(E,E)-1,2-Bis[3-(prop-2-yn-1-yl­oxy)benzyl­idene]hydrazine

Wisam Naji Atiyah Al-Mehana; Rosiyah Yahya; Faridah Sonsudin; Kong Mun Lo

doi:10.1107/S1600536812025524

. 2012 Jun 13;68(Pt 7):o2087. doi: 10.1107/S1600536812025524

(E,E)-1,2-Bis[3-(prop-2-yn-1-yloxy)benzylidene]hydrazine

Wisam Naji Atiyah Al-Mehana ^a, Rosiyah Yahya ^a, Faridah Sonsudin ^b, Kong Mun Lo ^a,^*

PMCID: PMC3393903 PMID: 22798768

Abstract

The molecule of the title compound, C₂₀H₁₆N₂O₂, is centrosymmetric, the inversion center being located at the mid-point of the central azine bond. The conformation around the C=N bond is E. The whole molecule (except for the H atoms) is essentially planar, with an r.m.s. deviation of 0.07 Å. In the crystal, molecules are linked head-to-tail by pairs of C—H⋯O hydrogen bonds, forming inversion dimers, and resulting in the formation of chains propagating along [011].

Related literature

For biological properties and practical appplications of diacetylene compounds, see: Zloh et al. (2007 ▶); Buckley & Neumeister (1992 ▶). For the structure of (E,E)-1,2-bis[3-(prop-2-yn-1-yloxy)benzylindene]hydrazine see: Al-Mehana et al. (2011 ▶).

Experimental

Crystal data

C₂₀H₁₆N₂O₂
M _r = 316.35
Triclinic,
a = 4.5700 (3) Å
b = 9.4947 (7) Å
c = 9.8920 (8) Å
α = 67.986 (7)°
β = 77.487 (6)°
γ = 84.132 (6)°
V = 388.37 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.1 × 0.08 × 0.08 mm

Data collection

Agilent SuperNova Dual (Cu) Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.440, T _max = 1.000
2956 measured reflections
1710 independent reflections
1508 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.122
S = 1.02
1710 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: pubCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812025524/su2430sup1.cif

e-68-o2087-sup1.cif^{(14.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025524/su2430Isup2.hkl

e-68-o2087-Isup2.hkl^{(84.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812025524/su2430Isup3.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
C5—H5⋯O1ⁱ	0.93	2.52	3.4467 (16)	177

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the University of Malaya (FRGS grant No. FP001/2010 A) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

supplementary crystallographic information

Comment

Diacetylene compounds are known to have antitumour and antimicrobial activities (Zloh et al., 2007). In addition to their biological activities, diacetylenes are also used as coating and surface treatment agents and as inner cladding material for silica fibre-optic cores (Buckley & Neumeister, 1992). A recent study detailed the crystal structure of (E,E)-1,2-Bis[4-(prop-2-yn-1-yloxy)benzylindene]hydrazine (Al-Mehana et al., 2011). Herein we report on the synthesis and crystal structure of the 3-substituted isomer of this diacetylene compound.

Like the above mentioned compound, the title compound, Fig. 1, is also centrosymmetric around the central azine bond [N1—N1ⁱ = 1.415 (1) Å; Symmetry code: (i) -x+2, -y+1, -z+2], with an E conformation about the N1═C10 bond [1.2810 (18) Å].

The title compound differs from the 4-substituted isomer (Al-Mehana et al., 2011) as it adopts a different type of C—H···O interaction in its crystal packing. Here, one of the aromatic H atoms is a hydrogen bond donor to the adjacent phenoxy O atom resulting in the formation of an infinite polymeric chain propagating along [011] (Table 1 and Fig. 2).

Experimental

3,3'-(E, E)-hydrazine-1,2-diylidene bis(methan-1-yl-1-ylidene)diphenol (L₁) was prepared by stirring 3-hydroxybenzaldehyde (3 g, 24.5 mmol), hydrazine sulfate (1.65 g, 12.6 mmol) and 1.5 ml of concentrated ammonium solution in a mixture of ethanol and water (20 ml) for 3 h. The product was obtained as a yellow crystalline solid, m.p. 487 - 488 K. A mixture of the diphenol, L₁ (2 g, 8.3 mmol) and anhydrous potassium carbonate (1.84 g, 8.6 mmol) in 20 ml of dry acetone was stirred for 30 minutes. Then an excess of propargyl bromide (2.28 g, 19.2 mmol) was added drop wise and the resulting mixture was left under reflux for 48 h. The solvent was then evaporated under reduced pressure. The product was extracted with 100 ml of diethyl ether. The organic layer was washed with brine and dried with MgSO₄. A yellow amorphous solid was obtained upon slow evaporation of the ethereal solution and was recrystallized with a 1:1 ethyl acetate-methanol mixture, to yield pure yellow block-like crystals of the title compound [M.p. 401 - 403 K].