supplementary materials


ng5346 scheme

Acta Cryst. (2013). E69, o1755    [ doi:10.1107/S1600536813030171 ]

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

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

Abstract top

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.

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).

Refinement top

All H atoms on C were placed in calculated positions, guided by difference maps, with C—H bond distances of 0.93 Å. H atoms were assigned Uiso(H) values of 1.2Ueq(carrier). Omitted owing to bad disagreement were reflections (1 0 1) and (-1 0 1). H atom of O2—H2' bond was located from difference maps and the bond distance is restrained to 0.84±0.02 Å.

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
[Figure 1] Fig. 1. ORTEP view of the title compound drawn with 50% probability displacement ellipsoids for the non-H atoms.
[Figure 2] Fig. 2. Hydrogen-bonding interactions in the crystal structure of C28H24N2O4.
[Figure 3] Fig. 3. Packing diagram of the compound along the b axis
5,5'-Bis(benzyloxy)-2,2'-[hydrazinediylidenebis(methanylylidene)]diphenol top
Crystal data top
C28H24N2O4F(000) = 476
Mr = 452.49Dx = 1.320 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1647 reflections
a = 12.4748 (17) Åθ = 3.3–27.3°
b = 5.3630 (6) ŵ = 0.09 mm1
c = 17.021 (2) ÅT = 296 K
β = 90.699 (5)°Needle, yellow
V = 1138.7 (2) Å30.40 × 0.20 × 0.20 mm
Z = 2
Data collection top
Bruker Kappa APEXII CCD
diffractometer
2738 independent reflections
Radiation source: fine-focus sealed tube1593 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω and φ scanθmax = 28.2°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1614
Tmin = 0.965, Tmax = 0.982k = 76
6320 measured reflectionsl = 2217
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122 w = 1/[σ2(Fo2) + (0.0436P)2 + 0.1778P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2738 reflectionsΔρmax = 0.13 e Å3
159 parametersΔρmin = 0.15 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0115 (19)
Crystal data top
C28H24N2O4V = 1138.7 (2) Å3
Mr = 452.49Z = 2
Monoclinic, P21/nMo Kα radiation
a = 12.4748 (17) ŵ = 0.09 mm1
b = 5.3630 (6) ÅT = 296 K
c = 17.021 (2) Å0.40 × 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)
Tmin = 0.965, Tmax = 0.982Rint = 0.027
6320 measured reflectionsθmax = 28.2°
Refinement top
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122Δρmax = 0.13 e Å3
S = 1.01Δρmin = 0.15 e Å3
2738 reflectionsAbsolute structure: ?
159 parametersAbsolute structure parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
O10.38498 (9)0.6629 (2)0.90134 (6)0.0614 (4)
O20.36761 (13)0.8385 (2)0.62715 (7)0.0803 (4)
N10.47835 (11)0.5470 (3)0.53460 (7)0.0601 (4)
C10.23742 (16)0.7056 (3)1.04210 (9)0.0663 (5)
H10.20710.57451.01380.080*
C20.22037 (16)0.7219 (4)1.12153 (10)0.0699 (5)
H20.17860.60281.14640.084*
C30.26443 (16)0.9118 (4)1.16380 (10)0.0665 (5)
H30.25220.92381.21750.080*
C40.32641 (17)1.0844 (4)1.12737 (11)0.0742 (6)
H40.35731.21331.15630.089*
C50.34358 (16)1.0684 (3)1.04737 (11)0.0706 (5)
H50.38621.18681.02280.085*
C60.29828 (14)0.8791 (3)1.00385 (9)0.0553 (4)
C70.31240 (16)0.8630 (3)0.91687 (9)0.0675 (5)
H7A0.24390.83200.89110.081*
H7B0.34101.01850.89700.081*
C80.40808 (13)0.6150 (3)0.82489 (9)0.0505 (4)
C90.37165 (14)0.7540 (3)0.76205 (9)0.0565 (4)
H90.32610.88870.77010.068*
C100.40315 (14)0.6925 (3)0.68662 (9)0.0539 (4)
C110.46947 (13)0.4874 (3)0.67316 (8)0.0512 (4)
C120.50273 (14)0.3498 (3)0.73856 (10)0.0611 (5)
H120.54610.21100.73100.073*
C130.47411 (14)0.4112 (3)0.81321 (9)0.0594 (5)
H130.49860.31730.85570.071*
C140.50412 (14)0.4193 (3)0.59605 (9)0.0581 (4)
H140.54660.27820.59020.070*
H2'0.3950 (16)0.782 (4)0.5836 (10)0.096 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0707 (8)0.0746 (8)0.0390 (6)0.0179 (6)0.0081 (5)0.0004 (5)
O20.1141 (12)0.0833 (9)0.0435 (7)0.0295 (8)0.0038 (7)0.0089 (6)
N10.0613 (9)0.0802 (10)0.0388 (7)0.0018 (8)0.0048 (6)0.0081 (7)
C10.0840 (14)0.0642 (11)0.0508 (10)0.0055 (10)0.0001 (9)0.0043 (8)
C20.0821 (14)0.0747 (13)0.0530 (10)0.0032 (10)0.0090 (9)0.0074 (9)
C30.0769 (13)0.0786 (13)0.0441 (9)0.0174 (11)0.0023 (9)0.0037 (9)
C40.0873 (15)0.0703 (12)0.0649 (12)0.0022 (11)0.0031 (10)0.0198 (10)
C50.0802 (14)0.0650 (12)0.0670 (12)0.0016 (10)0.0140 (10)0.0020 (9)
C60.0666 (11)0.0569 (10)0.0425 (9)0.0132 (9)0.0062 (8)0.0006 (7)
C70.0836 (14)0.0724 (12)0.0466 (10)0.0215 (10)0.0098 (9)0.0025 (8)
C80.0510 (9)0.0604 (10)0.0403 (8)0.0010 (8)0.0059 (7)0.0005 (7)
C90.0653 (11)0.0584 (10)0.0460 (9)0.0109 (9)0.0050 (8)0.0003 (8)
C100.0617 (11)0.0589 (10)0.0409 (8)0.0026 (8)0.0007 (7)0.0034 (7)
C110.0521 (10)0.0609 (10)0.0406 (8)0.0033 (8)0.0040 (7)0.0020 (7)
C120.0656 (12)0.0687 (12)0.0491 (10)0.0157 (9)0.0072 (8)0.0002 (8)
C130.0661 (11)0.0682 (11)0.0439 (9)0.0128 (9)0.0053 (8)0.0059 (8)
C140.0588 (11)0.0715 (11)0.0443 (9)0.0005 (9)0.0037 (8)0.0057 (8)
Geometric parameters (Å, º) top
O1—C81.3607 (17)C5—H50.9300
O1—C71.431 (2)C6—C71.496 (2)
O2—C101.3505 (19)C7—H7A0.9700
O2—H2'0.874 (15)C7—H7B0.9700
N1—C141.288 (2)C8—C91.376 (2)
N1—N1i1.396 (2)C8—C131.385 (2)
C1—C61.370 (2)C9—C101.387 (2)
C1—C21.374 (2)C9—H90.9300
C1—H10.9300C10—C111.397 (2)
C2—C31.359 (3)C11—C121.394 (2)
C2—H20.9300C11—C141.434 (2)
C3—C41.360 (3)C12—C131.364 (2)
C3—H30.9300C12—H120.9300
C4—C51.384 (2)C13—H130.9300
C4—H40.9300C14—H140.9300
C5—C61.374 (3)
C8—O1—C7117.41 (12)O1—C7—H7B110.1
C10—O2—H2'107.8 (14)C6—C7—H7B110.1
C14—N1—N1i113.47 (19)H7A—C7—H7B108.4
C6—C1—C2121.17 (17)O1—C8—C9124.69 (15)
C6—C1—H1119.4O1—C8—C13114.82 (14)
C2—C1—H1119.4C9—C8—C13120.49 (14)
C3—C2—C1120.14 (18)C8—C9—C10119.72 (16)
C3—C2—H2119.9C8—C9—H9120.1
C1—C2—H2119.9C10—C9—H9120.1
C2—C3—C4119.79 (17)O2—C10—C9117.49 (15)
C2—C3—H3120.1O2—C10—C11121.55 (14)
C4—C3—H3120.1C9—C10—C11120.95 (15)
C3—C4—C5120.15 (18)C12—C11—C10117.17 (14)
C3—C4—H4119.9C12—C11—C14120.39 (16)
C5—C4—H4119.9C10—C11—C14122.44 (15)
C6—C5—C4120.57 (18)C13—C12—C11122.50 (16)
C6—C5—H5119.7C13—C12—H12118.8
C4—C5—H5119.7C11—C12—H12118.8
C1—C6—C5118.16 (16)C12—C13—C8119.15 (16)
C1—C6—C7120.25 (16)C12—C13—H13120.4
C5—C6—C7121.58 (16)C8—C13—H13120.4
O1—C7—C6107.98 (13)N1—C14—C11122.21 (17)
O1—C7—H7A110.1N1—C14—H14118.9
C6—C7—H7A110.1C11—C14—H14118.9
C6—C1—C2—C30.3 (3)C8—C9—C10—O2178.25 (16)
C1—C2—C3—C40.7 (3)C8—C9—C10—C111.5 (3)
C2—C3—C4—C50.7 (3)O2—C10—C11—C12179.36 (16)
C3—C4—C5—C60.1 (3)C9—C10—C11—C120.4 (2)
C2—C1—C6—C51.1 (3)O2—C10—C11—C140.2 (3)
C2—C1—C6—C7177.71 (17)C9—C10—C11—C14179.61 (16)
C4—C5—C6—C11.0 (3)C10—C11—C12—C130.9 (3)
C4—C5—C6—C7177.77 (17)C14—C11—C12—C13178.29 (17)
C8—O1—C7—C6179.40 (14)C11—C12—C13—C81.1 (3)
C1—C6—C7—O174.4 (2)O1—C8—C13—C12179.31 (16)
C5—C6—C7—O1106.85 (19)C9—C8—C13—C120.1 (3)
C7—O1—C8—C94.0 (2)N1i—N1—C14—C11178.83 (17)
C7—O1—C8—C13176.67 (16)C12—C11—C14—N1177.39 (17)
O1—C8—C9—C10177.95 (16)C10—C11—C14—N11.8 (3)
C13—C8—C9—C101.4 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.87 (2)1.84 (2)2.625 (2)148 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2'···N10.87 (2)1.84 (2)2.625 (2)148 (2)
Acknowledgements top

NRS thanks the University Grants Commission (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.

references
References top

Acrovito, G., Bonamico, M., Dornenicano, A. & Vaciago, A. (1969). J. Chem. Soc. B, pp. 173–742.

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2004). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Gul, H. I., Gul, M., Vepsalainen, J., Erciyas, E. & Hanninen, O. (2003). Biol. Pharm. Bull. 26, 631–637.

Karmakar, A., Sarma, R. J. & Baruah, J. B. (2007). Polyhedron, 26, 1347–1355.

Kumaraswamy, M. N. & Vaidya, V. P. (2005). Indian J. Heterocycl. Chem. 14, 193–196.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sithambaresan, M. & Kurup, M. R. P. (2011). Acta Cryst. E67, o2972.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.