Di­ethyl 2,2′-({[1,4-phenyl­enebis(aza­nedi­yl)]bis­(methyl­ene)}bis­­(1H-pyrrole-2,1-di­yl))di­acetate

The complete mol­ecule of the title compound, C₂₄H₃₀N₄O₄, is generated by crystallographic inversion symmetry. The mol­ecule is S-shaped and the pyrrole groups have an anti or trans confirmation with respect to the central benzene ring, to which they are inclined by 76.38 (9)°. In the crystal, mol­ecules are linked via C—H⋯O hydrogen bonds, forming layers parallel to the ac plane. Within the layers there are C—H⋯π inter­actions present. There are, however, no significant inter­actions between the layers.

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Chemical scheme

Structure description

The preparation of the title secondary amine was based on three synthetic steps. The reaction of 1H-pyrrole-2-carbaldehyde with ethyl bromo­pro­acetate resulted in the formation of eth­yl(2-formyl-1H-pyrrole-1-yl)-acetate (Koriatopoulou et al., 2008; Singh & Pal, 2010). The reaction of two moles of the above with p-phenyl­enedi­amine (Yang et al., 2004; Ourari et al., 2013) gave the Schiff base. The reduction of the Schiff base (Higuchi et al., 2003; Nabipour et al., 2010) gave the the title secondary amine.

The whole mol­ecule of the title compound, Fig. 1, is generated by inversion symmetry. The pyrrole rings have an anti or trans-conformation with respect to the central benzene ring. They are inclined to the central benzene ring by 76.38 (9)°.

Figure 1 A view of the mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The unlabelled atoms are related to labelled atoms by the symmetry operation − x + 2, − y, − z + 1.

The infrared spectrum shows typical absorption bands of the functional N—H and carbonyl –C=O bonds at 3390 and 1630 cm⁻¹, respectively. The N7—C6 bond distance of 1.448 (2) Å is longer than the N7—C8 bond distance of 1.405 (2) Å, indicating single bond order. However, the N1—C5 bond distance of 1.371 (2) Å, confirms that a resonance occurs in the pyrrole system between the lone-pair electron of the N atom and the pyrrole ring.

In the crystal, mol­ecules are linked via C—H⋯O hydrogen bonds, forming layers parallel to the ac plane (Table 1 and Fig. 2). Within the layers there are C—H⋯π inter­actions present. There are no significant inter­actions between the layers (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C10/C8′–C10′ ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7⋯O16^i	0.87 (2)	2.20 (2)	3.025 (2)	159.5 (18)
C5—H5⋯O16^ii	0.95	2.51	3.453 (2)	172
C11—H11B⋯O13^iii	0.99	2.47	3.435 (2)	164
C11—H11A⋯Cg1^iv	0.99	2.88	3.794 (2)	153
C11—H11A⋯Cg1^iii	0.99	2.88	3.794 (2)	153
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y, -z; (iii) -x+1, -y, -z+1; (iv) x-1, y, z.

Figure 2 A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1). For clarity only the H atoms involved in the inter­molecular contacts have been included.

Figure 3 A view along the c axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1). For clarity only the H atoms involved in the inter­molecular contacts have been included.

Synthesis and crystallization

The title compound was synthesized in three steps.

1: ethyl (2-formyl-1H-pyrrole-1-yl)-acetate was prepared by reported procedures (Koriatopoulou et al., 2008; Singh & Pal, 2010). To a mixture of 1H-pyrrole-2-carbaldehyde (1.00 g, 10.51 mmol), K₂CO₃ (2.90 g, 21.02 mmol) and (2.64 g, 10.51 mmol) of 18-crown-6 in dry 1,4-dioxane (20 ml) was added a solution of ethyl bromo­acetate (2.00 g, 12 mmol) in dry 1,4-dioxane (20 ml) drop wise over a period of 30 min. The reaction mixture was allowed to reflux under nitro­gen atmos­phere for 6 h, and then the solvent was removed under reduced pressure. Water (50 ml) was added to the residue, and the mixture was extracted with ethyl acetate (3 × 15 ml). The combined organic layers were washed with brine (15 ml), and then dried over Na₂SO₄. The solvent was removed under reduced pressure, and the oily residue was purified by flash chromatography with an eluent mixture (33% ethyl acetate/hexa­ne), yielding the title compound as a yellow oil (yielded: 0.75 g, 75%). IR (ATR cm⁻¹): 1650 ν(C=O) aldehyde moiety. 1710 ν(C=O) ester group. ¹H (500 MHz, CDCl3, p.p.m.): 1.20 (3H, t, C1—H), 4.15 (2H, q, C2—H), 4.97 (2H, s, C4—H), 6.21 (1H, t, C6—H), 6.84 (1H, d, C7—H), 6.90 (1H, d, C5—H) and 9.45 (1H, s, C9—H). ¹³C (125.75 MHz, CDCl3), 14.13 C1, 50.25 C4, 61.63 C2, 110.20 C6, 124.61 C7, 131.71 C8 and 132.10 C5. C=O to the carboxyl­ate moiety 168.37 C9 and 179.74 C3, respectively. The positive ES mass spectrum at m/z = 182.4 (M + H)⁺ (62%) for C₉H₁₁NO₃, requires = 181.1. The other peaks detected at m/z = 153.4 (100%), 109.3 (6%), 95 (9%) and 67 (4%) correspond to [M − CH₂CH₃]⁺, M − (CH₂CH₃ + CO₂)]⁺, [M − (CH₂CH₃ + CO₂ + CH₂)]⁺ and [M − (CH₂CH₃ + CO₂ + CH₂ + CO)]⁺, respectively.

2: Synthesis of the title Schiff base was achieved using standard procedures (Koriatopoulou et al., 2008; Singh & Pal, 2010). To a mixture of ethyl (2-formyl-1H-pyrrole-1-yl)­acetate (1.81 g, 10 mmol) in ethanol (20 ml) with 3 drops of glacial acetic acid, a solution of 1,4-phenyl­enedi­amine (0.5 g, 5 mmol) in ethanol (20 ml) was added drop wise over a period of 20 min. The reaction mixture was allowed to reflux for 3 h, and then cooled to room temperature. A yellow precipitate was collected by filtration and recrystallized from ethanol, yield 1.18 g (65%). IR (cm^-1): 1600 ν(C=N), 1685 ν(C=O). NMR: ¹H (500 MHz, CDCl₃, p.p.m.): 1.17 (6H, t, C1, 1–H), 4.14 (4H, Q, C2, 2–H), 5.15 (4H, s, C4, 4–H), 6.20 (2H, t, C6, 6–H), 6.61 (2H, d, C7, 7–H), 6.74 (2H, d, C5, 5–H), 7.05 (4H, s, C11, 11-, C12, 12–H) and 8.26 (2H, s, C9, 9–H). ¹³C (125.75 MHz, CDCl₃): 14.26 (C1, 1-), 51.36 (C4, 4-), 61.30 (C2, 2-.), 109.39 (C5, 5-), 119.54 (C7, 7-), 121.48 (C11, 11-, C12, 12-), 129.26 (C6, 6-), 130.31 (C8, 8-), 149.19 (C9, 9-) and 149.23 (C10, 10-). C=O of the carboxyl­ate moiety 169.25 C3, 3-. The positive ES mass spectrum at m/z = 435.8 (M + H)⁺ (100%) for C₂₄H₂₆N4O₄, requires = 434.5. The other peaks detected at m/z = 406 (100%), 377 (22%), 289 (3%) and 261.1 (10%) correspond to [M − CH₂CH₃]⁺, [M − (2CH₂CH₃)]⁺, [M − (2CH₂CH₃ + 2CO₂)]⁺ and [M (2CH₂CH₃ + 2CO₂ + 2CH₂)]⁺, respectively.

3: The title compound was obtained by reduction of the Schiff base following reported procedures (Higuchi et al., 2003; Nabipour et al., 2010). A mixture of diethyl 2,2′-{2,2′-(1Z)-[1,4-phenyl­enebis(azan-1-yl-1-yl­idene)]bis­(methan-1-yl-1-yl­idene)bis(1H-pyrrole-2,1-di­yl)} di­acetate (0.43 g, 1 mmol) and SnCl₂ (0.45 g, 2 mmol) in a (1:1) molar ratio mixture of di­chloro­methane/aceto­nitrile (100 ml), was added to a solution of sodium borohydrate in 1:1 di­chloro­methane/aceto­nitrile (0.38 g. 5 mmol) drop wise over a period of 10 min. The mixture was stirred under nitro­gen for 1 h at room temperature, and then washed for four times with 1% tri­ethyl­amine. The organic layer was dried over sodium sulfate and the solvent removed under reduced pressure. A colourless solid was collected by filtration (yield: 0.17 g, 40%). IR (KBr disc, cm⁻¹) 3390 (N—H), 1630 (C=O). NMR: ¹H (500 MHz, CDCl3, p.p.m.): 1.15 (6H, t,C1,1–H), 4.04 (4H, s, C9,9–H), 4.09 (4H, q, C2, 2–H), 4.60 (4H, s, C4, 4–H), 6.06 (2H, d, C6, 6-H, C7, 7–H), 6.49 (4H, s, C11, 11- and C12, 12–H), 6.56 (2H, d, C5, 5–H) and 3.29 to NH. ¹³C (125.75 MHz, CDCl₃, p.p.m.): 14.31 (C1, 1-), 41.81 (C2, 2-), 51.38 (C4, 4-), 61.40 (C9, 9-), 107.63 (C7, 7-), 109.22 (C6, 6-), 116.71 (C11, 11), 116.78 (C12, 12-), 122.97 (C5, 5-), 130.65 (C8, 8-)and 140.90 (C10, 10-). C=O 159.45 (C3,3-). The positive ES mass spectrum at m/z = 439(M + H)⁺ (78%) for C₂₄H₃₀N₄O₄, requires = 438.22. The other peaks detected at m/z = 410 (3%), 366 (2%), 337 (4%), 293 (12%) and 265(7%) correspond to [M − (CH₂CH₃)]⁺, [M − (CH₂CH₃ + CO₂)]⁺, [M − (2CH₂CH₃ + CO₂)]⁺, [M − (2CH₂CH₃ + 2CO₂]⁺ and [M − (2CH₂CH₃ + 2CO₂ + 2CH₂)]⁺, respectively. Crystals for the X-ray diffraction study were obtained by recrystallization from a mixture of the title compound in di­chloro­metane/aceto­nitrile, in air at 291 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH H atom, attached to atom N7, was located in a difference Fourier map and freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	C24H30N4O4
Mr	438.52
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	150
a, b, c (Å)	8.1476 (2), 17.6289 (4), 8.8692 (3)
β (°)	114.835 (4)
V (Å^3)	1156.10 (6)
Z	2
Radiation type	Mo Kα
μ (mm^−1)	0.09
Crystal size (mm)	0.4 × 0.3 × 0.3
Data collection
Diffractometer	Agilent SuperNova, Single source at offset, Atlas diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)
Tmin, Tmax	0.666, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19988, 2992, 1926
Rint	0.058
(sin θ/λ)max (Å^−1)	0.693
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.054, 0.135, 1.03
No. of reflections	2992
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	0.23, −0.23
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS2014 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2008), OLEX2 (Dolomanov et al., 2009), SHELXL2014 (Sheldrick, 2015).

Structural data

S1. Experimental

The title compound was synthesized in three steps.

1: ethyl (2-formyl-1H-pyrrole-1-yl)-acetate was prepared by reported procedures (Koriatopoulou et al., 2008; Singh & Pal, 2010). To a mixture of 1H-pyrrole-2-carbaldehyde (1.00 g, 10.51 mmol), K2CO3 (2.90 g, 21.02 mmol) and (2.64 g, 10.51 mmol) of 18-crown-6 in dry 1,4-dioxane (20 ml) was added a solution of ethyl bromoacetate (2.00 g, 12 mmol) in dry 1,4-dioxane (20 ml) drop wise over a period of 30 min. The reaction mixture was allowed to reflux under nitrogen atmosphere for 6 h, and then the solvent was removed under reduced pressure. Water (50 ml) was added to the residue, and the mixture was extracted with ethyl acetate (3 × 15 ml). The combined organic layers were washed with brine (15 ml), and then dried over Na₂SO₄. The solvent was removed under reduced pressure, and the oily residue was purified by flash chromatography with an eluent mixture (33% ethyl acetate/hexane), yielding the title compound as a yellow oil (yielded: 0.75 g, 75%). IR (ATR cm⁻¹): 1650 ν(C=O) aldehyde moiety. 1710 ν(C=O) ester group. ¹H (500 MHz, CDCl~3~, p.p.m.): 1.20 (3H, t, C1—H), 4.15 (2H, q, C2—H), 4.97 (2H, s, C4—H), 6.21 (1H, t, C6—H), 6.84 (1H, d, C7—H), 6.90 (1H, d, C5—H) and 9.45 (1H, s, C9—H). ¹³C (125.75 MHz, CDCl~3~), 14.13 C1, 50.25 C4, 61.63 C2, 110.20 C6, 124.61 C7, 131.71 C8 and 132.10 C5. C=O to the carboxylate moiety 168.37 C9 and 179.74 C3, respectively. The positive ES mass spectrum at m/z = 182.4 (M + H)⁺ (62%) for C₉H₁₁NO₃, requires = 181.1. The other peaks detected at m/z =153.4 (100%), 109.3 (6%), 95 (9%) and 67 (4%) correspond to [M - CH₂CH₃]⁺, M - (CH₂CH₃ + CO₂)]⁺, [M - (CH₂CH₃ + CO₂ + CH₂)]⁺ and [M - (CH₂CH₃ + CO₂ + CH₂ + CO)]⁺, respectively.

2: Synthesis of the title Schiff base was achieved using standard procedures (Koriatopoulou et al., 2008; Singh & Pal, 2010). To a mixture of ethyl (2-formyl-1H-pyrrole-1-yl)-acetate (1.81 g, 10 mmol) in ethanol (20 ml) with 3 drops of glacial acetic acid, a solution of 1,4-phenylenediamine (0.5 g, 5 mmol) in ethanol (20 ml) was added drop wise over a period of 20 min. The reaction mixture was allowed to reflux for 3 h, and then cooled to room temperature. A yellow precipitate was collected by filtration and recrystallized from ethanol, yield 1.18 g (65%). IR (cm^-1): 1600 ν(C=N), 1685 ν(C=O). NMR: ¹H (500 MHz, CDCl₃, p.p.m.): 1.17 (6H, t, C1, 1–H), 4.14 (4H, Q, C2, 2–H), 5.15 (4H, s, C4, 4–H), 6.20 (2H, t, C6, 6–H), 6.61 (2H, d, C7, 7–H), 6.74 (2H, d, C5, 5–H), 7.05 (4H, s, C11, 11-, C12, 12–H) and 8.26 (2H, s, C9, 9–H). ¹³C (125.75 MHz, CDCl₃): 14.26 (C1, 1-), 51.36 (C4, 4-), 61.30 (C2, 2-.), 109.39 (C5, 5-), 119.54 (C7, 7-), 121.48 (C11, 11-, C12, 12-), 129.26 (C6, 6-), 130.31 (C8, 8-), 149.19 (C9, 9-) and 149.23 (C10, 10-). C=O of the carboxylate moiety 169.25 C3, 3-. The positive ES mass spectrum at m/z = 435.8 (M + H)⁺ (100%) for C₂₄H₂₆N4O₄, requires = 434.5. The other peaks detected at m/z = 406 (100%), 377 (22%), 289 (3%) and 261.1 (10%) correspond to [M - CH₂CH₃]⁺, [M - (2CH₂CH₃)]⁺, [M - (2CH₂CH₃ + 2CO₂)]⁺ and [M - (2CH₂CH₃ + 2CO₂ + 2CH₂)]⁺, respectively.

3: The title compound was obtained by reduction of the Schiff base following reported procedures (Higuchi et al., 2003; Nabipour et al., 2010). A mixture of diethyl 2,2'-(2,2'-(1Z)-(1,4-phenylenebis (azan-1-yl-1-ylidene)) bis(methan-1-yl-1-ylidene) bis (1H-pyrrole-2,1-diyl)) diacetate (0.43 g, 1 mmol) and SnCl₂ (0.45 g, 2 mmol) in a (1:1) molar ratio mixture of dichloromethane/acetonitrile (100 ml), was added to a solution of sodium borohydrate in 1:1 dichloromethane/acetonitrile (0.38 g. 5 mmol) drop wise over a period of 10 min. The mixture was stirred under nitrogen for 1 h at room temperature, and then washed for four times with 1% triethylamine. The organic layer was dried over sodium sulfate and the solvent removed under reduced pressure. A colourless solid was collected by filtration (yield: 0.17 g, 40%). IR (KBr disc, cm⁻¹) 3390 (N—H), 1630 (C=O). NMR: ¹H (500 MHz, CDCl~3~, p.p.m.): 1.15 (6H, t,C1,1–H), 4.04 (4H, s, C9,9–H), 4.09 (4H, q, C2, 2–H), 4.60 (4H, s, C4, 4–H), 6.06 (2H, d, C6, 6-H, C7, 7–H), 6.49 (4H, s, C11, 11- and C12, 12–H), 6.56 (2H, d, C5, 5–H) and 3.29 to NH. ¹³C (125.75 MHz, CDCl₃, p.p.m.): 14.31 (C1, 1-), 41.81 (C2, 2-), 51.38 (C4, 4-), 61.40 (C9, 9-), 107.63 (C7, 7-), 109.22 (C6, 6-), 116.71 (C11, 11), 116.78 (C12, 12-), 122.97 (C5, 5-), 130.65 (C8, 8-)and 140.90 (C10, 10-). C=O 159.45 (C3,3-). The positive ES mass spectrum at m/z = 439(M+H)⁺ (78%) for C₂₄H₃₀N₄O₄, requires = 438.22. The other peaks detected at m/z = 410 (3%), 366 (2%), 337 (4%), 293 (12%) and 265(7%) correspond to [M - (CH₂CH₃)]⁺, [M - (CH₂CH₃ + CO₂)]⁺, [M - (2CH₂CH₃ + CO₂)]⁺, [M - (2CH₂CH₃ + 2CO₂]⁺ and [M - (2CH₂CH₃ + 2CO₂ + 2CH₂)]⁺, respectively. Crystals for the X-ray diffraction study were obtained by recrystallization from a mixture of the title compound in dichlorometane/acetonitrile, in air at 291 K.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH H atom, attached to atom N7, was located in a difference Fourier map and freely refined.

Structure description

The preparation of the title secondary amine was based on three synthetic steps. The reaction of 1H-pyrrole-2-carbaldehyde with ethyl bromoproacetate resulted in the formation of ethyl(2-formyl-1H-pyrrole-1-yl)-acetate (Koriatopoulou et al., 2008; Singh & Pal, 2010). The reaction of two moles of the above with p-phenylenediamine (Yang et al., 2004; Ourari et al., 2013) gave the Schiff base. The reduction of the Schiff base (Higuchi et al., 2003; Nabipour et al., 2010) gave the the title secondary amine.

The whole molecule of the title compound, Fig. 1, is generated by inversion symmetry. The pyrrole rings have an anti or trans-conformation with respect to the central benzene ring. They are inclined to the central benzene ring by 76.38 (9)°.

The infrared spectrum shows typical absorption bands of the functional N—H and carbonyl –C═O bonds at 3390 and 1630 cm⁻¹, respectively. The N7—C6 bond distance of 1.448 (2) Å is longer than the N7—C8 bond distance of 1.405 (2) Å, indicating single bond order. However, the N1—C5 bond distance of 1.371 (2) Å, confirms that a resonance occurs in the pyrrole system between the lone-pair electron of the N atom and the pyrrole ring.

In the crystal, molecules are linked via C—H···O hydrogen bonds, forming layers parallel to the ac plane (Table 1 and Fig. 2). Within the layers there are C—H···π interactions present. There are no significant interactions between the layers (Fig. 3).

Computing details

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The unlabelled atoms are related to labelled atoms by the symmetry operation − x + 2, − y, − z + 1.
	Fig. 2. A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1). For clarity only the H atoms involved in the intermolecular contacts have been included.
	Fig. 3. A view along the c axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1). For clarity only the H atoms involved in the intermolecular contacts have been included.

Diethyl 2,2'-({[1,4-phenylenebis(azanediyl)]bis(methylene)}bis(1H-pyrrole-2,1-diyl))diacetate

Crystal data

C24H30N4O4	F(000) = 468
Mr = 438.52	Dx = 1.260 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.1476 (2) Å	Cell parameters from 5079 reflections
b = 17.6289 (4) Å	θ = 3.4–24.1°
c = 8.8692 (3) Å	µ = 0.09 mm^−1
β = 114.835 (4)°	T = 150 K
V = 1156.10 (6) Å^3	Block, colourless
Z = 2	0.4 × 0.3 × 0.3 mm

Data collection

Agilent SuperNova, Single source at offset, Atlas diffractometer	2992 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1926 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.058
Detector resolution: 10.3705 pixels mm^-1	θmax = 29.5°, θmin = 2.9°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −24→23
Tmin = 0.666, Tmax = 1.000	l = −12→12
19988 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: mixed
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0512P)^2 + 0.3701P] where P = (Fo^2 + 2Fc^2)/3
2992 reflections	(Δ/σ)max < 0.001
150 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O13	0.4133 (2)	−0.08680 (7)	0.32272 (16)	0.0505 (4)
O16	0.30365 (17)	−0.04392 (8)	0.06056 (15)	0.0453 (4)
N1	0.27770 (17)	0.10235 (8)	0.17147 (17)	0.0329 (3)
N7	0.66678 (18)	0.05720 (8)	0.26714 (19)	0.0324 (3)
H7	0.651 (3)	0.0463 (11)	0.166 (3)	0.045 (6)*
C2	0.4147 (2)	0.14531 (9)	0.1631 (2)	0.0309 (4)
C3	0.3366 (2)	0.19677 (10)	0.0379 (2)	0.0359 (4)
H3	0.3986	0.2340	0.0042	0.043*
C4	0.1478 (2)	0.18484 (10)	−0.0325 (2)	0.0403 (4)
H4	0.0597	0.2125	−0.1217	0.048*
C5	0.1156 (2)	0.12641 (10)	0.0511 (2)	0.0387 (4)
H5	0.0003	0.1057	0.0299	0.046*
C6	0.6077 (2)	0.13331 (9)	0.2811 (2)	0.0337 (4)
H6A	0.6848	0.1705	0.2572	0.040*
H6B	0.6217	0.1420	0.3961	0.040*
C8	0.83593 (19)	0.03144 (9)	0.38338 (19)	0.0273 (4)
C9	0.9039 (2)	−0.03605 (9)	0.3509 (2)	0.0302 (4)
H9	0.8393	−0.0611	0.2479	0.036*
C10	0.9362 (2)	0.06744 (9)	0.53483 (19)	0.0300 (4)
H10	0.8944	0.1140	0.5597	0.036*
C11	0.3011 (2)	0.03733 (10)	0.2779 (2)	0.0356 (4)
H11A	0.1900	0.0300	0.2956	0.043*
H11B	0.4023	0.0472	0.3873	0.043*
C12	0.3398 (2)	−0.03424 (10)	0.2052 (2)	0.0352 (4)
C14	0.4517 (4)	−0.16067 (13)	0.2705 (3)	0.0762 (8)
H14A	0.4647	−0.1555	0.1650	0.091*
H14B	0.3505	−0.1960	0.2520	0.091*
C15	0.6209 (4)	−0.19104 (13)	0.4013 (4)	0.0742 (8)
H15A	0.6428	−0.2422	0.3705	0.111*
H15B	0.6099	−0.1931	0.5071	0.111*
H15C	0.7222	−0.1579	0.4129	0.111*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O13	0.0797 (10)	0.0383 (7)	0.0357 (7)	0.0102 (7)	0.0263 (7)	0.0031 (6)
O16	0.0497 (8)	0.0538 (8)	0.0283 (7)	−0.0077 (6)	0.0123 (6)	−0.0049 (6)
N1	0.0286 (7)	0.0376 (8)	0.0291 (8)	0.0010 (6)	0.0087 (6)	0.0030 (6)
N7	0.0271 (7)	0.0374 (8)	0.0270 (8)	0.0027 (6)	0.0058 (6)	−0.0035 (6)
C2	0.0295 (8)	0.0325 (9)	0.0290 (9)	0.0015 (7)	0.0105 (7)	−0.0008 (7)
C3	0.0404 (10)	0.0312 (9)	0.0340 (10)	0.0048 (7)	0.0135 (8)	0.0032 (7)
C4	0.0390 (10)	0.0375 (10)	0.0333 (10)	0.0129 (8)	0.0045 (8)	0.0019 (8)
C5	0.0274 (8)	0.0432 (10)	0.0373 (10)	0.0034 (8)	0.0055 (7)	−0.0038 (8)
C6	0.0298 (8)	0.0339 (9)	0.0347 (10)	0.0000 (7)	0.0108 (7)	0.0011 (7)
C8	0.0228 (8)	0.0328 (8)	0.0253 (8)	−0.0029 (6)	0.0091 (6)	0.0004 (7)
C9	0.0264 (8)	0.0346 (9)	0.0261 (8)	−0.0028 (7)	0.0076 (7)	−0.0037 (7)
C10	0.0284 (8)	0.0293 (8)	0.0312 (9)	−0.0005 (7)	0.0115 (7)	−0.0034 (7)
C11	0.0356 (9)	0.0409 (10)	0.0306 (9)	−0.0019 (8)	0.0142 (7)	0.0034 (8)
C12	0.0336 (9)	0.0411 (10)	0.0296 (9)	−0.0068 (7)	0.0121 (7)	0.0004 (8)
C14	0.131 (2)	0.0439 (13)	0.0537 (15)	0.0229 (15)	0.0394 (15)	−0.0021 (11)
C15	0.0881 (18)	0.0460 (13)	0.118 (2)	0.0066 (12)	0.0718 (18)	0.0090 (14)

Geometric parameters (Å, º)

O13—C12	1.334 (2)	C6—H6B	0.9900
O13—C14	1.459 (2)	C8—C9	1.393 (2)
O16—C12	1.202 (2)	C8—C10	1.397 (2)
N1—C5	1.371 (2)	C9—C10^i	1.386 (2)
N1—C2	1.376 (2)	C9—H9	0.9500
N1—C11	1.445 (2)	C10—C9^i	1.386 (2)
N7—C8	1.405 (2)	C10—H10	0.9500
N7—C6	1.448 (2)	C11—C12	1.509 (2)
N7—H7	0.87 (2)	C11—H11A	0.9900
C2—C3	1.366 (2)	C11—H11B	0.9900
C2—C6	1.494 (2)	C14—C15	1.480 (4)
C3—C4	1.412 (2)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.358 (3)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—H5	0.9500	C15—H15C	0.9800
C6—H6A	0.9900
C12—O13—C14	117.26 (15)	C10^i—C9—C8	121.52 (15)
C5—N1—C2	108.99 (14)	C10^i—C9—H9	119.2
C5—N1—C11	124.99 (14)	C8—C9—H9	119.2
C2—N1—C11	125.74 (13)	C9^i—C10—C8	120.82 (15)
C8—N7—C6	119.71 (14)	C9^i—C10—H10	119.6
C8—N7—H7	111.2 (13)	C8—C10—H10	119.6
C6—N7—H7	112.4 (13)	N1—C11—C12	112.22 (14)
C3—C2—N1	107.35 (14)	N1—C11—H11A	109.2
C3—C2—C6	131.07 (16)	C12—C11—H11A	109.2
N1—C2—C6	121.55 (14)	N1—C11—H11B	109.2
C2—C3—C4	108.01 (16)	C12—C11—H11B	109.2
C2—C3—H3	126.0	H11A—C11—H11B	107.9
C4—C3—H3	126.0	O16—C12—O13	124.30 (17)
C5—C4—C3	107.20 (15)	O16—C12—C11	124.97 (16)
C5—C4—H4	126.4	O13—C12—C11	110.68 (14)
C3—C4—H4	126.4	O13—C14—C15	109.1 (2)
C4—C5—N1	108.44 (15)	O13—C14—H14A	109.9
C4—C5—H5	125.8	C15—C14—H14A	109.9
N1—C5—H5	125.8	O13—C14—H14B	109.9
N7—C6—C2	111.19 (13)	C15—C14—H14B	109.9
N7—C6—H6A	109.4	H14A—C14—H14B	108.3
C2—C6—H6A	109.4	C14—C15—H15A	109.5
N7—C6—H6B	109.4	C14—C15—H15B	109.5
C2—C6—H6B	109.4	H15A—C15—H15B	109.5
H6A—C6—H6B	108.0	C14—C15—H15C	109.5
C9—C8—C10	117.65 (14)	H15A—C15—H15C	109.5
C9—C8—N7	118.49 (14)	H15B—C15—H15C	109.5
C10—C8—N7	123.76 (15)
C5—N1—C2—C3	0.62 (19)	C6—N7—C8—C9	−168.51 (14)
C11—N1—C2—C3	174.76 (15)	C6—N7—C8—C10	15.1 (2)
C5—N1—C2—C6	178.91 (15)	C10—C8—C9—C10^i	1.1 (3)
C11—N1—C2—C6	−6.9 (2)	N7—C8—C9—C10^i	−175.50 (15)
N1—C2—C3—C4	−0.29 (19)	C9—C8—C10—C9^i	−1.1 (3)
C6—C2—C3—C4	−178.36 (17)	N7—C8—C10—C9^i	175.31 (15)
C2—C3—C4—C5	−0.1 (2)	C5—N1—C11—C12	91.1 (2)
C3—C4—C5—N1	0.5 (2)	C2—N1—C11—C12	−82.1 (2)
C2—N1—C5—C4	−0.7 (2)	C14—O13—C12—O16	0.0 (3)
C11—N1—C5—C4	−174.91 (15)	C14—O13—C12—C11	177.48 (19)
C8—N7—C6—C2	−171.17 (14)	N1—C11—C12—O16	−21.2 (2)
C3—C2—C6—N7	−121.41 (19)	N1—C11—C12—O13	161.25 (14)
N1—C2—C6—N7	60.8 (2)	C12—O13—C14—C15	143.89 (19)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C8–C10/C8'–C10' ring.

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O16^ii	0.87 (2)	2.20 (2)	3.025 (2)	159.5 (18)
C5—H5···O16^iii	0.95	2.51	3.453 (2)	172
C11—H11B···O13^iv	0.99	2.47	3.435 (2)	164
C11—H11A···Cg1^v	0.99	2.88	3.794 (2)	153
C11—H11A···Cg1^iv	0.99	2.88	3.794 (2)	153

Symmetry codes: (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1, −y, −z+1; (v) x−1, y, z.