Two intermediates in the synthesis of deca­hydro­iso­quinolines with NMDA and AMPA receptor antagonist activity

In 6-methyl-N-(4-nitro­benzoyl)-5,6-di­hydropyridin-2(1H)-one, C₁₃H₁₂N₂O₄, (I), the piperidone ring is in a distorted half-chair conformation. In 8-methoxy-3-methyl-N-(4-nitro­benzoyl)-1,2,3,4,5,6,7,8-octa­hydro­iso­quinoline-1,6-dione, C₁₈H₂₀N₂O₆, (II), the heterocyclic ring is in a slightly distorted half-boat conformation, while the other six-membered ring is in a distorted chair conformation. Compound (II) presents a strong intramolecular C—H...O hydrogen bond. In both (I) and (II), the mol­ecules interact through C—H...O interactions.

S1. Comment

Glutamate is the major excitatory neurotransmitter in the brain and can act on three major types of ligand-gated ion channels that are defined by the activity of the subtype-selective agonists NMDA (N-methyl-D-aspartate), kainate and AMPA (α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid) (Ornstein et al., 1994). In the search for new therapeutic agents which are potent and selective antagonists of glutamate, the excitatory amino acid antagonist activities of a series of decahydroisoquinoline-3-carboxylic acids were explored. It was found that compound (III) possessses both NMDA and AMPA receptor antagonist activity (Simmons et al., 1998; O'Neill et al., 1998). \sch

A new route to the synthesis of (III) was proposed, based on an intermolecular Diels-Alder cycloaddition reaction of a 6-substituted dihydropyridone with an appropriate diene. This key reaction would need a group at position 6 (to the nitrogen) in an axial position, so that, before the cycloaddition reaction was tried a crystal structure determination of (I) was undertaken. After confirmation that the methyl group (at position 6, labelled C5 in the figure) occupied an axial position, a thermally induced Diels-Alder reaction was done using the highly reactive Danishefsky's diene, (IV). As the Diels-Alder reaction could lead to several different products and as the relative stereochemistry of this product is of great importance for the next reaction steps, the crystal structure of (II) was determined.

The molecular structure of (I) is shown in Fig. 1. As stated, the methyl group at C5 is in an axial position, as required for the continuing of the reaction path. The piperidone ring is in a half-chair, distorted towards a half-boat, conformation, as indicated by the Cremer & Pople (1975) puckering parameters shown in Table 3. The lone pair of the piperidone nitrogen atom is involved in conjugation with the carbonyl groups. This is indicated by the slight lengthening of the C═O double bond [1.214 (3) Å] and the concomitant shortening of the two N-Csp² single bonds [1.395 (3) and 1.399 (3) Å]. Accordingly the state of hybridization of the nitrogen is sp² as shown by the sum (358.2°) of the angles around it, and the small deviation [-0.050 (2) Å] of the atom from the plane N1—C2—C4—C13.

The molecular diagram of (II) is seen in Fig. 2, showing that the two rings have a cis fused stereochemistry with a H1—C1—C6—H6 torsion angle of 41°. The heterocyclic ring is in a slightly distorted, towards a chair, half-boat conformation, whereas the other six-membered ring is in a distorted chair (towards a half-chair) conformation, as shown by the Cremer & Pople (1975) puckering parameters given in Table 6. The existence of a C—H···π interaction between C12—H12B and the C14 to C19 phenyl ring is noted. According to Ciunik et al. (1998), this kind of interaction should be characterized by three parameters. In the present structure these are the H12B···Cgⁱ (Cg is the centroid of the C14—C19 ring) distance of 2.69 Å, the C12—H12B···Cgⁱ angle of 158° and the angle between the H···Cg vector and the plane of the aromatic ring, which in this case is of 88° [symmetry code: (i) = 1/2 + x, 1 - y, z]. These values are in the expected ranges of 2.7–3.4 Å, 140–160° and 80–100°, respectively, as described by Ciunik et al. (1998). This compound also exhibits three intramolecular hydrogen bonds (Table 5); in fact C11—H11A···O4 and C15—H15···O3 are responsible for the particular arrangement of the phenyl ring. In order to study the influence of these hydrogen bonds in the molecular conformation a series of Potential Energy Surfaces (PES) calculations were performed (MOPAC7.01: Stewart, 1990 and Csern, 2000 and GAMESS98: Schmidt et al., 1993). The geometry optimization calculations, using AM1 and 6–31G*, showed that there is a change in the conformation involving the three C—H···O interactions, the H15···O3 distance changes from 2.49 to 2.58 Å, while the other two H5B···O3 and H11C···O4 shorten to 2.47 and 2.49 Å, respectively. The PES obtained after rotation of the C4—N1—C13—C14 torsion angle showed that there are two minima, one corresponding to the global minimimum (162.77°) which is close to the crystallographic conformation [144.0 (2)°] and the other one at -77.32°. This last conformation is around 7 kcal higher than the other and results in the loss of the C15—H15···O3 hydrogen bond. We can postulate that, in this case, the molecular conformation is driven more by the intramolecular interactions.

In both compounds the molecules interact through a series of C—H···O interactions as shown in Tables 2 and 5. Whether all these interactions are true hydrogen bonds is difficult to assert because, as pointed out by Cotton et al. (1997), `the field is getting muddier and muddier as the definition of a hydrogen bond is relaxed'. In any case the Tables include those with H···O distance less than the sum of the van der Waals radii (Pauling, 1960) plus 10% and having a C—H···O angle greater than 100°.

S2. Refinement

H atoms were located on stereochemical grounds, except those of the hydroxyl groups, and were refined riding on a carrier atom with an isotropic displacement parameter of 1.5 (for methyl H atoms) or 1.2 (for the other H atoms) times the value of the equivalent isotropic displacement parameter of the attached atom.

Computing details

For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1985) for (I); SIR92 (Altomare et al., 1993) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: PARST95 (Nardelli, 1995), PLATON (Spek, 1998) and WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular strucure of (I) showing tha atom labelling. 50% probability displacement ellipsoids are shown.
	Fig. 2. The molecular structure of (II) showing the atom labelling. 50% probability displacement ellipsoids are shown.

(I)

Crystal data

C13H12N2O4	Dx = 1.386 Mg m^−3
Mr = 260.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 7.3677 (9) Å	θ = 10.0–18.4°
b = 10.054 (1) Å	µ = 0.11 mm^−1
c = 16.834 (2) Å	T = 293 K
V = 1247.0 (2) Å^3	Irregular, colourless
Z = 4	0.20 × 0.10 × 0.05 mm
F(000) = 544

Data collection

Enraf-Nonius CAD4-Mach3 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 30.0°
Graphite monochromator	h = −1→10
ω/2θ scans	k = −14→0
2382 measured reflections	l = 0→23
2098 independent reflections	3 standard reflections every 30 min
995 reflections with F^2 > 2σF^2	intensity decay: 1.1%

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	Riding
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 0.029P] where P = (Fo^2 + 2Fc^2)/3
2098 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq
N1	0.5453 (3)	0.1671 (2)	0.83740 (12)	0.0460 (5)
N2	1.1771 (4)	0.2742 (3)	0.57630 (15)	0.0635 (7)
O1	0.7820 (3)	0.3077 (2)	0.85977 (13)	0.0663 (6)
O2	1.3167 (4)	0.2123 (3)	0.56791 (18)	0.0912 (8)
O3	0.6113 (3)	−0.04085 (18)	0.79363 (12)	0.0692 (7)
O4	1.1468 (4)	0.3809 (3)	0.54371 (14)	0.0912 (8)
C1	0.6204 (4)	0.2863 (3)	0.86503 (15)	0.0479 (6)
C2	0.4942 (4)	0.3845 (3)	0.89955 (17)	0.0551 (7)
H2	0.5347	0.4705	0.9096	0.066*
C3	0.3192 (5)	0.3512 (4)	0.9169 (3)	0.0857 (12)
H3	0.2513	0.4009	0.9528	0.103*
C4	0.2397 (4)	0.2321 (4)	0.8765 (2)	0.0710 (9)
H4A	0.2030	0.2563	0.8231	0.085*
H4B	0.1324	0.2034	0.9051	0.085*
C5	0.3731 (4)	0.1191 (3)	0.87248 (15)	0.0537 (7)
H5	0.3229	0.0512	0.8369	0.064*
C6	0.4086 (5)	0.0540 (3)	0.95254 (17)	0.0709 (10)
H6A	0.4990	−0.0140	0.9466	0.106*
H6B	0.2983	0.0152	0.9721	0.106*
H6C	0.4511	0.1198	0.9895	0.106*
C7	0.6457 (4)	0.0776 (3)	0.79180 (14)	0.0481 (7)
C8	0.7840 (4)	0.1313 (2)	0.73602 (14)	0.0423 (6)
C9	0.7464 (4)	0.2396 (3)	0.68826 (16)	0.0503 (7)
H9	0.6346	0.2821	0.6921	0.060*
C10	0.8738 (4)	0.2845 (3)	0.63531 (15)	0.0514 (7)
H10	0.8495	0.3574	0.6030	0.062*
C11	1.0369 (4)	0.2204 (2)	0.63066 (15)	0.0451 (6)
C12	1.0743 (4)	0.1105 (3)	0.67511 (17)	0.0544 (7)
H12	1.1849	0.0668	0.6700	0.065*
C13	0.9459 (4)	0.0654 (3)	0.72753 (17)	0.0510 (7)
H13	0.9688	−0.0104	0.7576	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0405 (12)	0.0525 (12)	0.0451 (11)	−0.0082 (10)	0.0065 (10)	−0.0066 (10)
N2	0.0636 (18)	0.0693 (16)	0.0576 (14)	−0.0089 (15)	0.0088 (13)	−0.0072 (14)
O1	0.0473 (12)	0.0748 (14)	0.0768 (14)	−0.0178 (11)	0.0087 (11)	−0.0246 (11)
O2	0.0747 (17)	0.0897 (17)	0.109 (2)	0.0008 (16)	0.0425 (15)	−0.0101 (15)
O3	0.0831 (16)	0.0493 (12)	0.0752 (14)	−0.0163 (11)	0.0254 (14)	−0.0079 (9)
O4	0.0856 (18)	0.0983 (18)	0.0897 (17)	−0.0168 (17)	0.0037 (15)	0.0384 (16)
C1	0.0485 (16)	0.0526 (15)	0.0428 (13)	−0.0068 (14)	0.0031 (13)	−0.0027 (12)
C2	0.0562 (18)	0.0500 (15)	0.0590 (17)	−0.0004 (15)	0.0070 (15)	−0.0098 (13)
C3	0.060 (2)	0.090 (2)	0.107 (3)	0.010 (2)	0.003 (2)	−0.040 (2)
C4	0.0401 (17)	0.095 (2)	0.078 (2)	−0.0012 (18)	0.0070 (16)	−0.0131 (19)
C5	0.0395 (14)	0.0688 (17)	0.0529 (14)	−0.0166 (16)	0.0051 (13)	−0.0107 (14)
C6	0.071 (2)	0.083 (2)	0.0581 (17)	−0.020 (2)	0.0075 (17)	−0.0029 (15)
C7	0.0505 (16)	0.0472 (14)	0.0465 (14)	−0.0069 (14)	0.0013 (14)	−0.0056 (12)
C8	0.0448 (14)	0.0386 (12)	0.0434 (12)	−0.0017 (13)	0.0026 (11)	−0.0066 (11)
C9	0.0435 (16)	0.0520 (14)	0.0553 (15)	0.0081 (13)	0.0019 (13)	0.0033 (13)
C10	0.0560 (17)	0.0521 (15)	0.0459 (13)	0.0042 (15)	0.0014 (14)	0.0076 (12)
C11	0.0505 (16)	0.0443 (13)	0.0406 (12)	−0.0039 (13)	0.0078 (12)	−0.0039 (11)
C12	0.0472 (16)	0.0488 (14)	0.0671 (16)	0.0100 (14)	0.0079 (14)	−0.0032 (13)
C13	0.0530 (18)	0.0420 (12)	0.0578 (15)	0.0061 (14)	0.0052 (14)	0.0058 (12)

Geometric parameters (Å, º)

N1—C7	1.395 (3)	C3—C4	1.497 (5)
N1—C1	1.399 (3)	C4—C5	1.504 (4)
N1—C5	1.481 (3)	C5—C6	1.521 (4)
N2—O2	1.210 (4)	C7—C8	1.487 (3)
N2—O4	1.226 (3)	C8—C13	1.372 (4)
N2—C11	1.482 (4)	C8—C9	1.382 (4)
O1—C1	1.214 (3)	C9—C10	1.371 (4)
O3—C7	1.218 (3)	C10—C11	1.366 (4)
C1—C2	1.475 (4)	C11—C12	1.363 (3)
C2—C3	1.364 (5)	C12—C13	1.370 (4)
C7—N1—C1	121.7 (2)	C4—C5—C6	113.4 (3)
C7—N1—C5	117.6 (2)	O3—C7—N1	120.4 (2)
C1—N1—C5	119.0 (2)	O3—C7—C8	120.9 (2)
O2—N2—O4	123.6 (3)	N1—C7—C8	118.5 (2)
O2—N2—C11	118.5 (3)	C13—C8—C9	119.6 (3)
O4—N2—C11	118.0 (3)	C13—C8—C7	119.1 (2)
O1—C1—N1	121.0 (3)	C9—C8—C7	121.0 (2)
O1—C1—C2	121.9 (3)	C10—C9—C8	120.0 (3)
N1—C1—C2	117.1 (3)	C11—C10—C9	119.0 (2)
C3—C2—C1	121.0 (3)	C12—C11—C10	121.9 (3)
C2—C3—C4	118.0 (3)	C12—C11—N2	119.6 (3)
C3—C4—C5	111.7 (3)	C10—C11—N2	118.4 (2)
N1—C5—C4	109.4 (2)	C11—C12—C13	118.8 (3)
N1—C5—C6	110.2 (3)	C12—C13—C8	120.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^i	0.93	2.69	3.619 (4)	174
C3—H3···O4^ii	0.93	2.78	3.446 (5)	130
C12—H12···O1^iii	0.93	2.66	3.276 (3)	124
C6—H6A···O4^iii	0.96	2.82	3.710 (5)	154
C9—H9···O3^iv	0.93	2.55	3.451 (4)	163

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

(II)

Crystal data

C18H20N2O6	F(000) = 1520
Mr = 360.36	Dx = 1.356 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 10.2455 (9) Å	Cell parameters from 25 reflections
b = 12.664 (1) Å	θ = 10.0–17.2°
c = 27.446 (3) Å	µ = 0.10 mm^−1
β = 97.441 (9)°	T = 293 K
V = 3531.1 (6) Å^3	Irregular, colourless
Z = 8	0.25 × 0.20 × 0.15 mm

Data collection

Enraf-Nonius CAD4 Mach3 diffractometer	Rint = 0.046
Radiation source: fine-focus sealed tube	θmax = 26.3°
Graphite monochromator	h = −12→0
ω/2θ scans	k = −15→15
7230 measured reflections	l = −33→34
3574 independent reflections	3 standard reflections every 30 min
1846 reflections with F^2 > 2σF^2	intensity decay: 1.6%

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0616P)^2 + 1.0264P] where P = (Fo^2 + 2Fc^2)/3
3574 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq
N1	−0.27051 (17)	0.27646 (13)	0.09344 (6)	0.0420 (4)
N2	−0.1820 (3)	0.7863 (2)	0.09830 (14)	0.1021 (10)
O1	−0.32587 (15)	0.35954 (13)	0.16095 (6)	0.0539 (4)
O2	0.1583 (2)	0.0669 (2)	0.22006 (10)	0.1270 (11)
O3	−0.00126 (15)	0.30550 (13)	0.17018 (5)	0.0504 (4)
O4	−0.38402 (19)	0.33586 (13)	0.02204 (6)	0.0677 (6)
O1N	−0.0839 (3)	0.80535 (19)	0.12680 (14)	0.1349 (11)
O2N	−0.2495 (4)	0.8533 (2)	0.07863 (16)	0.1860 (19)
C1	−0.1960 (2)	0.20576 (18)	0.17746 (8)	0.0466 (6)
H1	−0.2540	0.1868	0.2018	0.056*
C2	−0.2707 (2)	0.28589 (18)	0.14380 (8)	0.0427 (5)
C4	−0.2356 (2)	0.17599 (17)	0.07002 (8)	0.0487 (6)
H4	−0.2020	0.1946	0.0393	0.058*
C5	−0.1243 (2)	0.12273 (18)	0.10279 (8)	0.0506 (6)
H5A	−0.1026	0.0565	0.0880	0.061*
H5B	−0.0468	0.1675	0.1056	0.061*
C6	−0.1614 (2)	0.10179 (19)	0.15326 (9)	0.0540 (6)
H6	−0.2424	0.0598	0.1485	0.065*
C7	−0.0603 (3)	0.0368 (2)	0.18675 (11)	0.0764 (9)
H7A	−0.1070	−0.0033	0.2092	0.092*
H7B	−0.0206	−0.0136	0.1665	0.092*
C8	0.0465 (3)	0.0958 (2)	0.21611 (9)	0.0661 (8)
C9	0.0034 (3)	0.1907 (2)	0.24198 (9)	0.0658 (8)
H9A	0.0801	0.2282	0.2577	0.079*
H9B	−0.0487	0.1688	0.2673	0.079*
C10	−0.0780 (2)	0.2641 (2)	0.20581 (8)	0.0499 (6)
H10	−0.1106	0.3229	0.2240	0.060*
C11	−0.3544 (3)	0.1051 (2)	0.05681 (10)	0.0689 (8)
H11A	−0.3902	0.0856	0.0862	0.103*
H11B	−0.3281	0.0426	0.0408	0.103*
H11C	−0.4199	0.1421	0.0351	0.103*
C12	0.0886 (3)	0.3847 (3)	0.18940 (11)	0.0809 (9)
H12A	0.0428	0.4375	0.2057	0.121*
H12B	0.1277	0.4167	0.1631	0.121*
H12C	0.1562	0.3536	0.2125	0.121*
C13	−0.3227 (2)	0.35760 (18)	0.06124 (8)	0.0455 (6)
C14	−0.2879 (2)	0.46904 (17)	0.07405 (8)	0.0438 (5)
C15	−0.1688 (2)	0.49518 (19)	0.10161 (9)	0.0506 (6)
H15	−0.1123	0.4422	0.1149	0.061*
C16	−0.1346 (2)	0.5990 (2)	0.10913 (10)	0.0607 (7)
H16	−0.0553	0.6171	0.1277	0.073*
C17	−0.2185 (3)	0.67560 (19)	0.08899 (11)	0.0638 (7)
C18	−0.3371 (3)	0.6530 (2)	0.06144 (10)	0.0628 (7)
H18	−0.3931	0.7067	0.0484	0.075*
C19	−0.3703 (2)	0.54884 (19)	0.05383 (9)	0.0529 (6)
H19	−0.4492	0.5315	0.0348	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0420 (10)	0.0375 (10)	0.0451 (10)	0.0015 (8)	0.0011 (8)	−0.0004 (8)
N2	0.093 (2)	0.0453 (16)	0.166 (3)	−0.0085 (17)	0.010 (2)	−0.0033 (18)
O1	0.0454 (10)	0.0621 (11)	0.0557 (10)	0.0100 (9)	0.0120 (8)	−0.0025 (8)
O2	0.0651 (15)	0.164 (2)	0.142 (2)	0.0505 (16)	−0.0278 (15)	−0.0525 (19)
O3	0.0419 (9)	0.0640 (10)	0.0448 (8)	−0.0093 (8)	0.0041 (7)	−0.0077 (8)
O4	0.0803 (13)	0.0574 (11)	0.0569 (10)	0.0114 (10)	−0.0229 (10)	−0.0050 (9)
O1N	0.113 (2)	0.0641 (16)	0.221 (3)	−0.0273 (15)	−0.001 (2)	−0.0295 (18)
O2N	0.178 (3)	0.0435 (14)	0.312 (5)	−0.0020 (18)	−0.062 (3)	0.027 (2)
C1	0.0371 (12)	0.0592 (14)	0.0451 (12)	0.0010 (11)	0.0112 (10)	0.0118 (11)
C2	0.0315 (11)	0.0488 (13)	0.0478 (13)	−0.0028 (10)	0.0047 (10)	−0.0003 (11)
C4	0.0579 (15)	0.0391 (12)	0.0482 (13)	0.0006 (11)	0.0038 (11)	−0.0030 (10)
C5	0.0478 (14)	0.0394 (13)	0.0640 (15)	0.0046 (11)	0.0051 (11)	−0.0036 (11)
C6	0.0482 (14)	0.0502 (14)	0.0606 (15)	−0.0039 (11)	−0.0043 (12)	0.0100 (12)
C7	0.081 (2)	0.0606 (18)	0.0826 (19)	0.0099 (16)	−0.0083 (17)	0.0153 (15)
C8	0.0566 (17)	0.083 (2)	0.0556 (16)	0.0176 (15)	−0.0035 (13)	0.0084 (14)
C9	0.0585 (16)	0.094 (2)	0.0433 (13)	0.0141 (15)	−0.0012 (12)	0.0037 (14)
C10	0.0446 (13)	0.0658 (16)	0.0388 (12)	0.0085 (12)	0.0038 (10)	−0.0026 (11)
C11	0.0735 (19)	0.0509 (15)	0.0757 (18)	−0.0097 (14)	−0.0151 (15)	−0.0065 (14)
C12	0.0674 (19)	0.102 (2)	0.0717 (19)	−0.0344 (18)	0.0024 (15)	−0.0200 (17)
C13	0.0416 (13)	0.0468 (13)	0.0463 (13)	0.0052 (11)	−0.0014 (11)	−0.0001 (11)
C14	0.0408 (13)	0.0439 (13)	0.0467 (13)	0.0024 (10)	0.0054 (10)	0.0034 (10)
C15	0.0368 (12)	0.0457 (13)	0.0684 (15)	0.0025 (11)	0.0030 (11)	0.0030 (12)
C16	0.0416 (14)	0.0521 (15)	0.0877 (19)	−0.0060 (12)	0.0058 (13)	−0.0022 (14)
C17	0.0613 (18)	0.0411 (14)	0.0898 (19)	−0.0029 (13)	0.0131 (15)	−0.0001 (13)
C18	0.0671 (18)	0.0445 (15)	0.0758 (18)	0.0102 (13)	0.0056 (15)	0.0091 (13)
C19	0.0514 (14)	0.0525 (15)	0.0524 (14)	0.0057 (12)	−0.0023 (11)	0.0027 (12)

Geometric parameters (Å, º)

N1—C2	1.388 (3)	C4—C5	1.516 (3)
N1—C13	1.414 (3)	C4—C11	1.519 (3)
N1—C4	1.490 (3)	C5—C6	1.507 (3)
N2—O2N	1.180 (4)	C6—C7	1.533 (3)
N2—O1N	1.216 (4)	C7—C8	1.475 (4)
N2—C17	1.464 (4)	C8—C9	1.492 (4)
O1—C2	1.217 (2)	C9—C10	1.526 (3)
O2—C8	1.194 (3)	C13—C14	1.486 (3)
O3—C12	1.417 (3)	C14—C19	1.386 (3)
O3—C10	1.431 (3)	C14—C15	1.390 (3)
O4—C13	1.206 (2)	C15—C16	1.370 (3)
C1—C2	1.512 (3)	C16—C17	1.364 (4)
C1—C6	1.537 (3)	C17—C18	1.376 (4)
C1—C10	1.540 (3)	C18—C19	1.371 (3)
C2—N1—C13	120.7 (2)	O2—C8—C7	122.0 (3)
C2—N1—C4	122.3 (2)	O2—C8—C9	122.9 (3)
C13—N1—C4	116.3 (2)	C7—C8—C9	115.1 (2)
O2N—N2—O1N	122.5 (3)	C8—C9—C10	110.5 (2)
O2N—N2—C17	119.2 (3)	O3—C10—C9	111.4 (2)
O1N—N2—C17	118.3 (3)	O3—C10—C1	107.2 (2)
C12—O3—C10	113.2 (2)	C9—C10—C1	111.4 (2)
C2—C1—C6	116.0 (2)	O4—C13—N1	120.2 (2)
C2—C1—C10	106.8 (2)	O4—C13—C14	120.6 (2)
C6—C1—C10	114.8 (2)	N1—C13—C14	118.8 (2)
O1—C2—N1	120.8 (2)	C19—C14—C15	119.4 (2)
O1—C2—C1	120.1 (2)	C19—C14—C13	118.9 (2)
N1—C2—C1	119.0 (2)	C15—C14—C13	121.4 (2)
N1—C4—C5	109.2 (2)	C16—C15—C14	120.0 (2)
N1—C4—C11	112.2 (2)	C17—C16—C15	119.1 (2)
C5—C4—C11	113.4 (2)	C16—C17—C18	122.7 (2)
C6—C5—C4	111.3 (2)	C16—C17—N2	118.5 (3)
C5—C6—C7	114.5 (2)	C18—C17—N2	118.8 (3)
C5—C6—C1	110.3 (2)	C19—C18—C17	117.9 (2)
C7—C6—C1	112.1 (2)	C18—C19—C14	121.0 (2)
C8—C7—C6	116.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O3	0.97	2.49	3.124 (3)	123
C11—H11C···O4	0.96	2.52	3.078 (3)	118
C15—H15···O3	0.93	2.48	3.379 (3)	163
C4—H4···O4^i	0.98	2.68	3.576 (3)	152
C7—H7B···O1N^ii	0.97	2.58	3.354 (4)	136
C11—H11B···O2N^ii	0.96	2.69	3.393 (4)	130
C7—H7A···O2^iii	0.97	2.59	3.399 (4)	141
C9—H9B···O1^iv	0.97	2.51	3.473 (3)	171
C11—H11A···O1N^v	0.96	2.76	3.418 (5)	126
C12—H12C···O2^vi	0.96	2.67	3.407 (4)	134
C16—H16···O1^vii	0.93	2.43	3.337 (3)	166
C19—H19···O4^viii	0.93	2.73	3.382 (3)	128

Symmetry codes: (i) −x−1/2, y, −z; (ii) x, y−1, z; (iii) x−1/2, −y, z; (iv) −x−1/2, −y+1/2, −z+1/2; (v) x−1/2, −y+1, z; (vi) −x+1/2, −y+1/2, −z+1/2; (vii) x+1/2, −y+1, z; (viii) −x−1, −y+1, −z.