Imino Diels–Alder adducts. XII. Two pyrano[3,2-c]quinolines

The crystal structures of pyrano­quinolines 9-fluoro-5-phenyl-3,4,4a,5,6,10b-hexa­hydro-2H-pyrano[3,2-c]quinoline, C₁₈H₁₈FNO, and 9-methyl-5-phenyl-3,4,4a,5,6,10b-hexa­hydro-2H-pyrano­[3,2-c]quinoline, C₁₉H₂₁NO, are isomorphous. In both structures, the pyran ring is exo to the six-membered N-heterocyclic ring formed in the cyclo­addition step. The torsion angles across the phenyl linkage for the two structures are −91.2 (1) and −88.3 (2)°. The striking feature in both crystal packings is that they do not contain the expected conventional hydrogen bonds, in spite of the presence of good hydrogen-bonding functionalities. Possible C—H...π inter­actions are, however, observed.

S1. Comment

Pyranoquinoline systems are of interest because they constitute the parent ring structure of pyranoquinoline alkaloids, such as khaplofoline, simulenoline and zanthodiaoline. A range of biological activities have been reported for pyranoquinolines and their derivatives (Yamada et al., 1992; Nesterova et al., 1995), and these compounds are used as building blocks for the synthesis of various bridgehead N-heterocycles (Faber et al., 1984). Pyranoquinolines possess a diverse array of structural patterns in linear or angular forms, which provide to the organic chemist a challenging field for investigations of their structures and accomplishment of synthesis. Imino Diels–Alder reactions catalysed by Lewis acids are a powerful and efficient methodology for the construction of nitrogen-containing heterocyclic compounds. Recently, the synthesis of di-substituted pyrano and furoquinolines by the application of imino Diels–Alder reactions between N-benzylideneanilines as dienes and 3,4-dihydropyran or 2,3-dihydrofuran as dienophiles, using ZrCl₄ as a catalyst, have been reported (Mahesh et al., 2004). In the course of investigating how the products of Diels–Alder cycloadditions for endo/exo isomers depend on the relative orientation of the diene and the dienophile, the crystal structure of the title compounds, (Ia) and (Ib), were determined.

Compounds (Ia) and (Ib) have isomorphous crystal structures (Figs. 1 and 2), despite one having F (electron withdrawing) and the other having CH₃ (electron donating) substituents; the difference in volume is also significant (9.6 ų for F and 23.5 ų for CH₃; Kitaigorodsky, 1973; Bertault et al., 1998). The geometries of the molecules are very similar; differences ranging from 1.7 to 4.9° in bond angles involving atom C9 (Table 1 and 3) may be attributed to the nature of the substituent (F or CH₃). The C—F bond distance in (Ia) [1.3691 (15) Å] agrees well with the mean value for C—F distances for monofluoroarenes tabulated by Allen et al. (1987) [1.363 (8) Å].

The structures reveal that the dihydropyran ring is attached to the central N-heterocyclic ring in an exo (trans) fashion [C5—C4—C12—O1, 178.2 (1)° for (Ia) and 179.6 (1)° for (Ib)]. The H4—C4—C12—H12 torsion angle of 51.3° in (Ia) and 52.6° in (Ib) indicates that the junction between the pyran and the quinoline rings is cis. Similarly, the orientation of atoms H5 and H4, defined by the H5—C5—C4—H4 torsion angle [-62.9° in (Ia) and -61.0° in (Ib)] is also cis. This orientation facilitates the pyran and the phenyl rings being on the same side of the quinoline ring [C3—C4—C5—C13 = -63.4 (1)° in (Ia) and -61.0 (2)° in (Ib)]. This configuration is in accordance with the coupling constant J = 5.2 Hz observed among atoms H4 and H5 for compounds (Ia) and (Ib).

In both structures the fusion strain exerted during the quinoline ring formation in the Diels–Alder process can be seen from the twist about the C5···C11 vector. The twist can be seen from the C5—C4—C12—C11 [51.3 (1)° in (Ia) and 52.4 (2)° in (Ib)] and C5—N1—C6—C11 [-20.1 (2)° in (Ia) and -18.7 (2)° in (Ib)] torsion angles. The coordination of the quinoline N atom is significantly pyramidal, the sum of the angles at N being 347.6 (2)° in (Ia) and 349.2 (2)° in (Ib). The appropriate puckering description for the N-heterocycle ring in the quinoline ring system is half-chair in both structures, with asymmetry parameters (Nardelli, 1983) ΔC₂(C5—C4) of 0.024 (1) in (Ia) and 0.039 (1) in (Ib).

The pyran rings in both the structures orient almost perpendicular to the quinoline ring systems. Atom O1 is displaced above the N1/C6/C11/C12 least squares plane by 0.686 (1) Å in (Ia) and 0.651 (1) Å in (Ib). The conformation of the pyran ring in both the structures is a chair, as expected, with atoms C1, C3, C4 and O1 defining the plane, atom C2 being displaced by 0.660 (2) Å in (Ia) and by 0.661 (2) Å in (Ib), and atom C12 being displaced by -0.614 (1) Å in (Ia) and -0.623 (2) Å in (Ib).

The phenyl ring substituted at atom C5 in both compounds is planar and is rotated from the central N-heterocyclic ring about the C5—C13 bond by -91.2 (1)° in (Ia) and -88.3 (2)° in (Ib), so as to avoid short non-bonded interactions between the atoms of this ring and the atoms of the N-heterocycle [e.g. H1N···H18 = 2.70 Å in (Ia) and 2.62 Å in (Ib)]

A striking feature is that the structures of (Ia) and (Ib) do not contain conventional hydrogen bonds, although in principle they could be formed. Recently, Bhatt & Desiraju (2006) have reported a similar situation in the crystal structure of desloratadine, where the NH group is not hydrogen bonded in a conventional sense, although two acceptors are available. A similar situation has also been noted in the crystal structures of alloxan (Beyer et al., 2001; Coombes et al., 1997), an oxalic acid–phthalocyanine complex (Liu et al., 2002), and furo and pyrano quinolines (Ravikumar et al., 2004; Ravikumar et al., 2005). Amongst the π- bonded units, the phenyl ring provides a large volume of experimental material on C—H···π hydrogen bonds (Desiraju & Steiner, 1999). In both compounds geometry calculations show a significant C—H···π interaction involving C12—H12 and the centroid (Cg1) of the aromatic ring C6–C11 of an inversion-related molecule (Table 1). This interaction for (Ia) is shown in Fig. 3; that for (Ib) is similar.

S2. Experimental

To a solution of the appropriate N-benzylideneaniline (5.5 mmol) in dichloromethane (5 ml) at room temperature were added ZrCl₄ (10 mol%) and 3-dihydropyran (5.5 mmol) and the mixture was stirred for 90 min. The completed reaction was quenched with water and the crude product was purified by column chromatography using 2% ethylacetate and hexane to yield the title compounds. Crystals for X-ray study were obtained by recrystallization from a mixture of methanol and water (3:1).

S3. Refinement

The H atom attached to the quinoline N atom was located in a difference density map and refined isotropically. All other H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93–0.98 Å, and with U_iso(H) values of 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Perspective view of molecule (Ia). Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small circles of arbitrary radii.
	Fig. 2. Perspective view of molecule (Ib). Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small circles of arbitrary radii.
	Fig. 3. Crystal packing of (Ia), showing the formation of centrosymmetric dimers, through C—H···π hydrogen-bonding interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

(Ia) 9-fluoro-5-phenyl-3,4,4a,5,6,10b-hexahydro-2H-pyrano[3,2-c]quinoline

Crystal data

C18H18FNO	Z = 2
Mr = 283.33	F(000) = 300
TriclinicP1	Dx = 1.310 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3005 (9) Å	Cell parameters from 4848 reflections
b = 9.6401 (11) Å	θ = 2.3–28.0°
c = 10.0400 (11) Å	µ = 0.09 mm^−1
α = 66.154 (2)°	T = 273 K
β = 79.666 (2)°	Block, colorless
γ = 79.880 (2)°	0.20 × 0.15 × 0.10 mm
V = 718.11 (14) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2276 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scan	h = −9→9
6884 measured reflections	k = −11→11
2504 independent reflections	l = −11→11

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 0.1136P] where P = (Fo^2 + 2Fc^2)/3
2504 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.20 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
C1	0.78759 (19)	0.21187 (16)	0.29005 (18)	0.0569 (4)
H1A	0.6790	0.1885	0.2890	0.068*
H1B	0.8585	0.1163	0.3251	0.068*
C2	0.8553 (2)	0.30818 (17)	0.13617 (18)	0.0609 (4)
H2A	0.8559	0.2555	0.0717	0.073*
H2B	0.9680	0.3235	0.1351	0.073*
C3	0.75083 (17)	0.46253 (15)	0.08061 (14)	0.0478 (3)
H3A	0.8016	0.5268	−0.0144	0.057*
H3B	0.6422	0.4482	0.0689	0.057*
C4	0.73491 (15)	0.54039 (14)	0.18843 (13)	0.0398 (3)
H4	0.8445	0.5650	0.1887	0.048*
C5	0.61663 (15)	0.68952 (14)	0.15084 (14)	0.0410 (3)
H5	0.6109	0.7275	0.2288	0.049*
C6	0.38966 (15)	0.53214 (14)	0.26936 (14)	0.0407 (3)
C7	0.22056 (16)	0.51853 (16)	0.29418 (15)	0.0495 (3)
H7	0.1503	0.5948	0.2337	0.059*
C8	0.15590 (17)	0.39466 (17)	0.40615 (16)	0.0527 (4)
H8	0.0435	0.3865	0.4217	0.063*
C9	0.26223 (18)	0.28380 (16)	0.49396 (15)	0.0494 (3)
C10	0.42880 (17)	0.29224 (15)	0.47385 (14)	0.0456 (3)
H10	0.4972	0.2148	0.5353	0.055*
C11	0.49482 (15)	0.41687 (14)	0.36135 (13)	0.0387 (3)
C12	0.67729 (15)	0.43290 (14)	0.34402 (13)	0.0410 (3)
H12	0.6903	0.4810	0.4102	0.049*
C13	0.67311 (15)	0.81298 (14)	0.00660 (14)	0.0413 (3)
C14	0.77181 (16)	0.91504 (15)	0.00645 (15)	0.0476 (3)
H14	0.7973	0.9097	0.0950	0.057*
C15	0.83303 (18)	1.02471 (16)	−0.12356 (17)	0.0563 (4)
H15	0.9010	1.0909	−0.1217	0.068*
C16	0.79407 (19)	1.03653 (17)	−0.25556 (17)	0.0595 (4)
H16	0.8345	1.1108	−0.3428	0.071*
C17	0.6946 (2)	0.93714 (17)	−0.25695 (16)	0.0611 (4)
H17	0.6673	0.9448	−0.3457	0.073*
C18	0.63467 (19)	0.82572 (16)	−0.12722 (15)	0.0537 (4)
H18	0.5681	0.7589	−0.1298	0.064*
F1	0.19925 (12)	0.16108 (11)	0.60653 (11)	0.0741 (3)
N1	0.45220 (14)	0.65496 (13)	0.15041 (12)	0.0474 (3)
H1N	0.380 (2)	0.739 (2)	0.1249 (18)	0.065 (5)*
O1	0.77656 (11)	0.28841 (10)	0.38806 (10)	0.0507 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0513 (8)	0.0413 (7)	0.0702 (10)	0.0042 (6)	−0.0053 (7)	−0.0181 (7)
C2	0.0550 (9)	0.0550 (9)	0.0673 (10)	0.0022 (7)	0.0046 (7)	−0.0265 (8)
C3	0.0475 (7)	0.0479 (7)	0.0441 (7)	−0.0048 (6)	0.0011 (6)	−0.0169 (6)
C4	0.0332 (6)	0.0412 (7)	0.0421 (7)	−0.0067 (5)	−0.0061 (5)	−0.0116 (5)
C5	0.0429 (7)	0.0399 (7)	0.0396 (6)	−0.0052 (5)	−0.0051 (5)	−0.0144 (5)
C6	0.0387 (6)	0.0424 (7)	0.0407 (7)	−0.0032 (5)	−0.0029 (5)	−0.0170 (5)
C7	0.0385 (7)	0.0550 (8)	0.0513 (8)	−0.0030 (6)	−0.0060 (6)	−0.0175 (7)
C8	0.0400 (7)	0.0638 (9)	0.0581 (8)	−0.0142 (6)	0.0017 (6)	−0.0272 (7)
C9	0.0543 (8)	0.0469 (7)	0.0476 (7)	−0.0185 (6)	0.0047 (6)	−0.0182 (6)
C10	0.0513 (8)	0.0421 (7)	0.0420 (7)	−0.0060 (6)	−0.0052 (6)	−0.0146 (6)
C11	0.0402 (7)	0.0402 (6)	0.0373 (6)	−0.0048 (5)	−0.0027 (5)	−0.0173 (5)
C12	0.0406 (7)	0.0399 (7)	0.0415 (7)	−0.0031 (5)	−0.0103 (5)	−0.0131 (5)
C13	0.0406 (7)	0.0357 (6)	0.0430 (7)	−0.0007 (5)	−0.0056 (5)	−0.0117 (5)
C14	0.0462 (7)	0.0419 (7)	0.0525 (8)	−0.0038 (6)	−0.0098 (6)	−0.0150 (6)
C15	0.0477 (8)	0.0424 (7)	0.0696 (10)	−0.0091 (6)	−0.0062 (7)	−0.0109 (7)
C16	0.0601 (9)	0.0439 (8)	0.0538 (9)	−0.0025 (7)	0.0014 (7)	−0.0026 (6)
C17	0.0795 (11)	0.0531 (8)	0.0428 (8)	−0.0033 (8)	−0.0124 (7)	−0.0099 (7)
C18	0.0651 (9)	0.0467 (8)	0.0484 (8)	−0.0105 (7)	−0.0135 (7)	−0.0129 (6)
F1	0.0740 (6)	0.0636 (6)	0.0707 (6)	−0.0325 (5)	0.0062 (5)	−0.0076 (5)
N1	0.0369 (6)	0.0433 (6)	0.0494 (6)	−0.0009 (5)	−0.0060 (5)	−0.0061 (5)
O1	0.0447 (5)	0.0451 (5)	0.0523 (6)	0.0016 (4)	−0.0136 (4)	−0.0079 (4)

Geometric parameters (Å, º)

C1—O1	1.4325 (18)	C8—C9	1.373 (2)
C1—C2	1.509 (2)	C8—H8	0.9300
C1—H1A	0.9700	C9—F1	1.3691 (15)
C1—H1B	0.9700	C9—C10	1.373 (2)
C2—C3	1.525 (2)	C10—C11	1.3898 (18)
C2—H2A	0.9700	C10—H10	0.9300
C2—H2B	0.9700	C11—C12	1.5212 (17)
C3—C4	1.5243 (18)	C12—O1	1.4297 (15)
C3—H3A	0.9700	C12—H12	0.9800
C3—H3B	0.9700	C13—C14	1.3859 (18)
C4—C12	1.5297 (17)	C13—C18	1.3888 (19)
C4—C5	1.5399 (17)	C14—C15	1.3837 (19)
C4—H4	0.9800	C14—H14	0.9300
C5—N1	1.4618 (17)	C15—C16	1.376 (2)
C5—C13	1.5140 (17)	C15—H15	0.9300
C5—H5	0.9800	C16—C17	1.376 (2)
C6—N1	1.3957 (17)	C16—H16	0.9300
C6—C7	1.4008 (18)	C17—C18	1.386 (2)
C6—C11	1.4029 (18)	C17—H17	0.9300
C7—C8	1.3788 (19)	C18—H18	0.9300
C7—H7	0.9300	N1—H1N	0.896 (18)
O1—C1—C2	111.60 (12)	C7—C8—H8	121.0
O1—C1—H1A	109.3	F1—C9—C8	118.62 (13)
C2—C1—H1A	109.3	F1—C9—C10	118.93 (13)
O1—C1—H1B	109.3	C8—C9—C10	122.45 (13)
C2—C1—H1B	109.3	C9—C10—C11	119.79 (12)
H1A—C1—H1B	108.0	C9—C10—H10	120.1
C1—C2—C3	110.52 (12)	C11—C10—H10	120.1
C1—C2—H2A	109.5	C10—C11—C6	119.25 (12)
C3—C2—H2A	109.5	C10—C11—C12	120.33 (11)
C1—C2—H2B	109.5	C6—C11—C12	120.31 (11)
C3—C2—H2B	109.5	O1—C12—C11	112.36 (10)
H2A—C2—H2B	108.1	O1—C12—C4	112.44 (10)
C4—C3—C2	110.27 (12)	C11—C12—C4	111.04 (9)
C4—C3—H3A	109.6	O1—C12—H12	106.9
C2—C3—H3A	109.6	C11—C12—H12	106.9
C4—C3—H3B	109.6	C4—C12—H12	106.9
C2—C3—H3B	109.6	C14—C13—C18	118.14 (12)
H3A—C3—H3B	108.1	C14—C13—C5	119.08 (11)
C3—C4—C12	110.80 (10)	C18—C13—C5	122.74 (12)
C3—C4—C5	114.42 (10)	C15—C14—C13	120.96 (13)
C12—C4—C5	108.01 (10)	C15—C14—H14	119.5
C3—C4—H4	107.8	C13—C14—H14	119.5
C12—C4—H4	107.8	C16—C15—C14	120.44 (14)
C5—C4—H4	107.8	C16—C15—H15	119.8
N1—C5—C13	111.07 (10)	C14—C15—H15	119.8
N1—C5—C4	108.57 (10)	C15—C16—C17	119.22 (13)
C13—C5—C4	112.98 (10)	C15—C16—H16	120.4
N1—C5—H5	108.0	C17—C16—H16	120.4
C13—C5—H5	108.0	C16—C17—C18	120.61 (14)
C4—C5—H5	108.0	C16—C17—H17	119.7
N1—C6—C7	120.05 (12)	C18—C17—H17	119.7
N1—C6—C11	120.98 (11)	C17—C18—C13	120.61 (13)
C7—C6—C11	118.90 (12)	C17—C18—H18	119.7
C8—C7—C6	121.53 (13)	C13—C18—H18	119.7
C8—C7—H7	119.2	C6—N1—C5	118.11 (11)
C6—C7—H7	119.2	C6—N1—H1N	113.3 (11)
C9—C8—C7	118.08 (13)	C5—N1—H1N	111.9 (11)
C9—C8—H8	121.0	C12—O1—C1	113.69 (10)
O1—C1—C2—C3	−56.31 (17)	C6—C11—C12—C4	−24.25 (15)
C1—C2—C3—C4	53.81 (17)	C3—C4—C12—O1	52.12 (14)
C2—C3—C4—C12	−51.48 (14)	C5—C4—C12—O1	178.17 (9)
C2—C3—C4—C5	−173.87 (11)	C3—C4—C12—C11	−74.74 (13)
C3—C4—C5—N1	60.33 (13)	C5—C4—C12—C11	51.31 (13)
C12—C4—C5—N1	−63.57 (13)	N1—C5—C13—C14	146.49 (12)
C3—C4—C5—C13	−63.35 (14)	C4—C5—C13—C14	−91.22 (14)
C12—C4—C5—C13	172.75 (10)	N1—C5—C13—C18	−35.67 (17)
N1—C6—C7—C8	176.65 (12)	C4—C5—C13—C18	86.61 (15)
C11—C6—C7—C8	−0.2 (2)	C18—C13—C14—C15	−1.23 (19)
C6—C7—C8—C9	0.1 (2)	C5—C13—C14—C15	176.70 (12)
C7—C8—C9—F1	179.28 (12)	C13—C14—C15—C16	1.3 (2)
C7—C8—C9—C10	−0.1 (2)	C14—C15—C16—C17	−0.6 (2)
F1—C9—C10—C11	−179.18 (11)	C15—C16—C17—C18	−0.3 (2)
C8—C9—C10—C11	0.2 (2)	C16—C17—C18—C13	0.4 (2)
C9—C10—C11—C6	−0.31 (18)	C14—C13—C18—C17	0.4 (2)
C9—C10—C11—C12	175.96 (11)	C5—C13—C18—C17	−177.48 (13)
N1—C6—C11—C10	−176.53 (11)	C7—C6—N1—C5	163.06 (12)
C7—C6—C11—C10	0.32 (18)	C11—C6—N1—C5	−20.12 (18)
N1—C6—C11—C12	7.20 (18)	C13—C5—N1—C6	173.22 (10)
C7—C6—C11—C12	−175.95 (11)	C4—C5—N1—C6	48.40 (15)
C10—C11—C12—O1	32.61 (15)	C11—C12—O1—C1	70.66 (13)
C6—C11—C12—O1	−151.16 (11)	C4—C12—O1—C1	−55.49 (14)
C10—C11—C12—C4	159.52 (11)	C2—C1—O1—C12	57.64 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg(1)^i	0.98	2.68	3.647 (2)	170
C12—H12···Cg(1)^i	0.98	2.73	3.682 (2)	165

Symmetry code: (i) −x+1, −y+1, −z+1.

(Ib) 9-methyl-5-phenyl-3,4,4a,5,6,10b-hexahydro-2H-pyrano[3,2-c]quinoline

Crystal data

C19H21NO	Z = 2
Mr = 279.37	F(000) = 300
TriclinicP1	Dx = 1.244 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2596 (7) Å	Cell parameters from 3782 reflections
b = 10.0084 (9) Å	θ = 2.3–28.0°
c = 10.1134 (9) Å	µ = 0.08 mm^−1
α = 66.435 (1)°	T = 273 K
β = 81.927 (2)°	Needle, colorless
γ = 77.141 (1)°	0.20 × 0.11 × 0.08 mm
V = 745.85 (11) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2329 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scan	h = −9→9
7067 measured reflections	k = −11→11
2615 independent reflections	l = −12→12

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0509P)^2 + 0.2075P] where P = (Fo^2 + 2Fc^2)/3
2615 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.15 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
C1	0.7972 (2)	0.22906 (18)	0.2845 (2)	0.0542 (4)
H1A	0.6886	0.2098	0.2797	0.065*
H1B	0.8726	0.1345	0.3199	0.065*
C2	0.8587 (2)	0.32120 (19)	0.1354 (2)	0.0581 (5)
H2A	0.8590	0.2714	0.0704	0.070*
H2B	0.9718	0.3322	0.1379	0.070*
C3	0.74813 (19)	0.47329 (17)	0.07964 (17)	0.0450 (4)
H3A	0.7944	0.5344	−0.0128	0.054*
H3B	0.6382	0.4634	0.0657	0.054*
C4	0.73536 (17)	0.54652 (15)	0.18721 (15)	0.0374 (3)
H4	0.8465	0.5632	0.1922	0.045*
C5	0.61584 (18)	0.69682 (16)	0.14766 (16)	0.0388 (3)
H5	0.6151	0.7341	0.2238	0.047*
C6	0.38994 (17)	0.55592 (16)	0.25607 (15)	0.0379 (3)
C7	0.22016 (18)	0.55218 (19)	0.27381 (17)	0.0475 (4)
H7	0.1468	0.6320	0.2151	0.057*
C8	0.15964 (19)	0.43293 (19)	0.37621 (17)	0.0477 (4)
H8	0.0459	0.4332	0.3857	0.057*
C9	0.26481 (19)	0.31204 (18)	0.46578 (16)	0.0434 (4)
C10	0.43313 (18)	0.31737 (17)	0.44979 (15)	0.0405 (4)
H10	0.5054	0.2377	0.5100	0.049*
C11	0.49785 (17)	0.43687 (15)	0.34748 (14)	0.0349 (3)
C12	0.68119 (17)	0.44387 (15)	0.33826 (15)	0.0374 (3)
H12	0.6944	0.4886	0.4055	0.045*
C13	0.66676 (17)	0.81137 (15)	0.00551 (16)	0.0388 (3)
C14	0.77513 (19)	0.90001 (17)	0.00209 (18)	0.0466 (4)
H14	0.8137	0.8902	0.0882	0.056*
C15	0.8273 (2)	1.00265 (18)	−0.1264 (2)	0.0545 (4)
H15	0.9020	1.0596	−0.1261	0.065*
C16	0.7698 (2)	1.02128 (19)	−0.25445 (19)	0.0580 (5)
H16	0.8032	1.0918	−0.3409	0.070*
C17	0.6620 (2)	0.9343 (2)	−0.25324 (19)	0.0616 (5)
H17	0.6228	0.9456	−0.3396	0.074*
C18	0.6111 (2)	0.83004 (19)	−0.12493 (18)	0.0534 (4)
H18	0.5386	0.7716	−0.1261	0.064*
C19	0.1963 (2)	0.1805 (2)	0.5753 (2)	0.0638 (5)
H19A	0.1133	0.2125	0.6383	0.096*
H19B	0.2847	0.1093	0.6310	0.096*
H19C	0.1473	0.1360	0.5263	0.096*
N1	0.44900 (16)	0.67356 (15)	0.14412 (15)	0.0457 (3)
H1N	0.378 (2)	0.754 (2)	0.1215 (19)	0.054 (5)*
O1	0.78556 (12)	0.30080 (11)	0.38317 (11)	0.0473 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0446 (9)	0.0374 (9)	0.0715 (12)	−0.0012 (7)	−0.0020 (8)	−0.0154 (8)
C2	0.0516 (10)	0.0490 (10)	0.0674 (12)	−0.0034 (8)	0.0086 (8)	−0.0226 (9)
C3	0.0441 (8)	0.0450 (9)	0.0420 (8)	−0.0093 (7)	0.0047 (7)	−0.0145 (7)
C4	0.0285 (7)	0.0396 (8)	0.0421 (8)	−0.0109 (6)	−0.0029 (6)	−0.0107 (6)
C5	0.0396 (8)	0.0365 (8)	0.0399 (8)	−0.0101 (6)	−0.0003 (6)	−0.0131 (6)
C6	0.0349 (7)	0.0397 (8)	0.0375 (8)	−0.0084 (6)	0.0009 (6)	−0.0132 (6)
C7	0.0335 (8)	0.0527 (9)	0.0474 (9)	−0.0059 (7)	−0.0029 (6)	−0.0109 (7)
C8	0.0326 (8)	0.0652 (11)	0.0471 (9)	−0.0174 (7)	0.0019 (6)	−0.0203 (8)
C9	0.0451 (9)	0.0509 (9)	0.0387 (8)	−0.0208 (7)	0.0045 (6)	−0.0178 (7)
C10	0.0418 (8)	0.0411 (8)	0.0367 (8)	−0.0114 (6)	−0.0022 (6)	−0.0108 (6)
C11	0.0340 (7)	0.0385 (8)	0.0334 (7)	−0.0098 (6)	−0.0002 (6)	−0.0138 (6)
C12	0.0360 (7)	0.0356 (8)	0.0385 (8)	−0.0086 (6)	−0.0064 (6)	−0.0094 (6)
C13	0.0374 (8)	0.0311 (7)	0.0424 (8)	−0.0043 (6)	−0.0004 (6)	−0.0100 (6)
C14	0.0463 (9)	0.0405 (8)	0.0506 (9)	−0.0121 (7)	−0.0030 (7)	−0.0127 (7)
C15	0.0463 (9)	0.0405 (9)	0.0679 (12)	−0.0155 (7)	0.0029 (8)	−0.0098 (8)
C16	0.0556 (10)	0.0432 (9)	0.0518 (10)	−0.0069 (8)	0.0081 (8)	0.0014 (8)
C17	0.0725 (12)	0.0590 (11)	0.0423 (10)	−0.0132 (9)	−0.0073 (8)	−0.0063 (8)
C18	0.0584 (10)	0.0504 (10)	0.0483 (10)	−0.0190 (8)	−0.0080 (8)	−0.0093 (8)
C19	0.0620 (11)	0.0692 (12)	0.0574 (11)	−0.0345 (10)	0.0057 (9)	−0.0123 (9)
N1	0.0323 (7)	0.0369 (7)	0.0530 (8)	−0.0030 (6)	−0.0020 (6)	−0.0037 (6)
O1	0.0379 (6)	0.0418 (6)	0.0505 (6)	−0.0054 (5)	−0.0100 (5)	−0.0041 (5)

Geometric parameters (Å, º)

C1—O1	1.426 (2)	C9—C10	1.387 (2)
C1—C2	1.505 (2)	C9—C19	1.506 (2)
C1—H1A	0.9700	C10—C11	1.3880 (19)
C1—H1B	0.9700	C10—H10	0.9300
C2—C3	1.519 (2)	C11—C12	1.5196 (19)
C2—H2A	0.9700	C12—O1	1.4284 (17)
C2—H2B	0.9700	C12—H12	0.9800
C3—C4	1.518 (2)	C13—C14	1.382 (2)
C3—H3A	0.9700	C13—C18	1.386 (2)
C3—H3B	0.9700	C14—C15	1.379 (2)
C4—C12	1.5320 (19)	C14—H14	0.9300
C4—C5	1.538 (2)	C15—C16	1.371 (3)
C4—H4	0.9800	C15—H15	0.9300
C5—N1	1.4552 (19)	C16—C17	1.373 (3)
C5—C13	1.512 (2)	C16—H16	0.9300
C5—H5	0.9800	C17—C18	1.381 (2)
C6—N1	1.3931 (19)	C17—H17	0.9300
C6—C11	1.395 (2)	C18—H18	0.9300
C6—C7	1.396 (2)	C19—H19A	0.9600
C7—C8	1.371 (2)	C19—H19B	0.9600
C7—H7	0.9300	C19—H19C	0.9600
C8—C9	1.384 (2)	N1—H1N	0.855 (19)
C8—H8	0.9300
O1—C1—C2	112.00 (13)	C10—C9—C19	122.14 (15)
O1—C1—H1A	109.2	C9—C10—C11	122.59 (14)
C2—C1—H1A	109.2	C9—C10—H10	118.7
O1—C1—H1B	109.2	C11—C10—H10	118.7
C2—C1—H1B	109.2	C10—C11—C6	118.87 (13)
H1A—C1—H1B	107.9	C10—C11—C12	121.45 (12)
C1—C2—C3	110.56 (13)	C6—C11—C12	119.61 (12)
C1—C2—H2A	109.5	O1—C12—C11	112.91 (11)
C3—C2—H2A	109.5	O1—C12—C4	112.01 (11)
C1—C2—H2B	109.5	C11—C12—C4	110.98 (11)
C3—C2—H2B	109.5	O1—C12—H12	106.8
H2A—C2—H2B	108.1	C11—C12—H12	106.8
C4—C3—C2	109.78 (13)	C4—C12—H12	106.8
C4—C3—H3A	109.7	C14—C13—C18	117.60 (14)
C2—C3—H3A	109.7	C14—C13—C5	120.05 (14)
C4—C3—H3B	109.7	C18—C13—C5	122.33 (13)
C2—C3—H3B	109.7	C15—C14—C13	121.35 (16)
H3A—C3—H3B	108.2	C15—C14—H14	119.3
C3—C4—C12	110.58 (12)	C13—C14—H14	119.3
C3—C4—C5	114.48 (12)	C16—C15—C14	120.46 (16)
C12—C4—C5	108.37 (11)	C16—C15—H15	119.8
C3—C4—H4	107.7	C14—C15—H15	119.8
C12—C4—H4	107.7	C15—C16—C17	119.03 (15)
C5—C4—H4	107.7	C15—C16—H16	120.5
N1—C5—C13	110.63 (12)	C17—C16—H16	120.5
N1—C5—C4	108.56 (11)	C16—C17—C18	120.64 (17)
C13—C5—C4	112.80 (12)	C16—C17—H17	119.7
N1—C5—H5	108.2	C18—C17—H17	119.7
C13—C5—H5	108.2	C17—C18—C13	120.91 (16)
C4—C5—H5	108.2	C17—C18—H18	119.5
N1—C6—C11	121.46 (13)	C13—C18—H18	119.5
N1—C6—C7	119.80 (13)	C9—C19—H19A	109.5
C11—C6—C7	118.66 (13)	C9—C19—H19B	109.5
C8—C7—C6	121.18 (14)	H19A—C19—H19B	109.5
C8—C7—H7	119.4	C9—C19—H19C	109.5
C6—C7—H7	119.4	H19A—C19—H19C	109.5
C7—C8—C9	121.15 (14)	H19B—C19—H19C	109.5
C7—C8—H8	119.4	C6—N1—C5	119.13 (12)
C9—C8—H8	119.4	C6—N1—H1N	112.8 (12)
C8—C9—C10	117.52 (14)	C5—N1—H1N	112.3 (12)
C8—C9—C19	120.34 (14)	C1—O1—C12	113.60 (11)
O1—C1—C2—C3	−56.06 (19)	C6—C11—C12—C4	−26.25 (18)
C1—C2—C3—C4	54.44 (19)	C3—C4—C12—O1	53.38 (15)
C2—C3—C4—C12	−52.96 (16)	C5—C4—C12—O1	179.61 (11)
C2—C3—C4—C5	−175.69 (12)	C3—C4—C12—C11	−73.82 (15)
C3—C4—C5—N1	61.93 (15)	C5—C4—C12—C11	52.40 (15)
C12—C4—C5—N1	−61.99 (15)	N1—C5—C13—C14	149.92 (14)
C3—C4—C5—C13	−61.04 (16)	C4—C5—C13—C14	−88.26 (17)
C12—C4—C5—C13	175.04 (11)	N1—C5—C13—C18	−31.4 (2)
N1—C6—C7—C8	175.24 (14)	C4—C5—C13—C18	90.38 (17)
C11—C6—C7—C8	−1.6 (2)	C18—C13—C14—C15	−0.5 (2)
C6—C7—C8—C9	0.1 (3)	C5—C13—C14—C15	178.23 (14)
C7—C8—C9—C10	1.2 (2)	C13—C14—C15—C16	1.3 (3)
C7—C8—C9—C19	−178.55 (15)	C14—C15—C16—C17	−1.2 (3)
C8—C9—C10—C11	−0.9 (2)	C15—C16—C17—C18	0.4 (3)
C19—C9—C10—C11	178.80 (15)	C16—C17—C18—C13	0.4 (3)
C9—C10—C11—C6	−0.6 (2)	C14—C13—C18—C17	−0.3 (2)
C9—C10—C11—C12	176.31 (13)	C5—C13—C18—C17	−179.02 (15)
N1—C6—C11—C10	−174.97 (13)	C11—C6—N1—C5	−18.7 (2)
C7—C6—C11—C10	1.8 (2)	C7—C6—N1—C5	164.55 (14)
N1—C6—C11—C12	8.1 (2)	C13—C5—N1—C6	169.96 (13)
C7—C6—C11—C12	−175.14 (13)	C4—C5—N1—C6	45.69 (18)
C10—C11—C12—O1	30.15 (19)	C2—C1—O1—C12	56.99 (17)
C6—C11—C12—O1	−152.96 (13)	C11—C12—O1—C1	70.72 (15)
C10—C11—C12—C4	156.86 (13)	C4—C12—O1—C1	−55.44 (15)