2-[(3,5-Dimethyl-1-phenyl-1H-pyrazol-4-yl)methyl­idene]indan-1,3-dione

Abdullah M Asiri; Abdulrahman O Al-Youbi; Salman A Khan; M Nawaz Tahir

doi:10.1107/S1600536811049488

. 2011 Nov 25;67(Pt 12):o3419. doi: 10.1107/S1600536811049488

2-[(3,5-Dimethyl-1-phenyl-1H-pyrazol-4-yl)methylidene]indan-1,3-dione

Abdullah M Asiri ^a,^b, Abdulrahman O Al-Youbi ^a, Salman A Khan ^a, M Nawaz Tahir ^c,^*

PMCID: PMC3239055 PMID: 22199903

Abstract

In the title compound, C₂₁H₁₆N₂O₂, the five-membered heterocyclic ring makes a dihedral angle of 47.06 (6)° with the attached benzene ring, whereas the indan-1,3-dione ring system and the benzene ring are oriented at a dihedral angle of 21.92 (7)°. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R ₂ ²(22) loops. Aromatic π–π stacking interactions [centroid–centroid distances = 3.8325 (12)–3.8600 (12) Å] also occur.

Related literature

For background to donor–acceptor chromophores, see: Asiri et al. (2006 ▶); Asiri & Khan (2009 ▶); Koyuncu et al. (2010 ▶); Kulhanek et al. (2011 ▶); Wang et al. (2011 ▶). For related structures, see: Belyakov et al. (2008 ▶); Fun et al. (2010 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₁H₁₆N₂O₂
M _r = 328.36
Monoclinic,
a = 14.6655 (3) Å
b = 7.8902 (2) Å
c = 28.6651 (7) Å
β = 98.251 (1)°
V = 3282.61 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.26 × 0.23 × 0.21 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.975, T _max = 0.985
12302 measured reflections
2970 independent reflections
2106 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.112
S = 1.01
2970 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811049488/hb6509sup1.cif

e-67-o3419-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049488/hb6509Isup2.hkl

e-67-o3419-Isup2.hkl^{(142.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049488/hb6509Isup3.cml

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
C18—H18⋯O1ⁱ	0.93	2.58	3.377 (3)	145

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to thank the Chemistry Department, King Abdulaziz University, Jeddah, Saudi Arabia, for providing research facilities.

supplementary crystallographic information

Comment

Formation of the donor acceptor chromophores by the nucleophilic addition of an active hydrogen compound to a carbonyl group followed by a dehydration reaction is known as knoevenagel condensation (Asiri & Khan, 2009). Donor acceptor chromophores are applicable in the field of materials science such as third order non-linear optical (NLO) (Asiri et al. 2006), photonic materials and devices, optical limiting (Kulhanek et al. 2011), electrochemical sensing (Koyuncu et al. 2010) and langmuir film (Wang et al. 2011). Due to wide application of donor acceptor chromophores, we are reporting here the synthesiz and crystal structure of the title compound (I), (Fig. 1).

The crystal structures of (II) i.e., 2-(4,5,6,7,8,9-hexahydro-6a-azaphenylen-2-ylmethylene)indan-1,3-dione (Belyakov et al., 2008) and (III) i.e., 4-((E)((3,5-dimethyl- 1-phenyl-1H-pyrazol-4-yl)methylene)amino)-1,5-dimethyl-2-phenyl -1,2-dihydro-3H-pyrazol-3-one have been published which contain the moities present in (I).

In (I), the group A (C1—C9/O1/O2) of indan-1, 3-dione, the heterocyclic five membered ring B (C11/C12/C14/N1/N2) and the benzene ring C (C16—C21) of the aldehyde moiety are planar with r. m. s. deviation of 0.0345, 0.0099 and 0.0035 Å, respectively. The dihedral angle between A/B, A/C and B/C is 39.77 (4), 21.92 (7) and 47.06 (6)°, respectively. The title compound consists of dimers due to intermolecular H-bonds of C—H···O type, where O-atom is of carbonyl and H-atom is of benzene ring. This H-bondings form a R₂²(22) (Fig. 2) ring motif (Bernstein et al., 1995). There exists π–π interactions between the centroids of the rings of indan-1, 3-dione moieties at the separation of 3.8325 (12)–3.8600 (12) A°.

Experimental

A mixture of 3,5-dimethyl-1-phenylpyrazole-4-carbaldehyde (1.0 g, 5.0 mmol), indan-1, 3-dione (0.73 g, 5.0 mmol) and a few drops of pyridine in ethanol (15 ml) was heated for 3 h. The progress of the reaction was monitored by TLC. The solid that separated from the cooled mixture was collected and recrystallized from a methanol-chloroform mixture to give the yellow prisms of (I).

Yellow: 85%, m.p. 469–470 K.

IR (KBr) ν_max cm^-1: 3035 (Ar—H), 2859 (C—H), 1663 (C═O), 1578 (C═C).