N,N′-Bis[(E)-4-nitro­benzyl­idene]-4,4′-oxydianiline

Hee K Lee; Soon W Lee

doi:10.1107/S1600536809033844

. 2009 Aug 29;65(Pt 9):o2263. doi: 10.1107/S1600536809033844

N,N′-Bis[(E)-4-nitrobenzylidene]-4,4′-oxydianiline

Hee K Lee ^a, Soon W Lee ^a,^*

PMCID: PMC2969895 PMID: 21577659

Abstract

The title compound, C₂₆H₁₈N₄O₅, can be regarded as an extended ether with two terminal nitro groups. The two aryl rings bonded to the central O atom form a dihedral angle of 75.72 (6)°, and the terminal nitro groups are slightly twisted [by 6.4 (2) and 3.3 (3)°] from the benzene rings to which they are attached. The crystal packing exhibits weak intermolecular C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distances = 3.794 (3) Å].

Related literature

For applications of coordination polymers, see: Barnett & Champness (2003 ▶); Batten et al. (2009 ▶); Perry et al. (2009 ▶). For bis(pyridine)-, bis(furan)-, bis(thiophene)-, and (pyridine–amine)-type linking ligands as well as compounds that are structurally close to the title compound, see Yun et al. (2009 ▶) and references therein.

Experimental

Crystal data

C₂₆H₁₈N₄O₅
M _r = 466.44
Triclinic,
a = 8.3322 (11) Å
b = 9.0716 (16) Å
c = 17.107 (2) Å
α = 74.714 (9)°
β = 78.885 (10)°
γ = 64.643 (10)°
V = 1122.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.52 × 0.32 × 0.26 mm

Data collection

Siemens P4 diffractometer
Absorption correction: none
4200 measured reflections
3909 independent reflections
2972 reflections with I > 2σ(I)
R _int = 0.015
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.114
S = 1.02
3909 reflections
389 parameters
All H-atom parameters refined
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: XSCANS (Siemens, 1995 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033844/cv2603sup1.cif

e-65-o2263-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033844/cv2603Isup2.hkl

e-65-o2263-Isup2.hkl^{(191.6KB, 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
C19—H19⋯O1ⁱ	0.956 (19)	2.57 (2)	3.375 (2)	142.4 (14)
C20—H20⋯O5ⁱⁱ	1.016 (19)	2.48 (2)	3.323 (2)	139.7 (14)

Open in a new tab

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

Acknowledgments

This work was supported by the Korean Science and Engineering Foundation (KOSEF) grant funded by the Korean government (MEST) (grant No. 2009–007996).

supplementary crystallographic information

Comment

Coordination polymers gain continuous attention due to their desirable zeolite-like properties applicable to catalysis, nonlinear optical activity, spin crossover, luminescence, long-range magnetism, adsorption-desorption, and gas storage (Barnett & Champness, 2003; Batten et al., 2009; Perry IV et al., 2009). Carefule choice of relevant linking ligands is one of the key factors for the successful preparation of such polymers. We have continually reported long bis(pyridine)-, bis(furan)-, bis(thiophene)-, and (pyridine–amine)-type linking ligands and their coordination polymers (Yun et al., 2009). To an extension of our ongoing study of novel linking ligands and their coordination polymers, we prepared a long, potential linking ligand containing two terminal nitro groups.

The molecular structure of the title compound with the atom-numbering scheme is shown in Fig. 1. The overall structure can be regarded as a long ether possessing two terminal nitro (NO₂) groups. Two bis(pyridine)-type linking ligands containing an intervening oxydianilne fragment, which are structurally close to the title compound, were recently reported by our research group: [(3-py)—CHN—C₆H₄—O—C₆H₄—NCH—(3-py)] and [(4-py)—CHN—C₆H₄—O—C₆H₄—NCH—(4-py)] (Yun et al., 2009), which, however, were not structurally characterized. In the title compound, the dihedral angle between two aryl rings (C8–13 and C14–C19) bonded to the central oxygen (O13) is 75.72 (6)°. Terminal nitro groups are not coplanar with the phenyl rings to which they are attached, with the dihedral angle 6.4 (2) (N1, O1, O2) or 3.3 (3)° (N2, O4, O5). These bonding parameters might indicate the flexibility of the title compound. The crystal packing exhibits weak intermolecular C—H···O hydrogen bonds (Table 1) and π–π interactions proved by centroid-to-centroid distances of 3.794 (3) Å.

Experimental

4-Nitrobenzaldehyde (1.12 g, 7.41 mmol) and 4,4-oxydianiline (0.67 g, 3.31 mmol) were dissolved in methanol (80 ml), to which formic acid (0.15 ml) was added. The resulting mixture was stirred at room temperature for 1 h. Dichloromethane (50 ml) was then added to the mixture, which was further stirred for 24 h. The resulting solution was filtered to give a yellow solid, which was washed with hexane (20 ml × 2). X-ray quality crystals were obtained from dichloromethane/hexane. Yield: 92%. mp: 457–459 K. IR (KBr, cm^-1): 3427, 3099, 2846, 2441, 1595, 1517, 1490, 1340, 1240, 1104, 850.