2-(4,5,6,7,8,9-Hexahydro-6a-aza­phenyl­en-2-ylmethyl­ene)indan-1,3-dione

Sergey Belyakov; Valdis Kampars; Pauls J Pastors; Andrey Tokmakov

doi:10.1107/S1600536808016346

. 2008 Jun 7;64(Pt 7):o1200. doi: 10.1107/S1600536808016346

2-(4,5,6,7,8,9-Hexahydro-6a-azaphenylen-2-ylmethylene)indan-1,3-dione

Sergey Belyakov ^a,^*, Valdis Kampars ^b, Pauls J Pastors ^b, Andrey Tokmakov ^a

PMCID: PMC2961890 PMID: 21202841

Abstract

The title compound, C₂₂H₁₉NO₂, has potential for use as a new nonlinear optical material. Molecules are almost planar. One C atom of the heterocyclic ring system is disordered over two positions; the site occupancy factors are 0.6 and 0.4.

Related literature

For related literature, see: Honda et al. (1996 ▶); Allen (2002 ▶).

Experimental

Crystal data

C₂₂H₁₉NO₂
M _r = 329.38
Monoclinic,
a = 8.5125 (2) Å
b = 19.2973 (5) Å
c = 10.4969 (3) Å
β = 109.5301 (10)°
V = 1625.10 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.26 × 0.19 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
6190 measured reflections
3685 independent reflections
2852 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.155
S = 1.01
3685 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: KappaCCD Server Software (Nonius, 1999 ▶); cell refinement: KappaCCD Server Software; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: maXus (Mackay et al., 1999 ▶) and SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: maXus and SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016346/rk2090sup1.cif

e-64-o1200-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016346/rk2090Isup2.hkl

e-64-o1200-Isup2.hkl^{(180.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge financial support from the Latvian Council of Science.

supplementary crystallographic information

Comment

The molecular structure of the title compound, C₂₂H₁₉NO₂, (I), with atomic numbering scheme and thermal ellipsoids is presented in Fig. 1. The indandione fragment geometry is usual. The aromatic C14-C15 and C23-C24 bonds are shorter than other aromatic bonds in yulolidine system, indicating the quinoid character. Thus, presenting schematically the structure of I as two mesomeric forms (A or B) one can infer that the specific weight of the ionic form of B is increased (see Fig. 2). Therefore, the deep coloration occurs for the crystals I. A search of the Cambridge Structural Database (CSD, Version 5.29, November 2007; Allen, 2002) indicates that there are only 26 entries containing yulolidine fragments. For the title compound there is the disorder of crystal structure analogously to the crystal structure of "Coumarin 106" (Honda et al., 1996). In the yulolidine system the C17 atom is disordered and the site occupancies were initially refined then fixed at 0.6 and 0.4 for C17 and C17', respectively, in the final refinement. Atoms C17 and C17' are located on the opposite sides of the least-squares plane of the molecule. The atoms C17, C17' and C21 deviate from the molecule plane on 0.597 (4), -0.288 (6) and -0.527 (2)Å, respectively.

The packing diagram of the molecules is given in Fig. 3. The moderate π-π-stacking interaction in the crystal structure of (I) is between paris of inversion-related indandione systems. The five-membered cycle overlaps with the benzene ring of indandione; the centroids of these rings are separated by 3.509 (3)Å, but the distance between planes of these indandione systems is 3.435 (3)Å.

Experimental

A mixture of indan-1,3-dione, (0.44 g, 3.0 mmole), yulolidine-9-carbaldehyde (0.62 g, 3.1 mmole) of and 30 ml of absolute ethanol was boiled for 15 minutes, cooled to room temperature and filtered. Deep red crystals of I with metallic sheen were obtained after recrystallyzation from ethanol. M.p. is 504 K (decomp.); Yield 83%. Analysis calculated for C₂₂H₁₉NO₂: C 80.22, H 5.81, N 4.25%; found: C 80.07, H 5.43, N 4.30%.