4,4′-{[4-(2,2′:6′,2′′-Terpyridin-4′-yl)phen­yl]imino}­dibenzaldehyde

Wei-Biao Shen; Zhi-Wen Zhang; Li-Wen Wang; Jie-Ying Wu

doi:10.1107/S1600536812014833

. 2012 Apr 13;68(Pt 5):o1358. doi: 10.1107/S1600536812014833

4,4′-{[4-(2,2′:6′,2′′-Terpyridin-4′-yl)phenyl]imino}dibenzaldehyde

Wei-Biao Shen ^a, Zhi-Wen Zhang ^a, Li-Wen Wang ^a, Jie-Ying Wu ^a,^*

PMCID: PMC3344490 PMID: 22590252

Abstract

The central pyridine ring of the 2,2′:6′,2′′-terpyridine fragment of the title compound, C₃₅H₂₄N₄O₂, forms dihedral angles of 8.3 (2), 10.6 (3) and 39.4 (3)°, respectively, with the two outer pyridine rings and the attached benzene ring. In the crystal, weak C—H⋯O interactions link the molecules into chains in [010].

Related literature

For supramolecular assemblies and composite fluorescent sensors of related substituted terpyridines, see: Cargill Thompson (1997 ▶); Goodall et al. (2002 ▶); Mutai et al. (2001 ▶). For related reviews, see: Heller & Schubert (2003 ▶); Fallahpour et al. (2003 ▶). For details of the synthesis, see: Krohnke (1976 ▶).

Experimental

Crystal data

C₃₅H₂₄N₄O₂
M _r = 532.58
Orthorhombic,
a = 11.2518 (14) Å
b = 18.380 (2) Å
c = 25.860 (3) Å
V = 5348.1 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.983, T _max = 0.992
36182 measured reflections
4712 independent reflections
3293 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.123
S = 1.06
4712 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014833/cv5273sup1.cif

e-68-o1358-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014833/cv5273Isup2.hkl

e-68-o1358-Isup2.hkl^{(230.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812014833/cv5273Isup3.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
C27—H27⋯O1ⁱ	0.93	2.46	3.339 (3)	158

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 21071001) and the Education Committee of Anhui Province (grant No. KJ2010A030).

supplementary crystallographic information

Comment

Substituted terpyridines are frequently used as building blocks for supramolecular assemblies and composite fluorescent sensors (Cargill Thompson, 1997; Goodall et al., 2002; Mutai et al., 2001), and several reviews were published on the subject (Heller et al., 2003; Fallahpour et al., 2003). The title compound (I) can be used as intermediate in the synthesis of terpyridines, and here we report its crystal structure.

In (I) (Fig.1), the central pyridine ring of the 2,2':6',2''-terpyridine fragment forms dihedral angles of 8.3 (2), 10.6 (3) and 39.4 (3) °, respectively, with the two outer pyridine rings and the attached benzene ring. Weak intermolecular C—H···O interactions (Table 1) link the molecules into chains in [010].

Experimental

DMF (2 g, 27.4 mmol) was added to a three-necked flask in ice equipped with a magnetic stirrer and a reflux condenser, then POCl₃ (4.0 g, 26.4 mmol) was added dropwisely (about 30 min), then 4'-(4-(diphenylamino)phenyl)-2,2':6',2''-terpyridine)(3.0 g, 6.2 mmol), which was synthesized using Krohnke's method (Krohnke, 1976.), dissolved in 50 ml of chloroform and added to the frozen salt, stirring for 36 h at 355 K. After being cooled to room temperature, the mixture was poured into a large amount of ice water and adjusted to the pH= 8 with sodium hydroxide. After extraction with CH₂Cl₂ (4 x 20 ml), the combined organic phase was dried over anhydrous Na₂SO₄ and evaporated to give a yellow solid. Purification by column chromatography (silica, petroleum: ethyl acetate=5:1, yield: 50%) ¹H NMR (DMSO-d6, 400 MHz): 9.92 (s, 2H), 8.75–8.77 (m, 4H), 8.69 (d, 2H, J=7.6 Hz), 8.02–8.05 (m, 4H), 7.90 (d, 4H, J=7.6 Hz), 7.53 (t, 2H, J=6.4 Hz), 7.38 (d, 2H, J=8.8 Hz), 7.28 (d, 4H, J=8.4 Hz). MS: m/z (%) = 504.20 (100). FT—IR (KBr, cm^-1): 3464, 3060, 2919, 2850, 1714, 1546, 1508, 1474, 1434, 1365, 1321, 1179, 1111, 1069, 1015, 968, 834, 793, 769, 731, 702, 659, 637, 528.