Imino Diels-Alder adducts. I. Two furo­[3,2-c]­quinoline diastereoisomers

The structures of two diastereoisomers of 9-chloro-8-fluoro-4-phenyl-2,3,3a,4,5,9b-hexa­hydro­furo­[3,2-c]­quinoline, C₁₇H₁₅ClFNO, are very similar. The orientation of the furan ring, as a result of its fusion to the quinoline nucleus, constitutes the significant difference between the two structures. The dihedral angles between the furan and phenyl rings are 73.4 (1) and 63.8 (1)°.

S1. Comment

Pyrano- and furoquinoline moieties have been extensively studied for a range of biological applications such as psychotropic (Nesterova et al., 1995), anti-allergic (Yamada et al., 1992) and anti-inflammatory (Faber et al., 1984) applications. Hence, efforts have been directed to the synthesis of these compounds. We have recently synthesized and purified four diastereoisomers of disubstituted pyrano- and furoquinolines by the application of the imino Diels-Alder reaction using ZrCl₄ as a new catalyst (Mahesh et al., 2004). These diastereoisomers differ according to the stereochemistry (cis/trans) of the ring-junction H atoms and the orientation (endo/exo) of the furan ring. The contrasting responses of the different isomers to bactericidal and bacteriolytic activity prompted us to carry out crystal structure determinations, with a view to understanding the structure-activity relationships. We present here the structures of the two title diastereoisomers, (I) (Fig. 1) and (II) (Fig. 2). \sch

In all essential details, the two structures are similar as far as bond distances and angles are concerned (Tables 1 and 3). The greatest differences are 0.018 Å in the bond distances (for C2—C1) and 3.3° in the angles (for O1—C5—C6). Atoms H7 and H8 have a trans arrangement in (I); the H7—C7—C8—H8 torsion angle of −176.9° is in accordance with a larger coupling constant J = 10.8 Hz. In contrast, the other stereoisomer, (II), with a corresponding torsion angle of 55.3°, shows a coupling constant J = 5.2 Hz and is in a cis configuration.

The chloro- and fluoro-substituted phenyl ring of the quinoline ring system is planar, with deviations of 0.047 (1) and −0.018 (1) Å for (I) and (II), respectively. The non-planar pyridine ring adopts a sofa conformation in both structures, with asymmetry parameters (Nardelli, 1983) of ΔC_S(C3) = 0.053 (1) and ΔC₂(C3—C9) = 0.069 (1) in (I), and ΔC_S(C3) = 0.057 (1) and ΔC₂(C4—C3) = 0.088 (1) in (II).

The most significant distinctive pattern in both structures is the perpendicular orientation of the furan ring (Fig. 3). This is oriented above the least-squares plane (N1/C9/C3/C4/C7) of the quinoline ring system in (I), with atom O1 displaced by 1.325 (2) Å, and below in (II), with atom O1 displaced by −1.394 (2) Å. The C6—C7—C8—C12 torsion angle, between the furan and phenyl rings, shows the role of ring fusion, with values of −68.8 (2)° in (I) and 58.1 (2)° in (II).

The furan ring adopts a distorted envelope conformation in (I) [q₂ = 0.341 (2) Å and ϕ = 171.9 (5)°] and twist conformation in (II) [q₂ = 0.345 (2) Å and ϕ = 92.3 (2)°] (Cremer & Pople, 1975).

The phenyl substituent at C8 rotated through the C8—C12 bond by −134.6 (2)° in (I) and 32.8 (2)° in (II), perhaps to facilitate the cis/trans orientation for the H atoms at C8. A non-bonded interaction between atoms H17 and H8 of 2.36 Å is observed in (II), while this distance is 3.58 Å in (I).

The crystal structure is stabilized by a C—H···F intermolecular interaction in (I) (Table 2), whereas no such interaction is observed in (II). Furthermore, symmetry-related molecules are interlinked by weak C—H···π interactions in both compounds. In (I), atom H11 is 2.87 Å from the centroid of the phenyl substituent (C12—C17) at symmetry position (1/2 + x, 1/2 + y, z), with an angle of 159° and a C11···centroid distance of 3.752 (3) Å. Similarly in (II), atom H11 is 2.86 Å from the centroid of the phenyl substituent at symmetry position (2 − x, 1 − y, 1 − z), with an angle of 133° and a C11···.centroid distance of 3.561 (2) Å.

S2. Experimental

To a solution of 3-chloro-4-fluoro-N-benzylideneaniline (5.5 mmol) in dichloromethane (5 ml) at room temperature were added 2,3-dihydrofuran (5.5 mmol) and ZrCl₄ (10 mol%), and the resulting solution was stirred for 90 min. The reaction was quenched with water and the crude product was purified by column chromatography, using 2% ethyl acetate and hexane, to yield the title compounds. Crystals for X-ray study were obtained by recystallization from methanol–water (3:1) solutions.

S3. Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms, with aromatic C—H = 0.93 Å, methylene C—H = 0.98 Å, ethylene C—H = 0.97 Å and N—H = 0.90 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H and 1.2U_eq(C,N) for other H.

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: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. A view of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The orientational difference in the furan ring between the structures of (I) and (II), visualized through the least-squares plane fitting atoms N1/C9/C3/C4/C7.

(I) 9-Chloro-8-fluoro-4-phenyl-2,3,3a,4,5,9 b-hexahydrofuro[3,2-c]quinoline

Crystal data

C17H15ClFNO	F(000) = 1264
Mr = 303.75	Dx = 1.424 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 448 reflections
a = 17.0056 (17) Å	θ = 2.2–27.5°
b = 10.7527 (11) Å	µ = 0.28 mm^−1
c = 15.7079 (16) Å	T = 293 K
β = 99.367 (2)°	Needle, yellow
V = 2834.0 (5) Å^3	0.20 × 0.15 × 0.11 mm
Z = 8

Data collection

CCD area-etector diffractometer	2244 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 28.0°, θmin = 2.3°
ω scans	h = −22→21
8450 measured reflections	k = −14→13
3079 independent reflections	l = −18→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 1.4718P] where P = (Fo^2 + 2Fc^2)/3
3079 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.19 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 of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	1.13249 (4)	0.74432 (7)	−0.00429 (5)	0.0727 (3)
F1	1.20787 (8)	0.97953 (17)	0.04091 (10)	0.0831 (5)
O1	1.01402 (8)	0.62954 (14)	0.11530 (11)	0.0568 (4)
N1	0.91876 (10)	0.93423 (16)	0.15223 (12)	0.0496 (5)
H1	0.9205	0.9788	0.2010	0.059*
C1	1.13700 (13)	0.9681 (3)	0.06821 (16)	0.0576 (6)
C2	1.09425 (12)	0.8610 (2)	0.05275 (14)	0.0489 (5)
C3	1.02190 (11)	0.84542 (19)	0.08229 (13)	0.0414 (5)
C4	0.97463 (11)	0.72846 (19)	0.06420 (15)	0.0433 (5)
H4	0.9711	0.7074	0.0030	0.052*
C5	0.95679 (16)	0.5377 (3)	0.1223 (3)	0.0977 (12)
H5A	0.9648	0.5046	0.1806	0.117*
H5B	0.9621	0.4699	0.0829	0.117*
C6	0.87559 (13)	0.5936 (2)	0.10118 (17)	0.0556 (6)
H6A	0.8459	0.5819	0.1483	0.067*
H6B	0.8460	0.5565	0.0494	0.067*
C7	0.89060 (11)	0.73187 (18)	0.08725 (14)	0.0424 (5)
H7	0.8523	0.7646	0.0391	0.051*
C8	0.88984 (11)	0.80933 (19)	0.16835 (14)	0.0428 (5)
H8	0.9265	0.7716	0.2160	0.051*
C9	0.99256 (12)	0.94399 (19)	0.12591 (13)	0.0440 (5)
C10	1.03724 (15)	1.0536 (2)	0.13955 (15)	0.0547 (6)
H10	1.0177	1.1199	0.1679	0.066*
C11	1.10942 (15)	1.0646 (2)	0.11180 (16)	0.0622 (7)
H11	1.1393	1.1370	0.1225	0.075*
C12	0.80798 (12)	0.8189 (2)	0.19416 (14)	0.0460 (5)
C13	0.79063 (15)	0.7511 (2)	0.26345 (16)	0.0559 (6)
H13	0.8293	0.6998	0.2941	0.067*
C14	0.71607 (17)	0.7591 (3)	0.28757 (19)	0.0721 (8)
H14	0.7047	0.7126	0.3340	0.086*
C15	0.65904 (16)	0.8351 (3)	0.2435 (2)	0.0752 (9)
H15	0.6091	0.8405	0.2601	0.090*
C16	0.67533 (15)	0.9035 (3)	0.1747 (2)	0.0745 (8)
H16	0.6365	0.9552	0.1448	0.089*
C17	0.74990 (14)	0.8954 (2)	0.14955 (18)	0.0597 (6)
H17	0.7608	0.9415	0.1027	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0521 (4)	0.0957 (5)	0.0778 (5)	−0.0148 (3)	0.0328 (3)	−0.0158 (4)
F1	0.0508 (8)	0.1176 (13)	0.0827 (12)	−0.0397 (8)	0.0167 (8)	0.0114 (9)
O1	0.0371 (8)	0.0502 (9)	0.0842 (12)	−0.0054 (6)	0.0132 (8)	0.0054 (8)
N1	0.0508 (10)	0.0478 (10)	0.0516 (12)	−0.0075 (8)	0.0131 (9)	−0.0095 (8)
C1	0.0446 (12)	0.0776 (16)	0.0498 (15)	−0.0237 (11)	0.0049 (11)	0.0118 (12)
C2	0.0404 (11)	0.0659 (14)	0.0402 (13)	−0.0110 (10)	0.0056 (9)	0.0038 (10)
C3	0.0362 (10)	0.0511 (11)	0.0362 (12)	−0.0102 (8)	0.0041 (9)	0.0019 (9)
C4	0.0362 (10)	0.0506 (11)	0.0442 (13)	−0.0093 (8)	0.0095 (9)	−0.0053 (9)
C5	0.0497 (15)	0.0603 (16)	0.184 (4)	−0.0088 (12)	0.0204 (19)	0.028 (2)
C6	0.0438 (11)	0.0533 (13)	0.0733 (17)	−0.0151 (10)	0.0202 (11)	−0.0111 (11)
C7	0.0329 (9)	0.0507 (11)	0.0437 (13)	−0.0070 (8)	0.0070 (9)	−0.0047 (9)
C8	0.0349 (10)	0.0494 (11)	0.0445 (13)	−0.0040 (8)	0.0080 (9)	−0.0012 (9)
C9	0.0438 (11)	0.0478 (11)	0.0390 (12)	−0.0091 (9)	0.0026 (9)	0.0037 (9)
C10	0.0667 (14)	0.0496 (12)	0.0458 (14)	−0.0152 (11)	0.0035 (11)	0.0007 (10)
C11	0.0652 (15)	0.0649 (16)	0.0515 (15)	−0.0344 (12)	−0.0051 (12)	0.0119 (12)
C12	0.0408 (10)	0.0520 (12)	0.0473 (13)	−0.0033 (9)	0.0132 (10)	−0.0096 (10)
C13	0.0562 (13)	0.0676 (15)	0.0472 (14)	−0.0054 (11)	0.0183 (11)	−0.0061 (11)
C14	0.0743 (17)	0.0850 (19)	0.0668 (18)	−0.0158 (15)	0.0412 (15)	−0.0200 (14)
C15	0.0565 (15)	0.0787 (18)	0.101 (2)	−0.0076 (14)	0.0440 (16)	−0.0371 (17)
C16	0.0496 (14)	0.0671 (16)	0.109 (2)	0.0099 (12)	0.0182 (15)	−0.0180 (16)
C17	0.0487 (12)	0.0623 (14)	0.0703 (17)	0.0050 (11)	0.0161 (12)	0.0001 (12)

Geometric parameters (Å, º)

Cl1—C2	1.729 (2)	C7—C8	1.524 (3)
F1—C1	1.349 (2)	C7—H7	0.9800
O1—C5	1.404 (3)	C8—C12	1.516 (3)
O1—C4	1.432 (3)	C8—H8	0.9800
N1—C9	1.388 (3)	C9—C10	1.399 (3)
N1—C8	1.466 (3)	C10—C11	1.373 (3)
N1—H1	0.9000	C10—H10	0.9300
C1—C2	1.363 (3)	C11—H11	0.9300
C1—C11	1.367 (4)	C12—C13	1.381 (3)
C2—C3	1.394 (3)	C12—C17	1.385 (3)
C3—C9	1.398 (3)	C13—C14	1.384 (3)
C3—C4	1.495 (3)	C13—H13	0.9300
C4—C7	1.531 (3)	C14—C15	1.367 (4)
C4—H4	0.9800	C14—H14	0.9300
C5—C6	1.493 (4)	C15—C16	1.372 (4)
C5—H5A	0.9700	C15—H15	0.9300
C5—H5B	0.9700	C16—C17	1.391 (3)
C6—C7	1.530 (3)	C16—H16	0.9300
C6—H6A	0.9700	C17—H17	0.9300
C6—H6B	0.9700
C5—O1—C4	107.45 (18)	C6—C7—H7	110.8
C9—N1—C8	117.75 (17)	C4—C7—H7	110.8
C9—N1—H1	107.9	N1—C8—C12	109.43 (16)
C8—N1—H1	107.9	N1—C8—C7	107.91 (17)
F1—C1—C2	119.9 (2)	C12—C8—C7	113.19 (16)
F1—C1—C11	119.1 (2)	N1—C8—H8	108.7
C2—C1—C11	121.0 (2)	C12—C8—H8	108.7
C1—C2—C3	121.1 (2)	C7—C8—H8	108.7
C1—C2—Cl1	118.10 (17)	N1—C9—C3	120.07 (17)
C3—C2—Cl1	120.83 (17)	N1—C9—C10	120.9 (2)
C2—C3—C9	118.51 (18)	C3—C9—C10	119.03 (19)
C2—C3—C4	120.93 (19)	C11—C10—C9	121.0 (2)
C9—C3—C4	120.49 (17)	C11—C10—H10	119.5
O1—C4—C3	109.30 (16)	C9—C10—H10	119.5
O1—C4—C7	104.77 (16)	C1—C11—C10	119.4 (2)
C3—C4—C7	115.39 (17)	C1—C11—H11	120.3
O1—C4—H4	109.1	C10—C11—H11	120.3
C3—C4—H4	109.1	C13—C12—C17	119.1 (2)
C7—C4—H4	109.1	C13—C12—C8	119.9 (2)
O1—C5—C6	109.1 (2)	C17—C12—C8	121.0 (2)
O1—C5—H5A	109.9	C12—C13—C14	120.4 (3)
C6—C5—H5A	109.9	C12—C13—H13	119.8
O1—C5—H5B	109.9	C14—C13—H13	119.8
C6—C5—H5B	109.9	C15—C14—C13	120.3 (3)
H5A—C5—H5B	108.3	C15—C14—H14	119.9
C5—C6—C7	104.69 (17)	C13—C14—H14	119.9
C5—C6—H6A	110.8	C14—C15—C16	120.1 (2)
C7—C6—H6A	110.8	C14—C15—H15	119.9
C5—C6—H6B	110.8	C16—C15—H15	119.9
C7—C6—H6B	110.8	C15—C16—C17	120.0 (3)
H6A—C6—H6B	108.9	C15—C16—H16	120.0
C8—C7—C6	112.78 (19)	C17—C16—H16	120.0
C8—C7—C4	110.25 (16)	C12—C17—C16	120.1 (2)
C6—C7—C4	101.21 (16)	C12—C17—H17	119.9
C8—C7—H7	110.8	C16—C17—H17	119.9
F1—C1—C2—C3	178.2 (2)	C6—C7—C8—C12	−68.8 (2)
C11—C1—C2—C3	−1.3 (4)	C4—C7—C8—C12	178.91 (17)
F1—C1—C2—Cl1	−1.5 (3)	C8—N1—C9—C3	26.3 (3)
C11—C1—C2—Cl1	178.99 (19)	C8—N1—C9—C10	−156.1 (2)
C1—C2—C3—C9	2.1 (3)	C2—C3—C9—N1	176.61 (19)
Cl1—C2—C3—C9	−178.17 (16)	C4—C3—C9—N1	−0.5 (3)
C1—C2—C3—C4	179.2 (2)	C2—C3—C9—C10	−1.0 (3)
Cl1—C2—C3—C4	−1.1 (3)	C4—C3—C9—C10	−178.1 (2)
C5—O1—C4—C3	158.3 (2)	N1—C9—C10—C11	−178.5 (2)
C5—O1—C4—C7	34.1 (3)	C3—C9—C10—C11	−0.8 (3)
C2—C3—C4—O1	71.9 (2)	F1—C1—C11—C10	179.9 (2)
C9—C3—C4—O1	−111.1 (2)	C2—C1—C11—C10	−0.7 (4)
C2—C3—C4—C7	−170.42 (19)	C9—C10—C11—C1	1.7 (4)
C9—C3—C4—C7	6.6 (3)	N1—C8—C12—C13	−134.6 (2)
C4—O1—C5—C6	−18.8 (3)	C7—C8—C12—C13	105.0 (2)
O1—C5—C6—C7	−4.1 (4)	N1—C8—C12—C17	45.0 (3)
C5—C6—C7—C8	−94.4 (3)	C7—C8—C12—C17	−75.4 (3)
C5—C6—C7—C4	23.3 (3)	C17—C12—C13—C14	0.4 (3)
O1—C4—C7—C8	84.7 (2)	C8—C12—C13—C14	180.0 (2)
C3—C4—C7—C8	−35.5 (3)	C12—C13—C14—C15	−0.6 (4)
O1—C4—C7—C6	−34.9 (2)	C13—C14—C15—C16	0.3 (4)
C3—C4—C7—C6	−155.13 (19)	C14—C15—C16—C17	0.1 (4)
C9—N1—C8—C12	−178.64 (18)	C13—C12—C17—C16	0.1 (3)
C9—N1—C8—C7	−55.1 (2)	C8—C12—C17—C16	−179.6 (2)
C6—C7—C8—N1	169.97 (17)	C15—C16—C17—C12	−0.3 (4)
C4—C7—C8—N1	57.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···F1^i	0.97	2.47	3.108 (2)	123
C17—H17···F1^ii	0.93	2.55	3.460 (3)	167

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

(II) 9-Chloro-8-fluoro-4-phenyl-2,3,3a,4,5,9 b-hexahydrofuro[3,2-c]quinoline

Crystal data

C17H15ClFNO	F(000) = 632
Mr = 303.75	Dx = 1.427 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6613 reflections
a = 8.1796 (6) Å	θ = 2.3–27.8°
b = 17.9041 (12) Å	µ = 0.28 mm^−1
c = 9.6562 (7) Å	T = 293 K
β = 91.017 (1)°	Needle, colourless
V = 1413.91 (17) Å^3	0.18 × 0.15 × 0.13 mm
Z = 4

Data collection

CCD area-detector diffractometer	2940 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 28.0°, θmin = 2.3°
ω scans	h = −10→10
16081 measured reflections	k = −23→23
3334 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0746P)^2 + 0.326P] where P = (Fo^2 + 2Fc^2)/3
3334 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.19 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 of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	0.28950 (5)	0.39744 (3)	0.62978 (5)	0.05489 (17)
F1	0.43418 (15)	0.48664 (7)	0.84949 (12)	0.0697 (3)
O1	0.5172 (2)	0.27339 (8)	0.49004 (15)	0.0712 (5)
N1	0.88428 (17)	0.39391 (8)	0.46759 (15)	0.0463 (3)
H1	0.9695	0.4257	0.4699	0.056*
C1	0.5449 (2)	0.46426 (9)	0.75549 (17)	0.0482 (4)
C2	0.4946 (2)	0.42132 (8)	0.64381 (16)	0.0413 (3)
C3	0.60589 (19)	0.39669 (8)	0.54643 (15)	0.0381 (3)
C4	0.55288 (19)	0.34529 (9)	0.43037 (16)	0.0438 (4)
H4	0.4540	0.3653	0.3851	0.053*
C5	0.5883 (3)	0.21687 (11)	0.4092 (2)	0.0631 (5)
H5A	0.5134	0.2011	0.3359	0.076*
H5B	0.6162	0.1739	0.4660	0.076*
C6	0.7387 (2)	0.25067 (10)	0.3499 (2)	0.0604 (5)
H6A	0.7699	0.2253	0.2656	0.072*
H6B	0.8294	0.2493	0.4158	0.072*
C7	0.68430 (19)	0.33091 (9)	0.32040 (16)	0.0428 (3)
H7	0.6315	0.3325	0.2285	0.051*
C8	0.82138 (19)	0.38918 (8)	0.32491 (16)	0.0401 (3)
H8	0.7740	0.4377	0.2999	0.048*
C9	0.77051 (19)	0.41740 (8)	0.56399 (16)	0.0402 (3)
C10	0.8184 (2)	0.46077 (9)	0.67783 (17)	0.0491 (4)
H10	0.9277	0.4741	0.6893	0.059*
C11	0.7064 (2)	0.48409 (10)	0.77341 (18)	0.0531 (4)
H11	0.7395	0.5129	0.8490	0.064*
C12	0.95399 (19)	0.37150 (9)	0.22314 (17)	0.0417 (3)
C13	1.0879 (2)	0.32682 (10)	0.2567 (2)	0.0530 (4)
H13	1.1016	0.3088	0.3465	0.064*
C14	1.2011 (2)	0.30906 (11)	0.1568 (2)	0.0603 (5)
H14	1.2897	0.2787	0.1796	0.072*
C15	1.1829 (2)	0.33619 (12)	0.0239 (2)	0.0617 (5)
H15	1.2586	0.3238	−0.0431	0.074*
C16	1.0530 (3)	0.38150 (13)	−0.0093 (2)	0.0610 (5)
H16	1.0413	0.4002	−0.0987	0.073*
C17	0.9392 (2)	0.39948 (10)	0.08972 (18)	0.0496 (4)
H17	0.8520	0.4306	0.0665	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0430 (2)	0.0612 (3)	0.0605 (3)	0.00534 (18)	0.00292 (19)	−0.00376 (19)
F1	0.0742 (8)	0.0817 (8)	0.0534 (6)	0.0198 (6)	0.0029 (6)	−0.0177 (6)
O1	0.0907 (10)	0.0469 (7)	0.0773 (9)	−0.0286 (7)	0.0360 (8)	−0.0198 (6)
N1	0.0385 (7)	0.0528 (8)	0.0473 (8)	−0.0065 (6)	−0.0043 (6)	−0.0029 (6)
C1	0.0611 (10)	0.0433 (9)	0.0400 (8)	0.0117 (7)	−0.0013 (7)	−0.0014 (6)
C2	0.0449 (8)	0.0351 (7)	0.0438 (8)	0.0042 (6)	−0.0030 (6)	0.0038 (6)
C3	0.0428 (8)	0.0320 (7)	0.0393 (7)	0.0000 (5)	−0.0043 (6)	0.0017 (5)
C4	0.0388 (8)	0.0462 (8)	0.0464 (8)	−0.0058 (6)	−0.0019 (6)	−0.0074 (7)
C5	0.0685 (12)	0.0479 (10)	0.0731 (12)	−0.0083 (9)	0.0090 (10)	−0.0062 (9)
C6	0.0586 (11)	0.0427 (9)	0.0801 (13)	−0.0020 (8)	0.0097 (9)	−0.0063 (9)
C7	0.0406 (8)	0.0464 (8)	0.0412 (8)	−0.0028 (6)	−0.0026 (6)	−0.0055 (6)
C8	0.0400 (8)	0.0373 (7)	0.0429 (8)	0.0010 (6)	−0.0013 (6)	0.0014 (6)
C9	0.0448 (8)	0.0349 (7)	0.0407 (8)	−0.0036 (6)	−0.0054 (6)	0.0036 (6)
C10	0.0533 (9)	0.0458 (9)	0.0479 (9)	−0.0087 (7)	−0.0116 (7)	−0.0001 (7)
C11	0.0719 (12)	0.0438 (9)	0.0432 (9)	−0.0034 (8)	−0.0124 (8)	−0.0050 (7)
C12	0.0391 (8)	0.0376 (7)	0.0485 (8)	−0.0023 (6)	0.0000 (6)	−0.0010 (6)
C13	0.0493 (9)	0.0499 (9)	0.0600 (10)	0.0069 (7)	0.0012 (8)	0.0057 (8)
C14	0.0473 (10)	0.0524 (10)	0.0815 (14)	0.0099 (8)	0.0046 (9)	−0.0051 (9)
C15	0.0520 (10)	0.0692 (12)	0.0643 (11)	−0.0020 (9)	0.0117 (9)	−0.0186 (10)
C16	0.0592 (11)	0.0753 (13)	0.0486 (10)	−0.0031 (9)	0.0040 (8)	0.0004 (9)
C17	0.0444 (9)	0.0551 (10)	0.0493 (9)	0.0024 (7)	0.0002 (7)	0.0039 (7)

Geometric parameters (Å, º)

Cl1—C2	1.7342 (17)	C7—C8	1.531 (2)
F1—C1	1.354 (2)	C7—H7	0.9800
O1—C5	1.410 (2)	C8—C12	1.510 (2)
O1—C4	1.442 (2)	C8—H8	0.9800
N1—C9	1.393 (2)	C9—C10	1.396 (2)
N1—C8	1.465 (2)	C10—C11	1.377 (3)
N1—H1	0.9000	C10—H10	0.9300
C1—C11	1.376 (3)	C11—H11	0.9300
C1—C2	1.381 (2)	C12—C17	1.386 (2)
C2—C3	1.392 (2)	C12—C13	1.390 (2)
C3—C9	1.404 (2)	C13—C14	1.385 (3)
C3—C4	1.508 (2)	C13—H13	0.9300
C4—C7	1.546 (2)	C14—C15	1.378 (3)
C4—H4	0.9800	C14—H14	0.9300
C5—C6	1.494 (3)	C15—C16	1.370 (3)
C5—H5A	0.9700	C15—H15	0.9300
C5—H5B	0.9700	C16—C17	1.384 (3)
C6—C7	1.529 (2)	C16—H16	0.9300
C6—H6A	0.9700	C17—H17	0.9300
C6—H6B	0.9700
C5—O1—C4	109.33 (14)	C8—C7—H7	108.5
C9—N1—C8	114.73 (13)	C4—C7—H7	108.5
C9—N1—H1	108.6	N1—C8—C12	112.32 (13)
C8—N1—H1	108.6	N1—C8—C7	108.11 (13)
F1—C1—C11	119.44 (15)	C12—C8—C7	111.89 (13)
F1—C1—C2	119.62 (16)	N1—C8—H8	108.1
C11—C1—C2	120.94 (16)	C12—C8—H8	108.1
C1—C2—C3	120.95 (16)	C7—C8—H8	108.1
C1—C2—Cl1	118.22 (13)	N1—C9—C10	120.84 (15)
C3—C2—Cl1	120.82 (12)	N1—C9—C3	119.35 (14)
C2—C3—C9	118.16 (14)	C10—C9—C3	119.81 (15)
C2—C3—C4	120.84 (14)	C11—C10—C9	121.04 (16)
C9—C3—C4	120.90 (14)	C11—C10—H10	119.5
O1—C4—C3	107.78 (13)	C9—C10—H10	119.5
O1—C4—C7	105.89 (13)	C1—C11—C10	119.09 (15)
C3—C4—C7	114.70 (13)	C1—C11—H11	120.5
O1—C4—H4	109.4	C10—C11—H11	120.5
C3—C4—H4	109.4	C17—C12—C13	118.70 (16)
C7—C4—H4	109.4	C17—C12—C8	118.52 (14)
O1—C5—C6	105.8 (2)	C13—C12—C8	122.75 (15)
O1—C5—H5A	110.6	C14—C13—C12	120.20 (18)
C6—C5—H5A	110.6	C14—C13—H13	119.9
O1—C5—H5B	110.6	C12—C13—H13	119.9
C6—C5—H5B	110.6	C15—C14—C13	120.36 (18)
H5A—C5—H5B	108.7	C15—C14—H14	119.8
C5—C6—C7	102.31 (16)	C13—C14—H14	119.8
C5—C6—H6A	111.3	C16—C15—C14	119.80 (18)
C7—C6—H6A	111.3	C16—C15—H15	120.1
C5—C6—H6B	111.3	C14—C15—H15	120.1
C7—C6—H6B	111.3	C15—C16—C17	120.28 (18)
H6A—C6—H6B	109.2	C15—C16—H16	119.9
C6—C7—C8	115.10 (14)	C17—C16—H16	119.9
C6—C7—C4	103.42 (14)	C16—C17—C12	120.63 (17)
C8—C7—C4	112.63 (13)	C16—C17—H17	119.7
C6—C7—H7	108.5	C12—C17—H17	119.7
F1—C1—C2—C3	−179.19 (14)	C6—C7—C8—C12	58.1 (2)
C11—C1—C2—C3	0.2 (2)	C4—C7—C8—C12	176.34 (13)
F1—C1—C2—Cl1	−0.3 (2)	C8—N1—C9—C10	−146.11 (15)
C11—C1—C2—Cl1	179.04 (13)	C8—N1—C9—C3	34.3 (2)
C1—C2—C3—C9	−0.7 (2)	C2—C3—C9—N1	−179.61 (13)
Cl1—C2—C3—C9	−179.52 (11)	C4—C3—C9—N1	4.1 (2)
C1—C2—C3—C4	175.58 (14)	C2—C3—C9—C10	0.8 (2)
Cl1—C2—C3—C4	−3.2 (2)	C4—C3—C9—C10	−175.50 (14)
C5—O1—C4—C3	−134.74 (16)	N1—C9—C10—C11	−179.97 (15)
C5—O1—C4—C7	−11.54 (19)	C3—C9—C10—C11	−0.4 (2)
C2—C3—C4—O1	−69.75 (18)	F1—C1—C11—C10	179.64 (15)
C9—C3—C4—O1	106.42 (16)	C2—C1—C11—C10	0.2 (3)
C2—C3—C4—C7	172.60 (14)	C9—C10—C11—C1	−0.2 (3)
C9—C3—C4—C7	−11.2 (2)	N1—C8—C12—C17	−148.88 (15)
C4—O1—C5—C6	31.0 (2)	C7—C8—C12—C17	89.30 (18)
O1—C5—C6—C7	−37.0 (2)	N1—C8—C12—C13	32.8 (2)
C5—C6—C7—C8	152.09 (15)	C7—C8—C12—C13	−89.01 (19)
C5—C6—C7—C4	28.82 (18)	C17—C12—C13—C14	−2.0 (3)
O1—C4—C7—C6	−11.65 (17)	C8—C12—C13—C14	176.35 (16)
C3—C4—C7—C6	107.07 (16)	C12—C13—C14—C15	0.8 (3)
O1—C4—C7—C8	−136.54 (14)	C13—C14—C15—C16	0.6 (3)
C3—C4—C7—C8	−17.8 (2)	C14—C15—C16—C17	−0.6 (3)
C9—N1—C8—C12	173.88 (13)	C15—C16—C17—C12	−0.6 (3)
C9—N1—C8—C7	−62.18 (17)	C13—C12—C17—C16	1.9 (3)
C6—C7—C8—N1	−66.10 (18)	C8—C12—C17—C16	−176.51 (17)
C4—C7—C8—N1	52.13 (17)