N-(2,4-Dinitro-phen-yl)-N'-(1-p-tolyl-ethyl-idene)hydrazine.

In the title mol-ecule, C(15)H(14)N(4)O(4), the dihedral angle between the two benzene rings is 2.21 (7)°. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. The mean planes of the ortho- and para-nitro groups make dihedral angles of 2.17 (17) and 2.05 (16)°, respectively, with the benzene ring to which they are attached. In the crystal structure, weak inter-molecular C-H⋯O hydrogen bonds generate R(2) (2)(7), R(2) (2)(13) and R(2) (1)(10) ring motifs, linking symmetry-related mol-ecules into extended chains along the b axis. In addition, there are inter-molecular C⋯C [3.332 (2)-3.343 (2) Å] contacts which are shorter than the sum of the van der Waals radii. The crystal structure is further stabilized by inter-molecular C-H⋯π and π-π stacking inter-actions [centroid-centroid distance = 3.8090 (9) Å].

Related literature

For bond-length data, see: (Allen et al. 1987 ▶). For hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Fun et al. (2009 ▶); Kia et al. (2009 ▶). For background information on 2,4-dinitro­phenyl­hydrazones, see: Cordis et al. (1998 ▶); Guillaumont & Nakamura (2000 ▶); Lamberton et al. (1974 ▶); Niknam et al. (2005 ▶); Raj & Kurup (2006 ▶); Zegota (1999 ▶); Zlotorzynska & Lai (1999 ▶); For the synthetic procedure, see: Okabe et al. (1993 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C15H14N4O4

M = 314.30

Monoclinic,

a = 7.6948 (1) Å

b = 14.9092 (3) Å

c = 12.5224 (2) Å

β = 91.778 (1)°

V = 1435.92 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.25 × 0.23 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.974, T max = 0.984

16826 measured reflections

4211 independent reflections

3206 reflections with I > 2˘I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.143

S = 1.08

4211 reflections

214 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009957/lh2788sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009957/lh2788Isup2.hkl

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

C15H14N4O4	F(000) = 656
Mr = 314.30	Dx = 1.454 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5279 reflections
a = 7.6948 (1) Å	θ = 2.7–30.0°
b = 14.9092 (3) Å	µ = 0.11 mm−1
c = 12.5224 (2) Å	T = 100 K
β = 91.778 (1)°	Block, red
V = 1435.92 (4) Å3	0.25 × 0.23 × 0.15 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4211 independent reflections
Radiation source: fine-focus sealed tube	3206 reflections with I > 2˘I)
graphite	Rint = 0.030
φ and ω scans	θmax = 30.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.974, Tmax = 0.984	k = −20→17
16826 measured reflections	l = −17→17

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0631P)2 + 0.5547P] where P = (Fo2 + 2Fc2)/3
4211 reflections	(Δ/σ)max = 0.001
214 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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	0.17776 (17)	0.87567 (9)	1.02191 (10)	0.0328 (3)
O2	0.16471 (16)	1.01618 (9)	1.06678 (9)	0.0279 (3)
O3	0.45972 (17)	1.23529 (8)	0.87222 (10)	0.0312 (3)
O4	0.60603 (15)	1.20508 (8)	0.73223 (9)	0.0260 (3)
N1	0.62455 (17)	1.04202 (9)	0.66064 (10)	0.0176 (3)
N2	0.67704 (16)	0.97591 (9)	0.59199 (10)	0.0175 (3)
N3	0.21243 (18)	0.95518 (10)	1.00792 (10)	0.0228 (3)
N4	0.51408 (17)	1.18141 (9)	0.80690 (10)	0.0210 (3)
C1	0.47019 (19)	1.08784 (10)	0.81806 (11)	0.0167 (3)
C2	0.36357 (19)	1.06601 (10)	0.90212 (11)	0.0178 (3)
H2A	0.3226	1.1105	0.9469	0.021*
C3	0.3200 (2)	0.97796 (11)	0.91782 (11)	0.0180 (3)
C4	0.3812 (2)	0.90980 (11)	0.85198 (11)	0.0191 (3)
H4A	0.3528	0.8503	0.8653	0.023*
C5	0.4829 (2)	0.93102 (10)	0.76795 (11)	0.0177 (3)
H5A	0.5221	0.8854	0.7241	0.021*
C6	0.52995 (19)	1.02107 (10)	0.74630 (11)	0.0159 (3)
C7	0.74308 (19)	1.00482 (10)	0.50440 (11)	0.0169 (3)
C8	0.80349 (19)	0.93424 (10)	0.43032 (11)	0.0172 (3)
C9	0.7621 (2)	0.84429 (11)	0.44813 (12)	0.0208 (3)
H9A	0.6965	0.8292	0.5066	0.025*
C10	0.8168 (2)	0.77741 (11)	0.38063 (13)	0.0247 (4)
H10A	0.7869	0.7182	0.3943	0.030*
C11	0.9165 (2)	0.79729 (12)	0.29186 (12)	0.0223 (3)
C12	0.9582 (2)	0.88663 (12)	0.27404 (12)	0.0223 (3)
H12A	1.0245	0.9015	0.2158	0.027*
C13	0.9029 (2)	0.95450 (11)	0.34177 (11)	0.0198 (3)
H13A	0.9323	1.0138	0.3279	0.024*
C14	0.7563 (2)	1.10272 (11)	0.47653 (12)	0.0208 (3)
H14A	0.6455	1.1310	0.4853	0.031*
H14B	0.7899	1.1088	0.4037	0.031*
H14C	0.8418	1.1308	0.5229	0.031*
C15	0.9752 (2)	0.72351 (13)	0.21878 (14)	0.0298 (4)
H15A	0.8783	0.6855	0.2000	0.045*
H15B	1.0642	0.6887	0.2547	0.045*
H15C	1.0205	0.7494	0.1552	0.045*
H1N1	0.652 (3)	1.0963 (15)	0.6502 (15)	0.027 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0401 (8)	0.0280 (7)	0.0311 (6)	−0.0030 (6)	0.0136 (6)	0.0070 (5)
O2	0.0299 (6)	0.0348 (7)	0.0195 (5)	0.0014 (5)	0.0090 (5)	−0.0053 (5)
O3	0.0426 (8)	0.0173 (6)	0.0344 (7)	0.0007 (5)	0.0135 (6)	−0.0079 (5)
O4	0.0302 (6)	0.0173 (6)	0.0312 (6)	−0.0028 (5)	0.0114 (5)	0.0002 (5)
N1	0.0208 (6)	0.0129 (6)	0.0196 (6)	−0.0009 (5)	0.0067 (5)	−0.0008 (5)
N2	0.0175 (6)	0.0168 (6)	0.0183 (6)	0.0006 (5)	0.0035 (5)	−0.0022 (5)
N3	0.0218 (7)	0.0282 (8)	0.0184 (6)	0.0000 (6)	0.0030 (5)	0.0035 (5)
N4	0.0228 (7)	0.0164 (7)	0.0240 (6)	0.0008 (5)	0.0030 (5)	−0.0022 (5)
C1	0.0179 (7)	0.0147 (7)	0.0176 (6)	−0.0001 (6)	0.0008 (5)	−0.0014 (5)
C2	0.0180 (7)	0.0199 (8)	0.0157 (6)	0.0028 (6)	0.0021 (5)	−0.0035 (5)
C3	0.0185 (7)	0.0218 (8)	0.0139 (6)	−0.0007 (6)	0.0025 (5)	0.0014 (5)
C4	0.0208 (7)	0.0174 (7)	0.0190 (7)	−0.0013 (6)	−0.0001 (6)	0.0016 (6)
C5	0.0217 (8)	0.0155 (7)	0.0162 (6)	0.0007 (6)	0.0022 (6)	−0.0027 (5)
C6	0.0156 (7)	0.0163 (7)	0.0158 (6)	−0.0002 (5)	0.0007 (5)	−0.0013 (5)
C7	0.0150 (7)	0.0181 (7)	0.0176 (6)	−0.0006 (5)	0.0005 (5)	0.0013 (5)
C8	0.0152 (7)	0.0214 (8)	0.0150 (6)	0.0017 (6)	0.0014 (5)	0.0004 (6)
C9	0.0229 (8)	0.0210 (8)	0.0190 (7)	−0.0007 (6)	0.0076 (6)	0.0005 (6)
C10	0.0267 (8)	0.0218 (8)	0.0260 (8)	−0.0009 (7)	0.0058 (7)	−0.0026 (6)
C11	0.0188 (7)	0.0300 (9)	0.0182 (7)	0.0033 (6)	0.0012 (6)	−0.0040 (6)
C12	0.0186 (7)	0.0345 (9)	0.0140 (6)	0.0027 (7)	0.0035 (6)	0.0017 (6)
C13	0.0187 (7)	0.0237 (8)	0.0169 (6)	−0.0001 (6)	0.0015 (6)	0.0036 (6)
C14	0.0238 (8)	0.0187 (8)	0.0200 (7)	0.0005 (6)	0.0031 (6)	0.0041 (6)
C15	0.0267 (9)	0.0357 (10)	0.0270 (8)	0.0029 (7)	0.0046 (7)	−0.0097 (7)

O1—N3	1.2288 (19)	C7—C8	1.487 (2)
O2—N3	1.2336 (18)	C7—C14	1.505 (2)
O3—N4	1.2291 (16)	C8—C9	1.398 (2)
O4—N4	1.2412 (16)	C8—C13	1.3992 (19)
N1—C6	1.3515 (18)	C9—C10	1.381 (2)
N1—N2	1.3766 (17)	C9—H9A	0.9300
N1—H1N1	0.85 (2)	C10—C11	1.402 (2)
N2—C7	1.2968 (18)	C10—H10A	0.9300
N3—C3	1.4598 (18)	C11—C12	1.390 (2)
N4—C1	1.443 (2)	C11—C15	1.509 (2)
C1—C2	1.3931 (19)	C12—C13	1.395 (2)
C1—C6	1.4267 (19)	C12—H12A	0.9300
C2—C3	1.371 (2)	C13—H13A	0.9300
C2—H2A	0.9300	C14—H14A	0.9600
C3—C4	1.400 (2)	C14—H14B	0.9600
C4—C5	1.368 (2)	C14—H14C	0.9600
C4—H4A	0.9300	C15—H15A	0.9600
C5—C6	1.419 (2)	C15—H15B	0.9600
C5—H5A	0.9300	C15—H15C	0.9600
C6—N1—N2	120.39 (13)	C9—C8—C13	117.79 (13)
C6—N1—H1N1	118.9 (13)	C9—C8—C7	120.15 (12)
N2—N1—H1N1	120.7 (13)	C13—C8—C7	122.06 (14)
C7—N2—N1	114.86 (13)	C10—C9—C8	121.31 (13)
O1—N3—O2	123.78 (13)	C10—C9—H9A	119.3
O1—N3—C3	117.74 (13)	C8—C9—H9A	119.3
O2—N3—C3	118.47 (13)	C9—C10—C11	121.15 (16)
O3—N4—O4	121.96 (13)	C9—C10—H10A	119.4
O3—N4—C1	118.81 (12)	C11—C10—H10A	119.4
O4—N4—C1	119.23 (12)	C12—C11—C10	117.71 (14)
C2—C1—C6	121.45 (14)	C12—C11—C15	121.74 (14)
C2—C1—N4	116.36 (13)	C10—C11—C15	120.55 (16)
C6—C1—N4	122.18 (12)	C11—C12—C13	121.38 (13)
C3—C2—C1	118.99 (13)	C11—C12—H12A	119.3
C3—C2—H2A	120.5	C13—C12—H12A	119.3
C1—C2—H2A	120.5	C12—C13—C8	120.65 (15)
C2—C3—C4	121.51 (13)	C12—C13—H13A	119.7
C2—C3—N3	118.74 (13)	C8—C13—H13A	119.7
C4—C3—N3	119.71 (14)	C7—C14—H14A	109.5
C5—C4—C3	119.76 (14)	C7—C14—H14B	109.5
C5—C4—H4A	120.1	H14A—C14—H14B	109.5
C3—C4—H4A	120.1	C7—C14—H14C	109.5
C4—C5—C6	121.41 (13)	H14A—C14—H14C	109.5
C4—C5—H5A	119.3	H14B—C14—H14C	109.5
C6—C5—H5A	119.3	C11—C15—H15A	109.5
N1—C6—C5	121.14 (13)	C11—C15—H15B	109.5
N1—C6—C1	122.05 (14)	H15A—C15—H15B	109.5
C5—C6—C1	116.80 (12)	C11—C15—H15C	109.5
N2—C7—C8	115.51 (13)	H15A—C15—H15C	109.5
N2—C7—C14	123.34 (13)	H15B—C15—H15C	109.5
C8—C7—C14	121.14 (12)
C6—N1—N2—C7	169.80 (14)	C2—C1—C6—N1	175.87 (15)
O3—N4—C1—C2	1.7 (2)	N4—C1—C6—N1	−3.2 (2)
O4—N4—C1—C2	−178.66 (14)	C2—C1—C6—C5	−3.1 (2)
O3—N4—C1—C6	−179.24 (15)	N4—C1—C6—C5	177.86 (14)
O4—N4—C1—C6	0.4 (2)	N1—N2—C7—C8	178.89 (13)
C6—C1—C2—C3	2.0 (2)	N1—N2—C7—C14	−2.2 (2)
N4—C1—C2—C3	−178.88 (14)	N2—C7—C8—C9	10.5 (2)
C1—C2—C3—C4	0.5 (2)	C14—C7—C8—C9	−168.44 (14)
C1—C2—C3—N3	178.22 (13)	N2—C7—C8—C13	−169.26 (14)
O1—N3—C3—C2	−178.53 (15)	C14—C7—C8—C13	11.8 (2)
O2—N3—C3—C2	0.0 (2)	C13—C8—C9—C10	−0.2 (2)
O1—N3—C3—C4	−0.8 (2)	C7—C8—C9—C10	−179.92 (15)
O2—N3—C3—C4	177.71 (15)	C8—C9—C10—C11	0.2 (3)
C2—C3—C4—C5	−1.9 (2)	C9—C10—C11—C12	−0.1 (2)
N3—C3—C4—C5	−179.57 (14)	C9—C10—C11—C15	−179.98 (16)
C3—C4—C5—C6	0.7 (2)	C10—C11—C12—C13	−0.2 (2)
N2—N1—C6—C5	0.2 (2)	C15—C11—C12—C13	179.76 (15)
N2—N1—C6—C1	−178.72 (14)	C11—C12—C13—C8	0.2 (2)
C4—C5—C6—N1	−177.27 (15)	C9—C8—C13—C12	0.0 (2)
C4—C5—C6—C1	1.7 (2)	C7—C8—C13—C12	179.69 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4	0.85 (2)	1.96 (2)	2.5966 (18)	131.3 (18)
C4—H4A···O4i	0.93	2.51	3.232 (2)	135
C5—H5A···O3i	0.93	2.55	3.4409 (19)	161
C9—H9A···O3i	0.93	2.41	3.295 (2)	158
C14—H14C···Cg1ii	0.96	2.68	3.5635 (17)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O4	0.85 (2)	1.96 (2)	2.5966 (18)	131.3 (18)
C4—H4A⋯O4i	0.93	2.51	3.232 (2)	135
C5—H5A⋯O3i	0.93	2.55	3.4409 (19)	161
C9—H9A⋯O3i	0.93	2.41	3.295 (2)	158
C14—H14C⋯Cg1ii	0.96	2.68	3.5635 (17)	154

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C8–C13 benzene ring.