2,4,6-Trinitro-N-[4-(phenyl-diazen-yl)phen-yl]aniline.

The title compound, C(18)H(12)N(6)O(6), was prepared from the reaction of 4-(phenyl-diazen-yl)aniline (aniline yellow) with picryl-sulfonic acid. The dihedral angle formed by the two benzene rings of the diphenyl-diazenyl ring system is 6.55 (13)° and that formed by the rings of the picrate-aniline ring system is 48.76 (12)°. The mol-ecule contains an intra-molecular aniline-nitro N-H⋯O hydrogen bond.

Related literature

For the reaction of picryl chloride with isomeric amino­benzoic acids, see: Crocker & Matthews (1911 ▶). For the application of the title compound in dyeing technology, see: Beretta (1926 ▶);. For structural data on N-picryl-substituted anilines, see: Forlani et al. (1992 ▶); Pan et al. (2007 ▶); Smith et al. (2007) ▶; Braun et al. (2008 ▶); Smith et al. (2009 ▶). For diazenyl-protonated salts of aniline yellow, see: Mahmoudkhani & Langer (2001 ▶); Smith et al. (2009 ▶, 2011 ▶).

Experimental

Crystal data

C18H12N6O6

M = 408.34

Monoclinic,

a = 7.4255 (4) Å

b = 7.6613 (4) Å

c = 16.1510 (9) Å

β = 98.160 (5)°

V = 909.51 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 200 K

0.30 × 0.30 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.920, T max = 0.990

6768 measured reflections

2297 independent reflections

1407 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.058

S = 0.86

2297 reflections

271 parameters

1 restraint

H-atom parameters not refined

Δρmax = 0.15 e Å−3

Δρmin = −0.14 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101004X/lh5220sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101004X/lh5220Isup2.hkl

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

C18H12N6O6	F(000) = 420
Mr = 408.34	Dx = 1.491 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2105 reflections
a = 7.4255 (4) Å	θ = 3.5–28.5°
b = 7.6613 (4) Å	µ = 0.12 mm−1
c = 16.1510 (9) Å	T = 200 K
β = 98.160 (5)°	Plate, orange-red
V = 909.51 (9) Å3	0.30 × 0.30 × 0.15 mm
Z = 2

Oxford Diffraction Gemini-S CCD-detector diffractometer	2297 independent reflections
Radiation source: Enhance (Mo) X-ray source	1407 reflections with I > 2σ(I)
graphite	Rint = 0.036
Detector resolution: 16.077 pixels mm-1	θmax = 28.5°, θmin = 3.5°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −10→10
Tmin = 0.920, Tmax = 0.990	l = −21→21
6768 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058	H-atom parameters not refined
S = 0.86	w = 1/[σ2(Fo2) + (0.021P)2] where P = (Fo2 + 2Fc2)/3
2297 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.15 e Å−3
1 restraint	Δρmin = −0.14 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O21A	0.7894 (3)	0.0405 (2)	0.33042 (15)	0.0557 (8)
O22A	0.8395 (3)	−0.0131 (3)	0.20499 (15)	0.0673 (10)
O41A	0.7046 (3)	0.3737 (3)	−0.01934 (12)	0.0524 (8)
O42A	0.5573 (3)	0.6113 (3)	−0.00428 (13)	0.0733 (10)
O61A	0.4815 (3)	0.8150 (3)	0.26498 (14)	0.0582 (9)
O62A	0.4238 (2)	0.6124 (3)	0.35215 (12)	0.0467 (7)
N1	0.6941 (3)	0.3543 (3)	0.36913 (14)	0.0379 (8)
N2A	0.7860 (3)	0.0827 (3)	0.25675 (17)	0.0438 (10)
N4	0.8515 (3)	0.7986 (3)	0.64591 (15)	0.0376 (8)
N4A	0.6334 (3)	0.4775 (3)	0.02299 (15)	0.0403 (9)
N6A	0.4931 (3)	0.6655 (3)	0.29240 (16)	0.0397 (9)
N41	0.7964 (3)	0.7460 (3)	0.71112 (15)	0.0388 (8)
C1	0.7256 (3)	0.4761 (4)	0.43607 (17)	0.0343 (10)
C1A	0.6660 (3)	0.3836 (3)	0.28559 (17)	0.0304 (9)
C2	0.8086 (3)	0.6339 (3)	0.42983 (17)	0.0367 (10)
C2A	0.7143 (3)	0.2547 (3)	0.22900 (18)	0.0323 (9)
C3	0.8466 (3)	0.7381 (4)	0.50001 (17)	0.0363 (10)
C3A	0.7034 (3)	0.2855 (3)	0.14441 (17)	0.0325 (10)
C4	0.8030 (3)	0.6843 (4)	0.57641 (18)	0.0357 (10)
C4A	0.6397 (3)	0.4442 (4)	0.11242 (17)	0.0304 (9)
C5	0.7209 (4)	0.5221 (4)	0.58222 (18)	0.0420 (11)
C5A	0.5793 (3)	0.5688 (3)	0.16261 (17)	0.0321 (10)
C6	0.6810 (4)	0.4184 (4)	0.51302 (18)	0.0429 (11)
C6A	0.5887 (3)	0.5373 (3)	0.24652 (17)	0.0301 (9)
C11	0.9043 (4)	1.0521 (4)	0.92620 (19)	0.0475 (11)
C21	0.9363 (3)	1.1240 (4)	0.8506 (2)	0.0455 (11)
C31	0.9046 (3)	1.0274 (4)	0.77855 (17)	0.0361 (10)
C41	0.8401 (3)	0.8580 (3)	0.78142 (17)	0.0313 (10)
C51	0.8078 (3)	0.7876 (4)	0.85652 (18)	0.0391 (10)
C61	0.8423 (4)	0.8851 (4)	0.92962 (19)	0.0437 (11)
H1	0.69280	0.24650	0.38380	0.0450*
H2	0.83930	0.67080	0.37880	0.0440*
H3	0.90220	0.84590	0.49580	0.0430*
H3A	0.73870	0.19990	0.10920	0.0390*
H5	0.69290	0.48390	0.63360	0.0500*
H5A	0.53250	0.67380	0.14000	0.0390*
H6	0.62490	0.31080	0.51700	0.0510*
H11	0.92550	1.11840	0.97480	0.0570*
H21	0.97920	1.23780	0.84890	0.0540*
H31	0.92630	1.07520	0.72800	0.0430*
H51	0.76280	0.67450	0.85820	0.0470*
H61	0.82320	0.83690	0.98050	0.0520*

	U11	U22	U33	U12	U13	U23
O21A	0.0839 (16)	0.0368 (12)	0.0427 (14)	−0.0079 (11)	−0.0033 (12)	0.0064 (11)
O22A	0.0965 (18)	0.0423 (14)	0.0679 (18)	0.0221 (13)	0.0283 (14)	−0.0003 (12)
O41A	0.0661 (14)	0.0584 (14)	0.0361 (14)	−0.0002 (12)	0.0191 (11)	−0.0091 (11)
O42A	0.0923 (18)	0.0854 (17)	0.0449 (15)	0.0435 (16)	0.0196 (13)	0.0222 (14)
O61A	0.0700 (16)	0.0370 (14)	0.0701 (18)	0.0057 (11)	0.0187 (12)	−0.0105 (11)
O62A	0.0385 (11)	0.0683 (14)	0.0349 (13)	−0.0036 (11)	0.0107 (10)	−0.0101 (11)
N1	0.0475 (14)	0.0359 (13)	0.0305 (15)	−0.0133 (12)	0.0065 (12)	0.0030 (12)
N2A	0.0492 (16)	0.0339 (16)	0.0470 (19)	−0.0023 (12)	0.0022 (14)	0.0000 (14)
N4	0.0358 (13)	0.0478 (15)	0.0286 (16)	−0.0031 (12)	0.0022 (11)	−0.0014 (12)
N4A	0.0354 (14)	0.0543 (17)	0.0318 (16)	0.0028 (13)	0.0067 (12)	0.0020 (14)
N6A	0.0276 (13)	0.0496 (18)	0.0414 (17)	−0.0032 (12)	0.0031 (12)	−0.0160 (14)
N41	0.0429 (14)	0.0470 (15)	0.0268 (15)	−0.0013 (13)	0.0058 (11)	−0.0008 (13)
C1	0.0327 (16)	0.0389 (18)	0.0303 (18)	−0.0076 (14)	0.0014 (13)	−0.0048 (15)
C1A	0.0253 (15)	0.0353 (16)	0.0302 (18)	−0.0072 (13)	0.0028 (13)	−0.0062 (14)
C2	0.0347 (15)	0.0505 (19)	0.0246 (17)	−0.0113 (14)	0.0031 (12)	0.0061 (15)
C2A	0.0312 (15)	0.0283 (15)	0.0365 (18)	−0.0030 (13)	0.0019 (13)	−0.0032 (14)
C3	0.0359 (15)	0.0401 (17)	0.0318 (19)	−0.0123 (14)	0.0012 (13)	−0.0004 (15)
C3A	0.0278 (15)	0.0359 (17)	0.0343 (18)	−0.0073 (13)	0.0057 (13)	−0.0111 (14)
C4	0.0337 (16)	0.0433 (18)	0.0280 (18)	−0.0039 (14)	−0.0027 (13)	0.0004 (15)
C4A	0.0273 (14)	0.0397 (17)	0.0244 (16)	−0.0027 (13)	0.0039 (12)	−0.0024 (14)
C5	0.0560 (19)	0.0454 (19)	0.0251 (18)	−0.0117 (16)	0.0073 (14)	0.0015 (14)
C5A	0.0227 (14)	0.0357 (17)	0.0370 (19)	−0.0007 (13)	0.0010 (13)	0.0007 (14)
C6	0.0527 (18)	0.0401 (18)	0.0359 (19)	−0.0138 (14)	0.0065 (15)	0.0029 (14)
C6A	0.0229 (13)	0.0359 (16)	0.0323 (18)	−0.0024 (13)	0.0063 (12)	−0.0076 (14)
C11	0.0380 (17)	0.063 (2)	0.040 (2)	0.0134 (17)	0.0005 (15)	−0.0199 (17)
C21	0.0331 (17)	0.0445 (18)	0.057 (2)	−0.0013 (15)	0.0001 (15)	−0.0113 (17)
C31	0.0280 (15)	0.0444 (18)	0.035 (2)	0.0026 (14)	0.0014 (14)	0.0023 (15)
C41	0.0304 (15)	0.0346 (17)	0.0277 (18)	0.0030 (14)	−0.0004 (13)	−0.0009 (14)
C51	0.0387 (16)	0.0432 (19)	0.0345 (19)	0.0078 (14)	0.0018 (14)	−0.0046 (15)
C61	0.0434 (17)	0.053 (2)	0.0338 (19)	0.0094 (16)	0.0025 (14)	−0.0003 (17)

O21A—N2A	1.230 (4)	C3A—C4A	1.378 (4)
O22A—N2A	1.221 (3)	C4—C5	1.393 (4)
O41A—N4A	1.217 (3)	C4A—C5A	1.369 (4)
O42A—N4A	1.222 (3)	C5—C6	1.369 (4)
O61A—N6A	1.227 (3)	C5A—C6A	1.369 (4)
O62A—N6A	1.226 (3)	C11—C61	1.364 (4)
N1—C1	1.422 (4)	C11—C21	1.390 (4)
N1—C1A	1.354 (4)	C21—C31	1.371 (4)
N2A—C2A	1.467 (3)	C31—C41	1.386 (4)
N4—N41	1.250 (3)	C41—C51	1.379 (4)
N4—C4	1.429 (4)	C51—C61	1.390 (4)
N4A—C4A	1.461 (4)	C2—H2	0.9300
N6A—C6A	1.472 (3)	C3—H3	0.9300
N41—C41	1.423 (3)	C3A—H3A	0.9300
N1—H1	0.8600	C5—H5	0.9300
C1—C6	1.402 (4)	C5A—H5A	0.9300
C1—C2	1.367 (4)	C6—H6	0.9300
C1A—C2A	1.426 (4)	C11—H11	0.9300
C1A—C6A	1.418 (3)	C21—H21	0.9300
C2—C3	1.382 (4)	C31—H31	0.9300
C2A—C3A	1.378 (4)	C51—H51	0.9300
C3—C4	1.382 (4)	C61—H61	0.9300
C1—N1—C1A	129.4 (2)	C1—C6—C5	119.3 (3)
O21A—N2A—O22A	122.7 (2)	N6A—C6A—C1A	121.6 (2)
O21A—N2A—C2A	119.2 (2)	N6A—C6A—C5A	114.9 (2)
O22A—N2A—C2A	118.0 (3)	C1A—C6A—C5A	123.2 (2)
N41—N4—C4	112.9 (2)	C21—C11—C61	120.5 (3)
O41A—N4A—O42A	124.1 (2)	C11—C21—C31	120.1 (3)
O41A—N4A—C4A	119.1 (2)	C21—C31—C41	119.7 (3)
O42A—N4A—C4A	116.8 (2)	N41—C41—C51	114.7 (2)
O61A—N6A—O62A	125.3 (2)	N41—C41—C31	125.3 (2)
O61A—N6A—C6A	117.1 (2)	C31—C41—C51	120.0 (3)
O62A—N6A—C6A	117.5 (2)	C41—C51—C61	120.2 (3)
N4—N41—C41	114.4 (2)	C11—C61—C51	119.5 (3)
C1—N1—H1	115.00	C1—C2—H2	120.00
C1A—N1—H1	115.00	C3—C2—H2	120.00
N1—C1—C2	123.5 (2)	C2—C3—H3	120.00
C2—C1—C6	120.6 (3)	C4—C3—H3	120.00
N1—C1—C6	115.7 (3)	C2A—C3A—H3A	120.00
C2A—C1A—C6A	114.4 (2)	C4A—C3A—H3A	120.00
N1—C1A—C6A	125.2 (2)	C4—C5—H5	120.00
N1—C1A—C2A	120.4 (2)	C6—C5—H5	120.00
C1—C2—C3	119.5 (2)	C4A—C5A—H5A	120.00
C1A—C2A—C3A	122.2 (2)	C6A—C5A—H5A	120.00
N2A—C2A—C1A	122.7 (2)	C1—C6—H6	120.00
N2A—C2A—C3A	115.1 (2)	C5—C6—H6	120.00
C2—C3—C4	120.9 (3)	C21—C11—H11	120.00
C2A—C3A—C4A	119.5 (2)	C61—C11—H11	120.00
N4—C4—C5	123.9 (3)	C11—C21—H21	120.00
N4—C4—C3	117.0 (3)	C31—C21—H21	120.00
C3—C4—C5	119.1 (3)	C21—C31—H31	120.00
N4A—C4A—C5A	119.8 (2)	C41—C31—H31	120.00
N4A—C4A—C3A	119.1 (2)	C41—C51—H51	120.00
C3A—C4A—C5A	121.1 (3)	C61—C51—H51	120.00
C4—C5—C6	120.6 (3)	C11—C61—H61	120.00
C4A—C5A—C6A	119.3 (2)	C51—C61—H61	120.00
C1A—N1—C1—C2	−29.4 (4)	C6A—C1A—C2A—C3A	6.3 (3)
C1A—N1—C1—C6	156.3 (3)	N1—C1A—C6A—N6A	−14.0 (4)
C1—N1—C1A—C2A	152.5 (2)	N1—C1A—C6A—C5A	173.3 (2)
C1—N1—C1A—C6A	−27.7 (4)	C2A—C1A—C6A—N6A	165.7 (2)
O21A—N2A—C2A—C1A	7.0 (4)	C2A—C1A—C6A—C5A	−7.0 (3)
O21A—N2A—C2A—C3A	−175.4 (2)	C1—C2—C3—C4	0.5 (4)
O22A—N2A—C2A—C1A	−173.3 (2)	N2A—C2A—C3A—C4A	−179.3 (2)
O22A—N2A—C2A—C3A	4.3 (3)	C1A—C2A—C3A—C4A	−1.6 (4)
C4—N4—N41—C41	−179.2 (2)	C2—C3—C4—N4	178.5 (2)
N41—N4—C4—C3	175.4 (2)	C2—C3—C4—C5	0.5 (4)
N41—N4—C4—C5	−6.7 (4)	C2A—C3A—C4A—N4A	178.3 (2)
O41A—N4A—C4A—C3A	−8.9 (4)	C2A—C3A—C4A—C5A	−3.0 (4)
O41A—N4A—C4A—C5A	172.4 (2)	N4—C4—C5—C6	−178.9 (3)
O42A—N4A—C4A—C3A	172.0 (2)	C3—C4—C5—C6	−1.1 (4)
O42A—N4A—C4A—C5A	−6.7 (3)	N4A—C4A—C5A—C6A	−178.9 (2)
O61A—N6A—C6A—C1A	157.5 (2)	C3A—C4A—C5A—C6A	2.4 (4)
O61A—N6A—C6A—C5A	−29.3 (3)	C4—C5—C6—C1	0.8 (4)
O62A—N6A—C6A—C1A	−26.1 (3)	C4A—C5A—C6A—N6A	−170.2 (2)
O62A—N6A—C6A—C5A	147.1 (2)	C4A—C5A—C6A—C1A	2.9 (4)
N4—N41—C41—C31	12.6 (4)	C61—C11—C21—C31	0.4 (4)
N4—N41—C41—C51	−169.5 (2)	C21—C11—C61—C51	−1.2 (4)
N1—C1—C2—C3	−174.9 (2)	C11—C21—C31—C41	0.2 (4)
C6—C1—C2—C3	−0.8 (4)	C21—C31—C41—N41	178.0 (2)
N1—C1—C6—C5	174.7 (3)	C21—C31—C41—C51	0.1 (4)
C2—C1—C6—C5	0.2 (4)	N41—C41—C51—C61	−179.0 (2)
N1—C1A—C2A—N2A	3.5 (3)	C31—C41—C51—C61	−1.0 (4)
N1—C1A—C2A—C3A	−174.0 (2)	C41—C51—C61—C11	1.5 (4)
C6A—C1A—C2A—N2A	−176.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21A	0.86	1.98	2.607 (3)	129
C3A—H3A···O22A	0.93	2.30	2.633 (3)	100
C5—H5···O61Ai	0.93	2.58	3.453 (4)	157
C11—H11···O41Aii	0.93	2.56	3.068 (4)	115
C21—H21···O22Aiii	0.93	2.56	3.425 (4)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O21A	0.86	1.98	2.607 (3)	129