2-{[2-(2-Hy­droxy-5-meth­oxy­benzyl­idene)hydrazin-1-yl­idene]meth­yl}-4-meth­oxy­phenol

Taha, M.; Shah, S.A.A.; Sultan, S.; Ismail, N.H.; Yousuf, S.

doi:10.1107/S1600536813034636

organic compounds

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doi:10.1107/S1600536813034636

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2-{[2-(2-Hydroxy-5-methoxybenzylidene)hydrazin-1-ylidene]methyl}-4-methoxyphenol

Muhammad Taha,^a,^b Syed Adnan Ali Shah,^a,^c Sadia Sultan,^a,^c Nor Hadiani Ismail ^b and Sammer Yousuf ^d ^*

^aAtta-ur-Rahman Institute for Natural Product Discovery, Universiti Teknologi MARA (UiTM), Puncak Alam Campus, 42300 Bandar Puncak Alam, Selangor D. E., Malaysia, ^bFaculty of Applied Science, Universiti Teknologi MARA (UiTM), 40450 Shah Alam, Malaysia, ^cFaculty of Pharmacy, Universiti Teknologi MARA (UiTM), Puncak Alam Campus, 42300 Bandar Puncak Alam, Selangor Darul Ehsan, Malaysia, and ^dH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 25 October 2013; accepted 26 December 2013; online 11 January 2014)

The title phenylhydrazine derivative, C₁₆H₁₆N₂O₄, has a crystallographically imposed centre of symmetry. Except for the methyl group, all non-H atoms are almost coplanar (r.m.s. deviation = 0.0095 Å). Intramolecular O—H⋯N hydrogen bonds are observed, generating S(6) graph-set ring motifs.

CCDC reference: 978781

Related literature

For applications and the biological activity of phenylhydrazine derivatives, see: Khan et al. (2013 ); Patel et al. (1984 ); Taha, Baharudin et al. (2013 ); Taha, Ismail et al. (2013 ); Khan, Shah et al. (2012 ); Khan, Taha et al. (2012 ). For structures of related compounds, see: Taha et al. (2012 ); Kargar et al. (2012 ); Zhang et al. (2008 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₄
M_r = 300.31
Monoclinic, P 2₁ /c
a = 6.7132 (4) Å
b = 15.9369 (10) Å
c = 6.8022 (4) Å
β = 91.192 (2)°
V = 727.59 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 K
0.58 × 0.22 × 0.17 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.944, T_max = 0.983
4243 measured reflections
1327 independent reflections
1093 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.101
S = 1.06
1327 reflections
106 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.94 (2)	1.82 (2)	2.6451 (16)	145.0 (18)

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 978781

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813034636/rz5090sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813034636/rz5090Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813034636/rz5090Isup3.cml

checkCIF report

Comment top

Hydrazone derivatives constitute an important class of biologically active drugs (Khan, Shah et al., 2012). In particular, heterocyclic compounds containing the hydrazone moiety are known to possess excellent activity against Mycobacterium tuberculosis H37Rv (Patel et al., 1984). Recently the antioxidant, antiglycating, and antileishmanial activities of different hydrazine derivatives has also been reported by our group (Taha, Baharudin et al., 2013; Taha, Ismail et al., 2013; Khan, Taha et al., 2012; Khan et al., 2013).

The title compound (Fig. 1) has crystallographically imposed centre of symmetry, the inversion centre lying midway along the N—N bond. Except for the methyl group, all non-hydrogen atoms in the asymmetric unit are coplanar with an r.m.s. deviation of 0.0095 Å. The carbon atom of the methyl group is displaced by 0.1806 (17) Å from this plane. All bond angles and lengths are found to be normal and similar to those observed in structurally related compounds (Taha et al., 2012; Kargar et al., 2012; Zhang et al., 2008). The molecular configuration is stabilized by a pair of intramolecular O2—H2···N1 hydrogen interactions generating S(6) graph-set ring motifs. The crystal structure is stabilized only by van der Waals contacts (Fig. 2).

Related literature top

For applications and the biological activity of phenylhydrazine derivatives, see: Khan et al. (2013); Patel et al. (1984); Taha, Baharudin et al. (2013); Taha, Ismail et al. (2013); Khan, Shah et al. (2012); Khan, Taha et al. (2012). For structures of related compounds, see: Taha et al. (2012); Kargar et al. (2012); Zhang et al. (2008).

Experimental top

The title compound was synthesized by refluxing a mixture of 2-hydroxy-5-methoxybenzaldehyde (2 mmol, 0.304 g) and hydrazine hydrate (55%, 2 ml) in methanol with a catalytical amount of acetic acid for 1 hour. After completion of the reaction, the solvent was evaporated by vacuum to afford the crude product which was further recrystallized in methanol to obtain needle-like crystals suitable for X-ray analysis (yield 88%, 0.524 g).

Structure description top

For applications and the biological activity of phenylhydrazine derivatives, see: Khan et al. (2013); Patel et al. (1984); Taha, Baharudin et al. (2013); Taha, Ismail et al. (2013); Khan, Shah et al. (2012); Khan, Taha et al. (2012). For structures of related compounds, see: Taha et al. (2012); Kargar et al. (2012); Zhang et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Symmetry code: (A) -x, 1-y, 1-z.
	Fig. 2. Crystal packing of the title compound viewed down the a axis.

2,2'-[Hydrazine-1,2-diylidenebis(methan-1-yl-1-ylidene)]bis(4-methoxyphenol) top

Crystal data top

C₁₆H₁₆N₂O₄	F(000) = 316
M_r = 300.31	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1747 reflections
a = 6.7132 (4) Å	θ = 2.6–27.0°
b = 15.9369 (10) Å	µ = 0.10 mm⁻¹
c = 6.8022 (4) Å	T = 273 K
β = 91.192 (2)°	Needle, yellow
V = 727.59 (8) Å³	0.58 × 0.22 × 0.17 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1327 independent reflections
Radiation source: fine-focus sealed tube	1093 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scan	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→7
T_min = 0.944, T_max = 0.983	k = −18→19
4243 measured reflections	l = −7→8

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0505P)² + 0.0718P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1327 reflections	Δρ_max = 0.14 e Å⁻³
106 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.031 (6)

Crystal data top

C₁₆H₁₆N₂O₄	V = 727.59 (8) Å³
M_r = 300.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7132 (4) Å	µ = 0.10 mm⁻¹
b = 15.9369 (10) Å	T = 273 K
c = 6.8022 (4) Å	0.58 × 0.22 × 0.17 mm
β = 91.192 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1327 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1093 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.983	R_int = 0.016
4243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.14 e Å⁻³
1327 reflections	Δρ_min = −0.12 e Å⁻³
106 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	0.45722 (17)	0.62697 (7)	−0.27087 (17)	0.0865 (4)
O2	−0.21947 (15)	0.62524 (8)	0.17505 (19)	0.0767 (4)
H2	−0.199 (3)	0.5903 (15)	0.284 (3)	0.118 (8)*
N1	−0.01775 (16)	0.52608 (7)	0.41923 (16)	0.0588 (3)
C1	0.1157 (2)	0.67416 (8)	−0.2207 (2)	0.0626 (4)
H1C	0.1136	0.7055	−0.3361	0.075*
C2	−0.0501 (2)	0.67158 (9)	−0.1050 (2)	0.0636 (4)
H2B	−0.1632	0.7015	−0.1436	0.076*
C3	−0.0522 (2)	0.62571 (8)	0.0666 (2)	0.0562 (4)
C4	0.12003 (18)	0.58088 (7)	0.12530 (19)	0.0518 (3)
C5	0.28603 (19)	0.58474 (8)	0.0070 (2)	0.0585 (4)
H5A	0.4008	0.5559	0.0453	0.070*
C6	0.2857 (2)	0.63003 (8)	−0.1651 (2)	0.0594 (4)
C7	0.4762 (3)	0.68202 (11)	−0.4318 (2)	0.0842 (5)
H7A	0.6065	0.6762	−0.4856	0.126*
H7B	0.4577	0.7388	−0.3884	0.126*
H7C	0.3773	0.6686	−0.5307	0.126*
C8	0.12864 (19)	0.53066 (8)	0.3019 (2)	0.0564 (4)
H8A	0.2442	0.5006	0.3314	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0721 (7)	0.0981 (9)	0.0899 (8)	0.0108 (6)	0.0178 (6)	0.0323 (6)
O2	0.0593 (6)	0.0892 (8)	0.0818 (8)	0.0171 (5)	0.0052 (5)	0.0019 (6)
N1	0.0624 (7)	0.0524 (6)	0.0614 (7)	−0.0025 (5)	−0.0015 (5)	0.0012 (5)
C1	0.0741 (9)	0.0526 (8)	0.0607 (9)	0.0041 (6)	−0.0104 (7)	0.0025 (6)
C2	0.0633 (8)	0.0590 (8)	0.0678 (9)	0.0147 (6)	−0.0135 (7)	−0.0034 (6)
C3	0.0529 (7)	0.0509 (7)	0.0647 (9)	0.0039 (5)	−0.0051 (6)	−0.0089 (6)
C4	0.0528 (7)	0.0427 (6)	0.0597 (8)	−0.0012 (5)	−0.0049 (6)	−0.0028 (5)
C5	0.0524 (7)	0.0519 (7)	0.0711 (9)	0.0051 (5)	−0.0038 (6)	0.0063 (6)
C6	0.0591 (8)	0.0535 (7)	0.0654 (9)	−0.0007 (6)	−0.0010 (6)	0.0039 (6)
C7	0.0942 (12)	0.0909 (12)	0.0679 (10)	−0.0096 (9)	0.0087 (9)	0.0141 (8)
C8	0.0549 (7)	0.0473 (7)	0.0666 (9)	−0.0004 (5)	−0.0045 (6)	−0.0006 (6)

Geometric parameters (Å, º) top

O1—C6	1.3713 (17)	C2—H2B	0.9300
O1—C7	1.4105 (18)	C3—C4	1.4101 (18)
O2—C3	1.3563 (16)	C4—C5	1.3894 (17)
O2—H2	0.93 (2)	C4—C8	1.4436 (18)
N1—C8	1.2809 (15)	C5—C6	1.3752 (19)
N1—N1ⁱ	1.394 (2)	C5—H5A	0.9300
C1—C2	1.377 (2)	C7—H7A	0.9600
C1—C6	1.386 (2)	C7—H7B	0.9600
C1—H1C	0.9300	C7—H7C	0.9600
C2—C3	1.377 (2)	C8—H8A	0.9300

C6—O1—C7	118.38 (12)	C6—C5—C4	121.95 (12)
C3—O2—H2	109.0 (13)	C6—C5—H5A	119.0
C8—N1—N1ⁱ	113.84 (13)	C4—C5—H5A	119.0
C2—C1—C6	119.96 (14)	O1—C6—C5	116.20 (12)
C2—C1—H1C	120.0	O1—C6—C1	124.77 (13)
C6—C1—H1C	120.0	C5—C6—C1	119.03 (13)
C1—C2—C3	121.54 (12)	O1—C7—H7A	109.5
C1—C2—H2B	119.2	O1—C7—H7B	109.5
C3—C2—H2B	119.2	H7A—C7—H7B	109.5
O2—C3—C2	119.17 (12)	O1—C7—H7C	109.5
O2—C3—C4	121.76 (13)	H7A—C7—H7C	109.5
C2—C3—C4	119.07 (13)	H7B—C7—H7C	109.5
C5—C4—C3	118.45 (12)	N1—C8—C4	122.15 (12)
C5—C4—C8	119.20 (11)	N1—C8—H8A	118.9
C3—C4—C8	122.35 (12)	C4—C8—H8A	118.9

C6—C1—C2—C3	−0.1 (2)	C7—O1—C6—C5	−170.46 (14)
C1—C2—C3—O2	−179.95 (12)	C7—O1—C6—C1	10.2 (2)
C1—C2—C3—C4	0.4 (2)	C4—C5—C6—O1	−178.37 (12)
O2—C3—C4—C5	−179.65 (11)	C4—C5—C6—C1	1.0 (2)
C2—C3—C4—C5	−0.03 (18)	C2—C1—C6—O1	178.72 (13)
O2—C3—C4—C8	1.09 (19)	C2—C1—C6—C5	−0.6 (2)
C2—C3—C4—C8	−179.29 (12)	N1ⁱ—N1—C8—C4	179.45 (12)
C3—C4—C5—C6	−0.68 (19)	C5—C4—C8—N1	178.39 (12)
C8—C4—C5—C6	178.60 (12)	C3—C4—C8—N1	−2.36 (19)

Symmetry code: (i) −x, −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	0.94 (2)	1.82 (2)	2.6451 (16)	145.0 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.94 (2)	1.82 (2)	2.6451 (16)	145.0 (18)

Acknowledgements

The authors acknowledge Universiti Teknologi MARA (UiTM) for the financial support under the Principal Investigator Support Initiative Grant Scheme [600-RMI/DANA 5/3/PSI (251/2013)].

References

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CRYSTALLOGRAPHIC
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Volume 70| Part 2| February 2014| Page o131

doi:10.1107/S1600536813034636

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-{[2-(2-Hy­dr­oxy-5-meth­­oxy­benzyl­­idene)hydrazin-1-yl­­idene]meth­yl}-4-meth­­oxy­phenol

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-{[2-(2-Hydroxy-5-methoxybenzylidene)hydrazin-1-ylidene]methyl}-4-methoxyphenol