Polarized molecular–electronic ­structures and supramolecular ­aggregation in 1-(6-amino-1,3-benzodioxol-5-yl)-3-aryl­prop-2-en-1-ones

Low, J.N.; Cobo, J.; Nogueras, M.; Cuervo, P.; Abonia, R.; Glidewell, C.

doi:10.1107/S0108270104020414

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 10| October 2004| Pages o744-o750

doi:10.1107/S0108270104020414

Polarized molecular–electronic structures and supramolecular aggregation in 1-(6-amino-1,3-benzodioxol-5-yl)-3-arylprop-2-en-1-ones

John N. Low,^a Justo Cobo,^b Manuel Nogueras,^b Paola Cuervo,^c Rodrigo Abonia ^c and Christopher Glidewell ^d ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 12 August 2004; accepted 16 August 2004; online 18 September 2004)

Molecules of 1-(6-amino-1,3-benzodioxol-5-yl)-3-(4-methylphenyl)prop-2-en-1-one, C₁₇H₁₅NO₃, (I), 1-(6-amino-1,3-benzodioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, C₁₇H₁₅NO₄, (II), and 1-(6-amino-1,3-benzodioxol-5-yl)-3-[4-(trifluoromethyl)phenyl]prop-2-en-1-one, C₁₇H₁₂F₃NO₃, (III), all contain an intramolecular N—H⋯O hydrogen bond and all exhibit polarized molecular–electronic structures. The molecules of (I) are linked into simple sheets, generated by translation, by means of one N—H⋯O and one C—H⋯π(arene) hydrogen bond. Compound (II) crystallizes as two concomitant polymorphs, viz. (IIa), with Z′ = 1 in P2₁/c, and (IIb), with Z′ = 2 in P $[\overline 1]$ . In (IIa), intra- and intermolecular N—H⋯O hydrogen bonds generate a helical chain of rings, and these chains are linked into sheets by simple helical chains built from a C—H⋯π(arene) hydrogen bond, while in (IIb), the molecules are linked into simple chains by a C—H⋯O hydrogen bond. In (III), where Z′ = 2, each type of molecule forms a simple N—H⋯O hydrogen-bonded chain generated by translation and the two types of chain are linked by a single π–π stacking interaction.

Comment

A range of 2-aminochalcone derivatives have been prepared for use as intermediates in the synthesis of new 6,7-methylenedioxytetrahydroquinolin-4-ones, compounds with interesting biological and pharmacological properties (Donnelly & Farell, 1990 ; Prager & Thredgold, 1968 ; Kurasawa et al., 2002 ). We report here the molecular and supramolecular structures of three such compounds, (I)–(III), and compare them with two further examples, (IV) and (V) (Low et al., 2002 ).

Compounds (I) and (III) crystallize with Z′ values of 1 and 2, respectively, while compound (II) forms two polymorphs, viz. monoclinic and triclinic, denoted (IIa) and (IIb), respectively, which crystallize concomitantly from dimethylformamide, with Z′ values of 1 and 2, respectively (Figs. 1–4 ). Of the two polymorphs of (II), the monoclinic polymorph has a significantly higher density than the triclinic polymorph and hence is probably the thermodynamically more stable form (Burger & Ramberger, 1979 ).

There is significant bond fixation within the amino-substituted aryl rings of (I)–(III) (Table 1). In particular, the C3a—C4 and C7—C7a bonds are both short, while the C5—C6 and C6—C7 bonds are long. In addition, the C6—C8 bond is short for its type (mean value 1.488 Å; Allen et al., 1987 ), while C8—O8 is long (mean value 1.231 Å). These values point to the charge-separated form, (A) (see scheme below), as an important contributor to the overall molecular–electronic structure, alongside the delocalized form, (B). An entirely similar pattern of distances (Table 1) is observed in the analogous compounds (IV) and (V), the structures of which have recently been reported (Low et al., 2002), although this was not discussed or noted in the original report, which focused exclusively on the supramolecular aggregation of (IV) and (V).

In all cases, the molecular skeletons are fairly close to being planar but, as shown by the key torsion angles (Table 2), there are some significant deviations in most of the independent examples. The sole exception is the type 1 molecule (containing atom O11, etc.; Fig. 3a) of compound (III). The five-membered rings show some flexibility of conformational behaviour. Thus, this ring is planar in (IIa) [although not in (IIb)] and in the type 2 molecule of compound (III), but it adopts an envelope conformation, with a folding across the O⋯O line, in (I), in both molecules of (IIb) and in the type 1 molecule of (III). For these rings, the ring-puckering parameter φ₂ (Cremer & Pople, 1975 ) takes the values 31.1 (15) and 30.5 (9)° in (I) and (III), respectively, and 30.9 (5) and 213.7 (5)° in the two independent molecules of (IIb). The two independent molecules in (IIb) exhibit different conformations at the methoxy substituent (Table 2), and this alone is sufficient to preclude the possibility of any additional symmetry

All of the molecules contain an intramolecular N—H⋯O hydrogen bond (Tables 3–6 ), in each case generating an S(6) motif (Bernstein et al., 1995 ), and these may have some influence on the overall molecular conformations. The supramolecular structures of (I) and (IIa) both depend upon a combination of N—H⋯O and C—H⋯π(arene) hydrogen bonds to generate sheets, but the structures differ considerably in detail. In compound (I), the amine atom N5 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H5B, to ring atom O1 in the molecule at (x, y − 1, z), so generating by translation a C(7) chain running parallel to the [010] direction (Fig. 5). In addition, atom C2 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H2A, to the C11–C16 ring in the molecule at (x − 1, y, z), so generating by translation a chain running parallel to the [100] direction (Fig. 6). The combination of the [100] and [010] chains generates a sheet parallel to (001), lying in the domain $[{1 \over 2}]$ < z < $[{3 \over 4}]$ (Fig. 7). Four sheets of this type pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

The monoclinic polymorph (IIa) of compound (II) exhibits two C—H⋯π(arene) hydrogen bonds in addition to the two N—H⋯O interactions (Table 4). Amine atom N5 in the molecule at (x, y, z) acts as donor, again via atom H5B, but this time to carbonyl atom O8 in the molecule at (2 − x, y − $[{1 \over 2}]$ , $[{1 \over 2}]$ − z), so producing a helical C₂¹(4)C(6)[S(6)] chain of rings running parallel to the [010] direction and generated by the 2₁ screw axis along (1, y, $[{1 \over 4}]$ ) (Fig. 8). This chain of rings may be contrasted with the very simple chain formed by the N—H⋯O hydrogen bonds in compound (I) (Fig. 5). Of the two C—H⋯π(arene) hydrogen bonds, that having atom C2 as the donor simply reinforces the foregoing [010] chain. However, that involving atom C13 in the molecule at (x, y, z) as donor to the C11–C16 ring in the molecule at (1 − x, y − $[{1 \over 2}]$ , $[{1 \over 2}]$ − z) not only generates a second chain running parallel to [010], this time generated by the 2₁ axis along ( $[{1 \over 2}]$ , y, $[{1 \over 4}]$ ) (Fig. 9), but also serves to link all of the chain of rings into an (001) sheet (Fig. 10). In the triclinic polymorph (IIb), the type 1 molecules (Fig. 3a) are linked by means of a single C—H⋯O hydrogen bond into chains generated by translation, while the type 2 molecules (Fig. 3b) are pendent from these chains and linked to them by N—H⋯O hydrogen bonds (Fig. 11)

Each of the two independent molecules in compound (III) forms a simple C(7) chain. The amine atoms N15 and N25 in the molecules at (x, y, z) act as donors to, respectively, the ring atoms O11 and O21 in the molecules at (x − 1, y, z), so generating C(7) chains by translation (Table 5 and Fig. 12). These two chains are linked by an aromatic π–π stacking interaction between the C111–C116 and C211–C216 rings within the asymmetric unit. The dihedral angle between the planes of these two rings is only 4.5 (2)°, the interplanar spacing is ca 3.5 Å and the centroid–centroid separation is 3.618 (2) Å. Propagation of this interaction then links the two independent translational chains (Fig. 12)

The simple and complex sheets in (I) and (IIa), the single chains in (IIb) and the paired chains in (III) may be briefly compared with the supramolecular structures of the analogues (IV) and (V) (Low et al., 2002). In (IV), where Z′ = 1, the sole significant intermolecular interactions are a C—H⋯O hydrogen bond with a ring O atom as acceptor, which generates zigzag C(10) chains, and a π–π stacking interaction linking these chains into sheets. In (V), where Z′ = 2, two N—H⋯O hydrogen bonds generate centrosymmetric R₈⁴(16) tetramers, which are weakly linked into chains by two rather long C—H⋯O hydrogen bonds. Hence, for the five compounds (I)–(V), while their intramolecular properties are all very similar, their supramolecular aggregation patterns are all different. For no single example in this series could the supramolecular structure be predicted from a knowledge of the supramolecular structures of all the others.

Figure 1
The molecule of (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2
The molecule of (IIa

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 3
The two independent molecules of (IIb

), showing the atom-labelling scheme for (a) the type 1 molecule and (b) the type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 4
The two independent molecules of (III

Figure 5
Part of the crystal structure of (I

), showing the formation of a chain parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y − 1, z) and (x, 1 + y, z), respectively.

Figure 6
Part of the crystal structure of (I

), showing the formation of a chain parallel to [100]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, y, z) and (1 + x, y, z), respectively.

Figure 7
A stereoview of part of the crystal structure of (I

), showing the formation of a sheet parallel to (001). For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted.

Figure 8
Part of the crystal structure of polymorph (IIa

), showing the formation of a chain of rings parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (2 − x, y − $[{1 \over 2}]$ , $[{1 \over 2}]$ − z), (x, y − 1, z) and (2 − x, $[{1 \over 2}]$ + y, $[{1 \over 2}]$ − z), respectively.

Figure 9
A stereoview of part of the crystal structure of polymorph (IIa

), showing the formation of an [010] chain generated by C—H⋯π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 10
A stereoview of part of the crystal structure of polymorph (IIa

), showing the formation of a sheet parallel to (001). For the sake of clarity, the intramolecular hydrogen bond and H atoms bonded to C atoms and not involved in the motif shown have been omitted.

Figure 11
A stereoview of part of the crystal structure of polymorph (IIb

), showing the formation of a C(8) chain along [100]. For the sake of clarity, the intramolecular hydrogen bond and H atoms bonded to C atoms and not involved in the motif shown have been omitted.

Figure 12
Part of the crystal structure of (III

), showing the formation of a π-stacked pair of chains parallel to [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, y, z) and (1 + x, y, z), respectively.

Experimental

For the synthesis of (I), a solution of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol), 4-tolualdehyde (0.33 g, 2.75 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under reflux for 20 min. After cooling the mixture, the resulting precipitate was filtered off and washed with ethanol, yielding (I) as a yellow solid (yield 91%, m.p. 401 K). Spectroscopic analysis, IR (KBr disc, ν, cm⁻¹): 3454, 3278 (NH₂), 1646 (C=O), 1606 (C=C), 1224 (OCH₂O); ¹H NMR (DMSO-d₆, δ): 2.33 (3H, s, CH₃), 5.96 (2H, s, OCH₂O), 6.35 (1H, s), 7.23 (2H, d, J = 8.0 Hz), 7.53 (1H, d, J = 15.4 Hz), 7.65 (1H, s), 7.67 (2H, br s, NH₂), 7.73 (2H, d, J = 8.0 Hz), 7.81 (1H, d, J = 15.4 Hz); ¹³C NMR (DMSO-d₆, δ): 21.0 (CH₃), 95.8, 101.1 (OCH₂O), 108.0, 109.9, 122.7, 128.5, 129.4, 132.5, 137.7, 139.6, 141.0, 151.7, 152.7, 187.7 (C=O). MS (70 eV): m/e (%) 281 (41, [M⁺]), 190 (100, [M–C₇H₇]). Crystals of (I) suitable for single-crystal X-ray diffraction were grown from a solution in ethanol. For the synthesis of (II), a solution of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol), 4-methoxybenzaldehyde (0.38 g, 2.79 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under reflux for 30 min. After cooling the mixture, the resulting precipitate was filtered off and crystallized from ethanol, giving (II) as an orange solid (yield 50%, m.p. 405 K). Spectroscopic analysis, IR (KBr disc, ν, cm⁻¹): 3461, 3303 (NH₂), 1644 (C=O), 1603 (C=C), 1223 (OCH₂O); ¹H NMR (CDCl₃, δ): 3.89 (3H, s, OCH₃), 5.93 (2H, s, OCH₂O), 6.19 (1H, s), 6.57 (2H, br s, NH₂), 6.91 (2H, d, J = 8.0 Hz), 7.26 (1H, s), 7.35 (1H, d, J = 15.4 Hz), 7.47 (2H, d, J = 8.0 Hz), 7.71 (1H, d, J = 15.4 Hz); ¹³C NMR (CDCl₃, δ): 55.2 (OCH₃), 96.8, l01.5 (OCH₂O), 108.2, 112.0, 114.5, 121.2, 128.3, 130.0, 138.9, 142.1, 150.0, 153.5, 161.2, 189.0 (C=O). MS (70 eV): m/e (%) 297 (27, [M⁺]), 190 (100, [M–C₇H₇O]). Crystallization from dimethylformamide gave a mixture of the monoclinic polymorph (IIa) as red crystals (m.p. 382 K) and the triclinic polymorph (IIb) as yellow crystals (m.p. 389 K). For the synthesis of (III), a solution of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol), 4-(trifluoromethyl)benzaldehyde (0.49 g, 2.79 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under reflux for 25 min. After cooling the mixture, the resulting precipitate was filtered off and washed with ethanol, yielding (III) as an orange solid (yield 75%, m.p. 417 K). Spectroscopic analysis, IR (KBr disc, ν, cm⁻¹): 3468, 3305 (NH₂), 1646 (C=O), 1606 (C=C), 1228 (OCH₂O); ¹H NMR (DMSO-d₆, δ): 5.94 (1H, s, H2), 5.98 (2H, s, OCH₂O), 6.38 (1H, s, H6), 7.6 (1H, d, H8, J = 15.0 Hz), 7.69 (2H, br s, NH₂), 7.76 (2H, d, J = 8.0 Hz), 8.02 (1H, d, J = 15.4 Hz), 8.15 (2H, d, J = 8.0 Hz); ¹³C NMR (DMSO-d₆, δ): 95.8, 101.2 (OCH₂O), 108.0, 108.9, 113.5 (CF₃), 125.5, 126.7, 129.3, 138.0, 139.1, 139.4, 152.2, 153.2, 187.1 (C=O). MS (70 eV): m/e (%) 335 (100, [M⁺]). Crystals of (III) suitable for single-crystal X-ray diffraction were grown from a solution in ethanol.

Table 1
Selected bond distances (Å) for compounds (I)–(V)

Bond	(I)	(IIa)	(IIb)	(IIb)	(III)	(III)	(IV)	(V)	(V)
			Mol 1	Mol 2	Mol 1	Mol 2		Mol 1	Mol 2
x	nil	nil	1	2	1	2	nil	1	2
Cx3a—Cx4	1.368 (3)	1.357 (2)	1.357 (2)	1.359 (2)	1.358 (3)	1.355 (3)	1.361 (2)	1.358 (2)	1.351 (2)
Cx4—Cx5	1.402 (3)	1.416 (2)	1.418 (2)	1.418 (2)	1.415 (3)	1.417 (3)	1.417 (2)	1.419 (2)	1.418 (2)
Cx5—Cx6	1.424 (3)	1.430 (2)	1.423 (2)	1.422 (2)	1.429 (3)	1.419 (3)	1.426 (2)	1.426 (2)	1.431 (2)
Cx6—Cx7	1.428 (3)	1.430 (2)	1.420 (2)	1.435 (2)	1.428 (3)	1.421 (3)	1.428 (2)	1.426 (2)	1.423 (2)
Cx7—Cx7a	1.339 (3)	1.354 (2)	1.353 (2)	1.350 (2)	1.350 (3)	1.355 (3)	1.355 (2)	1.354 (2)	1.353 (2)
Cx7a—Cx3a	1.386 (3)	1.394 (2)	1.387 (2)	1.391 (2)	1.390 (3)	1.390 (3)	1.394 (2)	1.390 (2)	1.393 (2)
Cx5—Nx5	1.364 (3)	1.353 (2)	1.364 (2)	1.361 (2)	1.368 (2)	1.369 (3)	1.359 (2)	1.370 (2)	1.360 (2)
Cx6—Cx8	1.459 (3)	1.461 (2)	1.470 (2)	1.462 (2)	1.468 (2)	1.468 (3)	1.470 (2)	1.473 (2)	1.463 (2)
Cx8-Ox8	1.249 (3)	1.246 (2)	1.240 (2)	1.244 (2)	1.244 (4)	1.237 (2)	1.243 (2)	1.253 (2)	1.250 (2)

Table 2
Selected torsion angles (°) for compounds (I)–(III)

Parameter	(I)	(IIa)	(IIb)	(IIb)	(III)	(III)
			Mol 1	Mol 2	Mol 1	Mol 2
x	nil	nil	1	2	1	2
Cx5—Cx6—Cx8—Cx9	−177.8 (2)	179.63 (13)	−168.15 (13)	−175.23 (13)	−171.93 (18)	−156.36 (19)
Cx6—Cx8—Cx9—Cx10	−159.1 (2)	−175.03 (14)	−170.48 (13)	153.13 (14)	171.9 (2)	176.7 (2)
Cx8—Cx9—Cx10—Cx11	178.4 (2)	179.77 (14)	−178.12 (13)	−176.05 (13)	−177.59 (19)	−177.65 (19)
Cx9—Cx10—Cx11—Cx12	−9.0 (2)	5.1 (2)	−11.3 (2)	−16.8 (2)	0.7 (3)	−8.6 (3)
Cx13—Cx14—Ox14—Cx41		−175.91 (13)	1.4 (2)	−176.09 (14)

Compound (I)

Crystal data

C₁₇H₁₅NO₃
M_r = 281.30
Monoclinic, P2₁/n
a = 10.530 (5) Å
b = 7.362 (5) Å
c = 17.546 (5) Å
β = 91.719 (5)°
V = 1359.6 (12) Å³
Z = 4
D_x = 1.374 Mg m⁻³
Mo Kα radiation
Cell parameters from 3062 reflections
θ = 5.3–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Block, yellow
0.40 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (EvalCCD; Duisenberg et al., 2003 ) T_min = 0.958, T_max = 0.981
17 073 measured reflections
3062 independent reflections
2024 reflections with I > 2σ(I)
R_int = 0.065
θ_max = 27.5°
h = −13 → 12
k = −9 → 9
l = −22 → 22

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.135
S = 1.11
3062 reflections
191 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0198P)² + 1.4934P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 3
Hydrogen-bonding geometry (Å, °) for (I)

Cg1 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O8	0.96	1.88	2.612 (3)	131
N5—H5B⋯O1ⁱ	0.96	2.07	3.032 (3)	178
C2—H2A⋯Cg1ⁱⁱ	0.99	2.86	3.644 (4)	137
Symmetry codes: (i) x,y-1,z; (ii) x-1,y,z.

Polymorph (IIa)

Crystal data

C₁₇H₁₅NO₄
M_r = 297.30
Monoclinic, P2₁/c
a = 17.5560 (4) Å
b = 5.0914 (2) Å
c = 15.4869 (4) Å
β = 91.9240 (16)°
V = 1383.51 (7) Å³
Z = 4
D_x = 1.427 Mg m⁻³
Mo Kα radiation
Cell parameters from 3170 reflections
θ = 2.9–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Block, red
0.04 × 0.02 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.959, T_max = 0.998
14 325 measured reflections
3170 independent reflections
2271 reflections with I > 2σ(I)
R_int = 0.038
θ_max = 27.5°
h = −21 → 22
k = −6 → 6
l = −20 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.128
S = 1.04
3169 reflections
201 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0701P)² + 0.2374P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.007 (2)

Table 4
Hydrogen-bonding geometry (Å, °) for polymorph (IIa)

Cg1 is the centroid of the C11–C16 ring and Cg2 is the centroid of the C3a/C4–C7/C7a ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O8	0.96	1.95	2.6301 (15)	126
N5—H5B⋯O8ⁱ	0.96	2.49	3.1232 (15)	123
C2—H2B⋯Cg2ⁱⁱ	0.99	2.84	3.640 (2)	138
C13—H13⋯Cg1ⁱⁱⁱ	0.95	2.81	3.488 (2)	130
Symmetry codes: (i) $[2-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]$ ; (ii) x,y-1,z; (iii) $[1-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]$ .

Polymorph (IIb)

Crystal data

C₁₇H₁₅NO₄
M_r = 297.30
Triclinic, $[P\overline 1]$
a = 9.5352 (2) Å
b = 10.6193 (3) Å
c = 14.7611 (4) Å
α = 89.1400 (14)°
β = 81.0970 (17)°
γ = 75.7540 (14)°
V = 1430.83 (6) Å³
Z = 4
D_x = 1.380 Mg m⁻³
Mo Kα radiation
Cell parameters from 6517 reflections
θ = 3.1–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Block, yellow
0.45 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) T_min = 0.951, T_max = 0.981
23 999 measured reflections
6517 independent reflections
4940 reflections with I > 2σ(I)
R_int = 0.035
θ_max = 27.5°
h = −12 → 12
k = −13 → 13
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.137
S = 1.10
6512 reflections
399 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0778P)² + 0.1431P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 5
Hydrogen-bonding geometry (Å, °) for polymorph (IIb)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N15—H15B⋯O18	0.88	1.99	2.6451 (17)	130
N25—H25A⋯O28	0.88	1.95	2.6069 (19)	131
N25—H25B⋯O13	0.88	2.19	3.0586 (17)	170
C12—H12A⋯O18ⁱ	0.99	2.27	3.221 (2)	161
Symmetry code: (i) x-1,y,z.

Compound (III)

Crystal data

C₁₇H₁₂F₃NO₃
M_r = 335.28
Triclinic, $[P\overline 1]$
a = 7.3420 (2) Å
b = 10.9241 (3) Å
c = 18.7176 (5) Å
α = 85.0180 (11)°
β = 83.2280 (14)°
γ = 75.8180 (14)°
V = 1442.71 (7) Å³
Z = 4
D_x = 1.544 Mg m⁻³
Mo Kα radiation
Cell parameters from 6611 reflections
θ = 3.0–27.6°
μ = 0.13 mm⁻¹
T = 120 (2) K
Block, red
0.60 × 0.60 × 0.50 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) T_min = 0.920, T_max = 0.937
20 172 measured reflections
6611 independent reflections
4510 reflections with I > 2σ(I)
R_int = 0.038
θ_max = 27.6°
h = −9 → 6
k = −14 → 13
l = −24 → 24

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.157
S = 1.04
6611 reflections
433 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0874P)² + 0.3568P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 6
Hydrogen-bonding geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N15—H15A⋯O18	0.96	1.91	2.637 (2)	131
N15—H15B⋯O11ⁱ	0.96	2.26	3.161 (2)	156
N25—H25A⋯O28	0.96	1.91	2.662 (2)	134
N25—H25B⋯O21ⁱ	0.96	2.09	3.024 (2)	165
Symmetry code: (i) x-1,y,z.

For (I) and (IIa), the space groups P2₁/n and P2₁/c, respectively, were uniquely determined from the systematic absences. Crystals of (IIb) and (III) are triclinic, and the space group P $[\overline 1]$ was selected and then confirmed by the structure analysis. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H = 0.95 (CH), 0.98 (CH₃) or 0.99 Å (CH₂) and N—H = 0.96 Å, and with U_iso(H) = 1.2U_eq(C,N), or 1.5U_eq(C) for the methyl groups. In compound (III), the highest residual peak (0.77 e Å⁻³) is 1.26 Å from F141 and the deepest hole (−0.52 e Å⁻³) is 0.97 Å from F141. Careful inspection of electron-density maps indicated some libration of the CF₃ groups about the adjacent C—C bonds, but gave no grounds for modelling these groups with more than three F-atom sites per group.

For all four compounds, data collection: COLLECT (Nonius, 1998 ). For compound (I), cell refinement: DIRAX/LSQ (Duisenberg et al., 2000 ); data reduction: EvalCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: OSCAIL (McArdle, 2003 ) and SHELXL97 (Sheldrick, 1997). For compounds (IIa) and (III), cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97. For compound (IIb), cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL and SHELXS97; program(s) used to refine structure: OSCAIL and SHELXL97. For all four compounds, molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I, IIa, IIb, III. DOI: 10.1107/S0108270104020414/sk1762sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104020414/sk1762Isup2.hkl

Structure factors: contains datablock IIa. DOI: 10.1107/S0108270104020414/sk1762IIasup3.hkl

Structure factors: contains datablock IIb. DOI: 10.1107/S0108270104020414/sk1762IIbsup4.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270104020414/sk1762IIIsup5.hkl

Comment top

A range of 2-aminochalcone derivatives have been prepared for use as intermediates in the synthesis of new 6,7-methylenedioxytetrahydroquinolin-4-ones, compounds with interesting biological and pharmacological properties (Donnelly & Farell, 1990; Prager & Thredgold, 1968; Kurasawa et al., 2002). Here, we report the molecular and supramolecular structures of three such compounds, (I)-(III), and compare them with two further examples, (IV) and (V) (Low et al., 2002). \sch

Compounds (I) and (III) crystallize with Z' values of 1 and 2, respectively, while compound (II) forms two polymorphs, monoclinic and triclinic, denoted (IIa) and (IIb), respectively, which crystallize concomitantly from dimethylformamide, with Z' values of 1 and 2, respectively (Figs. 1–4). Of the two polymorphs of (II), the monoclinic polymorph has a significantly higher density than the triclinic polymorph and hence is probably the thermodynamically more stable form (Burger & Ramberger, 1979).

There is significant bond fixation within the amino-substituted aryl ring of (I)-(III) (Table 1). In particular, the C3a—C4 and C7—C7a bonds are both short, while the C5—C6 and C6—C7 bonds are long. In addition, the C6—C8 bond is short for its type (mean value 1.488 Å; Allen et al., 1987), while C8—O8 is long (mean value 1.231 Å). These values point to the charge-separated form, (A), as an important contributor to the overall molecular-electronic structure, alongside the delocalized form, (B). An entirely similar pattern of distances (Table 1) is observed in the analogous compounds (IV) and (V), the structures of which have recently been reported (Low et al., 2002), although this was not discussed or noted in the original report, which focused exclusively on the supramolecular aggregation of (IV) and (V).

In all cases, the molecular skeletons are fairly close to being planar but, as shown by the key torsion angles (Table 2), there are some significant deviations in most of the independent examples. The sole exception is the type 1 molecule (containing atom O11 etc.; Fig. 3a) of compound (III). The five-membered rings show some flexibility of conformational behaviour. Thus, this ring is planar in (IIa) [although not in (IIb)] and in the type 2 molecule of compound (III), but it adopts an envelope conformation, with a folding across the O···O line, in (I), in both molecules of (IIb) and in the type 1 molecule of (III). For these rings, the ring-puckering parameter ϕ₂ (Cremer & Pople, 1975) takes the values 31.1 (15) and 30.5 (9)° in (I) and (III), respectively, and 30.9 (5) and 213.7 (5)° in the two independent molecules of (IIb). The two independent molecules in (IIb) exhibit different conformations at the methoxy substituent (Table 2), and this alone is sufficient to preclude the possibility of any additional symmetry

All of the molecules contain an intramolecular N—H···O hydrogen bond (Tables 3–6), in each case generating an S(6) motif (Bernstein et al., 1995), and these may have some influence on the overall molecular conformations. The supramolecular structures of (I) and (IIa) both depend upon a combination of N—H···O and C—H···π(arene) hydrogen bonds to generate sheets, but the structures differ considerably in detail. In compound (I), the amino atom N5 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H5B, to ring atom O1 in the molecule at (x, y − 1, z), so generating by translation a C(7) chain running parallel to the [010] direction (Fig. 5). In addition, atom C2 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H2A, to the C11—C16 ring in the molecule at (x − 1, y, z), so generating by translation a chain running parallel to the [100] direction (Fig. 6). The combination of the [100] and [010] chains generates a sheet parallel to (001), lying in the domain 1/2 < z < 3/4 (Fig. 7). Four sheets of this type pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

The monoclinic polymorph (IIa) of compound (II) exhibits two C—H···π(arene) hydrogen bonds in addition to the two N—H···O interactions (Table 4). The amino atom N5 in the molecule at (x, y, z) acts as donor, again via atom H5B, but this time to the carbonyl atom O8 in the molecule at (2 − x, y − 1/2, 1/2 − z), so producing a helical C₂¹(4) C(6)[S(6)] chain of rings running parallel to the [010] direction and generated by the 2₁ screw axis along (1, y, 1/4) (Fig. 8). This chain of rings may be contrasted with the very simple chain formed by the N—H···O hydrogen bonds in compound (I) (Fig. 5). Of the two C—H···π(arene) hydrogen bonds, that having atom C2 as the donor simply reinforces the foregoing [010] chain. However, that involving atom C13 in the molecule at (x, y, z) as donor to the C11—C16 ring in the molecule at (1 − x, y − 1/2, 1/2 − z) not only generates a second chain running parallel to [010], this time generated by the 2₁ axis along (1/2, y, 1/4) (Fig. 9), but also serves to link all of the chain of rings into an (001) sheet (Fig. 10). In the triclinic polymorph (IIb), the type 1 molecules (Fig. 3a) are linked by means of a single C—H···O hydrogen bond into chains generated by translation, while the type 2 molecules (Fig. 3 b) are pendent from these chains and linked to them by N—H···O hydrogen bonds (Fig. 11)

Each of the two independent molecules in compound (III) forms a simple C(7) chain. The amino atoms N15 and N25 in the molecules at (x, y, z) act as donors to, respectively, the ring atoms O11 and O21 in the molecules at (x − 1, y, z), so generating C(7) chains by translation (Table 5, Fig. 12). These two chains are linked by an aromatic π–π stacking interaction between the C111—C116 and C211—C216 rings within the asymmetric unit. The dihedral angle between the planes of these two rings is only 4.5 (2)°, the interplanar spacing is ca 3.5 Å and the ring-centroid separation is 3.618 (2) Å. Propagation of this interaction then links the two independent translational chains (Fig. 12)

The simple and complex sheets in (I) and (IIa), the single chains in (IIb) and the paired chains in (III) may be briefly compared with the supramolecular structures of the analogues (IV) and (V) (Low et al., 2002). In (IV), where Z' = 1, the sole significant intermolecular interactions are a C—H···O hydrogen bond with a ring O atom as acceptor, which generates zigzag C(10) chains, and a π–π stacking interaction linking these chains into sheets. In (V), where Z' = 2, two N—H···O hydrogen bonds generate centrosymmetric R₈⁴(16) tetramers, which are weakly linked into chains by two rather long C—H···O hydrogen bonds. Hence, of the five compounds (I)-(V), while their intramolecular properties are all very similar, their supramolecular aggregation patterns are all different. For no single example in this series could the supramolecular structure be predicted from a knowledge of the supramolecular structures of all the others.

Table 1. Selected bond distances (Å) for compounds (I)-(V)

Table 2. Selected torsion angles (°) for compounds (I)-(III)

Table 3. Hydrogen-bond parameters (Å, °) for compound (I); Cg1 is the centroid of the C11—C16 ring.

Table 4. Hydrogen-bond parameters (Å, °) for polymorph (IIa); Cg1 is the centroid of the C11—C16 ring and Cg2 is the centroid of the C3a/C4—C7/C7a ring.

Table 5. Hydrogen-bond parameters (Å, °) for polymorph (IIb)

Table 6. Hydrogen-bond parameters (Å, °) for compound (III)

Experimental top

For the synthesis of (I), a solution of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol), 4-tolualdehyde (0.33 g, 2.75 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under reflux for 20 min. After cooling the mixture, the resulting precipitate was filtered and washed with ethanol, yielding (I) as a yellow solid (yield 91%, m.p. 401 K). Spectroscopic analysis: IR (KBr disc, ν, cm⁻¹): 3454, 3278 (NH₂), 1646 (C═O), 1606 (C═C), 1224 (OCH₂O); ¹H NMR (DMSO-d₆, δ, p.p.m.): 2.33 (3H, s, CH₃), 5.96 (2H, s, OCH₂O), 6.35 (1H, s), 7.23 (2H, d, J = 8.0 Hz), 7.53 (1H, d, J = 15.4 Hz), 7.65 (1H, s), 7.67 (2H, br s, NH₂), 7.73 (2H, d, J = 8.0 Hz), 7.81 (1H, d, J = 15.4 Hz); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 21.0 (CH₃), 95.8, 101.1 (OCH₂O), 108.0, 109.9, 122.7, 128.5, 129.4, 132.5, 137.7, 139.6, 141.0, 151.7, 152.7, 187.7 (C═O). MS (70 eV): m/e (%) 281 (41, [M+]), 190 (100, [M—C₇H₇]). Crystals of (I) suitable for single-crystal X-ray diffraction were grown from a solution in ethanol. For the synthesis of (II), a solution of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol), 4-methoxybenzaldehyde (0.38 g, 2.79 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under reflux for 30 min. After cooling the mixture, the resulting precipitate was filtered and crystallized from ethanol, giving an (II) as an orange solid (yield 50%, m.p. 405 K). Spectroscopic analysis: IR (KBr disc, ν, cm⁻¹): 3461, 3303 (NH₂), 1644 (C═O), 1603 (C═C), 1223 (OCH₂O); ¹H NMR (CDCl₃, δ, p.p.m.) 3.89 (3H, s, OCH₃), 5.93 (2H, s, OCH₂O), 6.19 (1H, s), 6.57 (2H, br s, NH₂), 6.91 (2H, d, J = 8.0 Hz), 7.26 (1H, s), 7.35 (1H, d, J = 15.4 Hz), 7.47 (2H, d, J = 8.0 Hz), 7.71 (1H, d, J = 15.4 Hz); ¹³C NMR (CDCl₃, δ, p.p.m.) 55.2 (OCH₃), 96.8, l01.5 (OCH₂O), 108.2, 112.0, 114.5, 121.2, 128.3, 130.0, 138.9, 142.1, 150.0, 153.5, 161.2, 189.0 (C═O). MS (70 eV): m/e (%) 297 (27, [M⁺]), 190 (100, [M—C₇H₇O]). Crystallization from dimethylformamide gave a mixture of the monoclinic polymorph (IIa) as red crystals (m.p. 382 K) and the triclinic polymorph (IIb) as yellow crystals (m.p. 389 K). For the synthesis of (III), a solution of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol), 4-trifluoromethylbenzaldehyde (0.49 g, 2.79 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under reflux for 25 min. After cooling the mixture, the resulting precipitate was filtered and washed with ethanol, yielding (III) as an orange solid (yield 75%, m.p. 417 K). Spectroscopic analysis: IR (KBr disc, ν, cm⁻¹): 3468, 3305 (NH₂), 1646 (C═O), 1606 (C═C), 1228 (OCH₂O); ¹H NMR (DMSO-d₆, δ, p.p.m.): 5.94 (1H, s, H2), 5.98 (2H, s, OCH₂O), 6.38 (1H, s, H6), 7.6 (1H, d, H8, J = 15.0 Hz), 7.69 (2H, br s, NH₂), 7.76 (2H, d, J = 8.0 Hz), 8.02 (1H, d, J = 15.4 Hz), 8.15 (2H, d, J = 8.0 Hz); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 95.8, 101.2 (OCH₂O), 108.0, 108.9, 113.5 (CF₃), 125.5, 126.7, 129.3, 138.0, 139.1, 139.4, 152.2, 153.2, 187.1 (C═O). MS (70 eV): m/e (%) 335 (100, [M⁺]). Crystals of (III) suitable for single-crystal X-ray diffraction were grown from a solution in ethanol.

Computing details top

For all compounds, data collection: COLLECT (Nonius, 1998). Cell refinement: DIRAX/LSQ (Duisenberg et al., 2000) for (I); DENZO (Otwinowski & Minor, 1997) and COLLECT for (IIa), (IIb), (III). Data reduction: EVALCCD (Duisenberg et al., 2003) for (I); DENZO and COLLECT for (IIa), (IIb), (III). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I); SHELXS97 (Sheldrick, 1997) for (IIa), (III); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (IIb). Program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997) for (I); SHELXL97 (Sheldrick, 1997) for (IIa), (III); OSCAIL and SHELXL97 (Sheldrick, 1997) for (IIb). For all compounds, molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecule of (IIa), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The two independent molecules of (IIb), showing the atom-labelling scheme. (a) The type 1 molecule. (b) The type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The two independent molecules of (III), showing the atom-labelling scheme. (a) The type 1 molecule. (b) The type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 5. Part of the crystal structure of (I), showing formation of a chain parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y − 1, z) and (x, 1 + y, z), respectively.
	Fig. 6. Part of the crystal structure of (I), showing formation of a chain parallel to [100]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, y, z) and (1 + x, y, z), respectively.
	Fig. 7. A stereoview of part of the crystal structure of (I), showing formation of a sheet parallel to (001). For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted.
	Fig. 8. Part of the crystal structure of polymorph (IIa), showing formation of a chain of rings parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), a hash (#) or an ampersand () are at the symmetry positions (2 − x, y − 1/2, 1/2 − z), (x, y − 1, z) and (2 − x, 1/2 + y, 1/2 − z), respectively.
	Fig. 9. A stereoview of part of the crystal structure of polymorph (IIa), showing formation of an [010] chain generated by C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 10. A stereoview of part of the crystal structure of polymorph (IIa), showing formation of a sheet parallel to (001). For the sake of clarity, the intramolecular hydrogen bond and H atoms bonded to C atoms and not involved in the motif shown have been omitted.
	Fig. 11. A stereoview of part of the crystal structure of polymorph (IIb), showing formation of a C(8) chain along [100]. For the sake of clarity, the intramolecular hydrogen bond and H atoms bonded to C atoms and not involved in the motif shown have been omitted.
	Fig. 12. Part of the crystal structure of (III), showing formation of a π-stacked pair of chains parallel to [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, y, z) and (1 + x, y, z), respectively.

(I) 1-(6-Amino-1,3-benzodioxol-5-yl)-3-(4-methylphenyl)prop-2-en-1-one top

Crystal data top

C₁₇H₁₅NO₃	F(000) = 592
M_r = 281.30	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3062 reflections
a = 10.530 (5) Å	θ = 5.3–27.5°
b = 7.362 (5) Å	µ = 0.10 mm⁻¹
c = 17.546 (5) Å	T = 120 K
β = 91.719 (5)°	Block, yellow
V = 1359.6 (12) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	3062 independent reflections
Radiation source: Finefocus Sealed Tube	2024 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 5.3°
Absorption correction: multi-scan (EVALCCD; Duisenberg et al., 2003)	h = −13→12
T_min = 0.958, T_max = 0.981	k = −9→9
17073 measured reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0198P)² + 1.4934P] where P = (F_o² + 2F_c²)/3
3062 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₇H₁₅NO₃	V = 1359.6 (12) Å³
M_r = 281.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.530 (5) Å	µ = 0.10 mm⁻¹
b = 7.362 (5) Å	T = 120 K
c = 17.546 (5) Å	0.40 × 0.30 × 0.20 mm
β = 91.719 (5)°

Data collection top

Nonius KappaCCD area-detector diffractometer	3062 independent reflections
Absorption correction: multi-scan (EVALCCD; Duisenberg et al., 2003)	2024 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.981	R_int = 0.065
17073 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.11	Δρ_max = 0.24 e Å⁻³
3062 reflections	Δρ_min = −0.21 e Å⁻³
191 parameters

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

	x	y	z	U_iso*/U_eq
O1	−0.00920 (16)	0.5248 (2)	0.70572 (10)	0.0377 (4)
C2	−0.1286 (2)	0.4763 (4)	0.73506 (16)	0.0395 (6)
O3	−0.14191 (15)	0.2809 (2)	0.72870 (10)	0.0376 (4)
O8	0.38327 (17)	−0.0352 (2)	0.61985 (11)	0.0420 (5)
N5	0.1656 (2)	−0.1693 (3)	0.66004 (12)	0.0349 (5)
C3a	−0.0267 (2)	0.2171 (3)	0.70827 (13)	0.0287 (5)
C4	0.0092 (2)	0.0401 (3)	0.69898 (13)	0.0296 (5)
C5	0.1324 (2)	0.0062 (3)	0.67436 (12)	0.0283 (5)
C6	0.2172 (2)	0.1534 (3)	0.66237 (12)	0.0272 (5)
C7	0.1736 (2)	0.3349 (3)	0.67335 (13)	0.0290 (5)
C7a	0.0542 (2)	0.3615 (3)	0.69493 (13)	0.0291 (5)
C8	0.3452 (2)	0.1205 (3)	0.63584 (13)	0.0305 (5)
C9	0.4315 (2)	0.2774 (3)	0.62687 (13)	0.0305 (5)
C10	0.5305 (2)	0.2676 (3)	0.58262 (13)	0.0316 (5)
C11	0.6208 (2)	0.4135 (3)	0.56747 (13)	0.0294 (5)
C12	0.6041 (2)	0.5939 (3)	0.59041 (13)	0.0332 (6)
C13	0.6932 (2)	0.7254 (3)	0.57474 (13)	0.0356 (6)
C14	0.8011 (2)	0.6835 (4)	0.53535 (13)	0.0342 (6)
C15	0.8158 (2)	0.5059 (4)	0.51085 (14)	0.0374 (6)
C16	0.7271 (2)	0.3723 (3)	0.52632 (14)	0.0351 (6)
C141	0.8975 (3)	0.8287 (4)	0.51910 (16)	0.0445 (7)
H2A	−0.1979	0.5376	0.7057	0.047*
H2B	−0.1329	0.5139	0.7891	0.047*
H4	−0.0476	−0.0568	0.7089	0.036*
H5A	0.2528	−0.1925	0.6488	0.042*
H5B	0.1103	−0.2648	0.6759	0.042*
H7	0.2285	0.4352	0.6655	0.035*
H9	0.4153	0.3870	0.6534	0.037*
H10	0.5446	0.1545	0.5582	0.038*
H12	0.5304	0.6263	0.6172	0.040*
H13	0.6801	0.8467	0.5913	0.043*
H15	0.8884	0.4747	0.4828	0.045*
H16	0.7394	0.2519	0.5085	0.042*
H14A	0.8545	0.9461	0.5134	0.067*
H14B	0.9406	0.7991	0.4719	0.067*
H14C	0.9602	0.8352	0.5614	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0316 (9)	0.0259 (9)	0.0564 (11)	0.0009 (7)	0.0126 (8)	0.0042 (8)
C2	0.0351 (13)	0.0329 (14)	0.0510 (16)	−0.0017 (11)	0.0112 (12)	0.0024 (12)
O3	0.0311 (9)	0.0317 (10)	0.0504 (10)	−0.0033 (8)	0.0093 (8)	0.0047 (8)
O8	0.0394 (10)	0.0289 (10)	0.0584 (12)	0.0014 (8)	0.0118 (9)	−0.0034 (8)
N5	0.0359 (11)	0.0233 (11)	0.0456 (12)	−0.0033 (9)	0.0042 (9)	0.0013 (9)
C3a	0.0272 (11)	0.0316 (13)	0.0273 (11)	−0.0020 (10)	0.0023 (9)	0.0038 (10)
C4	0.0313 (12)	0.0254 (13)	0.0322 (12)	−0.0081 (10)	0.0025 (10)	0.0037 (9)
C5	0.0318 (12)	0.0270 (13)	0.0259 (11)	−0.0018 (10)	−0.0020 (9)	0.0015 (9)
C6	0.0278 (11)	0.0263 (12)	0.0275 (11)	−0.0034 (10)	0.0019 (9)	0.0007 (9)
C7	0.0295 (12)	0.0266 (12)	0.0311 (12)	−0.0060 (10)	0.0033 (9)	0.0009 (9)
C7a	0.0340 (12)	0.0227 (12)	0.0307 (12)	−0.0011 (10)	0.0024 (9)	0.0016 (9)
C8	0.0314 (12)	0.0298 (13)	0.0301 (12)	−0.0017 (10)	−0.0007 (9)	0.0006 (10)
C9	0.0294 (12)	0.0289 (13)	0.0332 (12)	−0.0013 (10)	0.0023 (10)	−0.0041 (10)
C10	0.0324 (12)	0.0277 (13)	0.0347 (12)	0.0017 (10)	0.0014 (10)	−0.0015 (10)
C11	0.0285 (12)	0.0318 (13)	0.0280 (11)	0.0002 (10)	0.0006 (9)	0.0006 (10)
C12	0.0337 (13)	0.0346 (14)	0.0315 (12)	0.0005 (11)	0.0047 (10)	−0.0019 (10)
C13	0.0454 (14)	0.0292 (13)	0.0324 (12)	−0.0060 (11)	0.0008 (11)	−0.0020 (10)
C14	0.0353 (13)	0.0383 (15)	0.0287 (12)	−0.0085 (11)	−0.0035 (10)	0.0064 (11)
C15	0.0311 (13)	0.0415 (15)	0.0400 (14)	0.0012 (11)	0.0052 (11)	0.0040 (12)
C16	0.0344 (13)	0.0295 (13)	0.0418 (14)	0.0004 (11)	0.0054 (10)	−0.0019 (11)
C141	0.0408 (14)	0.0494 (17)	0.0429 (15)	−0.0157 (13)	−0.0030 (12)	0.0048 (13)

Geometric parameters (Å, º) top

O1—C7a	1.391 (3)	C8—C9	1.480 (3)
O1—C2	1.418 (3)	C9—C10	1.321 (3)
C2—O3	1.449 (3)	C9—H9	0.95
C2—H2A	0.99	C10—C11	1.464 (3)
C2—H2B	0.99	C10—H10	0.95
O3—C3a	1.359 (3)	C11—C16	1.383 (3)
C3a—C4	1.368 (3)	C11—C12	1.400 (3)
C3a—C7a	1.386 (3)	C12—C13	1.381 (3)
C4—C5	1.402 (3)	C12—H12	0.95
C4—H4	0.95	C13—C14	1.383 (4)
C5—N5	1.364 (3)	C13—H13	0.95
C5—C6	1.424 (3)	C14—C15	1.387 (4)
N5—H5A	0.96	C14—C141	1.507 (3)
N5—H5B	0.96	C141—H14A	0.98
C6—C7	1.428 (3)	C141—H14B	0.98
C6—C8	1.459 (3)	C141—H14C	0.98
C7—C7a	1.339 (3)	C15—C16	1.389 (4)
C7—H7	0.95	C15—H15	0.95
C8—O8	1.249 (3)	C16—H16	0.95

C7a—O1—C2	105.41 (18)	C6—C8—C9	118.7 (2)
O1—C2—O3	107.88 (19)	C10—C9—C8	121.2 (2)
O1—C2—H2A	110.1	C10—C9—H9	119.4
O3—C2—H2A	110.1	C8—C9—H9	119.4
O1—C2—H2B	110.1	C9—C10—C11	126.5 (2)
O3—C2—H2B	110.1	C9—C10—H10	116.7
H2A—C2—H2B	108.4	C11—C10—H10	116.7
C3a—O3—C2	106.14 (18)	C16—C11—C12	117.9 (2)
O3—C3a—C4	127.8 (2)	C16—C11—C10	118.3 (2)
O3—C3a—C7a	109.7 (2)	C12—C11—C10	123.8 (2)
C4—C3a—C7a	122.5 (2)	C13—C12—C11	121.0 (2)
C3a—C4—C5	117.9 (2)	C13—C12—H12	119.5
C3a—C4—H4	121.1	C11—C12—H12	119.5
C5—C4—H4	121.1	C12—C13—C14	121.1 (2)
N5—C5—C4	118.0 (2)	C12—C13—H13	119.5
N5—C5—C6	121.9 (2)	C14—C13—H13	119.5
C4—C5—C6	120.0 (2)	C13—C14—C15	117.8 (2)
C5—N5—H5A	117.3	C13—C14—C141	120.3 (2)
C5—N5—H5B	118.6	C15—C14—C141	121.9 (2)
H5A—N5—H5B	121.4	C14—C141—H14A	109.5
C5—C6—C7	119.1 (2)	C14—C141—H14B	109.5
C5—C6—C8	120.7 (2)	H14A—C141—H14B	109.5
C7—C6—C8	120.1 (2)	C14—C141—H14C	109.5
C7a—C7—C6	118.9 (2)	H14A—C141—H14C	109.5
C7a—C7—H7	120.5	H14B—C141—H14C	109.5
C6—C7—H7	120.5	C14—C15—C16	121.7 (2)
C7—C7a—C3a	121.5 (2)	C14—C15—H15	119.2
C7—C7a—O1	128.6 (2)	C16—C15—H15	119.2
C3a—C7a—O1	109.9 (2)	C11—C16—C15	120.4 (2)
O8—C8—C6	122.0 (2)	C11—C16—H16	119.8
O8—C8—C9	119.3 (2)	C15—C16—H16	119.8

C7a—O1—C2—O3	−9.7 (3)	C2—O1—C7a—C3a	6.7 (3)
O1—C2—O3—C3a	9.4 (3)	C5—C6—C8—O8	2.9 (3)
C2—O3—C3a—C4	176.6 (2)	C7—C6—C8—O8	−174.3 (2)
C2—O3—C3a—C7a	−5.3 (3)	C5—C6—C8—C9	−177.8 (2)
O3—C3a—C4—C5	177.4 (2)	C7—C6—C8—C9	5.0 (3)
C7a—C3a—C4—C5	−0.6 (3)	O8—C8—C9—C10	20.2 (3)
C3a—C4—C5—N5	−175.6 (2)	C6—C8—C9—C10	−159.1 (2)
C3a—C4—C5—C6	2.1 (3)	C8—C9—C10—C11	178.4 (2)
N5—C5—C6—C7	175.7 (2)	C9—C10—C11—C16	172.8 (2)
C4—C5—C6—C7	−2.0 (3)	C9—C10—C11—C12	−9.0 (4)
N5—C5—C6—C8	−1.6 (3)	C16—C11—C12—C13	−2.2 (3)
C4—C5—C6—C8	−179.2 (2)	C10—C11—C12—C13	179.7 (2)
C5—C6—C7—C7a	0.3 (3)	C11—C12—C13—C14	0.6 (4)
C8—C6—C7—C7a	177.5 (2)	C12—C13—C14—C15	1.2 (4)
C6—C7—C7a—C3a	1.3 (3)	C12—C13—C14—C141	−179.7 (2)
C6—C7—C7a—O1	−177.1 (2)	C13—C14—C15—C16	−1.3 (4)
O3—C3a—C7a—C7	−179.5 (2)	C141—C14—C15—C16	179.6 (2)
C4—C3a—C7a—C7	−1.2 (4)	C12—C11—C16—C15	2.1 (3)
O3—C3a—C7a—O1	−0.8 (3)	C10—C11—C16—C15	−179.6 (2)
C4—C3a—C7a—O1	177.4 (2)	C14—C15—C16—C11	−0.4 (4)
C2—O1—C7a—C7	−174.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O8	0.96	1.88	2.612 (3)	131
N5—H5B···O1ⁱ	0.96	2.07	3.032 (3)	178
C2—H2A···Cg1ⁱⁱ	0.99	2.86	3.644 (4)	137

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

(IIa) 1-(6-Amino-1,3-benzodioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, monoclinic polymorph top

Crystal data top

C₁₇H₁₅NO₄	F(000) = 624
M_r = 297.30	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3170 reflections
a = 17.5560 (4) Å	θ = 2.9–27.5°
b = 5.0914 (2) Å	µ = 0.10 mm⁻¹
c = 15.4869 (4) Å	T = 120 K
β = 91.9240 (16)°	Block, red
V = 1383.51 (7) Å³	0.04 × 0.02 × 0.02 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	3170 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2271 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
ϕ and ω scans	h = −21→22
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −6→6
T_min = 0.959, T_max = 0.998	l = −20→19
14325 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0701P)² + 0.2374P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
3169 reflections	Δρ_max = 0.26 e Å⁻³
201 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.007 (2)

Crystal data top

C₁₇H₁₅NO₄	V = 1383.51 (7) Å³
M_r = 297.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.5560 (4) Å	µ = 0.10 mm⁻¹
b = 5.0914 (2) Å	T = 120 K
c = 15.4869 (4) Å	0.04 × 0.02 × 0.02 mm
β = 91.9240 (16)°

Data collection top

Nonius KappaCCD area-detector diffractometer	3170 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2271 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.998	R_int = 0.038
14325 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
3169 reflections	Δρ_min = −0.21 e Å⁻³
201 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.78208 (6)	−0.4220 (2)	0.01174 (7)	0.0337 (3)
C2	0.83733 (8)	−0.5459 (4)	−0.03950 (11)	0.0340 (4)
O3	0.91051 (6)	−0.4401 (2)	−0.01723 (7)	0.0356 (3)
C3a	0.89963 (8)	−0.2603 (3)	0.04676 (9)	0.0252 (4)
C4	0.95265 (8)	−0.1077 (3)	0.08815 (10)	0.0267 (4)
C5	0.92780 (8)	0.0730 (3)	0.15079 (9)	0.0232 (3)
N5	0.98106 (6)	0.2294 (3)	0.18954 (8)	0.0277 (3)
C6	0.84914 (8)	0.0844 (3)	0.17162 (9)	0.0222 (3)
C7	0.79644 (8)	−0.0847 (3)	0.12632 (9)	0.0242 (3)
C7a	0.82251 (8)	−0.2480 (3)	0.06499 (9)	0.0244 (3)
C8	0.82376 (8)	0.2649 (3)	0.23813 (9)	0.0240 (3)
O8	0.86837 (5)	0.4110 (2)	0.28000 (7)	0.0303 (3)
C9	0.74153 (8)	0.2741 (3)	0.25819 (9)	0.0252 (4)
C10	0.71444 (8)	0.4477 (3)	0.31353 (9)	0.0248 (3)
C11	0.63473 (8)	0.4739 (3)	0.33750 (9)	0.0224 (3)
C12	0.57815 (8)	0.2974 (3)	0.30779 (9)	0.0240 (3)
C13	0.50314 (8)	0.3286 (3)	0.32865 (9)	0.0240 (3)
C14	0.48187 (8)	0.5373 (3)	0.38070 (9)	0.0228 (3)
O14	0.40540 (5)	0.5557 (2)	0.39519 (6)	0.0269 (3)
C141	0.38014 (8)	0.7774 (3)	0.44357 (10)	0.0302 (4)
C15	0.53670 (8)	0.7104 (3)	0.41239 (9)	0.0257 (4)
C16	0.61226 (8)	0.6771 (3)	0.39075 (10)	0.0261 (4)
H2A	0.8250	−0.5151	−0.1015	0.041*
H2B	0.8372	−0.7377	−0.0290	0.041*
H4	1.0051	−0.1217	0.0755	0.032*
H5A	0.9664	0.3721	0.2260	0.033*
H5B	1.0317	0.2275	0.1681	0.033*
H7	0.7439	−0.0824	0.1391	0.029*
H9	0.7075	0.1527	0.2308	0.030*
H10	0.7501	0.5657	0.3400	0.030*
H12	0.5920	0.1535	0.2726	0.029*
H13	0.4658	0.2076	0.3075	0.029*
H14A	0.4036	0.7724	0.5019	0.045*
H14B	0.3246	0.7715	0.4473	0.045*
H14C	0.3950	0.9397	0.4146	0.045*
H15	0.5228	0.8514	0.4488	0.031*
H16	0.6496	0.7966	0.4130	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0224 (6)	0.0406 (7)	0.0384 (6)	−0.0021 (5)	0.0042 (5)	−0.0136 (6)
C2	0.0247 (8)	0.0368 (10)	0.0407 (9)	0.0012 (7)	0.0044 (7)	−0.0109 (8)
O3	0.0232 (6)	0.0460 (8)	0.0380 (7)	0.0004 (5)	0.0057 (5)	−0.0161 (6)
C3a	0.0231 (7)	0.0292 (9)	0.0237 (8)	0.0048 (6)	0.0042 (6)	0.0003 (7)
C4	0.0159 (7)	0.0346 (9)	0.0299 (8)	0.0030 (6)	0.0046 (6)	0.0020 (7)
C5	0.0195 (7)	0.0258 (8)	0.0243 (7)	0.0011 (6)	0.0017 (6)	0.0059 (7)
N5	0.0159 (6)	0.0320 (8)	0.0354 (7)	−0.0018 (5)	0.0034 (5)	−0.0038 (6)
C6	0.0169 (7)	0.0252 (8)	0.0245 (7)	0.0017 (6)	0.0014 (6)	0.0043 (6)
C7	0.0160 (7)	0.0284 (8)	0.0283 (8)	−0.0005 (6)	0.0037 (6)	0.0014 (7)
C7a	0.0201 (7)	0.0272 (9)	0.0260 (8)	−0.0011 (6)	0.0003 (6)	0.0012 (7)
C8	0.0189 (7)	0.0281 (9)	0.0250 (7)	0.0001 (6)	0.0015 (6)	0.0037 (7)
O8	0.0200 (5)	0.0361 (7)	0.0350 (6)	−0.0021 (5)	0.0022 (4)	−0.0073 (5)
C9	0.0179 (7)	0.0327 (9)	0.0250 (7)	−0.0007 (6)	0.0014 (6)	−0.0024 (7)
C10	0.0210 (7)	0.0269 (8)	0.0263 (8)	−0.0010 (6)	0.0004 (6)	0.0000 (7)
C11	0.0192 (7)	0.0263 (8)	0.0217 (7)	0.0025 (6)	0.0010 (6)	0.0002 (6)
C12	0.0242 (7)	0.0271 (8)	0.0208 (7)	0.0022 (6)	0.0020 (6)	−0.0008 (6)
C13	0.0209 (7)	0.0286 (9)	0.0223 (7)	−0.0023 (6)	−0.0002 (6)	−0.0012 (6)
C14	0.0172 (7)	0.0297 (9)	0.0216 (7)	0.0024 (6)	0.0018 (6)	0.0025 (6)
O14	0.0183 (5)	0.0344 (7)	0.0282 (6)	0.0015 (4)	0.0050 (4)	−0.0047 (5)
C15	0.0255 (8)	0.0263 (8)	0.0253 (8)	0.0037 (6)	0.0026 (6)	−0.0035 (7)
C16	0.0218 (7)	0.0272 (8)	0.0292 (8)	−0.0014 (6)	0.0014 (6)	−0.0026 (7)
C141	0.0241 (8)	0.0348 (10)	0.0322 (8)	0.0051 (7)	0.0074 (6)	−0.0033 (7)

Geometric parameters (Å, º) top

O1—C7a	1.3890 (18)	C9—C10	1.330 (2)
O1—C2	1.4214 (18)	C9—H9	0.95
C2—O3	1.4248 (19)	C10—C11	1.4659 (19)
C2—H2A	0.99	C10—H10	0.95
C2—H2B	0.99	C11—C16	1.388 (2)
O3—C3a	1.3673 (18)	C11—C12	1.406 (2)
C3a—C4	1.357 (2)	C12—C13	1.376 (2)
C3a—C7a	1.3937 (19)	C12—H12	0.95
C4—C5	1.416 (2)	C13—C14	1.392 (2)
C4—H4	0.95	C13—H13	0.95
C5—N5	1.3531 (19)	C14—O14	1.3718 (17)
C5—C6	1.4297 (19)	C14—C15	1.383 (2)
N5—H5A	0.96	O14—C141	1.4332 (18)
N5—H5B	0.9599	C141—H14A	0.98
C6—C7	1.430 (2)	C141—H14B	0.98
C6—C8	1.461 (2)	C141—H14C	0.98
C7—C7a	1.354 (2)	C15—C16	1.3894 (19)
C7—H7	0.95	C15—H15	0.95
C8—O8	1.2460 (18)	C16—H16	0.95
C8—C9	1.4877 (19)

C7a—O1—C2	105.65 (11)	C10—C9—C8	121.71 (14)
O1—C2—O3	108.89 (13)	C10—C9—H9	119.1
O1—C2—H2A	109.9	C8—C9—H9	119.1
O3—C2—H2A	109.9	C9—C10—C11	126.05 (14)
O1—C2—H2B	109.9	C9—C10—H10	117.0
O3—C2—H2B	109.9	C11—C10—H10	117.0
H2A—C2—H2B	108.3	C16—C11—C12	117.33 (13)
C3a—O3—C2	106.38 (11)	C16—C11—C10	120.72 (13)
C4—C3a—O3	127.99 (13)	C12—C11—C10	121.95 (13)
C4—C3a—C7a	122.30 (14)	C13—C12—C11	121.39 (14)
O3—C3a—C7a	109.70 (13)	C13—C12—H12	119.3
C3a—C4—C5	118.25 (13)	C11—C12—H12	119.3
C3a—C4—H4	120.9	C12—C13—C14	120.11 (14)
C5—C4—H4	120.9	C12—C13—H13	119.9
N5—C5—C4	117.51 (13)	C14—C13—H13	119.9
N5—C5—C6	122.30 (14)	O14—C14—C15	124.88 (13)
C4—C5—C6	120.19 (14)	O14—C14—C13	115.46 (13)
C5—N5—H5A	120.7	C15—C14—C13	119.65 (13)
C5—N5—H5B	118.4	C14—O14—C141	117.45 (12)
H5A—N5—H5B	118.7	O14—C141—H14A	109.5
C5—C6—C7	118.61 (13)	O14—C141—H14B	109.5
C5—C6—C8	120.27 (13)	H14A—C141—H14B	109.5
C7—C6—C8	121.12 (12)	O14—C141—H14C	109.5
C7a—C7—C6	119.05 (13)	H14A—C141—H14C	109.5
C7a—C7—H7	120.5	H14B—C141—H14C	109.5
C6—C7—H7	120.5	C14—C15—C16	119.70 (14)
C7—C7a—O1	129.08 (13)	C14—C15—H15	120.1
C7—C7a—C3a	121.55 (14)	C16—C15—H15	120.1
O1—C7a—C3a	109.37 (12)	C11—C16—C15	121.78 (14)
O8—C8—C6	122.76 (12)	C11—C16—H16	119.1
O8—C8—C9	118.04 (13)	C15—C16—H16	119.1
C6—C8—C9	119.20 (13)

C7a—O1—C2—O3	−1.08 (17)	C5—C6—C8—O8	−1.2 (2)
O1—C2—O3—C3a	0.93 (18)	C7—C6—C8—O8	178.52 (14)
C2—O3—C3a—C4	−179.51 (16)	C5—C6—C8—C9	179.63 (13)
C2—O3—C3a—C7a	−0.40 (17)	C7—C6—C8—C9	−0.6 (2)
O3—C3a—C4—C5	177.80 (14)	O8—C8—C9—C10	5.8 (2)
C7a—C3a—C4—C5	−1.2 (2)	C6—C8—C9—C10	−175.03 (14)
C3a—C4—C5—N5	−177.99 (14)	C8—C9—C10—C11	179.77 (14)
C3a—C4—C5—C6	2.5 (2)	C9—C10—C11—C16	−174.69 (15)
N5—C5—C6—C7	178.83 (13)	C9—C10—C11—C12	5.1 (2)
C4—C5—C6—C7	−1.7 (2)	C16—C11—C12—C13	1.7 (2)
N5—C5—C6—C8	−1.4 (2)	C10—C11—C12—C13	−178.04 (14)
C4—C5—C6—C8	178.10 (13)	C11—C12—C13—C14	−0.4 (2)
C5—C6—C7—C7a	−0.5 (2)	C12—C13—C14—O14	177.87 (13)
C8—C6—C7—C7a	179.76 (14)	C12—C13—C14—C15	−1.0 (2)
C6—C7—C7a—O1	−178.04 (14)	C15—C14—O14—C141	2.9 (2)
C6—C7—C7a—C3a	1.8 (2)	C13—C14—O14—C141	−175.91 (13)
C2—O1—C7a—C7	−179.31 (16)	O14—C14—C15—C16	−177.65 (13)
C2—O1—C7a—C3a	0.83 (17)	C13—C14—C15—C16	1.1 (2)
C4—C3a—C7a—C7	−1.0 (2)	C12—C11—C16—C15	−1.6 (2)
O3—C3a—C7a—C7	179.86 (13)	C10—C11—C16—C15	178.15 (14)
C4—C3a—C7a—O1	178.89 (14)	C14—C15—C16—C11	0.2 (2)
O3—C3a—C7a—O1	−0.28 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O8	0.96	1.95	2.6301 (15)	126
N5—H5B···O8ⁱ	0.96	2.49	3.1232 (15)	123
C2—H2B···Cg2ⁱⁱ	0.99	2.84	3.640 (2)	138
C13—H13···Cg1ⁱⁱⁱ	0.95	2.81	3.488 (2)	130

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

(IIb) 1-(6-Amino-1,3-benzodioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, triclinic polymorph top

Crystal data top

C₁₇H₁₅NO₄	Z = 4
M_r = 297.30	F(000) = 624
Triclinic, P1	D_x = 1.380 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5352 (2) Å	Cell parameters from 6517 reflections
b = 10.6193 (3) Å	θ = 3.1–27.5°
c = 14.7611 (4) Å	µ = 0.10 mm⁻¹
α = 89.1400 (14)°	T = 120 K
β = 81.0970 (17)°	Block, yellow
γ = 75.7540 (14)°	0.45 × 0.30 × 0.20 mm
V = 1430.83 (6) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	6517 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4940 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
T_min = 0.951, T_max = 0.981	l = −19→19
23999 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0778P)² + 0.1431P] where P = (F_o² + 2F_c²)/3
6512 reflections	(Δ/σ)_max = 0.001
399 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₇H₁₅NO₄	γ = 75.7540 (14)°
M_r = 297.30	V = 1430.83 (6) Å³
Triclinic, P1	Z = 4
a = 9.5352 (2) Å	Mo Kα radiation
b = 10.6193 (3) Å	µ = 0.10 mm⁻¹
c = 14.7611 (4) Å	T = 120 K
α = 89.1400 (14)°	0.45 × 0.30 × 0.20 mm
β = 81.0970 (17)°

Data collection top

Nonius KappaCCD area-detector diffractometer	6517 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4940 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.981	R_int = 0.035
23999 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.10	Δρ_max = 0.30 e Å⁻³
6512 reflections	Δρ_min = −0.37 e Å⁻³
399 parameters

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

	x	y	z	U_iso*/U_eq
O11	0.93492 (11)	1.05175 (11)	−0.26740 (7)	0.0293 (3)
C12	0.82075 (18)	1.0549 (2)	−0.19306 (12)	0.0433 (5)
O13	0.88228 (11)	0.97686 (10)	−0.12149 (7)	0.0278 (3)
C13a	1.03083 (15)	0.96323 (13)	−0.14296 (10)	0.0219 (3)
C14	1.13545 (16)	0.91026 (14)	−0.09121 (10)	0.0233 (3)
C15	1.28298 (16)	0.90599 (13)	−0.12808 (10)	0.0212 (3)
N15	1.38864 (14)	0.85000 (13)	−0.07718 (9)	0.0303 (3)
C16	1.31659 (15)	0.95830 (13)	−0.21581 (9)	0.0196 (3)
C17	1.20217 (15)	1.00866 (13)	−0.26744 (10)	0.0211 (3)
C17a	1.06302 (15)	1.01012 (13)	−0.22988 (10)	0.0216 (3)
C18	1.46764 (15)	0.96232 (13)	−0.25280 (10)	0.0214 (3)
O18	1.57336 (11)	0.90408 (10)	−0.21638 (7)	0.0268 (2)
C19	1.49422 (16)	1.03991 (14)	−0.33514 (10)	0.0242 (3)
C110	1.62835 (16)	1.03311 (13)	−0.37915 (10)	0.0222 (3)
C111	1.67155 (15)	1.10589 (13)	−0.45907 (10)	0.0204 (3)
C112	1.57301 (15)	1.17991 (14)	−0.51147 (10)	0.0233 (3)
C113	1.61880 (16)	1.25048 (14)	−0.58487 (10)	0.0239 (3)
C114	1.76706 (16)	1.24714 (13)	−0.60766 (10)	0.0222 (3)
O114	1.82482 (11)	1.31281 (10)	−0.67802 (7)	0.0298 (3)
C141	1.72509 (19)	1.39249 (16)	−0.73043 (12)	0.0346 (4)
C115	1.86764 (15)	1.17362 (14)	−0.55668 (10)	0.0237 (3)
C116	1.82016 (15)	1.10385 (14)	−0.48380 (10)	0.0227 (3)
O21	0.90504 (13)	0.30396 (10)	−0.07496 (7)	0.0326 (3)
C22	1.01329 (19)	0.31569 (15)	−0.15102 (11)	0.0327 (4)
O23	1.02449 (12)	0.44767 (10)	−0.15327 (8)	0.0349 (3)
C23a	0.90742 (16)	0.51538 (14)	−0.09352 (10)	0.0252 (3)
C24	0.86521 (16)	0.64606 (14)	−0.07812 (10)	0.0265 (3)
C25	0.74048 (16)	0.69550 (14)	−0.01122 (10)	0.0232 (3)
N25	0.69942 (15)	0.82629 (12)	0.00494 (9)	0.0301 (3)
C26	0.66336 (16)	0.61005 (13)	0.03725 (10)	0.0223 (3)
C27	0.71473 (16)	0.47289 (14)	0.01813 (10)	0.0242 (3)
C27a	0.83396 (16)	0.43040 (14)	−0.04616 (10)	0.0237 (3)
C28	0.53670 (16)	0.66027 (14)	0.10777 (10)	0.0252 (3)
O28	0.48934 (13)	0.77871 (10)	0.12534 (8)	0.0372 (3)
C29	0.46453 (16)	0.56927 (14)	0.16273 (10)	0.0248 (3)
C210	0.39261 (16)	0.60410 (14)	0.24716 (10)	0.0259 (3)
C211	0.32337 (16)	0.52343 (14)	0.31214 (10)	0.0243 (3)
C212	0.29118 (17)	0.40866 (15)	0.28601 (11)	0.0282 (3)
C213	0.23095 (17)	0.33422 (15)	0.35017 (11)	0.0305 (4)
C214	0.20247 (16)	0.37000 (14)	0.44281 (11)	0.0264 (3)
O214	0.14627 (13)	0.28658 (11)	0.50080 (8)	0.0351 (3)
C241	0.1067 (2)	0.32327 (17)	0.59548 (12)	0.0388 (4)
C215	0.23255 (17)	0.48297 (15)	0.47021 (11)	0.0294 (3)
C216	0.29181 (17)	0.55836 (15)	0.40472 (11)	0.0295 (3)
H12A	0.7431	1.0199	−0.2130	0.052*
H12B	0.7770	1.1455	−0.1703	0.052*
H14	1.1107	0.8772	−0.0323	0.028*
H15A	1.3642	0.8180	−0.0234	0.036*
H15B	1.4813	0.8458	−0.0982	0.036*
H17	1.2229	1.0407	−0.3272	0.025*
H19	1.4131	1.0960	−0.3570	0.029*
H110	1.7057	0.9737	−0.3559	0.027*
H112	1.4719	1.1820	−0.4964	0.028*
H113	1.5497	1.3008	−0.6194	0.029*
H14A	1.6564	1.4607	−0.6906	0.052*
H14B	1.6707	1.3391	−0.7572	0.052*
H14C	1.7797	1.4324	−0.7796	0.052*
H115	1.9687	1.1715	−0.5720	0.028*
H116	1.8897	1.0533	−0.4496	0.027*
H22A	0.9846	0.2919	−0.2089	0.039*
H22B	1.1089	0.2567	−0.1441	0.039*
H24	0.9174	0.7023	−0.1110	0.032*
H25B	0.7498	0.8768	−0.0257	0.036*
H25A	0.6225	0.8604	0.0460	0.036*
H27	0.6660	0.4134	0.0499	0.029*
H29	0.4694	0.4860	0.1379	0.030*
H210	0.3856	0.6903	0.2672	0.031*
H212	0.3113	0.3821	0.2232	0.034*
H213	0.2084	0.2574	0.3311	0.037*
H24A	0.1946	0.3269	0.6210	0.058*
H24B	0.0608	0.2592	0.6284	0.058*
H24C	0.0374	0.4090	0.6022	0.058*
H215	0.2129	0.5088	0.5332	0.035*
H216	0.3115	0.6365	0.4238	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0194 (5)	0.0438 (7)	0.0250 (6)	−0.0092 (5)	−0.0023 (4)	0.0055 (5)
C12	0.0245 (8)	0.0760 (14)	0.0314 (10)	−0.0186 (9)	−0.0013 (7)	0.0129 (9)
O13	0.0211 (5)	0.0374 (6)	0.0255 (6)	−0.0124 (5)	0.0029 (4)	0.0035 (5)
C13a	0.0217 (7)	0.0221 (7)	0.0223 (7)	−0.0105 (6)	0.0038 (6)	−0.0024 (6)
C14	0.0277 (7)	0.0247 (7)	0.0176 (7)	−0.0101 (6)	0.0021 (6)	0.0024 (6)
C15	0.0253 (7)	0.0177 (7)	0.0207 (7)	−0.0070 (6)	−0.0014 (6)	0.0009 (5)
N15	0.0278 (7)	0.0384 (8)	0.0236 (7)	−0.0075 (6)	−0.0033 (6)	0.0130 (6)
C16	0.0221 (7)	0.0181 (7)	0.0183 (7)	−0.0068 (6)	0.0013 (6)	−0.0003 (5)
C17	0.0237 (7)	0.0222 (7)	0.0171 (7)	−0.0078 (6)	0.0008 (6)	0.0024 (5)
C17a	0.0210 (7)	0.0234 (7)	0.0204 (7)	−0.0067 (6)	−0.0019 (6)	0.0012 (6)
C18	0.0233 (7)	0.0192 (7)	0.0213 (7)	−0.0067 (6)	0.0001 (6)	−0.0015 (5)
O18	0.0219 (5)	0.0298 (6)	0.0273 (6)	−0.0046 (4)	−0.0027 (4)	0.0064 (4)
C19	0.0213 (7)	0.0256 (7)	0.0252 (8)	−0.0065 (6)	−0.0016 (6)	0.0052 (6)
C110	0.0233 (7)	0.0225 (7)	0.0206 (7)	−0.0062 (6)	−0.0019 (6)	0.0014 (6)
C111	0.0215 (7)	0.0199 (7)	0.0186 (7)	−0.0058 (6)	0.0018 (6)	−0.0017 (5)
C112	0.0194 (7)	0.0277 (8)	0.0232 (8)	−0.0086 (6)	−0.0006 (6)	0.0009 (6)
C113	0.0229 (7)	0.0266 (8)	0.0225 (8)	−0.0062 (6)	−0.0041 (6)	0.0033 (6)
C114	0.0265 (7)	0.0216 (7)	0.0177 (7)	−0.0076 (6)	0.0018 (6)	0.0014 (5)
O114	0.0280 (6)	0.0346 (6)	0.0260 (6)	−0.0099 (5)	0.0003 (5)	0.0115 (5)
C141	0.0372 (9)	0.0380 (9)	0.0298 (9)	−0.0119 (7)	−0.0061 (7)	0.0146 (7)
C115	0.0190 (7)	0.0258 (7)	0.0249 (8)	−0.0066 (6)	0.0022 (6)	0.0000 (6)
C116	0.0202 (7)	0.0237 (7)	0.0216 (7)	−0.0018 (6)	−0.0009 (6)	0.0016 (6)
O21	0.0424 (7)	0.0222 (6)	0.0282 (6)	−0.0069 (5)	0.0085 (5)	−0.0011 (4)
C22	0.0402 (9)	0.0279 (8)	0.0267 (8)	−0.0085 (7)	0.0055 (7)	−0.0015 (6)
O23	0.0357 (6)	0.0270 (6)	0.0365 (7)	−0.0074 (5)	0.0112 (5)	−0.0026 (5)
C23a	0.0250 (7)	0.0283 (8)	0.0215 (8)	−0.0076 (6)	0.0007 (6)	0.0011 (6)
C24	0.0278 (8)	0.0249 (8)	0.0275 (8)	−0.0100 (6)	−0.0010 (6)	0.0038 (6)
C25	0.0259 (7)	0.0228 (7)	0.0221 (7)	−0.0069 (6)	−0.0058 (6)	0.0033 (6)
N25	0.0318 (7)	0.0213 (7)	0.0349 (8)	−0.0081 (5)	0.0047 (6)	0.0022 (5)
C26	0.0249 (7)	0.0226 (7)	0.0195 (7)	−0.0065 (6)	−0.0033 (6)	0.0033 (6)
C27	0.0303 (8)	0.0239 (7)	0.0198 (7)	−0.0101 (6)	−0.0030 (6)	0.0043 (6)
C27a	0.0299 (8)	0.0206 (7)	0.0208 (7)	−0.0064 (6)	−0.0040 (6)	0.0008 (6)
C28	0.0279 (7)	0.0250 (8)	0.0215 (8)	−0.0048 (6)	−0.0029 (6)	0.0050 (6)
O28	0.0408 (7)	0.0243 (6)	0.0367 (7)	−0.0006 (5)	0.0111 (5)	0.0045 (5)
C29	0.0243 (7)	0.0252 (8)	0.0242 (8)	−0.0052 (6)	−0.0030 (6)	0.0038 (6)
C210	0.0274 (7)	0.0235 (7)	0.0252 (8)	−0.0049 (6)	−0.0014 (6)	0.0038 (6)
C211	0.0234 (7)	0.0233 (7)	0.0236 (8)	−0.0038 (6)	0.0009 (6)	0.0019 (6)
C212	0.0295 (8)	0.0313 (8)	0.0232 (8)	−0.0086 (7)	−0.0007 (6)	−0.0032 (6)
C213	0.0324 (8)	0.0262 (8)	0.0343 (9)	−0.0126 (7)	−0.0006 (7)	−0.0024 (7)
C214	0.0234 (7)	0.0245 (8)	0.0292 (8)	−0.0054 (6)	0.0010 (6)	0.0059 (6)
O214	0.0399 (6)	0.0315 (6)	0.0331 (7)	−0.0147 (5)	0.0056 (5)	0.0061 (5)
C241	0.0389 (9)	0.0411 (10)	0.0315 (9)	−0.0076 (8)	0.0051 (7)	0.0111 (7)
C215	0.0352 (8)	0.0301 (8)	0.0216 (8)	−0.0093 (7)	0.0015 (7)	0.0000 (6)
C216	0.0359 (9)	0.0251 (8)	0.0276 (8)	−0.0108 (7)	0.0002 (7)	−0.0017 (6)

Geometric parameters (Å, º) top

O11—C17a	1.3894 (17)	O21—C27a	1.3867 (18)
O11—C12	1.416 (2)	O21—C22	1.4289 (19)
C12—O13	1.440 (2)	C22—O23	1.4310 (19)
C12—H12A	0.99	C22—H22A	0.99
C12—H12B	0.99	C22—H22B	0.99
O13—C13a	1.3745 (17)	O23—C23a	1.3639 (18)
C13a—C14	1.357 (2)	C23a—C24	1.359 (2)
C13a—C17a	1.387 (2)	C23a—C27a	1.391 (2)
C14—C15	1.418 (2)	C24—C25	1.418 (2)
C14—H14	0.95	C24—H24	0.95
C15—N15	1.364 (2)	C25—N25	1.361 (2)
C15—C16	1.423 (2)	C25—C26	1.422 (2)
N15—H15A	0.88	N25—H25B	0.88
N15—H15B	0.88	N25—H25A	0.88
C16—C17	1.420 (2)	C26—C27	1.435 (2)
C16—C18	1.470 (2)	C26—C28	1.462 (2)
C17—C17a	1.353 (2)	C27—C27a	1.350 (2)
C17—H17	0.95	C27—H27	0.95
C18—O18	1.240 (2)	C28—O28	1.244 (2)
C18—C19	1.483 (2)	C28—C29	1.482 (2)
C19—C110	1.327 (2)	C29—C210	1.336 (2)
C19—H19	0.95	C29—H29	0.95
C110—C111	1.4620 (19)	C210—C211	1.465 (2)
C110—H110	0.95	C210—H210	0.95
C111—C112	1.3936 (19)	C211—C216	1.389 (2)
C111—C116	1.4024 (19)	C211—C212	1.401 (2)
C112—C113	1.384 (2)	C212—C213	1.373 (2)
C112—H112	0.95	C212—H212	0.95
C113—C114	1.393 (2)	C213—C214	1.392 (2)
C113—H113	0.95	C213—H213	0.95
C114—O114	1.3633 (17)	C214—O214	1.3688 (18)
C114—C115	1.390 (2)	C214—C215	1.380 (2)
O114—C141	1.4251 (18)	O214—C241	1.424 (2)
C141—H14A	0.98	C241—H24A	0.98
C141—H14B	0.98	C241—H24B	0.98
C141—H14C	0.98	C241—H24C	0.98
C115—C116	1.379 (2)	C215—C216	1.388 (2)
C115—H115	0.95	C215—H215	0.95
C116—H116	0.95	C216—H216	0.95

C17a—O11—C12	104.76 (11)	C27a—O21—C22	105.38 (11)
O11—C12—O13	107.95 (13)	O21—C22—O23	108.06 (12)
O11—C12—H12A	110.1	O21—C22—H22A	110.1
O13—C12—H12A	110.1	O23—C22—H22A	110.1
O11—C12—H12B	110.1	O21—C22—H22B	110.1
O13—C12—H12B	110.1	O23—C22—H22B	110.1
H12A—C12—H12B	108.4	H22A—C22—H22B	108.4
C13a—O13—C12	104.95 (11)	C23a—O23—C22	105.80 (12)
C14—C13a—O13	127.68 (13)	C24—C23a—O23	127.26 (14)
C14—C13a—C17a	122.81 (13)	C24—C23a—C27a	122.60 (14)
O13—C13a—C17a	109.50 (12)	O23—C23a—C27a	110.13 (13)
C13a—C14—C15	117.67 (13)	C23a—C24—C25	117.61 (14)
C13a—C14—H14	121.2	C23a—C24—H24	121.2
C15—C14—H14	121.2	C25—C24—H24	121.2
N15—C15—C14	117.80 (13)	N25—C25—C24	117.53 (13)
N15—C15—C16	122.27 (13)	N25—C25—C26	121.96 (14)
C14—C15—C16	119.93 (13)	C24—C25—C26	120.51 (13)
C15—N15—H15A	120.0	C25—N25—H25B	120.0
C15—N15—H15B	120.0	C25—N25—H25A	120.0
H15A—N15—H15B	120.0	H25B—N25—H25A	120.0
C17—C16—C15	119.39 (12)	C25—C26—C27	118.97 (13)
C17—C16—C18	119.79 (12)	C25—C26—C28	120.71 (13)
C15—C16—C18	120.81 (12)	C27—C26—C28	120.29 (13)
C17a—C17—C16	118.67 (13)	C27a—C27—C26	118.38 (13)
C17a—C17—H17	120.7	C27a—C27—H27	120.8
C16—C17—H17	120.7	C26—C27—H27	120.8
C17—C17a—C13a	121.45 (13)	C27—C27a—O21	128.93 (13)
C17—C17a—O11	129.04 (13)	C27—C27a—C23a	121.94 (14)
C13a—C17a—O11	109.50 (12)	O21—C27a—C23a	109.12 (13)
O18—C18—C16	121.90 (13)	O28—C28—C26	121.63 (13)
O18—C18—C19	119.03 (13)	O28—C28—C29	118.26 (14)
C16—C18—C19	119.07 (12)	C26—C28—C29	120.08 (13)
C110—C19—C18	121.78 (13)	C210—C29—C28	120.12 (14)
C110—C19—H19	119.1	C210—C29—H29	119.9
C18—C19—H19	119.1	C28—C29—H29	119.9
C19—C110—C111	127.91 (13)	C29—C210—C211	126.92 (14)
C19—C110—H110	116.0	C29—C210—H210	116.5
C111—C110—H110	116.0	C211—C210—H210	116.5
C112—C111—C116	117.67 (13)	C216—C211—C212	117.50 (14)
C112—C111—C110	123.79 (13)	C216—C211—C210	119.37 (13)
C116—C111—C110	118.52 (12)	C212—C211—C210	123.09 (14)
C113—C112—C111	121.63 (13)	C213—C212—C211	120.74 (14)
C113—C112—H112	119.2	C213—C212—H212	119.6
C111—C112—H112	119.2	C211—C212—H212	119.6
C112—C113—C114	119.47 (13)	C212—C213—C214	120.78 (14)
C112—C113—H113	120.3	C212—C213—H213	119.6
C114—C113—H113	120.3	C214—C213—H213	119.6
O114—C114—C115	115.27 (12)	O214—C214—C215	124.73 (14)
O114—C114—C113	124.73 (13)	O214—C214—C213	115.69 (13)
C115—C114—C113	120.00 (13)	C215—C214—C213	119.58 (14)
C114—O114—C141	117.17 (11)	C214—O214—C241	117.66 (13)
O114—C141—H14A	109.5	O214—C241—H24A	109.5
O114—C141—H14B	109.5	O214—C241—H24B	109.5
H14A—C141—H14B	109.5	H24A—C241—H24B	109.5
O114—C141—H14C	109.5	O214—C241—H24C	109.5
H14A—C141—H14C	109.5	H24A—C241—H24C	109.5
H14B—C141—H14C	109.5	H24B—C241—H24C	109.5
C116—C115—C114	119.77 (13)	C214—C215—C216	119.21 (14)
C116—C115—H115	120.1	C214—C215—H215	120.4
C114—C115—H115	120.1	C216—C215—H215	120.4
C115—C116—C111	121.44 (13)	C215—C216—C211	122.18 (14)
C115—C116—H116	119.3	C215—C216—H216	118.9
C111—C116—H116	119.3	C211—C216—H216	118.9

C17a—O11—C12—O13	−18.20 (18)	C27a—O21—C22—O23	12.11 (16)
O11—C12—O13—C13a	17.28 (18)	O21—C22—O23—C23a	−11.89 (17)
C12—O13—C13a—C14	171.96 (16)	C22—O23—C23a—C24	−174.23 (15)
C12—O13—C13a—C17a	−9.52 (16)	C22—O23—C23a—C27a	7.09 (17)
O13—C13a—C14—C15	179.64 (13)	O23—C23a—C24—C25	−178.94 (14)
C17a—C13a—C14—C15	1.3 (2)	C27a—C23a—C24—C25	−0.4 (2)
C13a—C14—C15—N15	−178.46 (13)	C23a—C24—C25—N25	179.21 (13)
C13a—C14—C15—C16	1.1 (2)	C23a—C24—C25—C26	−0.1 (2)
N15—C15—C16—C17	176.49 (13)	N25—C25—C26—C27	−178.63 (13)
C14—C15—C16—C17	−3.0 (2)	C24—C25—C26—C27	0.7 (2)
N15—C15—C16—C18	−4.4 (2)	N25—C25—C26—C28	−0.7 (2)
C14—C15—C16—C18	176.13 (12)	C24—C25—C26—C28	178.60 (13)
C15—C16—C17—C17a	2.6 (2)	C25—C26—C27—C27a	−0.7 (2)
C18—C16—C17—C17a	−176.55 (13)	C28—C26—C27—C27a	−178.60 (13)
C16—C17—C17a—C13a	−0.3 (2)	C26—C27—C27a—O21	178.58 (13)
C16—C17—C17a—O11	−178.61 (13)	C26—C27—C27a—C23a	0.2 (2)
C14—C13a—C17a—C17	−1.8 (2)	C22—O21—C27a—C27	173.61 (15)
O13—C13a—C17a—C17	179.65 (12)	C22—O21—C27a—C23a	−7.80 (16)
C14—C13a—C17a—O11	176.87 (13)	C24—C23a—C27a—C27	0.4 (2)
O13—C13a—C17a—O11	−1.74 (16)	O23—C23a—C27a—C27	179.17 (13)
C12—O11—C17a—C17	−169.12 (16)	C24—C23a—C27a—O21	−178.29 (13)
C12—O11—C17a—C13a	12.39 (17)	O23—C23a—C27a—O21	0.46 (17)
C17—C16—C18—O18	−169.98 (13)	C25—C26—C28—O28	2.6 (2)
C15—C16—C18—O18	10.9 (2)	C27—C26—C28—O28	−179.54 (13)
C17—C16—C18—C19	11.0 (2)	C25—C26—C28—C29	−175.23 (13)
C15—C16—C18—C19	−168.15 (13)	C27—C26—C28—C29	2.7 (2)
O18—C18—C19—C110	10.5 (2)	O28—C28—C29—C210	−24.7 (2)
C16—C18—C19—C110	−170.48 (13)	C26—C28—C29—C210	153.13 (14)
C18—C19—C110—C111	−178.12 (13)	C28—C29—C210—C211	−176.05 (13)
C19—C110—C111—C112	−11.3 (2)	C29—C210—C211—C216	160.90 (15)
C19—C110—C111—C116	167.29 (15)	C29—C210—C211—C212	−16.8 (2)
C116—C111—C112—C113	−0.7 (2)	C216—C211—C212—C213	−0.1 (2)
C110—C111—C112—C113	177.92 (13)	C210—C211—C212—C213	177.68 (14)
C111—C112—C113—C114	0.4 (2)	C211—C212—C213—C214	−1.0 (2)
C112—C113—C114—O114	−179.72 (13)	C212—C213—C214—O214	−178.20 (14)
C112—C113—C114—C115	−0.2 (2)	C212—C213—C214—C215	1.3 (2)
C115—C114—O114—C141	−178.20 (13)	C215—C214—O214—C241	4.5 (2)
C113—C114—O114—C141	1.4 (2)	C213—C214—O214—C241	−176.09 (14)
O114—C114—C115—C116	179.80 (13)	O214—C214—C215—C216	178.92 (14)
C113—C114—C115—C116	0.2 (2)	C213—C214—C215—C216	−0.5 (2)
C114—C115—C116—C111	−0.5 (2)	C214—C215—C216—C211	−0.6 (2)
C112—C111—C116—C115	0.7 (2)	C212—C211—C216—C215	0.9 (2)
C110—C111—C116—C115	−177.97 (13)	C210—C211—C216—C215	−176.98 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15B···O18	0.88	1.99	2.6451 (17)	130
N25—H25A···O28	0.88	1.95	2.6069 (19)	131
N25—H25B···O13	0.88	2.19	3.0586 (17)	170
C12—H12A···O18ⁱ	0.99	2.27	3.221 (2)	161

Symmetry code: (i) x−1, y, z.

(III) 1-(6-Amino-1,3-benzodioxol-5-yl)-3-[4-(trifluoromethyl)phenyl]prop-2-en-1-one top

Crystal data top

C₁₇H₁₂F₃NO₃	Z = 4
M_r = 335.28	F(000) = 688
Triclinic, P1	D_x = 1.544 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3420 (2) Å	Cell parameters from 6611 reflections
b = 10.9241 (3) Å	θ = 3.0–27.6°
c = 18.7176 (5) Å	µ = 0.13 mm⁻¹
α = 85.0180 (11)°	T = 120 K
β = 83.2280 (14)°	Block, red
γ = 75.8180 (14)°	0.60 × 0.60 × 0.50 mm
V = 1442.71 (7) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	6611 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4510 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 27.6°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→6
T_min = 0.920, T_max = 0.937	k = −14→13
20172 measured reflections	l = −24→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0874P)² + 0.3568P] where P = (F_o² + 2F_c²)/3
6611 reflections	(Δ/σ)_max < 0.001
433 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₇H₁₂F₃NO₃	γ = 75.8180 (14)°
M_r = 335.28	V = 1442.71 (7) Å³
Triclinic, P1	Z = 4
a = 7.3420 (2) Å	Mo Kα radiation
b = 10.9241 (3) Å	µ = 0.13 mm⁻¹
c = 18.7176 (5) Å	T = 120 K
α = 85.0180 (11)°	0.60 × 0.60 × 0.50 mm
β = 83.2280 (14)°

Data collection top

Nonius KappaCCD area-detector diffractometer	6611 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4510 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.937	R_int = 0.038
20172 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.04	Δρ_max = 0.77 e Å⁻³
6611 reflections	Δρ_min = −0.52 e Å⁻³
433 parameters

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

	x	y	z	U_iso*/U_eq
F141	0.7571 (4)	0.6220 (2)	0.35107 (10)	0.0990 (9)
F142	0.8294 (3)	0.48202 (16)	0.43056 (11)	0.0721 (6)
F143	0.5784 (2)	0.6202 (2)	0.44684 (13)	0.0963 (9)
O11	0.8022 (2)	−0.19815 (14)	0.06107 (8)	0.0288 (4)
O13	0.6180 (2)	−0.26762 (14)	−0.01200 (8)	0.0271 (3)
O18	0.0728 (2)	0.13519 (14)	0.19270 (8)	0.0272 (3)
N15	0.0344 (2)	−0.00119 (17)	0.08840 (9)	0.0250 (4)
C12	0.8092 (3)	−0.2675 (2)	−0.00123 (12)	0.0266 (5)
C13a	0.5051 (3)	−0.17842 (18)	0.03120 (10)	0.0213 (4)
C14	0.3142 (3)	−0.13762 (19)	0.03553 (11)	0.0220 (4)
C15	0.2260 (3)	−0.04596 (19)	0.08561 (10)	0.0201 (4)
C16	0.3368 (3)	0.00141 (18)	0.12949 (10)	0.0193 (4)
C17	0.5368 (3)	−0.04738 (19)	0.12315 (10)	0.0211 (4)
C17a	0.6138 (3)	−0.13464 (19)	0.07453 (10)	0.0204 (4)
C18	0.2472 (3)	0.09856 (19)	0.18044 (10)	0.0205 (4)
C19	0.3685 (3)	0.15777 (19)	0.21796 (11)	0.0240 (5)
C110	0.2951 (3)	0.2558 (2)	0.25768 (11)	0.0240 (4)
C111	0.3977 (3)	0.32596 (19)	0.29524 (11)	0.0222 (4)
C112	0.5947 (3)	0.2958 (2)	0.29228 (11)	0.0228 (4)
C113	0.6856 (3)	0.3665 (2)	0.32679 (11)	0.0241 (5)
C114	0.5816 (3)	0.46842 (19)	0.36509 (11)	0.0231 (4)
C115	0.3861 (3)	0.4992 (2)	0.36956 (11)	0.0278 (5)
C116	0.2954 (3)	0.4280 (2)	0.33448 (12)	0.0273 (5)
C141	0.6809 (3)	0.5487 (2)	0.39885 (12)	0.0311 (5)
F241	0.7526 (2)	0.43372 (14)	0.03458 (7)	0.0458 (4)
F242	0.70842 (19)	0.29796 (12)	0.11946 (7)	0.0360 (3)
F243	0.88822 (18)	0.42096 (14)	0.13137 (9)	0.0471 (4)
O21	0.1650 (2)	1.18306 (16)	0.45514 (9)	0.0351 (4)
O23	−0.1122 (2)	1.24138 (15)	0.53049 (8)	0.0307 (4)
O28	−0.2621 (2)	0.92780 (16)	0.28116 (8)	0.0341 (4)
N25	−0.4550 (2)	1.02100 (18)	0.40185 (10)	0.0290 (4)
C22	0.0792 (3)	1.2534 (2)	0.51624 (12)	0.0298 (5)
C23a	−0.1391 (3)	1.16850 (19)	0.47839 (11)	0.0222 (4)
C24	−0.2995 (3)	1.13411 (19)	0.46896 (11)	0.0238 (4)
C25	−0.2946 (3)	1.05837 (19)	0.41070 (11)	0.0219 (4)
C26	−0.1245 (3)	1.01753 (19)	0.36568 (10)	0.0208 (4)
C27	0.0388 (3)	1.05749 (19)	0.37799 (11)	0.0227 (4)
C27a	0.0266 (3)	1.1324 (2)	0.43324 (11)	0.0231 (4)
C28	−0.1177 (3)	0.9359 (2)	0.30665 (11)	0.0233 (4)
C29	0.0670 (3)	0.85498 (19)	0.27934 (11)	0.0233 (4)
C210	0.0779 (3)	0.7751 (2)	0.22836 (11)	0.0234 (4)
C211	0.2466 (3)	0.68672 (19)	0.19792 (10)	0.0215 (4)
C212	0.4279 (3)	0.6868 (2)	0.21305 (11)	0.0230 (4)
C213	0.5837 (3)	0.6000 (2)	0.18387 (11)	0.0230 (4)
C214	0.5600 (3)	0.51135 (19)	0.13917 (11)	0.0233 (4)
C215	0.3809 (3)	0.5099 (2)	0.12317 (11)	0.0254 (5)
C216	0.2268 (3)	0.5978 (2)	0.15186 (11)	0.0252 (5)
C241	0.7261 (3)	0.4169 (2)	0.10704 (12)	0.0284 (5)
H12A	0.8844	−0.3553	0.0063	0.032*
H12B	0.8690	−0.2271	−0.0440	0.032*
H14	0.2421	−0.1696	0.0059	0.026*
H15A	−0.0252	0.0449	0.1297	0.030*
H15B	−0.0348	−0.0493	0.0664	0.030*
H17	0.6137	−0.0191	0.1524	0.025*
H19	0.5014	0.1245	0.2133	0.029*
H110	0.1614	0.2838	0.2624	0.029*
H112	0.6664	0.2260	0.2663	0.027*
H113	0.8195	0.3456	0.3244	0.029*
H115	0.3151	0.5682	0.3963	0.033*
H116	0.1614	0.4491	0.3372	0.033*
H22A	0.0817	1.3436	0.5063	0.036*
H22B	0.1492	1.2202	0.5586	0.036*
H24	−0.4115	1.1599	0.5004	0.029*
H25A	−0.4550	0.9877	0.3560	0.035*
H25B	−0.5700	1.0655	0.4273	0.035*
H27	0.1538	1.0323	0.3482	0.027*
H29	0.1787	0.8604	0.2985	0.028*
H210	−0.0371	0.7756	0.2096	0.028*
H212	0.4448	0.7471	0.2438	0.028*
H213	0.7067	0.6012	0.1944	0.028*
H215	0.3644	0.4490	0.0928	0.030*
H216	0.1044	0.5978	0.1400	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F141	0.173 (2)	0.1098 (17)	0.0615 (12)	−0.1166 (18)	−0.0459 (13)	0.0215 (11)
F142	0.0742 (12)	0.0468 (10)	0.1064 (15)	−0.0045 (9)	−0.0628 (11)	−0.0210 (10)
F143	0.0447 (10)	0.1122 (17)	0.147 (2)	−0.0189 (11)	0.0043 (11)	−0.1106 (16)
O11	0.0201 (7)	0.0332 (9)	0.0337 (8)	−0.0036 (6)	−0.0005 (6)	−0.0163 (7)
O13	0.0238 (8)	0.0274 (8)	0.0316 (8)	−0.0060 (6)	0.0002 (6)	−0.0149 (7)
O18	0.0200 (7)	0.0285 (8)	0.0335 (8)	−0.0042 (6)	−0.0012 (6)	−0.0112 (7)
N15	0.0196 (9)	0.0291 (10)	0.0284 (10)	−0.0064 (7)	−0.0050 (7)	−0.0083 (8)
C12	0.0243 (11)	0.0268 (12)	0.0297 (11)	−0.0061 (9)	0.0003 (9)	−0.0103 (9)
C13a	0.0273 (11)	0.0166 (10)	0.0204 (10)	−0.0063 (8)	0.0006 (8)	−0.0042 (8)
C14	0.0245 (10)	0.0228 (11)	0.0221 (10)	−0.0101 (9)	−0.0044 (8)	−0.0044 (8)
C15	0.0202 (10)	0.0206 (10)	0.0212 (10)	−0.0078 (8)	−0.0033 (8)	−0.0012 (8)
C16	0.0198 (10)	0.0201 (10)	0.0197 (10)	−0.0071 (8)	−0.0019 (8)	−0.0042 (8)
C17	0.0218 (10)	0.0210 (10)	0.0230 (10)	−0.0081 (8)	−0.0031 (8)	−0.0049 (8)
C17a	0.0159 (9)	0.0219 (10)	0.0243 (10)	−0.0062 (8)	−0.0011 (8)	−0.0037 (8)
C18	0.0243 (11)	0.0184 (10)	0.0198 (10)	−0.0064 (8)	−0.0030 (8)	−0.0010 (8)
C19	0.0210 (10)	0.0242 (11)	0.0278 (11)	−0.0043 (9)	−0.0047 (8)	−0.0071 (9)
C110	0.0209 (10)	0.0245 (11)	0.0281 (11)	−0.0068 (9)	−0.0014 (8)	−0.0074 (9)
C111	0.0256 (11)	0.0196 (10)	0.0220 (10)	−0.0061 (9)	−0.0013 (8)	−0.0033 (8)
C112	0.0249 (11)	0.0208 (10)	0.0219 (10)	−0.0022 (8)	−0.0034 (8)	−0.0047 (8)
C113	0.0240 (11)	0.0238 (11)	0.0237 (11)	−0.0020 (9)	−0.0055 (8)	−0.0039 (9)
C114	0.0273 (11)	0.0202 (10)	0.0232 (10)	−0.0057 (9)	−0.0048 (8)	−0.0053 (8)
C115	0.0305 (12)	0.0246 (11)	0.0293 (12)	−0.0057 (9)	−0.0017 (9)	−0.0112 (9)
C116	0.0234 (11)	0.0270 (12)	0.0323 (12)	−0.0054 (9)	−0.0001 (9)	−0.0116 (9)
C141	0.0348 (13)	0.0263 (12)	0.0343 (13)	−0.0070 (10)	−0.0092 (10)	−0.0073 (10)
F241	0.0530 (9)	0.0404 (9)	0.0302 (8)	0.0075 (7)	0.0124 (6)	−0.0019 (6)
F242	0.0409 (8)	0.0208 (7)	0.0419 (8)	0.0000 (6)	0.0022 (6)	−0.0067 (6)
F243	0.0239 (7)	0.0449 (9)	0.0719 (10)	0.0018 (6)	−0.0050 (7)	−0.0294 (8)
O21	0.0249 (8)	0.0418 (10)	0.0436 (10)	−0.0131 (7)	0.0026 (7)	−0.0237 (8)
O23	0.0269 (8)	0.0326 (9)	0.0348 (9)	−0.0083 (7)	0.0012 (7)	−0.0169 (7)
O28	0.0219 (8)	0.0437 (10)	0.0363 (9)	−0.0003 (7)	−0.0075 (7)	−0.0165 (7)
N25	0.0170 (9)	0.0371 (11)	0.0341 (10)	−0.0086 (8)	0.0046 (7)	−0.0131 (9)
C22	0.0274 (11)	0.0280 (12)	0.0355 (13)	−0.0055 (9)	−0.0046 (9)	−0.0119 (10)
C23a	0.0252 (11)	0.0186 (10)	0.0220 (10)	−0.0030 (8)	−0.0013 (8)	−0.0047 (8)
C24	0.0211 (10)	0.0231 (11)	0.0251 (11)	−0.0029 (9)	0.0052 (8)	−0.0063 (9)
C25	0.0194 (10)	0.0216 (11)	0.0240 (10)	−0.0034 (8)	−0.0010 (8)	−0.0034 (8)
C26	0.0204 (10)	0.0198 (10)	0.0209 (10)	−0.0022 (8)	−0.0022 (8)	−0.0019 (8)
C27	0.0186 (10)	0.0242 (11)	0.0238 (10)	−0.0022 (8)	0.0009 (8)	−0.0052 (9)
C27a	0.0183 (10)	0.0243 (11)	0.0277 (11)	−0.0048 (8)	−0.0032 (8)	−0.0066 (9)
C28	0.0204 (10)	0.0247 (11)	0.0234 (10)	−0.0025 (8)	−0.0018 (8)	−0.0029 (9)
C29	0.0205 (10)	0.0255 (11)	0.0237 (10)	−0.0040 (9)	−0.0036 (8)	−0.0035 (9)
C210	0.0216 (10)	0.0242 (11)	0.0237 (11)	−0.0028 (9)	−0.0027 (8)	−0.0035 (9)
C211	0.0249 (10)	0.0187 (10)	0.0196 (10)	−0.0030 (8)	−0.0013 (8)	−0.0012 (8)
C212	0.0264 (11)	0.0221 (11)	0.0217 (10)	−0.0066 (9)	−0.0032 (8)	−0.0045 (8)
C213	0.0221 (10)	0.0228 (11)	0.0241 (10)	−0.0048 (9)	−0.0021 (8)	−0.0033 (8)
C214	0.0260 (11)	0.0184 (10)	0.0229 (10)	−0.0006 (8)	−0.0014 (8)	−0.0022 (8)
C215	0.0277 (11)	0.0215 (11)	0.0270 (11)	−0.0034 (9)	−0.0036 (9)	−0.0078 (9)
C216	0.0237 (11)	0.0241 (11)	0.0284 (11)	−0.0043 (9)	−0.0048 (9)	−0.0058 (9)
C241	0.0301 (12)	0.0247 (12)	0.0287 (12)	−0.0026 (9)	−0.0014 (9)	−0.0058 (9)

Geometric parameters (Å, º) top

O11—C17a	1.391 (2)	O21—C27a	1.386 (2)
O11—C12	1.434 (2)	O21—C22	1.429 (3)
C12—O13	1.442 (2)	C22—O23	1.436 (3)
C12—H12A	0.99	C22—H22A	0.99
C12—H12B	0.99	C22—H22B	0.99
O13—C13a	1.369 (2)	O23—C23a	1.372 (2)
C13a—C14	1.358 (3)	C23a—C24	1.355 (3)
C13a—C17a	1.390 (3)	C23a—C27a	1.390 (3)
C14—C15	1.415 (3)	C24—C25	1.417 (3)
C14—H14	0.95	C24—H24	0.95
C15—N15	1.368 (2)	C25—N25	1.369 (3)
C15—C16	1.429 (3)	C25—C26	1.419 (3)
N15—H15A	0.9599	N25—H25A	0.9599
N15—H15B	0.9599	N25—H25B	0.9598
C16—C17	1.428 (3)	C26—C27	1.421 (3)
C16—C18	1.468 (3)	C26—C28	1.468 (3)
C17—C17a	1.350 (3)	C27—C27a	1.355 (3)
C17—H17	0.95	C27—H27	0.95
C18—O18	1.244 (2)	C28—O28	1.237 (2)
C18—C19	1.488 (3)	C28—C29	1.486 (3)
C19—C110	1.323 (3)	C29—C210	1.331 (3)
C19—H19	0.95	C29—H29	0.95
C110—C111	1.466 (3)	C210—C211	1.461 (3)
C110—H110	0.95	C210—H210	0.95
C111—C116	1.396 (3)	C211—C212	1.393 (3)
C111—C112	1.398 (3)	C211—C216	1.397 (3)
C112—C113	1.379 (3)	C212—C213	1.385 (3)
C112—H112	0.95	C212—H212	0.95
C113—C114	1.389 (3)	C213—C214	1.388 (3)
C113—H113	0.95	C213—H213	0.95
C114—C115	1.385 (3)	C214—C215	1.387 (3)
C114—C141	1.490 (3)	C214—C241	1.494 (3)
C141—F143	1.287 (3)	C241—F242	1.335 (2)
C141—F141	1.316 (3)	C241—F243	1.336 (3)
C141—F142	1.326 (3)	C241—F241	1.350 (3)
C115—C116	1.387 (3)	C215—C216	1.380 (3)
C115—H115	0.95	C215—H215	0.95
C116—H116	0.95	C216—H216	0.95

C17a—O11—C12	105.14 (15)	C27a—O21—C22	106.12 (15)
O11—C12—O13	107.71 (16)	O21—C22—O23	108.18 (16)
O11—C12—H12A	110.2	O21—C22—H22A	110.1
O13—C12—H12A	110.2	O23—C22—H22A	110.1
O11—C12—H12B	110.2	O21—C22—H22B	110.1
O13—C12—H12B	110.2	O23—C22—H22B	110.1
H12A—C12—H12B	108.5	H22A—C22—H22B	108.4
C13a—O13—C12	105.69 (14)	C23a—O23—C22	106.25 (16)
C14—C13a—O13	127.59 (18)	C24—C23a—O23	127.64 (19)
C14—C13a—C17a	122.32 (18)	C24—C23a—C27a	122.38 (18)
O13—C13a—C17a	110.05 (17)	O23—C23a—C27a	109.98 (17)
C13a—C14—C15	117.85 (17)	C23a—C24—C25	117.79 (18)
C13a—C14—H14	121.1	C23a—C24—H24	121.1
C15—C14—H14	121.1	C25—C24—H24	121.1
N15—C15—C14	118.10 (17)	N25—C25—C24	118.06 (18)
N15—C15—C16	121.58 (18)	N25—C25—C26	121.56 (18)
C14—C15—C16	120.27 (18)	C24—C25—C26	120.29 (18)
C15—N15—H15A	116.2	C25—N25—H25A	114.7
C15—N15—H15B	117.3	C25—N25—H25B	116.6
H15A—N15—H15B	118.9	H25A—N25—H25B	121.1
C17—C16—C15	118.97 (17)	C25—C26—C27	119.24 (18)
C17—C16—C18	120.30 (16)	C25—C26—C28	120.35 (17)
C15—C16—C18	120.73 (17)	C27—C26—C28	120.41 (17)
C17a—C17—C16	118.38 (17)	C27a—C27—C26	118.50 (18)
C17a—C17—H17	120.8	C27a—C27—H27	120.8
C16—C17—H17	120.8	C26—C27—H27	120.8
C17—C17a—C13a	122.18 (18)	C27—C27a—O21	128.79 (18)
C17—C17a—O11	128.33 (17)	C27—C27a—C23a	121.75 (18)
C13a—C17a—O11	109.44 (17)	O21—C27a—C23a	109.46 (17)
O18—C18—C16	122.49 (17)	O28—C28—C26	122.06 (18)
O18—C18—C19	118.40 (18)	O28—C28—C29	118.85 (18)
C16—C18—C19	119.09 (17)	C26—C28—C29	119.01 (17)
C110—C19—C18	121.33 (19)	C210—C29—C28	120.89 (18)
C110—C19—H19	119.3	C210—C29—H29	119.6
C18—C19—H19	119.3	C28—C29—H29	119.6
C19—C110—C111	127.1 (2)	C29—C210—C211	127.38 (19)
C19—C110—H110	116.4	C29—C210—H210	116.3
C111—C110—H110	116.4	C211—C210—H210	116.3
C116—C111—C112	118.63 (18)	C212—C211—C216	118.20 (19)
C116—C111—C110	118.94 (19)	C212—C211—C210	122.71 (18)
C112—C111—C110	122.43 (19)	C216—C211—C210	119.09 (18)
C113—C112—C111	120.51 (19)	C213—C212—C211	120.79 (19)
C113—C112—H112	119.7	C213—C212—H212	119.6
C111—C112—H112	119.7	C211—C212—H212	119.6
C112—C113—C114	120.08 (19)	C212—C213—C214	119.89 (19)
C112—C113—H113	120.0	C212—C213—H213	120.1
C114—C113—H113	120.0	C214—C213—H213	120.1
C115—C114—C113	120.47 (18)	C215—C214—C213	120.26 (19)
C115—C114—C141	119.70 (19)	C215—C214—C241	118.92 (18)
C113—C114—C141	119.77 (19)	C213—C214—C241	120.82 (19)
F143—C141—F141	107.2 (2)	F242—C241—F243	106.69 (18)
F143—C141—F142	105.9 (2)	F242—C241—F241	104.94 (17)
F141—C141—F142	102.2 (2)	F243—C241—F241	106.09 (17)
F143—C141—C114	115.1 (2)	F242—C241—C214	112.93 (18)
F141—C141—C114	112.47 (19)	F243—C241—C214	113.07 (17)
F142—C141—C114	113.03 (19)	F241—C241—C214	112.50 (18)
C114—C115—C116	119.2 (2)	C216—C215—C214	119.36 (19)
C114—C115—H115	120.4	C216—C215—H215	120.3
C116—C115—H115	120.4	C214—C215—H215	120.3
C115—C116—C111	121.1 (2)	C215—C216—C211	121.49 (19)
C115—C116—H116	119.5	C215—C216—H216	119.3
C111—C116—H116	119.5	C211—C216—H216	119.3

C17a—O11—C12—O13	−14.0 (2)	C27a—O21—C22—O23	0.9 (2)
O11—C12—O13—C13a	13.3 (2)	O21—C22—O23—C23a	−1.3 (2)
C12—O13—C13a—C14	174.7 (2)	C22—O23—C23a—C24	−178.4 (2)
C12—O13—C13a—C17a	−7.4 (2)	C22—O23—C23a—C27a	1.2 (2)
O13—C13a—C14—C15	178.55 (19)	O23—C23a—C24—C25	179.64 (19)
C17a—C13a—C14—C15	0.9 (3)	C27a—C23a—C24—C25	0.1 (3)
C13a—C14—C15—N15	177.71 (18)	C23a—C24—C25—N25	178.58 (19)
C13a—C14—C15—C16	0.3 (3)	C23a—C24—C25—C26	1.9 (3)
N15—C15—C16—C17	−178.80 (18)	N25—C25—C26—C27	−178.95 (19)
C14—C15—C16—C17	−1.5 (3)	C24—C25—C26—C27	−2.4 (3)
N15—C15—C16—C18	1.3 (3)	N25—C25—C26—C28	1.6 (3)
C14—C15—C16—C18	178.61 (18)	C24—C25—C26—C28	178.13 (19)
C15—C16—C17—C17a	1.5 (3)	C25—C26—C27—C27a	0.8 (3)
C18—C16—C17—C17a	−178.59 (18)	C28—C26—C27—C27a	−179.72 (19)
C16—C17—C17a—C13a	−0.4 (3)	C26—C27—C27a—O21	−179.6 (2)
C16—C17—C17a—O11	−177.34 (19)	C26—C27—C27a—C23a	1.2 (3)
C14—C13a—C17a—C17	−0.9 (3)	C22—O21—C27a—C27	−179.4 (2)
O13—C13a—C17a—C17	−178.90 (18)	C22—O21—C27a—C23a	−0.2 (2)
C14—C13a—C17a—O11	176.60 (18)	C24—C23a—C27a—C27	−1.8 (3)
O13—C13a—C17a—O11	−1.4 (2)	O23—C23a—C27a—C27	178.65 (19)
C12—O11—C17a—C17	−173.1 (2)	C24—C23a—C27a—O21	178.93 (19)
C12—O11—C17a—C13a	9.6 (2)	O23—C23a—C27a—O21	−0.7 (2)
C17—C16—C18—O18	−173.09 (19)	C25—C26—C28—O28	20.2 (3)
C15—C16—C18—O18	6.8 (3)	C27—C26—C28—O28	−159.2 (2)
C17—C16—C18—C19	8.2 (3)	C25—C26—C28—C29	−156.36 (19)
C15—C16—C18—C19	−171.93 (18)	C27—C26—C28—C29	24.2 (3)
O18—C18—C19—C110	−6.9 (3)	O28—C28—C29—C210	0.0 (3)
C16—C18—C19—C110	171.9 (2)	C26—C28—C29—C210	176.7 (2)
C18—C19—C110—C111	−177.59 (19)	C28—C29—C210—C211	−177.65 (19)
C19—C110—C111—C116	179.6 (2)	C29—C210—C211—C212	−8.6 (3)
C19—C110—C111—C112	0.7 (3)	C29—C210—C211—C216	171.2 (2)
C116—C111—C112—C113	−0.7 (3)	C216—C211—C212—C213	−0.8 (3)
C110—C111—C112—C113	178.18 (19)	C210—C211—C212—C213	179.01 (19)
C111—C112—C113—C114	0.2 (3)	C211—C212—C213—C214	−0.2 (3)
C112—C113—C114—C115	0.6 (3)	C212—C213—C214—C215	0.5 (3)
C112—C113—C114—C141	−176.65 (19)	C212—C213—C214—C241	179.96 (19)
C115—C114—C141—F143	18.8 (3)	C215—C214—C241—F242	−53.3 (3)
C113—C114—C141—F143	−164.0 (2)	C213—C214—C241—F242	127.2 (2)
C115—C114—C141—F141	−104.3 (3)	C215—C214—C241—F243	−174.60 (18)
C113—C114—C141—F141	72.9 (3)	C213—C214—C241—F243	5.9 (3)
C115—C114—C141—F142	140.6 (2)	C215—C214—C241—F241	65.2 (3)
C113—C114—C141—F142	−42.1 (3)	C213—C214—C241—F241	−114.2 (2)
C113—C114—C115—C116	−0.9 (3)	C213—C214—C215—C216	0.3 (3)
C141—C114—C115—C116	176.4 (2)	C241—C214—C215—C216	−179.2 (2)
C114—C115—C116—C111	0.3 (3)	C214—C215—C216—C211	−1.3 (3)
C112—C111—C116—C115	0.5 (3)	C212—C211—C216—C215	1.6 (3)
C110—C111—C116—C115	−178.5 (2)	C210—C211—C216—C215	−178.22 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15A···O18	0.96	1.91	2.637 (2)	131
N15—H15B···O11ⁱ	0.96	2.26	3.161 (2)	156
N25—H25A···O28	0.96	1.91	2.662 (2)	134
N25—H25B···O21ⁱ	0.96	2.09	3.024 (2)	165

Symmetry code: (i) x−1, y, z.

Experimental details

	(I)	(IIa)	(IIb)	(III)
Crystal data
Chemical formula	C₁₇H₁₅NO₃	C₁₇H₁₅NO₄	C₁₇H₁₅NO₄	C₁₇H₁₂F₃NO₃
M_r	281.30	297.30	297.30	335.28
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c	Triclinic, P1	Triclinic, P1
Temperature (K)	120	120	120	120
a, b, c (Å)	10.530 (5), 7.362 (5), 17.546 (5)	17.5560 (4), 5.0914 (2), 15.4869 (4)	9.5352 (2), 10.6193 (3), 14.7611 (4)	7.3420 (2), 10.9241 (3), 18.7176 (5)
α, β, γ (°)	90, 91.719 (5), 90	90, 91.9240 (16), 90	89.1400 (14), 81.0970 (17), 75.7540 (14)	85.0180 (11), 83.2280 (14), 75.8180 (14)
V (Å³)	1359.6 (12)	1383.51 (7)	1430.83 (6)	1442.71 (7)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.10	0.10	0.10	0.13
Crystal size (mm)	0.40 × 0.30 × 0.20	0.04 × 0.02 × 0.02	0.45 × 0.30 × 0.20	0.60 × 0.60 × 0.50

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer	Nonius KappaCCD area-detector diffractometer	Nonius KappaCCD area-detector diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (EVALCCD; Duisenberg et al., 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.958, 0.981	0.959, 0.998	0.951, 0.981	0.920, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	17073, 3062, 2024	14325, 3170, 2271	23999, 6517, 4940	20172, 6611, 4510
R_int	0.065	0.038	0.035	0.038
(sin θ/λ)_max (Å⁻¹)	0.651	0.650	0.650	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.135, 1.11	0.045, 0.128, 1.04	0.049, 0.137, 1.10	0.052, 0.157, 1.04
No. of reflections	3062	3169	6512	6611
No. of parameters	191	201	399	433
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21	0.26, −0.21	0.30, −0.37	0.77, −0.52

Computer programs: COLLECT (Nonius, 1998), DIRAX/LSQ (Duisenberg et al., 2000), DENZO (Otwinowski & Minor, 1997) and COLLECT, EVALCCD (Duisenberg et al., 2003), DENZO and COLLECT, SIR97 (Altomare et al., 1999), OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

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

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O8	0.96	1.88	2.612 (3)	131
N5—H5B···O1ⁱ	0.96	2.07	3.032 (3)	178
C2—H2A···Cg1ⁱⁱ	0.99	2.86	3.644 (4)	137

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

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

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O8	0.96	1.95	2.6301 (15)	126
N5—H5B···O8ⁱ	0.96	2.49	3.1232 (15)	123
C2—H2B···Cg2ⁱⁱ	0.99	2.84	3.640 (2)	138
C13—H13···Cg1ⁱⁱⁱ	0.95	2.81	3.488 (2)	130

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

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

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15B···O18	0.88	1.99	2.6451 (17)	130
N25—H25A···O28	0.88	1.95	2.6069 (19)	131
N25—H25B···O13	0.88	2.19	3.0586 (17)	170
C12—H12A···O18ⁱ	0.99	2.27	3.221 (2)	161

Symmetry code: (i) x−1, y, z.

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

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15A···O18	0.96	1.91	2.637 (2)	131
N15—H15B···O11ⁱ	0.96	2.26	3.161 (2)	156
N25—H25A···O28	0.96	1.91	2.662 (2)	134
N25—H25B···O21ⁱ	0.96	2.09	3.024 (2)	165

Symmetry code: (i) x−1, y, z.

Selected bond distances (Å) for compounds (I)-(V) top

Parameter	(I)	(IIa)	(IIb)	(IIb)	(III)	(III)	(IV)	(V)	(V)
			Mol 1	Mol 2	Mol 1	Mol 2		Mol 1	Mol 2
x	nil	nil	1	2	1	2	nil	1	2
Cx3a-Cx4	1.368 (3)	1.357 (2)	1.357 (2)	1.359 (2)	1.358 (3)	1.355 (3)	1.361 (2)	1.358 (2)	1.351 (2)
Cx4-Cx5	1.402 (3)	1.416 (2)	1.418 (2)	1.418 (2)	1.415 (3)	1.417 (3)	1.417 (2)	1.419 (2)	1.418 (2)
Cx5-Cx6	1.424 (3)	1.430 (2)	1.423 (2)	1.422 (2)	1.429 (3)	1.419 (3)	1.426 (2)	1.426 (2)	1.431 (2)
Cx6-Cx7	1.428 (3)	1.430 (2)	1.420 (2)	1.435 (2)	1.428 (3)	1.421 (3)	1.428 (2)	1.426 (2)	1.423 (2)
Cx7-Cx7a	1.339 (3)	1.354 (2)	1.353 (2)	1.350 (2)	1.350 (3)	1.355 (3)	1.355 (2)	1.354 (2)	1.353 (2)
Cx7a-Cx3a	1.386 (3)	1.394 (2)	1.387 (2)	1.391 (2)	1.390 (3)	1.390 (3)	1.394 (2)	1.390 (2)	1.393 (2)
Cx5-Nx5	1.364 (3)	1.353 (2)	1.364 (2)	1.361 (2)	1.368 (2)	1.369 (3)	1.359 (2)	1.370 (2)	1.360 (2)
Cx6-Cx8	1.459 (3)	1.461 (2)	1.470 (2)	1.462 (2)	1.468 (2)	1.468 (3)	1.470 (2)	1.473 (2)	1.463 (2)
Cx8-Ox8	1.249 (3)	1.246 (2)	1.240 (2)	1.244 (2)	1.244 (4)	1.237 (2)	1.243 (2)	1.253 (2)	1.250 (2)

Selected torsion angles (°) for compounds (I)-(III) top

Parameter	(I)	(IIa)	(IIb)	(IIb)	(III)	(III)
			Mol 1	Mol 2	Mol 1	Mol 2
x	nil	nil	1	2	1	2
Cx5-Cx6-Cx8-Cx9	-177.8 (2)	179.63 (13)	-168.15 (13)	-175.23 (13)	-171.93 (18)	-156.36 (19)
Cx6-Cx8-Cx9-Cx10	-159.1 (2)	-175.03 (14)	-170.48 (13)	153.13 (14)	171.9 (2)	176.7 (2)
Cx8-Cx9-Cx10-Cx11	178.4 (2)	179.77 (14)	-178.12 (13)	-176.05 (13)	-177.59 (19)	-177.65 (19)
Cx9-Cx10-Cx11-Cx12	-9.0 (2)	5.1 (2)	-11.3 (2)	-16.8 (2)	0.7 (3)	-8.6 (3)
Cx13-Cx14-Ox14-Cx41		-175.91 (13)	1.4 (2)	-176.09 (14)

Acknowledgements

The X-ray data for compounds (II) and (III) were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. RA thanks `Fundación para la Promoción de la Investigación y la Tecnología (Banco de la República)' and Universidad del Valle for financial support. PC thanks COLCIENCIAS for a doctoral fellowship. JC and MN thank Consejería de Educación (Junta de Andalucía, Spain) for financial support.

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Volume 60| Part 10| October 2004| Pages o744-o750

doi:10.1107/S0108270104020414