(E,E)-1,2-Bis[4-(prop-2-yn-1-yl­oxy)benzyl­idene]hydrazine

Al-Mehana, W.N.A.; Yahya, R.; Lo, K.M.

doi:10.1107/S160053681104102X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2900

doi:10.1107/S160053681104102X

Open

access

(E,E)-1,2-Bis[4-(prop-2-yn-1-yloxy)benzylidene]hydrazine

Wisam Naji Atiyah Al-Mehana,^a Rosiyah Yahya ^a and Kong Mun Lo ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: kmlo@um.edu.my

(Received 21 September 2011; accepted 5 October 2011; online 8 October 2011)

The molecule of the title compound, C₂₀H₁₆N₂O₂, is centrosymmetric with the mid-point of the central N—N bond located on an inversion center. The configuration around the C=N bond is E. The whole molecule (except for the H atoms) is approximately planar, with an r.m.s. deviation of 0.07 Å. In the crystal, the presence of weak intermolecular C—H⋯O hydrogen bonding involving each acetylene H atom and the adjacent phenoxy O atom results in the formation of supramolecular chains.

Related literature

For the structure of (E,E)-1,2-bis[3-methoxy-4-(prop-2-yn-1-yloxy)benzylindene]hydrazine see: Al-Mehana et al. (2011 ).

Experimental

Crystal data

C₂₀H₁₆N₂O₂
M_r = 316.35
Monoclinic, P 2₁ /n
a = 7.6598 (1) Å
b = 8.1117 (1) Å
c = 12.9966 (2) Å
β = 94.466 (1)°
V = 805.08 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.16 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.975, T_max = 0.996
7404 measured reflections
1847 independent reflections
1698 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.111
S = 1.01
1847 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.928 (15)	2.383 (15)	3.2511 (13)	155.7 (13)
Symmetry code: (i) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681104102X/xu5328sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104102X/xu5328Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681104102X/xu5328Isup3.cml

checkCIF report

Comment top

The preceeding study reports the crystal structure of (E,E)-1,2-Bis[3-methoxy-4-(prop-2-yn-1-yloxy)benzylindene]hydrazine, in which the molecules are linked by C—H···O interaction between methylene H and methoxy O atoms, resulting in the formation of supramolecular chains (Al-Mehana et al. 2011). The title compound, C₂₀H₁₆N₂O₂, without the methoxy substituent on the aromatic ring, is also centrosymmetric around the central azine bond [N1—N1ⁱ = 1.412 (2) Å; symmetry operation i: -x + 1, -y - 1, -z + 2]. The molecule also adopts the E configuration around the N1=C10 bond [1.2825 (13) Å]. The title compound differs from the previous reported structure as it adopts a different type of C—H···O interaction in its crystal packing. In this case, each acetylene-H atom interacts with the adjacent phenoxy-O [C1—H1···O1ⁱⁱ =3.2511 (13) Å; symmetry operation ii: -0.5 - x, 1/2 + y, 1.5 - z]] resulting in the formation of a supramolecular network (Fig. 2).

Related literature top

For the structure of (E,E)-1,2-bis[3-methoxy-4-(prop-2-yn-1-yloxy)benzylindene]hydrazine see: Al-Mehana et al. (2011).

Experimental top

4,4'-(E, E)-hydrazine-1,2-diylidene bis(methan-1-yl-1-ylidene)diphenol (L₁) was prepared by stirring 4-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. 558 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 20 minutes. Then an excess of propargyl bromide (2.28 g, 19.2 mmol) was added dropwise 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 ethyl acetate-methanol mixture to yield the pure yellow crystal, m.p. 453 K.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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).

Figures top

	Fig. 1. The molecular structure of (E,E)-1,2-bis[4-(prop-2-yn-1-yloxy)benzylindene]hydrazine showing 70% probability displacement ellipsoids and the atom numbering. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. A view of the supramolecular network in the title compound showing the C—H···O interactions.

(E,E)-1,2-Bis[4-(prop-2-yn-1-yloxy)benzylidene]hydrazine top

Crystal data top

C₂₀H₁₆N₂O₂	F(000) = 332
M_r = 316.35	D_x = 1.305 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 453 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.6598 (1) Å	Cell parameters from 4790 reflections
b = 8.1117 (1) Å	θ = 3.0–28.3°
c = 12.9966 (2) Å	µ = 0.09 mm⁻¹
β = 94.466 (1)°	T = 100 K
V = 805.08 (2) Å³	Block, yellow
Z = 2	0.30 × 0.16 × 0.05 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1847 independent reflections
Radiation source: fine-focus sealed tube	1698 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.975, T_max = 0.996	k = −10→10
7404 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0717P)² + 0.215P] where P = (F_o² + 2F_c²)/3
1847 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₀H₁₆N₂O₂	V = 805.08 (2) Å³
M_r = 316.35	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.6598 (1) Å	µ = 0.09 mm⁻¹
b = 8.1117 (1) Å	T = 100 K
c = 12.9966 (2) Å	0.30 × 0.16 × 0.05 mm
β = 94.466 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1847 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1698 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.996	R_int = 0.021
7404 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.32 e Å⁻³
1847 reflections	Δρ_min = −0.26 e Å⁻³
113 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.03607 (9)	0.22226 (8)	0.83985 (5)	0.0188 (2)
N1	0.44709 (10)	−0.44532 (10)	0.96895 (6)	0.0200 (2)
C1	−0.20330 (14)	0.57486 (13)	0.80143 (8)	0.0249 (2)
H1	−0.285 (2)	0.6468 (19)	0.7698 (12)	0.040 (4)*
C2	−0.09922 (13)	0.48192 (12)	0.84201 (7)	0.0198 (2)
C3	0.02396 (12)	0.37108 (11)	0.89870 (7)	0.0185 (2)
H3A	0.1381	0.4229	0.9089	0.022*
H3B	−0.0166	0.3462	0.9658	0.022*
C4	0.13140 (11)	0.09661 (11)	0.88750 (7)	0.0165 (2)
C5	0.14991 (13)	−0.04424 (12)	0.82692 (7)	0.0196 (2)
H5	0.1006	−0.0473	0.7592	0.024*
C6	0.24152 (12)	−0.17843 (12)	0.86805 (7)	0.0192 (2)
H6	0.2533	−0.2721	0.8279	0.023*
C7	0.31723 (12)	−0.17477 (11)	0.97012 (7)	0.0179 (2)
C8	0.29749 (12)	−0.03295 (12)	1.02859 (7)	0.0186 (2)
H8	0.3473	−0.0293	1.0961	0.022*
C9	0.20532 (12)	0.10295 (12)	0.98860 (7)	0.0181 (2)
H9	0.1932	0.1966	1.0287	0.022*
C10	0.42043 (12)	−0.31051 (12)	1.01685 (7)	0.0188 (2)
H10	0.4689	−0.2987	1.0843	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0219 (4)	0.0157 (4)	0.0182 (3)	0.0023 (2)	−0.0021 (3)	−0.0015 (2)
N1	0.0182 (4)	0.0175 (4)	0.0238 (4)	0.0006 (3)	−0.0008 (3)	0.0045 (3)
C1	0.0271 (5)	0.0247 (5)	0.0224 (5)	0.0053 (4)	−0.0016 (4)	−0.0010 (4)
C2	0.0215 (5)	0.0192 (5)	0.0187 (4)	−0.0009 (4)	0.0008 (3)	−0.0028 (3)
C3	0.0198 (5)	0.0161 (4)	0.0191 (4)	0.0004 (3)	−0.0011 (3)	−0.0021 (3)
C4	0.0146 (4)	0.0155 (4)	0.0195 (5)	−0.0007 (3)	0.0014 (3)	0.0018 (3)
C5	0.0216 (5)	0.0197 (5)	0.0173 (4)	−0.0006 (3)	−0.0001 (3)	−0.0008 (3)
C6	0.0211 (5)	0.0159 (4)	0.0207 (5)	−0.0002 (3)	0.0021 (3)	−0.0014 (3)
C7	0.0162 (4)	0.0169 (5)	0.0208 (5)	−0.0013 (3)	0.0028 (3)	0.0028 (3)
C8	0.0175 (4)	0.0204 (5)	0.0176 (4)	−0.0020 (3)	0.0001 (3)	0.0012 (3)
C9	0.0183 (5)	0.0171 (4)	0.0191 (4)	−0.0011 (3)	0.0019 (3)	−0.0017 (3)
C10	0.0166 (4)	0.0192 (5)	0.0205 (4)	−0.0019 (3)	0.0009 (3)	0.0030 (3)

Geometric parameters (Å, º) top

O1—C4	1.3730 (11)	C5—C4	1.4010 (13)
O1—C3	1.4359 (11)	C5—H5	0.9300
N1—C10	1.2825 (13)	C6—H6	0.9300
N1—N1ⁱ	1.4120 (15)	C7—C8	1.3934 (13)
C1—H1	0.929 (16)	C7—C6	1.4062 (13)
C2—C1	1.1902 (15)	C8—C9	1.3881 (13)
C2—C3	1.4606 (13)	C8—H8	0.9300
C3—H3A	0.9700	C9—H9	0.9300
C3—H3B	0.9700	C10—C7	1.4599 (13)
C4—C9	1.3906 (13)	C10—H10	0.9300
C5—C6	1.3800 (13)

O1—C4—C9	124.18 (8)	C5—C6—H6	119.7
O1—C4—C5	115.18 (8)	C6—C7—C10	123.14 (9)
O1—C3—C2	108.35 (7)	C6—C5—C4	119.75 (9)
O1—C3—H3A	110.0	C6—C5—H5	120.1
O1—C3—H3B	110.0	C7—C6—H6	119.7
N1—C10—C7	122.86 (9)	C7—C10—H10	118.6
N1—C10—H10	118.6	C7—C8—H8	119.2
C1—C2—C3	176.00 (10)	C8—C9—C4	118.83 (9)
C2—C3—H3A	110.0	C8—C9—H9	120.6
C2—C3—H3B	110.0	C8—C7—C6	118.53 (9)
C2—C1—H1	179.5 (10)	C8—C7—C10	118.30 (8)
H3A—C3—H3B	108.4	C9—C4—C5	120.63 (9)
C4—C5—H5	120.1	C9—C8—C7	121.68 (9)
C4—O1—C3	115.98 (7)	C9—C8—H8	119.2
C4—C9—H9	120.6	C10—N1—N1ⁱ	111.36 (10)
C5—C6—C7	120.57 (9)

O1—C4—C9—C8	179.33 (8)	C5—C4—C9—C8	−0.16 (13)
N1ⁱ—N1—C10—C7	179.14 (9)	C6—C5—C4—O1	−179.17 (8)
N1—C10—C7—C8	−179.44 (9)	C6—C5—C4—C9	0.36 (14)
N1—C10—C7—C6	−1.46 (15)	C6—C7—C8—C9	0.16 (14)
C1—C2—C3—O1	140.8 (15)	C7—C8—C9—C4	−0.10 (14)
C3—O1—C4—C9	3.86 (13)	C8—C7—C6—C5	0.05 (14)
C3—O1—C4—C5	−176.63 (7)	C10—C7—C8—C9	178.23 (8)
C4—O1—C3—C2	−172.83 (7)	C10—C7—C6—C5	−177.92 (8)
C4—C5—C6—C7	−0.31 (14)

Symmetry code: (i) −x+1, −y−1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱⁱ	0.928 (15)	2.383 (15)	3.2511 (13)	155.7 (13)

Symmetry code: (ii) −x−1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₆N₂O₂
M_r	316.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.6598 (1), 8.1117 (1), 12.9966 (2)
β (°)	94.466 (1)
V (Å³)	805.08 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.16 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.975, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	7404, 1847, 1698
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.111, 1.01
No. of reflections	1847
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.26

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), pubCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.928 (15)	2.383 (15)	3.2511 (13)	155.7 (13)

Symmetry code: (i) −x−1/2, y+1/2, −z+3/2.

Acknowledgements

We thank the University of Malaya (FRGS grant No. FP001/2010 A) for supporting this study.

References

Al-Mehana, W. N. A., Shakir, R. M., Yahya, R., Abd Halim, S. N. & Tiekink, E. R. T. (2011). Acta Cryst. E67, o1659. Web of Science CSD CrossRef IUCr Journals Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar