N-(2,4-Dinitro-phen-yl)-N'-[nitro-(phenyl)-methyl-ene]hydrazine.

The title compound, C(13)H(9)N(5)O(6), contains three nitro groups. It is prepared by the reaction of benzaldehyde 2,4-dinitro-phenyl-hydrazone with nitric oxide at ambient temperature. The imine group is nearly coplanar with the (2,4-dinitro-phen-yl)-hydrazine unit. The second benzene ring and the third nitro group are twisted away from this plane, with dihedral angles of 48.5 (3) and 15.2 (3)°, respectively. Weak intra-molecular N-H⋯O inter-actions are observed.

Related literature

For related literature regarding NO, see: Garthwaite et al. (1989 ▶); Murad (1999 ▶). For aryl­hydrazones, see: Chan et al. (2001 ▶); Försterling & Barnes (2001 ▶); Paschalidis et al. (2000 ▶). For the structure of benzaldehyde 2,4-dinitro­phenyl­hydrazone, see Shan et al. (2003 ▶).

Experimental

Crystal data

C13H9N5O6

M = 331.25

Orthorhombic,

a = 6.9790 (1) Å

b = 13.469 (2) Å

c = 29.448 (8) Å

V = 2768.1 (9) Å3

Z = 8

Mo Kα radiation

μ = 0.13 mm−1

T = 289 (2) K

0.52 × 0.48 × 0.22 mm

Data collection

Siemens P4 diffractometer

Absorption correction: none

3591 measured reflections

3018 independent reflections

1537 reflections with I > 2σ(I)

R int = 0.0000

3 standard reflections every 97 reflections intensity decay: 1.0%

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.059

S = 0.98

3018 reflections

222 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.14 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808036179/ez2141sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036179/ez2141Isup2.hkl

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

C13H9N5O6	Dx = 1.590 Mg m−3
Mr = 331.25	Mo Kα radiation λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 26 reflections
a = 6.9790 (1) Å	θ = 3.4–12.5º
b = 13.469 (2) Å	µ = 0.13 mm−1
c = 29.448 (8) Å	T = 289 (2) K
V = 2768.1 (9) Å3	Prism, yellow
Z = 8	0.52 × 0.48 × 0.22 mm
F000 = 1360

Siemens P4 diffractometer	Rint = 0.0000
Radiation source: normal-focus sealed tube	θmax = 27.0º
Monochromator: graphite	θmin = 1.4º
T = 289(2) K	h = 0→8
ω scans	k = 0→17
Absorption correction: none	l = 0→37
3591 measured reflections	3 standard reflections
3018 independent reflections	every 97 reflections
1537 reflections with I > 2σ(I)	intensity decay: 1.0%

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.0116P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.059	(Δ/σ)max = 0.001
S = 0.98	Δρmax = 0.20 e Å−3
3018 reflections	Δρmin = −0.14 e Å−3
222 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00375 (18)
Secondary atom site location: difference Fourier map

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	0.2792 (2)	0.72703 (10)	0.26225 (4)	0.0655 (5)
O2	0.4128 (2)	0.58358 (10)	0.27056 (4)	0.0696 (5)
O3	0.5250 (2)	0.37214 (9)	0.30832 (4)	0.0587 (4)
O4	0.5513 (2)	0.23410 (9)	0.34501 (4)	0.0668 (5)
O5	0.7770 (3)	0.22039 (11)	0.49622 (4)	0.0826 (6)
O6	0.8082 (2)	0.35414 (10)	0.53534 (4)	0.0827 (6)
N1	0.5194 (2)	0.63895 (10)	0.35787 (5)	0.0411 (4)
N2	0.5362 (2)	0.54088 (11)	0.35121 (5)	0.0423 (4)
N3	0.3764 (3)	0.66797 (13)	0.28337 (5)	0.0489 (5)
N4	0.5574 (2)	0.32486 (12)	0.34320 (5)	0.0463 (4)
N5	0.7673 (3)	0.31066 (14)	0.50021 (5)	0.0599 (5)
C1	0.3799 (3)	0.82777 (13)	0.38520 (6)	0.0409 (5)
H1	0.3459	0.7770	0.4050	0.049*
C2	0.3749 (3)	0.92498 (14)	0.39969 (6)	0.0459 (5)
H2	0.3372	0.9394	0.4293	0.055*
C3	0.4251 (3)	1.00085 (14)	0.37089 (6)	0.0490 (6)
H3	0.4223	1.0663	0.3810	0.059*
C4	0.4797 (3)	0.97942 (14)	0.32689 (6)	0.0509 (6)
H4	0.5137	1.0307	0.3073	0.061*
C5	0.4842 (3)	0.88204 (14)	0.31166 (6)	0.0449 (5)
H5	0.5195	0.8682	0.2819	0.054*
C6	0.4359 (3)	0.80519 (13)	0.34096 (6)	0.0368 (5)
C7	0.4514 (3)	0.69945 (13)	0.32858 (6)	0.0387 (5)
C8	0.5928 (3)	0.48344 (13)	0.38722 (6)	0.0376 (5)
C9	0.6383 (3)	0.52778 (13)	0.42912 (6)	0.0433 (5)
H9	0.6295	0.5964	0.4322	0.052*
C10	0.6953 (3)	0.47186 (14)	0.46549 (6)	0.0453 (5)
H10	0.7271	0.5023	0.4928	0.054*
C11	0.7052 (3)	0.37003 (14)	0.46136 (6)	0.0424 (5)
C12	0.6595 (3)	0.32304 (13)	0.42157 (6)	0.0422 (5)
H12	0.6654	0.2542	0.4194	0.051*
C13	0.6048 (3)	0.37961 (13)	0.38483 (6)	0.0376 (5)
H2N	0.508 (2)	0.5131 (11)	0.3244 (5)	0.045 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0715 (11)	0.0759 (10)	0.0491 (9)	0.0080 (10)	−0.0181 (8)	−0.0017 (8)
O2	0.1089 (14)	0.0566 (9)	0.0433 (8)	0.0080 (10)	−0.0062 (9)	−0.0146 (7)
O3	0.0786 (12)	0.0550 (9)	0.0426 (8)	−0.0004 (9)	−0.0118 (8)	−0.0065 (7)
O4	0.0932 (13)	0.0360 (8)	0.0711 (10)	0.0018 (9)	−0.0160 (9)	−0.0131 (7)
O5	0.1295 (16)	0.0517 (10)	0.0666 (10)	0.0200 (12)	−0.0158 (11)	0.0040 (9)
O6	0.1324 (17)	0.0721 (11)	0.0437 (8)	0.0087 (11)	−0.0200 (10)	−0.0044 (8)
N1	0.0411 (11)	0.0381 (9)	0.0443 (9)	0.0011 (9)	0.0036 (8)	0.0007 (8)
N2	0.0489 (12)	0.0416 (10)	0.0365 (10)	−0.0013 (9)	−0.0036 (9)	−0.0058 (8)
N3	0.0519 (13)	0.0583 (12)	0.0366 (10)	−0.0064 (11)	0.0015 (9)	0.0009 (9)
N4	0.0429 (12)	0.0467 (11)	0.0492 (10)	0.0015 (9)	−0.0012 (10)	−0.0086 (9)
N5	0.0738 (15)	0.0586 (13)	0.0471 (11)	0.0100 (12)	−0.0023 (11)	0.0012 (10)
C1	0.0408 (13)	0.0460 (12)	0.0358 (11)	0.0008 (11)	−0.0005 (10)	0.0064 (9)
C2	0.0467 (13)	0.0548 (13)	0.0362 (11)	0.0046 (12)	0.0001 (10)	−0.0056 (10)
C3	0.0483 (14)	0.0410 (12)	0.0577 (13)	0.0047 (11)	−0.0079 (12)	−0.0038 (11)
C4	0.0557 (15)	0.0493 (13)	0.0478 (12)	−0.0006 (12)	−0.0034 (12)	0.0138 (10)
C5	0.0477 (14)	0.0556 (13)	0.0315 (10)	0.0000 (11)	−0.0016 (10)	0.0050 (10)
C6	0.0350 (12)	0.0441 (11)	0.0312 (10)	0.0009 (10)	−0.0025 (9)	0.0009 (9)
C7	0.0397 (13)	0.0449 (12)	0.0314 (10)	−0.0033 (11)	0.0025 (10)	−0.0002 (9)
C8	0.0357 (12)	0.0393 (11)	0.0377 (11)	−0.0021 (10)	0.0033 (10)	0.0007 (9)
C9	0.0518 (14)	0.0379 (11)	0.0404 (11)	0.0013 (11)	0.0042 (10)	−0.0063 (9)
C10	0.0509 (15)	0.0497 (12)	0.0352 (11)	0.0000 (12)	0.0022 (10)	−0.0045 (10)
C11	0.0462 (14)	0.0458 (12)	0.0352 (10)	0.0029 (12)	0.0016 (10)	0.0022 (10)
C12	0.0402 (12)	0.0377 (11)	0.0488 (12)	0.0020 (10)	0.0046 (10)	−0.0015 (10)
C13	0.0362 (12)	0.0398 (11)	0.0367 (10)	−0.0014 (10)	0.0006 (10)	−0.0080 (9)

O1—N3	1.2163 (17)	C2—H2	0.9300
O2—N3	1.2244 (17)	C3—C4	1.381 (2)
O3—N4	1.2296 (17)	C3—H3	0.9300
O4—N4	1.2244 (17)	C4—C5	1.386 (2)
O5—N5	1.2233 (17)	C4—H4	0.9300
O6—N5	1.2227 (18)	C5—C6	1.389 (2)
N1—C7	1.2779 (19)	C5—H5	0.9300
N1—N2	1.3405 (18)	C6—C7	1.474 (2)
N2—C8	1.371 (2)	C8—C13	1.403 (2)
N2—H2N	0.894 (15)	C8—C9	1.407 (2)
N3—C7	1.492 (2)	C9—C10	1.368 (2)
N4—C13	1.468 (2)	C9—H9	0.9300
N5—C11	1.462 (2)	C10—C11	1.379 (2)
C1—C2	1.378 (2)	C10—H10	0.9300
C1—C6	1.394 (2)	C11—C12	1.369 (2)
C1—H1	0.9300	C12—C13	1.377 (2)
C2—C3	1.373 (2)	C12—H12	0.9300
C7—N1—N2	124.20 (15)	C4—C5—H5	120.0
N1—N2—C8	117.91 (15)	C6—C5—H5	120.0
N1—N2—H2N	121.5 (10)	C5—C6—C1	119.08 (16)
C8—N2—H2N	120.6 (10)	C5—C6—C7	123.26 (16)
O1—N3—O2	124.43 (17)	C1—C6—C7	117.56 (16)
O1—N3—C7	117.78 (16)	N1—C7—C6	118.45 (16)
O2—N3—C7	117.76 (17)	N1—C7—N3	123.46 (16)
O4—N4—O3	123.17 (16)	C6—C7—N3	117.99 (16)
O4—N4—C13	118.22 (16)	N2—C8—C13	122.75 (17)
O3—N4—C13	118.61 (15)	N2—C8—C9	120.25 (16)
O6—N5—O5	122.99 (18)	C13—C8—C9	116.98 (17)
O6—N5—C11	118.00 (17)	C10—C9—C8	121.21 (17)
O5—N5—C11	119.01 (17)	C10—C9—H9	119.4
C2—C1—C6	120.27 (17)	C8—C9—H9	119.4
C2—C1—H1	119.9	C9—C10—C11	119.55 (17)
C6—C1—H1	119.9	C9—C10—H10	120.2
C3—C2—C1	120.63 (17)	C11—C10—H10	120.2
C3—C2—H2	119.7	C12—C11—C10	121.58 (18)
C1—C2—H2	119.7	C12—C11—N5	119.07 (17)
C2—C3—C4	119.61 (17)	C10—C11—N5	119.35 (17)
C2—C3—H3	120.2	C11—C12—C13	118.75 (17)
C4—C3—H3	120.2	C11—C12—H12	120.6
C3—C4—C5	120.49 (18)	C13—C12—H12	120.6
C3—C4—H4	119.8	C12—C13—C8	121.91 (17)
C5—C4—H4	119.8	C12—C13—N4	116.14 (16)
C4—C5—C6	119.90 (17)	C8—C13—N4	121.95 (17)
C7—N1—N2—C8	−173.30 (18)	N2—C8—C9—C10	−179.95 (17)
C6—C1—C2—C3	−0.1 (3)	C13—C8—C9—C10	1.3 (3)
C1—C2—C3—C4	0.5 (3)	C8—C9—C10—C11	−1.2 (3)
C2—C3—C4—C5	0.0 (3)	C9—C10—C11—C12	0.1 (3)
C3—C4—C5—C6	−0.8 (3)	C9—C10—C11—N5	179.60 (17)
C4—C5—C6—C1	1.2 (3)	O6—N5—C11—C12	179.67 (19)
C4—C5—C6—C7	−175.08 (19)	O5—N5—C11—C12	0.0 (3)
C2—C1—C6—C5	−0.7 (3)	O6—N5—C11—C10	0.2 (3)
C2—C1—C6—C7	175.76 (18)	O5—N5—C11—C10	−179.5 (2)
N2—N1—C7—C6	178.19 (17)	C10—C11—C12—C13	0.8 (3)
N2—N1—C7—N3	1.8 (3)	N5—C11—C12—C13	−178.71 (17)
C5—C6—C7—N1	137.61 (19)	C11—C12—C13—C8	−0.6 (3)
C1—C6—C7—N1	−38.7 (3)	C11—C12—C13—N4	−179.89 (16)
C5—C6—C7—N3	−45.8 (3)	N2—C8—C13—C12	−179.11 (17)
C1—C6—C7—N3	137.86 (16)	C9—C8—C13—C12	−0.4 (3)
O1—N3—C7—N1	164.76 (18)	N2—C8—C13—N4	0.1 (3)
O2—N3—C7—N1	−13.5 (3)	C9—C8—C13—N4	178.85 (16)
O1—N3—C7—C6	−11.6 (3)	O4—N4—C13—C12	7.0 (3)
O2—N3—C7—C6	170.13 (18)	O3—N4—C13—C12	−173.35 (17)
N1—N2—C8—C13	176.35 (17)	O4—N4—C13—C8	−172.31 (18)
N1—N2—C8—C9	−2.3 (3)	O3—N4—C13—C8	7.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2	0.894 (15)	1.966 (15)	2.591 (2)	125.7 (13)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O2	0.894 (15)	1.966 (15)	2.591 (2)	125.7 (13)