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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2479.
Published online 2008 November 29. doi:  10.1107/S1600536808039445
PMCID: PMC2959835

3,7-Dihydr­oxy-3,7-diphenyl-2H,6H-pyrrolo[3,4-f]isoindole-1,5(3H,7H)-dione methanol disolvate

Abstract

The asymmetric unit of the title compound, C22H16N2O4·2CH4O, contains one half-mol­ecule and a methanol solvent mol­ecule. The aromatic ring is oriented at a dihedral angle of 82.91 (3)° with respect to the planar indole ring systems. In the crystal structure, inter­molecular O—H(...)O and N—H(...)O hydrogen bonds link the mol­ecules into chains along the b axis.

Related literature

For general background, see: Antoniadis et al. (1994 [triangle]); Kolosov et al. (2002 [triangle]); Tonzola et al. (2003 [triangle]). For a related structure, see: Liu et al. (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o2479-scheme1.jpg

Experimental

Crystal data

  • C22H16N2O4·2CH4O
  • M r = 436.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2479-efi3.jpg
  • a = 17.767 (4) Å
  • b = 6.6300 (13) Å
  • c = 20.215 (4) Å
  • β = 106.59 (3)°
  • V = 2282.1 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.973, T max = 0.991
  • 4477 measured reflections
  • 2245 independent reflections
  • 1050 reflections with I > 2σ(I)
  • R int = 0.075
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.070
  • wR(F 2) = 0.156
  • S = 1.04
  • 2245 reflections
  • 152 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 [triangle]); cell refinement: CAD-4 Software; 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: 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/S1600536808039445/hk2579sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039445/hk2579Isup2.hkl

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

Acknowledgments

This work was supported by the Science Fundamental Research Fund of the Education Department, Jiangsu Province (grant No. 06KJB150024). The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

supplementary crystallographic information

Comment

The title compound is an important intermediate used to synthesize the monomer 2,5-dibenzoyl-1,4-phenylenediamine, which can be utilized to synthesize organic semiconductors and conjugated polymers (Tonzola et al., 2003), which are of wide current interest for applications in electronic and optoelectronic devices including light-emitting diodes (Kolosov et al., 2002), thin film transistors and photovoltaic cells (Antoniadis et al., 1994). We report herein the crystal structure of the title compound, which is of interest to us in the field.

The asymmetric unit of the title compound (Fig. 1) contains one-half molecule and a methanol molecule, where the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (N/C7-C8/C11A) and C (C9-C11/C9A-C11A) are, of course, planar, and the dihedral angle between rings B and C is B/C = 1.66 (3)° [symmetry code: (A) 1/2 - x, 3/2 - y, 1 - z]. So, the indole ring is essentially planar. Ring A is oriented with respect to the planar indole ring at a dihedral angle of 82.91 (3)°. The intramolecular C-H···O hydrogen bond (Table 1) results in the formation of a nonplanar five-membered ring D (O1/C1/C6/C7/H1B) adopting envelope conformation with O1 atom displaced by 0.288 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular O-H···O and N-H···O hydrogen bonds (Table 1) link the molecules into chains along b axis (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

The title compound was prepared according to the literature method (Liu et al., 2008). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.5 g) in methanol (50 ml), and evaporating the solvent slowly at room temperature for about 30 d.

Refinement

H atom (for NH) was located in difference synthesis and refined isotropically [N-H = 0.84 (4) Å and Uiso(H) = 0.042 (11) Å2]. Remaining H atoms were positioned geometrically, with O-H = 0.82 Å (for OH) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,O), where x = 1.2 for aromatic H and x = 1.5 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level [symmetry code: (A) 1/2 - x, 3/2 - y, 1 - z]. Hydrogen bonds are shown as dashed lines.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C22H16N2O4·2CH4OF000 = 920
Mr = 436.20Dx = 1.270 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 17.767 (4) Åθ = 9–12º
b = 6.6300 (13) ŵ = 0.09 mm1
c = 20.215 (4) ÅT = 298 (2) K
β = 106.59 (3)ºBlock, colorless
V = 2282.1 (9) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.075
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 2.1º
T = 298(2) Kh = −21→21
ω/2θ scansk = 0→8
Absorption correction: ψ scan(North et al., 1968)l = −24→24
Tmin = 0.973, Tmax = 0.9913 standard reflections
4477 measured reflections every 120 min
2245 independent reflections intensity decay: none
1050 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.071H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.156  w = 1/[σ2(Fo2) + (0.0378P)2 + 1.8P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2245 reflectionsΔρmax = 0.21 e Å3
152 parametersΔρmin = −0.25 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 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)

xyzUiso*/Ueq
N0.10301 (18)0.4308 (5)0.49495 (17)0.0429 (13)
H0.060 (2)0.372 (5)0.4881 (17)0.042 (11)*
O10.04932 (13)0.7469 (4)0.51464 (13)0.0451 (7)
H10.04430.78010.47450.068*
O20.15728 (14)0.2655 (4)0.41962 (14)0.0537 (8)
O30.05976 (17)0.9420 (4)0.40414 (15)0.0657 (9)
H30.09821.01630.41170.099*
C10.0891 (3)0.6807 (7)0.6511 (2)0.0689 (14)
H1B0.05490.78340.63020.083*
C20.1022 (3)0.6438 (10)0.7205 (3)0.0911 (18)
H2A0.07710.72240.74590.109*
C30.1513 (3)0.4939 (10)0.7521 (3)0.0879 (17)
H3A0.15970.46840.79890.106*
C40.1878 (3)0.3827 (8)0.7149 (3)0.0908 (17)
H4A0.22180.28020.73620.109*
C50.1753 (3)0.4194 (7)0.6454 (2)0.0721 (14)
H5A0.20090.34120.62040.086*
C60.12522 (19)0.5704 (6)0.61275 (19)0.0404 (10)
C70.11403 (18)0.6157 (5)0.53721 (19)0.0373 (9)
C80.15509 (19)0.4032 (6)0.45934 (19)0.0392 (9)
C90.21057 (18)0.5789 (5)0.47727 (17)0.0343 (9)
C100.27381 (18)0.6211 (5)0.45295 (18)0.0364 (9)
H10A0.28920.53630.42250.044*
C110.31286 (17)0.7995 (5)0.47725 (18)0.0325 (8)
C120.0478 (4)0.8537 (9)0.3413 (3)0.127 (3)
H12A0.01320.74060.33770.191*
H12B0.09710.80850.33610.191*
H12C0.02470.94970.30580.191*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0334 (13)0.0397 (16)0.0656 (19)−0.0020 (12)0.0198 (13)0.0084 (14)
O20.0631 (17)0.0341 (16)0.0733 (19)−0.0195 (14)0.0342 (15)−0.0183 (15)
O30.078 (2)0.0487 (19)0.067 (2)−0.0248 (16)0.0150 (17)0.0023 (16)
N0.037 (2)0.0300 (19)0.068 (3)−0.0188 (15)0.0243 (18)−0.0108 (16)
C10.067 (3)0.080 (4)0.066 (3)0.022 (3)0.030 (3)0.006 (3)
C20.088 (4)0.128 (5)0.065 (4)0.025 (4)0.034 (3)−0.010 (4)
C30.092 (4)0.116 (5)0.060 (4)−0.015 (4)0.028 (3)0.011 (4)
C40.118 (5)0.072 (4)0.075 (4)0.022 (3)0.017 (3)0.029 (3)
C50.096 (4)0.049 (3)0.074 (3)0.020 (3)0.029 (3)0.006 (3)
C60.0344 (19)0.036 (2)0.057 (3)−0.0061 (18)0.0232 (19)0.001 (2)
C70.0263 (17)0.0260 (19)0.063 (3)−0.0051 (16)0.0189 (18)−0.0024 (19)
C80.039 (2)0.030 (2)0.051 (2)−0.0055 (18)0.0179 (19)0.001 (2)
C90.0321 (18)0.027 (2)0.044 (2)−0.0042 (16)0.0120 (17)−0.0015 (18)
C100.0365 (19)0.0251 (19)0.053 (2)−0.0032 (17)0.0222 (17)−0.0049 (18)
C110.0281 (18)0.0277 (19)0.045 (2)−0.0066 (15)0.0161 (16)−0.0002 (17)
C120.223 (8)0.071 (4)0.077 (4)−0.022 (5)0.026 (5)−0.020 (3)

Geometric parameters (Å, °)

N—C81.337 (4)C6—C71.512 (5)
N—C71.475 (4)C7—O11.410 (4)
N—H0.84 (4)C7—C11i1.518 (4)
O1—H10.8200C8—O21.224 (4)
O3—H30.8200C8—C91.502 (5)
C1—C61.353 (5)C9—C11i1.373 (4)
C1—C21.377 (6)C9—C101.378 (4)
C1—H1B0.9300C10—C111.389 (4)
C2—C31.357 (7)C10—H10A0.9300
C2—H2A0.9300C11—C9i1.373 (4)
C3—C41.344 (7)C11—C7i1.518 (4)
C3—H3A0.9300C12—O31.359 (5)
C4—C51.380 (6)C12—H12A0.9600
C4—H4A0.9300C12—H12B0.9600
C5—C61.376 (5)C12—H12C0.9600
C5—H5A0.9300
C8—N—C7115.3 (3)O1—C7—C6108.0 (3)
C8—N—H126 (2)N—C7—C6112.2 (3)
C7—N—H116 (2)O1—C7—C11i111.9 (3)
C7—O1—H1109.5N—C7—C11i100.1 (3)
C12—O3—H3109.5C6—C7—C11i113.3 (3)
C6—C1—C2121.2 (5)O2—C8—N127.7 (3)
C6—C1—H1B119.4O2—C8—C9126.5 (3)
C2—C1—H1B119.4N—C8—C9105.7 (3)
C3—C2—C1120.6 (5)C11i—C9—C10123.6 (3)
C3—C2—H2A119.7C11i—C9—C8108.3 (3)
C1—C2—H2A119.7C10—C9—C8128.1 (3)
C4—C3—C2119.1 (5)C9—C10—C11115.0 (3)
C4—C3—H3A120.5C9—C10—H10A122.5
C2—C3—H3A120.5C11—C10—H10A122.5
C3—C4—C5120.6 (5)C9i—C11—C10121.4 (3)
C3—C4—H4A119.7C9i—C11—C7i110.6 (3)
C5—C4—H4A119.7C10—C11—C7i128.0 (3)
C6—C5—C4120.7 (4)O3—C12—H12A109.5
C6—C5—H5A119.6O3—C12—H12B109.5
C4—C5—H5A119.6H12A—C12—H12B109.5
C1—C6—C5117.7 (4)O3—C12—H12C109.5
C1—C6—C7121.6 (4)H12A—C12—H12C109.5
C5—C6—C7120.6 (3)H12B—C12—H12C109.5
O1—C7—N111.4 (3)
C6—C1—C2—C3−0.5 (8)C5—C6—C7—N45.5 (4)
C1—C2—C3—C40.6 (9)C1—C6—C7—C11i110.5 (4)
C2—C3—C4—C5−0.4 (9)C5—C6—C7—C11i−66.9 (4)
C3—C4—C5—C60.0 (8)C7—N—C8—O2−178.1 (4)
C2—C1—C6—C50.2 (7)C7—N—C8—C91.1 (4)
C2—C1—C6—C7−177.3 (4)O2—C8—C9—C11i179.1 (4)
C4—C5—C6—C10.1 (7)N—C8—C9—C11i−0.1 (4)
C4—C5—C6—C7177.6 (4)O2—C8—C9—C100.3 (6)
C8—N—C7—O1116.9 (3)N—C8—C9—C10−178.9 (4)
C8—N—C7—C6−122.0 (3)C11i—C9—C10—C11−0.7 (6)
C8—N—C7—C11i−1.6 (4)C8—C9—C10—C11177.9 (3)
C1—C6—C7—O1−14.0 (5)C9—C10—C11—C9i0.7 (6)
C5—C6—C7—O1168.6 (3)C9—C10—C11—C7i177.4 (3)
C1—C6—C7—N−137.1 (4)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O30.821.862.633 (4)156
O3—H3···O2ii0.821.942.719 (4)158
N—H···O1iii0.84 (4)2.08 (4)2.907 (4)170
C1—H1B···O10.932.322.681 (5)102

Symmetry codes: (ii) x, y+1, z; (iii) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2579).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Antoniadis, H., Hsieh, B. R., Abkowitz, M. A., Jenekhe, S. A. & Stolka, M. (1994). Synth. Met 62, 265–271.
  • Enraf–Nonius (1985). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Kolosov, S., Adamovich, V., Djurovich, P., Thompson, M. E. & Adachi, C. (2002). J. Am. Chem. Soc.124, 9945–9954. [PubMed]
  • Liu, S., Jiang, P., Song, G. L., Liu, R. & Zhu, H. J. (2008). Dyes Pigm doi:10.1016/j.dyepig.2008.10.010.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tonzola, C. J., Alam, M. M., Kaminsky, W. & Jenekhe, S. A. (2003). J. Am. Chem. Soc.125, 13548–13558. [PubMed]

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