5,5′-Bis(benz­yloxy)-2,2′-[hydrazine­diylidenebis(methanylyl­idene)]diphenol

Sajitha, N.R.; Sithambaresan, M.; Kurup, M.R.P.

doi:10.1107/S1600536813030171

organic compounds

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Volume 69| Part 12| December 2013| Page o1755

doi:10.1107/S1600536813030171

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5,5′-Bis(benzyloxy)-2,2′-[hydrazinediylidenebis(methanylylidene)]diphenol

N. R. Sajitha,^a M. Sithambaresan ^b ^* and M. R. Prathapachandra Kurup ^a

^aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, and ^bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
^*Correspondence e-mail: eesans@yahoo.com

(Received 29 October 2013; accepted 4 November 2013; online 9 November 2013)

The title azine molecule, C₂₈H₂₄N₂O₄, lies about a center of inversion. The dihedral angle between the phenyl ring and the hydroxy-substituted ring is 70.3 (5)°. The phenolic O–H group forms an intramolecular hydrogen bond to the azine N atom.

CCDC reference: 969910

Related literature

For the biological activity of azines, see: Gul et al. (2003 ); Kumaraswamy & Vaidya (2005 ). For related structures, see: Acrovito et al. (1969 ); Sithambaresan & Kurup (2011 ). For a related synthesis, see: Karmakar et al. (2007 ).

Experimental

Crystal data

C₂₈H₂₄N₂O₄
M_r = 452.49
Monoclinic, P 2₁ /n
a = 12.4748 (17) Å
b = 5.3630 (6) Å
c = 17.021 (2) Å
β = 90.699 (5)°
V = 1138.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.965, T_max = 0.982
6320 measured reflections
2738 independent reflections
1593 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.122
S = 1.01
2738 reflections
159 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2′⋯N1	0.87 (2)	1.84 (2)	2.625 (2)	148 (2)

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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, 2012 ) and DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 969910

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813030171/ng5346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030171/ng5346Isup2.hkl

checkCIF report

Comment top

Azines are 2,3-diaza analogous compounds of 1,3-butadiene. Compounds containing azine moiety exhibit a broad spectrum of bilogical activity such as antitumor (Gul et al., 2003), antibacterial (Kumaraswamy & Vaidya, 2005) and many others.

The present compound is analogous to salicylaldehyde azine, in which the fourth position is substituted. The salicyladehyde azine was characterized previously (Acrovito et al., 1969) as luminescent and thermochromic substance in the solid state.

The title compound (Fig. 1) adopts an E configuration with respect to C14=N1 (bond distance: 1.288 (21) Å) and is close to the formal C= N bond [1.2758 (19) Å] (Sithambaresan & Kurup, 2011) confirming the azomethine bond formation and the presence of benzylidene moiety. The azomethine and benzaldehyde moieties are nearly planar with interplanar dihedral angle of 2.396 (7)°. The dihedral angle between benzene ring and benzaldehyde ring is 70.329 (46)°. The phenolic O–H forms an intramolecular O–H···N hydrogen bond with a D···A distance of 2.6245 (18) Å (Table 1, Fig. 2). There are very few weak short ring interactions found in the crystal system, but they are not significant to support the network since centriod-centroid distances are above 4 Å. Fig. 3 shows a packing diagram of the title compound viewed along b axis.

Related literature top

For the biological activity of azines, see: Gul et al. (2003); Kumaraswamy & Vaidya (2005). For related structures, see: Acrovito et al. (1969); Sithambaresan & Kurup (2011). For a related synthesis, see: Karmakar et al. (2007).

Experimental top

The title compound was prepared by adapting a reported procedure (Karmakar et al., 2007). 4-Benzyloxy-2-hydroxybenzaldehyde (0.4564 g, 2 mmol) was dissolved in methanol (30 ml). The solution was acidified with 5 drops of glacial acetic acid and hydrazine monohydrate (0.501 g, 1 mmol). The mixture was stirred for 1 h at room temperature. An yellow solution obtained was kept for crystallization for 3 days and the crystalline substance formed was seperated and washed with hexane and dried over P₄O₁₀ in vacuo. This crystalline substance was recrystallized from dimethylformamide (20 ml) to give yellow needles of 4-benzyloxy-2-hydroxybenzaldehyde azine. The compound was obtained in 65% yield (0.181 g).

IR (KBr, ν in cm^-1): 1183, 1277, 1213, 1455, 1614, 2945, 3032. ¹H NMR (400 MHz, DMSO-d₆, δ in p.p.m.): 8.583 (s, 1H), 5.103 (s, 2H), 7.224 (s, 1H), 7.333–7.446 (m, 5H), 6.585–6.618 (m, 3H).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP view of the title compound drawn with 50% probability displacement ellipsoids for the non-H atoms.
	Fig. 2. Hydrogen-bonding interactions in the crystal structure of C₂₈H₂₄N₂O₄.
	Fig. 3. Packing diagram of the compound along the b axis

5,5'-Bis(benzyloxy)-2,2'-[hydrazinediylidenebis(methanylylidene)]diphenol top

Crystal data top

C₂₈H₂₄N₂O₄	F(000) = 476
M_r = 452.49	D_x = 1.320 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1647 reflections
a = 12.4748 (17) Å	θ = 3.3–27.3°
b = 5.3630 (6) Å	µ = 0.09 mm⁻¹
c = 17.021 (2) Å	T = 296 K
β = 90.699 (5)°	Needle, yellow
V = 1138.7 (2) Å³	0.40 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	2738 independent reflections
Radiation source: fine-focus sealed tube	1593 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and ϕ scan	θ_max = 28.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −16→14
T_min = 0.965, T_max = 0.982	k = −7→6
6320 measured reflections	l = −22→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0436P)² + 0.1778P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2738 reflections	Δρ_max = 0.13 e Å⁻³
159 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0115 (19)

Crystal data top

C₂₈H₂₄N₂O₄	V = 1138.7 (2) Å³
M_r = 452.49	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.4748 (17) Å	µ = 0.09 mm⁻¹
b = 5.3630 (6) Å	T = 296 K
c = 17.021 (2) Å	0.40 × 0.20 × 0.20 mm
β = 90.699 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2738 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1593 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.982	R_int = 0.027
6320 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.13 e Å⁻³
2738 reflections	Δρ_min = −0.15 e Å⁻³
159 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	0.38498 (9)	0.6629 (2)	0.90134 (6)	0.0614 (4)
O2	0.36761 (13)	0.8385 (2)	0.62715 (7)	0.0803 (4)
N1	0.47835 (11)	0.5470 (3)	0.53460 (7)	0.0601 (4)
C1	0.23742 (16)	0.7056 (3)	1.04210 (9)	0.0663 (5)
H1	0.2071	0.5745	1.0138	0.080*
C2	0.22037 (16)	0.7219 (4)	1.12153 (10)	0.0699 (5)
H2	0.1786	0.6028	1.1464	0.084*
C3	0.26443 (16)	0.9118 (4)	1.16380 (10)	0.0665 (5)
H3	0.2522	0.9238	1.2175	0.080*
C4	0.32641 (17)	1.0844 (4)	1.12737 (11)	0.0742 (6)
H4	0.3573	1.2133	1.1563	0.089*
C5	0.34358 (16)	1.0684 (3)	1.04737 (11)	0.0706 (5)
H5	0.3862	1.1868	1.0228	0.085*
C6	0.29828 (14)	0.8791 (3)	1.00385 (9)	0.0553 (4)
C7	0.31240 (16)	0.8630 (3)	0.91687 (9)	0.0675 (5)
H7A	0.2439	0.8320	0.8911	0.081*
H7B	0.3410	1.0185	0.8970	0.081*
C8	0.40808 (13)	0.6150 (3)	0.82489 (9)	0.0505 (4)
C9	0.37165 (14)	0.7540 (3)	0.76205 (9)	0.0565 (4)
H9	0.3261	0.8887	0.7701	0.068*
C10	0.40315 (14)	0.6925 (3)	0.68662 (9)	0.0539 (4)
C11	0.46947 (13)	0.4874 (3)	0.67316 (8)	0.0512 (4)
C12	0.50273 (14)	0.3498 (3)	0.73856 (10)	0.0611 (5)
H12	0.5461	0.2110	0.7310	0.073*
C13	0.47411 (14)	0.4112 (3)	0.81321 (9)	0.0594 (5)
H13	0.4986	0.3173	0.8557	0.071*
C14	0.50412 (14)	0.4193 (3)	0.59605 (9)	0.0581 (4)
H14	0.5466	0.2782	0.5902	0.070*
H2'	0.3950 (16)	0.782 (4)	0.5836 (10)	0.096 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0707 (8)	0.0746 (8)	0.0390 (6)	0.0179 (6)	0.0081 (5)	0.0004 (5)
O2	0.1141 (12)	0.0833 (9)	0.0435 (7)	0.0295 (8)	0.0038 (7)	0.0089 (6)
N1	0.0613 (9)	0.0802 (10)	0.0388 (7)	−0.0018 (8)	0.0048 (6)	−0.0081 (7)
C1	0.0840 (14)	0.0642 (11)	0.0508 (10)	−0.0055 (10)	−0.0001 (9)	−0.0043 (8)
C2	0.0821 (14)	0.0747 (13)	0.0530 (10)	−0.0032 (10)	0.0090 (9)	0.0074 (9)
C3	0.0769 (13)	0.0786 (13)	0.0441 (9)	0.0174 (11)	0.0023 (9)	−0.0037 (9)
C4	0.0873 (15)	0.0703 (12)	0.0649 (12)	0.0022 (11)	−0.0031 (10)	−0.0198 (10)
C5	0.0802 (14)	0.0650 (12)	0.0670 (12)	−0.0016 (10)	0.0140 (10)	−0.0020 (9)
C6	0.0666 (11)	0.0569 (10)	0.0425 (9)	0.0132 (9)	0.0062 (8)	−0.0006 (7)
C7	0.0836 (14)	0.0724 (12)	0.0466 (10)	0.0215 (10)	0.0098 (9)	0.0025 (8)
C8	0.0510 (9)	0.0604 (10)	0.0403 (8)	−0.0010 (8)	0.0059 (7)	−0.0005 (7)
C9	0.0653 (11)	0.0584 (10)	0.0460 (9)	0.0109 (9)	0.0050 (8)	−0.0003 (8)
C10	0.0617 (11)	0.0589 (10)	0.0409 (8)	−0.0026 (8)	−0.0007 (7)	0.0034 (7)
C11	0.0521 (10)	0.0609 (10)	0.0406 (8)	−0.0033 (8)	0.0040 (7)	−0.0020 (7)
C12	0.0656 (12)	0.0687 (12)	0.0491 (10)	0.0157 (9)	0.0072 (8)	0.0002 (8)
C13	0.0661 (11)	0.0682 (11)	0.0439 (9)	0.0128 (9)	0.0053 (8)	0.0059 (8)
C14	0.0588 (11)	0.0715 (11)	0.0443 (9)	−0.0005 (9)	0.0037 (8)	−0.0057 (8)

Geometric parameters (Å, º) top

O1—C8	1.3607 (17)	C5—H5	0.9300
O1—C7	1.431 (2)	C6—C7	1.496 (2)
O2—C10	1.3505 (19)	C7—H7A	0.9700
O2—H2'	0.874 (15)	C7—H7B	0.9700
N1—C14	1.288 (2)	C8—C9	1.376 (2)
N1—N1ⁱ	1.396 (2)	C8—C13	1.385 (2)
C1—C6	1.370 (2)	C9—C10	1.387 (2)
C1—C2	1.374 (2)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.397 (2)
C2—C3	1.359 (3)	C11—C12	1.394 (2)
C2—H2	0.9300	C11—C14	1.434 (2)
C3—C4	1.360 (3)	C12—C13	1.364 (2)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.384 (2)	C13—H13	0.9300
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.374 (3)

C8—O1—C7	117.41 (12)	O1—C7—H7B	110.1
C10—O2—H2'	107.8 (14)	C6—C7—H7B	110.1
C14—N1—N1ⁱ	113.47 (19)	H7A—C7—H7B	108.4
C6—C1—C2	121.17 (17)	O1—C8—C9	124.69 (15)
C6—C1—H1	119.4	O1—C8—C13	114.82 (14)
C2—C1—H1	119.4	C9—C8—C13	120.49 (14)
C3—C2—C1	120.14 (18)	C8—C9—C10	119.72 (16)
C3—C2—H2	119.9	C8—C9—H9	120.1
C1—C2—H2	119.9	C10—C9—H9	120.1
C2—C3—C4	119.79 (17)	O2—C10—C9	117.49 (15)
C2—C3—H3	120.1	O2—C10—C11	121.55 (14)
C4—C3—H3	120.1	C9—C10—C11	120.95 (15)
C3—C4—C5	120.15 (18)	C12—C11—C10	117.17 (14)
C3—C4—H4	119.9	C12—C11—C14	120.39 (16)
C5—C4—H4	119.9	C10—C11—C14	122.44 (15)
C6—C5—C4	120.57 (18)	C13—C12—C11	122.50 (16)
C6—C5—H5	119.7	C13—C12—H12	118.8
C4—C5—H5	119.7	C11—C12—H12	118.8
C1—C6—C5	118.16 (16)	C12—C13—C8	119.15 (16)
C1—C6—C7	120.25 (16)	C12—C13—H13	120.4
C5—C6—C7	121.58 (16)	C8—C13—H13	120.4
O1—C7—C6	107.98 (13)	N1—C14—C11	122.21 (17)
O1—C7—H7A	110.1	N1—C14—H14	118.9
C6—C7—H7A	110.1	C11—C14—H14	118.9

C6—C1—C2—C3	−0.3 (3)	C8—C9—C10—O2	−178.25 (16)
C1—C2—C3—C4	−0.7 (3)	C8—C9—C10—C11	1.5 (3)
C2—C3—C4—C5	0.7 (3)	O2—C10—C11—C12	179.36 (16)
C3—C4—C5—C6	0.1 (3)	C9—C10—C11—C12	−0.4 (2)
C2—C1—C6—C5	1.1 (3)	O2—C10—C11—C14	0.2 (3)
C2—C1—C6—C7	−177.71 (17)	C9—C10—C11—C14	−179.61 (16)
C4—C5—C6—C1	−1.0 (3)	C10—C11—C12—C13	−0.9 (3)
C4—C5—C6—C7	177.77 (17)	C14—C11—C12—C13	178.29 (17)
C8—O1—C7—C6	179.40 (14)	C11—C12—C13—C8	1.1 (3)
C1—C6—C7—O1	−74.4 (2)	O1—C8—C13—C12	−179.31 (16)
C5—C6—C7—O1	106.85 (19)	C9—C8—C13—C12	0.1 (3)
C7—O1—C8—C9	4.0 (2)	N1ⁱ—N1—C14—C11	178.83 (17)
C7—O1—C8—C13	−176.67 (16)	C12—C11—C14—N1	−177.39 (17)
O1—C8—C9—C10	177.95 (16)	C10—C11—C14—N1	1.8 (3)
C13—C8—C9—C10	−1.4 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2′···N1	0.87 (2)	1.84 (2)	2.625 (2)	148 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2'···N1	0.87 (2)	1.84 (2)	2.625 (2)	148 (2)

Acknowledgements

NRS thanks the Council of Scientific and Industrial Research (India) for a Junior Research Fellowship. MRPK thanks the University Grants Commission, New Delhi, for a UGC–BSR one-time grant to faculty. The authors thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, for the diffraction measurements.

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