organic compounds
2-{[2-(2-Hydroxy-5-methoxybenzylidene)hydrazin-1-ylidene]methyl}-4-methoxyphenol
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
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
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Data collection: SMART (Bruker, 2000); cell 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
10.1107/S1600536813034636/rz5090sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813034636/rz5090Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813034636/rz5090Isup3.cml
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).
H atoms were positioned geometrically with C—H = 0.93-0.96 Å and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating group model was applied to the methyl group. The hydroxy H atom was located in a difference Fourier map and refined isotropically.
Hydrazone derivatives constitute an important class of biologically active drugs (Khan, Shah et al., 2012). In particular,
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
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 is stabilized only by van der Waals contacts (Fig. 2).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).
Data collection: SMART (Bruker, 2000); cell
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).C16H16N2O4 | F(000) = 316 |
Mr = 300.31 | Dx = 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 |
Bruker SMART APEX CCD area-detector diffractometer | 1327 independent reflections |
Radiation source: fine-focus sealed tube | 1093 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scan | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→7 |
Tmin = 0.944, Tmax = 0.983 | k = −18→19 |
4243 measured reflections | l = −7→8 |
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(Fo2) + (0.0505P)2 + 0.0718P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1327 reflections | Δρmax = 0.14 e Å−3 |
106 parameters | Δρmin = −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) |
C16H16N2O4 | V = 727.59 (8) Å3 |
Mr = 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)° |
Bruker SMART APEX CCD area-detector diffractometer | 1327 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1093 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.983 | Rint = 0.016 |
4243 measured reflections |
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 | Δρmax = 0.14 e Å−3 |
1327 reflections | Δρmin = −0.12 e Å−3 |
106 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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) |
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)].
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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).