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

Cang, H.; Jin, D.; Wang, S.-Q.; Liu, S.; Wang, J.-T.

doi:10.1107/S1600536808016668

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1221

doi:10.1107/S1600536808016668

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

Hui Cang,^a Dong Jin,^b Si-Qing Wang,^a Shan Liu ^a and Jin-Tang Wang ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wjt@njut.edu.cn

(Received 29 May 2008; accepted 31 May 2008; online 7 June 2008)

In the molecule of the title compound, C₁₇H₁₁N₃, the 4,5-diazafluorenylidene unit is nearly planar and is oriented with respect to the phenyl ring at a dihedral angle of 75.75 (3)°. In the crystal structure, the molecules are aligned in the [100] direction in such a way that neighbouring 4,5-diazafluorenylidene planes face each other in an antiparallel fashion.

Related literature

For related literature, see: Wang & Rillema (1997 ); Wang et al. (2006 ); Peters et al. (1998 ); Glagovich et al. (2004a ,b ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₇H₁₁N₃
M_r = 257.29
Triclinic, $[P \overline 1]$
a = 7.1950 (14) Å
b = 8.5860 (17) Å
c = 11.876 (2) Å
α = 80.63 (3)°
β = 74.78 (3)°
γ = 66.46 (3)°
V = 647.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.984, T_max = 0.996
2529 measured reflections
2326 independent reflections
1642 reflections with I > 2σ(I)
R_int = 0.057
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.178
S = 1.02
2326 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016668/hk2468sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016668/hk2468Isup2.hkl

checkCIF report

Comment top

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).

In the molecule of (I) (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, which are comparable with the corresponding values in other fluorenylidene compounds (II), 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). Rings A (C1–C6), B (N2/C8–C12), C (C7/C8/C12/C13/C17) and D (N3/C13–C17) are, of course, planar. In the 4,5-diazafluorenylidene unit, the dihedral angles between the rings are B/C = 0.29 (3)°, C/D = 2.30 (3)° and B/D = 2.15 (3)°. So, rings B, C and D are nearly coplanar. The coplanar ring system is oriented with respect to ring A at a dihedral angle of 75.75 (3)°, in which it is reported as 65.1 (1)° in (II).

In the crystal structure, the molecules are aligned in the [100] direction, in such a way that neighbouring 4,5-diazafluorenylidene planes face in anti-parallel fashion (Fig. 2), as in (II).

Related literature top

For related literature, see: Wang & Rillema (1997); Wang et al. (2006); Peters et al. (1998); Glagovich et al. (2004a,b). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared according to the literature method (Wang & Rillema, 1997). Crystals suitable for X-ray analysis were obtained by dissolving (I) (2.0 g, 6.3 mmol) in acetate ester solution (50 ml, 1.0 mol/L) and evaporating the solvent slowly at room temperature for about 5 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I).

N-(4,5-diazafluoren-9-ylidene)aniline top

Crystal data top

C₁₇H₁₁N₃	Z = 2
M_r = 257.29	F(000) = 268
Triclinic, P1	D_x = 1.319 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1950 (14) Å	Cell parameters from 25 reflections
b = 8.5860 (17) Å	θ = 9–13°
c = 11.876 (2) Å	µ = 0.08 mm⁻¹
α = 80.63 (3)°	T = 298 K
β = 74.78 (3)°	Needle, colourless
γ = 66.46 (3)°	0.20 × 0.10 × 0.05 mm
V = 647.6 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1642 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
Graphite monochromator	θ_max = 25.2°, θ_min = 1.8°
ω/2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = −9→10
T_min = 0.984, T_max = 0.996	l = 0→14
2529 measured reflections	3 standard reflections every 120 min
2326 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.08P)² + 0.4P] where P = (F_o² + 2F_c²)/3
2326 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₇H₁₁N₃	γ = 66.46 (3)°
M_r = 257.29	V = 647.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.1950 (14) Å	Mo Kα radiation
b = 8.5860 (17) Å	µ = 0.08 mm⁻¹
c = 11.876 (2) Å	T = 298 K
α = 80.63 (3)°	0.20 × 0.10 × 0.05 mm
β = 74.78 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1642 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.057
T_min = 0.984, T_max = 0.996	3 standard reflections every 120 min
2529 measured reflections	intensity decay: none
2326 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
2326 reflections	Δρ_min = −0.25 e Å⁻³
181 parameters

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 > 2sigma(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

	x	y	z	U_iso*/U_eq
N1	0.1000 (4)	1.2848 (3)	0.6315 (2)	0.0491 (6)
N2	0.3187 (4)	0.7234 (3)	0.4917 (2)	0.0492 (6)
N3	0.3994 (4)	0.9717 (3)	0.2888 (2)	0.0503 (6)
C1	0.0047 (6)	1.2899 (6)	0.9516 (3)	0.0808 (12)
H1B	0.0717	1.2935	1.0078	0.097*
C2	−0.1937 (6)	1.2891 (5)	0.9852 (3)	0.0778 (11)
H2B	−0.2605	1.2921	1.0638	0.093*
C3	−0.2916 (6)	1.2841 (5)	0.9021 (3)	0.0675 (9)
H3B	−0.4257	1.2845	0.9249	0.081*
C4	−0.1951 (5)	1.2783 (4)	0.7855 (3)	0.0561 (8)
H4A	−0.2637	1.2753	0.7301	0.067*
C5	0.0048 (5)	1.2772 (3)	0.7513 (2)	0.0470 (7)
C6	0.1040 (5)	1.2853 (4)	0.8350 (3)	0.0616 (9)
H6A	0.2369	1.2877	0.8124	0.074*
C7	0.1686 (4)	1.1567 (3)	0.5708 (2)	0.0401 (6)
C8	0.1856 (4)	0.9756 (3)	0.6012 (2)	0.0385 (6)
C9	0.1347 (4)	0.8860 (4)	0.7046 (2)	0.0454 (7)
H9A	0.0739	0.9384	0.7750	0.055*
C10	0.1782 (5)	0.7148 (4)	0.6987 (3)	0.0501 (7)
H10A	0.1470	0.6498	0.7662	0.060*
C11	0.2673 (5)	0.6404 (4)	0.5935 (3)	0.0530 (8)
H11A	0.2936	0.5253	0.5929	0.064*
C12	0.2774 (4)	0.8874 (3)	0.4993 (2)	0.0409 (6)
C13	0.3186 (4)	1.0075 (3)	0.4004 (2)	0.0405 (6)
C14	0.4125 (5)	1.1058 (4)	0.2161 (3)	0.0574 (8)
H14A	0.4674	1.0878	0.1371	0.069*
C15	0.3502 (5)	1.2689 (4)	0.2504 (3)	0.0538 (8)
H15A	0.3631	1.3562	0.1951	0.065*
C16	0.2688 (4)	1.3018 (4)	0.3668 (3)	0.0502 (7)
H16A	0.2265	1.4099	0.3924	0.060*
C17	0.2534 (4)	1.1661 (3)	0.4432 (2)	0.0398 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0548 (14)	0.0417 (13)	0.0454 (14)	−0.0158 (11)	−0.0029 (11)	−0.0071 (11)
N2	0.0500 (14)	0.0445 (14)	0.0527 (15)	−0.0180 (11)	−0.0079 (11)	−0.0066 (11)
N3	0.0466 (14)	0.0543 (15)	0.0451 (14)	−0.0190 (11)	0.0006 (11)	−0.0072 (11)
C1	0.079 (3)	0.109 (3)	0.048 (2)	−0.027 (2)	−0.0153 (19)	−0.010 (2)
C2	0.080 (3)	0.102 (3)	0.046 (2)	−0.032 (2)	−0.0057 (18)	−0.0088 (19)
C3	0.065 (2)	0.072 (2)	0.059 (2)	−0.0299 (18)	0.0026 (17)	−0.0032 (17)
C4	0.064 (2)	0.0534 (18)	0.0501 (18)	−0.0241 (15)	−0.0077 (15)	−0.0049 (14)
C5	0.0553 (17)	0.0351 (15)	0.0422 (16)	−0.0116 (12)	−0.0043 (13)	−0.0044 (12)
C6	0.0573 (19)	0.065 (2)	0.0533 (19)	−0.0150 (16)	−0.0067 (15)	−0.0076 (15)
C7	0.0352 (13)	0.0419 (15)	0.0407 (15)	−0.0114 (11)	−0.0091 (11)	−0.0023 (12)
C8	0.0351 (13)	0.0410 (14)	0.0432 (15)	−0.0152 (11)	−0.0133 (11)	−0.0029 (11)
C9	0.0472 (16)	0.0462 (16)	0.0405 (15)	−0.0140 (13)	−0.0111 (12)	−0.0034 (12)
C10	0.0534 (17)	0.0437 (16)	0.0510 (18)	−0.0192 (13)	−0.0116 (14)	0.0056 (13)
C11	0.0542 (18)	0.0402 (16)	0.061 (2)	−0.0160 (13)	−0.0102 (15)	−0.0026 (14)
C12	0.0334 (13)	0.0409 (15)	0.0465 (16)	−0.0125 (11)	−0.0073 (12)	−0.0038 (12)
C13	0.0311 (13)	0.0457 (16)	0.0429 (16)	−0.0142 (11)	−0.0040 (11)	−0.0054 (12)
C14	0.0544 (18)	0.067 (2)	0.0446 (17)	−0.0258 (16)	0.0040 (14)	−0.0045 (15)
C15	0.0518 (17)	0.0566 (19)	0.0495 (18)	−0.0250 (14)	−0.0032 (14)	0.0057 (14)
C16	0.0450 (16)	0.0456 (17)	0.0511 (18)	−0.0124 (13)	−0.0039 (13)	−0.0020 (13)
C17	0.0350 (13)	0.0431 (15)	0.0411 (15)	−0.0152 (11)	−0.0073 (11)	−0.0021 (11)

Geometric parameters (Å, º) top

N1—C7	1.269 (3)	C7—C17	1.480 (4)
N1—C5	1.410 (3)	C7—C8	1.500 (4)
N2—C12	1.331 (3)	C8—C9	1.384 (4)
N2—C11	1.343 (4)	C8—C12	1.398 (4)
N3—C13	1.333 (3)	C9—C10	1.385 (4)
N3—C14	1.341 (4)	C9—H9A	0.9300
C1—C2	1.380 (5)	C10—C11	1.375 (4)
C1—C6	1.381 (5)	C10—H10A	0.9300
C1—H1B	0.9300	C11—H11A	0.9300
C2—C3	1.369 (5)	C12—C13	1.482 (4)
C2—H2B	0.9300	C13—C17	1.386 (4)
C3—C4	1.375 (4)	C14—C15	1.385 (4)
C3—H3B	0.9300	C14—H14A	0.9300
C4—C5	1.385 (4)	C15—C16	1.380 (4)
C4—H4A	0.9300	C15—H15A	0.9300
C5—C6	1.392 (4)	C16—C17	1.379 (4)
C6—H6A	0.9300	C16—H16A	0.9300

C7—N1—C5	121.5 (2)	C8—C9—C10	117.0 (3)
C12—N2—C11	114.6 (2)	C8—C9—H9A	121.5
C13—N3—C14	114.1 (3)	C10—C9—H9A	121.5
C2—C1—C6	120.2 (4)	C11—C10—C9	120.4 (3)
C2—C1—H1B	119.9	C11—C10—H10A	119.8
C6—C1—H1B	119.9	C9—C10—H10A	119.8
C3—C2—C1	119.6 (3)	N2—C11—C10	124.1 (3)
C3—C2—H2B	120.2	N2—C11—H11A	117.9
C1—C2—H2B	120.2	C10—C11—H11A	117.9
C2—C3—C4	121.2 (3)	N2—C12—C8	125.8 (3)
C2—C3—H3B	119.4	N2—C12—C13	125.6 (2)
C4—C3—H3B	119.4	C8—C12—C13	108.6 (2)
C3—C4—C5	119.6 (3)	N3—C13—C17	125.4 (3)
C3—C4—H4A	120.2	N3—C13—C12	126.3 (2)
C5—C4—H4A	120.2	C17—C13—C12	108.3 (2)
C4—C5—C6	119.6 (3)	N3—C14—C15	124.7 (3)
C4—C5—N1	120.3 (3)	N3—C14—H14A	117.6
C6—C5—N1	119.8 (3)	C15—C14—H14A	117.6
C1—C6—C5	119.9 (3)	C16—C15—C14	119.8 (3)
C1—C6—H6A	120.1	C16—C15—H15A	120.1
C5—C6—H6A	120.1	C14—C15—H15A	120.1
N1—C7—C17	122.3 (2)	C17—C16—C15	116.6 (3)
N1—C7—C8	132.7 (2)	C17—C16—H16A	121.7
C17—C7—C8	105.0 (2)	C15—C16—H16A	121.7
C9—C8—C12	118.0 (2)	C16—C17—C13	119.3 (3)
C9—C8—C7	133.7 (2)	C16—C17—C7	130.9 (3)
C12—C8—C7	108.3 (2)	C13—C17—C7	109.7 (2)

C6—C1—C2—C3	−0.1 (6)	C9—C8—C12—N2	0.9 (4)
C1—C2—C3—C4	0.5 (6)	C7—C8—C12—N2	179.7 (2)
C2—C3—C4—C5	0.2 (5)	C9—C8—C12—C13	−179.9 (2)
C3—C4—C5—C6	−1.3 (5)	C7—C8—C12—C13	−1.1 (3)
C3—C4—C5—N1	−175.0 (3)	C14—N3—C13—C17	−0.7 (4)
C7—N1—C5—C4	−75.0 (4)	C14—N3—C13—C12	177.4 (3)
C7—N1—C5—C6	111.3 (3)	N2—C12—C13—N3	1.2 (4)
C2—C1—C6—C5	−1.0 (6)	C8—C12—C13—N3	−177.9 (2)
C4—C5—C6—C1	1.7 (5)	N2—C12—C13—C17	179.7 (2)
N1—C5—C6—C1	175.5 (3)	C8—C12—C13—C17	0.5 (3)
C5—N1—C7—C17	174.9 (2)	C13—N3—C14—C15	0.2 (4)
C5—N1—C7—C8	−4.7 (5)	N3—C14—C15—C16	0.4 (5)
N1—C7—C8—C9	−0.6 (5)	C14—C15—C16—C17	−0.4 (4)
C17—C7—C8—C9	179.8 (3)	C15—C16—C17—C13	0.0 (4)
N1—C7—C8—C12	−179.1 (3)	C15—C16—C17—C7	−177.7 (3)
C17—C7—C8—C12	1.2 (3)	N3—C13—C17—C16	0.7 (4)
C12—C8—C9—C10	−0.3 (4)	C12—C13—C17—C16	−177.8 (2)
C7—C8—C9—C10	−178.7 (3)	N3—C13—C17—C7	178.8 (2)
C8—C9—C10—C11	−0.3 (4)	C12—C13—C17—C7	0.3 (3)
C12—N2—C11—C10	0.3 (4)	N1—C7—C17—C16	−2.9 (4)
C9—C10—C11—N2	0.3 (5)	C8—C7—C17—C16	176.9 (3)
C11—N2—C12—C8	−0.9 (4)	N1—C7—C17—C13	179.3 (2)
C11—N2—C12—C13	−180.0 (2)	C8—C7—C17—C13	−1.0 (3)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₁N₃
M_r	257.29
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.1950 (14), 8.5860 (17), 11.876 (2)
α, β, γ (°)	80.63 (3), 74.78 (3), 66.46 (3)
V (Å³)	647.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.984, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	2529, 2326, 1642
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.178, 1.02
No. of reflections	2326
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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