2,4,6-Trinitro-N-[4-(phenyl­diazen­yl)phen­yl]aniline

Smith, G.; Wermuth, U.D.

doi:10.1107/S160053681101004X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o948

doi:10.1107/S160053681101004X

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2,4,6-Trinitro-N-[4-(phenyldiazenyl)phenyl]aniline

Graham Smith ^a ^* and Urs D. Wermuth ^a

^aFaculty of Science and Technology, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 10 March 2011; accepted 17 March 2011; online 23 March 2011)

The title compound, C₁₈H₁₂N₆O₆, was prepared from the reaction of 4-(phenyldiazenyl)aniline (aniline yellow) with picrylsulfonic acid. The dihedral angle formed by the two benzene rings of the diphenyldiazenyl ring system is 6.55 (13)° and that formed by the rings of the picrate–aniline ring system is 48.76 (12)°. The molecule contains an intramolecular 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_r = 408.34
Monoclinic, P 2₁
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 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.058
S = 0.86
2297 reflections
271 parameters
1 restraint
H-atom parameters not refined
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.14 e Å⁻³

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

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

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

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

checkCIF report

Comment top

The diazo-dye precursor aniline yellow [4-(phenyldiazenyl)aniline] reacts with strong acids to form purple-black to red-black diazenyl-protonated salts (Mahmoudkhani & Langer, 2001; Smith et al., 2009, 2011). However, our 1:1 stoichiometric reaction of aniline yellow with 2,4,6-trinitrobenzenesulfonic acid (picrylsulfonic acid) in 50% ethanol-water atypically gave orange-red crystals. This indicated a substitution reaction typical of this acid with anilines, giving N-picryl products with elimination of the sulfonate group. Reaction of picryl chloride with the isomeric aniline carboxylates to give similar products was reported by Crocker & Matthews (1911) while the application of picryl substituted azoanilines including the title compound, (I), in dyeing, was discussed by Beretta (1926). A number of structures of picryl-substituted anilines and other aromatic amines have been reported (e.g. Forlani et al., 1992; Braun et al., 2008; Pan et al., 2007; Smith et al., 2007).

In the title compound, (I), picryl-substitution of the aniline group of the 4-(phenyldiazenyl)aniline molecule has occurred. The molecular structure of (I) is shown Fig. 1. The diphenyldiazenyl ring system is non-planar [torsion angles C3—C4—N4—N41 and C51—C41—N41—N4: 175.4 (2) and -169.5 (2)°, respectively] as is the picrate to aniline ring system [torsion angles C2A—C1A—N1—C1 and C6—C1—N1—C1A: 152.5 (2) and 156.3 (3)° respectively]. Within the picrate moiety, one of the two ortho-related nitro groups is rotated out of the benzene plane [torsion angle C5A—C6A—N6A—O62A, 147.1 (2)°], while the other, which is associated with an intramolecular hydrogen bond [N1—H···O21A (Table 1)] is close to coplanar [C1A—C2A—N2A—O22A, -173.3 (2)°]. The para-related nitro group is also essentially coplanar with the ring [C3A—C4A—N4A—O42A, 172.0 (2)°]. There is one short intermolecular non-bonding nitro group interaction [O41A···O42Aⁱ, 2.860 (3) Å: symmetry code (i) -x + 1, y - 1/2, -z]. In addition, there are weak π···π ring interactions with a centroid to centroid distance 3.7744 (16) Å.

Related literature top

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 top

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of 4-(phenyldiazenyl)aniline (aniline yellow) and 2,4,6-trinitrobenzenesulfonic acid (picrylsulfonic acid) in 50 ml of 50% ethanol-water. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave orange-red prisms of (I) from which a specimen was cleaved for the X-ray analysis.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound. The intramolecular hydrogen bond is shown as a dashed line and displacement ellipsoids are drawn at the 40% probability level.

2,4,6-Trinitro-N-[4-(phenyldiazenyl)phenyl]aniline top

Crystal data top

C₁₈H₁₂N₆O₆	F(000) = 420
M_r = 408.34	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.021P)²] where P = (F_o² + 2F_c²)/3
2297 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₈H₁₂N₆O₆	V = 909.51 (9) Å³
M_r = 408.34	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.4255 (4) Å	µ = 0.12 mm⁻¹
b = 7.6613 (4) Å	T = 200 K
c = 16.1510 (9) Å	0.30 × 0.30 × 0.15 mm
β = 98.160 (5)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2297 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1407 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.990	R_int = 0.036
6768 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.058	H-atom parameters not refined
S = 0.86	Δρ_max = 0.15 e Å⁻³
2297 reflections	Δρ_min = −0.14 e Å⁻³
271 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, y+1, z+1; (iii) −x+2, y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₂N₆O₆
M_r	408.34
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	200
a, b, c (Å)	7.4255 (4), 7.6613 (4), 16.1510 (9)
β (°)	98.160 (5)
V (Å³)	909.51 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.30 × 0.15

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.920, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	6768, 2297, 1407
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.058, 0.86
No. of reflections	2297
No. of parameters	271
No. of restraints	1
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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

Acknowledgements

The authors acknowledge financial support from the Australian Research Council, the Faculty of Science and Technology and the University Library, Queensland University of Technology.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Beretta, A. (1926). Ann. Chim. Appl. 16, 211–216. CAS Google Scholar
Braun, D. E., Gelbrich, J., Jetti, R. K. R., Kahlenberg, X., Price, S. L. & Griesser, U. J. (2008). Cryst. Growth Des. 8, 1977–1989. CrossRef CAS Google Scholar
Crocker, J. C. & Matthews, F. (1911). J. Chem. Soc. Trans. 99, 301–313. CrossRef Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Forlani, L., Battaglia, L. P., Corradi, A. B. & Sgarabotto, P. (1992). J. Crystallogr. Spectrosc. Res. 22, 705–712. CrossRef CAS Google Scholar
Mahmoudkhani, A. H. & Langer, V. (2001). Acta Cryst. E57, o839–o841. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Pan, W.-L., Huang, K.-L., Tang, W., Xu, Y.-Q. & Hu, C.-W. (2007). Chin. J. Chem. 25, 1451–1454. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2011). Acta Cryst. E67, o878. Web of Science CSD CrossRef IUCr Journals Google Scholar
Smith, G., Wermuth, U. D., Young, D. J. & White, J. M. (2009). Acta Cryst. C65, o543–o548. Web of Science CSD CrossRef IUCr Journals Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2007). Acta Cryst. E63, o4803. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar