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

The title compound, C16H16N4O7, is close to being planar, with a dihedral angle of 3.15 (11)° between the benzene rings. The meth-oxy groups at the ortho- and para-positions of the 2,4,5-tri-meth-oxy-phenyl group are almost coplanar with the ring [deviations of the C atoms = 0.017 (2) and -0.025 (2) Å, respectively], whereas the meta-meth-oxy group deviates slightly [C-atom displacement = 0.162 (2) Å]. Both the ortho- and para-nitro groups are close to being coplanar with their attached ring [dihedral angles = 7.81 (12) and 8.56 (11)°, respectively]. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds involving the same H atom as the intra-molecular bond generate R 2 (2)(12) loops. The dimers are linked by weak C-H⋯O inter-actions into sheets parallel to the (10-4) plane and the sheets are stacked by π-π inter-actions, with a centroid-centroid distance of 3.5974 (14) Å.

Related literature

For related structures, see: Fun et al. (2011 ▶, 2012 ▶). For background to the biological activity of hydro­zones, see: Angelusiu et al. (2010 ▶); Cui et al. (2010 ▶); Gokce et al. (2009 ▶); Molyneux (2004 ▶); Török et al. (2013 ▶); Wang et al. (2009 ▶).

Experimental

Crystal data

C16H16N4O7

M = 376.33

Monoclinic,

a = 8.0273 (13) Å

b = 15.048 (2) Å

c = 13.686 (2) Å

β = 101.546 (3)°

V = 1619.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 100 K

0.33 × 0.06 × 0.05 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.961, T max = 0.994

14507 measured reflections

4296 independent reflections

2385 reflections with I > 2σ(I)

R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.144

S = 1.01

4296 reflections

251 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.33 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 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813018345/hb7102sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018345/hb7102Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813018345/hb7102Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H16N4O7	F(000) = 784
Mr = 376.33	Dx = 1.543 Mg m−3
Monoclinic, P21/c	Melting point = 528–529 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.0273 (13) Å	Cell parameters from 4296 reflections
b = 15.048 (2) Å	θ = 2.0–29.0°
c = 13.686 (2) Å	µ = 0.12 mm−1
β = 101.546 (3)°	T = 100 K
V = 1619.7 (4) Å3	Needle, red
Z = 4	0.33 × 0.06 × 0.05 mm

Bruker SMART APEXII DUO CCD diffractometer	4296 independent reflections
Radiation source: fine-focus sealed tube	2385 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
φ and ω scans	θmax = 29.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.961, Tmax = 0.994	k = −17→20
14507 measured reflections	l = −18→18

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0544P)2 + 0.5503P] where P = (Fo2 + 2Fc2)/3
4296 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.33 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 100.0 (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	1.12652 (19)	0.44523 (11)	0.52056 (12)	0.0210 (4)
O2	1.38293 (19)	0.39446 (11)	0.56829 (12)	0.0204 (4)
O3	1.4973 (2)	0.08730 (12)	0.60481 (14)	0.0302 (5)
O4	1.2974 (2)	−0.00920 (12)	0.55543 (14)	0.0292 (5)
O5	0.33101 (19)	0.48609 (11)	0.33462 (13)	0.0226 (4)
O6	−0.05504 (19)	0.24861 (11)	0.19418 (12)	0.0201 (4)
O7	0.18289 (19)	0.13357 (11)	0.24418 (12)	0.0187 (4)
N1	0.8715 (2)	0.33762 (14)	0.44831 (15)	0.0166 (5)
H1N1	0.891 (4)	0.394 (2)	0.466 (2)	0.041 (9)*
N2	0.7106 (2)	0.30856 (14)	0.40437 (14)	0.0171 (5)
N3	1.2304 (2)	0.38263 (13)	0.53664 (14)	0.0164 (5)
N4	1.3513 (2)	0.06807 (14)	0.56381 (15)	0.0194 (5)
C1	0.9955 (3)	0.27522 (16)	0.46967 (16)	0.0142 (5)
C2	1.1676 (3)	0.29321 (15)	0.51555 (16)	0.0149 (5)
C3	1.2840 (3)	0.22554 (16)	0.54419 (16)	0.0153 (5)
H3A	1.3951	0.2386	0.5756	0.018*
C4	1.2341 (3)	0.13928 (16)	0.52577 (17)	0.0162 (5)
C5	1.0706 (3)	0.11895 (17)	0.47365 (17)	0.0182 (6)
H5A	1.0407	0.0602	0.4579	0.022*
C6	0.9552 (3)	0.18490 (16)	0.44595 (16)	0.0169 (5)
H6A	0.8472	0.1705	0.4106	0.020*
C7	0.5914 (3)	0.36708 (16)	0.38720 (16)	0.0163 (5)
H7A	0.6128	0.4261	0.4056	0.020*
C8	0.4214 (3)	0.33803 (16)	0.33783 (16)	0.0144 (5)
C9	0.2900 (3)	0.39983 (16)	0.31141 (17)	0.0157 (5)
C10	0.1277 (3)	0.37208 (16)	0.26307 (17)	0.0163 (5)
H10A	0.0409	0.4135	0.2453	0.020*
C11	0.0970 (3)	0.28289 (16)	0.24183 (16)	0.0151 (5)
C12	0.2279 (3)	0.21986 (16)	0.26910 (16)	0.0155 (5)
C13	0.3866 (3)	0.24807 (16)	0.31568 (16)	0.0158 (5)
H13A	0.4733	0.2065	0.3330	0.019*
C14	0.2019 (3)	0.55210 (17)	0.3101 (2)	0.0251 (6)
H14A	0.2473	0.6090	0.3333	0.038*
H14B	0.1084	0.5377	0.3414	0.038*
H14C	0.1629	0.5540	0.2391	0.038*
C15	−0.1945 (3)	0.30917 (17)	0.16478 (18)	0.0212 (6)
H15A	−0.2911	0.2775	0.1284	0.032*
H15B	−0.1623	0.3549	0.1232	0.032*
H15C	−0.2233	0.3356	0.2231	0.032*
C16	0.3069 (3)	0.06688 (16)	0.28081 (18)	0.0208 (6)
H16A	0.2600	0.0092	0.2623	0.031*
H16B	0.3380	0.0709	0.3521	0.031*
H16C	0.4058	0.0759	0.2525	0.031*

	U11	U22	U33	U12	U13	U23
O1	0.0171 (8)	0.0103 (9)	0.0338 (9)	0.0024 (7)	0.0009 (7)	−0.0002 (7)
O2	0.0122 (8)	0.0163 (9)	0.0305 (9)	−0.0031 (7)	−0.0009 (7)	−0.0019 (7)
O3	0.0140 (8)	0.0199 (10)	0.0520 (11)	0.0024 (7)	−0.0048 (8)	0.0026 (9)
O4	0.0239 (9)	0.0111 (9)	0.0488 (11)	−0.0020 (7)	−0.0020 (8)	0.0018 (8)
O5	0.0148 (8)	0.0091 (9)	0.0412 (10)	0.0022 (7)	−0.0008 (8)	−0.0012 (8)
O6	0.0118 (8)	0.0155 (9)	0.0305 (9)	0.0012 (7)	−0.0021 (7)	−0.0011 (7)
O7	0.0148 (8)	0.0106 (9)	0.0286 (9)	0.0013 (7)	−0.0007 (7)	−0.0019 (7)
N1	0.0112 (9)	0.0111 (11)	0.0257 (10)	−0.0010 (8)	−0.0004 (8)	0.0006 (9)
N2	0.0099 (9)	0.0170 (11)	0.0232 (9)	0.0000 (8)	0.0001 (8)	−0.0001 (8)
N3	0.0161 (9)	0.0110 (10)	0.0211 (10)	0.0015 (8)	0.0017 (8)	−0.0002 (8)
N4	0.0156 (10)	0.0123 (11)	0.0301 (11)	0.0019 (8)	0.0039 (9)	0.0005 (9)
C1	0.0118 (10)	0.0128 (12)	0.0180 (10)	0.0013 (9)	0.0032 (9)	0.0007 (9)
C2	0.0138 (10)	0.0102 (12)	0.0198 (10)	−0.0005 (9)	0.0016 (9)	−0.0008 (9)
C3	0.0110 (10)	0.0139 (12)	0.0204 (11)	0.0008 (9)	0.0014 (9)	−0.0006 (9)
C4	0.0131 (11)	0.0128 (12)	0.0216 (11)	0.0039 (9)	0.0012 (9)	0.0010 (10)
C5	0.0166 (11)	0.0157 (13)	0.0223 (12)	−0.0014 (10)	0.0035 (10)	−0.0005 (10)
C6	0.0107 (10)	0.0177 (13)	0.0212 (11)	−0.0006 (9)	0.0004 (9)	0.0011 (10)
C7	0.0153 (11)	0.0112 (12)	0.0215 (11)	−0.0009 (9)	0.0018 (9)	−0.0002 (9)
C8	0.0102 (10)	0.0125 (12)	0.0203 (11)	0.0012 (9)	0.0027 (9)	0.0013 (9)
C9	0.0153 (11)	0.0100 (12)	0.0213 (11)	−0.0011 (9)	0.0024 (9)	−0.0007 (9)
C10	0.0133 (11)	0.0125 (12)	0.0222 (11)	0.0040 (9)	0.0013 (9)	0.0017 (10)
C11	0.0104 (10)	0.0148 (13)	0.0199 (11)	−0.0008 (9)	0.0025 (9)	0.0000 (9)
C12	0.0160 (11)	0.0107 (12)	0.0198 (11)	−0.0001 (9)	0.0035 (9)	−0.0008 (9)
C13	0.0133 (11)	0.0115 (12)	0.0220 (11)	0.0041 (9)	0.0019 (9)	0.0005 (9)
C14	0.0203 (12)	0.0119 (13)	0.0408 (14)	0.0062 (10)	0.0006 (11)	0.0003 (11)
C15	0.0122 (11)	0.0199 (14)	0.0292 (12)	0.0048 (10)	−0.0014 (10)	0.0000 (11)
C16	0.0177 (12)	0.0122 (13)	0.0312 (12)	0.0049 (10)	0.0018 (10)	0.0015 (10)

O1—N3	1.248 (2)	C5—C6	1.359 (3)
O2—N3	1.227 (2)	C5—H5A	0.9300
O3—N4	1.228 (2)	C6—H6A	0.9300
O4—N4	1.238 (3)	C7—C8	1.463 (3)
O5—C9	1.361 (3)	C7—H7A	0.9300
O5—C14	1.427 (3)	C8—C9	1.398 (3)
O6—C11	1.364 (2)	C8—C13	1.403 (3)
O6—C15	1.437 (3)	C9—C10	1.401 (3)
O7—C12	1.372 (3)	C10—C11	1.385 (3)
O7—C16	1.432 (3)	C10—H10A	0.9300
N1—C1	1.357 (3)	C11—C12	1.410 (3)
N1—N2	1.382 (2)	C12—C13	1.373 (3)
N1—H1N1	0.88 (3)	C13—H13A	0.9300
N2—C7	1.287 (3)	C14—H14A	0.9600
N3—C2	1.446 (3)	C14—H14B	0.9600
N4—C4	1.452 (3)	C14—H14C	0.9600
C1—C6	1.420 (3)	C15—H15A	0.9600
C1—C2	1.424 (3)	C15—H15B	0.9600
C2—C3	1.385 (3)	C15—H15C	0.9600
C3—C4	1.367 (3)	C16—H16A	0.9600
C3—H3A	0.9300	C16—H16B	0.9600
C4—C5	1.396 (3)	C16—H16C	0.9600
C9—O5—C14	118.60 (17)	C9—C8—C7	120.4 (2)
C11—O6—C15	117.78 (18)	C13—C8—C7	121.0 (2)
C12—O7—C16	116.49 (16)	O5—C9—C8	116.05 (18)
C1—N1—N2	117.2 (2)	O5—C9—C10	123.6 (2)
C1—N1—H1N1	121.4 (19)	C8—C9—C10	120.4 (2)
N2—N1—H1N1	121.2 (19)	C11—C10—C9	119.8 (2)
C7—N2—N1	117.3 (2)	C11—C10—H10A	120.1
O2—N3—O1	122.47 (19)	C9—C10—H10A	120.1
O2—N3—C2	119.27 (19)	O6—C11—C10	124.9 (2)
O1—N3—C2	118.25 (17)	O6—C11—C12	114.9 (2)
O3—N4—O4	123.2 (2)	C10—C11—C12	120.29 (19)
O3—N4—C4	118.7 (2)	O7—C12—C13	125.6 (2)
O4—N4—C4	118.03 (17)	O7—C12—C11	115.18 (18)
N1—C1—C6	119.28 (19)	C13—C12—C11	119.2 (2)
N1—C1—C2	124.6 (2)	C12—C13—C8	121.6 (2)
C6—C1—C2	116.1 (2)	C12—C13—H13A	119.2
C3—C2—C1	121.7 (2)	C8—C13—H13A	119.2
C3—C2—N3	116.05 (18)	O5—C14—H14A	109.5
C1—C2—N3	122.3 (2)	O5—C14—H14B	109.5
C4—C3—C2	119.31 (19)	H14A—C14—H14B	109.5
C4—C3—H3A	120.3	O5—C14—H14C	109.5
C2—C3—H3A	120.3	H14A—C14—H14C	109.5
C3—C4—C5	120.9 (2)	H14B—C14—H14C	109.5
C3—C4—N4	119.29 (18)	O6—C15—H15A	109.5
C5—C4—N4	119.8 (2)	O6—C15—H15B	109.5
C6—C5—C4	120.1 (2)	H15A—C15—H15B	109.5
C6—C5—H5A	120.0	O6—C15—H15C	109.5
C4—C5—H5A	120.0	H15A—C15—H15C	109.5
C5—C6—C1	121.61 (19)	H15B—C15—H15C	109.5
C5—C6—H6A	119.2	O7—C16—H16A	109.5
C1—C6—H6A	119.2	O7—C16—H16B	109.5
N2—C7—C8	118.1 (2)	H16A—C16—H16B	109.5
N2—C7—H7A	121.0	O7—C16—H16C	109.5
C8—C7—H7A	121.0	H16A—C16—H16C	109.5
C9—C8—C13	118.60 (19)	H16B—C16—H16C	109.5
C1—N1—N2—C7	177.6 (2)	N2—C7—C8—C9	−175.7 (2)
N2—N1—C1—C6	0.3 (3)	N2—C7—C8—C13	4.0 (4)
N2—N1—C1—C2	−179.5 (2)	C14—O5—C9—C8	−179.6 (2)
N1—C1—C2—C3	173.6 (2)	C14—O5—C9—C10	1.0 (4)
C6—C1—C2—C3	−6.2 (4)	C13—C8—C9—O5	−179.9 (2)
N1—C1—C2—N3	−5.3 (4)	C7—C8—C9—O5	−0.2 (3)
C6—C1—C2—N3	174.9 (2)	C13—C8—C9—C10	−0.5 (4)
O2—N3—C2—C3	7.3 (3)	C7—C8—C9—C10	179.2 (2)
O1—N3—C2—C3	−173.5 (2)	O5—C9—C10—C11	179.7 (2)
O2—N3—C2—C1	−173.7 (2)	C8—C9—C10—C11	0.4 (4)
O1—N3—C2—C1	5.4 (3)	C15—O6—C11—C10	−0.8 (3)
C1—C2—C3—C4	1.7 (4)	C15—O6—C11—C12	179.6 (2)
N3—C2—C3—C4	−179.4 (2)	C9—C10—C11—O6	−179.2 (2)
C2—C3—C4—C5	3.6 (4)	C9—C10—C11—C12	0.3 (4)
C2—C3—C4—N4	−174.4 (2)	C16—O7—C12—C13	8.0 (4)
O3—N4—C4—C3	−5.7 (4)	C16—O7—C12—C11	−173.1 (2)
O4—N4—C4—C3	172.5 (2)	O6—C11—C12—O7	−0.3 (3)
O3—N4—C4—C5	176.2 (2)	C10—C11—C12—O7	−179.9 (2)
O4—N4—C4—C5	−5.6 (3)	O6—C11—C12—C13	178.7 (2)
C3—C4—C5—C6	−4.2 (4)	C10—C11—C12—C13	−0.9 (4)
N4—C4—C5—C6	173.9 (2)	O7—C12—C13—C8	179.6 (2)
C4—C5—C6—C1	−0.8 (4)	C11—C12—C13—C8	0.7 (4)
N1—C1—C6—C5	−174.1 (2)	C9—C8—C13—C12	0.0 (4)
C2—C1—C6—C5	5.7 (3)	C7—C8—C13—C12	−179.8 (2)
N1—N2—C7—C8	178.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.89 (3)	2.04 (3)	2.642 (3)	124 (3)
N1—H1N1···O1i	0.89 (3)	2.43 (3)	3.295 (3)	164 (3)
C14—H14A···O6ii	0.96	2.59	3.180 (3)	120
C16—H16C···O2iii	0.96	2.53	3.143 (3)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	0.89 (3)	2.04 (3)	2.642 (3)	124 (3)
N1—H1N1⋯O1i	0.89 (3)	2.43 (3)	3.295 (3)	164 (3)
C14—H14A⋯O6ii	0.96	2.59	3.180 (3)	120
C16—H16C⋯O2iii	0.96	2.53	3.143 (3)	122

Symmetry codes: (i) ; (ii) ; (iii) .