organic compounds
1-(2,4-Dinitrophenyl)-2-[(E)-(3,4,5-trimethoxybenzylidene)]hydrazine
aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, bFaculty of Traditional Thai Medicine, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: suchada.c@psu.ac.th
Molecules of the title compound, C16H16N4O7, are not planar with a dihedral angle of 5.50 (11)° between the substituted benzene rings. The two meta-methoxy groups of the 3,4,5-trimethoxybenzene moiety lie in the plane of the attached ring [Cmethyl–O–C–C torsion angles −0.1 (4)° and −3.7 (3)°] while the para-methoxy substituent lies out of the plane [Cmethyl—O—C—C, −86.0 (3)°]. An intramolecular N—H⋯O hydrogen bond involving the 2-nitro substituent generates an S(6) ring motif. In the molecules are linked by weak C—H⋯O interactions into screw chains, that are arranged into a sheet parallel to the bc plane. These sheets are connected by π–π stacking interactions between the nitro and methoxy substituted aromatic rings with a centroid–centroid separation of 3.9420 (13) Å. C—H⋯π contacts further stabilize the two-dimensional network.
CCDC reference: 982029
Related literature
For background to the biological activity of hydrozones, see: Angelusiu et al. (2010); Cui et al. (2010), Gokce et al. (2009); Molyneux (2004); Sathyadevi et al. (2012); Wang et al. (2009). For details of hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Fun et al. (2011, 2012, 2013).
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 982029
10.1107/S1600536814001238/sj5380sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814001238/sj5380Isup2.hkl
The title compound (I) was synthesized by dissolving 2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) in ethanol (10.00 ml) and H2SO4 (conc.) (98 %, 0.50 ml) was added slowly with stirring. A solution of 3,4,5-trimethoxybenzaldehyde (0.40 g, 2 mmol) in ethanol (20.00 ml) was then added to the solution with continuous stirring for 1 hr, yielding an orange solid which was filtered off and washed with methanol. Orange block-shaped single crystals of the title compound suitable for X-ray
were recrystallized from acetone by slow evaporation of the solvent at room temperature over a few weeks, Mp. 496–497 K.The hydrazine H atom was located from a difference Fourier map and refined freely. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C-H) = 0.93 Å for CH and aromatic, and 0.96 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the
for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.There are numerous reports of the various biological activities of
and their complexes which show antibacterial, antifungal, antitumor, anti-inflammatory and antioxidant activities (Angelusiu et al., 2010; Cui et al., 2010; Gokce et al., 2009; Sathyadevi et al., 2012 and Wang et al., 2009).In previous works, we synthesized a number of hydrazone derivatives from the reaction of 2,4-dinitrophenylhydrazine and various substituted
(Fun et al., 2011, 2012 and 2013). The title hydrazone (I) was again synthesized using 2,4-dinitrophenylhydrazine but with 3,4,5-trimethoxybenzaldehyde as the aldehyde. Our evaluation of the antioxidant activity of (I) by the DPPH scavenging method [DPPH = 2,2-diphenyl-1-picrylhydrazyl] (Molyneux, 2004) showed that it displays weak antioxidant activity with 17.6% inhibition. This further confirms observations from previous works (Fun et al., 2011, 2012 and 2013) that the antioxidant ability of such compounds is controlled by the number and substitution pattern of the methoxy substituents. Herein we report the synthesis and of (I).In Fig. 1, the whole molecular structure of (I), C16H16N4O7 is not planar, with the dihedral angle between the two substituted benzene rings being 5.50 (11)°. Both nitro groups lie close to the plane of the attached benzene ring [torsion angles O1–N3–C2–C1 = 4.7 (4)°, O2–N3–C2–C3 = 5.1 (4)°, O3–N4–C4–C3 = -1.9 (3)° and O4–N4–C4–C5 = -0.8 (3)°]. The mean plane through the central N1/N2/C7 bridge makes dihedral angles of 6.8 (2)° and 12.3 (2)° with the two adjacent C1–C6 and C8–C13 benzene rings, respectively. The three methoxy groups of the 3,4,5-trimethoxyphenyl unit have two different orientations: the two meta-methoxy groups (at C10 and C12) are co-planar with the benzene ring plane (Fig. 3) with torsion angles C14–O5–C10–C9 = -3.7 (3)° and C16–O7–C12–C13 = -0.1 (4)° whereas the para-methoxy substituent (at C11) is out of the plane with the torsion angle C15–O6–C11–C10 = -86.0 (3)°. An intramolecular N1—H1N1···O1 hydrogen bond (Fig. 1 and Table 1) generates an S(6) ring motif (Bernstein et al., 1995). Bond distances for (I) are comparable to those found in closely related structures (Fun et al., 2011, 2012, 2013).
In the crystal packing (Fig. 2), molecules are linked by a weak intermolecular C16—H16C···O2 interaction (Table 1) into screw chains. These chains are arranged into sheets and further stacked along the a axis by π···π interactions with distances of Cg1···Cg2iii, iv = 3.9420 (13) Å [Cg1 and Cg2 are the centroids of the C1···C6 and C8···C13 benzene rings, respectively; symmetry codes (iii) = 1/2-x, 1-y, -1/2+z and (iv) = 1/2+x, 1-y, 1/2+z] (Fig. 3). The molecules are linked into two dimensional network by weak C—H···O interactions. These C—H···π contacts further stabilize the two-dimensional network (Table 1).
For background to the biological activity of hydrozones, see: Angelusiu et al. (2010); Cui et al. (2010), Gokce et al. (2009); Molyneux (2004); Sathyadevi et al. (2012); Wang et al. (2009). For details of hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Fun et al. (2011, 2012, 2013).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids and the atom-numbering scheme. An intramolecular N—H···O hydrogen bond is shown as a dashed line. | |
Fig. 2. The crystal packing of (I) viewed along the a axis. Hydrogen bonds are shown as dashed lines. | |
Fig. 3. The π···π stacking interaction between the two substituted benzene rings. H atoms were omitted for clarity. |
C16H16N4O7 | Dx = 1.447 Mg m−3 |
Mr = 376.33 | Melting point = 496–497 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2855 reflections |
a = 7.4724 (4) Å | θ = 2.5–30.0° |
b = 14.3106 (7) Å | µ = 0.12 mm−1 |
c = 16.1549 (7) Å | T = 100 K |
V = 1727.52 (15) Å3 | Block, orange |
Z = 4 | 0.58 × 0.30 × 0.24 mm |
F(000) = 784 |
Bruker APEXII CCD area detector diffractometer | 2855 independent reflections |
Radiation source: sealed tube | 2243 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
φ and ω scans | θmax = 30.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.936, Tmax = 0.972 | k = −17→20 |
20053 measured reflections | l = −22→22 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0489P)2 + 0.1811P] where P = (Fo2 + 2Fc2)/3 |
2855 reflections | (Δ/σ)max = 0.001 |
251 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C16H16N4O7 | V = 1727.52 (15) Å3 |
Mr = 376.33 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.4724 (4) Å | µ = 0.12 mm−1 |
b = 14.3106 (7) Å | T = 100 K |
c = 16.1549 (7) Å | 0.58 × 0.30 × 0.24 mm |
Bruker APEXII CCD area detector diffractometer | 2855 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2243 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.972 | Rint = 0.039 |
20053 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.14 e Å−3 |
2855 reflections | Δρmin = −0.22 e Å−3 |
251 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.4866 (3) | 0.35711 (12) | 0.69622 (11) | 0.0629 (5) | |
O2 | 0.4403 (4) | 0.38109 (15) | 0.56725 (12) | 0.0928 (9) | |
O3 | 0.2099 (3) | 0.66252 (15) | 0.46266 (11) | 0.0705 (6) | |
O4 | 0.1541 (4) | 0.77886 (16) | 0.54355 (13) | 0.0804 (7) | |
O5 | 0.6955 (2) | 0.40878 (11) | 1.21814 (9) | 0.0482 (4) | |
O6 | 0.6333 (2) | 0.58591 (11) | 1.26663 (9) | 0.0467 (4) | |
O7 | 0.5222 (3) | 0.71519 (11) | 1.16062 (10) | 0.0620 (5) | |
N1 | 0.4733 (3) | 0.49707 (14) | 0.80101 (11) | 0.0419 (4) | |
H1N1 | 0.520 (3) | 0.4462 (17) | 0.7932 (14) | 0.041 (7)* | |
N2 | 0.4873 (3) | 0.53900 (13) | 0.87742 (10) | 0.0436 (4) | |
N3 | 0.4436 (3) | 0.40829 (14) | 0.63849 (13) | 0.0516 (5) | |
N4 | 0.2094 (3) | 0.69931 (16) | 0.53100 (13) | 0.0535 (5) | |
C1 | 0.4052 (3) | 0.54403 (15) | 0.73618 (12) | 0.0374 (4) | |
C2 | 0.3933 (3) | 0.50496 (15) | 0.65539 (13) | 0.0391 (5) | |
C3 | 0.3317 (3) | 0.55573 (17) | 0.58869 (13) | 0.0428 (5) | |
H3A | 0.3279 | 0.5292 | 0.5362 | 0.051* | |
C4 | 0.2756 (3) | 0.64651 (16) | 0.60122 (14) | 0.0425 (5) | |
C5 | 0.2773 (3) | 0.68693 (16) | 0.67997 (14) | 0.0445 (5) | |
H5A | 0.2349 | 0.7474 | 0.6878 | 0.053* | |
C6 | 0.3416 (3) | 0.63669 (16) | 0.74534 (14) | 0.0434 (5) | |
H6A | 0.3438 | 0.6642 | 0.7975 | 0.052* | |
C7 | 0.5672 (3) | 0.48885 (17) | 0.93111 (13) | 0.0439 (5) | |
H7A | 0.6149 | 0.4317 | 0.9148 | 0.053* | |
C8 | 0.5867 (3) | 0.51809 (16) | 1.01780 (13) | 0.0422 (5) | |
C9 | 0.6408 (3) | 0.45032 (17) | 1.07387 (13) | 0.0419 (5) | |
H9A | 0.6717 | 0.3909 | 1.0554 | 0.050* | |
C10 | 0.6487 (3) | 0.47149 (16) | 1.15789 (13) | 0.0401 (5) | |
C11 | 0.6106 (3) | 0.56190 (16) | 1.18476 (13) | 0.0408 (5) | |
C12 | 0.5579 (3) | 0.63001 (15) | 1.12739 (14) | 0.0446 (5) | |
C13 | 0.5446 (4) | 0.60796 (16) | 1.04410 (13) | 0.0467 (6) | |
H13A | 0.5080 | 0.6529 | 1.0061 | 0.056* | |
C14 | 0.7279 (4) | 0.31452 (17) | 1.19216 (17) | 0.0543 (6) | |
H14A | 0.7677 | 0.2782 | 1.2386 | 0.081* | |
H14B | 0.8182 | 0.3140 | 1.1499 | 0.081* | |
H14C | 0.6193 | 0.2882 | 1.1706 | 0.081* | |
C15 | 0.4822 (4) | 0.5655 (2) | 1.31779 (15) | 0.0589 (7) | |
H15A | 0.5073 | 0.5840 | 1.3737 | 0.088* | |
H15B | 0.4581 | 0.4996 | 1.3162 | 0.088* | |
H15C | 0.3797 | 0.5991 | 1.2978 | 0.088* | |
C16 | 0.4671 (7) | 0.78726 (19) | 1.10517 (18) | 0.0905 (13) | |
H16A | 0.4494 | 0.8442 | 1.1355 | 0.136* | |
H16B | 0.3571 | 0.7695 | 1.0788 | 0.136* | |
H16C | 0.5578 | 0.7966 | 1.0639 | 0.136* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0928 (15) | 0.0415 (8) | 0.0545 (10) | 0.0056 (11) | −0.0095 (11) | −0.0040 (8) |
O2 | 0.157 (3) | 0.0725 (13) | 0.0492 (11) | 0.0356 (16) | −0.0179 (14) | −0.0286 (10) |
O3 | 0.0917 (15) | 0.0789 (13) | 0.0410 (10) | −0.0034 (13) | −0.0048 (10) | 0.0092 (9) |
O4 | 0.1078 (19) | 0.0642 (13) | 0.0691 (13) | 0.0249 (14) | 0.0022 (13) | 0.0156 (10) |
O5 | 0.0592 (11) | 0.0459 (9) | 0.0394 (8) | 0.0015 (8) | −0.0075 (7) | 0.0025 (7) |
O6 | 0.0545 (10) | 0.0552 (9) | 0.0304 (7) | −0.0098 (8) | −0.0006 (7) | −0.0059 (7) |
O7 | 0.1072 (16) | 0.0410 (8) | 0.0376 (8) | 0.0064 (11) | 0.0011 (10) | −0.0034 (7) |
N1 | 0.0522 (12) | 0.0412 (10) | 0.0322 (9) | 0.0014 (10) | 0.0006 (8) | −0.0061 (7) |
N2 | 0.0522 (12) | 0.0476 (10) | 0.0309 (8) | −0.0034 (9) | 0.0013 (8) | −0.0056 (7) |
N3 | 0.0627 (14) | 0.0454 (10) | 0.0468 (11) | 0.0015 (11) | −0.0025 (10) | −0.0120 (9) |
N4 | 0.0556 (13) | 0.0585 (13) | 0.0465 (12) | −0.0041 (11) | 0.0039 (10) | 0.0121 (10) |
C1 | 0.0364 (11) | 0.0419 (11) | 0.0338 (10) | −0.0058 (9) | 0.0027 (8) | −0.0034 (8) |
C2 | 0.0432 (12) | 0.0397 (11) | 0.0345 (10) | −0.0020 (10) | 0.0015 (9) | −0.0079 (9) |
C3 | 0.0442 (12) | 0.0530 (13) | 0.0313 (10) | −0.0056 (11) | 0.0008 (9) | −0.0057 (9) |
C4 | 0.0409 (12) | 0.0473 (13) | 0.0393 (11) | −0.0054 (10) | 0.0002 (9) | 0.0051 (9) |
C5 | 0.0461 (12) | 0.0395 (12) | 0.0479 (12) | −0.0003 (10) | 0.0027 (11) | −0.0031 (10) |
C6 | 0.0472 (13) | 0.0444 (12) | 0.0387 (11) | −0.0001 (11) | 0.0033 (10) | −0.0086 (9) |
C7 | 0.0505 (14) | 0.0474 (12) | 0.0338 (10) | −0.0023 (11) | 0.0026 (10) | −0.0050 (9) |
C8 | 0.0451 (13) | 0.0502 (13) | 0.0312 (10) | −0.0030 (10) | −0.0011 (9) | −0.0019 (8) |
C9 | 0.0438 (13) | 0.0434 (12) | 0.0384 (11) | −0.0010 (10) | −0.0004 (10) | −0.0060 (9) |
C10 | 0.0389 (12) | 0.0452 (12) | 0.0361 (10) | −0.0036 (10) | −0.0039 (9) | 0.0004 (8) |
C11 | 0.0455 (12) | 0.0455 (12) | 0.0315 (10) | −0.0065 (10) | −0.0008 (9) | −0.0027 (9) |
C12 | 0.0573 (15) | 0.0409 (11) | 0.0356 (10) | −0.0028 (11) | 0.0012 (10) | −0.0036 (9) |
C13 | 0.0617 (16) | 0.0462 (12) | 0.0321 (10) | −0.0020 (12) | 0.0023 (10) | 0.0012 (8) |
C14 | 0.0585 (15) | 0.0468 (14) | 0.0576 (15) | 0.0035 (12) | −0.0082 (13) | 0.0014 (11) |
C15 | 0.0664 (17) | 0.0673 (16) | 0.0429 (13) | −0.0129 (15) | 0.0121 (13) | −0.0077 (11) |
C16 | 0.172 (4) | 0.0442 (14) | 0.0557 (16) | 0.019 (2) | −0.002 (2) | 0.0042 (12) |
O1—N3 | 1.229 (3) | C5—C6 | 1.365 (3) |
O2—N3 | 1.215 (3) | C5—H5A | 0.9300 |
O3—N4 | 1.223 (3) | C6—H6A | 0.9300 |
O4—N4 | 1.228 (3) | C7—C8 | 1.469 (3) |
O5—C10 | 1.369 (3) | C7—H7A | 0.9300 |
O5—C14 | 1.433 (3) | C8—C9 | 1.387 (3) |
O6—C11 | 1.377 (2) | C8—C13 | 1.391 (3) |
O6—C15 | 1.430 (3) | C9—C10 | 1.392 (3) |
O7—C12 | 1.358 (3) | C9—H9A | 0.9300 |
O7—C16 | 1.427 (3) | C10—C11 | 1.394 (3) |
N1—C1 | 1.344 (3) | C11—C12 | 1.402 (3) |
N1—N2 | 1.376 (2) | C12—C13 | 1.386 (3) |
N1—H1N1 | 0.82 (2) | C13—H13A | 0.9300 |
N2—C7 | 1.274 (3) | C14—H14A | 0.9600 |
N3—C2 | 1.459 (3) | C14—H14B | 0.9600 |
N4—C4 | 1.450 (3) | C14—H14C | 0.9600 |
C1—C6 | 1.416 (3) | C15—H15A | 0.9600 |
C1—C2 | 1.423 (3) | C15—H15B | 0.9600 |
C2—C3 | 1.379 (3) | C15—H15C | 0.9600 |
C3—C4 | 1.380 (3) | C16—H16A | 0.9600 |
C3—H3A | 0.9300 | C16—H16B | 0.9600 |
C4—C5 | 1.398 (3) | C16—H16C | 0.9600 |
C10—O5—C14 | 116.87 (18) | C9—C8—C7 | 116.9 (2) |
C11—O6—C15 | 114.02 (18) | C13—C8—C7 | 122.2 (2) |
C12—O7—C16 | 117.21 (18) | C8—C9—C10 | 119.8 (2) |
C1—N1—N2 | 120.63 (18) | C8—C9—H9A | 120.1 |
C1—N1—H1N1 | 119.1 (17) | C10—C9—H9A | 120.1 |
N2—N1—H1N1 | 119.6 (17) | O5—C10—C9 | 124.1 (2) |
C7—N2—N1 | 113.60 (19) | O5—C10—C11 | 116.05 (19) |
O2—N3—O1 | 122.2 (2) | C9—C10—C11 | 119.8 (2) |
O2—N3—C2 | 118.4 (2) | O6—C11—C10 | 120.4 (2) |
O1—N3—C2 | 119.38 (19) | O6—C11—C12 | 119.7 (2) |
O3—N4—O4 | 123.3 (2) | C10—C11—C12 | 119.80 (19) |
O3—N4—C4 | 118.7 (2) | O7—C12—C13 | 125.0 (2) |
O4—N4—C4 | 118.0 (2) | O7—C12—C11 | 114.71 (18) |
N1—C1—C6 | 120.90 (19) | C13—C12—C11 | 120.3 (2) |
N1—C1—C2 | 122.81 (19) | C12—C13—C8 | 119.4 (2) |
C6—C1—C2 | 116.3 (2) | C12—C13—H13A | 120.3 |
C3—C2—C1 | 122.1 (2) | C8—C13—H13A | 120.3 |
C3—C2—N3 | 116.06 (18) | O5—C14—H14A | 109.5 |
C1—C2—N3 | 121.9 (2) | O5—C14—H14B | 109.5 |
C2—C3—C4 | 118.87 (19) | H14A—C14—H14B | 109.5 |
C2—C3—H3A | 120.6 | O5—C14—H14C | 109.5 |
C4—C3—H3A | 120.6 | H14A—C14—H14C | 109.5 |
C3—C4—C5 | 121.4 (2) | H14B—C14—H14C | 109.5 |
C3—C4—N4 | 118.6 (2) | O6—C15—H15A | 109.5 |
C5—C4—N4 | 120.0 (2) | O6—C15—H15B | 109.5 |
C6—C5—C4 | 119.3 (2) | H15A—C15—H15B | 109.5 |
C6—C5—H5A | 120.4 | O6—C15—H15C | 109.5 |
C4—C5—H5A | 120.4 | H15A—C15—H15C | 109.5 |
C5—C6—C1 | 122.0 (2) | H15B—C15—H15C | 109.5 |
C5—C6—H6A | 119.0 | O7—C16—H16A | 109.5 |
C1—C6—H6A | 119.0 | O7—C16—H16B | 109.5 |
N2—C7—C8 | 122.3 (2) | H16A—C16—H16B | 109.5 |
N2—C7—H7A | 118.8 | O7—C16—H16C | 109.5 |
C8—C7—H7A | 118.8 | H16A—C16—H16C | 109.5 |
C9—C8—C13 | 120.9 (2) | H16B—C16—H16C | 109.5 |
C1—N1—N2—C7 | −174.7 (2) | N2—C7—C8—C9 | 166.5 (2) |
N2—N1—C1—C6 | −1.8 (3) | N2—C7—C8—C13 | −10.3 (4) |
N2—N1—C1—C2 | 177.9 (2) | C13—C8—C9—C10 | 1.8 (4) |
N1—C1—C2—C3 | −176.6 (2) | C7—C8—C9—C10 | −175.1 (2) |
C6—C1—C2—C3 | 3.1 (3) | C14—O5—C10—C9 | −3.7 (3) |
N1—C1—C2—N3 | 4.2 (4) | C14—O5—C10—C11 | 177.5 (2) |
C6—C1—C2—N3 | −176.1 (2) | C8—C9—C10—O5 | 178.1 (2) |
O2—N3—C2—C3 | 5.1 (4) | C8—C9—C10—C11 | −3.1 (4) |
O1—N3—C2—C3 | −174.5 (2) | C15—O6—C11—C10 | −86.0 (3) |
O2—N3—C2—C1 | −175.7 (3) | C15—O6—C11—C12 | 97.3 (3) |
O1—N3—C2—C1 | 4.7 (4) | O5—C10—C11—O6 | 4.6 (3) |
C1—C2—C3—C4 | −1.7 (4) | C9—C10—C11—O6 | −174.2 (2) |
N3—C2—C3—C4 | 177.6 (2) | O5—C10—C11—C12 | −178.6 (2) |
C2—C3—C4—C5 | −1.2 (4) | C9—C10—C11—C12 | 2.5 (4) |
C2—C3—C4—N4 | −179.4 (2) | C16—O7—C12—C13 | −0.1 (4) |
O3—N4—C4—C3 | −1.9 (3) | C16—O7—C12—C11 | −179.8 (3) |
O4—N4—C4—C3 | 177.5 (3) | O6—C11—C12—O7 | −4.0 (3) |
O3—N4—C4—C5 | 179.8 (2) | C10—C11—C12—O7 | 179.2 (2) |
O4—N4—C4—C5 | −0.8 (3) | O6—C11—C12—C13 | 176.3 (2) |
C3—C4—C5—C6 | 2.4 (4) | C10—C11—C12—C13 | −0.5 (4) |
N4—C4—C5—C6 | −179.4 (2) | O7—C12—C13—C8 | 179.4 (2) |
C4—C5—C6—C1 | −0.8 (4) | C11—C12—C13—C8 | −0.9 (4) |
N1—C1—C6—C5 | 177.8 (2) | C9—C8—C13—C12 | 0.3 (4) |
C2—C1—C6—C5 | −1.8 (3) | C7—C8—C13—C12 | 177.0 (2) |
N1—N2—C7—C8 | −176.2 (2) |
Cg1 is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1 | 0.82 (2) | 2.04 (2) | 2.624 (3) | 129 (2) |
C16—H16C···O2i | 0.96 | 2.44 | 3.169 (4) | 133 |
C14—H14B···Cg1ii | 0.96 | 2.89 | 3.514 (3) | 123 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+3/2, −y+1, z+1/2. |
Cg1 is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1 | 0.82 (2) | 2.04 (2) | 2.624 (3) | 129 (2) |
C16—H16C···O2i | 0.96 | 2.44 | 3.169 (4) | 133 |
C14—H14B···Cg1ii | 0.96 | 2.89 | 3.514 (3) | 123 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+3/2, −y+1, z+1/2. |
Acknowledgements
The authors thank the Prince of Songkla University for generous support. CSCK thanks the Universiti Sains Malaysia for a postdoctoral research fellowship. The authors extend their appreciation to the Universiti Sains Malaysia for the APEX DE2012 grant No. 1002/PFIZIK/910323.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
There are numerous reports of the various biological activities of hydrazones and their complexes which show antibacterial, antifungal, antitumor, anti-inflammatory and antioxidant activities (Angelusiu et al., 2010; Cui et al., 2010; Gokce et al., 2009; Sathyadevi et al., 2012 and Wang et al., 2009).
In previous works, we synthesized a number of hydrazone derivatives from the reaction of 2,4-dinitrophenylhydrazine and various substituted aldehydes (Fun et al., 2011, 2012 and 2013). The title hydrazone (I) was again synthesized using 2,4-dinitrophenylhydrazine but with 3,4,5-trimethoxybenzaldehyde as the aldehyde. Our evaluation of the antioxidant activity of (I) by the DPPH free radical scavenging method [DPPH = 2,2-diphenyl-1-picrylhydrazyl] (Molyneux, 2004) showed that it displays weak antioxidant activity with 17.6% inhibition. This further confirms observations from previous works (Fun et al., 2011, 2012 and 2013) that the antioxidant ability of such compounds is controlled by the number and substitution pattern of the methoxy substituents. Herein we report the synthesis and crystal structure of (I).
In Fig. 1, the whole molecular structure of (I), C16H16N4O7 is not planar, with the dihedral angle between the two substituted benzene rings being 5.50 (11)°. Both nitro groups lie close to the plane of the attached benzene ring [torsion angles O1–N3–C2–C1 = 4.7 (4)°, O2–N3–C2–C3 = 5.1 (4)°, O3–N4–C4–C3 = -1.9 (3)° and O4–N4–C4–C5 = -0.8 (3)°]. The mean plane through the central N1/N2/C7 bridge makes dihedral angles of 6.8 (2)° and 12.3 (2)° with the two adjacent C1–C6 and C8–C13 benzene rings, respectively. The three methoxy groups of the 3,4,5-trimethoxyphenyl unit have two different orientations: the two meta-methoxy groups (at C10 and C12) are co-planar with the benzene ring plane (Fig. 3) with torsion angles C14–O5–C10–C9 = -3.7 (3)° and C16–O7–C12–C13 = -0.1 (4)° whereas the para-methoxy substituent (at C11) is out of the plane with the torsion angle C15–O6–C11–C10 = -86.0 (3)°. An intramolecular N1—H1N1···O1 hydrogen bond (Fig. 1 and Table 1) generates an S(6) ring motif (Bernstein et al., 1995). Bond distances for (I) are comparable to those found in closely related structures (Fun et al., 2011, 2012, 2013).
In the crystal packing (Fig. 2), molecules are linked by a weak intermolecular C16—H16C···O2 interaction (Table 1) into screw chains. These chains are arranged into sheets and further stacked along the a axis by π···π interactions with distances of Cg1···Cg2iii, iv = 3.9420 (13) Å [Cg1 and Cg2 are the centroids of the C1···C6 and C8···C13 benzene rings, respectively; symmetry codes (iii) = 1/2-x, 1-y, -1/2+z and (iv) = 1/2+x, 1-y, 1/2+z] (Fig. 3). The molecules are linked into two dimensional network by weak C—H···O interactions. These C—H···π contacts further stabilize the two-dimensional network (Table 1).