Isomers and polymorphs of (E,E)-1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadienes

Glidewell, C.; Low, J.N.; Skakle, J.M.S.; Wardell, J.L.

doi:10.1107/S010876810601439X

research papers

STRUCTURAL SCIENCE
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ISSN: 2052-5206

Volume 62| Part 4| August 2006| Pages 666-675

doi:10.1107/S010876810601439X

Isomers and polymorphs of (E,E)-1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadienes

Christopher Glidewell,^a ^* John N. Low,^b Janet M. S. Skakle ^b and James L. Wardell ^c

^aSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro-RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 28 February 2006; accepted 20 April 2006)

The structures of five of the possible six isomers of (E,E)-1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadiene are reported, including two polymorphs of one of the isomers. (E,E)-1,4-Bis(2-nitrophenyl)-2,3-diaza-1,3-butadiene, C₁₄H₁₀N₄O₄ (I), crystallizes in two polymorphic forms (Ia) and (Ib) in which the molecules lie across centres of inversion in space groups P2₁/n and P2₁/c, respectively: the molecules in (Ia) and (Ib) are linked into chains by aromatic π⋯π stacking interactions and C—H⋯π(arene) hydrogen bonds, respectively. Molecules of (E,E)-1-(2-nitrophenyl)-4-(3-nitrophenyl)-2,3-diaza-1,3-butadiene (II) are linked into sheets by two independent C—H⋯O hydrogen bonds. The molecules of (E,E)-1,4-bis(3-nitrophenyl)-2,3-diaza-1,3-butadiene (III) lie across inversion centres in the space group P2₁/n, and a combination of a C—H⋯O hydrogen bond and a π⋯π stacking interaction links the molecules into sheets. A total of four independent C—H⋯O hydrogen bonds link the molecules of (E,E)-1-(3-nitrophenyl)-4-(4-nitrophenyl)-2,3-diaza-1,3-butadiene (IV) into sheets. In (E,E)-1,4-bis(4-nitrophenyl)-2,3-diaza-1,3-butadiene (V) the molecules, which lie across centres of inversion in the space group P2₁/n, are linked by just two independent C—H⋯O hydrogen bonds into a three-dimensional framework.

Keywords: supramolecular structures; direction-specific intermolecular interactions; polymorphism; hydrogen bonding.

1. Introduction

We have recently reported the supramolecular structures of the three isomeric (E,E)-1-(2-iodophenyl)-4-(nitrophenyl)-2,3-diaza-1,3-butadienes (Glidewell, Low, Skakle & Wardell, 2005 ). In this series, the 2-nitro isomer forms chains, the 3-nitro isomer forms a three-dimensional framework structure, while the 4-nitro isomer forms a sheet structure. In each isomer, a different array of direction-specific intermolecular interactions is manifest: an iodo⋯nitro interaction in the 2-nitro isomer, C—H⋯O and C—H⋯I hydrogen bonds and aromatic π⋯π stacking interactions in the 3-nitro isomer, and a C—H⋯O hydrogen bond and an iodo⋯nitro interaction in the 4-nitro isomer. Intrigued by the changes in intermolecular interactions and the corresponding structural changes consequent upon a simple positional change of a single substituent, we have developed the earlier study to an even simpler series of positional isomers, namely the isomeric (E,E)-1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadienes, O₂NC₆H₄CH=N—N=CHC₆H₄NO₂, and again we observe wide structural variation. We report here the molecular and supramolecular structures of five of the possible six isomeric 1,4-bis(nitrophenyl)-2,3-diaza-1,3-butadienes, compounds (I)–(V) (see Scheme, and Figs. 1–6) and, in addition, we have identified two polymorphs of 1,4-bis(2-nitrophenyl)-2,3-diazabutadiene (I) (Figs. 1 and 2), but we have consistently failed in attempts to synthesize the sixth isomer 1-(2-nitrophenyl)-4-(4-nitrophenyl)-2,3-diaza-1,3-butadiene (VI). Both polymorphs of (I) are monoclinic, but their b-axis vectors differ by a factor of more than two: we denote the polymorph with the shorter b axis as (Ia) and that with the longer b axis as (Ib). The structure of the polymorph denoted here as (Ia) was determined some years ago (Hsu et al., 1993 ) using ambient-temperature diffraction data: however, no discussion of the supramolecular aggregation was given; in particular, the occurrence of the π⋯π stacking interactions (see §3.2.1) went unreported.

Figure 1
The molecule of polymorph (Ia) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and the atoms marked with `a' are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 2
The molecule of polymorph (Ib) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and the atoms marked with `a' are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 3
The molecule of isomer (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4
The molecule of isomer (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and the atoms marked with `a' are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 5
The molecule of isomer (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 6
The molecule of isomer (V) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and the atoms marked with `a' are at the symmetry position (1 − x, 1 − y, 1 − z).

2. Experimental

2.1. Synthesis

Isomers (Ia), (III) and (V) were obtained by heating under reflux a mixture of the appropriate nitrobenzaldehyde (3 mmol) and hydrazine hydrate (1.5 mmol) in methanol (20 cm³) for 30 min, and then leaving the reaction solution at room temperature for 24 h. The products were collected and recrystallized from 1,2-dichloroethane: m.p.s (Ia) 483–486 K, (III) 475–477 K, (V) >500 K. Similar reactions of 3-nitrobenzaldehyde hydrazone with 2-nitro- or 4-nitrobenzaldehyde yielded isomers (II) and (IV); (II) was recrystallized from methanol, m.p. 471–473 K after partial liquifaction at 421–423 K; (IV) was recrystallized from 1,2-dichloroethane, m.p. 480–483 K. Polymorph (Ib) was isolated by recrystallization, from 1,2-dichloroethane, of the initial product obtained by reaction of 2-nitrobenzaldehyde hydrazone and 2-iodobenzaldehyde, m.p. 443–446 K, following loss of crystallinity at 423 K. Despite the reasonably straightforward preparations of the 2,3′ and 3,4′ isomers (II) and (IV), numerous attempts to prepare a sample of the 2,4′ isomer (VI) (see Scheme) have consistently proved fruitless: using either the reaction of 2-nitrobenzaldehyde with 4-nitrobenzaldehyde hydrazone, or that of 4-nitrobenzaldehyde with 2-nitrobenzaldehyde hydrazone, the only crystalline products obtained were the symmetrical isomers (I) and (V). The reasons for this behaviour, so different from that in the preparations of isomers (II) and (IV), are entirely unclear.

2.2. Data collection, structure solution and refinement

Diffraction data for compounds (I)–(III) and (V) were collected at 120 (2) K using a Nonius–Kappa CCD diffractometer; in all these cases graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) was employed. Data for (IV) were collected at 120 (2) K using a Bruker SMART APEX2 diffractometer and synchrotron radiation (λ = 0.6778 Å). Other details of cell data, data collection and refinement are summarized in Table 1, together with details of the software employed.

Table 1
Experimental table

	(Ia)	(Ib)	(II)
Crystal data
Chemical formula	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄
M_r	298.26	298.26	298.26
Cell setting, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c	Monoclinic, P2₁
Temperature (K)	120 (2)	120 (2)	120 (2)
a, b, c (Å)	9.1379 (4), 6.1776 (3), 11.7682 (4)	7.7809 (2), 14.7825 (6), 6.2196 (2)	7.8036 (2), 7.0914 (3), 12.3424 (4)
β (°)	93.853 (3)	113.106 (2)	101.742 (2)
V (Å³)	662.82 (5)	658.00 (4)	668.72 (4)
Z	2	2	2
D_x (Mg m⁻³)	1.494	1.505	1.481
Radiation type	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	1511	1503	1653
θ range (°)	3.5–27.5	3.2–27.5	3.3–27.5
μ (mm⁻¹)	0.11	0.11	0.11
Crystal form, colour	Block, yellow	Block, yellow	Blade, orange
Crystal size (mm)	0.46 × 0.34 × 0.18	0.48 × 0.22 × 0.08	0.50 × 0.32 × 0.12

Data collection
Diffractometer	Bruker–Nonius 95 mm CCD camera on κ-goniostat	Bruker–Nonius 95 mm CCD camera on κ-goniostat	Bruker–Nonius 95 mm CCD camera on κ-goniostat
Data collection method	φ and ω scans	φ and ω scans	φ and ω scans
Absorption correction	Multi-scan	Multi-scan	Multi-scan
T_min	0.967	0.957	0.936
T_max	0.980	0.991	0.987
No. of measured, independent and observed reflections	8093, 1511, 1232	10 780, 1503, 1222	7771, 1653, 1519
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
R_int	0.034	0.043	0.031
θ_max (°)	27.5	27.5	27.5
Range of h, k, l	−10 → h → 11	−9 → h → 10	−10 → h → 10
	−7 → k → 8	−19 → k → 19	−8 → k → 9
	−15 → l → 15	−8 → l → 8	−15 → l → 14

Refinement
Refinement on	F²	F²	F²
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.124, 1.00	0.060, 0.160, 1.02	0.040, 0.107, 1.25
No. of reflections	1511	1503	1653
No. of parameters	100	100	199
H-atom treatment	Constrained to parent site	Constrained to parent site	Constrained to parent site
Weighting scheme	w = 1/[σ²(F_o²) + (0.093P)² + 0.0092P], where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0754P)² + 0.8974P], where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0658P)² + 0.0096P], where P = (F_o² + 2F_c²)/3
(Δ/σ)_max	<0.0001	<0.0001	<0.0001
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.29	1.44, −0.31	0.27, −0.31

	(III)	(IV)	(V)
Crystal data
Chemical formula	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄
M_r	298.26	298.26	298.26
Cell setting, space group	Monoclinic, P2₁/n	Monoclinic, C2/c	Monoclinic, P2₁/n
Temperature (K)	120 (2)	120 (2)	120 (2)
a, b, c (Å)	7.0128 (4), 7.6318 (5), 12.8037 (5)	30.865 (3), 4.7660 (5), 21.736 (2)	3.7318 (2), 7.2442 (3), 23.9367 (10)
β (°)	105.825 (3)	123.926 (2)	94.053 (2)
V (Å³)	659.29 (6)	2653.1 (5)	645.48 (5)
Z	2	8	2
D_x (Mg m⁻³)	1.502	1.493	1.535
Radiation type	Mo Kα	Synchrotron	Mo Kα
No. of reflections for cell parameters	1507	2789	1479
θ range (°)	3.1–27.6	3.0–28.8	2.9–27.6
μ (mm⁻¹)	0.11	0.11	0.12
Crystal form, colour	Plate, yellow	Lath, yellow	Lath, yellow
Crystal size (mm)	0.43 × 0.30 × 0.08	0.10 × 0.06 × 0.01	0.40 × 0.10 × 0.01

Data collection
Diffractometer	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker SMART APEX2 CCD diffractometer	Bruker–Nonius 95 mm CCD camera on κ goniostat
Data collection method	φ and ω scans	Fine-slice ω scans	φ and ω scans
Absorption correction	Multi-scan	Multi-scan	Multi-scan
T_min	0.969	0.980	0.949
T_max	0.991	0.999	0.999
No. of measured, independent and observed reflections	7854, 1507, 1095	14 589, 3961, 2817	6443, 1479, 1239
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
R_int	0.061	0.034	0.049
θ_max (°)	27.6	29.0	27.6
Range of h, k, l	−9 → h → 9	−43 → h → 44	−4 → h → 4
	−9 → k → 9	−6 → k → 6	−9 → k → 9
	−16 → l → 14	−30 → l → 30	−30 → l → 31

Refinement
Refinement on	F²	F²	F²
R[F²> 2σ(F²)], wR(F²), S	0.044, 0.122, 1.04	0.057, 0.170, 1.09	0.041, 0.110, 1.06
No. of reflections	1507	3961	1479
No. of parameters	100	199	100
H-atom treatment	Constrained to parent site	Constrained to parent site	Constrained to parent site
Weighting scheme	w = 1/[σ²(F_o²) + (0.068P)² + 0.1014P], where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.095P)² + 1.033P], where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0454P)² + 0.3185P], where P = (F_o² + 2F_c²)/3
(Δ/σ)_max	<0.0001	0.001	0.001
Δρ_max, Δρ_min (e Å^–3)	0.20, −0.35	0.44, −0.26	0.24, −0.24
Computer programs used: COLLECT (Hooft, 1999 ), APEX2 (Bruker AXS Inc., 2004 ), DENZO (Otwinowski & Minor, 1997 ), SAINT (Bruker AXS Inc., 2004), OSCAIL (McArdle, 2003 ), SHELXS97 (Sheldrick, 1997 ), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PRPKAPPA (Ferguson, 1999 ), SADABS (Sheldrick, 2003 ).

For each of (Ia), (III) and (V), the space group P2₁/n was uniquely assigned from the systematic absences; likewise the space group P2₁/c was uniquely assigned for (Ib). For isomer (II) the systematic absences permitted P2₁ and P2₁/m as possible space groups: from a consideration of the unit-cell volume and the likely value of Z′, the space group P2₁ was selected and subsequently confirmed by the structure analysis. For isomer (IV), the systematic absences permitted Cc and C2/c as possible space groups: C2/c was selected and subsequently confirmed by the structure analysis.

The structures were solved by direct methods and refined with all data on F². A weighting scheme based upon P = [F_o² + 2F_c²]/3 was employed in order to reduce statistical bias (Wilson, 1976 ). All H atoms were located from difference maps and then treated as riding atoms with C—H distances of 0.95 Å and with U_iso(H) = 1.2U_eq(C). In the absence of significant anomalous dispersion, the Flack parameter (Flack, 1983 ) for (II) was inconclusive (Flack & Bernardinelli, 2000 ): hence the Friedel-equivalent reflections were merged prior to the final refinements and it was not possible to determine the correct orientation of the structure relative to the polar-axis direction (Jones, 1986 ). In isomer (Ib), the maximum residual density, 1.438 e Å⁻³, is located 0.93 Å from the C4 atom, lying almost equidistant from H4 and H5, while the largest hole, −0.306 e Å⁻³, is located 0.62 Å from N2: no plausible disorder model can be developed to take account of these extrema.

Supramolecular analyses were made and the diagrams were prepared with the aid of PLATON (Spek, 2003 ). Details of molecular conformations are given in Table 2, and details of hydrogen-bond dimensions are given in Table 3.¹

Table 2
Selected torsional angles (°)

(a) Centrosymmetric isomers
Parameter	(Ia)	(Ib)	(III)	(V)
N1ⁱ—N1—C7—C1	−176.75 (11)	−176.8 (2)	−179.28 (14)	179.48 (13)
N1—C7—C1—C2	−146.55 (12)	−149.4 (2)	−3.0 (2)	178.82 (13)
C1—C2—N2—O21	19.17 (15)	21.2 (3)	–	–
C2—C3—N3—O31	–	–	−3.83 (19)	–
C3—C4—N4—O41	–	–	–	9.71 (19)

(b) Non-centrosymmetric isomers
Parameter	(II)	(IV)
C17—N11—N21—C27	175.13 (18)	−172.53 (14)
N21—N11—C17—C11	−179.66 (18)	−179.43 (13)
N11—C17—C11—C12	−159.7 (2)	6.4 (2)
N11—N21—C27—C21	179.39 (17	−178.92 (14)
N21—C27—C21—C22	165.11 (19)	−175.28 (15)
C11—C12—N12—O121	25.1 (3)	–
C22—C23—N23—O231	−3.9 (3)	–
C12—C13—N13—O131	–	−1.5 (2)
C23—C24—N24—O241	–	−0.1 (2)
Symmetry code: (i) 1 − x, 1 − y, 1 − z.

Table 3
Selected hydrogen-bond parameters (Å, ^o)

D—H⋯A	H⋯A	D⋯A	D—H⋯A
(Ib)
C3—H3⋯Cg1ⁱ†	2.89	3.568 (2)	129

(II)
C14—H14⋯O232ⁱⁱ	2.45	3.178 (3)	134
C22—H22⋯O231ⁱⁱⁱ	2.51	3.289 (3)	139

(III)
C4—H4⋯O32^iv	2.50	3.448 (2)	176

(IV)
C14—H14⋯O132^v	2.44	3.309 (3)	151
C17—H17⋯O242^vi	2.42	3.262 (2)	147
C22—H22⋯O131^vii	2.51	3.363 (3)	149
C27—H27⋯O131^vii	2.53	3.383 (2)	149

(V)
C3—H3⋯O41^viii	2.50	3.186 (2)	129
C7—H7⋯O42^ix	2.47	3.343 (2)	152
Symmetry codes: (i) $[x, {3\over 2}- y, -{1\over 2} + z]$ ; (ii) 1 + x, 2 + y, z; (iii) $[1 - x, {1\over 2} + y, 1 - z]$ ; (iv) -1 - x, -y, 1 - z; (v) 1 - x, -2 - y, 1 - z; (vi) $[{3\over 2} - x, {3\over 2} - y, 1 - z]$ ; (vii) $[1 - x, 1 + y, {1\over 2} - z]$ ; (viii) $[{3\over 2} - x, -{1\over 2} + y, {3\over 2} - z]$ ; (ix) 1 + x, -1 + y, z.

†Cg1 is the centroid of ring C1–C6.

3. Results and discussion

3.1. Molecular conformations

In the symmetrically substituted isomers (I), (III) and (V), the molecules lie across centres of inversion, and in all of the isomers the central C—C=N—N=C—C fragment has an all-transoid conformation and it is essentially planar, as shown by the leading torsional angles (Table 2). In both polymorphs of (I), where there is a 2-nitro substituent, the aryl rings are significantly twisted out of the plane of the central spacer unit, and the molecular conformations are very similar, as shown by the leading torsional angles (Table 2). However, in isomers (III) and (V), containing 3-nitro and 4-nitro substituents, respectively, the aryl rings are almost coplanar with the spacer unit. In (III) the nitro group is on the edge of the molecule remote from the methine C—H bond, whereas in both polymorphs of (I) the two groups are on the same edge (Table 2; Figs. 1, 2 and 4). In isomer (II) both of the independent nitro groups are on the same edges of the molecules as the nearest methine C—H bond, whereas the 3-nitro group in isomer (IV) is remote from the corresponding C—H bond (Table 2; Figs. 3 and 5). In all of compounds (I)–(V), the bond lengths and angles present no unusual features.

3.2. Supramolecular aggregation

3.2.1. Polymorphs of isomer (I), 1,4-bis(2-nitrophenyl)-2,3-diaza-1,3-butadiene

The supramolecular aggregation of the two polymorphs (Ia) and (Ib) of isomer (I) differs significantly: the supramolecular aggregation is determined in (Ia) by an aromatic π⋯π stacking interaction and in (Ib) by a C—H⋯π(arene) hydrogen bond: π⋯π stacking interactions are absent from the structure of (Ib).

The aryl rings in (Ia) at (x, y, z) and (−x, 2 − y, 1 − z) are components of the molecules across the inversion centres at (0.5, 0.5, 0.5) and (−0.5, 1.5, 0.5), respectively. These two rings are strictly parallel with an interplanar spacing of 3.569 (2) Å; the ring–centroid separation is 3.887 (2) Å, corresponding to a nearly ideal centroid offset of 1.539 (2) Å. Propagation by inversion of this interaction then leads to the formation of a π-stacked chain of centrosymmetric molecules running parallel to the [ $[1\bar10]$ ] direction (Fig. 7).

Figure 7
Stereoview of part of the crystal structure of polymorph (Ia) showing the formation of a π-stacked chain along [ $[1\bar10]$ ]. For the sake of clarity the H atoms have all been omitted.

In polymorph (Ib) the chain structure is generated by a single C—H⋯π(arene) hydrogen bond (Table 3). The aryl C3 atom in the ring at (x, y, z) is part of the molecule centred across (½, ½, ½): this atom acts as a hydrogen-bond donor to the aryl ring at (x, $[{3\over 2}]$ − y, −½ + z), which forms part of the molecule centred across (½, 1, 0). Propagation of this hydrogen bond then forms a zigzag chain running parallel to the [ $[01\bar1]$ ] direction and generated by the c-glide plane at y = 0.75 (Fig. 8). In the structures of both (Ia) and (Ib) two chains pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

Figure 8
Stereoview of part of the crystal structure of polymorph (Ib) showing the formation of a hydrogen-bonded chain along [ $[01\bar1]$ ]. For the sake of clarity the H atoms not involved in the motif shown have been omitted.

3.2.2. Isomer (II), 1-(2-nitrophenyl)-4-(3-nitrophenyl)-2,3-diaza-1,3-butadiene

In contrast to the dimorphism observed for (I), only a single polymorph has been observed for the isomeric 1-(2-nitrophenyl)-4-(3-nitrophenyl)-2,3-diazabutadiene (II) (Fig. 3). In this isomer the molecules lie in general positions in the non-centrosymmetric space group P2₁, but the molecular skeleton apart from the nitro groups is nearly centrosymmetric, as shown by the principal torsional angles (Table 2).

The two-dimensional supramolecular structure of isomer (II) is built from two independent C—H⋯O hydrogen bonds (Table 3), augmented by a π⋯π stacking interaction: C—H⋯π(arene) hydrogen bonds are absent, however. The aryl C22 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the nitro O231 atom in the molecule at (1 − x, ½ + y, 1 − z), so forming a spiral C(5) chain (Bernstein et al., 1995 ) running parallel to the [010] direction and generated by the 2₁ screw axis along (½, y, ½) (Fig. 9). At the same time, the aryl C14 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the nitro O232 atom in the molecule at (1 + x, 2 + y, z), so generating by translation a C(14) chain running parallel to the [120] direction (Fig. 10). It is notable that the two O acceptor atoms in (II) belong to the same nitro group: the second nitro group containing the N12 atom plays no part in the hydrogen bonding. The combination of the [101] and [120] chains generates a (001) sheet, which is reinforced by the π⋯π stacking interaction.

Figure 9
Stereoview of part of the crystal structure of isomer (II) showing the formation of a hydrogen-bonded C(5) chain along [010]. For the sake of clarity the H atoms not involved in the motif shown have been omitted.

Figure 10
Stereoview of part of the crystal structure of isomer (II) showing the formation of a hydrogen-bonded C(14) chain along [120]. For the sake of clarity the H atoms not involved in the motif shown have been omitted.

The aryl rings C11–C16 and C21–C26 in the molecules at (x, y, z) and (1 + x, 1 + y, z), respectively, make a dihedral angle of only 1.1 (2)°. The ring–centroid separation is 3.722 (2) Å and the interplanar spacing is ca 3.42 Å, corresponding to a centroid offset of ca 1.48 Å. In this manner a [110] chain is produced (Fig. 11), which lies wholly within the hydrogen-bonded (001) sheet. There are no direction-specific interactions between adjacent sheets.

Figure 11
Stereoview of part of the crystal structure of isomer (II) showing the formation of a π-stacked chain along [110]. For the sake of clarity the H atoms have all been omitted.

3.2.3. Isomer (III), 1,4-bis(3-nitrophenyl)-2,3-diaza-1,3-butadiene

The molecules of the 3,3′ isomer (III) (Fig. 4) lie across centres of inversion in the space group P2₁/n with the reference molecule selected as that lying across (½, ½, ½). The molecules are effectively planar, and they are linked into chains of rings by a single C—H⋯O hydrogen bond (Table 3), and the chains are further linked into sheets by a single π⋯π stacking interaction. The aryl C4 atom at (x, y, z), which lies in the molecule centred at (½, ½, ½), acts as a hydrogen-bond donor to the nitro O32 atom at (−1 − x, −y, 1 − z), which lies in the molecule centred at (− $[3\over 2]$ , −½, ½): propagation by inversion of this single hydrogen bond then generates a C(14)[R₂²(10)] chain of rings running parallel to the [210] direction (Fig. 12).

Figure 12
Stereoview of part of the crystal structure of isomer (III) showing the formation of a hydrogen-bonded chain of rings along [210]. For the sake of clarity the H atoms not involved in the motif shown have been omitted.

The aryl rings at (x, y, z) and (−x, −y, 1 − z), which form parts of the molecules of (III) centred at (½, ½, ½) and (−½, −½, ½), respectively, are strictly parallel with an interplanar spacing of 3.344 (2) Å; the ring–centroid separation is 3.784 (2) Å, corresponding to a ring offset of 1.770 (2) Å. Propagation by inversion of this π-stacking interaction then generates a chain running parallel to the [110] direction (Fig. 13). The combination of [110] and [210] chains generates a (001) sheet, but there are no direction-specific interactions between adjacent sheets.

Figure 13
Stereoview of part of the crystal structure of isomer (III) showing the formation of a π-stacked chain along [110]. For the sake of clarity the H atoms have been omitted.

3.2.4. Isomer (IV), 1-(3-nitrophenyl)-4-(4-nitrophenyl)-2,3-diaza-1,3-butadiene

Although the molecules of the 3,4′ isomer (IV) (Fig. 5) have no crystallographic symmetry, nonetheless they are very nearly planar. The two-dimensional aggregation is determined by four C—H⋯O hydrogen bonds (Table 3), but it can readily be analysed in terms of two one-dimensional substructures. In the first of these substructures, the aryl C14 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the nitro O132 atom in the molecule at (1 − x, −2 − y, 1 − z), thereby forming an R₂²(10) ring centred at (½, −1, ½): similarly, the methine C17 atom at (x, y, z) acts as a donor to the nitro O242 atom in the molecule at ( $[3\over 2]$ − x, $[3\over 2]$ − y, 1 − z), so forming an R₂²(22) ring centred at ( $[3\over 4]$ , $[3\over 4]$ , ½). Propagation by inversion of these two interactions then generates a C₂²(22)[R₂²(10)][R₂²(22)] chain of rings running parallel to the [170] direction (Fig. 14). In the second substructure, atoms C22 and C27 in the molecule at (x, y, z) both act as donors to the nitro O131 atom in the molecule at (1 − x, 1 + y, ½ − z), while C22 and C27 at (1 − x, 1 + y, ½ − z) in turn act as donors to O131 at (x, 2 + y, z). In this way a pair of C(10)C(12)[R₂¹(6)] chains of rings (Fig. 15) is generated by the twofold rotation axis along (½, y, $[1\over 4]$ ), forming a double helix running parallel to the [010] direction (Fig. 16). The combination of the [170] and [010] chains generates a (001) sheet.

Figure 14
Stereoview of part of the crystal structure of isomer (IV) showing the formation of a chain along [170] containing R₂²(10) and R₂²(22) rings. For the sake of clarity the H atoms not involved in the motif shown have been omitted.

Figure 15
Part of the crystal structure of isomer (IV) showing the formation of a [010] chain of rings along [010]. For the sake of clarity the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, 1 + y, ½ − z) and (x, 2 + y, z), respectively.

Figure 16
Stereoview of part of the crystal structure of isomer (IV), showing the formation of a hydrogen-bonded double helix along [010]. For the sake of clarity the H atoms not involved in the motif shown have been omitted.

3.2.5. Isomer (V), 1,4-bis(4-nitrophenyl)-2,3-diaza-1,3-butadiene

The molecules of the 4,4′ isomer (V) (Fig. 6) lie across centres of inversion in the space group P2₁/n with the reference molecule selected as that lying across (½, ½, ½). With the exception of the nitro groups, the molecules are effectively planar (Table 2). The supramolecular aggregation in (V) is dominated by two C—H⋯O hydrogen bonds, one much stronger than the other (Table 3). The overall effect of these interactions is to link the molecules into a three-dimensional framework, and the formation of this framework is most readily analysed in terms of two substructures, each generated by a single hydrogen bond. In the stronger interaction, the methine C7 atom at (x, y, z) acts as a hydrogen-bond donor to the nitro O41 atom at (1 + x, −1 + y, z): propagation of this interaction by translation and inversion then leads to the formation of a chain of edge-fused centrosymmetric R₂²(22) rings running parallel to the [ $[1\bar10]$ ] direction (Fig. 17).

Figure 17
Part of the crystal structure of isomer (V) showing the formation of a chain of edge-fused R₂²(22) rings along [ $[1\bar10]$ ]. For the sake of clarity the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1 − x, 1 − y, 1 − z), (1 + x, −1 + y, z) and (2 − x, −y, 1 − z), respectively.

In contrast to the stronger hydrogen bond, which generates a one-dimensional substructure, the weaker interaction generates a substructure which is two-dimensional. The aryl atoms C3 at (x, y, z) and (1 − x, 1 − y, 1 − z), which both form part of the molecule centred at (½, ½, ½), act as hydrogen-bond donors, respectively, to the nitro O41 atoms at ( $[3\over 2]$ − x, −½ + y, $[3\over 2]$ − z) and (−½ + x, $[3\over 2]$ − y, −½ + z), which themselves lie in the molecules centred at (1, 0, 1) and (0, 1, 0), respectively. Similarly, the O41 atoms at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from C3 atoms at ( $[3\over 2]$ − x, ½ + y, $[3\over 2]$ − z) and (−½ + x, ½ − y, −½ + z), respectively, which are components of the molecules centred at (1, 1, 1) and (0, 0, 0), respectively. Propagation of this hydrogen bond then generates a ( $[10\bar1]$ ) sheet in the form of a (4, 4) net (Batten & Robson, 1998 ) built from a single type of R₄⁴(38) ring (Fig. 18). The combination of the [ $[1\bar10]$ ] chains and ( $[10\bar1]$ ) sheets suffices to link all of the molecules into a single framework, from which C—H⋯π(arene) hydrogen bonds and aromatic π⋯π stacking interactions are, however, both absent.

Figure 18
Stereoview of part of the crystal structure of isomer (V) showing the formation of a sheet of R₄⁴(38) rings parallel to ( $[10\bar1]$ ). For the sake of clarity the H atoms not involved in the motif shown have been omitted.

3.2.6. General discussion of the structures

In making comparisons between the supramolecular aggregation patterns of the various forms of bis(nitrobenzaldehyde)azine, it is convenient to consider firstly the symmetrically substituted isomers and then the non-symmetric forms. The supramolecular structures of the two polymorphs (Ia) and (Ib) of the 2,2′-isomer are both one-dimensional (Figs. 7 and 8), but they depend upon different intermolecular interactions, π⋯π stacking in (Ia) and a C—H⋯π(arene) hydrogen bond in (Ib). In the 3,3′-isomer (III) the supramolecular structure is two-dimensional, utilizing a C—H⋯O hydrogen bond and a π⋯π stacking interaction, while in the 4,4′-isomer (V) the only direction-specific intermolecular interactions are two independent C—H⋯O hydrogen bonds which generate a three-dimensional structure. Thus, these symmetrical isomers can form supramolecular structures which are one-, two- or three-dimensional, and in which no two exhibit the same types of intermolecular interaction.

Amongst the three non-symmetrically substituted isomers, the 2,3′-isomer (II) forms a two-dimensional supramolecular structure dominated by two C—H⋯O hydrogen bonds, and the structure of the 3,4′-isomer (IV) is again two-dimensional but here determined by four independent C—H⋯O hydrogen bonds.

Within the two- and three-dimensional structures a wide variety of low-dimensional substructures can be discerned, including simple chains in the 2,3′-isomer (II) (Figs. 9 and 10), chains of rings in both the 3,3′-isomer (III) and the 3,4′-isomer (IV), including a double-helical chain in (IV) (Figs. 12, 14, 15 and 16), and both chains of edge-fused rings and sheets of R₄⁴(38) rings in the 4,4′-isomer (V) (Figs. 17 and 18).

These supramolecular structures are built from C—H⋯O and C—H⋯π(arene) hydrogen bonds and aromatic π⋯π stacking interactions although, perhaps surprisingly, C—H⋯N hydrogen bonds are absent. All of these interactions are comparatively weak; accordingly, the computational modelling and prediction of crystal structures in which interactions of this type are the only direction-specific intermolecular interactions present, is fraught with difficulty. Despite considerable effort in recent years, reliable predictive methods for such structures remain elusive: extended series of isomeric compounds, such as those whose structures are described here, will provide a keen test of computational methods for structure prediction.

4. Concluding remarks

The supramolecular structures of (Ia), (Ib) and (II)–(V) all exhibit different combinations of direction-specific intermolecular interactions, and different overall patterns of supramolecular aggregation. Accordingly it is not possible to make a reliable prediction of the supramolecular molecular structure of isomer (VI). To the extent that no one structure in this series can be predicted, even with knowledge of all the others, the series under study here neatly mimics the behaviour of other extended series of simple positional isomers which we have studied recently, including iodo-arene-nitroarenesulfonamides (Kelly et al., 2002 ), nitrobenzylidene-iodoanilines, where solvent-dependent polymorphism occurs (Glidewell, Howie et al., 2002 ; Ferguson et al., 2005 ), iodo-N-(nitrobenzyl)anilines (Glidewell, Low et al., 2002 ) and N-iodophenyl)nitrophthalimides (Glidewell, Low, Skakle, Wardell & Wardell, 2005 ). In each of these series, every isomer manifests a distinct pattern of intermolecular interactions such that predictions on further isomers become merely speculative. The occurrence of polymorphism in two of these series adds to the overall complexity, which presents a keen challenge to computational methods for crystal structure prediction.

Supporting information

Crystal structure: contains datablocks global, Ia, Ib, II, III, IV, V. DOI: 10.1107/S010876810601439X/bm5032sup1.cif

Structure factors: contains datablock . DOI: 10.1107/S010876810601439X/bm5032Iasup2.fcf

Structure factors: contains datablock . DOI: 10.1107/S010876810601439X/bm5032Ibsup3.fcf

Structure factors: contains datablock . DOI: 10.1107/S010876810601439X/bm5032IIsup4.fcf

Structure factors: contains datablock . DOI: 10.1107/S010876810601439X/bm5032IIIsup5.fcf

Structure factors: contains datablock . DOI: 10.1107/S010876810601439X/bm5032IVsup6.fcf

Structure factors: contains datablock . DOI: 10.1107/S010876810601439X/bm5032Vsup7.fcf

Comment top

In full text version

Experimental top

In full text version

Computing details top

Data collection: COLLECT (Hooft, 1999) for (Ia), (Ib), (II), (III), (V); Bruker APEX2 for (IV). Cell refinement: DENZO (Otwinowski & Minor, 1997) & COLLECT for (Ia), (Ib), (II), (III), (V); Bruker SAINT for (IV). Data reduction: DENZO & COLLECT for (Ia), (Ib), (II), (III), (V); Bruker SAINT for (IV). Program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (Ia), (Ib), (II), (III), (V); SHELXS97 (Sheldrick, 1997) for (IV). Program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997) for (Ia), (Ib), (II), (III), (V); SHELXL97 (Sheldrick, 1997) for (IV). For all compounds, molecular graphics: PLATON (Spek, 2003). Software used to prepare material for publication: SHELXL97 macro PRPKAPPA (Ferguson, 1999) for (Ia), (Ib), (II), (III), (V); SHELXL97 and PRPKAPPA (Ferguson, 1999) for (IV).

Figures top

In full text version

(Ia) (E,E)-1,4-Bis(2-nitrophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀N₄O₄	F(000) = 308
M_r = 298.26	D_x = 1.494 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1511 reflections
a = 9.1379 (4) Å	θ = 3.5–27.5°
b = 6.1776 (3) Å	µ = 0.11 mm⁻¹
c = 11.7682 (4) Å	T = 120 K
β = 93.853 (3)°	Block, yellow
V = 662.82 (5) Å³	0.46 × 0.34 × 0.18 mm
Z = 2

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	1511 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1232 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ϕ & ω scans	h = −10→11
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	k = −7→8
T_min = 0.967, T_max = 0.980	l = −15→15
8093 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.093P)² + 0.0092P] where P = (F_o² + 2F_c²)/3
1511 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₄	V = 662.82 (5) Å³
M_r = 298.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1379 (4) Å	µ = 0.11 mm⁻¹
b = 6.1776 (3) Å	T = 120 K
c = 11.7682 (4) Å	0.46 × 0.34 × 0.18 mm
β = 93.853 (3)°

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	1511 independent reflections
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	1232 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.980	R_int = 0.034
8093 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
1511 reflections	Δρ_min = −0.29 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
O21	0.46979 (8)	0.98902 (15)	0.69804 (7)	0.0251 (3)
O22	0.30848 (9)	1.22318 (15)	0.74435 (7)	0.0301 (3)
N1	0.46268 (10)	0.58815 (16)	0.47246 (8)	0.0211 (3)
N2	0.35647 (10)	1.09231 (16)	0.67747 (8)	0.0202 (3)
C1	0.29761 (12)	0.87752 (18)	0.50217 (9)	0.0193 (3)
C2	0.27452 (12)	1.06186 (19)	0.56715 (9)	0.0185 (3)
C3	0.17968 (12)	1.22613 (19)	0.53063 (10)	0.0236 (3)
C4	0.10725 (14)	1.2111 (2)	0.42404 (11)	0.0294 (3)
C5	0.12914 (13)	1.0315 (2)	0.35656 (10)	0.0288 (3)
C6	0.22146 (13)	0.8663 (2)	0.39507 (10)	0.0249 (3)
C7	0.39007 (12)	0.69393 (18)	0.54258 (9)	0.0194 (3)
H3	0.1646	1.3474	0.5781	0.028*
H4	0.0428	1.3232	0.3971	0.035*
H5	0.0801	1.0221	0.2830	0.035*
H6	0.2335	0.7432	0.3482	0.030*
H7	0.3955	0.6546	0.6208	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O21	0.0213 (5)	0.0273 (5)	0.0260 (4)	0.0033 (4)	−0.0032 (3)	−0.0006 (3)
O22	0.0314 (5)	0.0331 (6)	0.0261 (5)	0.0043 (4)	0.0042 (4)	−0.0111 (4)
N1	0.0226 (5)	0.0182 (5)	0.0228 (5)	0.0019 (4)	0.0031 (4)	0.0005 (4)
N2	0.0208 (5)	0.0194 (5)	0.0206 (5)	−0.0013 (4)	0.0034 (4)	−0.0009 (4)
C1	0.0172 (6)	0.0215 (6)	0.0195 (6)	−0.0012 (5)	0.0042 (4)	0.0007 (5)
C2	0.0159 (6)	0.0215 (6)	0.0183 (5)	−0.0011 (4)	0.0019 (4)	0.0016 (4)
C3	0.0213 (6)	0.0210 (6)	0.0288 (6)	0.0002 (5)	0.0030 (5)	0.0010 (5)
C4	0.0238 (6)	0.0301 (7)	0.0336 (7)	0.0039 (5)	−0.0025 (5)	0.0096 (5)
C5	0.0257 (7)	0.0389 (8)	0.0212 (6)	−0.0017 (6)	−0.0030 (5)	0.0048 (5)
C6	0.0231 (6)	0.0307 (7)	0.0211 (6)	−0.0017 (5)	0.0019 (5)	−0.0030 (5)
C7	0.0198 (6)	0.0194 (6)	0.0188 (5)	−0.0016 (4)	0.0012 (4)	−0.0009 (4)

Geometric parameters (Å, º) top

N1—C7	1.2735 (15)	N2—O22	1.2295 (13)
N1—N1ⁱ	1.4186 (18)	C3—C4	1.3815 (17)
C7—C1	1.4739 (16)	C3—H3	0.95
C7—H7	0.95	C4—C5	1.386 (2)
C1—C2	1.3956 (16)	C4—H4	0.95
C1—C6	1.3998 (16)	C5—C6	1.3814 (18)
C2—C3	1.3840 (16)	C5—H5	0.95
C2—N2	1.4667 (14)	C6—H6	0.95
N2—O21	1.2265 (12)

C7—N1—N1ⁱ	110.69 (11)	C4—C3—C2	118.96 (11)
N1—C7—C1	119.87 (10)	C4—C3—H3	120.5
N1—C7—H7	120.1	C2—C3—H3	120.5
C1—C7—H7	120.1	C3—C4—C5	119.69 (11)
C2—C1—C6	116.72 (11)	C3—C4—H4	120.2
C2—C1—C7	123.75 (10)	C5—C4—H4	120.2
C6—C1—C7	119.46 (11)	C6—C5—C4	120.78 (11)
C3—C2—C1	122.87 (11)	C6—C5—H5	119.6
C3—C2—N2	116.91 (10)	C4—C5—H5	119.6
C1—C2—N2	120.18 (10)	C5—C6—C1	120.95 (11)
O21—N2—O22	123.27 (9)	C5—C6—H6	119.5
O21—N2—C2	118.82 (9)	C1—C6—H6	119.5
O22—N2—C2	117.91 (9)

N1ⁱ—N1—C7—C1	−176.75 (11)	C3—C2—N2—O22	20.50 (15)
N1—C7—C1—C2	−146.55 (12)	C1—C2—N2—O22	−161.76 (11)
N1—C7—C1—C6	36.77 (16)	C1—C2—C3—C4	−1.80 (18)
C6—C1—C2—C3	1.16 (18)	N2—C2—C3—C4	175.89 (10)
C7—C1—C2—C3	−175.60 (10)	C2—C3—C4—C5	0.85 (18)
C6—C1—C2—N2	−176.45 (9)	C3—C4—C5—C6	0.7 (2)
C7—C1—C2—N2	6.79 (17)	C4—C5—C6—C1	−1.3 (2)
C3—C2—N2—O21	−158.58 (10)	C2—C1—C6—C5	0.40 (18)
C1—C2—N2—O21	19.17 (15)	C7—C1—C6—C5	177.31 (11)

Symmetry code: (i) −x+1, −y+1, −z+1.

(Ib) (E,E)-1,4-Bis(2-nitrophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀N₄O₄	F(000) = 308
M_r = 298.26	D_x = 1.505 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1503 reflections
a = 7.7809 (2) Å	θ = 3.2–27.5°
b = 14.7825 (6) Å	µ = 0.11 mm⁻¹
c = 6.2196 (2) Å	T = 120 K
β = 113.106 (2)°	Block, yellow
V = 658.00 (4) Å³	0.48 × 0.22 × 0.08 mm
Z = 2

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	1503 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ & ω scans	h = −9→10
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	k = −19→19
T_min = 0.957, T_max = 0.991	l = −8→8
10780 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0754P)² + 0.8974P] where P = (F_o² + 2F_c²)/3
1503 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 1.44 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₄	V = 658.00 (4) Å³
M_r = 298.26	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7809 (2) Å	µ = 0.11 mm⁻¹
b = 14.7825 (6) Å	T = 120 K
c = 6.2196 (2) Å	0.48 × 0.22 × 0.08 mm
β = 113.106 (2)°

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	1503 independent reflections
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	1222 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.991	R_int = 0.043
10780 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.02	Δρ_max = 1.44 e Å⁻³
1503 reflections	Δρ_min = −0.31 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
O21	0.7127 (2)	0.61167 (11)	0.0804 (3)	0.0260 (4)
O22	0.6322 (2)	0.71425 (11)	−0.1895 (3)	0.0295 (4)
N1	0.4327 (3)	0.50685 (13)	0.3852 (3)	0.0227 (4)
N2	0.5951 (3)	0.65689 (12)	−0.0702 (3)	0.0214 (4)
C1	0.3442 (3)	0.60172 (14)	0.0518 (4)	0.0202 (5)
C2	0.3975 (3)	0.64220 (14)	−0.1167 (4)	0.0195 (5)
C3	0.2679 (3)	0.66893 (15)	−0.3334 (4)	0.0241 (5)
C4	0.0765 (4)	0.65544 (17)	−0.3887 (4)	0.0309 (6)
C5	0.0223 (3)	0.61676 (17)	−0.2229 (4)	0.0307 (6)
C6	0.1530 (3)	0.59099 (16)	−0.0072 (4)	0.0251 (5)
C7	0.4746 (3)	0.57464 (15)	0.2876 (4)	0.0198 (5)
H3	0.3082	0.6962	−0.4438	0.029*
H4	−0.0139	0.6726	−0.5372	0.037*
H5	−0.1068	0.6078	−0.2577	0.037*
H6	0.1115	0.5653	0.1041	0.030*
H7	0.5876	0.6070	0.3656	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O21	0.0241 (8)	0.0289 (9)	0.0234 (8)	0.0034 (6)	0.0078 (7)	0.0022 (6)
O22	0.0322 (9)	0.0272 (9)	0.0353 (10)	−0.0017 (7)	0.0197 (8)	0.0071 (7)
N1	0.0283 (10)	0.0227 (10)	0.0168 (9)	−0.0007 (7)	0.0086 (8)	0.0015 (7)
N2	0.0255 (10)	0.0190 (9)	0.0226 (9)	−0.0004 (7)	0.0123 (8)	−0.0023 (7)
C1	0.0249 (11)	0.0152 (10)	0.0215 (11)	−0.0010 (8)	0.0102 (9)	−0.0009 (8)
C2	0.0206 (10)	0.0174 (10)	0.0211 (10)	−0.0001 (8)	0.0090 (8)	−0.0013 (8)
C3	0.0292 (12)	0.0220 (11)	0.0213 (11)	0.0015 (9)	0.0102 (9)	0.0028 (8)
C4	0.0352 (13)	0.0315 (13)	0.0222 (11)	0.0090 (10)	0.0073 (10)	0.0067 (10)
C5	0.0233 (11)	0.0331 (13)	0.0341 (13)	−0.0001 (10)	0.0094 (10)	0.0021 (11)
C6	0.0252 (12)	0.0251 (11)	0.0263 (12)	−0.0021 (9)	0.0115 (9)	0.0015 (9)
C7	0.0221 (10)	0.0202 (10)	0.0179 (10)	−0.0013 (8)	0.0085 (8)	−0.0006 (8)

Geometric parameters (Å, º) top

N1—C7	1.278 (3)	N2—O22	1.233 (2)
N1—N1ⁱ	1.415 (4)	C3—C4	1.405 (4)
C7—C1	1.474 (3)	C3—H3	0.95
C7—H7	0.95	C4—C5	1.382 (4)
C1—C6	1.395 (3)	C4—H4	0.95
C1—C2	1.403 (3)	C5—C6	1.381 (3)
C2—C3	1.386 (3)	C5—H5	0.95
C2—N2	1.465 (3)	C6—H6	0.95
N2—O21	1.221 (2)

C7—N1—N1ⁱ	111.4 (2)	C2—C3—C4	119.6 (2)
N1—C7—C1	118.77 (19)	C2—C3—H3	120.2
N1—C7—H7	120.6	C4—C3—H3	120.2
C1—C7—H7	120.6	C5—C4—C3	118.7 (2)
C6—C1—C2	116.7 (2)	C5—C4—H4	120.6
C6—C1—C7	118.50 (19)	C3—C4—H4	120.6
C2—C1—C7	124.69 (19)	C6—C5—C4	121.0 (2)
C3—C2—C1	122.1 (2)	C6—C5—H5	119.5
C3—C2—N2	117.17 (19)	C4—C5—H5	119.5
C1—C2—N2	120.70 (19)	C5—C6—C1	121.8 (2)
O21—N2—O22	123.76 (19)	C5—C6—H6	119.1
O21—N2—C2	118.92 (18)	C1—C6—H6	119.1
O22—N2—C2	117.31 (18)

N1ⁱ—N1—C7—C1	−176.8 (2)	C3—C2—N2—O22	21.2 (3)
N1—C7—C1—C6	34.0 (3)	C1—C2—N2—O22	−159.54 (19)
N1—C7—C1—C2	−149.4 (2)	C1—C2—C3—C4	−0.1 (3)
C6—C1—C2—C3	−1.2 (3)	N2—C2—C3—C4	179.2 (2)
C7—C1—C2—C3	−177.9 (2)	C2—C3—C4—C5	0.9 (4)
C6—C1—C2—N2	179.58 (19)	C3—C4—C5—C6	−0.5 (4)
C7—C1—C2—N2	2.9 (3)	C4—C5—C6—C1	−0.8 (4)
C3—C2—N2—O21	−157.95 (19)	C2—C1—C6—C5	1.6 (3)
C1—C2—N2—O21	21.3 (3)	C7—C1—C6—C5	178.5 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg1ⁱⁱ	0.95	2.89	3.568 (2)	129

Symmetry code: (ii) x, −y+3/2, z−1/2.

(II) (E,E)-1-(2-nitrophenyl)-4-(3-nitrophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀N₄O₄	F(000) = 308
M_r = 298.26	D_x = 1.481 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1653 reflections
a = 7.8036 (2) Å	θ = 3.3–27.5°
b = 7.0914 (3) Å	µ = 0.11 mm⁻¹
c = 12.3424 (4) Å	T = 120 K
β = 101.742 (2)°	Blade, orange
V = 668.72 (4) Å³	0.50 × 0.32 × 0.12 mm
Z = 2

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	1653 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1519 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ϕ & ω scans	h = −10→10
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	k = −8→9
T_min = 0.936, T_max = 0.987	l = −15→14
7771 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.25	w = 1/[σ²(F_o²) + (0.0658P)² + 0.0096P] where P = (F_o² + 2F_c²)/3
1653 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.27 e Å⁻³
1 restraint	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₄	V = 668.72 (4) Å³
M_r = 298.26	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.8036 (2) Å	µ = 0.11 mm⁻¹
b = 7.0914 (3) Å	T = 120 K
c = 12.3424 (4) Å	0.50 × 0.32 × 0.12 mm
β = 101.742 (2)°

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	1653 independent reflections
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	1519 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.987	R_int = 0.031
7771 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.107	H-atom parameters constrained
S = 1.25	Δρ_max = 0.27 e Å⁻³
1653 reflections	Δρ_min = −0.31 e Å⁻³
199 parameters

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

	x	y	z	U_iso*/U_eq
O121	0.7741 (2)	0.6427 (3)	0.03301 (14)	0.0344 (4)
O122	0.9832 (2)	0.8362 (4)	0.02160 (15)	0.0457 (6)
O231	0.4814 (3)	−0.5798 (3)	0.45405 (13)	0.0442 (5)
O232	0.3223 (2)	−0.7467 (3)	0.32540 (16)	0.0417 (5)
N11	0.7767 (2)	0.2780 (3)	0.26739 (15)	0.0248 (4)
N12	0.9066 (2)	0.7306 (3)	0.07464 (16)	0.0273 (5)
N21	0.6911 (2)	0.1230 (3)	0.20885 (15)	0.0234 (4)
N23	0.4115 (2)	−0.6066 (3)	0.35745 (17)	0.0283 (5)
C11	0.9397 (2)	0.5555 (3)	0.25359 (19)	0.0221 (5)
C12	0.9748 (3)	0.7147 (4)	0.19415 (19)	0.0221 (5)
C13	1.0706 (3)	0.8679 (4)	0.2440 (2)	0.0282 (5)
C14	1.1331 (3)	0.8666 (4)	0.3577 (2)	0.0303 (5)
C15	1.1008 (3)	0.7117 (4)	0.4192 (2)	0.0281 (5)
C16	1.0079 (3)	0.5606 (4)	0.36847 (19)	0.0256 (5)
C17	0.8447 (3)	0.3876 (3)	0.20532 (18)	0.0228 (5)
C21	0.5404 (2)	−0.1642 (3)	0.23476 (17)	0.0197 (5)
C22	0.5212 (3)	−0.3015 (3)	0.31221 (17)	0.0206 (5)
C23	0.4325 (3)	−0.4645 (3)	0.27564 (18)	0.0213 (5)
C24	0.3595 (3)	−0.4982 (4)	0.16492 (18)	0.0238 (5)
C25	0.3778 (3)	−0.3598 (4)	0.08904 (17)	0.0245 (5)
C26	0.4661 (3)	−0.1947 (4)	0.12280 (17)	0.0231 (5)
C27	0.6356 (3)	0.0081 (3)	0.27403 (18)	0.0221 (5)
H13	1.0930	0.9724	0.2008	0.034*
H14	1.1975	0.9710	0.3931	0.036*
H15	1.1433	0.7102	0.4970	0.034*
H16	0.9889	0.4556	0.4123	0.031*
H17	0.8337	0.3604	0.1288	0.027*
H22	0.5684	−0.2829	0.3887	0.025*
H24	0.2991	−0.6124	0.1421	0.029*
H25	0.3289	−0.3788	0.0128	0.029*
H26	0.4766	−0.1007	0.0697	0.028*
H27	0.6572	0.0360	0.3509	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O121	0.0312 (8)	0.0366 (10)	0.0335 (9)	0.0000 (8)	0.0021 (7)	0.0024 (8)
O122	0.0365 (8)	0.0612 (14)	0.0401 (11)	−0.0057 (10)	0.0094 (8)	0.0268 (11)
O231	0.0662 (11)	0.0377 (11)	0.0253 (9)	−0.0099 (10)	0.0011 (8)	0.0102 (9)
O232	0.0526 (10)	0.0240 (10)	0.0486 (11)	−0.0093 (9)	0.0103 (9)	0.0048 (9)
N11	0.0294 (9)	0.0217 (10)	0.0242 (9)	−0.0031 (8)	0.0077 (7)	−0.0022 (8)
N12	0.0225 (8)	0.0314 (11)	0.0292 (10)	0.0060 (9)	0.0079 (7)	0.0089 (9)
N21	0.0263 (8)	0.0203 (10)	0.0237 (9)	−0.0037 (8)	0.0056 (7)	−0.0037 (8)
N23	0.0342 (9)	0.0201 (11)	0.0308 (10)	0.0000 (8)	0.0070 (8)	0.0037 (8)
C11	0.0200 (9)	0.0237 (12)	0.0246 (11)	0.0015 (9)	0.0090 (8)	−0.0006 (9)
C12	0.0183 (9)	0.0247 (12)	0.0250 (11)	0.0043 (9)	0.0081 (8)	0.0039 (9)
C13	0.0233 (9)	0.0225 (12)	0.0402 (13)	0.0024 (10)	0.0097 (9)	0.0079 (10)
C14	0.0265 (10)	0.0227 (13)	0.0406 (13)	−0.0016 (10)	0.0041 (9)	−0.0039 (11)
C15	0.0302 (10)	0.0279 (13)	0.0269 (12)	0.0008 (10)	0.0070 (9)	−0.0022 (10)
C16	0.0303 (10)	0.0242 (12)	0.0240 (11)	−0.0007 (10)	0.0093 (9)	0.0023 (10)
C17	0.0265 (10)	0.0220 (12)	0.0213 (10)	−0.0009 (9)	0.0080 (8)	−0.0015 (9)
C21	0.0199 (8)	0.0186 (12)	0.0212 (10)	0.0013 (9)	0.0057 (7)	−0.0014 (9)
C22	0.0223 (9)	0.0242 (12)	0.0157 (10)	0.0036 (8)	0.0046 (7)	0.0001 (8)
C23	0.0239 (10)	0.0180 (11)	0.0234 (11)	0.0032 (9)	0.0081 (8)	0.0020 (9)
C24	0.0227 (10)	0.0214 (11)	0.0263 (11)	0.0010 (9)	0.0026 (8)	−0.0059 (10)
C25	0.0252 (10)	0.0305 (13)	0.0166 (10)	0.0024 (10)	0.0011 (8)	−0.0035 (10)
C26	0.0250 (9)	0.0268 (12)	0.0189 (10)	0.0023 (9)	0.0073 (8)	0.0033 (10)
C27	0.0254 (10)	0.0234 (11)	0.0181 (10)	0.0015 (9)	0.0057 (8)	−0.0001 (9)

Geometric parameters (Å, º) top

N11—C17	1.280 (3)	N21—C27	1.281 (3)
N11—N21	1.407 (3)	C27—C21	1.461 (3)
C17—C11	1.464 (3)	C27—H27	0.95
C17—H17	0.95	C21—C22	1.393 (3)
C11—C12	1.404 (3)	C21—C26	1.402 (3)
C11—C16	1.410 (3)	C22—C23	1.376 (3)
C12—C13	1.389 (3)	C22—H22	0.95
C12—N12	1.467 (3)	C23—C24	1.390 (3)
N12—O121	1.227 (3)	C23—N23	1.459 (3)
N12—O122	1.227 (3)	N23—O231	1.221 (3)
C13—C14	1.389 (3)	N23—O232	1.231 (3)
C13—H13	0.95	C24—C25	1.384 (3)
C14—C15	1.387 (3)	C24—H24	0.95
C14—H14	0.95	C25—C26	1.380 (4)
C15—C16	1.371 (3)	C25—H25	0.95
C15—H15	0.95	C26—H26	0.95
C16—H16	0.95

C17—N11—N21	112.23 (18)	C27—N21—N11	111.11 (17)
N11—C17—C11	119.19 (19)	N21—C27—C21	122.55 (18)
N11—C17—H17	120.4	N21—C27—H27	118.7
C11—C17—H17	120.4	C21—C27—H27	118.7
C12—C11—C16	115.5 (2)	C22—C21—C26	119.2 (2)
C12—C11—C17	125.32 (19)	C22—C21—C27	118.37 (18)
C16—C11—C17	119.1 (2)	C26—C21—C27	122.4 (2)
C13—C12—C11	122.8 (2)	C23—C22—C21	118.63 (18)
C13—C12—N12	116.0 (2)	C23—C22—H22	120.7
C11—C12—N12	121.2 (2)	C21—C22—H22	120.7
O121—N12—O122	123.2 (2)	C22—C23—C24	123.0 (2)
O121—N12—C12	118.98 (18)	C22—C23—N23	118.24 (18)
O122—N12—C12	117.83 (19)	C24—C23—N23	118.7 (2)
C14—C13—C12	119.3 (2)	O231—N23—O232	123.4 (2)
C14—C13—H13	120.4	O231—N23—C23	118.53 (19)
C12—C13—H13	120.4	O232—N23—C23	118.08 (18)
C15—C14—C13	119.5 (2)	C25—C24—C23	117.7 (2)
C15—C14—H14	120.3	C25—C24—H24	121.1
C13—C14—H14	120.3	C23—C24—H24	121.1
C16—C15—C14	120.5 (2)	C26—C25—C24	120.76 (18)
C16—C15—H15	119.8	C26—C25—H25	119.6
C14—C15—H15	119.8	C24—C25—H25	119.6
C15—C16—C11	122.4 (2)	C25—C26—C21	120.6 (2)
C15—C16—H16	118.8	C25—C26—H26	119.7
C11—C16—H16	118.8	C21—C26—H26	119.7

N21—N11—C17—C11	−179.66 (18)	C17—N11—N21—C27	175.13 (18)
N11—C17—C11—C12	−159.7 (2)	N11—N21—C27—C21	179.39 (17)
N11—C17—C11—C16	22.3 (3)	N21—C27—C21—C22	165.11 (19)
C16—C11—C12—C13	0.2 (3)	N21—C27—C21—C26	−15.8 (3)
C17—C11—C12—C13	−177.91 (19)	C26—C21—C22—C23	1.2 (3)
C16—C11—C12—N12	−177.96 (19)	C27—C21—C22—C23	−179.64 (17)
C17—C11—C12—N12	4.0 (3)	C21—C22—C23—C24	−0.6 (3)
C13—C12—N12—O121	−153.2 (2)	C21—C22—C23—N23	−179.36 (18)
C11—C12—N12—O121	25.1 (3)	C22—C23—N23—O231	−3.9 (3)
C13—C12—N12—O122	24.8 (3)	C24—C23—N23—O231	177.3 (2)
C11—C12—N12—O122	−157.0 (2)	C22—C23—N23—O232	175.31 (18)
C11—C12—C13—C14	−0.9 (3)	C24—C23—N23—O232	−3.5 (3)
N12—C12—C13—C14	177.31 (19)	C22—C23—C24—C25	−0.1 (3)
C12—C13—C14—C15	0.8 (3)	N23—C23—C24—C25	178.64 (19)
C13—C14—C15—C16	0.0 (3)	C23—C24—C25—C26	0.2 (3)
C14—C15—C16—C11	−0.8 (3)	C24—C25—C26—C21	0.5 (3)
C12—C11—C16—C15	0.7 (3)	C22—C21—C26—C25	−1.2 (3)
C17—C11—C16—C15	178.88 (19)	C27—C21—C26—C25	179.71 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O232ⁱ	0.95	2.45	3.178 (3)	134
C22—H22···O231ⁱⁱ	0.95	2.51	3.289 (3)	139

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

(III) (E,E)-1,4-Bis(2-nitrophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀N₄O₄	F(000) = 308
M_r = 298.26	D_x = 1.502 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1507 reflections
a = 7.0128 (4) Å	θ = 3.1–27.6°
b = 7.6318 (5) Å	µ = 0.11 mm⁻¹
c = 12.8037 (5) Å	T = 120 K
β = 105.825 (3)°	Plate, yellow
V = 659.29 (6) Å³	0.43 × 0.30 × 0.08 mm
Z = 2

Data collection top

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	1507 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	1095 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.1°
ϕ & ω scans	h = −9→9
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −9→9
T_min = 0.969, T_max = 0.991	l = −16→14
7854 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.068P)² + 0.1014P] where P = (F_o² + 2F_c²)/3
1507 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₄	V = 659.29 (6) Å³
M_r = 298.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0128 (4) Å	µ = 0.11 mm⁻¹
b = 7.6318 (5) Å	T = 120 K
c = 12.8037 (5) Å	0.43 × 0.30 × 0.08 mm
β = 105.825 (3)°

Data collection top

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	1507 independent reflections
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	1095 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.991	R_int = 0.061
7854 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
1507 reflections	Δρ_min = −0.35 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
O31	−0.09983 (16)	0.27543 (15)	0.68104 (8)	0.0329 (3)
O32	−0.34487 (15)	0.11164 (15)	0.59533 (9)	0.0359 (3)
N1	0.41253 (17)	0.46167 (16)	0.50700 (9)	0.0250 (3)
N3	−0.19378 (18)	0.19608 (16)	0.59948 (10)	0.0254 (3)
C1	0.1283 (2)	0.29160 (18)	0.41783 (11)	0.0223 (3)
C2	0.0541 (2)	0.28839 (19)	0.50926 (11)	0.0224 (3)
C3	−0.1216 (2)	0.20250 (19)	0.50200 (11)	0.0224 (3)
C4	−0.2296 (2)	0.1181 (2)	0.40910 (12)	0.0267 (4)
C5	−0.1544 (2)	0.1209 (2)	0.31907 (12)	0.0277 (4)
C6	0.0221 (2)	0.20644 (19)	0.32335 (11)	0.0260 (4)
C7	0.3159 (2)	0.37952 (19)	0.42187 (11)	0.0236 (3)
H2	0.1238	0.3444	0.5748	0.027*
H4	−0.3506	0.0603	0.4068	0.032*
H5	−0.2247	0.0636	0.2541	0.033*
H6	0.0713	0.2071	0.2612	0.031*
H7	0.3666	0.3755	0.3603	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O31	0.0301 (6)	0.0435 (7)	0.0268 (6)	−0.0042 (5)	0.0105 (4)	−0.0020 (5)
O32	0.0262 (6)	0.0419 (7)	0.0445 (7)	−0.0069 (5)	0.0182 (5)	0.0003 (5)
N1	0.0197 (6)	0.0272 (7)	0.0308 (7)	−0.0011 (5)	0.0114 (5)	0.0007 (5)
N3	0.0211 (7)	0.0266 (7)	0.0304 (6)	0.0022 (5)	0.0103 (5)	0.0039 (5)
C1	0.0220 (7)	0.0209 (8)	0.0250 (7)	0.0029 (6)	0.0082 (5)	0.0021 (6)
C2	0.0223 (8)	0.0218 (8)	0.0237 (7)	0.0013 (6)	0.0071 (5)	0.0002 (6)
C3	0.0196 (7)	0.0245 (8)	0.0242 (7)	0.0031 (6)	0.0077 (5)	0.0033 (6)
C4	0.0184 (7)	0.0286 (8)	0.0322 (8)	0.0001 (6)	0.0053 (6)	0.0039 (6)
C5	0.0247 (8)	0.0312 (9)	0.0239 (7)	−0.0004 (7)	0.0011 (5)	0.0005 (6)
C6	0.0277 (8)	0.0286 (9)	0.0229 (7)	0.0027 (6)	0.0087 (6)	0.0023 (6)
C7	0.0229 (7)	0.0255 (8)	0.0249 (7)	0.0031 (6)	0.0108 (6)	0.0024 (6)

Geometric parameters (Å, º) top

N1—C7	1.2797 (18)	C3—N3	1.4699 (18)
N1—N1ⁱ	1.414 (2)	N3—O32	1.2289 (16)
C7—C1	1.465 (2)	N3—O31	1.2313 (15)
C7—H7	0.95	C4—C5	1.392 (2)
C1—C6	1.396 (2)	C4—H4	0.95
C1—C2	1.4050 (19)	C5—C6	1.387 (2)
C2—C3	1.376 (2)	C5—H5	0.95
C2—H2	0.95	C6—H6	0.95
C3—C4	1.383 (2)

C7—N1—N1ⁱ	111.77 (13)	O32—N3—O31	123.38 (12)
N1—C7—C1	121.09 (12)	O32—N3—C3	118.24 (12)
N1—C7—H7	119.5	O31—N3—C3	118.38 (12)
C1—C7—H7	119.5	C3—C4—C5	117.59 (13)
C6—C1—C2	118.86 (13)	C3—C4—H4	121.2
C6—C1—C7	120.36 (13)	C5—C4—H4	121.2
C2—C1—C7	120.76 (12)	C6—C5—C4	120.63 (14)
C3—C2—C1	118.69 (13)	C6—C5—H5	119.7
C3—C2—H2	120.7	C4—C5—H5	119.7
C1—C2—H2	120.7	C5—C6—C1	120.85 (13)
C2—C3—C4	123.38 (13)	C5—C6—H6	119.6
C2—C3—N3	117.88 (13)	C1—C6—H6	119.6
C4—C3—N3	118.71 (13)

N1ⁱ—N1—C7—C1	−179.28 (14)	C2—C3—N3—O31	3.83 (19)
N1—C7—C1—C6	178.32 (14)	C4—C3—N3—O31	−178.09 (13)
N1—C7—C1—C2	−3.0 (2)	C2—C3—C4—C5	0.2 (2)
C6—C1—C2—C3	−0.5 (2)	N3—C3—C4—C5	−177.78 (12)
C7—C1—C2—C3	−179.26 (13)	C3—C4—C5—C6	−0.3 (2)
C1—C2—C3—C4	0.2 (2)	C4—C5—C6—C1	0.0 (2)
C1—C2—C3—N3	178.21 (12)	C2—C1—C6—C5	0.4 (2)
C2—C3—N3—O32	−176.15 (12)	C7—C1—C6—C5	179.16 (13)
C4—C3—N3—O32	1.9 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O32ⁱⁱ	0.95	2.50	3.448 (2)	176

Symmetry code: (ii) −x−1, −y, −z+1.

(IV) (E,E)-1-(3-nitrophenyl)-4-(4-nitrophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀N₄O₄	F(000) = 1232
M_r = 298.26	D_x = 1.493 Mg m⁻³
Monoclinic, C2/c	Synchrotron radiation, λ = 0.6778 Å
Hall symbol: -C 2yc	Cell parameters from 2789 reflections
a = 30.865 (3) Å	θ = 3.0–28.8°
b = 4.7660 (5) Å	µ = 0.11 mm⁻¹
c = 21.736 (2) Å	T = 120 K
β = 123.926 (2)°	Lath, yellow
V = 2653.1 (5) Å³	0.10 × 0.06 × 0.01 mm
Z = 8

Data collection top

Bruker SMART APEX2 CCD diffractometer	3961 independent reflections
Radiation source: Daresbury SRS station 9.8	2817 reflections with I > 2σ(I)
Silicon 111 monochromator	R_int = 0.034
fine–slice ω scans	θ_max = 29.0°, θ_min = 2.2°
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	h = −43→44
T_min = 0.980, T_max = 0.999	k = −6→6
14589 measured reflections	l = −30→30

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.095P)² + 1.033P] where P = (F_o² + 2F_c²)/3
3961 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₄	V = 2653.1 (5) Å³
M_r = 298.26	Z = 8
Monoclinic, C2/c	Synchrotron radiation, λ = 0.6778 Å
a = 30.865 (3) Å	µ = 0.11 mm⁻¹
b = 4.7660 (5) Å	T = 120 K
c = 21.736 (2) Å	0.10 × 0.06 × 0.01 mm
β = 123.926 (2)°

Data collection top

Bruker SMART APEX2 CCD diffractometer	3961 independent reflections
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	2817 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.999	R_int = 0.034
14589 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.09	Δρ_max = 0.44 e Å⁻³
3961 reflections	Δρ_min = −0.26 e Å⁻³
199 parameters

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

	x	y	z	U_iso*/U_eq
O131	0.47646 (6)	−0.6159 (3)	0.32018 (8)	0.0490 (4)
O132	0.47144 (5)	−0.8936 (3)	0.39427 (8)	0.0406 (4)
O241	0.71080 (5)	1.3799 (3)	0.24123 (7)	0.0301 (3)
O242	0.78120 (5)	1.3094 (3)	0.34947 (6)	0.0287 (3)
N11	0.61784 (6)	0.0894 (3)	0.41626 (8)	0.0255 (3)
N13	0.49204 (6)	−0.6999 (3)	0.38204 (8)	0.0309 (3)
N21	0.65162 (6)	0.2929 (3)	0.41794 (7)	0.0246 (3)
N24	0.73536 (6)	1.2586 (3)	0.30096 (7)	0.0241 (3)
C11	0.60740 (6)	−0.2324 (3)	0.49114 (9)	0.0225 (3)
C12	0.56194 (6)	−0.3538 (3)	0.43126 (9)	0.0238 (3)
C13	0.53815 (6)	−0.5646 (3)	0.44561 (9)	0.0245 (3)
C14	0.55621 (7)	−0.6589 (4)	0.51591 (10)	0.0270 (4)
C15	0.60081 (7)	−0.5358 (4)	0.57473 (9)	0.0274 (4)
C16	0.62627 (6)	−0.3254 (3)	0.56259 (9)	0.0247 (3)
C17	0.63593 (6)	−0.0149 (3)	0.48018 (9)	0.0229 (3)
C21	0.65817 (6)	0.6351 (3)	0.34322 (8)	0.0231 (3)
C22	0.63189 (7)	0.7801 (3)	0.27598 (9)	0.0260 (4)
C23	0.65688 (7)	0.9832 (3)	0.26155 (8)	0.0253 (3)
C24	0.70876 (6)	1.0414 (3)	0.31580 (8)	0.0224 (3)
C25	0.73586 (6)	0.9054 (3)	0.38355 (8)	0.0237 (3)
C26	0.71045 (6)	0.7001 (3)	0.39661 (9)	0.0240 (3)
C27	0.63041 (7)	0.4180 (3)	0.35565 (9)	0.0245 (3)
H12	0.5478	−0.2925	0.3820	0.029*
H14	0.5386	−0.8036	0.5237	0.032*
H15	0.6142	−0.5958	0.6239	0.033*
H16	0.6570	−0.2436	0.6036	0.030*
H17	0.6685	0.0496	0.5214	0.027*
H22	0.5963	0.7382	0.2397	0.031*
H23	0.6390	1.0808	0.2156	0.030*
H25	0.7711	0.9523	0.4202	0.028*
H26	0.7287	0.6016	0.4424	0.029*
H27	0.5959	0.3691	0.3165	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O131	0.0444 (8)	0.0471 (9)	0.0276 (7)	−0.0090 (7)	0.0028 (6)	0.0051 (6)
O132	0.0360 (7)	0.0366 (8)	0.0441 (8)	−0.0121 (6)	0.0192 (6)	−0.0036 (6)
O241	0.0337 (7)	0.0268 (6)	0.0231 (6)	0.0012 (5)	0.0116 (5)	0.0058 (5)
O242	0.0267 (6)	0.0276 (6)	0.0241 (6)	−0.0037 (5)	0.0094 (5)	−0.0043 (5)
N11	0.0286 (7)	0.0217 (6)	0.0239 (7)	0.0009 (5)	0.0133 (6)	0.0005 (5)
N13	0.0276 (7)	0.0261 (7)	0.0303 (8)	0.0011 (6)	0.0108 (6)	0.0002 (6)
N21	0.0280 (7)	0.0215 (6)	0.0223 (6)	0.0002 (5)	0.0129 (6)	−0.0001 (5)
N24	0.0291 (7)	0.0187 (6)	0.0217 (6)	0.0003 (5)	0.0123 (6)	−0.0018 (5)
C11	0.0229 (7)	0.0184 (7)	0.0228 (7)	0.0035 (6)	0.0107 (6)	−0.0001 (5)
C12	0.0243 (7)	0.0219 (7)	0.0205 (7)	0.0056 (6)	0.0095 (6)	0.0010 (6)
C13	0.0205 (7)	0.0211 (7)	0.0263 (8)	0.0016 (6)	0.0097 (6)	−0.0034 (6)
C14	0.0284 (8)	0.0227 (8)	0.0316 (9)	0.0011 (6)	0.0179 (7)	0.0012 (6)
C15	0.0326 (8)	0.0261 (8)	0.0244 (8)	0.0019 (7)	0.0164 (7)	0.0019 (6)
C16	0.0267 (8)	0.0208 (7)	0.0218 (7)	0.0019 (6)	0.0107 (6)	−0.0006 (6)
C17	0.0247 (7)	0.0191 (7)	0.0208 (7)	0.0024 (6)	0.0102 (6)	−0.0006 (5)
C21	0.0285 (8)	0.0191 (7)	0.0203 (7)	0.0013 (6)	0.0127 (6)	−0.0017 (5)
C22	0.0256 (8)	0.0236 (8)	0.0210 (8)	−0.0005 (6)	0.0081 (6)	−0.0011 (6)
C23	0.0286 (8)	0.0226 (8)	0.0175 (7)	0.0018 (6)	0.0084 (6)	0.0009 (6)
C24	0.0273 (8)	0.0166 (7)	0.0213 (7)	0.0012 (6)	0.0123 (6)	−0.0001 (5)
C25	0.0237 (7)	0.0224 (7)	0.0186 (7)	0.0018 (6)	0.0077 (6)	−0.0006 (5)
C26	0.0276 (8)	0.0219 (7)	0.0177 (7)	0.0041 (6)	0.0095 (6)	0.0012 (6)
C27	0.0273 (8)	0.0203 (7)	0.0218 (7)	0.0011 (6)	0.0113 (6)	−0.0013 (6)

Geometric parameters (Å, º) top

N11—C17	1.274 (2)	N21—C27	1.276 (2)
N11—N21	1.409 (2)	C27—C21	1.462 (2)
C17—C11	1.463 (2)	C27—H27	0.95
C17—H17	0.95	C21—C22	1.396 (2)
C11—C16	1.392 (2)	C21—C26	1.399 (2)
C11—C12	1.400 (2)	C22—C23	1.379 (2)
C12—C13	1.379 (2)	C22—H22	0.95
C12—H12	0.95	C23—C24	1.387 (2)
C13—C14	1.377 (2)	C23—H23	0.95
C13—N13	1.468 (2)	C24—C25	1.383 (2)
N13—O131	1.216 (2)	C24—N24	1.465 (2)
N13—O132	1.231 (2)	N24—O241	1.2228 (17)
C14—C15	1.382 (2)	N24—O242	1.2276 (18)
C14—H14	0.95	C25—C26	1.379 (2)
C15—C16	1.387 (2)	C25—H25	0.95
C15—H15	0.95	C26—H26	0.95
C16—H16	0.95

C17—N11—N21	111.88 (14)	C27—N21—N11	111.10 (14)
N11—C17—C11	121.12 (15)	N21—C27—C21	121.36 (15)
N11—C17—H17	119.4	N21—C27—H27	119.3
C11—C17—H17	119.4	C21—C27—H27	119.3
C16—C11—C12	118.94 (15)	C22—C21—C26	119.09 (15)
C16—C11—C17	119.49 (14)	C22—C21—C27	119.07 (15)
C12—C11—C17	121.56 (14)	C26—C21—C27	121.84 (14)
C13—C12—C11	118.34 (15)	C23—C22—C21	120.92 (15)
C13—C12—H12	120.8	C23—C22—H22	119.5
C11—C12—H12	120.8	C21—C22—H22	119.5
C14—C13—C12	123.49 (15)	C22—C23—C24	118.30 (14)
C14—C13—N13	118.71 (15)	C22—C23—H23	120.9
C12—C13—N13	117.77 (15)	C24—C23—H23	120.9
O131—N13—O132	123.55 (16)	C25—C24—C23	122.44 (15)
O131—N13—C13	118.26 (15)	C25—C24—N24	119.05 (14)
O132—N13—C13	118.18 (15)	C23—C24—N24	118.50 (14)
C13—C14—C15	117.74 (16)	O241—N24—O242	123.58 (14)
C13—C14—H14	121.1	O241—N24—C24	118.44 (14)
C15—C14—H14	121.1	O242—N24—C24	117.97 (13)
C14—C15—C16	120.56 (15)	C26—C25—C24	118.45 (15)
C14—C15—H15	119.7	C26—C25—H25	120.8
C16—C15—H15	119.7	C24—C25—H25	120.8
C15—C16—C11	120.91 (15)	C25—C26—C21	120.78 (14)
C15—C16—H16	119.5	C25—C26—H26	119.6
C11—C16—H16	119.5	C21—C26—H26	119.6

N21—N11—C17—C11	−179.43 (13)	N11—N21—C27—C21	−178.92 (14)
N11—C17—C11—C16	−174.89 (15)	N21—C27—C21—C22	−175.28 (15)
N11—C17—C11—C12	6.4 (2)	N21—C27—C21—C26	5.2 (2)
C16—C11—C12—C13	−1.0 (2)	C26—C21—C22—C23	0.6 (2)
C17—C11—C12—C13	177.72 (14)	C27—C21—C22—C23	−178.95 (15)
C11—C12—C13—C14	1.2 (2)	C21—C22—C23—C24	−0.4 (2)
C11—C12—C13—N13	−176.98 (14)	C22—C23—C24—C25	−0.6 (2)
C14—C13—N13—O131	−179.81 (17)	C22—C23—C24—N24	−179.52 (14)
C12—C13—N13—O131	−1.5 (2)	C25—C24—N24—O241	−179.08 (14)
C14—C13—N13—O132	−0.3 (2)	C23—C24—N24—O241	−0.1 (2)
C12—C13—N13—O132	178.02 (15)	C25—C24—N24—O242	0.7 (2)
C12—C13—C14—C15	−0.6 (3)	C23—C24—N24—O242	179.67 (14)
N13—C13—C14—C15	177.60 (15)	C23—C24—C25—C26	1.5 (2)
C13—C14—C15—C16	−0.2 (3)	N24—C24—C25—C26	−179.59 (14)
C14—C15—C16—C11	0.4 (3)	C24—C25—C26—C21	−1.4 (2)
C12—C11—C16—C15	0.3 (2)	C22—C21—C26—C25	0.4 (2)
C17—C11—C16—C15	−178.49 (15)	C27—C21—C26—C25	179.86 (15)
C17—N11—N21—C27	−172.53 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O132ⁱ	0.95	2.44	3.309 (3)	151
C17—H17···O242ⁱⁱ	0.95	2.42	3.262 (2)	147
C22—H22···O131ⁱⁱⁱ	0.95	2.51	3.363 (3)	149
C27—H27···O131ⁱⁱⁱ	0.95	2.53	3.383 (3)	149

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

(V) (E,E)-1,4-Bis(4-nitrophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀N₄O₄	F(000) = 308
M_r = 298.26	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1479 reflections
a = 3.7318 (2) Å	θ = 2.9–27.6°
b = 7.2442 (3) Å	µ = 0.12 mm⁻¹
c = 23.9367 (10) Å	T = 120 K
β = 94.053 (2)°	Lath, yellow
V = 645.48 (5) Å³	0.40 × 0.10 × 0.01 mm
Z = 2

Data collection top

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	1479 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1239 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 2.9°
ϕ & ω scans	h = −4→4
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −9→9
T_min = 0.949, T_max = 0.999	l = −30→31
6443 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0454P)² + 0.3185P] where P = (F_o² + 2F_c²)/3
1479 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₄	V = 645.48 (5) Å³
M_r = 298.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.7318 (2) Å	µ = 0.12 mm⁻¹
b = 7.2442 (3) Å	T = 120 K
c = 23.9367 (10) Å	0.40 × 0.10 × 0.01 mm
β = 94.053 (2)°

Data collection top

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	1479 independent reflections
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	1239 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.999	R_int = 0.049
6443 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
1479 reflections	Δρ_min = −0.24 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
O41	0.4336 (3)	1.28743 (16)	0.72674 (4)	0.0330 (3)
O42	0.1025 (3)	1.38990 (14)	0.65597 (4)	0.0306 (3)
N1	0.4502 (3)	0.58742 (16)	0.50989 (5)	0.0218 (3)
N4	0.2944 (3)	1.27087 (17)	0.67923 (5)	0.0212 (3)
C1	0.4796 (4)	0.77966 (19)	0.59139 (6)	0.0184 (3)
C2	0.5886 (4)	0.7945 (2)	0.64823 (5)	0.0200 (3)
C3	0.5298 (4)	0.95619 (19)	0.67713 (5)	0.0198 (3)
C4	0.3602 (3)	1.10060 (18)	0.64832 (5)	0.0181 (3)
C5	0.2477 (4)	1.09149 (19)	0.59169 (6)	0.0191 (3)
C6	0.3100 (3)	0.92931 (19)	0.56356 (5)	0.0193 (3)
C7	0.5506 (4)	0.60798 (19)	0.56165 (6)	0.0201 (3)
H2	0.7037	0.6931	0.6672	0.024*
H3	0.6041	0.9675	0.7158	0.024*
H5	0.1320	1.1933	0.5730	0.023*
H6	0.2368	0.9192	0.5249	0.023*
H7	0.6735	0.5102	0.5813	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O41	0.0403 (7)	0.0350 (7)	0.0221 (5)	0.0060 (5)	−0.0080 (5)	−0.0090 (5)
O42	0.0377 (6)	0.0235 (6)	0.0297 (6)	0.0106 (5)	−0.0043 (5)	−0.0031 (4)
N1	0.0247 (6)	0.0182 (6)	0.0226 (6)	0.0038 (5)	0.0021 (5)	−0.0017 (5)
N4	0.0201 (6)	0.0217 (6)	0.0217 (6)	−0.0002 (5)	0.0012 (4)	−0.0022 (5)
C1	0.0153 (6)	0.0201 (7)	0.0201 (6)	−0.0004 (5)	0.0023 (5)	0.0003 (5)
C2	0.0187 (7)	0.0214 (7)	0.0197 (7)	0.0018 (5)	−0.0003 (5)	0.0032 (5)
C3	0.0182 (6)	0.0240 (7)	0.0169 (6)	−0.0013 (5)	−0.0003 (5)	0.0007 (5)
C4	0.0168 (6)	0.0185 (7)	0.0192 (6)	−0.0013 (5)	0.0016 (5)	−0.0032 (5)
C5	0.0175 (6)	0.0190 (7)	0.0207 (6)	0.0007 (5)	0.0007 (5)	0.0026 (5)
C6	0.0189 (7)	0.0229 (7)	0.0158 (6)	−0.0004 (5)	−0.0003 (5)	−0.0003 (5)
C7	0.0184 (7)	0.0204 (7)	0.0215 (6)	0.0017 (5)	0.0008 (5)	0.0013 (5)

Geometric parameters (Å, º) top

C1—C2	1.3963 (18)	C5—C6	1.3820 (19)
C1—C6	1.4000 (19)	C5—H5	0.95
C1—C7	1.4663 (19)	C6—H6	0.95
C2—C3	1.386 (2)	N4—O41	1.2225 (16)
C2—H2	0.95	N4—O42	1.2288 (15)
C3—C4	1.3816 (19)	C7—N1	1.2775 (18)
C3—H3	0.95	C7—H7	0.95
C4—C5	1.3919 (18)	N1—N1ⁱ	1.411 (2)
C4—N4	1.4679 (17)

C2—C1—C6	119.65 (12)	C6—C5—H5	121.1
C2—C1—C7	119.21 (12)	C4—C5—H5	121.1
C6—C1—C7	121.13 (12)	C5—C6—C1	120.83 (12)
C3—C2—C1	120.39 (12)	C5—C6—H6	119.6
C3—C2—H2	119.8	C1—C6—H6	119.6
C1—C2—H2	119.8	O41—N4—O42	123.26 (12)
C4—C3—C2	118.29 (12)	O41—N4—C4	118.43 (12)
C4—C3—H3	120.9	O42—N4—C4	118.31 (11)
C2—C3—H3	120.9	N1—C7—C1	121.27 (13)
C3—C4—C5	123.10 (12)	N1—C7—H7	119.4
C3—C4—N4	118.15 (12)	C1—C7—H7	119.4
C5—C4—N4	118.75 (12)	C7—N1—N1ⁱ	111.35 (14)
C6—C5—C4	117.73 (12)

C6—C1—C2—C3	0.0 (2)	C7—C1—C6—C5	−179.24 (13)
C7—C1—C2—C3	179.01 (12)	C3—C4—N4—O41	9.71 (19)
C1—C2—C3—C4	0.3 (2)	C5—C4—N4—O41	−170.66 (13)
C2—C3—C4—C5	−0.3 (2)	C3—C4—N4—O42	−170.44 (12)
C2—C3—C4—N4	179.26 (12)	C5—C4—N4—O42	9.19 (19)
C3—C4—C5—C6	0.1 (2)	C2—C1—C7—N1	178.82 (13)
N4—C4—C5—C6	−179.50 (12)	C6—C1—C7—N1	−2.2 (2)
C4—C5—C6—C1	0.2 (2)	C1—C7—N1—N1ⁱ	179.48 (13)
C2—C1—C6—C5	−0.2 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O41ⁱⁱ	0.95	2.50	3.186 (2)	129
C7—H7···O42ⁱⁱⁱ	0.95	2.47	3.343 (2)	152

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

Experimental details

	(Ia)	(Ib)	(II)	(III)
Crystal data
Chemical formula	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄
M_r	298.26	298.26	298.26	298.26
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c	Monoclinic, P2₁	Monoclinic, P2₁/n
Temperature (K)	120	120	120	120
a, b, c (Å)	9.1379 (4), 6.1776 (3), 11.7682 (4)	7.7809 (2), 14.7825 (6), 6.2196 (2)	7.8036 (2), 7.0914 (3), 12.3424 (4)	7.0128 (4), 7.6318 (5), 12.8037 (5)
β (°)	93.853 (3)	113.106 (2)	101.742 (2)	105.825 (3)
V (Å³)	662.82 (5)	658.00 (4)	668.72 (4)	659.29 (6)
Z	2	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.11	0.11	0.11	0.11
Crystal size (mm)	0.46 × 0.34 × 0.18	0.48 × 0.22 × 0.08	0.50 × 0.32 × 0.12	0.43 × 0.30 × 0.08

Data collection
Diffractometer	Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer
Absorption correction	Multi-scan SADABS V2.10 (Sheldrick, 2003)	Multi-scan SADABS V2.10 (Sheldrick, 2003)	Multi-scan SADABS V2.10 (Sheldrick, 2003)	Multi-scan SADABS 2.10 (Sheldrick, 2003)
T_min, T_max	0.967, 0.980	0.957, 0.991	0.936, 0.987	0.969, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	8093, 1511, 1232	10780, 1503, 1222	7771, 1653, 1519	7854, 1507, 1095
R_int	0.034	0.043	0.031	0.061
(sin θ/λ)_max (Å⁻¹)	0.649	0.649	0.649	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.124, 1.00	0.060, 0.160, 1.02	0.040, 0.107, 1.25	0.044, 0.122, 1.04
No. of reflections	1511	1503	1653	1507
No. of parameters	100	100	199	100
No. of restraints	0	0	1	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.29	1.44, −0.31	0.27, −0.31	0.20, −0.35

	(IV)	(V)
Crystal data
Chemical formula	C₁₄H₁₀N₄O₄	C₁₄H₁₀N₄O₄
M_r	298.26	298.26
Crystal system, space group	Monoclinic, C2/c	Monoclinic, P2₁/n
Temperature (K)	120	120
a, b, c (Å)	30.865 (3), 4.7660 (5), 21.736 (2)	3.7318 (2), 7.2442 (3), 23.9367 (10)
β (°)	123.926 (2)	94.053 (2)
V (Å³)	2653.1 (5)	645.48 (5)
Z	8	2
Radiation type	Synchrotron, λ = 0.6778 Å	Mo Kα
µ (mm⁻¹)	0.11	0.12
Crystal size (mm)	0.10 × 0.06 × 0.01	0.40 × 0.10 × 0.01

Data collection
Diffractometer	Bruker SMART APEX2 CCD diffractometer	Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer
Absorption correction	Multi-scan SADABS 2.10 (Sheldrick, 2003)	Multi-scan SADABS 2.10 (Sheldrick, 2003)
T_min, T_max	0.980, 0.999	0.949, 0.999
No. of measured, independent and observed [I > 2σ(I)] reflections	14589, 3961, 2817	6443, 1479, 1239
R_int	0.034	0.049
(sin θ/λ)_max (Å⁻¹)	0.715	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.170, 1.09	0.041, 0.110, 1.06
No. of reflections	3961	1479
No. of parameters	199	100
No. of restraints	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.26	0.24, −0.24

Computer programs: COLLECT (Hooft, 1999), Bruker APEX2, DENZO (Otwinowski & Minor, 1997) & COLLECT, Bruker SAINT, DENZO & COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 macro PRPKAPPA (Ferguson, 1999), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (Ib) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg1ⁱ	0.95	2.89	3.568 (2)	129

Symmetry code: (i) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O232ⁱ	0.95	2.45	3.178 (3)	134
C22—H22···O231ⁱⁱ	0.95	2.51	3.289 (3)	139

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

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O32ⁱ	0.95	2.50	3.448 (2)	176

Symmetry code: (i) −x−1, −y, −z+1.

Hydrogen-bond geometry (Å, º) for (IV) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O132ⁱ	0.95	2.44	3.309 (3)	151
C17—H17···O242ⁱⁱ	0.95	2.42	3.262 (2)	147
C22—H22···O131ⁱⁱⁱ	0.95	2.51	3.363 (3)	149
C27—H27···O131ⁱⁱⁱ	0.95	2.53	3.383 (3)	149

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

Hydrogen-bond geometry (Å, º) for (V) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O41ⁱ	0.95	2.50	3.186 (2)	129
C7—H7···O42ⁱⁱ	0.95	2.47	3.343 (2)	152

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

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: BM5032 ). Services for accessing these data are described at the back of the journal.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, UK, and at the Daresbury SRS station 9.8: the authors thank the staff of these facilities for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

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Volume 62| Part 4| August 2006| Pages 666-675

doi:10.1107/S010876810601439X