1-(2,4-Di-nitro-phen-yl)-2-[(E)-(3,4,5-tri-meth-oxy-benzyl-idene)]hydrazine.

Mol-ecules of the title compound, C16H16N4O7, are not planar with a dihedral angle of 5.50 (11)° between the substituted benzene rings. The two meta-meth-oxy groups of the 3,4,5-tri-meth-oxy-benzene moiety lie in the plane of the attached ring [Cmeth-yl-O-C-C torsion angles -0.1 (4)° and -3.7 (3)°] while the para-meth-oxy substituent lies out of the plane [Cmeth-yl-O-C-C, -86.0 (3)°]. An intra-molecular N-H⋯O hydrogen bond involving the 2-nitro substituent generates an S(6) ring motif. In the crystal structure, mol-ecules are linked by weak C-H⋯O inter-actions into screw chains, that are arranged into a sheet parallel to the bc plane. These sheets are connected by π-π stacking inter-actions between the nitro and meth-oxy substituted aromatic rings with a centroid-centroid separation of 3.9420 (13) Å. C-H⋯π contacts further stabilize the two-dimensional network.

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

C16H16N4O7

M = 376.33

Orthorhombic,

a = 7.4724 (4) Å

b = 14.3106 (7) Å

c = 16.1549 (7) Å

V = 1727.52 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 100 K

0.58 × 0.30 × 0.24 mm

Data collection

Bruker APEXII CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.936, T max = 0.972

20053 measured reflections

2855 independent reflections

2243 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.107

S = 1.08

2855 reflections

251 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.14 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814001238/sj5380sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001238/sj5380Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

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)

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

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) .