A combinatorial chemistry approach to new materials for non-linear optics. I. Five Schiff bases

A combinatorial chemistry approach has been used to synthesize an array of Schiff bases, five of which, namely N-[(E,2E)-3-(4-methoxy­phenyl)-2-propenyl­idene]-3-nitro­aniline, C₁₆H₁₄N₂O₃, (1a), N-[(E,2E)-3-(4-methoxy­phenyl)-2-propenyl­idene]-4-nitro­aniline, C₁₆H₁₄N₂O₃, (2a), N-{(E,2E)-3-[4-(di­methyl­amino)­phenyl]-2-propenyl­idene}-3-nitro­aniline, C₁₇H₁₇N₃O₂, (1b), N-{(E,2E)-3-[4-(di­methyl­amino)­phenyl]-2-propenyl­idene}-4-nitro­aniline, C₁₇H₁₇N₃O₂, (2b), and N-{(E,2E)-3-[4-(di­methyl­amino)­phenyl]-2-propenyl­idene}-2-methyl-4-nitro­aniline, C₁₈H₁₉N₃O₂, (3b), have been structurally characterized. A stack structure is observed for (1a) and (1b) in the crystal phase. Experimental and calculated molecular structures are discussed for these compounds which belong to a chemical class having potential applications as non-linear optical materials.

S1. Comment

Combinatorial chemistry is a new field of synthetic chemistry which leads to fast synthesis of a wide variety (libraries) of products for particular applications. The recent success of combinatorial methods in the field of drug discovery (Tarby et al., 1996) has triggered exploration in the field of materials such as inorganic luminescent materials and catalysts (Danielson et al., 1997; Shimizu et al., 1997).

There are two approaches in combinatorial synthesis which lead to either diverse or focused combinatorial libraries. Recently we started an investigation of the combinatorial synthesis procedure for the rapid formation of large libraries of polar compounds (a focused library) which can be used for preparation of nonlinear optical (NLO) materials (Zyss et al., 1994). We performed quantum chemical evaluations of the first order molecular hyperpolarizabilities β of the compounds in question before undertaking the synthesis of a small combinatorial library. Since the crystal structure is a very important characteristic of such materials, we performed X-ray analyses of the products in all cases where we were able to obtain suitable single crystals. To our knowledge, this study represents the first systematic application of chemical crystallography to the investigation of an array of combinatorial products. For the targetted library, we used amines (1–4) and aldehydes (a, b) as the building blocks and we assumed that we would be able to synthesize eight polar Schiff bases by condensation reactions (Scheme 1). \sch

Because of the structural characteristics of the Schiff-base products (i.e. electron donor and acceptor groups connected to a π-conjugated chain) they will have potential as NLO or electrooptical materials. Quantum chemical calculations of average molecular hyperpolarizabilities (β) support this conclusion. One can see from Table 1 that the β values increase in the series (1) → (4) and (a) → (b), in agreement with the activity of donor and acceptor groups in these compounds.

In each case the colour of the product in comparison to that of the starting material indicated that the expected chemical reaction had taken place. In all cases we also observed precipitation of crystalline products. We were able to obtain suitable single crystals for all products except for (3a), where the crystals were too small. The results of structure investigations indicated that the conditions we used for the condensation reactions were not favorable for obtaining the Schiff base for adducts (4a) and (4 b). In these two cases a complex consisting of starting materials (a) and (4) and one of the starting materials (b) were found in the precipitates of the reactions in question. The structures of these two compounds are described in the following paper (Nesterov et al., 2000).

Bond-length alternation is observed in the central π-conjugated chain of all five molecules (1a), (2a), (1 b), (2 b) and (3 b) (see Figs. 1–5, respectively, and Table 2). Similar alternations were previously found in Schiff bases with different substitients (Cl, Br or Me) on one of the phenyl rings (Karaev & Furmanova, 1984; Childs et al., 1989; Ercan et al., 1996). The C1—N1, N1═C7 and C8—C9 bond lengths in the chains are similar both in the five molecules studied here (Table 2) and in four analogous molecules (Karaev & Furmanova, 1984; Childs et al., 1989; Ercan et al., 1996). In contrast the C7—C8 and C9—C10 distances in (1 b) and (3 b) are considerably shorter than those observed in all other compounds. It should be noted that phenyl rings with a dimethylamino substituent, as seen in (1 b) and (3 b), exhibit noticeable quinoid character demonstrated by the shortening of the C11—C12 and C14—C15 bond lengths (Table 2) compared to the standard C≐C distance of 1.398 Å (Allen et al., 1987). The shortening of these bonds is less pronounced in (1a), (2a) and (2 b). Other phenyl-ring bond lengths lie close to that of the standard C≐C bond. Quinoid character of the phenyl ring is actually rather typical for rings bearing electron-donor and acceptor substituents in para-positions (Domenicano, 1992), and this feature is considered important in potential NLO compounds (Zyss & Chemla, 1987).

Molecules of (2a), (2 b) and (3 b) (Figs. 2, 4 and 5, respectively) are non-planar due to rotation of both phenyl rings with respect to the central planar molecular fragment, but the rotation of the nitrophenyl ring is consistently greater than that of the other aromatic ring: AM1 calculations (Dewar et al., 1985) reproduce the features of the non-planarity in these molecules very well (Table 2). A parallel observation was made for related compounds where rotations of the aniline rings were about 40° (Karaev & Furmanova, 1984; Childs et al., 1989; Ercan et al., 1996).

In contrast, molecules of (1 b) (Fig. 3) are almost planar in the solid state (Table 2). Since AM1 calculations predict non-planarity of this molecule (Table 2) the influence of crystal-packing forces might be invoked to explain the discrepancy between experimental and theoretical results. Indeed, molecules are stacked along [100] with a separation of only 3.31 (1) Å between the least squares mean planes of neighboring molecules. In addition similar packing but in the direction [010] is observed in the crystal (1a). In consequence the molecule (1a) is more close to planarity than (2a), (2 b) and (3 b) (Table 2). Significantly, such stacking is absent in the structures (2a), (2 b) and (3 b).

Our results show the potential use of combinatorial synthesis for obtaining targetted libraries in materials chemistry. Although in this case six Schiff base compounds from a small array of eight possible products were synthesized, all five which were the subject of successful structure determination were found to crystallize in centrosymmetric space groups. Since in centrosymmetric crystals the superposition of inverted tensors of the third rank which describe molecular hyperpolarizability (β) is equal to zero, such crystals do not generate second harmonics (Zyss & Chemla, 1987). This precludes the application of bulk crystals or crystalline films of the compounds studied as NLO materials. On the other hand, the centrosymmetric patterns might be easily destroyed by introducing these compounds into polymer matrices doped by an active NLO choromophore (Agullo-Lopez et al., 1994). Thus the title compounds might be utilized as active dopants in polymer-based second harmonic generating, electrooptic or photorefractive materials.

S2. Experimental

All Schiff bases were obtained by the reaction of 4-methoxyaminocinnamaldehyde (a) or 4-dimethylaminocinnamaldehyde (b) (0.005 mol) with amines (1)–(4) (0.005 mol) in the presence of a catalytic amount of acetic acid in ethanol (20 ml) under reflux for 1–3 min. The precipitates were isolated and recrystallized from ethanol (30 ml) in the presence of a small amount of acetic acid. Yields: (1a) 78%, (1 b) 74%, (2a) 85%, (2 b) 82%, (3a) 78%, (3 b) 70%. Crystals were obtained by isothermal evaporation from CH₃CN solutions. UV/vis(λ_max/nm, acetone solution): 381 (1a), 413 (1 b), 365 (2a), 444 (2 b), 355 (3a), 431 (3 b).

S3. Refinement

Molecular structures of (1a)–(4 b) were calculated by the AM1 semi-empirical quantum-chemical method (Dewar et al., 1985) with full geometry optimization using the GAMESS program (Schmidt et al., 1993). Calculations of average molecular hyperpolarizabilities (β in 10⁻⁵¹ C m³ V⁻²) were carried out with the finite field approach using modified MOPAC (AM1) and HYPER programs (Cardelino et al., 1991, 1997).

In (1a), (2a) and (2 b) hydrogen atoms were located from ΔF syntheses and thereafter refined freely. For the remaining structures (1 b) and (3 b) methyl H atoms were located in a ΔF synthesis and thereafter refined as part of a rigid rotating group, while others were placed in geometrically calculated positions and refined using a riding model.

For the five compounds (1a), (1 b), (2a), (2 b) and (3 b), the respective total number of reflections suppressed with I<2σ(I) was 13, 55, 47, 52 and 79; the corresponding number suppressed due to systematic errors was 11, 30, 32 28 and 62.

Computing details

Data collection: SMART (Siemens, 1994) for (1a); CAD-4 Software (Enraf-Nonius, 1989) for (2a), (1b), (2b), (3b). Cell refinement: SMART for (1a); CAD-4 Software for (2a), (1b), (2b), (3b). Data reduction: SHELXTL-Plus (Sheldrick, 1994) for (1a); PROFIT (Streltsov & Zavodnik, 1989) for (2a), (1b), (2b), (3b). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (1a); SHELXTL-Plus (Sheldrick, 1994) for (2a), (1b), (2b), (3b). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (1a); SHELXTL for (2a), (1b), (2b), (3b). Molecular graphics: SHELXTL-Plus for (1a); SHELXTL for (2a), (1b), (2b), (3b). Software used to prepare material for publication: SHELXTL-Plus for (1a); SHELXTL for (2a), (1b), (2b), (3b).

Figures

Fig. 1. View of (1a) with the non-H atoms shown with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary small radius for clarity. Fig. 2. View of (2a) with the non-H atoms shown with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary small radius for clarity. Fig. 3. View of (1 b) with the non-H atoms shown with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary small radius for clarity. Fig. 4. View of (2 b) with the non-H atoms shown with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary small radius for clarity. Fig. 5. View of (3 b) with the non-H atoms shown with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary small radius for clarity.

(1a) N-[(E,2E)-3-(4-methoxyphenyl)-2-propenylidene]-3-nitroaniline

Crystal data

C16H14N2O3	Dx = 1.391 Mg m^−3
Mr = 282.29	Melting point: 141(1) K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.7883 (8) Å	Cell parameters from 5200 reflections
b = 3.9239 (2) Å	θ = 2–24°
c = 22.6063 (11) Å	µ = 0.10 mm^−1
β = 105.767 (1)°	T = 100 K
V = 1347.80 (12) Å^3	Square prism, yellow
Z = 4	0.3 × 0.1 × 0.1 mm
F(000) = 592

Data collection

Siemens SMART CCD area detector diffractometer	2603 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 30.0°, θmin = 1.4°
ϕ and ω scans	h = −22→20
14296 measured reflections	k = −5→5
3938 independent reflections	l = −31→31

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	All H-atom parameters refined
wR(F^2) = 0.126	Calculated w = 1/[σ^2(Fo^2) + (0.0889P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max = 0.001
3925 reflections	Δρmax = 0.50 e Å^−3
246 parameters	Δρmin = −0.22 e Å^−3
0 restraints

Special details

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 on F² for ALL reflections except for 13 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.71571 (7)	0.8307 (3)	0.47857 (5)	0.0230 (2)
N2	0.58671 (8)	1.3183 (3)	0.63606 (6)	0.0301 (3)
O1	0.52247 (7)	1.4097 (3)	0.59496 (5)	0.0394 (3)
O2	0.59540 (8)	1.3733 (3)	0.69088 (5)	0.0437 (3)
O3	0.54119 (6)	0.8769 (2)	0.06917 (4)	0.0257 (2)
C1	0.71743 (8)	0.9150 (3)	0.53949 (6)	0.0210 (3)
C2	0.64822 (9)	1.0745 (3)	0.55690 (6)	0.0226 (3)
H2	0.5942 (11)	1.138 (4)	0.5271 (7)	0.028 (4)*
C3	0.65833 (9)	1.1368 (3)	0.61860 (6)	0.0236 (3)
C4	0.73237 (9)	1.0458 (3)	0.66461 (6)	0.0260 (3)
H4	0.7366 (11)	1.097 (4)	0.7085 (7)	0.038 (4)*
C5	0.80030 (9)	0.8853 (3)	0.64703 (6)	0.0255 (3)
H5	0.8529 (12)	0.815 (4)	0.6774 (7)	0.038 (4)*
C6	0.79286 (9)	0.8229 (3)	0.58547 (6)	0.0234 (3)
H6	0.8377 (11)	0.714 (4)	0.5731 (7)	0.032 (4)*
C7	0.66406 (8)	0.9937 (3)	0.43370 (6)	0.0230 (3)
H7	0.6275 (10)	1.180 (4)	0.4396 (6)	0.020 (3)*
C8	0.65983 (9)	0.9134 (3)	0.37074 (6)	0.0229 (3)
H8	0.6997 (11)	0.733 (4)	0.3628 (7)	0.034 (4)*
C9	0.60137 (8)	1.0693 (3)	0.32388 (6)	0.0219 (3)
H9	0.5599 (10)	1.227 (4)	0.3332 (6)	0.024 (4)*
C10	0.58973 (8)	1.0143 (3)	0.25832 (5)	0.0203 (3)
C11	0.51440 (8)	1.1443 (3)	0.21595 (6)	0.0216 (3)
H11	0.4748 (11)	1.273 (4)	0.2310 (7)	0.032 (4)*
C12	0.50053 (8)	1.0972 (3)	0.15374 (6)	0.0227 (3)
H12	0.4502 (11)	1.190 (4)	0.1240 (7)	0.032 (4)*
C13	0.56219 (8)	0.9180 (3)	0.13143 (6)	0.0211 (3)
C14	0.63867 (8)	0.7953 (3)	0.17250 (6)	0.0218 (3)
H14	0.6816 (10)	0.670 (4)	0.1561 (6)	0.024 (4)*
C15	0.65141 (8)	0.8408 (3)	0.23524 (6)	0.0213 (3)
H15	0.7062 (10)	0.747 (4)	0.2635 (6)	0.023 (4)*
C16	0.60435 (10)	0.7113 (4)	0.04374 (7)	0.0268 (3)
H16C	0.6175 (10)	0.487 (4)	0.0605 (6)	0.027 (4)*
H16B	0.6583 (11)	0.851 (4)	0.0515 (7)	0.032 (4)*
H16A	0.5766 (10)	0.699 (4)	−0.0017 (7)	0.031 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0232 (5)	0.0245 (5)	0.0222 (5)	0.0005 (4)	0.0075 (4)	−0.0016 (4)
N2	0.0297 (6)	0.0289 (6)	0.0371 (7)	0.0004 (5)	0.0183 (5)	−0.0004 (5)
O1	0.0295 (6)	0.0480 (7)	0.0441 (6)	0.0102 (5)	0.0158 (5)	0.0049 (5)
O2	0.0468 (7)	0.0547 (7)	0.0364 (6)	0.0049 (6)	0.0229 (5)	−0.0075 (5)
O3	0.0250 (5)	0.0301 (5)	0.0214 (4)	0.0018 (4)	0.0055 (4)	−0.0009 (4)
C1	0.0209 (6)	0.0192 (6)	0.0239 (6)	−0.0020 (5)	0.0080 (5)	0.0000 (5)
C2	0.0197 (6)	0.0230 (6)	0.0252 (6)	−0.0010 (5)	0.0062 (5)	0.0019 (5)
C3	0.0230 (6)	0.0210 (6)	0.0301 (7)	−0.0018 (5)	0.0129 (5)	−0.0007 (5)
C4	0.0305 (7)	0.0230 (6)	0.0251 (6)	−0.0041 (5)	0.0089 (5)	−0.0014 (5)
C5	0.0237 (6)	0.0254 (7)	0.0250 (6)	−0.0020 (5)	0.0022 (5)	0.0016 (5)
C6	0.0206 (6)	0.0223 (6)	0.0282 (7)	0.0011 (5)	0.0079 (5)	0.0010 (5)
C7	0.0214 (6)	0.0215 (6)	0.0261 (6)	−0.0009 (5)	0.0067 (5)	−0.0008 (5)
C8	0.0227 (6)	0.0213 (6)	0.0249 (6)	−0.0018 (5)	0.0069 (5)	−0.0014 (5)
C9	0.0199 (6)	0.0213 (6)	0.0250 (6)	−0.0005 (5)	0.0068 (5)	−0.0012 (5)
C10	0.0197 (6)	0.0182 (6)	0.0232 (6)	−0.0022 (5)	0.0060 (5)	−0.0004 (5)
C11	0.0189 (6)	0.0211 (6)	0.0262 (6)	−0.0001 (5)	0.0086 (5)	−0.0009 (5)
C12	0.0174 (6)	0.0237 (6)	0.0256 (6)	0.0003 (5)	0.0035 (5)	0.0021 (5)
C13	0.0220 (6)	0.0200 (6)	0.0215 (6)	−0.0030 (5)	0.0062 (5)	0.0000 (5)
C14	0.0190 (6)	0.0210 (6)	0.0266 (6)	0.0000 (5)	0.0082 (5)	0.0000 (5)
C15	0.0179 (6)	0.0209 (6)	0.0242 (6)	−0.0012 (5)	0.0041 (5)	0.0011 (5)
C16	0.0294 (7)	0.0262 (7)	0.0265 (7)	0.0020 (6)	0.0103 (6)	−0.0010 (5)

Geometric parameters (Å, º)

N1—C7	1.286 (2)	C7—H7	0.964 (15)
N1—C1	1.409 (2)	C8—C9	1.348 (2)
N2—O2	1.2284 (15)	C8—H8	1.00 (2)
N2—O1	1.228 (2)	C9—C10	1.459 (2)
N2—C3	1.478 (2)	C9—H9	0.97 (2)
O3—C13	1.3651 (14)	C10—C15	1.400 (2)
O3—C16	1.435 (2)	C10—C11	1.405 (2)
C1—C6	1.399 (2)	C11—C12	1.376 (2)
C1—C2	1.405 (2)	C11—H11	0.94 (2)
C2—C3	1.382 (2)	C12—C13	1.401 (2)
C2—H2	0.96 (2)	C12—H12	0.96 (2)
C3—C4	1.384 (2)	C13—C14	1.394 (2)
C4—C5	1.392 (2)	C14—C15	1.389 (2)
C4—H4	1.00 (2)	C14—H14	0.99 (2)
C5—C6	1.386 (2)	C15—H15	1.00 (2)
C5—H5	0.96 (2)	C16—H16C	0.96 (2)
C6—H6	0.93 (2)	C16—H16B	0.99 (2)
C7—C8	1.441 (2)	C16—H16A	1.002 (15)
C7—N1—C1	119.59 (11)	C5—C6—C1	121.54 (12)
O2—N2—O1	123.70 (12)	N1—C7—C8	121.30 (12)
O2—N2—C3	118.05 (12)	C9—C8—C7	121.00 (12)
O1—N2—C3	118.24 (11)	C8—C9—C10	126.98 (12)
C13—O3—C16	117.78 (10)	C15—C10—C11	117.92 (11)
C6—C1—C2	118.49 (12)	C15—C10—C9	122.83 (11)
C6—C1—N1	116.86 (11)	C11—C10—C9	119.24 (11)
C2—C1—N1	124.62 (11)	C12—C11—C10	121.23 (12)
C3—C2—C1	118.43 (12)	C11—C12—C13	120.14 (12)
C2—C3—C4	123.72 (12)	O3—C13—C14	124.74 (11)
C2—C3—N2	117.90 (12)	O3—C13—C12	115.63 (11)
C4—C3—N2	118.36 (12)	C14—C13—C12	119.63 (11)
C3—C4—C5	117.48 (12)	C15—C14—C13	119.66 (12)
C6—C5—C4	120.33 (12)	C14—C15—C10	121.38 (11)
C7—N1—C1—C6	−158.33 (12)	N1—C7—C8—C9	175.50 (12)
C7—N1—C1—C2	23.5 (2)	C7—C8—C9—C10	179.95 (11)
C6—C1—C2—C3	0.8 (2)	C8—C9—C10—C15	−14.2 (2)
N1—C1—C2—C3	178.88 (12)	C8—C9—C10—C11	166.91 (13)
C1—C2—C3—C4	−1.1 (2)	C15—C10—C11—C12	1.3 (2)
C1—C2—C3—N2	177.37 (11)	C9—C10—C11—C12	−179.71 (11)
O2—N2—C3—C2	179.83 (12)	C10—C11—C12—C13	−0.3 (2)
O1—N2—C3—C2	−1.2 (2)	C16—O3—C13—C14	−3.4 (2)
O2—N2—C3—C4	−1.6 (2)	C16—O3—C13—C12	176.68 (11)
O1—N2—C3—C4	177.43 (12)	C11—C12—C13—O3	178.24 (11)
C2—C3—C4—C5	0.6 (2)	C11—C12—C13—C14	−1.6 (2)
N2—C3—C4—C5	−177.89 (11)	O3—C13—C14—C15	−177.44 (11)
C3—C4—C5—C6	0.3 (2)	C12—C13—C14—C15	2.4 (2)
C4—C5—C6—C1	−0.6 (2)	C13—C14—C15—C10	−1.4 (2)
C2—C1—C6—C5	0.1 (2)	C11—C10—C15—C14	−0.5 (2)
N1—C1—C6—C5	−178.19 (11)	C9—C10—C15—C14	−179.44 (11)
C1—N1—C7—C8	−179.49 (11)

(2a) N-[(E,2E)-3-(4-methoxyphenyl)-2-propenylidene]-4-nitroaniline

Crystal data

C16H14N2O3	Dx = 1.316 Mg m^−3
Mr = 282.29	Melting point: 147(1) K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 10.413 (2) Å	Cell parameters from 24 reflections
b = 7.5990 (15) Å	θ = 10–11°
c = 36.010 (7) Å	µ = 0.09 mm^−1
V = 2849.4 (10) Å^3	T = 298 K
Z = 8	Plate, yellow
F(000) = 1184	0.60 × 0.40 × 0.30 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.044
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 1.1°
Graphite monochromator	h = −13→0
θ/2θ scans	k = −10→0
3579 measured reflections	l = 0→47
3400 independent reflections	2 standard reflections every 98 reflections
1593 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.050	Calculated w = 1/[σ^2(Fo^2) + (0.0427P)^2 + 1.1439P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.106	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.13 e Å^−3
3346 reflections	Δρmin = −0.15 e Å^−3
247 parameters	Extinction correction: SHELXTL-Plus (Sheldrick, 1994), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0137 (14)
Primary atom site location: structure-invariant direct methods

Special details

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 on F² for ALL reflections except for 54 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.2563 (2)	0.3754 (3)	0.87216 (5)	0.0527 (5)
N2	0.2493 (3)	0.6600 (3)	1.01598 (5)	0.0618 (6)
O1	0.3496 (2)	0.6913 (3)	1.03176 (5)	0.0967 (8)
O2	0.1457 (2)	0.6880 (4)	1.03010 (6)	0.1014 (9)
O3	0.3823 (2)	0.2294 (2)	0.63136 (4)	0.0623 (5)
C1	0.2604 (3)	0.4497 (3)	0.90804 (6)	0.0462 (6)
C2	0.3727 (3)	0.4871 (4)	0.92671 (7)	0.0557 (7)
H2	0.453 (2)	0.465 (3)	0.9170 (6)	0.053 (7)*
C3	0.3691 (3)	0.5566 (4)	0.96207 (7)	0.0555 (7)
H3	0.443 (3)	0.581 (3)	0.9752 (7)	0.069 (8)*
C4	0.2523 (3)	0.5870 (3)	0.97854 (6)	0.0467 (6)
C5	0.1393 (3)	0.5495 (4)	0.96057 (7)	0.0568 (7)
H5	0.060 (3)	0.573 (3)	0.9732 (7)	0.065 (8)*
C6	0.1440 (3)	0.4782 (4)	0.92553 (7)	0.0556 (7)
H6	0.070 (2)	0.444 (3)	0.9135 (6)	0.047 (7)*
C7	0.3359 (3)	0.4263 (3)	0.84786 (6)	0.0480 (6)
H7	0.398 (2)	0.516 (3)	0.8527 (6)	0.057 (7)*
C8	0.3315 (3)	0.3565 (3)	0.81039 (6)	0.0479 (6)
H8	0.268 (2)	0.268 (4)	0.8065 (6)	0.059 (7)*
C9	0.4046 (3)	0.4120 (3)	0.78252 (6)	0.0459 (6)
H9	0.469 (3)	0.498 (4)	0.7890 (7)	0.069 (8)*
C10	0.3957 (2)	0.3588 (3)	0.74357 (6)	0.0414 (6)
C11	0.4865 (3)	0.4167 (3)	0.71798 (7)	0.0483 (6)
H11	0.553 (3)	0.488 (3)	0.7260 (6)	0.060 (8)*
C12	0.4795 (3)	0.3713 (4)	0.68120 (7)	0.0511 (6)
H12	0.542 (3)	0.413 (3)	0.6649 (7)	0.070 (8)*
C13	0.3810 (2)	0.2661 (3)	0.66847 (6)	0.0465 (6)
C14	0.2888 (3)	0.2071 (3)	0.69320 (7)	0.0492 (6)
H14	0.223 (2)	0.131 (3)	0.6858 (6)	0.050 (7)*
C15	0.2969 (2)	0.2547 (3)	0.73006 (6)	0.0471 (6)
H15	0.232 (2)	0.214 (3)	0.7470 (6)	0.049 (6)*
C16	0.2855 (4)	0.1184 (5)	0.61684 (9)	0.0782 (11)
H16A	0.305 (3)	0.105 (4)	0.5907 (9)	0.095 (10)*
H16B	0.202 (3)	0.166 (4)	0.6209 (7)	0.070 (10)*
H16C	0.289 (3)	−0.004 (5)	0.6292 (9)	0.104 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0619 (12)	0.0555 (12)	0.0407 (10)	−0.0088 (11)	0.0015 (11)	−0.0024 (10)
N2	0.0685 (15)	0.070 (2)	0.0466 (11)	−0.0012 (14)	0.0010 (14)	−0.0081 (11)
O1	0.080 (2)	0.148 (2)	0.0626 (13)	−0.0073 (15)	−0.0123 (11)	−0.0410 (14)
O2	0.079 (2)	0.156 (2)	0.0691 (14)	0.004 (2)	0.0151 (11)	−0.0449 (15)
O3	0.0813 (13)	0.0673 (12)	0.0385 (9)	−0.0055 (11)	0.0018 (8)	−0.0035 (9)
C1	0.0559 (15)	0.0454 (13)	0.0374 (11)	−0.0062 (12)	0.0018 (12)	0.0012 (10)
C2	0.047 (2)	0.075 (2)	0.0452 (15)	0.0028 (14)	0.0023 (12)	−0.0063 (13)
C3	0.048 (2)	0.070 (2)	0.0484 (15)	−0.0024 (14)	−0.0092 (12)	−0.0035 (13)
C4	0.0560 (14)	0.0477 (14)	0.0364 (11)	−0.0009 (12)	0.0018 (13)	0.0007 (10)
C5	0.049 (2)	0.071 (2)	0.050 (2)	−0.0024 (14)	0.0049 (13)	−0.0016 (14)
C6	0.051 (2)	0.072 (2)	0.0442 (15)	−0.0130 (14)	−0.0049 (12)	−0.0028 (13)
C7	0.056 (2)	0.0451 (14)	0.0432 (13)	−0.0008 (13)	−0.0023 (12)	−0.0008 (11)
C8	0.056 (2)	0.0435 (13)	0.0438 (13)	−0.0044 (13)	0.0006 (12)	−0.0034 (11)
C9	0.053 (2)	0.0392 (14)	0.0454 (13)	−0.0014 (12)	−0.0029 (11)	−0.0049 (11)
C10	0.0500 (14)	0.0344 (11)	0.0397 (12)	0.0030 (11)	0.0025 (10)	−0.0028 (10)
C11	0.048 (2)	0.046 (2)	0.051 (2)	−0.0047 (12)	0.0013 (12)	−0.0005 (11)
C12	0.0522 (15)	0.057 (2)	0.0439 (14)	−0.0019 (13)	0.0096 (12)	0.0037 (12)
C13	0.0579 (15)	0.0422 (13)	0.0393 (12)	0.0060 (12)	−0.0001 (11)	0.0032 (11)
C14	0.060 (2)	0.0431 (14)	0.0446 (13)	−0.0087 (13)	−0.0001 (11)	−0.0033 (11)
C15	0.0565 (15)	0.0427 (13)	0.0421 (13)	−0.0070 (13)	0.0070 (11)	−0.0015 (11)
C16	0.110 (3)	0.076 (2)	0.049 (2)	−0.019 (2)	−0.003 (2)	−0.010 (2)

Geometric parameters (Å, º)

N1—C7	1.266 (3)	C7—H7	0.96 (3)
N1—C1	1.411 (3)	C8—C9	1.328 (3)
N2—O1	1.212 (3)	C8—H8	0.96 (3)
N2—O2	1.212 (3)	C9—C10	1.462 (3)
N2—C4	1.458 (3)	C9—H9	0.96 (3)
O3—C13	1.365 (3)	C10—C15	1.386 (3)
O3—C16	1.415 (4)	C10—C11	1.391 (3)
C1—C2	1.379 (4)	C11—C12	1.370 (3)
C1—C6	1.383 (3)	C11—H11	0.92 (3)
C2—C3	1.379 (3)	C12—C13	1.379 (3)
C2—H2	0.93 (2)	C12—H12	0.93 (3)
C3—C4	1.373 (3)	C13—C14	1.384 (3)
C3—H3	0.92 (3)	C14—C15	1.378 (3)
C4—C5	1.372 (3)	C14—H14	0.93 (2)
C5—C6	1.374 (4)	C15—H15	0.96 (2)
C5—H5	0.96 (3)	C16—H16A	0.97 (3)
C6—H6	0.92 (2)	C16—H16B	0.96 (3)
C7—C8	1.450 (3)	C16—H16C	1.03 (4)
C7—N1—C1	119.4 (2)	C5—C6—C1	120.7 (2)
O1—N2—O2	122.4 (2)	N1—C7—C8	120.7 (3)
O1—N2—C4	119.4 (3)	C9—C8—C7	124.7 (3)
O2—N2—C4	118.2 (3)	C8—C9—C10	126.9 (2)
C13—O3—C16	118.5 (2)	C15—C10—C11	116.9 (2)
C2—C1—C6	119.3 (2)	C15—C10—C9	122.8 (2)
C2—C1—N1	123.7 (2)	C11—C10—C9	120.4 (2)
C6—C1—N1	117.0 (2)	C12—C11—C10	121.7 (2)
C3—C2—C1	120.4 (3)	C11—C12—C13	120.4 (2)
C4—C3—C2	119.2 (2)	O3—C13—C12	115.9 (2)
C5—C4—C3	121.4 (2)	O3—C13—C14	124.8 (2)
C5—C4—N2	119.8 (2)	C12—C13—C14	119.4 (2)
C3—C4—N2	118.8 (2)	C15—C14—C13	119.5 (2)
C4—C5—C6	119.0 (3)	C14—C15—C10	122.2 (2)
C7—N1—C1—C2	−40.2 (4)	N1—C7—C8—C9	174.6 (3)
C7—N1—C1—C6	142.7 (3)	C7—C8—C9—C10	−173.6 (2)
C6—C1—C2—C3	−1.7 (4)	C8—C9—C10—C15	7.7 (4)
N1—C1—C2—C3	−178.7 (3)	C8—C9—C10—C11	−174.3 (3)
C1—C2—C3—C4	0.4 (4)	C15—C10—C11—C12	−0.7 (4)
C2—C3—C4—C5	0.1 (4)	C9—C10—C11—C12	−178.9 (2)
C2—C3—C4—N2	179.8 (2)	C10—C11—C12—C13	0.1 (4)
O1—N2—C4—C5	179.4 (3)	C16—O3—C13—C12	178.4 (3)
O2—N2—C4—C5	−1.0 (4)	C16—O3—C13—C14	−2.2 (4)
O1—N2—C4—C3	−0.3 (4)	C11—C12—C13—O3	179.6 (2)
O2—N2—C4—C3	179.3 (3)	C11—C12—C13—C14	0.2 (4)
C3—C4—C5—C6	0.7 (4)	O3—C13—C14—C15	−179.2 (2)
N2—C4—C5—C6	−179.0 (2)	C12—C13—C14—C15	0.1 (4)
C4—C5—C6—C1	−2.1 (4)	C13—C14—C15—C10	−0.8 (4)
C2—C1—C6—C5	2.5 (4)	C11—C10—C15—C14	1.1 (4)
N1—C1—C6—C5	179.8 (3)	C9—C10—C15—C14	179.2 (2)
C1—N1—C7—C8	−178.1 (2)

(1b) N-{(E,2E)-3-[4-(dimethylamino)phenyl]-2-propenylidene}-3-nitroaniline

Crystal data

C17H17N3O2	F(000) = 312
Mr = 295.34	Dx = 1.299 Mg m^−3
Triclinic, P1	Melting point: 138(1) K
a = 6.7910 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.204 (2) Å	Cell parameters from 24 reflections
c = 12.185 (2) Å	θ = 10–11°
α = 113.20 (3)°	µ = 0.09 mm^−1
β = 98.97 (3)°	T = 295 K
γ = 95.53 (3)°	Plate, yellow
V = 754.9 (3) Å^3	0.60 × 0.30 × 0.30 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.047
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.9°
Graphite monochromator	h = 0→8
θ/2θ scans	k = −12→12
2899 measured reflections	l = −14→14
2650 independent reflections	2 standard reflections every 98 reflections
1255 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.094	Calculated w = 1/[σ^2(Fo^2) + (0.0578P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
2595 reflections	Δρmax = 0.11 e Å^−3
201 parameters	Δρmin = −0.14 e Å^−3

Special details

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 on F² for ALL reflections except for 55 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4301 (3)	0.7782 (2)	0.3477 (2)	0.0575 (5)
N2	−0.2314 (3)	0.7066 (3)	0.0780 (2)	0.0681 (6)
N3	1.3680 (3)	0.2012 (2)	0.2510 (2)	0.0660 (6)
O1	−0.3821 (3)	0.7578 (2)	0.0578 (2)	0.0948 (7)
O2	−0.2091 (3)	0.5847 (2)	0.01351 (15)	0.0870 (6)
C1	0.2475 (3)	0.8211 (2)	0.3127 (2)	0.0497 (6)
C2	0.0966 (3)	0.7386 (2)	0.2089 (2)	0.0544 (6)
H2	0.1103 (3)	0.6466 (2)	0.1559 (2)	0.065*
C3	−0.0722 (3)	0.7953 (2)	0.1863 (2)	0.0518 (6)
C4	−0.1004 (4)	0.9294 (3)	0.2608 (2)	0.0689 (7)
H4	−0.2163 (4)	0.9651 (3)	0.2426 (2)	0.083*
C5	0.0470 (4)	1.0101 (3)	0.3633 (2)	0.0771 (8)
H5	0.0312 (4)	1.1017 (3)	0.4158 (2)	0.092*
C6	0.2173 (3)	0.9565 (2)	0.3888 (2)	0.0609 (7)
H6	0.3152 (3)	1.0126 (2)	0.4590 (2)	0.073*
C7	0.4750 (3)	0.6606 (2)	0.2792 (2)	0.0526 (6)
H7	0.3836 (3)	0.6038 (2)	0.2062 (2)	0.063*
C8	0.6554 (3)	0.6085 (2)	0.3056 (2)	0.0561 (6)
H8	0.7467 (3)	0.6623 (2)	0.3793 (2)	0.067*
C9	0.6980 (3)	0.4848 (2)	0.2279 (2)	0.0576 (6)
H9	0.5998 (3)	0.4350 (2)	0.1565 (2)	0.069*
C10	0.8706 (3)	0.4170 (2)	0.2373 (2)	0.0515 (6)
C11	0.8874 (4)	0.2902 (3)	0.1405 (2)	0.0643 (7)
H11	0.7850 (4)	0.2522 (3)	0.0704 (2)	0.077*
C12	1.0472 (3)	0.2192 (3)	0.1439 (2)	0.0610 (7)
H12	1.0505 (3)	0.1350 (3)	0.0766 (2)	0.073*
C13	1.2059 (3)	0.2706 (2)	0.2464 (2)	0.0516 (6)
C14	1.1904 (3)	0.3975 (2)	0.3449 (2)	0.0586 (6)
H14	1.2912 (3)	0.4346 (2)	0.4157 (2)	0.070*
C15	1.0301 (3)	0.4675 (2)	0.3389 (2)	0.0581 (6)
H15	1.0274 (3)	0.5525 (2)	0.4055 (2)	0.070*
C16	1.5241 (4)	0.2490 (3)	0.3610 (2)	0.0756 (8)
H16A	1.6207 (15)	0.1845 (11)	0.3478 (6)	0.113*
H16B	1.4638 (5)	0.2490 (17)	0.4272 (4)	0.113*
H16C	1.5912 (17)	0.3451 (8)	0.3808 (9)	0.113*
C17	1.3793 (4)	0.0704 (3)	0.1491 (2)	0.0802 (8)
H17A	1.5054 (12)	0.0395 (11)	0.1659 (7)	0.120*
H17B	1.371 (3)	0.0884 (5)	0.0770 (4)	0.120*
H17C	1.2691 (15)	−0.0039 (6)	0.1364 (10)	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0494 (12)	0.0569 (12)	0.0524 (11)	0.0178 (10)	−0.0003 (9)	0.0104 (10)
N2	0.0646 (14)	0.076 (2)	0.0536 (13)	0.0164 (12)	−0.0013 (11)	0.0207 (12)
N3	0.0636 (13)	0.0642 (13)	0.0596 (12)	0.0268 (11)	0.0034 (10)	0.0148 (10)
O1	0.0683 (12)	0.108 (2)	0.0886 (14)	0.0350 (12)	−0.0166 (10)	0.0280 (12)
O2	0.0840 (13)	0.0793 (14)	0.0627 (11)	0.0188 (11)	−0.0116 (9)	0.0024 (10)
C1	0.0488 (14)	0.0484 (14)	0.0466 (13)	0.0108 (11)	0.0044 (11)	0.0158 (11)
C2	0.0559 (14)	0.0485 (13)	0.0521 (14)	0.0140 (12)	0.0070 (12)	0.0145 (11)
C3	0.0459 (14)	0.0571 (15)	0.0490 (13)	0.0107 (12)	0.0017 (11)	0.0211 (12)
C4	0.061 (2)	0.062 (2)	0.075 (2)	0.0244 (14)	0.0018 (14)	0.0211 (14)
C5	0.072 (2)	0.056 (2)	0.082 (2)	0.0239 (15)	0.0028 (15)	0.0091 (14)
C6	0.058 (2)	0.0534 (14)	0.0568 (14)	0.0146 (12)	0.0014 (12)	0.0109 (12)
C7	0.0444 (13)	0.0554 (15)	0.0482 (13)	0.0059 (12)	0.0009 (11)	0.0153 (12)
C8	0.0490 (14)	0.057 (2)	0.0549 (14)	0.0098 (12)	0.0027 (11)	0.0182 (12)
C9	0.0502 (14)	0.061 (2)	0.0531 (14)	0.0116 (12)	0.0013 (11)	0.0181 (12)
C10	0.0464 (13)	0.0503 (14)	0.0532 (14)	0.0119 (11)	0.0069 (11)	0.0175 (11)
C11	0.062 (2)	0.061 (2)	0.0516 (14)	0.0163 (13)	−0.0009 (12)	0.0089 (12)
C12	0.061 (2)	0.0567 (15)	0.0508 (14)	0.0188 (13)	0.0040 (12)	0.0083 (12)
C13	0.0519 (14)	0.0513 (14)	0.0512 (13)	0.0132 (12)	0.0106 (11)	0.0199 (11)
C14	0.0523 (15)	0.0578 (15)	0.0526 (14)	0.0142 (12)	−0.0031 (11)	0.0136 (12)
C15	0.060 (2)	0.0505 (14)	0.0532 (14)	0.0168 (12)	0.0068 (12)	0.0113 (11)
C16	0.070 (2)	0.080 (2)	0.073 (2)	0.0236 (15)	0.0039 (14)	0.0288 (15)
C17	0.087 (2)	0.076 (2)	0.074 (2)	0.042 (2)	0.0175 (15)	0.0205 (15)

Geometric parameters (Å, º)

N1—C7	1.261 (2)	C4—C5	1.372 (3)
N1—C1	1.413 (2)	C5—C6	1.370 (3)
N2—O2	1.220 (2)	C7—C8	1.423 (3)
N2—O1	1.227 (2)	C8—C9	1.337 (3)
N2—C3	1.468 (3)	C9—C10	1.429 (3)
N3—C13	1.371 (3)	C10—C15	1.394 (3)
N3—C17	1.440 (3)	C10—C11	1.396 (3)
N3—C16	1.449 (3)	C11—C12	1.366 (3)
C1—C6	1.384 (3)	C12—C13	1.397 (3)
C1—C2	1.397 (3)	C13—C14	1.404 (3)
C2—C3	1.371 (3)	C14—C15	1.366 (3)
C3—C4	1.363 (3)
C7—N1—C1	120.4 (2)	C6—C5—C4	120.4 (2)
O2—N2—O1	123.2 (2)	C5—C6—C1	121.7 (2)
O2—N2—C3	118.5 (2)	N1—C7—C8	124.7 (2)
O1—N2—C3	118.3 (2)	C9—C8—C7	122.2 (2)
C13—N3—C17	120.5 (2)	C8—C9—C10	130.2 (2)
C13—N3—C16	121.7 (2)	C15—C10—C11	115.2 (2)
C17—N3—C16	117.6 (2)	C15—C10—C9	124.8 (2)
C6—C1—C2	117.8 (2)	C11—C10—C9	120.0 (2)
C6—C1—N1	116.6 (2)	C12—C11—C10	123.0 (2)
C2—C1—N1	125.6 (2)	C11—C12—C13	121.3 (2)
C3—C2—C1	119.0 (2)	N3—C13—C12	122.1 (2)
C4—C3—C2	123.0 (2)	N3—C13—C14	121.6 (2)
C4—C3—N2	118.5 (2)	C12—C13—C14	116.3 (2)
C2—C3—N2	118.5 (2)	C15—C14—C13	121.3 (2)
C3—C4—C5	118.1 (2)	C14—C15—C10	122.8 (2)
C7—N1—C1—C6	−175.3 (2)	C7—C8—C9—C10	178.9 (2)
C7—N1—C1—C2	4.9 (3)	C8—C9—C10—C15	4.0 (4)
C6—C1—C2—C3	0.7 (3)	C8—C9—C10—C11	−176.4 (3)
N1—C1—C2—C3	−179.5 (2)	C15—C10—C11—C12	0.3 (3)
C1—C2—C3—C4	−0.1 (3)	C9—C10—C11—C12	−179.4 (2)
C1—C2—C3—N2	−179.0 (2)	C10—C11—C12—C13	0.0 (4)
O2—N2—C3—C4	−177.6 (2)	C17—N3—C13—C12	−0.5 (3)
O1—N2—C3—C4	1.2 (3)	C16—N3—C13—C12	−175.2 (2)
O2—N2—C3—C2	1.3 (3)	C17—N3—C13—C14	179.4 (2)
O1—N2—C3—C2	−179.8 (2)	C16—N3—C13—C14	4.7 (3)
C2—C3—C4—C5	−0.4 (4)	C11—C12—C13—N3	−179.6 (2)
N2—C3—C4—C5	178.5 (2)	C11—C12—C13—C14	0.5 (3)
C3—C4—C5—C6	0.3 (4)	N3—C13—C14—C15	178.8 (2)
C4—C5—C6—C1	0.4 (4)	C12—C13—C14—C15	−1.2 (3)
C2—C1—C6—C5	−0.9 (3)	C13—C14—C15—C10	1.6 (4)
N1—C1—C6—C5	179.3 (2)	C11—C10—C15—C14	−1.0 (3)
C1—N1—C7—C8	179.4 (2)	C9—C10—C15—C14	178.6 (2)
N1—C7—C8—C9	−178.0 (2)

(2b) N-{(E,2E)-3-[4-(dimethylamino)phenyl]-2-propenylidene}-4-nitroaniline

Crystal data

C17H17N3O2	F(000) = 312
Mr = 295.34	Dx = 1.296 Mg m^−3
Triclinic, P1	Melting point: 195(1) K
a = 6.1650 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2730 (15) Å	Cell parameters from 24 reflections
c = 17.158 (3) Å	θ = 10–11°
α = 90.70 (3)°	µ = 0.09 mm^−1
β = 100.10 (3)°	T = 298 K
γ = 91.37 (3)°	Square prism, dark yellow
V = 757.1 (3) Å^3	0.40 × 0.20 × 0.20 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.031
Radiation source: fine-focus sealed tube	θmax = 29.0°, θmin = 1.2°
Graphite monochromator	h = 0→8
θ/2θ scans	k = −9→9
4620 measured reflections	l = −23→23
4007 independent reflections	2 standard reflections every 98 reflections
1534 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	All H-atom parameters refined
wR(F^2) = 0.107	Calculated w = 1/[σ^2(Fo^2) + (0.0454P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
3955 reflections	Δρmax = 0.16 e Å^−3
267 parameters	Δρmin = −0.17 e Å^−3
0 restraints

Special details

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 on F² for ALL reflections except for 52 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4643 (4)	0.7254 (3)	−0.06229 (12)	0.0461 (6)
N2	0.6366 (5)	0.7422 (3)	−0.37293 (14)	0.0606 (7)
N3	−0.1100 (4)	0.7689 (3)	0.37508 (12)	0.0522 (6)
O1	0.5158 (4)	0.6588 (4)	−0.42520 (13)	0.0946 (8)
O2	0.8034 (5)	0.8222 (4)	−0.38343 (13)	0.1092 (10)
C1	0.4906 (4)	0.7336 (3)	−0.14213 (14)	0.0396 (6)
C2	0.3502 (5)	0.6457 (4)	−0.2042 (2)	0.0459 (7)
H2	0.230 (4)	0.577 (3)	−0.1945 (13)	0.053 (8)*
C3	0.3962 (5)	0.6488 (4)	−0.2798 (2)	0.0479 (7)
H3	0.296 (4)	0.584 (3)	−0.3235 (14)	0.054 (7)*
C4	0.5828 (4)	0.7427 (3)	−0.29287 (14)	0.0429 (6)
C5	0.7240 (5)	0.8345 (4)	−0.2330 (2)	0.0463 (7)
H5	0.850 (4)	0.898 (3)	−0.2441 (14)	0.066 (9)*
C6	0.6765 (4)	0.8284 (3)	−0.1582 (2)	0.0435 (7)
H6	0.769 (3)	0.894 (3)	−0.1145 (13)	0.034 (6)*
C7	0.2721 (5)	0.7256 (4)	−0.0446 (2)	0.0444 (6)
H7	0.132 (4)	0.734 (3)	−0.0862 (14)	0.056 (8)*
C8	0.2390 (5)	0.7133 (4)	0.0362 (2)	0.0467 (7)
H8	0.368 (4)	0.691 (3)	0.0730 (15)	0.062 (9)*
C9	0.0466 (5)	0.7398 (4)	0.0594 (2)	0.0457 (7)
H9	−0.072 (5)	0.773 (4)	0.0230 (15)	0.066 (9)*
C10	0.0072 (4)	0.7428 (3)	0.14075 (13)	0.0373 (6)
C11	−0.1818 (4)	0.8220 (3)	0.1591 (2)	0.0423 (7)
H11	−0.282 (4)	0.866 (3)	0.1153 (13)	0.043 (7)*
C12	−0.2200 (5)	0.8351 (4)	0.23552 (15)	0.0423 (6)
H12	−0.349 (4)	0.893 (3)	0.2450 (12)	0.038 (6)*
C13	−0.0720 (4)	0.7641 (3)	0.29870 (15)	0.0407 (6)
C14	0.1183 (5)	0.6836 (4)	0.2800 (2)	0.0428 (6)
H14	0.229 (4)	0.633 (3)	0.3219 (14)	0.049 (7)*
C15	0.1558 (4)	0.6747 (4)	0.2037 (2)	0.0438 (7)
H15	0.288 (4)	0.622 (3)	0.1942 (13)	0.045 (7)*
C16	0.0616 (7)	0.7185 (7)	0.4404 (2)	0.0754 (11)
H16A	0.012 (5)	0.731 (4)	0.490 (2)	0.105 (12)*
H16B	0.198 (7)	0.791 (6)	0.440 (2)	0.16 (2)*
H16C	0.102 (5)	0.590 (5)	0.4342 (18)	0.098 (12)*
C17	−0.2927 (7)	0.8689 (7)	0.3950 (2)	0.0786 (11)
H17A	−0.316 (6)	0.848 (5)	0.446 (2)	0.122 (14)*
H17B	−0.433 (7)	0.837 (5)	0.359 (2)	0.144 (18)*
H17C	−0.259 (7)	1.005 (6)	0.392 (3)	0.17 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0461 (14)	0.0521 (14)	0.0426 (13)	−0.0002 (11)	0.0149 (11)	0.0024 (10)
N2	0.079 (2)	0.066 (2)	0.0423 (15)	0.0064 (15)	0.0242 (14)	0.0021 (13)
N3	0.061 (2)	0.060 (2)	0.0397 (13)	0.0056 (12)	0.0199 (12)	0.0030 (11)
O1	0.107 (2)	0.130 (2)	0.0473 (13)	−0.012 (2)	0.0175 (13)	−0.0180 (13)
O2	0.128 (2)	0.141 (2)	0.073 (2)	−0.046 (2)	0.063 (2)	−0.0086 (14)
C1	0.039 (2)	0.041 (2)	0.0409 (15)	0.0038 (12)	0.0117 (12)	0.0024 (12)
C2	0.046 (2)	0.043 (2)	0.050 (2)	−0.0074 (13)	0.0124 (14)	−0.0010 (12)
C3	0.051 (2)	0.050 (2)	0.042 (2)	−0.0041 (14)	0.0075 (14)	−0.0047 (13)
C4	0.055 (2)	0.042 (2)	0.0351 (15)	0.0067 (13)	0.0157 (13)	0.0042 (12)
C5	0.047 (2)	0.048 (2)	0.047 (2)	−0.0030 (14)	0.0164 (14)	0.0039 (13)
C6	0.041 (2)	0.047 (2)	0.042 (2)	−0.0023 (13)	0.0062 (13)	−0.0050 (12)
C7	0.042 (2)	0.050 (2)	0.041 (2)	−0.0002 (13)	0.0094 (13)	0.0010 (12)
C8	0.048 (2)	0.056 (2)	0.037 (2)	−0.0062 (14)	0.0094 (14)	0.0009 (12)
C9	0.050 (2)	0.049 (2)	0.039 (2)	−0.0003 (14)	0.0100 (14)	0.0022 (12)
C10	0.036 (2)	0.0402 (15)	0.0365 (14)	−0.0058 (12)	0.0091 (12)	0.0002 (11)
C11	0.036 (2)	0.048 (2)	0.042 (2)	−0.0027 (13)	0.0044 (13)	0.0053 (12)
C12	0.038 (2)	0.047 (2)	0.044 (2)	0.0065 (13)	0.0115 (13)	0.0040 (12)
C13	0.044 (2)	0.0368 (15)	0.043 (2)	−0.0057 (12)	0.0125 (13)	0.0003 (11)
C14	0.045 (2)	0.045 (2)	0.039 (2)	0.0027 (13)	0.0070 (13)	0.0065 (12)
C15	0.036 (2)	0.050 (2)	0.047 (2)	0.0062 (13)	0.0132 (13)	0.0039 (12)
C16	0.094 (3)	0.096 (3)	0.039 (2)	0.026 (3)	0.015 (2)	0.010 (2)
C17	0.082 (3)	0.114 (4)	0.049 (2)	0.027 (2)	0.033 (2)	−0.002 (2)

Geometric parameters (Å, º)

N1—C7	1.274 (3)	C8—C9	1.333 (4)
N1—C1	1.409 (3)	C8—H8	0.95 (3)
N2—O1	1.208 (3)	C9—C10	1.459 (3)
N2—O2	1.211 (3)	C9—H9	0.91 (3)
N2—C4	1.469 (3)	C10—C15	1.392 (3)
N3—C13	1.372 (3)	C10—C11	1.394 (3)
N3—C17	1.443 (4)	C11—C12	1.375 (3)
N3—C16	1.457 (4)	C11—H11	0.95 (2)
C1—C2	1.387 (3)	C12—C13	1.401 (3)
C1—C6	1.394 (3)	C12—H12	0.95 (2)
C2—C3	1.377 (4)	C13—C14	1.408 (3)
C2—H2	0.93 (2)	C14—C15	1.370 (4)
C3—C4	1.377 (3)	C14—H14	0.98 (2)
C3—H3	0.99 (2)	C15—H15	0.95 (2)
C4—C5	1.378 (3)	C16—H16A	0.96 (3)
C5—C6	1.366 (3)	C16—H16B	0.98 (4)
C5—H5	0.95 (2)	C16—H16C	0.98 (4)
C6—H6	0.97 (2)	C17—H17A	0.92 (4)
C7—C8	1.439 (4)	C17—H17B	0.99 (4)
C7—H7	1.02 (2)	C17—H17C	1.01 (4)
C7—N1—C1	120.1 (2)	C6—C5—C4	118.1 (3)
O1—N2—O2	122.6 (3)	C5—C6—C1	121.6 (3)
O1—N2—C4	118.8 (3)	N1—C7—C8	121.6 (3)
O2—N2—C4	118.6 (3)	C9—C8—C7	124.1 (3)
C13—N3—C17	120.5 (3)	C8—C9—C10	126.4 (3)
C13—N3—C16	120.4 (3)	C15—C10—C11	116.8 (2)
C17—N3—C16	117.0 (3)	C15—C10—C9	122.8 (3)
C2—C1—C6	118.7 (2)	C11—C10—C9	120.3 (3)
C2—C1—N1	124.1 (2)	C12—C11—C10	122.1 (3)
C6—C1—N1	117.1 (2)	C11—C12—C13	121.1 (3)
C3—C2—C1	120.6 (3)	N3—C13—C12	122.3 (2)
C4—C3—C2	118.7 (3)	N3—C13—C14	121.0 (2)
C3—C4—C5	122.3 (2)	C12—C13—C14	116.7 (2)
C3—C4—N2	119.1 (3)	C15—C14—C13	121.5 (3)
C5—C4—N2	118.6 (3)	C14—C15—C10	121.8 (3)
C7—N1—C1—C2	−37.3 (4)	C7—C8—C9—C10	−175.0 (2)
C7—N1—C1—C6	146.2 (2)	C8—C9—C10—C15	−16.0 (4)
C6—C1—C2—C3	1.4 (4)	C8—C9—C10—C11	161.7 (3)
N1—C1—C2—C3	−175.1 (3)	C15—C10—C11—C12	0.8 (4)
C1—C2—C3—C4	−0.8 (4)	C9—C10—C11—C12	−177.0 (2)
C2—C3—C4—C5	−0.4 (4)	C10—C11—C12—C13	−1.8 (4)
C2—C3—C4—N2	178.2 (2)	C17—N3—C13—C12	−7.8 (4)
O1—N2—C4—C3	−0.2 (4)	C16—N3—C13—C12	−171.0 (3)
O2—N2—C4—C3	−178.6 (3)	C17—N3—C13—C14	173.3 (3)
O1—N2—C4—C5	178.5 (3)	C16—N3—C13—C14	10.2 (4)
O2—N2—C4—C5	0.2 (4)	C11—C12—C13—N3	−177.4 (2)
C3—C4—C5—C6	1.0 (4)	C11—C12—C13—C14	1.5 (3)
N2—C4—C5—C6	−177.6 (2)	N3—C13—C14—C15	178.7 (2)
C4—C5—C6—C1	−0.4 (4)	C12—C13—C14—C15	−0.3 (4)
C2—C1—C6—C5	−0.8 (4)	C13—C14—C15—C10	−0.7 (4)
N1—C1—C6—C5	175.9 (2)	C11—C10—C15—C14	0.4 (4)
C1—N1—C7—C8	178.6 (2)	C9—C10—C15—C14	178.2 (3)
N1—C7—C8—C9	169.7 (3)

(3b) N-{(E,2E)-3-[4-(dimethylamino)phenyl]-2-propenylidene}-2-methyl- −4-nitroaniline

Crystal data

C18H19N3O2	F(000) = 328
Mr = 309.36	Dx = 1.260 Mg m^−3
Triclinic, P1	Melting point: 175(1) K
a = 8.438 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.609 (2) Å	Cell parameters from 24 reflections
c = 10.546 (2) Å	θ = 10–11°
α = 72.95 (3)°	µ = 0.08 mm^−1
β = 86.13 (3)°	T = 295 K
γ = 89.81 (3)°	Plate, yellow
V = 815.5 (3) Å^3	0.40 × 0.20 × 0.20 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.086
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.0°
Graphite monochromator	h = 0→10
θ/2θ scans	k = −11→11
3073 measured reflections	l = −12→12
2858 independent reflections	2 standard reflections every 98 reflections
1393 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.080	H-atom parameters constrained
wR(F^2) = 0.201	Calculated w = 1/[σ^2(Fo^2) + (0.1556P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2779 reflections	Δρmax = 0.24 e Å^−3
211 parameters	Δρmin = −0.21 e Å^−3
0 restraints

Special details

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 on F² for ALL reflections except for 79 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6735 (4)	−0.1821 (3)	−0.0962 (3)	0.0633 (9)
N2	1.2668 (4)	−0.3062 (4)	−0.3050 (5)	0.0792 (12)
N3	−0.2696 (4)	−0.2255 (3)	0.3330 (4)	0.0743 (10)
O1	1.3629 (4)	−0.3717 (4)	−0.2290 (4)	0.1051 (12)
O2	1.2919 (4)	−0.2646 (4)	−0.4252 (4)	0.121 (2)
C1	0.8196 (4)	−0.2226 (3)	−0.1455 (4)	0.0540 (10)
C2	0.9322 (4)	−0.2949 (4)	−0.0634 (4)	0.0610 (10)
H2	0.9096 (4)	−0.3246 (4)	0.0282 (4)	0.073*
C3	1.0777 (5)	−0.3233 (4)	−0.1159 (5)	0.0648 (11)
H3	1.1533 (5)	−0.3736 (4)	−0.0605 (5)	0.078*
C4	1.1102 (4)	−0.2772 (3)	−0.2498 (4)	0.0581 (10)
C5	0.9985 (5)	−0.2072 (4)	−0.3343 (4)	0.0620 (11)
H5	1.0216 (5)	−0.1804 (4)	−0.4258 (4)	0.074*
C6	0.8523 (4)	−0.1768 (3)	−0.2828 (4)	0.0576 (10)
C7	0.5892 (4)	−0.2733 (4)	−0.0033 (4)	0.0613 (10)
H7	0.6245 (4)	−0.3681 (4)	0.0292 (4)	0.074*
C8	0.4441 (4)	−0.2343 (4)	0.0515 (4)	0.0626 (11)
H8	0.4132 (4)	−0.1379 (4)	0.0207 (4)	0.075*
C9	0.3485 (4)	−0.3265 (4)	0.1444 (4)	0.0614 (10)
H9	0.3851 (4)	−0.4207 (4)	0.1778 (4)	0.074*
C10	0.1954 (4)	−0.2970 (3)	0.1988 (4)	0.0530 (9)
C11	0.1011 (4)	−0.4073 (3)	0.2855 (4)	0.0597 (10)
H11	0.1430 (4)	−0.5000 (3)	0.3142 (4)	0.072*
C12	−0.0487 (4)	−0.3866 (4)	0.3304 (4)	0.0617 (11)
H12	−0.1071 (4)	−0.4651 (4)	0.3867 (4)	0.074*
C13	−0.1180 (4)	−0.2466 (4)	0.2928 (4)	0.0578 (10)
C14	−0.0221 (5)	−0.1347 (3)	0.2080 (4)	0.0641 (11)
H14	−0.0625 (5)	−0.0413 (3)	0.1804 (4)	0.077*
C15	0.1275 (5)	−0.1578 (4)	0.1650 (4)	0.0648 (11)
H15	0.1877 (5)	−0.0791 (4)	0.1112 (4)	0.078*
C16	−0.3465 (5)	−0.0888 (5)	0.2782 (5)	0.0867 (14)
H16A	−0.4537 (13)	−0.0943 (13)	0.316 (3)	0.130*
H16B	−0.347 (4)	−0.0687 (18)	0.1835 (7)	0.130*
H16C	−0.290 (2)	−0.0123 (7)	0.298 (3)	0.130*
C17	−0.3698 (5)	−0.3452 (5)	0.4134 (5)	0.0846 (14)
H17A	−0.4717 (13)	−0.3089 (7)	0.434 (3)	0.127*
H17B	−0.3212 (18)	−0.391 (2)	0.4946 (13)	0.127*
H17C	−0.383 (3)	−0.4147 (17)	0.3654 (12)	0.127*
C18	0.7321 (5)	−0.0946 (5)	−0.3736 (5)	0.0869 (14)
H18A	0.692 (3)	−0.016 (2)	−0.342 (2)	0.130*
H18B	0.646 (2)	−0.1591 (10)	−0.375 (3)	0.130*
H18C	0.7812 (12)	−0.056 (3)	−0.4619 (9)	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.056 (2)	0.044 (2)	0.084 (2)	−0.0060 (14)	0.018 (2)	−0.015 (2)
N2	0.069 (2)	0.038 (2)	0.124 (4)	−0.003 (2)	0.028 (2)	−0.021 (2)
N3	0.063 (2)	0.045 (2)	0.109 (3)	0.001 (2)	0.025 (2)	−0.020 (2)
O1	0.070 (2)	0.095 (2)	0.150 (3)	0.024 (2)	0.001 (2)	−0.038 (2)
O2	0.109 (3)	0.097 (3)	0.127 (3)	0.027 (2)	0.061 (2)	−0.001 (2)
C1	0.055 (2)	0.031 (2)	0.074 (3)	−0.009 (2)	0.012 (2)	−0.016 (2)
C2	0.060 (2)	0.046 (2)	0.074 (3)	−0.007 (2)	0.007 (2)	−0.017 (2)
C3	0.057 (2)	0.043 (2)	0.094 (3)	−0.001 (2)	0.000 (2)	−0.020 (2)
C4	0.056 (2)	0.028 (2)	0.088 (3)	−0.006 (2)	0.017 (2)	−0.018 (2)
C5	0.074 (3)	0.030 (2)	0.077 (3)	−0.007 (2)	0.016 (2)	−0.013 (2)
C6	0.057 (2)	0.031 (2)	0.080 (3)	−0.006 (2)	0.011 (2)	−0.012 (2)
C7	0.059 (2)	0.041 (2)	0.080 (3)	−0.005 (2)	0.006 (2)	−0.014 (2)
C8	0.056 (2)	0.044 (2)	0.081 (3)	−0.003 (2)	0.012 (2)	−0.010 (2)
C9	0.059 (2)	0.044 (2)	0.077 (3)	−0.005 (2)	0.004 (2)	−0.015 (2)
C10	0.058 (2)	0.034 (2)	0.066 (2)	−0.0082 (15)	0.008 (2)	−0.016 (2)
C11	0.063 (2)	0.033 (2)	0.071 (2)	0.000 (2)	0.010 (2)	0.000 (2)
C12	0.065 (2)	0.031 (2)	0.078 (3)	−0.011 (2)	0.017 (2)	−0.003 (2)
C13	0.063 (2)	0.037 (2)	0.073 (3)	−0.005 (2)	0.012 (2)	−0.019 (2)
C14	0.077 (3)	0.025 (2)	0.085 (3)	−0.003 (2)	0.016 (2)	−0.012 (2)
C15	0.074 (3)	0.027 (2)	0.088 (3)	−0.011 (2)	0.021 (2)	−0.015 (2)
C16	0.075 (3)	0.061 (3)	0.129 (4)	0.017 (2)	0.000 (3)	−0.036 (3)
C17	0.066 (3)	0.071 (3)	0.107 (3)	−0.008 (2)	0.027 (2)	−0.019 (2)
C18	0.078 (3)	0.075 (3)	0.097 (3)	0.006 (2)	0.006 (3)	−0.011 (2)

Geometric parameters (Å, º)

N1—C7	1.281 (4)	C4—C5	1.375 (5)
N1—C1	1.404 (4)	C5—C6	1.379 (5)
N2—O2	1.215 (5)	C6—C18	1.501 (6)
N2—O1	1.219 (5)	C7—C8	1.415 (5)
N2—C4	1.468 (5)	C8—C9	1.336 (5)
N3—C13	1.354 (4)	C9—C10	1.439 (5)
N3—C16	1.443 (5)	C10—C11	1.390 (5)
N3—C17	1.447 (5)	C10—C15	1.409 (5)
C1—C2	1.374 (5)	C11—C12	1.354 (5)
C1—C6	1.392 (5)	C12—C13	1.422 (5)
C2—C3	1.373 (5)	C13—C14	1.398 (5)
C3—C4	1.359 (6)	C14—C15	1.352 (5)
C7—N1—C1	120.8 (3)	C5—C6—C1	118.7 (4)
O2—N2—O1	123.9 (4)	C5—C6—C18	120.3 (4)
O2—N2—C4	117.4 (4)	C1—C6—C18	121.0 (3)
O1—N2—C4	118.7 (4)	N1—C7—C8	122.0 (3)
C13—N3—C16	121.0 (3)	C9—C8—C7	124.5 (3)
C13—N3—C17	121.5 (3)	C8—C9—C10	127.6 (3)
C16—N3—C17	116.6 (3)	C11—C10—C15	115.2 (3)
C2—C1—C6	120.4 (3)	C11—C10—C9	121.4 (3)
C2—C1—N1	122.3 (4)	C15—C10—C9	123.3 (3)
C6—C1—N1	117.1 (3)	C12—C11—C10	123.4 (3)
C3—C2—C1	120.3 (4)	C11—C12—C13	121.0 (3)
C4—C3—C2	119.3 (4)	N3—C13—C14	122.6 (3)
C3—C4—C5	121.5 (4)	N3—C13—C12	121.6 (3)
C3—C4—N2	119.0 (4)	C14—C13—C12	115.8 (3)
C5—C4—N2	119.5 (4)	C15—C14—C13	122.1 (3)
C4—C5—C6	119.7 (4)	C14—C15—C10	122.4 (3)
C7—N1—C1—C2	−47.6 (5)	C1—N1—C7—C8	177.8 (3)
C7—N1—C1—C6	137.2 (4)	N1—C7—C8—C9	177.0 (4)
C6—C1—C2—C3	−0.3 (5)	C7—C8—C9—C10	−176.0 (4)
N1—C1—C2—C3	−175.5 (3)	C8—C9—C10—C11	173.3 (4)
C1—C2—C3—C4	1.1 (5)	C8—C9—C10—C15	−4.1 (6)
C2—C3—C4—C5	−2.4 (5)	C15—C10—C11—C12	3.2 (6)
C2—C3—C4—N2	179.2 (3)	C9—C10—C11—C12	−174.4 (4)
O2—N2—C4—C3	179.5 (4)	C10—C11—C12—C13	−1.5 (6)
O1—N2—C4—C3	0.4 (5)	C16—N3—C13—C14	7.0 (6)
O2—N2—C4—C5	0.9 (5)	C17—N3—C13—C14	175.8 (4)
O1—N2—C4—C5	−178.1 (3)	C16—N3—C13—C12	−170.4 (4)
C3—C4—C5—C6	2.9 (5)	C17—N3—C13—C12	−1.6 (6)
N2—C4—C5—C6	−178.6 (3)	C11—C12—C13—N3	177.5 (4)
C4—C5—C6—C1	−2.1 (5)	C11—C12—C13—C14	0.0 (6)
C4—C5—C6—C18	177.3 (3)	N3—C13—C14—C15	−177.8 (4)
C2—C1—C6—C5	0.9 (5)	C12—C13—C14—C15	−0.3 (6)
N1—C1—C6—C5	176.2 (3)	C13—C14—C15—C10	2.2 (6)
C2—C1—C6—C18	−178.5 (3)	C11—C10—C15—C14	−3.5 (6)
N1—C1—C6—C18	−3.2 (5)	C9—C10—C15—C14	174.1 (4)