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

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

doi:10.1107/S1600536808039627

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o6

doi:10.1107/S1600536808039627

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

Hui Cang,^a Dong Jin,^b Si-Qing Wang,^a Bin Xu ^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 16 November 2008; accepted 25 November 2008; online 3 December 2008)

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.

Related literature

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

Crystal data

C₁₈H₁₃N₃
M_r = 271.31
Triclinic, $[P \overline 1]$
a = 7.5970 (15) Å
b = 8.6100 (17) Å
c = 10.998 (2) Å
α = 77.11 (3)°
β = 87.48 (3)°
γ = 85.79 (3)°
V = 699.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.977, T_max = 0.985
2742 measured reflections
2534 independent reflections
1829 reflections with I > 2σ(I)
R_int = 0.025
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.167
S = 1.00
2534 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); 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/S1600536808039627/bx2187sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039627/bx2187Isup2.hkl

checkCIF report

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.

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

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

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

Crystal data top

C₁₈H₁₃N₃	Z = 2
M_r = 271.31	F(000) = 284
Triclinic, P1	D_x = 1.289 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5970 (15) Å	Cell parameters from 25 reflections
b = 8.6100 (17) Å	θ = 10–13°
c = 10.998 (2) Å	µ = 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 tube	R_int = 0.026
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = −9→10
T_min = 0.977, T_max = 0.985	l = 0→13
2742 measured reflections	3 standard reflections every 200 reflections
2534 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.167	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.05P)² + 0.85P] where P = (F_o² + 2F_c²)/3
2534 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₈H₁₃N₃	γ = 85.79 (3)°
M_r = 271.31	V = 699.1 (2) Å³
Triclinic, P1	Z = 2
a = 7.5970 (15) Å	Mo Kα radiation
b = 8.6100 (17) Å	µ = 0.08 mm⁻¹
c = 10.998 (2) Å	T = 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)	R_int = 0.026
T_min = 0.977, T_max = 0.985	3 standard reflections every 200 reflections
2742 measured reflections	intensity decay: none
2534 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.167	H-atom parameters constrained
S = 1.01	Δρ_max = 0.50 e Å⁻³
2534 reflections	Δρ_min = −0.28 e Å⁻³
190 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 > 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

	x	y	z	U_iso*/U_eq
N1	0.2577 (3)	1.3579 (3)	0.5598 (2)	0.0539 (7)
C1	0.0220 (6)	1.2134 (6)	1.0717 (3)	0.0953 (14)
H1B	−0.0898	1.2705	1.0794	0.143*
H1C	0.1063	1.2457	1.1223	0.143*
H1D	0.0091	1.1008	1.0992	0.143*
N2	0.2970 (3)	0.8734 (3)	0.3984 (2)	0.0507 (6)
C2	0.0855 (5)	1.2499 (5)	0.9378 (3)	0.0658 (9)
N3	0.4535 (3)	1.1454 (3)	0.2071 (2)	0.0526 (6)
C3	0.2450 (4)	1.1836 (4)	0.8993 (3)	0.0584 (8)
H3B	0.3152	1.1156	0.9583	0.070*
C4	0.3018 (4)	1.2158 (4)	0.7759 (3)	0.0551 (8)
H4A	0.4094	1.1703	0.7528	0.066*
C5	0.1987 (4)	1.3158 (3)	0.6866 (3)	0.0501 (7)
C6	0.0411 (4)	1.3877 (4)	0.7236 (3)	0.0602 (8)
H6A	−0.0268	1.4590	0.6650	0.072*
C7	−0.0137 (5)	1.3531 (5)	0.8469 (3)	0.0723 (10)
H7A	−0.1203	1.4002	0.8701	0.087*
C8	0.2867 (4)	1.2521 (3)	0.4951 (2)	0.0432 (6)
C9	0.2518 (3)	1.0803 (3)	0.5183 (2)	0.0398 (6)
C10	0.1712 (4)	0.9757 (3)	0.6156 (3)	0.0463 (7)
H10A	0.1279	1.0086	0.6868	0.056*
C11	0.1576 (4)	0.8219 (4)	0.6030 (3)	0.0490 (7)
H11A	0.1044	0.7485	0.6663	0.059*
C12	0.2236 (4)	0.7763 (4)	0.4952 (3)	0.0537 (8)
H12A	0.2157	0.6705	0.4907	0.064*
C13	0.3085 (3)	1.0227 (3)	0.4114 (2)	0.0421 (6)
C14	0.3829 (3)	1.1547 (3)	0.3185 (2)	0.0429 (6)
C15	0.5163 (4)	1.2817 (4)	0.1427 (3)	0.0586 (8)
H15A	0.5670	1.2820	0.0641	0.070*
C16	0.5114 (4)	1.4213 (4)	0.1839 (3)	0.0617 (9)
H16A	0.5590	1.5111	0.1338	0.074*
C17	0.4364 (4)	1.4296 (4)	0.2994 (3)	0.0545 (8)
H17A	0.4317	1.5228	0.3292	0.065*
C18	0.3691 (4)	1.2917 (3)	0.3673 (2)	0.0457 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0653 (17)	0.0495 (14)	0.0480 (14)	0.0060 (12)	0.0035 (12)	−0.0170 (11)
C1	0.086 (3)	0.149 (4)	0.054 (2)	−0.014 (3)	0.016 (2)	−0.029 (2)
N2	0.0502 (15)	0.0541 (15)	0.0501 (14)	0.0092 (11)	−0.0023 (11)	−0.0200 (12)
C2	0.058 (2)	0.097 (3)	0.0483 (18)	−0.0093 (18)	0.0060 (16)	−0.0284 (18)
N3	0.0500 (15)	0.0690 (17)	0.0361 (13)	0.0112 (12)	−0.0010 (11)	−0.0111 (12)
C3	0.059 (2)	0.072 (2)	0.0459 (17)	0.0002 (16)	−0.0022 (14)	−0.0174 (15)
C4	0.0563 (19)	0.0615 (19)	0.0507 (18)	0.0054 (15)	0.0036 (14)	−0.0233 (15)
C5	0.0569 (18)	0.0489 (16)	0.0487 (17)	0.0000 (13)	0.0049 (14)	−0.0220 (13)
C6	0.0562 (19)	0.068 (2)	0.057 (2)	0.0105 (15)	0.0007 (15)	−0.0220 (16)
C7	0.055 (2)	0.106 (3)	0.060 (2)	0.0086 (19)	0.0085 (17)	−0.036 (2)
C8	0.0416 (15)	0.0473 (15)	0.0401 (15)	0.0086 (12)	−0.0030 (12)	−0.0117 (12)
C9	0.0340 (14)	0.0480 (15)	0.0382 (14)	0.0065 (11)	−0.0050 (11)	−0.0135 (12)
C10	0.0424 (15)	0.0585 (18)	0.0401 (15)	0.0051 (13)	−0.0046 (12)	−0.0171 (13)
C11	0.0469 (17)	0.0540 (18)	0.0452 (16)	0.0011 (13)	−0.0054 (13)	−0.0096 (13)
C12	0.0573 (19)	0.0476 (17)	0.0589 (19)	0.0029 (14)	−0.0046 (15)	−0.0186 (15)
C13	0.0368 (15)	0.0523 (16)	0.0375 (14)	0.0120 (12)	−0.0069 (11)	−0.0142 (12)
C14	0.0348 (14)	0.0567 (17)	0.0363 (14)	0.0108 (12)	−0.0068 (11)	−0.0116 (12)
C15	0.0571 (19)	0.081 (2)	0.0335 (15)	0.0107 (17)	0.0004 (13)	−0.0087 (15)
C16	0.062 (2)	0.074 (2)	0.0424 (17)	0.0018 (16)	−0.0010 (15)	−0.0003 (15)
C17	0.0590 (19)	0.0542 (18)	0.0468 (17)	0.0046 (14)	−0.0015 (14)	−0.0062 (14)
C18	0.0436 (16)	0.0542 (17)	0.0366 (14)	0.0103 (12)	−0.0056 (12)	−0.0078 (12)

Geometric parameters (Å, º) top

N1—C8	1.277 (3)	C7—H7A	0.9300
N1—C5	1.422 (4)	C8—C9	1.486 (4)
C1—C2	1.501 (5)	C8—C18	1.491 (4)
C1—H1B	0.9600	C9—C10	1.387 (4)
C1—H1C	0.9600	C9—C13	1.414 (4)
C1—H1D	0.9600	C10—C11	1.373 (4)
N2—C12	1.327 (4)	C10—H10A	0.9300
N2—C13	1.334 (4)	C11—C12	1.392 (4)
C2—C7	1.388 (5)	C11—H11A	0.9300
C2—C3	1.391 (5)	C12—H12A	0.9300
N3—C14	1.332 (3)	C13—C14	1.477 (4)
N3—C15	1.337 (4)	C14—C18	1.397 (4)
C3—C4	1.380 (4)	C15—C16	1.374 (5)
C3—H3B	0.9300	C15—H15A	0.9300
C4—C5	1.382 (4)	C16—C17	1.383 (4)
C4—H4A	0.9300	C16—H16A	0.9300
C5—C6	1.394 (4)	C17—C18	1.375 (4)
C6—C7	1.374 (4)	C17—H17A	0.9300
C6—H6A	0.9300

C8—N1—C5	121.0 (3)	C10—C9—C13	117.7 (3)
C2—C1—H1B	109.5	C10—C9—C8	133.8 (2)
C2—C1—H1C	109.5	C13—C9—C8	108.3 (2)
H1B—C1—H1C	109.5	C11—C10—C9	117.7 (3)
C2—C1—H1D	109.5	C11—C10—H10A	121.2
H1B—C1—H1D	109.5	C9—C10—H10A	121.2
H1C—C1—H1D	109.5	C10—C11—C12	119.8 (3)
C12—N2—C13	115.1 (2)	C10—C11—H11A	120.1
C7—C2—C3	117.2 (3)	C12—C11—H11A	120.1
C7—C2—C1	120.8 (3)	N2—C12—C11	124.6 (3)
C3—C2—C1	122.0 (4)	N2—C12—H12A	117.7
C14—N3—C15	114.0 (3)	C11—C12—H12A	117.7
C4—C3—C2	121.8 (3)	N2—C13—C9	125.1 (3)
C4—C3—H3B	119.1	N2—C13—C14	126.4 (2)
C2—C3—H3B	119.1	C9—C13—C14	108.5 (2)
C3—C4—C5	119.9 (3)	N3—C14—C18	125.3 (3)
C3—C4—H4A	120.0	N3—C14—C13	126.1 (3)
C5—C4—H4A	120.0	C18—C14—C13	108.6 (2)
C4—C5—C6	119.2 (3)	N3—C15—C16	124.8 (3)
C4—C5—N1	121.3 (3)	N3—C15—H15A	117.6
C6—C5—N1	119.3 (3)	C16—C15—H15A	117.6
C7—C6—C5	119.9 (3)	C15—C16—C17	120.6 (3)
C7—C6—H6A	120.1	C15—C16—H16A	119.7
C5—C6—H6A	120.1	C17—C16—H16A	119.7
C6—C7—C2	121.9 (3)	C18—C17—C16	115.9 (3)
C6—C7—H7A	119.1	C18—C17—H17A	122.0
C2—C7—H7A	119.1	C16—C17—H17A	122.0
N1—C8—C9	133.1 (3)	C17—C18—C14	119.4 (3)
N1—C8—C18	121.3 (3)	C17—C18—C8	131.6 (3)
C9—C8—C18	105.6 (2)	C14—C18—C8	108.9 (2)

C7—C2—C3—C4	−1.2 (5)	C12—N2—C13—C14	−179.6 (3)
C1—C2—C3—C4	179.2 (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—C6	2.5 (5)	C10—C9—C13—C14	177.7 (2)
C3—C4—C5—N1	176.7 (3)	C8—C9—C13—C14	0.8 (3)
C8—N1—C5—C4	63.1 (4)	C15—N3—C14—C18	1.2 (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—N3	178.4 (2)
C5—C6—C7—C2	1.3 (6)	N2—C13—C14—C18	179.5 (3)
C3—C2—C7—C6	0.7 (6)	C9—C13—C14—C18	−1.0 (3)
C1—C2—C7—C6	−179.7 (4)	C14—N3—C15—C16	0.0 (4)
C5—N1—C8—C9	8.7 (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—C10	2.4 (5)	C16—C17—C18—C14	1.2 (4)
C18—C8—C9—C10	−176.5 (3)	C16—C17—C18—C8	177.0 (3)
N1—C8—C9—C13	178.6 (3)	N3—C14—C18—C17	−1.9 (4)
C18—C8—C9—C13	−0.3 (3)	C13—C14—C18—C17	177.4 (2)
C13—C9—C10—C11	2.2 (4)	N3—C14—C18—C8	−178.6 (2)
C8—C9—C10—C11	178.1 (3)	C13—C14—C18—C8	0.7 (3)
C9—C10—C11—C12	0.0 (4)	N1—C8—C18—C17	4.5 (5)
C13—N2—C12—C11	1.5 (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—C9	0.9 (4)	C9—C8—C18—C14	−0.3 (3)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₃N₃
M_r	271.31
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5970 (15), 8.6100 (17), 10.998 (2)
α, β, γ (°)	77.11 (3), 87.48 (3), 85.79 (3)
V (Å³)	699.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.977, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	2742, 2534, 1829
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.167, 1.01
No. of reflections	2534
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), 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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