7
C4—C9—C10120.54 (13)C21—C20—C19122.60 (17)
C8—C9—C10119.81 (15)C21—C20—H20118.7
O2—C10—C9120.76 (13)C19—C20—H20118.7
O2—C10—C11121.17 (14)C20—C21—H21A120.0
C9—C10—C11118.07 (13)C20—C21—H21B120.0
C12—C11—C2121.62 (13)H21A—C21—H21B120.0
C12—C11—C10116.87 (13)
C15—N1—C1—C2178.83 (15)C1—C2—C11—C10−177.23 (12)
C19—N1—C1—C2−15.3 (3)C3—C2—C11—C108.7 (2)
C15—N1—C1—C14−0.69 (16)O2—C10—C11—C12−1.9 (2)
C19—N1—C1—C14165.13 (14)C9—C10—C11—C12179.00 (13)
N1—C1—C2—C11176.13 (15)O2—C10—C11—C2178.30 (14)
C14—C1—C2—C11−4.39 (18)C9—C10—C11—C2−0.8 (2)
N1—C1—C2—C3−10.1 (2)C2—C11—C12—C130.1 (2)
C14—C1—C2—C3169.38 (12)C10—C11—C12—C13−179.75 (14)
C1—C2—C3—O1−10.6 (2)C11—C12—C13—C14−1.6 (2)
C11—C2—C3—O1163.09 (14)C12—C13—C14—N2−178.38 (14)
C1—C2—C3—C4173.42 (12)C12—C13—C14—C1−0.1 (2)
C11—C2—C3—C4−12.91 (19)C15—N2—C14—C13176.95 (15)
O1—C3—C4—C9−166.55 (14)C16—N2—C14—C13−3.9 (3)
C2—C3—C4—C99.6 (2)C15—N2—C14—C1−1.58 (16)
O1—C3—C4—C510.9 (2)C16—N2—C14—C1177.55 (14)
C2—C3—C4—C5−172.99 (13)N1—C1—C14—C13−177.27 (13)
C9—C4—C5—C60.0 (2)C2—C1—C14—C133.1 (2)
C3—C4—C5—C6−177.51 (15)N1—C1—C14—N21.38 (15)
C4—C5—C6—C70.4 (3)C2—C1—C14—N2−178.24 (12)
C5—C6—C7—C8−0.5 (3)C14—N2—C15—O3−177.54 (17)
C6—C7—C8—C90.3 (3)C16—N2—C15—O33.3 (3)
C5—C4—C9—C8−0.2 (2)C14—N2—C15—N11.15 (17)
C3—C4—C9—C8177.27 (14)C16—N2—C15—N1−178.04 (13)
C5—C4—C9—C10−179.13 (14)C1—N1—C15—O3178.43 (16)
C3—C4—C9—C10−1.7 (2)C19—N1—C15—O310.1 (3)
C7—C8—C9—C40.0 (2)C1—N1—C15—N2−0.26 (18)
C7—C8—C9—C10178.99 (15)C19—N1—C15—N2−168.54 (12)
C4—C9—C10—O2178.08 (14)C15—N2—C16—C1776.63 (19)
C8—C9—C10—O2−0.9 (2)C14—N2—C16—C17−102.40 (18)
C4—C9—C10—C11−2.8 (2)N2—C16—C17—C18116.73 (19)
C8—C9—C10—C11178.24 (14)C1—N1—C19—C20109.60 (18)
C1—C2—C11—C122.9 (2)C15—N1—C19—C20−85.41 (17)
C3—C2—C11—C12−171.10 (13)N1—C19—C20—C21126.87 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C13—H13···O3i0.932.493.406 (2)168
C16—H16B···O3i0.972.423.362 (2)165

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5112).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Guimarães, T. T., Da Silva Júnior, E. N., Carvalho, C. E. M., De Simone, C. A. & Pinto, A. V. (2009). Acta Cryst. E65, o1063. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43 Submitted.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography