4,5-Diaza-9H-fluoren-9-imine

Cang, H.; Ji, J.-X.; Wang, S.-Q.; Wang, J.-T.

doi:10.1107/S1600536810020441

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1802

doi:10.1107/S1600536810020441

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4,5-Diaza-9H-fluoren-9-imine

Hui Cang,^a Jin-Xiu Ji,^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, ^bResearch & Development Center, Sinochem Jiangsu Corporation, Nanjing 210005, 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 14 May 2010; accepted 29 May 2010; online 26 June 2010)

In the title compound, C₁₁H₇N₃, the diazafluorene rings are almost coplanar with an r.m.s. deviation of 0.0160 Å. In the crystal structure, C—H⋯N hydrogen bonds link molecules into sheets parallel to the ab plane. Molecules are also stacked regularly along the c axis by a variety of π–π interactions with centroid–centroid distances in the range 3.527 (2)–3.908 (2) Å.

Related literature

For the use of the title compound in synthesizing 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

C₁₁H₇N₃
M_r = 181.20
Monoclinic, P 2₁ /c
a = 10.008 (2) Å
b = 12.407 (3) Å
c = 6.8140 (14) Å
β = 99.74 (3)°
V = 833.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.991
1638 measured reflections
1503 independent reflections
1010 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.194
S = 1.06
1503 reflections
127 parameters
40 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯N3ⁱ	0.93	2.45	3.382 (4)	178
C4—H4A⋯N1ⁱⁱ	0.93	2.69	3.536 (4)	152
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -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/S1600536810020441/sj5007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020441/sj5007Isup2.hkl

checkCIF report

Comment top

4,5-diazafluorene-9-imine is one of the important 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, and the selected geometric parameters are given in Table 1. The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The diazafluorene rings are almost coplanar with an rms deviation 0.0160 Å.

In the crystal structure C—H···N hydrogen bonds link molecules into sheets 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 = 3.876 (2) /%A, Cg2···Cg2 = 3.572 (2) /%A, Cg(3)···Cg3 = 3.908 (2) and Cg1···Cg2 3.776 (2) Å and 3.863 (2) Å. Symmetry operations x, 1/2-y, 1/2+z, and x, 1/2-y, -1/2+z; Cg1, Cg2 and Cg3 are the centroids of the C2,C3,C5,C7,C8; N2,C1,C2,C3,C4,C5 and N3,C6,C7,C10,C11 rings, respectively.

Related literature top

For the use of the title compound in synthesizing 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, 11.0 mmol) in ethyl acetate(50 ml), 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). Hydrogen bonds are drawn as dashed lines.

4,5-Diaza-9H-fluoren-9-imine top

Crystal data top

C₁₁H₇N₃	F(000) = 376
M_r = 181.20	D_x = 1.443 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.008 (2) Å	θ = 10–13°
b = 12.407 (3) Å	µ = 0.09 mm⁻¹
c = 6.8140 (14) Å	T = 293 K
β = 99.74 (3)°	Block, colourless
V = 833.9 (3) Å³	0.30 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1010 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
T_min = 0.973, T_max = 0.991	l = 0→8
1638 measured reflections	3 standard reflections every 200 reflections
1503 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0948P)² + 0.5792P] where P = (F_o² + 2F_c²)/3
1503 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.28 e Å⁻³
40 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₇N₃	V = 833.9 (3) Å³
M_r = 181.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.008 (2) Å	µ = 0.09 mm⁻¹
b = 12.407 (3) Å	T = 293 K
c = 6.8140 (14) Å	0.30 × 0.10 × 0.10 mm
β = 99.74 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1010 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.022
T_min = 0.973, T_max = 0.991	3 standard reflections every 200 reflections
1638 measured reflections	intensity decay: none
1503 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	40 restraints
wR(F²) = 0.194	H-atom parameters constrained
S = 1.06	Δρ_max = 0.28 e Å⁻³
1503 reflections	Δρ_min = −0.21 e Å⁻³
127 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.8062 (3)	0.5097 (2)	0.3404 (5)	0.0530 (8)
H1	0.7491	0.5497	0.3246	0.079*
N2	0.7922 (3)	0.1271 (2)	0.3022 (4)	0.0488 (8)
N3	0.5012 (3)	0.2137 (2)	0.2363 (4)	0.0455 (7)
C1	0.9253 (4)	0.1124 (3)	0.3376 (5)	0.0540 (10)
H1A	0.9567	0.0418	0.3391	0.065*
C2	0.7547 (3)	0.2304 (2)	0.3049 (5)	0.0410 (8)
C3	0.8433 (3)	0.3171 (2)	0.3340 (4)	0.0389 (8)
C4	0.9804 (4)	0.2998 (3)	0.3749 (5)	0.0508 (9)
H4A	1.0425	0.3559	0.4027	0.061*
C5	1.0202 (4)	0.1925 (3)	0.3720 (6)	0.0545 (10)
H5A	1.1119	0.1751	0.3935	0.065*
C6	0.6122 (3)	0.2709 (2)	0.2711 (4)	0.0360 (7)
C7	0.6173 (3)	0.3850 (2)	0.2811 (5)	0.0422 (8)
C8	0.7604 (3)	0.4188 (2)	0.3239 (5)	0.0441 (8)
C9	0.3856 (3)	0.2703 (3)	0.2096 (5)	0.0496 (9)
H9A	0.3044	0.2324	0.1837	0.060*
C10	0.3791 (3)	0.3820 (3)	0.2181 (6)	0.0546 (10)
H10A	0.2955	0.4167	0.2002	0.066*
C11	0.4973 (3)	0.4412 (3)	0.2531 (5)	0.0505 (9)
H11A	0.4959	0.5161	0.2576	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0453 (17)	0.0273 (15)	0.083 (2)	−0.0112 (13)	0.0014 (15)	0.0041 (14)
N2	0.0498 (18)	0.0401 (16)	0.0546 (17)	0.0120 (14)	0.0033 (13)	0.0013 (13)
N3	0.0466 (17)	0.0278 (14)	0.0614 (17)	−0.0041 (12)	0.0071 (13)	−0.0015 (12)
C1	0.058 (2)	0.041 (2)	0.063 (2)	0.0158 (18)	0.0088 (17)	0.0032 (17)
C2	0.0445 (18)	0.0317 (17)	0.0454 (18)	0.0036 (14)	0.0032 (14)	−0.0001 (14)
C3	0.0430 (18)	0.0370 (17)	0.0380 (15)	−0.0060 (14)	0.0105 (13)	0.0004 (13)
C4	0.045 (2)	0.046 (2)	0.059 (2)	−0.0079 (16)	0.0011 (16)	0.0065 (16)
C5	0.0399 (19)	0.065 (3)	0.058 (2)	0.0084 (18)	0.0070 (15)	0.0018 (18)
C6	0.0387 (16)	0.0285 (16)	0.0390 (16)	−0.0005 (13)	0.0011 (12)	−0.0013 (12)
C7	0.0478 (19)	0.0246 (16)	0.0516 (18)	−0.0031 (14)	0.0013 (14)	0.0001 (13)
C8	0.0497 (19)	0.0282 (16)	0.0536 (19)	−0.0097 (15)	0.0062 (15)	−0.0024 (14)
C9	0.0339 (18)	0.045 (2)	0.068 (2)	−0.0037 (15)	0.0030 (15)	−0.0008 (17)
C10	0.045 (2)	0.040 (2)	0.079 (3)	0.0097 (17)	0.0094 (17)	−0.0004 (18)
C11	0.056 (2)	0.0250 (17)	0.069 (2)	0.0054 (16)	0.0049 (17)	0.0010 (16)

Geometric parameters (Å, º) top

N1—C8	1.216 (4)	C4—C5	1.391 (5)
N1—H1	0.7500	C4—H4A	0.9300
N2—C1	1.325 (4)	C5—H5A	0.9300
N2—C2	1.336 (4)	C6—C7	1.417 (4)
N3—C6	1.305 (4)	C7—C11	1.373 (4)
N3—C9	1.340 (4)	C7—C8	1.473 (4)
C1—C5	1.367 (5)	C9—C10	1.389 (5)
C1—H1A	0.9300	C9—H9A	0.9300
C2—C3	1.386 (4)	C10—C11	1.379 (5)
C2—C6	1.493 (4)	C10—H10A	0.9300
C3—C4	1.371 (5)	C11—H11A	0.9300
C3—C8	1.505 (4)

C8—N1—H1	109.5	N3—C6—C7	125.1 (3)
C1—N2—C2	113.9 (3)	N3—C6—C2	127.3 (3)
C6—N3—C9	115.4 (3)	C7—C6—C2	107.6 (3)
N2—C1—C5	125.4 (3)	C11—C7—C6	118.5 (3)
N2—C1—H1A	117.3	C11—C7—C8	132.9 (3)
C5—C1—H1A	117.3	C6—C7—C8	108.6 (3)
N2—C2—C3	124.9 (3)	N1—C8—C7	128.4 (3)
N2—C2—C6	125.7 (3)	N1—C8—C3	125.3 (3)
C3—C2—C6	109.4 (3)	C7—C8—C3	106.3 (2)
C4—C3—C2	120.1 (3)	N3—C9—C10	124.3 (3)
C4—C3—C8	131.7 (3)	N3—C9—H9A	117.9
C2—C3—C8	108.0 (3)	C10—C9—H9A	117.9
C3—C4—C5	115.2 (3)	C11—C10—C9	119.5 (3)
C3—C4—H4A	122.4	C11—C10—H10A	120.2
C5—C4—H4A	122.4	C9—C10—H10A	120.2
C1—C5—C4	120.4 (3)	C7—C11—C10	117.3 (3)
C1—C5—H5A	119.8	C7—C11—H11A	121.3
C4—C5—H5A	119.8	C10—C11—H11A	121.3

C2—N2—C1—C5	−0.8 (5)	N3—C6—C7—C11	0.2 (5)
C1—N2—C2—C3	2.3 (5)	C2—C6—C7—C11	179.6 (3)
C1—N2—C2—C6	−179.7 (3)	N3—C6—C7—C8	179.7 (3)
N2—C2—C3—C4	−4.0 (5)	C2—C6—C7—C8	−0.9 (4)
C6—C2—C3—C4	177.8 (3)	C11—C7—C8—N1	−1.9 (6)
N2—C2—C3—C8	179.3 (3)	C6—C7—C8—N1	178.7 (4)
C6—C2—C3—C8	1.1 (3)	C11—C7—C8—C3	−179.1 (3)
C2—C3—C4—C5	3.7 (5)	C6—C7—C8—C3	1.5 (4)
C8—C3—C4—C5	179.5 (3)	C4—C3—C8—N1	5.0 (6)
N2—C1—C5—C4	1.0 (6)	C2—C3—C8—N1	−178.9 (3)
C3—C4—C5—C1	−2.4 (5)	C4—C3—C8—C7	−177.8 (3)
C9—N3—C6—C7	−0.2 (5)	C2—C3—C8—C7	−1.6 (3)
C9—N3—C6—C2	−179.5 (3)	C6—N3—C9—C10	−0.4 (5)
N2—C2—C6—N3	1.0 (5)	N3—C9—C10—C11	1.0 (6)
C3—C2—C6—N3	179.3 (3)	C6—C7—C11—C10	0.4 (5)
N2—C2—C6—C7	−178.4 (3)	C8—C7—C11—C10	−179.0 (3)
C3—C2—C6—C7	−0.1 (3)	C9—C10—C11—C7	−0.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···N3ⁱ	0.93	2.45	3.382 (4)	178
C4—H4A···N1ⁱⁱ	0.93	2.69	3.536 (4)	152

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₇N₃
M_r	181.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.008 (2), 12.407 (3), 6.8140 (14)
β (°)	99.74 (3)
V (Å³)	833.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	1638, 1503, 1010
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.194, 1.06
No. of reflections	1503
No. of parameters	127
No. of restraints	40
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.21

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
C11—H11A···N3ⁱ	0.93	2.45	3.382 (4)	178.1
C4—H4A···N1ⁱⁱ	0.93	2.69	3.536 (4)	151.5

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z+1.

Acknowledgements

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

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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Y. X. & Rillema, D. P. (1997). Tetrahedron, 37, 12377–12390. CrossRef Web of Science Google Scholar