4-[(E)-2-(2,4,6-Trinitro­phenyl)ethyl­idene]benzonitrile

De Borger, R.; Collas, A.; Blockhuys, F.

doi:10.1107/S1600536810038584

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2694

doi:10.1107/S1600536810038584

Open

access

4-[(E)-2-(2,4,6-Trinitrophenyl)ethylidene]benzonitrile

Roeland De Borger,^a Alain Collas ^a and Frank Blockhuys ^a ^*

^aDepartment of Chemistry, University of Antwerp, Universiteitsplein 1, B-2610 Wilrijk, Belgium
^*Correspondence e-mail: frank.blockhuys@ua.ac.be

(Received 24 September 2010; accepted 27 September 2010; online 30 September 2010)

In the crystal of the title compound, C₁₅H₈N₄O₆, the molecules are organized in layers due to their linkage by weak C—H⋯N hydrogen bonds. The layers are themselves interconnected by weak C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distances = 3.8690 (15) and 3.9017 (16) Å]. The dihedral angle between the rings is 31.9 (1)°.

Related literature

For related nitrostilbenes, see: Hanson et al. (2005 ); Oehlke et al. (2007 ); Gérard & Hardy (1988 ). The title compound was synthesized as a new ligand for iron–phosphine complexes for use in non-linear optical (NLO) applications, see: Wenseleers et al. (1998 ); Garcia et al. (2001 ); Robalo et al. (2006 ); Garcia et al. (2007 ).

Experimental

Crystal data

C₁₅H₈N₄O₆
M_r = 340.25
Monoclinic, P 2₁ /c
a = 11.183 (1) Å
b = 8.520 (1) Å
c = 15.459 (4) Å
β = 94.09 (4)°
V = 1469.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.4 × 0.4 × 0.3 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
5370 measured reflections
2689 independent reflections
1849 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.02
2689 reflections
258 parameters
All H-atom parameters refined
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O32ⁱ	0.95 (3)	2.50 (2)	3.294 (3)	142.1 (17)
C5A—H5A⋯N1Cⁱⁱ	0.96 (2)	2.53 (2)	3.427 (3)	156.3 (19)
C7—H7⋯O21ⁱⁱⁱ	0.97 (2)	2.53 (2)	3.354 (3)	143.3 (19)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038584/zl2310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038584/zl2310Isup2.hkl

checkCIF report

Comment top

The title compound was synthesized as a new ligand for iron-phosphine complexes for use in non-linear optical (NLO) applications [Wenseleers et al. (1998), Garcia et al. (2001), Robalo et al. (2006), Garcia et al. (2007)]. The molecular structure of the title compound (Fig. 1) is mainly determined by steric factors involving the nitro groups, which force the nitro-substituted ring out of the plane of the CH=CH fragment by 54.0 (3)°. In addition, the nitro group in the 6-position is twisted by 56.6 (3)° out of the plane of the benzene ring, whereas the nitro groups in the 2- and 4-positions remain almost in the latter plane, with torsion angles of 6.2 (3)° and 3.6 (4)°, respectively. A similar conformation of the nitro-substituted ring can be seen in other trinitrostilbenes, such as MALZOP [Hanson et al. (2005)], PIGBAJ [Oehlke et al. (2007)] and GIMBOT [Gérard & Hardy (1988)]. In the case of the latter, the two rings are parallel to each other, but the ethenylic link is rotated by approximately 90° with respect to both rings.

The fact that the nitro group in the 6-position is twisted so much more than the other two may be linked to the weak intermolecular hydrogen bond involving O32 of the nitro group and H3 of the neighbouring molecule (Table 1). As a consequence of this twist, the second oxygen atom of this nitro group, O31, comes quite close to O12 of a neighbouring molecule within the layer depicted in Fig. 2 [O31···O12^iv, 2.821 (3) Å, symm. code iv = x, 1+y, z], but this should not be seen as a stabilizing contact. In fact, these layers are rather formed by the weak hydrogen bond involving H5A and the nitrogen atom N1C of the nitrile group (Table 1). The layers display a typical herringbone structure and extend along the [-1 0 2] plane. A final weak hydrogen bond, involving H7 and an oxygen atom of the nitro group in the 4-position (O21), is responsible for the organization of the molecules in the direction perpendicular to these layers (Table 1). Finally, the crystal structure displays two π–π interactions. The first involves two nitrile-substituted rings (1) of neighbouring molecules contacting each other: Cg(1)···Cg(1)^v, 3.8690 (15) Å, 25.01°, symm. code v = 2–x, –y, 1–z. The second involves a nitrile- (1) of one and a nitro-substituted ring (2) of another molecule: Cg(1)···Cg(2)^vi, 3.9017 (16) Å, 26.52°, symm. code vi = 2–x, 1/2+y, 1/2–z.

Related literature top

For related nitrostilbenes, see: Hanson et al. (2005); Oehlke et al. (2007); Gérard & Hardy (1988). The title compound was synthesized as a new ligand for iron–phosphine complexes for use in non-linear optical (NLO) applications, see: Wenseleers et al. (1998); Garcia et al. (2001); Robalo et al. (2006); Garcia et al. (2007).

Experimental top

2,4,6-Trinitrotoluene (2.2 g, 0.0096 mol) and 4-cyanobenzaldehyde (1.3 g, 0.0096 mol) were dissolved in benzene (50 ml). Ten drops of piperidine were added, and the mixture was refluxed overnight. After cooling, the precipitate was collected by filtration. The crude product was refluxed for 4 h in p-xylene (25 ml) in the presence of a catalytic amount of iodine. After cooling, a mixture of yellow powder and orange-red crystals was collected, and both powder and crystals turned out to be the desired product. The yield was 12%. M.p. (uncorrected) 490–491 K. ¹H NMR (400 MHz, CDCl₃, TMS): δ 6.72 (d, 16.33 Hz, 1H, H7), 7.46 (d, 16.33 Hz, 1H, H8), 7.57 (d, 8.32 Hz, 2H, H2 and H6), 7.70 (d, 8.32 Hz, 2H, H3 and H5), 8.93 (s, 2H, H13 and H15) p.p.m. ¹³C NMR (100 MHz, CDCl₃, TMS): δ 113.31 (C4), 118.24 (CN), 120.54 (C7), 122.42 (C2 and C6), 127.85 (C3 and C5), 132.78 (C13 and C15), 133.01 (C11), 135.83 (C8), 138.91 (C1), 150.32 (C14) p.p.m.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), Mercury (Macrae et al., 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the title compound showing the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level; hydrogen atoms are represented by spheres with an arbitrary radius.
	Fig. 2. Representation of one layer of the title compound, showing the herringbone arrangement of the molecules and the associated weak hydrogen bond.

4-[(E)-2-(2,4,6-Trinitrophenyl)ethylidene]benzonitrile top

Crystal data top

C₁₅H₈N₄O₆	F(000) = 696
M_r = 340.25	D_x = 1.538 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 490 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.183 (1) Å	Cell parameters from 25 reflections
b = 8.520 (1) Å	θ = 5.7–20.3°
c = 15.459 (4) Å	µ = 0.12 mm⁻¹
β = 94.09 (4)°	T = 293 K
V = 1469.2 (4) Å³	Prism, orange
Z = 4	0.4 × 0.4 × 0.3 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.026
Radiation source: fine-focus sealed tube	θ_max = 25.3°, θ_min = 1.8°
Graphite monochromator	h = −13→13
non–profiled ω/2θ scans	k = 0→10
5370 measured reflections	l = −18→18
2689 independent reflections	3 standard reflections every 60 min
1849 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0596P)² + 0.3738P] where P = (F_o² + 2F_c²)/3
2689 reflections	(Δ/σ)_max < 0.001
258 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₅H₈N₄O₆	V = 1469.2 (4) Å³
M_r = 340.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.183 (1) Å	µ = 0.12 mm⁻¹
b = 8.520 (1) Å	T = 293 K
c = 15.459 (4) Å	0.4 × 0.4 × 0.3 mm
β = 94.09 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.026
5370 measured reflections	3 standard reflections every 60 min
2689 independent reflections	intensity decay: none
1849 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	All H-atom parameters refined
S = 1.02	Δρ_max = 0.17 e Å⁻³
2689 reflections	Δρ_min = −0.22 e Å⁻³
258 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
H2	1.241 (2)	−0.019 (3)	0.4595 (14)	0.054 (6)*
H8	0.935 (2)	−0.129 (3)	0.2627 (13)	0.053 (6)*
H3	1.0738 (19)	−0.105 (3)	0.3753 (14)	0.056 (6)*
H7	0.800 (2)	0.102 (3)	0.3391 (14)	0.059 (6)*
H5A	0.530 (2)	−0.005 (3)	0.1028 (15)	0.067 (7)*
H5	0.922 (2)	0.319 (3)	0.4044 (16)	0.073 (7)*
H3A	0.5894 (19)	−0.444 (3)	0.1969 (14)	0.060 (6)*
H6	1.093 (2)	0.408 (3)	0.4864 (16)	0.081 (8)*
C3	1.07779 (17)	−0.0016 (2)	0.39786 (13)	0.0451 (5)
C4	0.98073 (17)	0.0976 (2)	0.37989 (12)	0.0423 (4)
C1	1.18268 (18)	0.1991 (2)	0.47949 (12)	0.0465 (5)
C2	1.17765 (18)	0.0471 (2)	0.44706 (13)	0.0467 (5)
C6A	0.67988 (18)	−0.0359 (2)	0.17933 (13)	0.0471 (5)
C2A	0.71612 (18)	−0.2887 (2)	0.23434 (12)	0.0457 (5)
C8	0.86810 (18)	−0.0745 (2)	0.27531 (13)	0.0473 (5)
C5	0.9867 (2)	0.2489 (3)	0.41437 (14)	0.0537 (5)
C3A	0.6117 (2)	−0.3410 (3)	0.19242 (14)	0.0535 (5)
N1	0.7863 (2)	−0.4074 (2)	0.28671 (11)	0.0619 (5)
C1C	1.2883 (2)	0.2523 (3)	0.52933 (14)	0.0558 (5)
C7	0.87283 (18)	0.0455 (2)	0.32863 (13)	0.0479 (5)
N3	0.7162 (2)	0.1266 (2)	0.16228 (15)	0.0732 (6)
C5A	0.57307 (19)	−0.0814 (3)	0.13789 (14)	0.0546 (5)
C1A	0.75697 (17)	−0.1337 (2)	0.22990 (12)	0.0429 (5)
O11	0.88345 (18)	−0.3743 (2)	0.31976 (14)	0.0890 (6)
C6	1.0866 (2)	0.2992 (3)	0.46302 (14)	0.0569 (6)
C4A	0.54232 (17)	−0.2368 (3)	0.14446 (14)	0.0534 (5)
O12	0.7390 (3)	−0.5339 (2)	0.29474 (15)	0.1157 (9)
N2	0.43278 (19)	−0.2919 (3)	0.09634 (17)	0.0789 (7)
O32	0.8093 (2)	0.1460 (2)	0.12878 (15)	0.1011 (7)
O31	0.6471 (2)	0.2295 (2)	0.18090 (18)	0.1197 (9)
O22	0.37527 (18)	−0.2012 (3)	0.05063 (17)	0.1101 (8)
N1C	1.37272 (19)	0.2969 (3)	0.56717 (15)	0.0788 (7)
O21	0.4056 (2)	−0.4286 (3)	0.10513 (19)	0.1266 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0469 (11)	0.0378 (11)	0.0491 (11)	0.0004 (8)	−0.0065 (9)	−0.0040 (9)
C4	0.0451 (10)	0.0411 (10)	0.0397 (9)	0.0012 (8)	−0.0041 (8)	−0.0012 (8)
C1	0.0503 (11)	0.0514 (12)	0.0366 (9)	−0.0088 (9)	−0.0047 (8)	−0.0014 (8)
C2	0.0440 (11)	0.0485 (11)	0.0465 (10)	0.0030 (9)	−0.0059 (9)	0.0007 (9)
C6A	0.0514 (11)	0.0383 (10)	0.0498 (11)	−0.0012 (9)	−0.0104 (9)	−0.0035 (8)
C2A	0.0546 (12)	0.0432 (10)	0.0387 (9)	0.0006 (9)	−0.0007 (9)	−0.0016 (8)
C8	0.0420 (11)	0.0511 (12)	0.0475 (11)	0.0035 (10)	−0.0068 (9)	−0.0040 (9)
C5	0.0591 (13)	0.0443 (11)	0.0553 (12)	0.0106 (10)	−0.0119 (10)	−0.0083 (9)
C3A	0.0590 (13)	0.0495 (13)	0.0526 (12)	−0.0124 (10)	0.0072 (10)	−0.0040 (10)
N1	0.0905 (15)	0.0464 (11)	0.0474 (10)	0.0094 (10)	−0.0049 (10)	−0.0008 (8)
C1C	0.0575 (13)	0.0616 (13)	0.0471 (11)	−0.0099 (11)	−0.0046 (10)	−0.0048 (10)
C7	0.0425 (11)	0.0510 (12)	0.0484 (11)	0.0042 (9)	−0.0085 (9)	−0.0049 (9)
N3	0.0892 (16)	0.0438 (12)	0.0799 (14)	−0.0076 (11)	−0.0406 (13)	0.0026 (10)
C5A	0.0505 (12)	0.0550 (13)	0.0557 (12)	0.0062 (10)	−0.0136 (10)	−0.0084 (10)
C1A	0.0453 (10)	0.0443 (11)	0.0383 (10)	−0.0002 (8)	−0.0018 (8)	−0.0035 (8)
O11	0.0780 (13)	0.0843 (13)	0.1003 (14)	0.0135 (10)	−0.0249 (11)	0.0245 (11)
C6	0.0695 (14)	0.0422 (12)	0.0568 (12)	0.0000 (10)	−0.0104 (11)	−0.0118 (10)
C4A	0.0395 (10)	0.0625 (14)	0.0576 (12)	−0.0098 (10)	−0.0015 (9)	−0.0139 (10)
O12	0.180 (2)	0.0462 (11)	0.1130 (17)	−0.0147 (13)	−0.0469 (16)	0.0161 (10)
N2	0.0495 (12)	0.0910 (18)	0.0940 (16)	−0.0141 (12)	−0.0099 (11)	−0.0279 (14)
O32	0.1167 (18)	0.0734 (13)	0.1105 (17)	−0.0391 (12)	−0.0114 (14)	0.0248 (11)
O31	0.1395 (19)	0.0462 (11)	0.165 (2)	0.0184 (12)	−0.0491 (17)	−0.0185 (12)
O22	0.0677 (12)	0.1224 (19)	0.1324 (19)	0.0063 (12)	−0.0469 (13)	−0.0296 (15)
N1C	0.0676 (13)	0.0894 (16)	0.0764 (14)	−0.0197 (12)	−0.0161 (11)	−0.0150 (12)
O21	0.0924 (16)	0.1044 (18)	0.177 (3)	−0.0517 (14)	−0.0298 (15)	−0.0160 (17)

Geometric parameters (Å, º) top

C3—C2	1.370 (3)	C8—H8	0.91 (2)
C3—C4	1.389 (3)	C5—C6	1.371 (3)
C3—H3	0.95 (2)	C5—H5	0.94 (3)
C4—C5	1.395 (3)	C3A—C4A	1.363 (3)
C4—C7	1.464 (3)	C3A—H3A	0.92 (2)
C1—C6	1.381 (3)	N1—O11	1.200 (3)
C1—C2	1.388 (3)	N1—O12	1.211 (3)
C1—C1C	1.437 (3)	C1C—N1C	1.139 (3)
C2—H2	0.91 (2)	C7—H7	0.97 (2)
C6A—C5A	1.370 (3)	N3—O32	1.206 (3)
C6A—C1A	1.397 (3)	N3—O31	1.217 (3)
C6A—N3	1.472 (3)	C5A—C4A	1.374 (3)
C2A—C3A	1.369 (3)	C5A—H5A	0.96 (2)
C2A—C1A	1.401 (3)	C6—H6	1.00 (3)
C2A—N1	1.484 (3)	C4A—N2	1.464 (3)
C8—C7	1.312 (3)	N2—O22	1.202 (3)
C8—C1A	1.472 (3)	N2—O21	1.213 (3)

C2—C3—C4	121.39 (19)	C2A—C3A—H3A	120.2 (14)
C2—C3—H3	120.1 (13)	O11—N1—O12	123.6 (2)
C4—C3—H3	118.5 (13)	O11—N1—C2A	119.96 (19)
C3—C4—C5	118.13 (18)	O12—N1—C2A	116.4 (2)
C3—C4—C7	121.71 (18)	N1C—C1C—C1	178.3 (3)
C5—C4—C7	120.14 (18)	C8—C7—C4	124.83 (19)
C6—C1—C2	119.91 (18)	C8—C7—H7	119.5 (13)
C6—C1—C1C	120.16 (19)	C4—C7—H7	115.5 (13)
C2—C1—C1C	119.92 (19)	O32—N3—O31	125.8 (2)
C3—C2—C1	119.59 (19)	O32—N3—C6A	117.7 (2)
C3—C2—H2	121.1 (14)	O31—N3—C6A	116.5 (3)
C1—C2—H2	119.3 (13)	C6A—C5A—C4A	116.9 (2)
C5A—C6A—C1A	125.10 (19)	C6A—C5A—H5A	117.8 (14)
C5A—C6A—N3	115.15 (18)	C4A—C5A—H5A	125.1 (14)
C1A—C6A—N3	119.60 (17)	C6A—C1A—C2A	113.55 (17)
C3A—C2A—C1A	123.62 (19)	C6A—C1A—C8	121.90 (17)
C3A—C2A—N1	115.90 (18)	C2A—C1A—C8	124.53 (18)
C1A—C2A—N1	120.48 (18)	C5—C6—C1	120.1 (2)
C7—C8—C1A	124.16 (19)	C5—C6—H6	121.8 (15)
C7—C8—H8	122.3 (13)	C1—C6—H6	118.1 (15)
C1A—C8—H8	113.6 (13)	C3A—C4A—C5A	122.16 (19)
C6—C5—C4	120.9 (2)	C3A—C4A—N2	119.4 (2)
C6—C5—H5	118.5 (15)	C5A—C4A—N2	118.4 (2)
C4—C5—H5	120.7 (15)	O22—N2—O21	123.7 (2)
C4A—C3A—C2A	118.6 (2)	O22—N2—C4A	119.0 (2)
C4A—C3A—H3A	121.2 (14)	O21—N2—C4A	117.2 (3)

C2—C3—C4—C5	−0.8 (3)	N3—C6A—C5A—C4A	173.1 (2)
C2—C3—C4—C7	−178.91 (19)	C5A—C6A—C1A—C2A	0.9 (3)
C4—C3—C2—C1	−0.3 (3)	N3—C6A—C1A—C2A	−174.5 (2)
C6—C1—C2—C3	0.9 (3)	C5A—C6A—C1A—C8	−177.5 (2)
C1C—C1—C2—C3	−178.44 (19)	N3—C6A—C1A—C8	7.2 (3)
C3—C4—C5—C6	1.4 (3)	C3A—C2A—C1A—C6A	0.9 (3)
C7—C4—C5—C6	179.5 (2)	N1—C2A—C1A—C6A	−178.91 (18)
C1A—C2A—C3A—C4A	−0.9 (3)	C3A—C2A—C1A—C8	179.2 (2)
N1—C2A—C3A—C4A	178.93 (18)	N1—C2A—C1A—C8	−0.6 (3)
C3A—C2A—N1—O11	174.0 (2)	C7—C8—C1A—C6A	53.8 (3)
C1A—C2A—N1—O11	−6.2 (3)	C7—C8—C1A—C2A	−124.3 (2)
C3A—C2A—N1—O12	−7.4 (3)	C4—C5—C6—C1	−0.9 (3)
C1A—C2A—N1—O12	172.4 (2)	C2—C1—C6—C5	−0.3 (3)
C6—C1—C1C—N1C	−71 (9)	C1C—C1—C6—C5	179.0 (2)
C2—C1—C1C—N1C	109 (9)	C2A—C3A—C4A—C5A	−0.9 (3)
C1A—C8—C7—C4	174.55 (19)	C2A—C3A—C4A—N2	177.55 (19)
C3—C4—C7—C8	−20.7 (3)	C6A—C5A—C4A—C3A	2.4 (3)
C5—C4—C7—C8	161.3 (2)	C6A—C5A—C4A—N2	−176.0 (2)
C5A—C6A—N3—O32	−119.2 (2)	C3A—C4A—N2—O22	−176.2 (2)
C1A—C6A—N3—O32	56.6 (3)	C5A—C4A—N2—O22	2.3 (3)
C5A—C6A—N3—O31	58.5 (3)	C3A—C4A—N2—O21	3.6 (3)
C1A—C6A—N3—O31	−125.7 (2)	C5A—C4A—N2—O21	−177.9 (2)
C1A—C6A—C5A—C4A	−2.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O32ⁱ	0.95 (3)	2.50 (2)	3.294 (3)	142.1 (17)
C5A—H5A···N1Cⁱⁱ	0.96 (2)	2.53 (2)	3.427 (3)	156.3 (19)
C7—H7···O21ⁱⁱⁱ	0.97 (2)	2.53 (2)	3.354 (3)	143.3 (19)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₈N₄O₆
M_r	340.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.183 (1), 8.520 (1), 15.459 (4)
β (°)	94.09 (4)
V (Å³)	1469.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.4 × 0.4 × 0.3

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5370, 2689, 1849
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.02
No. of reflections	2689
No. of parameters	258
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.22

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999), Mercury (Macrae et al., 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O32ⁱ	0.95 (3)	2.50 (2)	3.294 (3)	142.1 (17)
C5A—H5A···N1Cⁱⁱ	0.96 (2)	2.53 (2)	3.427 (3)	156.3 (19)
C7—H7···O21ⁱⁱⁱ	0.97 (2)	2.53 (2)	3.354 (3)	143.3 (19)

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

Acknowledgements

RDB and AC wish to thank the Institute for the Promotion of Innovation by Science and Technology in Flanders (IWT) for a predoctoral grant. Financial support by the University of Antwerp under grant No. GOA-2404 is gratefully acknowledged.

References

Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Garcia, M. H., Mendes, P. J., Robalo, M. P., Dias, A. R., Campo, J., Wenseleers, W. & Goovaerts, E. (2007). J. Organomet. Chem. 692, 3027–3041. Web of Science CrossRef CAS Google Scholar
Garcia, M. H., Robalo, M. P., Dias, A. R., Piedade, M. F. M., Galvao, A., Wenseleers, W. & Goovaerts, E. (2001). J. Organomet. Chem. 619, 252–264. Web of Science CSD CrossRef CAS Google Scholar
Gérard, F. & Hardy, A. (1988). Acta Cryst. C44, 1283–1287. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hanson, J. R., Hitchcock, P. B. & Jones, A. B. (2005). J. Chem. Res. pp. 138–140. CrossRef Google Scholar
Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oehlke, A., Auer, A. A., Jahre, I., Walfort, B., Ruffer, T., Zoufala, P., Lang, H. & Spange, S. (2007). J. Org. Chem. 72, 4328–4339. Web of Science CSD CrossRef PubMed CAS Google Scholar
Robalo, M. P., Teixeira, A. P. S., Garcia, M. H., da Piedade, M. F. M., Duarte, M. T., Dias, A. R., Campo, J., Wenseleers, W. & Goovaerts, E. (2006). Eur. J. Inorg. Chem. pp. 2175–2185. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wenseleers, W., Gerbrandij, A. W., Goovaerts, E., Garcia, M. H., Robalo, M. P., Mendes, P. J., Rodrigues, J. C. & Dias, A. R. (1998). J. Mater. Chem. 8, 925–930. Web of Science CrossRef CAS Google Scholar