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

Cang, H.; Bian, J.-F.; Wang, S.-Q.; Wang, J.-T.

doi:10.1107/S1600536810023275

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1804

doi:10.1107/S1600536810023275

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

Hui Cang,^a ^* Jin-Fa Bian,^b Si-Qing Wang ^c and Jin-Tang Wang ^c

^aChemical and Biological Engineering College, Yancheng Institute of Technology, Yancheng 224051, People's Republic of China, ^bDepartment of Chemical Engineering, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China, and ^cDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: canghui@ycit.edu.cn

(Received 11 June 2010; accepted 16 June 2010; online 26 June 2010)

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 ). For reference bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₈H₁₃N₃O
M_r = 287.31
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.081
wR(F²) = 0.212
S = 1.03
2498 reflections
193 parameters
48 restraints
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯Oⁱ	0.93	2.42	3.337 (6)	169
Symmetry code: (i) -x, -y+1, -z+1.

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/S1600536810023275/sj5020sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

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. 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.

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

Crystal data top

C₁₈H₁₃N₃O	F(000) = 600
M_r = 287.31	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.3070 (17) Å	θ = 9–12°
b = 12.839 (3) Å	µ = 0.09 mm⁻¹
c = 13.233 (3) Å	T = 298 K
β = 97.12 (3)°	Block, colourless
V = 1400.5 (5) Å³	0.30 × 0.10 × 0.05 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1599 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 25.1°, θ_min = 2.2°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.974, T_max = 0.996	l = 0→15
2678 measured reflections	3 standard reflections every 200 reflections
2498 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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.050P)² + 5.P] where P = (F_o² + 2F_c²)/3
2498 reflections	(Δ/σ)_max = 0.001
193 parameters	Δρ_max = 0.37 e Å⁻³
48 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₈H₁₃N₃O	V = 1400.5 (5) Å³
M_r = 287.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3070 (17) Å	µ = 0.09 mm⁻¹
b = 12.839 (3) Å	T = 298 K
c = 13.233 (3) Å	0.30 × 0.10 × 0.05 mm
β = 97.12 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1599 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.025
T_min = 0.974, T_max = 0.996	3 standard reflections every 200 reflections
2678 measured reflections	intensity decay: none
2498 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	48 restraints
wR(F²) = 0.212	H-atom parameters constrained
S = 1.03	Δρ_max = 0.37 e Å⁻³
2498 reflections	Δρ_min = −0.40 e Å⁻³
193 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
O	0.1797 (4)	0.1191 (2)	0.5460 (2)	0.0455 (8)
N1	−0.4360 (4)	0.2396 (3)	0.3622 (3)	0.045
C1	0.2903 (6)	0.0674 (4)	0.4883 (4)	0.0580 (14)
H1B	0.3927	0.0584	0.5298	0.087*
H1C	0.3054	0.1085	0.4296	0.087*
H1D	0.2473	0.0005	0.4668	0.087*
N2	−0.4715 (5)	0.6162 (3)	0.3850 (3)	0.0417 (9)
C2	0.0291 (5)	0.1441 (3)	0.4969 (3)	0.0354 (10)
C3	−0.0260 (5)	0.1213 (3)	0.3959 (3)	0.0426 (11)
H3A	0.0405	0.0853	0.3563	0.051*
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	−0.2162	0.1317	0.2881	0.051*
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	−0.2908	0.2678	0.5489	0.054*
C7	−0.0708 (5)	0.2028 (3)	0.5526 (3)	0.0392 (10)
H7A	−0.0342	0.2218	0.6193	0.047*
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	−0.1533	0.4096	0.4233	0.051*
C11	−0.1965 (6)	0.5636 (4)	0.4337 (4)	0.0490 (12)
H11A	−0.0902	0.5835	0.4554	0.059*
C12	−0.3178 (6)	0.6378 (4)	0.4197 (3)	0.0433 (11)
H12A	−0.2906	0.7066	0.4355	0.052*
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	−1.0208	0.5047	0.2307	0.070*
C16	−0.9214 (6)	0.3612 (5)	0.2422 (4)	0.0564 (14)
H16A	−1.0131	0.3252	0.2137	0.068*
C17	−0.7832 (5)	0.3104 (4)	0.2738 (3)	0.0467 (12)
H17A	−0.7777	0.2384	0.2674	0.056*
C18	−0.6499 (5)	0.3656 (4)	0.3156 (3)	0.0365 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0423 (18)	0.0440 (19)	0.050 (2)	0.0081 (14)	0.0058 (14)	−0.0014 (15)
N1	0.045	0.045	0.045	0.000	0.006	0.000
C1	0.049 (3)	0.057 (3)	0.073 (4)	0.006 (2)	0.027 (3)	0.003 (3)
N2	0.053 (2)	0.035 (2)	0.038 (2)	−0.0018 (17)	0.0143 (17)	−0.0024 (17)
C2	0.047 (3)	0.023 (2)	0.039 (2)	0.0055 (18)	0.0183 (19)	−0.0003 (18)
C3	0.048 (3)	0.041 (3)	0.043 (3)	0.000 (2)	0.018 (2)	−0.011 (2)
N3	0.041 (2)	0.069 (3)	0.041 (2)	0.002 (2)	0.0099 (18)	0.011 (2)
C4	0.045 (3)	0.049 (3)	0.035 (2)	−0.006 (2)	0.010 (2)	−0.012 (2)
C5	0.042 (2)	0.026 (2)	0.035 (2)	−0.0025 (17)	0.0137 (18)	0.0017 (18)
C6	0.060 (3)	0.044 (3)	0.035 (3)	0.015 (2)	0.023 (2)	0.000 (2)
C7	0.048 (3)	0.040 (3)	0.031 (2)	−0.002 (2)	0.0088 (19)	0.002 (2)
C8	0.046 (2)	0.028 (2)	0.026 (2)	−0.0012 (18)	0.0140 (18)	−0.0042 (17)
C9	0.048 (2)	0.039 (2)	0.021 (2)	−0.0006 (18)	0.0102 (17)	0.0019 (18)
C10	0.042 (2)	0.041 (2)	0.046 (3)	0.0099 (19)	0.008 (2)	0.009 (2)
C11	0.046 (3)	0.055 (3)	0.046 (3)	−0.005 (2)	0.001 (2)	0.011 (2)
C12	0.059 (3)	0.034 (2)	0.037 (2)	0.007 (2)	0.009 (2)	−0.001 (2)
C13	0.039 (2)	0.041 (2)	0.026 (2)	0.0035 (18)	0.0123 (17)	0.0068 (18)
C14	0.036 (2)	0.048 (3)	0.027 (2)	0.0026 (19)	0.0131 (18)	0.008 (2)
C15	0.036 (3)	0.088 (4)	0.052 (3)	0.010 (3)	0.008 (2)	0.015 (3)
C16	0.033 (3)	0.087 (4)	0.051 (3)	−0.014 (3)	0.012 (2)	0.005 (3)
C17	0.043 (3)	0.059 (3)	0.039 (3)	−0.008 (2)	0.007 (2)	0.009 (2)
C18	0.036 (2)	0.051 (3)	0.024 (2)	0.003 (2)	0.0083 (17)	0.000 (2)

Geometric parameters (Å, º) top

O—C2	1.375 (5)	C6—H6A	0.9300
O—C1	1.429 (5)	C7—H7A	0.9300
N1—C8	1.280 (5)	C8—C9	1.482 (6)
N1—C5	1.418 (5)	C8—C18	1.510 (6)
C1—H1B	0.9600	C9—C10	1.383 (6)
C1—H1C	0.9600	C9—C13	1.392 (6)
C1—H1D	0.9600	C10—C11	1.375 (7)
N2—C13	1.323 (5)	C10—H10A	0.9300
N2—C12	1.331 (6)	C11—C12	1.382 (6)
C2—C3	1.389 (6)	C11—H11A	0.9300
C2—C7	1.397 (6)	C12—H12A	0.9300
C3—C4	1.374 (6)	C13—C14	1.477 (6)
C3—H3A	0.9300	C14—C18	1.412 (6)
N3—C14	1.328 (5)	C15—C16	1.407 (8)
N3—C15	1.333 (6)	C15—H15A	0.9300
C4—C5	1.389 (6)	C16—C17	1.341 (7)
C4—H4A	0.9300	C16—H16A	0.9300
C5—C6	1.388 (6)	C17—C18	1.372 (6)
C6—C7	1.378 (6)	C17—H17A	0.9300

C2—O—C1	117.6 (4)	C10—C9—C13	117.2 (4)
C8—N1—C5	120.2 (4)	C10—C9—C8	133.5 (4)
O—C1—H1B	109.5	C13—C9—C8	109.0 (4)
O—C1—H1C	109.5	C11—C10—C9	117.9 (4)
H1B—C1—H1C	109.5	C11—C10—H10A	121.1
O—C1—H1D	109.5	C9—C10—H10A	121.1
H1B—C1—H1D	109.5	C10—C11—C12	119.8 (4)
H1C—C1—H1D	109.5	C10—C11—H11A	120.1
C13—N2—C12	115.3 (4)	C12—C11—H11A	120.1
O—C2—C3	125.3 (4)	N2—C12—C11	123.7 (4)
O—C2—C7	116.2 (4)	N2—C12—H12A	118.1
C3—C2—C7	118.4 (4)	C11—C12—H12A	118.1
C4—C3—C2	120.1 (4)	N2—C13—C9	125.8 (4)
C4—C3—H3A	119.9	N2—C13—C14	124.9 (4)
C2—C3—H3A	119.9	C9—C13—C14	109.3 (4)
C14—N3—C15	116.0 (5)	N3—C14—C18	123.3 (4)
C3—C4—C5	122.2 (4)	N3—C14—C13	128.3 (4)
C3—C4—H4A	118.9	C18—C14—C13	108.4 (4)
C5—C4—H4A	118.9	N3—C15—C16	124.2 (5)
C6—C5—C4	117.1 (4)	N3—C15—H15A	117.9
C6—C5—N1	122.7 (4)	C16—C15—H15A	117.9
C4—C5—N1	120.0 (4)	C17—C16—C15	118.5 (5)
C7—C6—C5	121.6 (4)	C17—C16—H16A	120.7
C7—C6—H6A	119.2	C15—C16—H16A	120.7
C5—C6—H6A	119.2	C16—C17—C18	119.4 (5)
C6—C7—C2	120.4 (4)	C16—C17—H17A	120.3
C6—C7—H7A	119.8	C18—C17—H17A	120.3
C2—C7—H7A	119.8	C17—C18—C14	118.5 (4)
N1—C8—C9	133.8 (4)	C17—C18—C8	133.6 (4)
N1—C8—C18	120.6 (4)	C14—C18—C8	107.8 (4)
C9—C8—C18	105.5 (3)

C1—O—C2—C3	1.4 (6)	C12—N2—C13—C9	1.5 (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—C5	4.4 (7)	C10—C9—C13—C14	173.3 (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—C18	0.1 (6)
C8—N1—C5—C6	62.1 (6)	C15—N3—C14—C13	177.1 (4)
C8—N1—C5—C4	−124.2 (5)	N2—C13—C14—N3	1.3 (7)
C4—C5—C6—C7	4.9 (6)	C9—C13—C14—N3	−177.2 (4)
N1—C5—C6—C7	178.8 (4)	N2—C13—C14—C18	178.7 (4)
C5—C6—C7—C2	−4.1 (7)	C9—C13—C14—C18	0.2 (5)
O—C2—C7—C6	179.2 (4)	C14—N3—C15—C16	0.4 (7)
C3—C2—C7—C6	3.1 (6)	N3—C15—C16—C17	−0.4 (8)
C5—N1—C8—C9	1.7 (7)	C15—C16—C17—C18	0.0 (7)
C5—N1—C8—C18	−174.5 (3)	C16—C17—C18—C14	0.4 (6)
N1—C8—C9—C10	11.8 (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—C13	1.8 (4)	N3—C14—C18—C8	178.5 (4)
C13—C9—C10—C11	4.6 (6)	C13—C14—C18—C8	0.9 (4)
C8—C9—C10—C11	177.6 (4)	N1—C8—C18—C17	−5.8 (7)
C9—C10—C11—C12	−1.1 (7)	C9—C8—C18—C17	177.0 (4)
C13—N2—C12—C11	2.6 (6)	N1—C8—C18—C14	175.5 (4)
C10—C11—C12—N2	−2.8 (7)	C9—C8—C18—C14	−1.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···Oⁱ	0.93	2.42	3.337 (6)	169

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₃N₃O
M_r	287.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.3070 (17), 12.839 (3), 13.233 (3)
β (°)	97.12 (3)
V (Å³)	1400.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.10 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.974, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	2678, 2498, 1599
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.212, 1.03
No. of reflections	2498
No. of parameters	193
No. of restraints	48
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.40

Computer programs: CAD-4 Software (Enraf-Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···Oⁱ	0.9300	2.4200	3.337 (6)	169.00

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

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

References

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