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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1804.
Published online 2010 June 26. doi:  10.1107/S1600536810023275
PMCID: PMC3006891

N-(4,5-Diaza-9H-fluoren-9-yl­idene)-4-meth­oxy­aniline

Abstract

In the title compound, C18H13N3O, the diaza­fluorene ring system is almost coplanar (r.m.s. deviation = 0.0640 Å) and subtends an angle of 61.5 (4)° with the plane of the meth­oxy-substituted benzene ring. In the crystal structure, pairs of C—H(...)O hydrogen bonds link mol­ecules into centrosymmetric dimers parallel to the ab plane. Mol­ecules are also stacked in an obverse fashion along the c axis by a variety of π–π inter­actions with centroid–centroid distances in the range 3.557 (2)–3.921 (2) Å.

Related literature

For the use of the title compound in the synthesis of complexes with inter­esting photochemical properties and for the synthesis, see: Wang & Rillema (1997 [triangle]). For reference bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-66-o1804-scheme1.jpg

Experimental

Crystal data

  • C18H13N3O
  • M r = 287.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1804-efi1.jpg
  • a = 8.3070 (17) Å
  • b = 12.839 (3) Å
  • c = 13.233 (3) Å
  • β = 97.12 (3)°
  • V = 1400.5 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 K
  • 0.30 × 0.10 × 0.05 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.974, T max = 0.996
  • 2678 measured reflections
  • 2498 independent reflections
  • 1599 reflections with I > 2σ(I)
  • R int = 0.025
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.081
  • wR(F 2) = 0.212
  • S = 1.03
  • 2498 reflections
  • 193 parameters
  • 48 restraints
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.40 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/S1600536810023275/sj5020sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023275/sj5020Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

supplementary crystallographic information

Comment

N-(5H-cyclopenta[1,2 - b:5,4 - b']dipyridin-5-ylidene)-4-methoxyaniline and its derivatives are an important class of ligands, being utilized to synthesize complexes with interesting photochemical properties (Wang & Rillema, 1997). Here we report the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987). The diazafluorene rings are almost coplanar with an r.m.s. deviation 0.0640 Å and this plane is inclined to the plane of the C2···C7 benzene ring by 61.5 (4)°.

In the crystal structure C—H···O hydrogen bonds link molecules into centrosymmetric dimers parallel to the ab plane, Table 1. An extensive system of π–π contacts stacks molecules in an obverse fashion down the c axis, Fig. 2, with Cg1···Cg1 = 3.921 (2) Å, Cg2···Cg2 = 3.921 (2) Å and Cg1···Cg2 = 3.557 (2) Å. Symmetry operations 1/2-X, 1/2+Y, 1/2-Z; 3-X, –Y, –Z; Cg1 and Cg2 are the centroids of the C10,C9,C13,N2,C12,C11 and C18,C8,C9,C13,C14 rings, respectively.

Experimental

The title compound was synthesized by a method reported in literature (Wang & Rillema, 1997). Crystals were obtained by dissolving the compound (2.0 g, 6.96 mmol) in ethyl acetate(50 ml), and evaporating the solvent slowly at room temperature for about 7 d.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.93Å, Uiso=1.2Ueq (C) for aromatic 0.96Å, Uiso = 1.5Ueq (C) for CH3 atoms

Figures

Fig. 1.
The structure or (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A packing diagram for (I). Hydrogen bonds are drawn as dashed lines.

Crystal data

C18H13N3OF(000) = 600
Mr = 287.31Dx = 1.363 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 8.3070 (17) Åθ = 9–12°
b = 12.839 (3) ŵ = 0.09 mm1
c = 13.233 (3) ÅT = 298 K
β = 97.12 (3)°Block, colourless
V = 1400.5 (5) Å30.30 × 0.10 × 0.05 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer1599 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 25.1°, θmin = 2.2°
ω/2θ scansh = −9→9
Absorption correction: ψ scan (North et al., 1968)k = 0→15
Tmin = 0.974, Tmax = 0.996l = 0→15
2678 measured reflections3 standard reflections every 200 reflections
2498 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.081Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.212H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.050P)2 + 5.P] where P = (Fo2 + 2Fc2)/3
2498 reflections(Δ/σ)max = 0.001
193 parametersΔρmax = 0.37 e Å3
48 restraintsΔρmin = −0.40 e Å3

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
O0.1797 (4)0.1191 (2)0.5460 (2)0.0455 (8)
N1−0.4360 (4)0.2396 (3)0.3622 (3)0.045
C10.2903 (6)0.0674 (4)0.4883 (4)0.0580 (14)
H1B0.39270.05840.52980.087*
H1C0.30540.10850.42960.087*
H1D0.24730.00050.46680.087*
N2−0.4715 (5)0.6162 (3)0.3850 (3)0.0417 (9)
C20.0291 (5)0.1441 (3)0.4969 (3)0.0354 (10)
C3−0.0260 (5)0.1213 (3)0.3959 (3)0.0426 (11)
H3A0.04050.08530.35630.051*
N3−0.7987 (5)0.5270 (3)0.2939 (3)0.0498 (11)
C4−0.1786 (5)0.1517 (4)0.3544 (3)0.0425 (11)
H4A−0.21620.13170.28810.051*
C5−0.2786 (5)0.2115 (3)0.4081 (3)0.0337 (10)
C6−0.2233 (6)0.2327 (4)0.5093 (3)0.0448 (12)
H6A−0.29080.26780.54890.054*
C7−0.0708 (5)0.2028 (3)0.5526 (3)0.0392 (10)
H7A−0.03420.22180.61930.047*
C8−0.4781 (5)0.3355 (3)0.3556 (3)0.0325 (9)
C9−0.3939 (5)0.4347 (3)0.3850 (3)0.0353 (10)
C10−0.2335 (5)0.4605 (4)0.4154 (3)0.0429 (11)
H10A−0.15330.40960.42330.051*
C11−0.1965 (6)0.5636 (4)0.4337 (4)0.0490 (12)
H11A−0.09020.58350.45540.059*
C12−0.3178 (6)0.6378 (4)0.4197 (3)0.0433 (11)
H12A−0.29060.70660.43550.052*
C13−0.5040 (5)0.5164 (3)0.3679 (3)0.0346 (10)
C14−0.6635 (5)0.4748 (4)0.3245 (3)0.0363 (10)
C15−0.9247 (6)0.4701 (5)0.2532 (4)0.0583 (15)
H15A−1.02080.50470.23070.070*
C16−0.9214 (6)0.3612 (5)0.2422 (4)0.0564 (14)
H16A−1.01310.32520.21370.068*
C17−0.7832 (5)0.3104 (4)0.2738 (3)0.0467 (12)
H17A−0.77770.23840.26740.056*
C18−0.6499 (5)0.3656 (4)0.3156 (3)0.0365 (10)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O0.0423 (18)0.0440 (19)0.050 (2)0.0081 (14)0.0058 (14)−0.0014 (15)
N10.0450.0450.0450.0000.0060.000
C10.049 (3)0.057 (3)0.073 (4)0.006 (2)0.027 (3)0.003 (3)
N20.053 (2)0.035 (2)0.038 (2)−0.0018 (17)0.0143 (17)−0.0024 (17)
C20.047 (3)0.023 (2)0.039 (2)0.0055 (18)0.0183 (19)−0.0003 (18)
C30.048 (3)0.041 (3)0.043 (3)0.000 (2)0.018 (2)−0.011 (2)
N30.041 (2)0.069 (3)0.041 (2)0.002 (2)0.0099 (18)0.011 (2)
C40.045 (3)0.049 (3)0.035 (2)−0.006 (2)0.010 (2)−0.012 (2)
C50.042 (2)0.026 (2)0.035 (2)−0.0025 (17)0.0137 (18)0.0017 (18)
C60.060 (3)0.044 (3)0.035 (3)0.015 (2)0.023 (2)0.000 (2)
C70.048 (3)0.040 (3)0.031 (2)−0.002 (2)0.0088 (19)0.002 (2)
C80.046 (2)0.028 (2)0.026 (2)−0.0012 (18)0.0140 (18)−0.0042 (17)
C90.048 (2)0.039 (2)0.021 (2)−0.0006 (18)0.0102 (17)0.0019 (18)
C100.042 (2)0.041 (2)0.046 (3)0.0099 (19)0.008 (2)0.009 (2)
C110.046 (3)0.055 (3)0.046 (3)−0.005 (2)0.001 (2)0.011 (2)
C120.059 (3)0.034 (2)0.037 (2)0.007 (2)0.009 (2)−0.001 (2)
C130.039 (2)0.041 (2)0.026 (2)0.0035 (18)0.0123 (17)0.0068 (18)
C140.036 (2)0.048 (3)0.027 (2)0.0026 (19)0.0131 (18)0.008 (2)
C150.036 (3)0.088 (4)0.052 (3)0.010 (3)0.008 (2)0.015 (3)
C160.033 (3)0.087 (4)0.051 (3)−0.014 (3)0.012 (2)0.005 (3)
C170.043 (3)0.059 (3)0.039 (3)−0.008 (2)0.007 (2)0.009 (2)
C180.036 (2)0.051 (3)0.024 (2)0.003 (2)0.0083 (17)0.000 (2)

Geometric parameters (Å, °)

O—C21.375 (5)C6—H6A0.9300
O—C11.429 (5)C7—H7A0.9300
N1—C81.280 (5)C8—C91.482 (6)
N1—C51.418 (5)C8—C181.510 (6)
C1—H1B0.9600C9—C101.383 (6)
C1—H1C0.9600C9—C131.392 (6)
C1—H1D0.9600C10—C111.375 (7)
N2—C131.323 (5)C10—H10A0.9300
N2—C121.331 (6)C11—C121.382 (6)
C2—C31.389 (6)C11—H11A0.9300
C2—C71.397 (6)C12—H12A0.9300
C3—C41.374 (6)C13—C141.477 (6)
C3—H3A0.9300C14—C181.412 (6)
N3—C141.328 (5)C15—C161.407 (8)
N3—C151.333 (6)C15—H15A0.9300
C4—C51.389 (6)C16—C171.341 (7)
C4—H4A0.9300C16—H16A0.9300
C5—C61.388 (6)C17—C181.372 (6)
C6—C71.378 (6)C17—H17A0.9300
C2—O—C1117.6 (4)C10—C9—C13117.2 (4)
C8—N1—C5120.2 (4)C10—C9—C8133.5 (4)
O—C1—H1B109.5C13—C9—C8109.0 (4)
O—C1—H1C109.5C11—C10—C9117.9 (4)
H1B—C1—H1C109.5C11—C10—H10A121.1
O—C1—H1D109.5C9—C10—H10A121.1
H1B—C1—H1D109.5C10—C11—C12119.8 (4)
H1C—C1—H1D109.5C10—C11—H11A120.1
C13—N2—C12115.3 (4)C12—C11—H11A120.1
O—C2—C3125.3 (4)N2—C12—C11123.7 (4)
O—C2—C7116.2 (4)N2—C12—H12A118.1
C3—C2—C7118.4 (4)C11—C12—H12A118.1
C4—C3—C2120.1 (4)N2—C13—C9125.8 (4)
C4—C3—H3A119.9N2—C13—C14124.9 (4)
C2—C3—H3A119.9C9—C13—C14109.3 (4)
C14—N3—C15116.0 (5)N3—C14—C18123.3 (4)
C3—C4—C5122.2 (4)N3—C14—C13128.3 (4)
C3—C4—H4A118.9C18—C14—C13108.4 (4)
C5—C4—H4A118.9N3—C15—C16124.2 (5)
C6—C5—C4117.1 (4)N3—C15—H15A117.9
C6—C5—N1122.7 (4)C16—C15—H15A117.9
C4—C5—N1120.0 (4)C17—C16—C15118.5 (5)
C7—C6—C5121.6 (4)C17—C16—H16A120.7
C7—C6—H6A119.2C15—C16—H16A120.7
C5—C6—H6A119.2C16—C17—C18119.4 (5)
C6—C7—C2120.4 (4)C16—C17—H17A120.3
C6—C7—H7A119.8C18—C17—H17A120.3
C2—C7—H7A119.8C17—C18—C14118.5 (4)
N1—C8—C9133.8 (4)C17—C18—C8133.6 (4)
N1—C8—C18120.6 (4)C14—C18—C8107.8 (4)
C9—C8—C18105.5 (3)
C1—O—C2—C31.4 (6)C12—N2—C13—C91.5 (6)
C1—O—C2—C7−174.4 (4)C12—N2—C13—C14−176.8 (4)
O—C2—C3—C4−179.0 (4)C10—C9—C13—N2−5.1 (6)
C7—C2—C3—C4−3.2 (6)C8—C9—C13—N2−179.8 (4)
C2—C3—C4—C54.4 (7)C10—C9—C13—C14173.3 (4)
C3—C4—C5—C6−5.1 (7)C8—C9—C13—C14−1.3 (4)
C3—C4—C5—N1−179.1 (4)C15—N3—C14—C180.1 (6)
C8—N1—C5—C662.1 (6)C15—N3—C14—C13177.1 (4)
C8—N1—C5—C4−124.2 (5)N2—C13—C14—N31.3 (7)
C4—C5—C6—C74.9 (6)C9—C13—C14—N3−177.2 (4)
N1—C5—C6—C7178.8 (4)N2—C13—C14—C18178.7 (4)
C5—C6—C7—C2−4.1 (7)C9—C13—C14—C180.2 (5)
O—C2—C7—C6179.2 (4)C14—N3—C15—C160.4 (7)
C3—C2—C7—C63.1 (6)N3—C15—C16—C17−0.4 (8)
C5—N1—C8—C91.7 (7)C15—C16—C17—C180.0 (7)
C5—N1—C8—C18−174.5 (3)C16—C17—C18—C140.4 (6)
N1—C8—C9—C1011.8 (8)C16—C17—C18—C8−178.2 (4)
C18—C8—C9—C10−171.6 (4)N3—C14—C18—C17−0.5 (6)
N1—C8—C9—C13−174.8 (5)C13—C14—C18—C17−178.0 (4)
C18—C8—C9—C131.8 (4)N3—C14—C18—C8178.5 (4)
C13—C9—C10—C114.6 (6)C13—C14—C18—C80.9 (4)
C8—C9—C10—C11177.6 (4)N1—C8—C18—C17−5.8 (7)
C9—C10—C11—C12−1.1 (7)C9—C8—C18—C17177.0 (4)
C13—N2—C12—C112.6 (6)N1—C8—C18—C14175.5 (4)
C10—C11—C12—N2−2.8 (7)C9—C8—C18—C14−1.6 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C12—H12A···Oi0.932.423.337 (6)169

Symmetry codes: (i) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ5020).

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.
  • Enraf-Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • 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]
  • Wang, Y. X. & Rillema, D. P. (1997). Tetrahedron, 37, 12377–12390.

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