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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 9| September 2011| Pages o364-o369
doi:10.1107/S0108270111030952

(E)-4-[2-(3,4,5-Trimeth­­oxy­phenyl)ethen­yl]nitro­benzene and its `bridge-flipped' analogues

CROSSMARK_Color_square_no_text.svg
Alain Collasa and Frank Blockhuysa*

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

(Received 5 July 2011; accepted 1 August 2011; online 17 August 2011)

The solid-state structures of three push–pull acceptor-π-donor (A-π-D) systems differing only in the nature of the π-spacer have been determined. (E)-1-Nitro-4-[2-(3,4,5-trimeth­oxy­phenyl)ethenyl]benzene, C17H17NO5, (I), and its `bridge-flipped' imine analogues, (E)-3,4,5-trimeth­oxy-N-(4-nitro­benzyl­idene)aniline, C16H16N2O5, (II), and (E)-4-nitro-N-(3,4,5-trimeth­oxy­benzyl­idene)aniline, C16H16N2O5, (III), display different kinds of supra­molecular networks, viz. corrugated planes, a herringbone pattern and a layered structure, respectively, all with zero overall dipole moments. Only (III) crystallizes in a non­centro­symmetric space group (P212121) and is, therefore, a potential material for second-harmonic generation (SHG).

Comment

For several years now, the liquid-crystal-forming properties of N-benzyl­idene­aniline (BA) and its derivatives have been studied in great detail (Kitamura et al., 1986[Kitamura, T., Mukoh, A., Isogai, M., Inukai, T., Furukawa, K. & Terashima, K. (1986). Mol. Cryst. Liq. Cryst. 136, 167-173.]; Ajeetha & Pisipati, 2006[Ajeetha, N. & Pisipati, V. G. K. M. (2006). Mol. Cryst. Liq. Cryst. 457, 3-25.]; Fakruddin et al., 2009[Fakruddin, K., Kumar, R. J., Prasad, P. V. D. & Pisipati, V. G. K. M. (2009). Mol. Cryst. Liq. Cryst. 511, 1616-1627.]); their rod-like shape is the basis of a number of unique properties which lead to calamitic liquid crystals that may find application in customizable electro-optical switches. The aromatic moieties in BAs have been described as the main recognition points of the mesogens used in the organization of the liquid-crystalline superstructure (Neuvonen et al., 2006[Neuvonen, H., Neuvonen, K. & Fulop, F. (2006). J. Org. Chem. 71, 3141-3148.]). Extended alkyl or alk­oxy chains are substituted onto these aromatic fragments to introduce the necessary flexibility into the mol­ecular structure, and this flexibility is further enhanced by the imine spacers present in the BA. It is the subtle equilibrium between the rigid rod-like structure and the presence of flexible groups that determines the physical properties of the liquid-crystalline phase. Since the solid-state structures of these materials can not be studied in the liquid-crystalline phase, the extended side chains must be replaced by shorter ones, such as meth­oxy groups, in order to investigate the inter­molecular inter­actions involving the mesogen.

Push–pull acceptor-π-donor (A-π-D) systems are of particular inter­est in this context because of their superior charge-transfer-related nonlinear electrical and optical properties, such as the electro-optic effect (EO) and second-harmonic generation (SHG). Unfortunately, the large mol­ecular dipoles associated with such push–pull systems usually lead to centrosymmetric organization of the mol­ecules in the crystal structure, annihilating bulk second-order optical effects such as SHG. It has been suggested that whether or not an asymmetric dipolar BA crystallizes centrosymmetrically is largely dependent on the mol­ecular planarity, which may be directly

[Scheme 1]
related to the mol­ecular rigidity mentioned above; more planar mol­ecules have a greater possibility of crystallizing in a noncentrosymmetric space group (Zhang, 2002[Zhang, D.-C. (2002). Acta Cryst. C58, o351-o352.]). To verify Zhang's correlation, a search of the Cambridge Structural Database (CSD, Version 5.32, with update of February 2011; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) was conducted for all stilbenes and BAs having no ortho substituents. Indeed, since ortho substituents can easily give rise to steric hindrance or intra­molecular hydrogen bonding, a correlation involving the planarity of the systems would be biased. Erroneous, co­crystal, polymeric, ionic, powder and organometallic structures, and symmetric structures with Z′ = 0.5, were also excluded. On the other hand, heterocyclic rings with the heteroatom in the 3-, 4- or 5-position were allowed. For the stilbenes, only E configurations [τ(C1—C7—C8—C9) = 180±15°] were considered. The distribution of torsion angles in the resulting structures is given in Fig. 1[link]. As can be seen from these polar histograms, the stilbenes are all quasiplanar (Fig. 1[link]a). The majority of the BAs, on the other hand, display conformations with torsion angles within the ±45° range (Fig. 1[link]b). 64 of the 169 stilbenes and 44 of the 178 BAs found belong to noncentrosymmetric space groups. 53 stilbenes and 81 BAs are donor–acceptor (DA) systems. 17 and 19 of these, respectively, belong to noncentrosymmetric space groups. As can be seen from Fig. 1[link](c) though, the torsion angles of these 19 BAs (or 23 structures, with the addition of four polymorphs) are quite well distributed over the entire ±45° range. Based on these results, the suggested correlation seems unlikely.

It is inter­esting to note that usually just one of the structures of the three possible stilbene/BA derivatives (i.e. with —CH=CH—, —CH=N— or —N=CH— as spacer) is available, so that a direct comparison of the effect of the spacer on the supra­molecular structure is impossible. In order to make just such a comparison, the stilbene (E)-1-nitro-4-[2-(3,4,5-trimeth­oxy­phenyl)ethenyl]benzene, (I)[link], and its two `bridge-flipped' (Ojala et al., 2009[Ojala, W. H., Lystad, K. M., Deal, T. L., Engelbretson, J. E., Spude, J. M., Balidemaj, B. & Ojala, C. R. (2009). Cryst. Growth Des. 9, 964-970.]) imine derivatives, (E)-3,4,5-trimeth­oxy-N-(4-nitro­benzyl­idene)aniline, (II)[link], and (E)-4-nitro-N-(3,4,5-trimeth­oxy­benzyl­idene)aniline, (III)[link] (Fig. 2[link]), were prepared and structurally characterized.

Compounds (I)[link] and (II)[link] crystallize in the centrosymmetric space group P21/c, while (III)[link] crystallizes in the chiral space group P212121. Compound (I)[link] is quasiplanar, while the imine derivatives (II)[link] and (III)[link] display the typical 40° twist around the C—N bond which is also found in the calculated gas-phase structures, as evidenced by the values of τ(C1—N2) for (II)[link] and τ(N2—C9) for (III)[link] in Table 1[link].

The quasiplanar mol­ecules of (I)[link] (Fig. 3[link]a) form pairs, in which the two mol­ecules are held together by dipolar forces and πδ+–πδ− inter­actions, with CgA⋯CgBi = 3.936 (4) Å [CgA and CgB are the centroids of the nitro-substituted (A) and trimethoxy-substituted (B) benzene rings, respectively; symmetry code: (i) −x, −y + 1, −z], α = 2.20 (14)° and γ = 30.07°, where α is defined as the dihedral angle between the least-squares (LS) planes through rings A and B, and γ as the angle between the CgA⋯CgB vector and the normal to the LS plane through ring B (Fig. 3[link]b). This two-by-two arrangement leads to layers in which the distance between the mol­ecules is less than 4.2 Å – the photochemical criterion (Schmidt, 1971[Schmidt, G. M. J. (1971). Pure Appl. Chem. 27, 647-678.]) – and, as a consequence, this crystal structure should be photosensitive, but this was not observed during the manipulation of the compound. These nonpolar pairs are further stabilized on both sides by weak hydrogen bonds involving the O atom of the nitro group (Fig. 3[link]d and entry 1 in Table 2[link]) and an O atom of a meth­oxy group (Fig. 3[link]d and entry 2 in Table 2[link]), which gives a structure formed of planes two mol­ecules thick. These planes are then fused together by reciprocal OCH3⋯π contacts (Fig. 3[link]c and entry 3 in Table 2[link]). The overall result is a supra­molecular structure of corrugated planes (Fig. 3[link]a).

The crystal structure of (II)[link] is also based on pairs of mol­ecules in which their large individual dipoles are cancelled. As a result, π–π stacking can be easily recognized [CgA⋯CgAv = 3.993 (1) Å, α = 0.0° and γ = 25.79°; symmetry code: (v) −x + 1, −y + 2, −z + 1] (Fig. 4[link]). These dimers are further stabilized by a mutual weak hydrogen bond involving atom H6 and an O atom of the nitro group (Fig. 4[link]b and entry 1 in Table 3[link]). Ribbons are then generated by a weak C—H⋯O hydrogen bond between the meth­oxy groups in the 4- and 5-positions (Fig. 4[link]b and entry 2 in Table 3[link]). Simultaneously, atom H41B engages in a C—H⋯π contact with the π-system of the meth­oxy-substituted aniline fragment (entry 3 in Table 3[link], not shown in Fig. 4[link]). Perpendicular to these ribbons, another OCH3⋯π contact is initiated by the meth­oxy group in the 3-position, which is made possible by the twist of the aniline ring (entry 4 in Table 3[link], not shown in Fig. 4[link]). In the third direction, a C—H⋯O inter­action (entry 5 in Table 3[link]) and an OCH3⋯π inter­action (entry 6 in Table 3[link]) stabilize the structure further (not shown in Fig. 4[link]). Both the imine N atom and the relatively acidic H8 atom remain unused in this structure.

Compound (III)[link], which crystallizes in the chiral space group P212121, does not form these anti­parallel assemblies. It is remarkable that a hydrogen bond involving imine atom N2 as acceptor generates a ribbon of mol­ecules in the bc plane (Fig. 5[link]b and entry 1 in Table 4[link]). These ribbons are further expanded into a plane of mol­ecules by an additional hydrogen bond (Fig. 5[link]b and entry 2 in Table 4[link]). In the direction perpendicular to the plane, the [100] direction, atom O2 of the nitro group contacts the π-systems of the aniline rings in the planes above (Fig. 5[link]a and entry 3 in Table 4[link]) and below the mol­ecule (entry 4 in Table 4[link], not shown in Fig. 5[link]). Thus, the layered structure (Fig. 5[link]c) is stabilized in all three directions, but as a result of this particular stacking, the mol­ecular dipoles add up to zero, in keeping with the observed space group symmetry.

It may be clear from the above that (I)[link] and (II)[link] aggregate as dimers, cancelling out the net dipole in each case and constructing centrosymmetric corrugated layered and herringbone networks, respectively. π–π stacking involving the nitro-substituted A rings occurs in the solid-state structures of (I)[link] and (II)[link] as a consequence of the contribution of dipolar forces (see Table 1[link] for the calculated dipole moments). The meth­oxy groups are engaged in almost equal numbers of OCH3⋯π and C—H⋯O inter­actions. Surprisingly, compound (III)[link] possesses the largest dipole but displays a noncentrosymmetric network based on weak hydrogen bonds involving the imine N atom. The chiral network is essential for displaying nonlinear responses based on the second-order nonlinear electrical susceptibility (χ(2)).

[Figure 1]
Figure 1
Polar histograms illustrating the distribution of (a) torsion angles τ(C2—C1—C7—C8) in stilbenes, (b) torsion angles τ(C2—C1—N2—C8) in BAs and (c) torsion angles of donor–acceptor BAs in noncentrosymmetric space groups; see Comment for details.
[Figure 2]
Figure 2
The mol­ecular structures of (I)[link], (II)[link] and (III)[link], showing the atom-numbering scheme. In each case, the nitro-substituted ring is labelled A. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by spheres of arbitrary radii and bear the same number as the C atom to which they are attached.
[Figure 3]
Figure 3
(a) The corrugated planes in the structure of (I)[link], held together by (b) π–π, (c) OCH3⋯π and (d) C—H⋯O inter­actions (all inter­actions are shown as dashed lines). Symmetry codes are as in Table 2.
[Figure 4]
Figure 4
(a) The herringbone pattern in the structure of (II)[link], viewed along the a axis and (b) the various other inter­molecular contacts (dashed lines). Symmetry codes are as in Table 3.
[Figure 5]
Figure 5
(a) The NO⋯π contacts, (b) the inter­actions within the layers and (c) the layered structure of (III)[link], viewed along b (all inter­actions are shown as dashed lines). Symmetry codes are as in Table 4.

Experimental

All reagents and solvents were obtained from ACROS and used as received. All NMR spectra were recorded on a Bruker Avance II spectrometer at frequencies of 400 MHz for 1H and 100 MHz for 13C in CDCl3 with tetra­methyl­silane (TMS) as inter­nal standard; chemical shifts δ are given in p.p.m. and coupling constants J in Hz. Melting points were obtained with an open capillary electrothermal melting-point apparatus and are uncorrected.

(E)-1-Nitro-4-[2-(3,4,5-trimeth­oxy­phenyl)­ethenyl]­benzene, (I)[link], was prepared by adding LiOH (0.7 g, 0.03 mol) to a stirred solution of (4-nitro­benzyl)­triphenyl­phosphon­ium chloride (13.1 g, 0.03 mol) and 3,4,5-trimeth­oxy­benzaldehyde (6.0 g, 0.03 mol) in propan-2-ol (110 ml). The resulting suspension was refluxed for 18 h. After cooling to room temperature, water (100 ml) was added, and since no precipitate was formed the solution was extracted with diethyl ether (3 × 50 ml). The organic layer was separated off and evaporated to dryness. Isomerization of the crude product in p-xylene (50 ml) with a catalytic amount of I2 yielded 2.4 g (0.007 mol, 23%) of long yellow needles of (I)[link]. Characterization: m.p. 466 K; 1H NMR: δ 3.89 (s, 3H,4-OCH3), 3.93 (s, 6H, 3-OCH3 and 5-OCH3), 6.78 (s, 2H, H2 and H6), 7.03 (d, 3J = 16.1, 1H, H7), 7.19 (d, 3J = 16.1, 1H, H8), 7.61 (d, 3J = 8.2, 2H, H11 and H13), 8.20 (d, 3J = 8.2, 2H, H10 and H14); 13C NMR: δ 56.22 (3-OCH3 and 5-OCH3), 60.98 (4-OCH3), 104.32 (C2 and C6), 124.15 (C10 and C14), 125.69 (C8), 126.74 (C7), 131.86 (C11 and C13), 133.31 (C1), 139.13 (C4), 143.82 (C12), 146.73 (C9), 153.56 (C3 and C5). Crystals used in the diffraction experiment were grown by slow cooling of an ethyl acetate–hexane (1:1 v/v) solution.

(E)-3,4,5-Trimeth­oxy-N-(4-nitro­benzyl­idene)aniline, (II)[link], was prepared by dissolving 3,4,5-trimeth­oxy­aniline (1.8 g, 0.01 mol) and 4-nitro­benzaldehyde (1.5 g, 0.01 mol) in ethanol (100 ml) and stirring the solution overnight. The orange precipitate which formed was filtered off, yielding 3.0 g (9.5 mmol, 95%) of (II)[link]. Characterization: m.p. 430 K; 1H NMR: δ 3.88 (s, 3H, 4-OCH3), 3.92 (s, 6H, 3-OCH3 and 5-OCH3), 6.56 (s, 2H, H2 and H6), 8.07 (d, 3J = 8.8, 2H, H10 and H14), 8.32 (d, 3J = 8.8, 2H, H11 and H13), 8.57 (s, 1H, H8); 13C NMR: δ 56.23 (3-OCH3 and 5-OCH3), 61.02 (4-OCH3), 98.60 (C2 and C6), 124.03 (C11 and C13), 129.31 (C10 and C14), 137.58 (C4), 141.53 (C9), 146.63 (C1), 149.31 (C12), 153.86 (C3 and C5), 156.40 (C8). Crystals used in the diffraction experiment were grown by slow evaporation from a CH2Cl2 solution.

(E)-4-Nitro-N-(3,4,5-trimeth­oxy­benzyl­idene)aniline, (III)[link], was pre­pared by refluxing 3,4,5-trimeth­oxy­benzaldehyde (3.0 g, 0.015 mol) and 4-nitro­aniline (2.1 g, 0.015 mol) in methanol (100 ml) for 3 h. The resulting yellow precipitate was collected by filtration and recrystallized from acetonitrile, yielding 3.5 g (11 mmol, 75%) of (III)[link]. Crystals from this batch were used in the crystallographic experiment. Characterization: m.p. 428 K; 1H NMR: δ 3.94 (s, 3H, 4-OCH3), 3.95 (s, 6H, 3-OCH3 and 5-OCH3), 7.18 (s, 2H, H2 and H6), 7.23 (dd, 3J = 8.9, 4J = 1.9, 2H, H10 and H14), 8.25 (dd, 3J = 8.9, 4J = 1.9, 2H, H11 and H13), 8.32 (s, 1H, H7); 13C NMR: δ 56.33 (3-OCH3 and 5-OCH3), 61.03 (4-OCH3), 106.44 (C2 and C6), 121.29 (C10 and C14), 125.04 (C11 and C13), 130.81 (C1), 142.01 (C4), 145.45 (C12), 153.65 (C3 and C5), 157.87 (C9), 162.08 (C7).

Compound (I)[link]

Crystal data

  • C17H17NO5

  • Mr = 315.32

  • Monoclinic, P 21 /c

  • a = 10.459 (2) Å

  • b = 12.88 (1) Å

  • c = 14.021 (4) Å

  • β = 124.069 (15)°

  • V = 1564.6 (13) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 K

  • 0.42 × 0.39 × 0.39 mm
Data collection

  • Enraf–Nonius CAD-4 diffractometer

  • 5901 measured reflections

  • 2867 independent reflections

  • 1500 reflections with I > 2σ(I)

  • Rint = 0.043

  • 3 standard reflections every 60 min intensity decay: none
Refinement

  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.135

  • S = 1.00

  • 2867 reflections

  • 211 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.14 e Å−3

Compound (II)[link]

Crystal data

  • C16H16N2O5

  • Mr = 316.31

  • Monoclinic, P 21 /c

  • a = 7.512 (2) Å

  • b = 7.895 (1) Å

  • c = 26.441 (6) Å

  • β = 104.667 (19)°

  • V = 1517.0 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 K

  • 0.3 × 0.3 × 0.3 mm
Data collection

  • Enraf–Nonius CAD-4 diffractometer

  • 5826 measured reflections

  • 2803 independent reflections

  • 2023 reflections with I > 2σ(I)

  • Rint = 0.052

  • 3 standard reflections every 60 min intensity decay: 4%
Refinement

  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.104

  • S = 1.05

  • 2803 reflections

  • 211 parameters

  • H-atom parameters constrained

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.18 e Å−3

Compound (III)[link]

Crystal data

  • C16H16N2O5

  • Mr = 316.31

  • Orthorhombic, P 21 21 21

  • a = 7.215 (3) Å

  • b = 14.429 (2) Å

  • c = 14.595 (5) Å

  • V = 1519.4 (8) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 K

  • 0.4 × 0.4 × 0.3 mm
Data collection

  • Enraf–Nonius CAD-4 diffractometer

  • 4683 measured reflections

  • 1618 independent reflections

  • 1358 reflections with I > 2σ(I)

  • Rint = 0.057

  • 3 standard reflections every 60 min intensity decay: 10%
Refinement

  • R[F2 > 2σ(F2)] = 0.052

  • wR(F2) = 0.141

  • S = 1.07

  • 1618 reflections

  • 212 parameters

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Selected geometric data for (I)[link], (II)[link] and (III)[link]; calculated (DFT) and experimental (XRD) torsion angles in degrees (°), and calculated dipole moments μ in Debye

Compound Parameter XRD DFT μ
(I)[link] C2—C1—C7—C8 −11.0 (5) 176.2  
  C1—C7—C8—C9 178.7 (3) 0.3 5.48
  C7—C8—C9—C10 −172.1 (3) 4.2  
(II)[link] C2—C1—N2—C8 −38.4 (2) 31.6  
  C1—N2—C8—C9 179.4 (1) 177.4 4.59
  N2—C8—C9—C10 −11.5 (2) 1.4  
(III)[link] C2—C1—C7—N2 4.1 (4) 1.4  
  C1—C7—N2—C9 177.8 (2) 176.4 6.15
  C7—N2—C9—C10 −39.5 (4) 42.5  

Table 2
Weak hydrogen bonds in (I)[link] (Å, °)

Entry D H A H⋯A D⋯A D—H⋯A
1 C14 H14 O2ii 2.69 3.526 (4) 151
2 C7 H7 O4iii 2.57 3.447 (3) 158
3 C31 H31B CgBiv 2.83 3.718 (5) 154
Symmetry codes: (ii) x, −y + [{1\over 2}], z − [{1\over 2}]; (iii) x, −y + [{3\over 2}], z + [{1\over 2}]; (iv) x + 1, −y + 1, −z.

Table 3
Weak hydrogen bonds in (II)[link] (Å, °)

Entry D H A H⋯A D⋯A D—H⋯A
1 C6 H6 O2v 2.54 3.423 (2) 160
2 C41 H41C O5vi 2.50 3.450 (3) 168
3 C41 H41B CgBvii 2.96 3.626 (3) 128
4 C31 H31A CgBviii 2.78 3.463 (3) 129
5 C31 H31B O1ix 2.71 3.542 (3) 145
6 C51 H51B CgAx 2.94 3.631 (3) 130
Symmetry codes: (v) −x + 1, −y + 2, −z + 1; (vi) −x + 3, y + [{1\over 2}], −z + [{3\over 2}]; (vii) −x + 3, y − [{1\over 2}], −z + [{3\over 2}]; (viii) −x + 2, y + [{1\over 2}], −z + [{3\over 2}]; (ix) x + 1, −y + [{3\over 2}], z + [{1\over 2}]; (x) x + 1, y − 1, z.

Table 4
Short contacts in (III)[link] (Å, °)

Entry D X A X⋯A D⋯A D—X⋯A
1 C41 H41B N2xi 2.66 3.537 (4) 153
2 C6 H6 O1xii 2.58 3.450 (4) 156
3 N1 O2 CgBxiii 3.610 (4) 3.587 (4) 79.1 (2)
4 N1 O2 CgBxiv 3.912 (4) 4.578 (4) 115.7 (2)
Symmetry codes: (xi) −x, [{1\over 2}] + y, [{1\over 2}] − z; (xii) −x, [{1\over 2}] + y, −[{1\over 2}] − z; (xiii) −[{1\over 2}] + x, [{1\over 2}] − y, −z; (xiv) [{1\over 2}] + x, [{1\over 2}] − y, −z.

The mol­ecular structures of isolated mol­ecules of (I)[link], (II)[link] and (III)[link] were optimized at the DFT/B3LYP/6-31G* level of theory using the GAUSSIAN09 program package (Frisch et al., 2009[Frisch, M. J., et al. (2009). GAUSSIAN09. Revision A.02. Gaussian Inc., Pittsburgh, Pennsylvania, USA.]); the functional and basis set were used as they are implemented in the program. Frequency calculations were performed to ascertain that the resulting structures are minima on the potential-energy surface (PES). Mol­ecular dipoles of the four mol­ecules in the unit cell of (III)[link] were calculated in their solid-state geometries at the same level of theory. The resulting vectors were then transformed from the Cartesian to the unit-cell coordinate system. The polar histograms were generated using the VISTA program in the CSD suite.

All H atoms were treated as riding using SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) defaults at 293 (1) K, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The displacement parameters of atoms C7 and C8 in (I)[link] seem to suggest disorder typical of ethenylic spacers in stilbene-type systems (see Vande Velde et al., 2011[Vande Velde, C. M. L., Collas, A., De Borger, R. & Blockhuys, F. (2011). Chem. Eur. J. 17, 912-919.]), but attempts to refine a disordered model did not lead to satisfactory results. However, since only a small fraction of misoriented fragments is present, the quality of the nondisordered model was found to be sufficient, even though this leads to slightly larger displacement ellipsoids for the mentioned atoms. For (III)[link], Friedel pairs were collected independently but were merged (MERG 3 command in SHELXL97) for the final refinement. In the absence of a heavy atom [Z > 14 (Si)], and with the use of Mo radiation, anomalous scattering could not be used to determine an absolute structure and thus it was chosen arbitrarily.

For all compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994[Enraf-Nonius (1994). CAD-4 EXPRESS. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996[Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks I, II, III, global. DOI: 10.1107/S0108270111030952/fa3256sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270111030952/fa3256Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270111030952/fa3256IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270111030952/fa3256IIIsup4.hkl


Comment top

For several years now, the liquid-crystal forming properties of N-benzylideneaniline (BA) and its derivatives have been studied in great detail (Kitamura et al., 1986; Ajeetha & Pisipati, 2006; Fakruddin et al., 2009): their rod-like shape is the basis of a number of unique properties which lead to calamitic liquid crystals that may find application in customizable electro-optical switches. The aromatic moieties in BAs have been described as the main recognition points of the mesogens, used in the organization of the liquid-crystalline superstructure (Neuvonen et al., 2006). Extended alkyl or alkoxy chains are substituted ontothese aromatic fragments to introduce the necessary flexibility into the molecular structure, and this flexibility is further enhanced by the imine spacers present in the BA. It is the subtle equilibrium between the rigid rod-like structure and the presence of flexible groups that determines the physical properties of the liquid-crystalline phase. Since the solid-state structures of these materials can not be studied in the liquid-crystalline phase, the extended side chains must be replaced by shorter ones, such as methoxy groups, in order to investigate the intermolecular interactions involving the mesogen.

Push–pull acceptor-π-donor (A-π-D) systems are of particular interest in this context because of their superior charge-transfer related nonlinear electrical and optical properties, such as the electro-optic effect (EO) and second-harmonic generation (SHG). Unfortunately, the large molecular dipoles associated with such push–pull systems usually lead to centrosymmetric organization of the molecules in the crystal structure, annihilating bulk second-order optical effects such as SHG. It has been suggested that whether or not an asymmetrical dipolar BA crystallizes centrosymmetrically is largely dependent on the molecular planarity, which may be directly related to the molecular rigidity mentioned above: more planar molecules have a greater possibility of crystallizing in a noncentrosymmetric space group (Zhang, 2002). To verify Zhang's correlation, a search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) was conducted for all stilbenes and BAs without ortho substituents. Indeed, since ortho substituents can easily give rise to steric hindrance or intramolecular hydrogen bonding, a correlation involving the planarity of the systems would be biased. Erroneous, co-crystal, polymeric, ionic, powder and organometallic structures, and symmetric structures with Z' = 0.5, were also excluded. On the other hand, heterocyclic rings with the heteroatom in the 3-, 4- or 5-position were allowed. For the stilbenes, only E configurations [τ(C1—C7—C8—C9) = 180±15°] were considered. The distribution of torsion angles in the resulting structures is given in Fig. 1. As can be seen from these polar histograms, the stilbenes are all quasi-planar (Fig. 1a). The majority of the BAs, on the other hand, display conformations with torsion angles within the ±45° range (Fig. 1b). 64 of the 169 stilbenes and 44 of the 178 BAs found belong to noncentrosymmetric space groups. 53 stilbenes and 81 BAs are donor–acceptor (DA) systems. 17 and 19 of these, respectively, belong to noncentrosymmetric space groups. As can be seen from Fig. 1(c), though, the torsion angles of these 19 BAs (or 23 structures, with the addition of four polymorphs) are quite well distributed over the entire ±45° range. Based on these results, the suggested correlation seems unlikely.

It is interesting to note that usually just one of the structures of the three possible stilbene/BA derivatives (i.e. with —CH═CH—, —CH═ N— or —N═CH— as spacer) is available, so that a direct comparison of the effect of the spacer on the supramolecular structure is impossible. In order to make just such a comparison, the stilbene (E)-1-nitro-4-[2-(3,4,5-trimethoxyphenyl)ethenyl]benzene, (I), and its two `bridge-flipped' (Ojala et al., 2009) imine derivatives, (E)-3,4,5-trimethoxy-N-(4-nitrobenzylidene)aniline, (II), and (E)-4-nitro-N-(3,4,5-trimethoxybenzylidene)aniline, (III) (Fig. 2), were prepared and structurally characterized.

Compounds (I) and (II) crystallize in the centrosymmetric space group P21/c, while (III) crystallizes in the chiral space group P212121. Compound (I) is quasiplanar, while the imine derivatives (II) and (III) display the typical 40° twist around the C—N bond which is also found in the calculated gas-phase structures, as evidenced by the values of τ(C1—N2) for (II) and τ(N2—C9) for (III) in Table 1.

The quasiplanar molecules of (I) (Fig. 3a) form pairs, in which the two molecules are held together by dipolar forces and πδ+···πδ- interactions, with CgA···CgBi = 3.936 (4) Å [CgA and CgB are the centroids of rings A and B, respectively; symmetry code: (i) -x, 1 - y, -z], α = 2.20 (14)° and γ = 30.07°, where α is defined as the dihedral angle between the least-squares (LS) planes through rings A and B, and γ as the angle between the CgA···CgB vector and the normal to the LS plane through ring B (Fig. 3b). This two-by-two arrangement leads to layers in which the distance between the molecules is less than 4.2 Å - the photochemical criterion (Schmidt, 1971) - and, as a consequence, this crystal structure should be photosensitive, but this was not observed during the manipulation of the compound. These nonpolar pairs are further stabilized on both sides by weak hydrogen bonds involving the O atom of the nitro group (Fig. 3d and Table 2, entry 1) and an O atom of a methoxy group (Fig. 3d and Table 2, entry 2), which gives a structure formed of planes two molecules thick. These planes are then fused together by reciprocal OCH3···π contacts (Fig. 3c and Table 2, entry 3). The overall result is a supramolecular structure of corrugated planes (Fig. 3a).

The crystal structure of (II) is also based on pairs of molecules in which their large individual dipoles are cancelled. As a result, π–π stacking can be easily recognized [CgA···CgAv = 3.993 (1) Å, α = 0.0° and γ = 25.79°; symmetry code: (v) 1 - x, 2 - y, 1 - z] (Fig. 4). These dimers are stabilized further by a mutual weak hydrogen bond involving atom H6 and an O atom of the nitro group (Fig. 4b and Table 3, entry 1). Ribbons are then generated by a weak C—H···O hydrogen bond between the methoxy groups in the 4- and 5-positions (Fig. 4b and Table 3, entry 2). Simultaneously, atom H41B engages in a C—H···π contact with the π-system of the methoxy-substituted aniline fragment (Table 3, entry 3, not shown in Fig. 4). Perpendicular to these ribbons, another OCH3···π contact is initiated by the methoxy group in the 3-position, which is made possible by the twist of the aniline ring (Table 3, entry 4, not shown in Fig. 4). In the third direction, a C—H···O interaction (Table 3, entry 5) and an OCH3···π interaction (Table 3, entry 6) stabilize the structure further (not shown in Fig. 4). Both the imine N atom and the relatively acidic atom H8 remain unused in this structure.

Compound (III), which crystallizes in the chiral space group P212121, does not form these antiparallel assemblies. It is remarkable that a hydrogen bond involving imine atom N2 as acceptor generates a ribbon of molecules in the bc plane (Fig. 5b and Table 4, entry 1). These ribbons are further expanded into a plane of molecules by an additional hydrogen bond (Fig. 5b and Table 4, entry 2). In the direction perpendicular to the plane, the [100] direction, atom O2 of the nitro group contacts the π-systems of the aniline rings in the planes above (Fig. 5a and Table 4, entry 3) and below the molecule (Table 4, entry 4, not shown in Fig. 5). Thus, the layered structure (Fig. 5c) is stabilized in all three directions, but as a result of this particular stacking the molecular dipoles add up to zero, in keeping with the observed space group symmetry.

It may be clear from the above that (I) and (II) aggregate as dimers, cancelling out the net dipole in each case and constructing centrosymmetric corrugated layered and herringbone networks, respectively. π–π stacking involving the nitro-substituted A rings occurs in the solid-state structures of (I) and (II) as a consequence of the contribution of dipolar forces (see Table 1 for the calculated dipole moments). The methoxy groups are engaged in almost equal numbers of OCH3···π and C—H···O interactions. Surprisingly, compound (III) possesses the largest dipole but displays a noncentrosymmetric network based on weak hydrogen bonds involving the imine N atom. The chiral network is essential for displaying nonlinear responses based on the second-order nonlinear electrical susceptibility (χ(2)).

Related literature top

For related literature, see: Ajeetha & Pisipati (2006); Allen (2002); Fakruddin et al. (2009); Frisch (2009); Kitamura et al. (1986); Neuvonen et al. (2006); Ojala et al. (2009); Schmidt (1971); Sheldrick (2008); Vande Velde, Collas, De Borger & Blockhuys (2011); Zhang (2002).

Experimental top

The molecular structures of isolated molecules of (I), (II) and (III) were optimized at the DFT/B3LYP/6-31G* level of theory using the GAUSSIAN09 program package (Frisch et al., 2009); the functional and basis set were used as they are implemented in the program. Frequency calculations were performed to ascertain that the resulting structures are minima on the potential-energy surface (PES). Molecular dipoles of the four molecules in the unit cell of (III) were calculated in their solid-state geometries at the same level of theory. The resulting vectors were then transformed from the Cartesian to the unit-cell coordinate system. The polar histograms were generated using the VISTA program in the CSD suite.

All reagents and solvents were obtained from ACROS and used as received. All NMR spectra were recorded on a Bruker Avance II spectrometer at frequencies of 400 MHz for 1H and 100 MHz for 13C in CDCl3 with tetramethylsilane (TMS) as internal standard; chemical shifts δ are given in p.p.m. and coupling constants J in Hz. Melting points were obtained with an open capillary electrothermal melting-point apparatus and are uncorrected.

(E)-1-Nitro-4-[2-(3,4,5-trimethoxyphenyl)ethenyl]benzene, (I), was prepared by adding LiOH (0.7 g, 0.03 mol) to a stirred solution of (4-nitrobenzyl)triphenylphosphonium chloride (13.1 g, 0.03 mol) and 3,4,5-trimethoxybenzaldehyde (6.0 g, 0.03 mol) in propan-2-ol (110 ml). The resulting suspension was refluxed for 18 h. After cooling to room temperature, water (100 ml) was added, and since no precipitate was formed the solution was extracted with diethyl ether (3 × 50 ml). The organic layer was separated off and evaporated to dryness. Isomerization of the crude product in p-xylene (50 ml) with a catalytic amount of I2 yielded 2.4 g (0.007 mol, 23%) of long yellow needles of (I). Characterisation: m.p. 466 K; δ1H 3.89 (s, 3H, 4-OCH3), 3.93 (s, 6H, 3-OCH3 and 5-OCH3), 6.78 (s, 2H, H2 and H6), 7.03 (d, 3J = 16.1, 1H, H7), 7.19 (d, 3J = 16.1, 1H, H8), 7.61 (d, 3J = 8.2, 2H, H11 and H13), 8.20 (d, 3J = 8.2, 2H, H10 and H14); δ13C 56.22 (3-OCH3 and 5-OCH3), 60.98 (4-OCH3), 104.32 (C2 and C6), 124.15 (C10 and C14), 125.69 (C8), 126.74 (C7), 131.86 (C11 and C13), 133.31 (C1), 139.13 (C4), 143.82 (C12), 146.73 (C9), 153.56 (C3 and C5). Crystals used in the diffraction experiment were grown by slow cooling of an ethyl acetate/hexane (Solvent ratio?) solution.

(E)-3,4,5-Trimethoxy-N-(4-nitrobenzylidene)aniline, (II), was prepared by dissolving 3,4,5-trimethoxyaniline (1.8 g, 0.01 mol) and 4-nitrobenzaldehyde (1.5 g, 0.01 mol) in ethanol (Volume?) and stirring the solution overnight. The orange precipitate which formed was filtered off, yielding 3.0 g (9.5 mmol, 95%) of (II). Characterisation: m.p. 430 K; δ1H 3.88 (s, 3H, 4-OCH3), 3.92 (s, 6H, 3-OCH3 and 5-OCH3), 6.56 (s, 2H, H2 and H6), 8.07 (d, 3J = 8.8, 2H, H10 and H14), 8.32 (d, 3J = 8.8, 2H, H11 and H13), 8.57 (s, 1H, H8); δ13C 56.23 (3-OCH3 and 5-OCH3), 61.02 (4-OCH3), 98.60 (C2 and C6), 124.03 (C11 and C13), 129.31 (C10 and C14), 137.58 (C4), 141.53 (C9), 146.63 (C1), 149.31 (C12), 153.86 (C3 and C5), 156.40 (C8). Crystals used in the diffraction experiment were grown by slow evaporation of a CH2Cl2 solution.

(E)-4-Nitro-N-(3,4,5-trimethoxybenzylidene)aniline, (III), was prepared by refluxing 3,4,5-trimethoxybenzaldehyde (3.0 g, 0.015 mol) and 4-nitroaniline (2.1 g, 0.015 mol) in methanol (??ml Volume missing?) for 3 h. The resulting yellow precipitate was collected by filtration and recrystallized from acetonitrile, yielding 3.5 g (11 mmol, 75%) of (III). Crystals from this batch were used in the crystallographic experiment. Characterisation: m.p. 428 K; δ1H 3.94 (s, 3H, 4-OCH3), 3.95 (s, 6H, 3-OCH3 and 5-OCH3), 7.18 (s, 2H, H2 and H6), 7.23 (dd, 3J = 8.9, 4J = 1.9, 2H, H10 and H14), 8.25 (dd, 3J = 8.9, 4J = 1.9, 2H, H11 and H13), 8.32 (s, 1H, H7); δ13C 56.33 (3-OCH3 and 5-OCH3), 61.03 (4-OCH3), 106.44 (C2 and C6), 121.29 (C10 and C14), 125.04 (C11 and C13), 130.81 (C1), 142.01 (C4), 145.45 (C12), 153.65 (C3 and C5), 157.87 (C9), 162.08 (C7).

Refinement top

All H atoms were treated as riding using the SHELXL97 (Sheldrick, 2008) defaults at 293 (1) K, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The displacement parameters of atoms C7 and C8 in (I) seem to suggest disorder typical of ethenylic spacers in stilbene-type systems (see Vande Velde et al., 2011), but attempts to refine a disordered model did not lead to satisfactory results. However, since only a small fraction of misoriented fragments is present, the quality of the non-disordered model was found to be sufficient, even though this leads to slightly larger displacement ellipsoids for the mentioned atoms. For (III), Friedel pairs were collected independently but were merged (MERG 3 command in SHELXL97) for the final refinement. In the absence of a heavy atom [Z > Si], anomalous scattering could not be used to determine an absolute structure and it was chosen arbitrarily.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Polar histograms illustrating the distribution of (a) torsion angles τ(C2—C1—C7—C8) in stilbenes, (b) torsion angles τ(C2—C1—N2—C8) in BAs and (c) torsion angles of donor–acceptor BAs in noncentrosymmetric space groups; see Comment for details.
[Figure 2] Fig. 2. The molecular structures of (I), (II) and (III), showing the atom-numbering scheme. In each case, the nitro-substituted ring is labelled A. Displacement ellipsoids are drawn at the 50% probability level; H atoms are represented by spheres of arbitrary radii and bear the same number as the C atom to which they are attached. Atom N2 replaces either C7 or C8.
[Figure 3] Fig. 3. (a) The corrugated planes in the structure of (I), held together by (b) π–π, (c) OCH3···π and (d) C—H···O interactions (all interactions shown as dashed lines).
[Figure 4] Fig. 4. (a) The herringbone pattern in the structure of (II), viewed along the a axis, and (b) the various other intermolecular contacts (dashed lines).
[Figure 5] Fig. 5. (a) The NO···π contacts, (b) the interactions within the layers and (c) the layered structure of (III) (all interactions shown as dashed lines).
(I) (E)-1-nitro-4-[2-(3,4,5-trimethoxyphenyl)ethenyl]benzene top
Crystal data top
C17H17NO5F(000) = 664
Mr = 315.32Dx = 1.339 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 10.459 (2) Åθ = 5.4–10.1°
b = 12.88 (1) ŵ = 0.10 mm−1
c = 14.021 (4) ÅT = 293 K
β = 124.069 (15)°Block, yellow
V = 1564.6 (13) Å30.42 × 0.39 × 0.39 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.043
Radiation source: fine-focus sealed tubeθmax = 25.4°, θmin = 2.4°
Graphite monochromatorh = −12→0
θ/2ω scansk = −15→15
5901 measured reflectionsl = −13→16
2867 independent reflections3 standard reflections every 60 min
1500 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0536P)2 + 0.4441P]
where P = (Fo2 + 2Fc2)/3
2867 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.14 e Å−3
Crystal data top
C17H17NO5V = 1564.6 (13) Å3
Mr = 315.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.459 (2) ŵ = 0.10 mm−1
b = 12.88 (1) ÅT = 293 K
c = 14.021 (4) Å0.42 × 0.39 × 0.39 mm
β = 124.069 (15)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.043
5901 measured reflections3 standard reflections every 60 min
2867 independent reflections intensity decay: none
1500 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.00Δρmax = 0.35 e Å−3
2867 reflectionsΔρmin = −0.14 e Å−3
211 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2949 (3)0.6123 (2)0.0449 (2)0.0500 (6)
C20.2913 (3)0.55632 (19)−0.0414 (2)0.0512 (6)
H20.26110.4870−0.05370.061*
C30.3328 (3)0.6036 (2)−0.1089 (2)0.0500 (6)
C40.3792 (3)0.70753 (19)−0.0895 (2)0.0484 (6)
C50.3820 (3)0.7628 (2)−0.0030 (2)0.0519 (6)
C60.3401 (3)0.7153 (2)0.0635 (2)0.0532 (7)
H60.34220.75260.12120.064*
C70.2517 (3)0.5678 (2)0.1199 (2)0.0592 (7)
H70.27560.60780.18320.071*
C80.1847 (3)0.4801 (2)0.1088 (2)0.0583 (7)
H80.16190.43840.04700.070*
C90.1411 (3)0.4402 (2)0.1861 (2)0.0512 (6)
C140.0873 (3)0.3402 (2)0.1730 (2)0.0595 (7)
H140.07740.29880.11480.071*
C130.0482 (3)0.3004 (2)0.2437 (2)0.0585 (7)
H130.01350.23230.23460.070*
C120.0607 (3)0.3618 (2)0.3282 (2)0.0520 (6)
C110.1111 (3)0.4624 (2)0.3438 (2)0.0609 (7)
H110.11740.50360.40080.073*
C100.1525 (3)0.5014 (2)0.2726 (2)0.0597 (7)
H100.18840.56930.28260.072*
C310.2920 (4)0.4510 (2)−0.2184 (3)0.0751 (9)
H31A0.18970.4416−0.23620.113*
H31B0.36380.4110−0.15140.113*
H31C0.29490.4283−0.28230.113*
C510.4430 (4)0.9222 (2)0.1004 (3)0.0788 (9)
H51A0.51920.89030.17240.118*
H51B0.34570.92380.09240.118*
H51C0.47440.99180.09850.118*
C4110.5782 (4)0.7551 (3)−0.1094 (3)0.0818 (9)
H41A0.61360.6847−0.10020.123*
H41B0.63220.7889−0.03570.123*
H41C0.59770.7914−0.15980.123*
N10.0198 (3)0.3190 (2)0.4046 (2)0.0728 (7)
O10.0234 (3)0.3758 (2)0.4752 (2)0.1155 (9)
O2−0.0113 (3)0.2273 (2)0.3958 (2)0.1119 (9)
O30.3325 (2)0.55781 (14)−0.19659 (15)0.0661 (5)
O40.4183 (2)0.75565 (14)−0.15702 (14)0.0608 (5)
O50.4280 (2)0.86429 (14)0.00886 (15)0.0674 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0453 (14)0.0654 (17)0.0449 (14)0.0061 (12)0.0287 (12)0.0104 (13)
C20.0459 (15)0.0497 (15)0.0569 (16)0.0024 (12)0.0281 (13)0.0088 (12)
C30.0458 (15)0.0592 (16)0.0446 (14)0.0073 (12)0.0250 (12)0.0042 (12)
C40.0478 (14)0.0559 (16)0.0432 (14)0.0040 (12)0.0265 (12)0.0100 (12)
C50.0481 (15)0.0570 (16)0.0473 (14)0.0031 (12)0.0248 (13)0.0079 (12)
C60.0537 (16)0.0597 (17)0.0475 (14)0.0027 (13)0.0292 (14)0.0038 (12)
C70.0519 (16)0.0617 (18)0.0607 (17)0.0000 (14)0.0294 (14)0.0001 (13)
C80.0518 (16)0.0615 (18)0.0579 (16)0.0043 (14)0.0285 (14)−0.0023 (13)
C90.0461 (14)0.0636 (17)0.0455 (14)0.0050 (13)0.0268 (12)0.0059 (13)
C140.0625 (18)0.0555 (17)0.0632 (17)−0.0007 (13)0.0369 (16)−0.0034 (13)
C130.0585 (17)0.0536 (16)0.0637 (17)−0.0044 (13)0.0344 (15)0.0055 (14)
C120.0480 (15)0.0616 (17)0.0459 (15)−0.0041 (13)0.0260 (12)0.0095 (13)
C110.0643 (18)0.0645 (18)0.0527 (16)−0.0069 (14)0.0321 (15)−0.0042 (13)
C100.0614 (17)0.0510 (15)0.0682 (18)−0.0087 (13)0.0371 (15)0.0068 (14)
C310.083 (2)0.0676 (19)0.076 (2)0.0016 (16)0.0458 (18)−0.0132 (16)
C510.094 (2)0.0665 (19)0.0691 (19)−0.0079 (18)0.0413 (18)−0.0118 (16)
C4110.069 (2)0.108 (3)0.084 (2)−0.0072 (18)0.0520 (18)0.0097 (19)
N10.0767 (18)0.0812 (19)0.0606 (16)−0.0120 (15)0.0385 (14)0.0113 (14)
O10.172 (3)0.122 (2)0.0974 (18)−0.0251 (19)0.103 (2)−0.0089 (16)
O20.155 (3)0.0953 (19)0.1022 (18)−0.0450 (17)0.0825 (19)0.0046 (14)
O30.0825 (14)0.0673 (12)0.0597 (11)−0.0036 (10)0.0467 (11)−0.0081 (10)
O40.0672 (13)0.0707 (12)0.0515 (10)0.0000 (9)0.0377 (10)0.0141 (9)
O50.0890 (14)0.0547 (11)0.0653 (12)−0.0062 (10)0.0474 (11)−0.0016 (9)
Geometric parameters (Å, º) top
C1—C61.383 (4)C13—H130.9300
C1—C21.392 (3)C12—C111.369 (4)
C1—C71.474 (3)C12—N11.464 (3)
C2—C31.384 (3)C11—C101.387 (3)
C2—H20.9300C11—H110.9300
C3—O31.362 (3)C10—H100.9300
C3—C41.398 (4)C31—O31.421 (3)
C4—O41.372 (3)C31—H31A0.9600
C4—C51.392 (3)C31—H31B0.9600
C5—O51.370 (3)C31—H31C0.9600
C5—C61.377 (3)C51—O51.415 (3)
C6—H60.9300C51—H51A0.9600
C7—C81.291 (4)C51—H51B0.9600
C7—H70.9300C51—H51C0.9600
C8—C91.484 (3)C411—O41.411 (3)
C8—H80.9300C411—H41A0.9600
C9—C141.377 (4)C411—H41B0.9600
C9—C101.394 (3)C411—H41C0.9600
C14—C131.366 (4)N1—O21.214 (3)
C14—H140.9300N1—O11.215 (3)
C13—C121.369 (4)
C6—C1—C2120.0 (2)C13—C12—C11121.8 (2)
C6—C1—C7116.6 (2)C13—C12—N1119.3 (3)
C2—C1—C7123.3 (2)C11—C12—N1118.9 (3)
C3—C2—C1120.1 (2)C12—C11—C10118.4 (3)
C3—C2—H2120.0C12—C11—H11120.8
C1—C2—H2120.0C10—C11—H11120.8
O3—C3—C2125.7 (2)C11—C10—C9120.8 (3)
O3—C3—C4114.6 (2)C11—C10—H10119.6
C2—C3—C4119.7 (2)C9—C10—H10119.6
O4—C4—C5120.1 (2)O3—C31—H31A109.5
O4—C4—C3120.2 (2)O3—C31—H31B109.5
C5—C4—C3119.7 (2)H31A—C31—H31B109.5
O5—C5—C6124.4 (2)O3—C31—H31C109.5
O5—C5—C4115.4 (2)H31A—C31—H31C109.5
C6—C5—C4120.2 (3)H31B—C31—H31C109.5
C5—C6—C1120.2 (2)O5—C51—H51A109.5
C5—C6—H6119.9O5—C51—H51B109.5
C1—C6—H6119.9H51A—C51—H51B109.5
C8—C7—C1128.1 (3)O5—C51—H51C109.5
C8—C7—H7116.0H51A—C51—H51C109.5
C1—C7—H7116.0H51B—C51—H51C109.5
C7—C8—C9125.6 (3)O4—C411—H41A109.5
C7—C8—H8117.2O4—C411—H41B109.5
C9—C8—H8117.2H41A—C411—H41B109.5
C14—C9—C10118.4 (2)O4—C411—H41C109.5
C14—C9—C8119.8 (2)H41A—C411—H41C109.5
C10—C9—C8121.8 (2)H41B—C411—H41C109.5
C13—C14—C9121.3 (3)O2—N1—O1123.6 (3)
C13—C14—H14119.3O2—N1—C12117.6 (3)
C9—C14—H14119.3O1—N1—C12118.8 (3)
C14—C13—C12119.3 (3)C3—O3—C31117.5 (2)
C14—C13—H13120.3C4—O4—C411113.8 (2)
C12—C13—H13120.3C5—O5—C51117.8 (2)
C6—C1—C2—C3−0.1 (4)C10—C9—C14—C13−1.1 (4)
C7—C1—C2—C3179.7 (2)C8—C9—C14—C13179.0 (2)
C1—C2—C3—O3−179.2 (2)C9—C14—C13—C121.0 (4)
C1—C2—C3—C40.4 (3)C14—C13—C12—C110.1 (4)
O3—C3—C4—O40.7 (3)C14—C13—C12—N1−179.6 (2)
C2—C3—C4—O4−179.0 (2)C13—C12—C11—C10−1.0 (4)
O3—C3—C4—C5179.1 (2)N1—C12—C11—C10178.7 (2)
C2—C3—C4—C5−0.6 (3)C12—C11—C10—C90.9 (4)
O4—C4—C5—O5−1.1 (3)C14—C9—C10—C110.2 (4)
C3—C4—C5—O5−179.5 (2)C8—C9—C10—C11−180.0 (2)
O4—C4—C5—C6178.8 (2)C13—C12—N1—O26.1 (4)
C3—C4—C5—C60.4 (4)C11—C12—N1—O2−173.6 (3)
O5—C5—C6—C1179.9 (2)C13—C12—N1—O1−176.1 (3)
C4—C5—C6—C10.0 (4)C11—C12—N1—O14.2 (4)
C2—C1—C6—C5−0.1 (4)C2—C3—O3—C31−2.6 (4)
C7—C1—C6—C5−179.9 (2)C4—C3—O3—C31177.8 (2)
C6—C1—C7—C8168.7 (3)C5—C4—O4—C41186.2 (3)
C2—C1—C7—C8−11.1 (4)C3—C4—O4—C411−95.4 (3)
C1—C7—C8—C9−178.7 (2)C6—C5—O5—C514.3 (4)
C7—C8—C9—C14−172.1 (3)C4—C5—O5—C51−175.8 (2)
C7—C8—C9—C108.0 (4)
(II) (E)-3,4,5-trimethoxy-N-(4-nitrobenzylidene)aniline top
Crystal data top
C16H16N2O5F(000) = 664
Mr = 316.31Dx = 1.385 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.512 (2) Åθ = 5.4–14.7°
b = 7.895 (1) ŵ = 0.10 mm−1
c = 26.441 (6) ÅT = 293 K
β = 104.667 (19)°Block, yellow
V = 1517.0 (6) Å30.3 × 0.3 × 0.3 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.052
Radiation source: fine-focus sealed tubeθmax = 25.6°, θmin = 1.6°
Graphite monochromatorh = 0→9
θ/2ω scansk = −9→9
5826 measured reflectionsl = −31→30
2803 independent reflections3 standard reflections every 60 min
2023 reflections with I > 2σ(I) intensity decay: 4%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0418P)2 + 0.3031P]
where P = (Fo2 + 2Fc2)/3
2803 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.14 e Å−3
0 restraintsΔρmin = −0.18 e Å−3
Crystal data top
C16H16N2O5V = 1517.0 (6) Å3
Mr = 316.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.512 (2) ŵ = 0.10 mm−1
b = 7.895 (1) ÅT = 293 K
c = 26.441 (6) Å0.3 × 0.3 × 0.3 mm
β = 104.667 (19)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.052
5826 measured reflections3 standard reflections every 60 min
2803 independent reflections intensity decay: 4%
2023 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.05Δρmax = 0.14 e Å−3
2803 reflectionsΔρmin = −0.18 e Å−3
211 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.0234 (2)0.87162 (19)0.66274 (6)0.0420 (4)
C21.0351 (2)0.88660 (19)0.71593 (6)0.0429 (4)
H20.94960.95130.72740.051*
C31.1754 (2)0.80434 (18)0.75161 (6)0.0410 (3)
C41.3010 (2)0.70573 (19)0.73430 (6)0.0430 (4)
C51.2858 (2)0.6907 (2)0.68100 (6)0.0447 (4)
C61.1481 (2)0.7743 (2)0.64526 (6)0.0451 (4)
H61.13950.76510.60970.054*
C80.7306 (2)0.9767 (2)0.62901 (6)0.0478 (4)
H80.70220.93090.65840.057*
C90.5866 (2)1.0666 (2)0.59074 (6)0.0450 (4)
C100.6235 (2)1.1632 (2)0.55095 (6)0.0507 (4)
H100.74361.17330.54790.061*
C110.4829 (2)1.2443 (2)0.51605 (7)0.0540 (4)
H110.50711.31060.48950.065*
C120.3055 (2)1.2262 (2)0.52080 (6)0.0505 (4)
C130.2643 (2)1.1313 (2)0.55953 (7)0.0562 (4)
H130.14351.11960.56190.067*
C140.4064 (2)1.0538 (2)0.59465 (7)0.0541 (4)
H140.38150.99110.62180.065*
C311.0868 (3)0.9150 (3)0.82531 (7)0.0651 (5)
H31A1.09631.03000.81450.098*
H31B1.12270.90870.86280.098*
H31C0.96200.87690.81280.098*
C411.6137 (2)0.6981 (3)0.77813 (8)0.0659 (5)
H41A1.65330.69310.74640.099*
H41B1.69990.63830.80520.099*
H41C1.60730.81420.78830.099*
C511.3954 (3)0.5540 (3)0.61467 (8)0.0830 (7)
H51A1.27520.50760.60010.124*
H51B1.48710.47300.61140.124*
H51C1.41010.65570.59620.124*
N10.1548 (3)1.3158 (2)0.48429 (6)0.0671 (4)
N20.89150 (18)0.95908 (17)0.62363 (5)0.0478 (3)
O10.1956 (2)1.4109 (2)0.45293 (6)0.0940 (5)
O2−0.0028 (2)1.2896 (2)0.48683 (6)0.0906 (5)
O31.20364 (15)0.81114 (14)0.80444 (4)0.0525 (3)
O41.43646 (15)0.62201 (14)0.76993 (4)0.0538 (3)
O51.41580 (17)0.59177 (16)0.66791 (5)0.0627 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0435 (8)0.0387 (8)0.0430 (8)−0.0062 (7)0.0098 (7)0.0015 (7)
C20.0437 (8)0.0388 (8)0.0475 (9)0.0004 (7)0.0140 (7)−0.0018 (7)
C30.0483 (8)0.0352 (8)0.0408 (8)−0.0039 (7)0.0137 (7)−0.0018 (6)
C40.0464 (8)0.0351 (8)0.0485 (9)−0.0003 (7)0.0135 (7)0.0030 (7)
C50.0482 (9)0.0386 (8)0.0504 (9)−0.0014 (7)0.0181 (7)−0.0039 (7)
C60.0510 (9)0.0451 (9)0.0412 (9)−0.0067 (7)0.0151 (7)−0.0029 (7)
C80.0523 (9)0.0471 (9)0.0435 (9)−0.0059 (8)0.0110 (7)0.0028 (7)
C90.0505 (9)0.0439 (9)0.0397 (8)−0.0061 (7)0.0100 (7)−0.0027 (7)
C100.0502 (9)0.0560 (10)0.0471 (9)−0.0036 (8)0.0148 (7)0.0010 (8)
C110.0682 (11)0.0541 (10)0.0407 (9)−0.0026 (9)0.0159 (8)0.0035 (8)
C120.0572 (10)0.0501 (9)0.0390 (9)0.0026 (8)0.0027 (7)−0.0053 (7)
C130.0477 (9)0.0641 (11)0.0556 (11)−0.0035 (8)0.0105 (8)−0.0001 (9)
C140.0531 (10)0.0589 (11)0.0513 (10)−0.0063 (8)0.0151 (8)0.0082 (8)
C310.0720 (12)0.0773 (13)0.0473 (10)0.0197 (10)0.0176 (9)−0.0079 (9)
C410.0532 (10)0.0672 (12)0.0713 (13)0.0139 (9)0.0047 (9)0.0011 (10)
C510.1043 (17)0.0874 (16)0.0638 (13)0.0250 (13)0.0334 (12)−0.0185 (12)
N10.0748 (11)0.0689 (11)0.0483 (9)0.0102 (9)−0.0016 (8)−0.0060 (8)
N20.0493 (8)0.0477 (8)0.0455 (8)−0.0018 (6)0.0104 (6)0.0008 (6)
O10.1057 (12)0.0869 (11)0.0763 (11)0.0074 (9)−0.0015 (9)0.0302 (9)
O20.0629 (9)0.1285 (15)0.0722 (11)0.0233 (9)0.0020 (7)0.0061 (9)
O30.0620 (7)0.0543 (7)0.0419 (6)0.0137 (6)0.0148 (5)0.0003 (5)
O40.0585 (7)0.0473 (7)0.0558 (7)0.0111 (6)0.0146 (6)0.0092 (5)
O50.0701 (8)0.0660 (8)0.0562 (8)0.0169 (6)0.0239 (6)−0.0077 (6)
Geometric parameters (Å, º) top
C1—C61.379 (2)C11—H110.9300
C1—C21.392 (2)C12—C131.366 (2)
C1—N21.417 (2)C12—N11.470 (2)
C2—C31.385 (2)C13—C141.369 (2)
C2—H20.9300C13—H130.9300
C3—O31.3598 (18)C14—H140.9300
C3—C41.388 (2)C31—O31.4115 (19)
C4—O41.3690 (19)C31—H31A0.9600
C4—C51.390 (2)C31—H31B0.9600
C5—O51.3618 (19)C31—H31C0.9600
C5—C61.380 (2)C41—O41.427 (2)
C6—H60.9300C41—H41A0.9600
C8—N21.260 (2)C41—H41B0.9600
C8—C91.464 (2)C41—H41C0.9600
C8—H80.9300C51—O51.409 (2)
C9—C101.383 (2)C51—H51A0.9600
C9—C141.387 (2)C51—H51B0.9600
C10—C111.372 (2)C51—H51C0.9600
C10—H100.9300N1—O11.214 (2)
C11—C121.377 (2)N1—O21.221 (2)
C6—C1—C2120.76 (14)C11—C12—N1119.50 (17)
C6—C1—N2115.83 (14)C12—C13—C14117.87 (16)
C2—C1—N2123.35 (14)C12—C13—H13121.1
C3—C2—C1119.42 (14)C14—C13—H13121.1
C3—C2—H2120.3C13—C14—C9121.68 (16)
C1—C2—H2120.3C13—C14—H14119.2
O3—C3—C2125.11 (14)C9—C14—H14119.2
O3—C3—C4114.75 (14)O3—C31—H31A109.5
C2—C3—C4120.14 (14)O3—C31—H31B109.5
O4—C4—C3119.54 (14)H31A—C31—H31B109.5
O4—C4—C5120.84 (14)O3—C31—H31C109.5
C3—C4—C5119.61 (14)H31A—C31—H31C109.5
O5—C5—C6124.18 (15)H31B—C31—H31C109.5
O5—C5—C4115.24 (14)O4—C41—H41A109.5
C6—C5—C4120.57 (14)O4—C41—H41B109.5
C1—C6—C5119.49 (15)H41A—C41—H41B109.5
C1—C6—H6120.3O4—C41—H41C109.5
C5—C6—H6120.3H41A—C41—H41C109.5
N2—C8—C9122.52 (15)H41B—C41—H41C109.5
N2—C8—H8118.7O5—C51—H51A109.5
C9—C8—H8118.7O5—C51—H51B109.5
C10—C9—C14118.93 (15)H51A—C51—H51B109.5
C10—C9—C8122.55 (15)O5—C51—H51C109.5
C14—C9—C8118.52 (15)H51A—C51—H51C109.5
C11—C10—C9120.05 (16)H51B—C51—H51C109.5
C11—C10—H10120.0O1—N1—O2123.94 (18)
C9—C10—H10120.0O1—N1—C12117.43 (18)
C10—C11—C12119.21 (16)O2—N1—C12118.62 (18)
C10—C11—H11120.4C8—N2—C1119.00 (14)
C12—C11—H11120.4C3—O3—C31118.29 (13)
C13—C12—C11122.23 (16)C4—O4—C41113.80 (13)
C13—C12—N1118.25 (17)C5—O5—C51118.16 (15)
C6—C1—C2—C30.8 (2)C10—C11—C12—C130.6 (3)
N2—C1—C2—C3−176.13 (14)C10—C11—C12—N1178.61 (16)
C1—C2—C3—O3178.86 (14)C11—C12—C13—C140.6 (3)
C1—C2—C3—C4−1.0 (2)N1—C12—C13—C14−177.39 (16)
O3—C3—C4—O41.6 (2)C12—C13—C14—C9−1.7 (3)
C2—C3—C4—O4−178.51 (14)C10—C9—C14—C131.5 (3)
O3—C3—C4—C5−179.60 (14)C8—C9—C14—C13−178.48 (17)
C2—C3—C4—C50.3 (2)C13—C12—N1—O1173.90 (18)
O4—C4—C5—O5−1.4 (2)C11—C12—N1—O1−4.2 (3)
C3—C4—C5—O5179.79 (13)C13—C12—N1—O2−6.7 (3)
O4—C4—C5—C6179.47 (14)C11—C12—N1—O2175.19 (17)
C3—C4—C5—C60.7 (2)C9—C8—N2—C1179.44 (14)
C2—C1—C6—C50.1 (2)C6—C1—N2—C8144.52 (15)
N2—C1—C6—C5177.31 (14)C2—C1—N2—C8−38.4 (2)
O5—C5—C6—C1−179.94 (14)C2—C3—O3—C31−2.7 (2)
C4—C5—C6—C1−0.9 (2)C4—C3—O3—C31177.16 (15)
N2—C8—C9—C10−11.5 (3)C3—C4—O4—C41−104.66 (17)
N2—C8—C9—C14168.44 (16)C5—C4—O4—C4176.53 (19)
C14—C9—C10—C11−0.2 (3)C6—C5—O5—C51−8.6 (3)
C8—C9—C10—C11179.77 (16)C4—C5—O5—C51172.27 (17)
C9—C10—C11—C12−0.8 (3)
(III) (E)-4-nitro-N-(3,4,5-trimethoxybenzylidene)aniline top
Crystal data top
C16H16N2O5F(000) = 664
Mr = 316.31Dx = 1.383 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 7.215 (3) Åθ = 7.2–18.2°
b = 14.429 (2) ŵ = 0.10 mm−1
c = 14.595 (5) ÅT = 293 K
V = 1519.4 (8) Å3Prism, yellow
Z = 40.4 × 0.4 × 0.3 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.057
Radiation source: fine-focus sealed tubeθmax = 25.3°, θmin = 2.0°
Graphite monochromatorh = 0→8
θ/2ω scansk = −17→17
4683 measured reflectionsl = −17→17
1618 independent reflections3 standard reflections every 60 min
1358 reflections with I > 2σ(I) intensity decay: 10%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.1044P)2]
where P = (Fo2 + 2Fc2)/3
1618 reflections(Δ/σ)max < 0.001
212 parametersΔρmax = 0.30 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Crystal data top
C16H16N2O5V = 1519.4 (8) Å3
Mr = 316.31Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.215 (3) ŵ = 0.10 mm−1
b = 14.429 (2) ÅT = 293 K
c = 14.595 (5) Å0.4 × 0.4 × 0.3 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.057
4683 measured reflections3 standard reflections every 60 min
1618 independent reflections intensity decay: 10%
1358 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.07Δρmax = 0.30 e Å−3
1618 reflectionsΔρmin = −0.21 e Å−3
212 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.0091 (4)0.48584 (17)0.05506 (17)0.0436 (6)
C2−0.0484 (5)0.47394 (17)0.14689 (19)0.0456 (7)
H2−0.08010.41560.16910.055*
C3−0.0406 (4)0.54894 (19)0.20568 (19)0.0462 (7)
C40.0069 (4)0.63696 (17)0.1717 (2)0.0455 (7)
C50.0429 (4)0.64850 (17)0.0790 (2)0.0466 (7)
C60.0359 (4)0.57333 (18)0.02054 (19)0.0466 (7)
H60.06100.5809−0.04150.056*
C7−0.0123 (4)0.40613 (19)−0.00762 (17)0.0445 (6)
H70.02220.4143−0.06850.053*
C9−0.0694 (4)0.25169 (17)−0.04233 (17)0.0411 (6)
C10−0.1345 (4)0.26034 (18)−0.13153 (18)0.0468 (7)
H10−0.17400.3178−0.15280.056*
C11−0.1409 (5)0.1841 (2)−0.18876 (17)0.0499 (7)
H11−0.18470.1893−0.24850.060*
C12−0.0801 (4)0.09929 (17)−0.1548 (2)0.0455 (7)
C13−0.0206 (5)0.08857 (19)−0.0666 (2)0.0525 (7)
H130.01740.0308−0.04540.063*
C14−0.0178 (5)0.1647 (2)−0.0095 (2)0.0509 (7)
H140.01870.15790.05130.061*
C31−0.1129 (7)0.4565 (2)0.3360 (2)0.0708 (11)
H31A−0.21710.42910.30530.106*
H31B−0.14060.46330.40000.106*
H31C−0.00630.41740.32870.106*
C410.1940 (6)0.7206 (2)0.2719 (2)0.0613 (9)
H41A0.23270.66190.29630.092*
H41B0.18760.76540.32050.092*
H41C0.28170.74100.22670.092*
C510.0999 (7)0.7539 (2)−0.0426 (2)0.0714 (11)
H51A0.20340.7202−0.06700.107*
H51B0.11750.8189−0.05300.107*
H51C−0.01180.7338−0.07230.107*
N1−0.0798 (5)0.01880 (18)−0.2159 (2)0.0600 (7)
N2−0.0612 (4)0.32647 (16)0.01965 (15)0.0444 (6)
O1−0.1346 (5)0.02823 (17)−0.29360 (16)0.0831 (9)
O2−0.0239 (5)−0.05534 (17)−0.1858 (2)0.0897 (10)
O3−0.0755 (4)0.54563 (14)0.29720 (12)0.0604 (6)
O40.0162 (4)0.71109 (13)0.23073 (14)0.0572 (6)
O50.0860 (4)0.73709 (14)0.05276 (15)0.0608 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0486 (16)0.0328 (12)0.0494 (13)0.0009 (13)−0.0048 (13)−0.0050 (10)
C20.0553 (17)0.0319 (12)0.0497 (13)−0.0020 (13)0.0008 (13)−0.0043 (11)
C30.0523 (17)0.0378 (14)0.0485 (13)0.0027 (13)−0.0005 (14)−0.0070 (12)
C40.0504 (15)0.0307 (11)0.0553 (14)0.0059 (13)−0.0029 (14)−0.0085 (11)
C50.0490 (15)0.0315 (12)0.0594 (15)−0.0009 (12)−0.0032 (13)0.0008 (11)
C60.0575 (17)0.0372 (13)0.0451 (12)−0.0041 (13)−0.0020 (14)−0.0027 (11)
C70.0527 (15)0.0398 (13)0.0411 (12)−0.0030 (13)0.0004 (13)−0.0063 (11)
C90.0451 (15)0.0336 (13)0.0446 (12)−0.0033 (12)0.0017 (11)−0.0020 (10)
C100.0588 (18)0.0364 (12)0.0452 (12)0.0031 (14)0.0000 (14)−0.0008 (10)
C110.0622 (19)0.0449 (13)0.0426 (13)−0.0045 (14)−0.0016 (14)−0.0015 (11)
C120.0469 (14)0.0338 (12)0.0559 (14)−0.0075 (13)0.0046 (13)−0.0086 (11)
C130.0612 (18)0.0295 (11)0.0668 (16)0.0008 (14)−0.0108 (16)−0.0010 (12)
C140.0626 (17)0.0400 (13)0.0500 (14)−0.0038 (14)−0.0124 (15)0.0009 (12)
C310.105 (3)0.0579 (17)0.0499 (15)−0.011 (2)0.010 (2)0.0023 (15)
C410.075 (2)0.0458 (15)0.0636 (18)0.0009 (17)−0.0075 (17)−0.0193 (14)
C510.090 (3)0.053 (2)0.0713 (19)−0.017 (2)−0.001 (2)0.0165 (17)
N10.0650 (17)0.0478 (14)0.0671 (15)−0.0104 (15)0.0034 (14)−0.0197 (13)
N20.0544 (14)0.0360 (11)0.0429 (10)−0.0016 (11)−0.0007 (11)−0.0031 (10)
O10.122 (3)0.0680 (15)0.0594 (13)−0.0143 (18)0.0109 (17)−0.0232 (12)
O20.108 (2)0.0402 (12)0.120 (2)0.0076 (14)−0.025 (2)−0.0200 (13)
O30.0918 (17)0.0426 (10)0.0469 (10)0.0007 (13)0.0120 (12)−0.0061 (8)
O40.0691 (15)0.0323 (10)0.0702 (13)0.0084 (10)0.0041 (13)−0.0179 (9)
O50.0841 (17)0.0314 (10)0.0668 (12)−0.0059 (12)−0.0026 (13)0.0050 (9)
Geometric parameters (Å, º) top
C1—C21.381 (4)C11—H110.9300
C1—C61.397 (4)C12—C131.365 (4)
C1—C71.470 (3)C12—N11.464 (3)
C2—C31.382 (4)C13—C141.378 (4)
C2—H20.9300C13—H130.9300
C3—O31.360 (3)C14—H140.9300
C3—C41.406 (4)C31—O31.431 (4)
C4—O41.375 (3)C31—H31A0.9600
C4—C51.388 (4)C31—H31B0.9600
C5—O51.370 (3)C31—H31C0.9600
C5—C61.381 (4)C41—O41.423 (5)
C6—H60.9300C41—H41A0.9600
C7—N21.267 (4)C41—H41B0.9600
C7—H70.9300C41—H41C0.9600
C9—C101.389 (4)C51—O51.415 (4)
C9—C141.395 (4)C51—H51A0.9600
C9—N21.409 (3)C51—H51B0.9600
C10—C111.382 (4)C51—H51C0.9600
C10—H100.9300N1—O11.209 (4)
C11—C121.391 (4)N1—O21.225 (4)
C2—C1—C6120.7 (2)C11—C12—N1118.7 (2)
C2—C1—C7120.2 (2)C12—C13—C14119.0 (3)
C6—C1—C7119.1 (2)C12—C13—H13120.5
C1—C2—C3119.8 (2)C14—C13—H13120.5
C1—C2—H2120.1C13—C14—C9120.3 (2)
C3—C2—H2120.1C13—C14—H14119.8
O3—C3—C2125.1 (3)C9—C14—H14119.8
O3—C3—C4115.0 (2)O3—C31—H31A109.5
C2—C3—C4119.9 (2)O3—C31—H31B109.5
O4—C4—C5120.5 (2)H31A—C31—H31B109.5
O4—C4—C3119.6 (2)O3—C31—H31C109.5
C5—C4—C3119.9 (2)H31A—C31—H31C109.5
O5—C5—C6124.6 (3)H31B—C31—H31C109.5
O5—C5—C4115.3 (2)O4—C41—H41A109.5
C6—C5—C4120.1 (2)O4—C41—H41B109.5
C5—C6—C1119.7 (2)H41A—C41—H41B109.5
C5—C6—H6120.2O4—C41—H41C109.5
C1—C6—H6120.2H41A—C41—H41C109.5
N2—C7—C1121.3 (2)H41B—C41—H41C109.5
N2—C7—H7119.4O5—C51—H51A109.5
C1—C7—H7119.4O5—C51—H51B109.5
C10—C9—C14119.6 (2)H51A—C51—H51B109.5
C10—C9—N2123.1 (2)O5—C51—H51C109.5
C14—C9—N2117.2 (2)H51A—C51—H51C109.5
C11—C10—C9120.4 (3)H51B—C51—H51C109.5
C11—C10—H10119.8O1—N1—O2122.9 (3)
C9—C10—H10119.8O1—N1—C12118.8 (3)
C10—C11—C12118.3 (2)O2—N1—C12118.3 (3)
C10—C11—H11120.8C7—N2—C9120.3 (2)
C12—C11—H11120.8C3—O3—C31117.1 (2)
C13—C12—C11122.3 (2)C4—O4—C41112.6 (2)
C13—C12—N1119.0 (3)C5—O5—C51116.8 (2)
C6—C1—C2—C3−1.0 (5)C10—C11—C12—C132.2 (5)
C7—C1—C2—C3178.4 (3)C10—C11—C12—N1−177.8 (3)
C1—C2—C3—O3−179.7 (3)C11—C12—C13—C14−1.1 (5)
C1—C2—C3—C40.2 (5)N1—C12—C13—C14178.9 (3)
O3—C3—C4—O40.5 (4)C12—C13—C14—C9−2.0 (5)
C2—C3—C4—O4−179.3 (3)C10—C9—C14—C133.9 (5)
O3—C3—C4—C5−179.2 (3)N2—C9—C14—C13−179.3 (3)
C2—C3—C4—C51.0 (5)C13—C12—N1—O1179.1 (4)
O4—C4—C5—O5−0.3 (4)C11—C12—N1—O1−0.9 (5)
C3—C4—C5—O5179.4 (3)C13—C12—N1—O2−0.9 (5)
O4—C4—C5—C6179.0 (3)C11—C12—N1—O2179.1 (4)
C3—C4—C5—C6−1.3 (5)C1—C7—N2—C9177.8 (3)
O5—C5—C6—C1179.8 (3)C10—C9—N2—C7−39.5 (4)
C4—C5—C6—C10.5 (5)C14—C9—N2—C7143.8 (3)
C2—C1—C6—C50.6 (5)C2—C3—O3—C313.7 (5)
C7—C1—C6—C5−178.8 (3)C4—C3—O3—C31−176.2 (3)
C2—C1—C7—N24.1 (5)C5—C4—O4—C41−92.6 (3)
C6—C1—C7—N2−176.4 (3)C3—C4—O4—C4187.8 (4)
C14—C9—C10—C11−2.7 (5)C6—C5—O5—C518.7 (5)
N2—C9—C10—C11−179.3 (3)C4—C5—O5—C51−172.0 (3)
C9—C10—C11—C12−0.2 (5)

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC17H17NO5C16H16N2O5C16H16N2O5
Mr315.32316.31316.31
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cOrthorhombic, P212121
Temperature (K)293293293
a, b, c (Å)10.459 (2), 12.88 (1), 14.021 (4)7.512 (2), 7.895 (1), 26.441 (6)7.215 (3), 14.429 (2), 14.595 (5)
α, β, γ (°)90, 124.069 (15), 9090, 104.667 (19), 9090, 90, 90
V (Å3)1564.6 (13)1517.0 (6)1519.4 (8)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm−1)0.100.100.10
Crystal size (mm)0.42 × 0.39 × 0.390.3 × 0.3 × 0.30.4 × 0.4 × 0.3
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer		Enraf–Nonius CAD-4
diffractometer		Enraf–Nonius CAD-4
diffractometer
Absorption correction–––
No. of measured, independent and
observed [I > 2σ(I)] reflections		5901, 2867, 1500 5826, 2803, 2023 4683, 1618, 1358
Rint0.0430.0520.057
(sin θ/λ)max (Å−1)0.6020.6080.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.135, 1.00 0.036, 0.104, 1.05 0.052, 0.141, 1.07
No. of reflections286728031618
No. of parameters211211212
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.35, −0.140.14, −0.180.30, −0.21

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

Selected geometric data for (I), (II) and (III): calculated (DFT) and experimental (XRD) torsion angles in degrees, and calculated dipole moments µ in debye top
CompoundParameterXRDDFTµ
(I)C2–C1–C7–C8-11.0 (5)176.2
C1–C7–C8–C9178.7 (3)0.35.48
C7–C8–C9–C10-172.1 (3)4.2
(II)C2–C1–N2–C8-38.4 (2)31.6
C1–N2–C8–C9179.4 (1)177.44.59
N2–C8–C9–C10-11.5 (2)1.4
(III)C2–C1–C7–N24.1 (4)1.4
C1–C7–N2–C9177.8 (2)176.46.15
C7–N2–C9–C10-39.5 (4)42.5
List of weak hydrogen bonds in the crystal packing of (I) (Å, °) top
EntryDHAH···AD···AD—H···A
1C14H14O2ii2.693.526 (4)151
2C7H7O4iii2.573.447 (3)158
3C31H31BCgBiv2.833.718 (5)154
Symmetry codes: (ii) x, -y + 1/2, z - 1/2; (iii) x, -y + 3/2, z + 1/2; (iv) x + 1, -y + 1, -z.
List of weak hydrogen bonds in the crystal packing of (II) (Å, °) top
EntryDHAH···AD···AD—H···A
1C6H6O2v2.543.423 (2)160
2C41H41CO5vi2.503.450 (3)168
3C41H41BCgBvii2.963.626 (3)128
4C31H31ACgBviii2.783.463 (3)129
5C31H31BO1ix2.713.542 (3)145
6C51H51BCgAx2.943.631 (3)130
Symmetry codes: (vi) -x + 3, y + 1/2, -z + 3/2; (vii) -x + 3, y - 1/2, -z + 3/2; (viii) -x + 2, y + 1/2, -z + 3/2; (ix) x + 1, -y + 3/2, z + 1/2; (x) x + 1, y - 1, z.
List of short contacts in the crystal packing of (III) (Å, °) top
EntryDXAX···AD···AD—X···A
1C41H41BN2xi2.663.537 (4)153
2C6H6O1xii2.583.450 (4)156
3N1O2CgBxiii3.610 (4)3.587 (4)79.1 (2)
4N1O2CgBxiv3.912 (4)4.578 (4)115.7 (2)
Symmetry codes: (xi) -x, 1/2 + y, 1/2 - z; (xii) -x, 1/2 + y, -1/2 - z; (xiii) -1/2 + x, 1/2 - y, -z; (xiv) 1/2 + x, 1/2 - y, -z.
 

Acknowledgements

AC thanks the Institute for the Promotion of Innovation by Science and Technology in Flanders (IWT) for his predoctoral grants. Financial support by FWO–Vlaanderen under grant No. G.0129.05 and by the University of Antwerp under grant No. GOA-2404 is gratefully acknowledged.

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 9| September 2011| Pages o364-o369
doi:10.1107/S0108270111030952
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