(E)-2-{2-tert-Butyl-6-[2-(4-hy­droxy­phen­yl)ethen­yl]-1-propyl-1,4-dihydro­pyridin-4-yl­idene}indane-1,3-dione

Kwang Ha; Sae Byul Park; Hyung Jin Kim

doi:10.1107/S1600536810051044

. 2010 Dec 15;67(Pt 1):o141. doi: 10.1107/S1600536810051044

(E)-2-{2-tert-Butyl-6-[2-(4-hydroxyphenyl)ethenyl]-1-propyl-1,4-dihydropyridin-4-ylidene}indane-1,3-dione

Kwang Ha ^a, Sae Byul Park ^a, Hyung Jin Kim ^a,^*

PMCID: PMC3050276 PMID: 21522650

Abstract

The title compound, C₂₉H₂₉NO₃, the nearly planar nine-membered indanedione ring [maximum deviation = 0.027 (2) Å] is located approximately parallel to its carrier pyridine ring [maximum deviation = 0.021 (2) Å] with a dihedral angle of 1.8 (1)° between the planes. However, because of steric hindrance, the benzene ring [maximum deviation = 0.006 (2) Å] is not parallel to the pyridine ring [dihedral angle = 37.29 (8)°]. The molecules display numerous intermolecular π–π interactions between the five- and six-membered rings, the shortest centroid–centroid distance being 3.796 (2) Å. There are inter- and intramolecular O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the synthesis of the starting material, see: Yao et al. (2006a ▶). For the synthesis of the title compound, see: Peng et al. (2006 ▶). For background to luminescent materials, see: Andreu et al. (2009 ▶); Kim et al. (2004 ▶); Yao et al. (2006a ▶,b ▶).

Experimental

Crystal data

C₂₉H₂₉NO₃
M _r = 439.53
Monoclinic,
a = 9.1330 (8) Å
b = 12.4857 (12) Å
c = 20.440 (2) Å
β = 97.775 (3)°
V = 2309.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 200 K
0.25 × 0.15 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.809, T _max = 1.000
16959 measured reflections
5724 independent reflections
2458 reflections with I > 2σ(I)
R _int = 0.097

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.144
S = 0.95
5724 reflections
303 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051044/pb2048sup1.cif

e-67-0o141-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051044/pb2048Isup2.hkl

e-67-0o141-Isup2.hkl^{(280.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.84	1.79	2.626 (2)	177
C2—H2⋯O2	0.95	2.24	2.927 (3)	128
C4—H4⋯O3	0.95	2.29	2.966 (3)	127
C15—H15⋯O3ⁱ	0.95	2.55	3.210 (3)	127
C16—H16⋯O1ⁱⁱ	0.95	2.57	3.500 (3)	166
C29—H29B⋯O2ⁱⁱⁱ	0.98	2.59	3.515 (3)	158

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This study was supported financially by Chonnam National University, 2008.

supplementary crystallographic information

Comment

Indene-1,3(2H)-dione moiety is used as a strong electron acceptor for luminescent materials such as organic light-emitting diodes (OLED) (Yao et al., 2006a,b; Andreu et al., 2009; Kim et al., 2004). For the purpose of finding a pH-sensing luminescent dye, we designed the title compound which includes indene-1,3(2H)-dione moiety conjugated with 1,4-dihydropyridine ring possessing a 4-hydroxystyryl group. The title compound was synthesized by the Knoevenagel condensation of 2-(2-tert-butyl-6-methyl-1-propylpyridin-4(1H)-ylidene)-1H-indene-1,3(2H)-dione with 4-hydroxybenzaldehyde in a sealed tube and its structure was confirmed by NMR spectra and X-ray crystal analysis.

The title compound, C₂₉H₂₉NO₃, is a 1,4-dihydropyridine ring with four distinct substituents (Fig. 1). In the crystal structure, the nearly planar 9-membered ring [maximum deviation of 0.027 (2) Å for C17] is located approximately parallel to its carrier pyridine ring [maximum deviation of 0.021 (2) Å for C3] with the dihedral angle of 1.8 (1)° between the planes. However, because of the steric hindrance, the benzne ring [maximum deviation of 0.006 (2) Å for C14] is not parallel to the pyridine ring. The dihedral angle between the pyridine and the benzene rings is 37.29 (8)°. The molecules display numerous intermolecular π-π interactions between the 5- and 6-membered rings. The shortest centroid-centroid distance is 3.796 (2) Å and the dihedral angle between the ring planes is 1.7 (1)°. Moreover, there are inter- and intramolecular O—H···O and C—H···O hydrogen bonds with d(O···O) = 2.626 (2) Å and d(C···O) = 2.927 (3) Å–3.515 (3) Å (Fig. 2, Table 1).

Experimental

A mixture of 2-(2-tert-butyl-6-methyl-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (900 mg, 7.13 mmol) and propylamine (15 ml) was heated at 150 °C for 3 h. The mixture was cooled and concentrated under vacuum. The residue was crystallized from CHCl₃ to give 2-(2-tert-butyl-6-methyl-1-propylpyridin-4(1H)-ylidene)-1H-indene-1,3(2H)-dione (750 mg, 73%). A mixture of 2-(2-tert-butyl-6-methyl-1-propylpyridin-4(1H)-ylidene)-1H-indene-1,3(2H)-dione (500 mg, 1.5 mmol), 4-hydroxybenzaldehyde (364 mg, 3.0 mmol), piperidine (600 mg, 7.0 mmol), n-butanol (10 ml) and molecular sieve (4 Å, 3 g) was heated in a sealed tube at 140 °C for 12 h. The reaction mixture was filtered and the filtrate was concentrated under vacuum to give crude product, which was chromatographed on SiO₂ eluting with a mixture of CHCl₃/acetone (10:1) solution to afford the title compound (130 mg, 20%) as a yellow solid. Crystals suitable for X-ray analysis were obtained by slow evaporation from a CHCl₃/EtOH solution at room temperature. Mp 211 °C (dec.). ¹H NMR (300 MHz, DMSO-d₆): δ 9.94 (s, 1H, OH), 8.91 (d, 1H, J = 1.85 Hz, C—CH=C—N), 8.81 (d, 1H, J = 1.85 Hz, C—CH=C—N), 7.62–6.84 (m, 10H, Ar), 7.42 (d, 1H, J = 15.6 Hz, HC=CH—C₆H₄OH), 7.22 (d, 1H, J = 15.6 Hz, HC=CH-C₆H₄OH), 4.48 (t, 2H, J = 8.1 Hz, NCH₂CH₂CH₃), 2.0 (m, 2H, NCH₂CH₂CH₃), 1.53 [s, 9H, –C(CH₃)₃], 0.88 (t, 3H, J = 7.2 Hz, NCH₂CH₂CH₃). ¹³C NMR (75 MHz, DMSO-d₆): δ 190.5, 158.6, 158.5, 151.9, 148.4, 139.3, 137.5, 131.2, 128.9, 126.1, 118.8, 117.8, 118.0, 115.2, 113.1, 112.9, 51.1, 36.7, 30.2, 22.9, 9.8.