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Acta Cryst. (2009). E65, o6    [ doi:10.1107/S1600536808039627 ]

N-(4,5-Diazafluoren-9-ylidene)-4-methylaniline

H. Cang, D. Jin, S.-Q. Wang, B. Xu and J.-T. Wang

Abstract top

In the molecule of the title compound, C18H13N3, the 4,5-diazafluorenylidene unit is nearly planar and is oriented at a dihedral angle of 66.31 (1)° with respect to the benzene ring. In the crystal structure, molecules are stacked regularly along the c axis.

Comment top

4-Methyl-N-(4,5-diazafluorenylidene)benzenamine, is one of the important ligands, being utilized to synthesize complexes with interesting photochemical properties (Wang & Rillema, 1997). The crystal structure of 4-methyl-N-(4,5-diazafluorenylidene)benzenamine monohydrate, (II) (Wang et al., 2006) was reported, previously. We report herein the crystal structure of the title compound, (I), Fig. 1.The bond lengths and angles are comparable with the solvated form (II), and with other fluorenylidene compounds : N-fluorenylidene-aniline-benzene (4/1) (III) (Peters et al., 1998), N-(9H-fluoren-9-ylidene)-N-(4-methoxyphenyl)amine, (IV) (Glagovich et al., 2004a) and N-9H-fluoren-9-ylidene-3,4-dimethyl- aniline, (V) (Glagovich et al., 2004b). The coplanar ring system is oriented with respect to benzene ring at a dihedral angle of 66.31 (1)°.In the crystal of the title compound, no obvious hydrogen bond is observed, and molecules are stacked regularly along c axis, Fig. 2.

Related literature top

For the photochemical properties of 4-methyl-N-(4,5-diazafluorenylidene)benzenamine, see: Wang & Rillema (1997). For related structures, see: Glagovich et al. (2004a,b); Peters et al. (1998); Wang et al. (2006).

Experimental top

The title compound was synthesized by a method reported in literature (Wang & Rillema, 1997). The crystals were obtained by dissolving compound (I) (2.0 g, 6.3 mmol) into solution of acetic ether (50 ml, 1.0 mol/L), and evaporating the solvent slowly at room temperature for about 5 d.

Refinement top

H atoms were positioned geometrically, with O—H = 0.82 and C—H = 0.93Å for aromatic H, 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 other H.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. A drawing of the title molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I).
N-(4,5-Diazafluoren-9-ylidene)-4-methylaniline top
Crystal data top
C18H13N3Z = 2
Mr = 271.31F(000) = 284
Triclinic, P1Dx = 1.289 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5970 (15) ÅCell parameters from 25 reflections
b = 8.6100 (17) Åθ = 10–13°
c = 10.998 (2) ŵ = 0.08 mm−1
α = 77.11 (3)°T = 293 K
β = 87.48 (3)°Plate, yellow
γ = 85.79 (3)°0.30 × 0.20 × 0.20 mm
V = 699.1 (2) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		1829 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
graphiteθmax = 25.3°, θmin = 1.9°
ω/2θ scansh = −9→9
Absorption correction: ψ scan
(North et al., 1968)		k = −9→10
Tmin = 0.977, Tmax = 0.985l = 0→13
2742 measured reflections3 standard reflections every 200 reflections
2534 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.05P)2 + 0.85P]
where P = (Fo2 + 2Fc2)/3
2534 reflections(Δ/σ)max < 0.001
190 parametersΔρmax = 0.50 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C18H13N3γ = 85.79 (3)°
Mr = 271.31V = 699.1 (2) Å3
Triclinic, P1Z = 2
a = 7.5970 (15) ÅMo Kα radiation
b = 8.6100 (17) ŵ = 0.08 mm−1
c = 10.998 (2) ÅT = 293 K
α = 77.11 (3)°0.30 × 0.20 × 0.20 mm
β = 87.48 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1829 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.026
Tmin = 0.977, Tmax = 0.985θmax = 25.3°
2742 measured reflections3 standard reflections every 200 reflections
2534 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.167Δρmax = 0.50 e Å−3
S = 1.00Δρmin = −0.28 e Å−3
2534 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
N10.2577 (3)1.3579 (3)0.5598 (2)0.0539 (7)
C10.0220 (6)1.2134 (6)1.0717 (3)0.0953 (14)
H1B−0.08981.27051.07940.143*
H1C0.10631.24571.12230.143*
H1D0.00911.10081.09920.143*
N20.2970 (3)0.8734 (3)0.3984 (2)0.0507 (6)
C20.0855 (5)1.2499 (5)0.9378 (3)0.0658 (9)
N30.4535 (3)1.1454 (3)0.2071 (2)0.0526 (6)
C30.2450 (4)1.1836 (4)0.8993 (3)0.0584 (8)
H3B0.31521.11560.95830.070*
C40.3018 (4)1.2158 (4)0.7759 (3)0.0551 (8)
H4A0.40941.17030.75280.066*
C50.1987 (4)1.3158 (3)0.6866 (3)0.0501 (7)
C60.0411 (4)1.3877 (4)0.7236 (3)0.0602 (8)
H6A−0.02681.45900.66500.072*
C7−0.0137 (5)1.3531 (5)0.8469 (3)0.0723 (10)
H7A−0.12031.40020.87010.087*
C80.2867 (4)1.2521 (3)0.4951 (2)0.0432 (6)
C90.2518 (3)1.0803 (3)0.5183 (2)0.0398 (6)
C100.1712 (4)0.9757 (3)0.6156 (3)0.0463 (7)
H10A0.12791.00860.68680.056*
C110.1576 (4)0.8219 (4)0.6030 (3)0.0490 (7)
H11A0.10440.74850.66630.059*
C120.2236 (4)0.7763 (4)0.4952 (3)0.0537 (8)
H12A0.21570.67050.49070.064*
C130.3085 (3)1.0227 (3)0.4114 (2)0.0421 (6)
C140.3829 (3)1.1547 (3)0.3185 (2)0.0429 (6)
C150.5163 (4)1.2817 (4)0.1427 (3)0.0586 (8)
H15A0.56701.28200.06410.070*
C160.5114 (4)1.4213 (4)0.1839 (3)0.0617 (9)
H16A0.55901.51110.13380.074*
C170.4364 (4)1.4296 (4)0.2994 (3)0.0545 (8)
H17A0.43171.52280.32920.065*
C180.3691 (4)1.2917 (3)0.3673 (2)0.0457 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0653 (17)0.0495 (14)0.0480 (14)0.0060 (12)0.0035 (12)−0.0170 (11)
C10.086 (3)0.149 (4)0.054 (2)−0.014 (3)0.016 (2)−0.029 (2)
N20.0502 (15)0.0541 (15)0.0501 (14)0.0092 (11)−0.0023 (11)−0.0200 (12)
C20.058 (2)0.097 (3)0.0483 (18)−0.0093 (18)0.0060 (16)−0.0284 (18)
N30.0500 (15)0.0690 (17)0.0361 (13)0.0112 (12)−0.0010 (11)−0.0111 (12)
C30.059 (2)0.072 (2)0.0459 (17)0.0002 (16)−0.0022 (14)−0.0174 (15)
C40.0563 (19)0.0615 (19)0.0507 (18)0.0054 (15)0.0036 (14)−0.0233 (15)
C50.0569 (18)0.0489 (16)0.0487 (17)0.0000 (13)0.0049 (14)−0.0220 (13)
C60.0562 (19)0.068 (2)0.057 (2)0.0105 (15)0.0007 (15)−0.0220 (16)
C70.055 (2)0.106 (3)0.060 (2)0.0086 (19)0.0085 (17)−0.036 (2)
C80.0416 (15)0.0473 (15)0.0401 (15)0.0086 (12)−0.0030 (12)−0.0117 (12)
C90.0340 (14)0.0480 (15)0.0382 (14)0.0065 (11)−0.0050 (11)−0.0135 (12)
C100.0424 (15)0.0585 (18)0.0401 (15)0.0051 (13)−0.0046 (12)−0.0171 (13)
C110.0469 (17)0.0540 (18)0.0452 (16)0.0011 (13)−0.0054 (13)−0.0096 (13)
C120.0573 (19)0.0476 (17)0.0589 (19)0.0029 (14)−0.0046 (15)−0.0186 (15)
C130.0368 (15)0.0523 (16)0.0375 (14)0.0120 (12)−0.0069 (11)−0.0142 (12)
C140.0348 (14)0.0567 (17)0.0363 (14)0.0108 (12)−0.0068 (11)−0.0116 (12)
C150.0571 (19)0.081 (2)0.0335 (15)0.0107 (17)0.0004 (13)−0.0087 (15)
C160.062 (2)0.074 (2)0.0424 (17)0.0018 (16)−0.0010 (15)−0.0003 (15)
C170.0590 (19)0.0542 (18)0.0468 (17)0.0046 (14)−0.0015 (14)−0.0062 (14)
C180.0436 (16)0.0542 (17)0.0366 (14)0.0103 (12)−0.0056 (12)−0.0078 (12)
Geometric parameters (Å, °) top
N1—C81.277 (3)C7—H7A0.9300
N1—C51.422 (4)C8—C91.486 (4)
C1—C21.501 (5)C8—C181.491 (4)
C1—H1B0.9600C9—C101.387 (4)
C1—H1C0.9600C9—C131.414 (4)
C1—H1D0.9600C10—C111.373 (4)
N2—C121.327 (4)C10—H10A0.9300
N2—C131.334 (4)C11—C121.392 (4)
C2—C71.388 (5)C11—H11A0.9300
C2—C31.391 (5)C12—H12A0.9300
N3—C141.332 (3)C13—C141.477 (4)
N3—C151.337 (4)C14—C181.397 (4)
C3—C41.380 (4)C15—C161.374 (5)
C3—H3B0.9300C15—H15A0.9300
C4—C51.382 (4)C16—C171.383 (4)
C4—H4A0.9300C16—H16A0.9300
C5—C61.394 (4)C17—C181.375 (4)
C6—C71.374 (4)C17—H17A0.9300
C6—H6A0.9300
C8—N1—C5121.0 (3)C10—C9—C13117.7 (3)
C2—C1—H1B109.5C10—C9—C8133.8 (2)
C2—C1—H1C109.5C13—C9—C8108.3 (2)
H1B—C1—H1C109.5C11—C10—C9117.7 (3)
C2—C1—H1D109.5C11—C10—H10A121.2
H1B—C1—H1D109.5C9—C10—H10A121.2
H1C—C1—H1D109.5C10—C11—C12119.8 (3)
C12—N2—C13115.1 (2)C10—C11—H11A120.1
C7—C2—C3117.2 (3)C12—C11—H11A120.1
C7—C2—C1120.8 (3)N2—C12—C11124.6 (3)
C3—C2—C1122.0 (4)N2—C12—H12A117.7
C14—N3—C15114.0 (3)C11—C12—H12A117.7
C4—C3—C2121.8 (3)N2—C13—C9125.1 (3)
C4—C3—H3B119.1N2—C13—C14126.4 (2)
C2—C3—H3B119.1C9—C13—C14108.5 (2)
C3—C4—C5119.9 (3)N3—C14—C18125.3 (3)
C3—C4—H4A120.0N3—C14—C13126.1 (3)
C5—C4—H4A120.0C18—C14—C13108.6 (2)
C4—C5—C6119.2 (3)N3—C15—C16124.8 (3)
C4—C5—N1121.3 (3)N3—C15—H15A117.6
C6—C5—N1119.3 (3)C16—C15—H15A117.6
C7—C6—C5119.9 (3)C15—C16—C17120.6 (3)
C7—C6—H6A120.1C15—C16—H16A119.7
C5—C6—H6A120.1C17—C16—H16A119.7
C6—C7—C2121.9 (3)C18—C17—C16115.9 (3)
C6—C7—H7A119.1C18—C17—H17A122.0
C2—C7—H7A119.1C16—C17—H17A122.0
N1—C8—C9133.1 (3)C17—C18—C14119.4 (3)
N1—C8—C18121.3 (3)C17—C18—C8131.6 (3)
C9—C8—C18105.6 (2)C14—C18—C8108.9 (2)
C7—C2—C3—C4−1.2 (5)C12—N2—C13—C14−179.6 (3)
C1—C2—C3—C4179.2 (3)C10—C9—C13—N2−2.8 (4)
C2—C3—C4—C5−0.4 (5)C8—C9—C13—N2−179.6 (2)
C3—C4—C5—C62.5 (5)C10—C9—C13—C14177.7 (2)
C3—C4—C5—N1176.7 (3)C8—C9—C13—C140.8 (3)
C8—N1—C5—C463.1 (4)C15—N3—C14—C181.2 (4)
C8—N1—C5—C6−122.7 (3)C15—N3—C14—C13−178.0 (3)
C4—C5—C6—C7−2.9 (5)N2—C13—C14—N3−1.2 (4)
N1—C5—C6—C7−177.3 (3)C9—C13—C14—N3178.4 (2)
C5—C6—C7—C21.3 (6)N2—C13—C14—C18179.5 (3)
C3—C2—C7—C60.7 (6)C9—C13—C14—C18−1.0 (3)
C1—C2—C7—C6−179.7 (4)C14—N3—C15—C160.0 (4)
C5—N1—C8—C98.7 (5)N3—C15—C16—C17−0.6 (5)
C5—N1—C8—C18−172.5 (3)C15—C16—C17—C18−0.1 (4)
N1—C8—C9—C102.4 (5)C16—C17—C18—C141.2 (4)
C18—C8—C9—C10−176.5 (3)C16—C17—C18—C8177.0 (3)
N1—C8—C9—C13178.6 (3)N3—C14—C18—C17−1.9 (4)
C18—C8—C9—C13−0.3 (3)C13—C14—C18—C17177.4 (2)
C13—C9—C10—C112.2 (4)N3—C14—C18—C8−178.6 (2)
C8—C9—C10—C11178.1 (3)C13—C14—C18—C80.7 (3)
C9—C10—C11—C120.0 (4)N1—C8—C18—C174.5 (5)
C13—N2—C12—C111.5 (4)C9—C8—C18—C17−176.4 (3)
C10—C11—C12—N2−2.0 (5)N1—C8—C18—C14−179.3 (3)
C12—N2—C13—C90.9 (4)C9—C8—C18—C14−0.3 (3)
Acknowledgements top

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

references
References top

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