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

8-Chloro-9-fluoro-5-phen­yl-3,4,4a,5,6,10b-hexa­hydro-2H-pyrano[3,2-c]quinoline and 10-chloro-9-fluoro-5-phen­yl-3,4,4a,5,6,10b-hexa­hydro-2H-pyrano­[3,2-c]quinoline, both C₁₈H₁₇ClFNO, are diastereo­isomers, formed as the result of the imino Diels-Alder reactions of N-benzyl­ideneanilines with 3,4-dihydro-2H-pyran. The crystal structures reveal the stereochemistry of the pyran ring, which is endo/exo to the quinoline ring system formed in the cyclo­addition step. In both structures, the pyran ring adopts a chair conformation, while the nitrogen-containing heterocyclic ring prefers a half-chair conformation. The structures differ essentially in the relative orientation of the ring junction H atoms.

S1. Comment

The pyranoquinoline moiety is commonly found in many alkaloids, viz. findersine, oricine and verprisine, and derivatives of these alkaloids possess a significant range of biological activities, such as anti-allergic, psychotropic and anti-inflammatory activities (Yamada et al., 1992; Faber et al., 1984; Nesterova et al., 1995). In addition, pyranoquinoline derivatives are used as potential pharmaceuticals (Mohamed, 1994). It is therefore not surprising that efforts are ongoing for synthesis of these compounds by different methods (Ma et al., 1999, Mahesh, Makesh & Perumal, 2004; Mahesh, Venkateswar Reddy et al., 2004). The Diels–Alder reaction catalysed by Lewis acids between N-benzylideneanilines and nucleophilic olefins is one of the powerful synthetic tools for constructing nitrogen-containing six-membered heterocyclic compounds. In this context, we have been examining a variety of conditions to achieve different product distributions. Recently, we described the synthesis and characterization of di-substituted pyrano and furano quinolines, by application of the imino Diels–Alder reaction using ZrCl₄ as a potential green catalyst. The individual diastereoisomers thus obtained differ according to the stereochemistry (cis/trans) of the ring junction H atoms and the orientation (endo/exo) of the pyran ring. To elucidate the reaction stereochemistry and the molecular geometry of the structures, we have undertaken structural investigations of the title compounds, (I) and (II).

Both (I) and (II) crystallize in space group P1, with two independent molecules in the asymmetric unit. The geometries of the two independent molecules are very similar as far as interatomic distances and angles are concerned, the greatest differences being 0.008 Å [N1—C4 in (I)] and 0.030 Å [C16—C17 in (II)], and 1.8° [C4—N1—C5 in (I)] and 1.3° [C16—C17—C18 in (II)].

The geometric parameters of the two structures (Figs. 1 and 2) are not very different from the values found in the literature for other quinoline derivatives. More relevant differences between the structures are observed in the torsion angles, as a result of both the different configuration at the C6 ring junction and the different packing of the crystals. One significant difference is the orientation of atoms H5 and H6. The H5—C5—C6—H6 torsion angle, of −62.8 and −61.4° in (I), indicates a cis arrangement and is in accordance with the coupling constant J = 5.2 Hz. Consequently, the structure of (II), with a corresponding torsion angle of −173.5 and −173.8° showing a larger coupling constant, J = 10.8 Hz, is in a trans configuration.

In both the structures, the substitutions of the quinoline ring system produce a considerable twist about the C5···C11 vector. The twist can be seen from the C5—C6—C10—C11 and C5—N1—C4—C11 torsion angles of 48.5 (2)/51.1 (2) and −21.7 (3)/-16.4 (3)° in (I), and −51.0 (3)/-51.0 (3) and 14.5 (4)/13.5 (4)° in (II), respectively. In addition, these values indicate the fusion strain exerted during the ring formation in the Diels–Alder cycloaddition process.

It is interesting to note that in both structures the pyran ring is almost perpendicular to the quinoline ring system. In (I), atom O1 is displaced below the N1/C4/C11/C10 least-squares plane by −0.744 (2) Å in molecule 1 and above this plane by 0.694 (2) Å in molecule 2. Similarly, the corresponding displacements of atom O1 in (II) is −1.335 (2) and −1.335 (2) Å, respectively. The relative configuration/orientation of the quinoline ring system and the pyran ring can be seen from the C5—C6—C10—O1 torsion angle [175.4 (2) and 177.7 (2)° trans (exo) for (I), and 69.6 (3) and 69.7 (3)° cis (endo) for (II)].

The most appropriate puckering description for the pyridine ring is half-chair in both the structures, with an asymmetry parameter (Nardelli, 1983) ΔC₂(C4—C11) of 0.005 (1) and 0.043 (1) in (I), and 0.034 (1) and 0.038 (1) in (II). The conformation of the pyran ring in both the structures is a chair as expected, with atoms C6, C8, C9 and C10 defining the plane, atoms C7 and O1 being displaced by −0.626 (3)/-0.637 (2) and 0.592 (2)/0.602 (2) Å in (I), and by 0.621 (3)/0.622 (3) and −0.679 (2)/-0.670 (2) Å in (II), respectively. The phenyl ring substituted at atom C5 is rotated through the C5—C13 bond, the N1—C5—C13—C14 torsion angles being −21.8 (3) and −23.9 (3)° in (I), and 50.4 (4) and 53.6 (4)° in (II), perhaps to facilitate the cis/trans orientation for the H atoms at C5. The dihedral angles between the planes of the halogen-substituted phenyl ring and the C5-phenyl ring are 44.5 (1) and 44.6 (1)° in (I), and 68.4 (1) and 71.0 (1)° in (II), respectively.

A striking feature is observed in the crystal packing of the two compounds. Interesting C—H···A contacts [A = Cl, F, O and N] are listed in Table 2. In (I), the N atom of the quinoline ring system is involved in intermolecular hydrogen-bond formation with the O atom of the pyran ring, in both the molecules present in the asymmetric unit (Fig. 3). Unusually, in (II), this conventional N—H···O hydrogen bond is not observed, even though good hydrogen-bonding functionalities are present. A similar feature has been noted in the structures of alloxan (Beyer et al., 2001; Coombes et al., 1997) and furoquinoline (Ravikumar et al., 2004). This complements the views of Desiraju (2002): `Hydrogen bonds are ubiquitous, directional and strong, and they do control the crystal packing rather effectively, but in the rarest of cases they can be absent. After all, any way to minimize the free energy of a crystal is a respectable way, and given that crystal structures are being determined in the numbers that they are, even axioms will be bypassed on occasion.'

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, yielding 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 atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93 (aromatic), 0.98 Å (CH) and 0.97 Å (CH₂), a N—H distances of 0.90 Å, and U_iso(H) values of 1.2U_eq(C,N). The data coverage is 100% of all independent reflections to 2θ = 50° (a d-spacing of 0.841 Å); close examination revealed that missing reflections [12 and 20 reflections for (I) and (II), respectively] lie only in high angle (2θ > 45°) regions.

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); 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. A packing diagram for (I), highlighting N—H···O intermolecular hydrogen bonds (dashed lines) forming molecular columns along the a axis. H atoms not involved in the interactions shown have been omitted for clarity.

(I) 8-chloro-9-fluoro-5-phenyl-3,4,4a,5,6,10b-hexahydro-2H-pyrano[3,2-c]quinoline

Crystal data

C18H17ClFNO	Z = 4
Mr = 317.78	F(000) = 664
Triclinic, P1	Dx = 1.358 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5399 (7) Å	Cell parameters from 4707 reflections
b = 11.2005 (7) Å	θ = 2.4–26.2°
c = 13.4950 (9) Å	µ = 0.26 mm^−1
α = 82.597 (1)°	T = 273 K
β = 83.890 (1)°	Needle, colorless
γ = 80.884 (1)°	0.19 × 0.11 × 0.09 mm
V = 1553.85 (18) Å^3

Data collection

Bruker Smart APEX CCD area-detector diffractometer	4629 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 25°, θmin = 1.9°
ω scans	h = −12→12
15105 measured reflections	k = −13→13
5469 independent reflections	l = −16→16

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) = 0.129	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0541P)^2 + 0.6549P] where P = (Fo^2 + 2Fc^2)/3
5469 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 0.37 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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.38827 (7)	0.39601 (8)	0.56352 (5)	0.0695 (2)
F1	0.60640 (17)	0.19713 (17)	0.56734 (11)	0.0764 (5)
O1	0.70194 (16)	0.02413 (15)	0.23647 (13)	0.0529 (5)
N1	0.43372 (17)	0.33660 (16)	0.19241 (13)	0.0397 (4)
H1A	0.4097	0.4178	0.1858	0.048*
C1	0.5646 (2)	0.2317 (2)	0.47448 (17)	0.0495 (6)
C2	0.4632 (2)	0.3241 (2)	0.46186 (16)	0.0451 (6)
C3	0.4213 (2)	0.3602 (2)	0.36792 (16)	0.0410 (5)
H3	0.3530	0.4232	0.3593	0.049*
C4	0.4804 (2)	0.30291 (19)	0.28576 (15)	0.0355 (5)
C5	0.5187 (2)	0.3061 (2)	0.10376 (15)	0.0368 (5)
H5	0.5906	0.3532	0.0976	0.044*
C6	0.5735 (2)	0.1701 (2)	0.12050 (16)	0.0383 (5)
H6	0.6307	0.1497	0.0610	0.046*
C7	0.4702 (2)	0.0878 (2)	0.13540 (19)	0.0480 (6)
H71	0.4285	0.0938	0.0739	0.058*
H72	0.4053	0.1144	0.1877	0.058*
C8	0.5277 (3)	−0.0438 (2)	0.1644 (2)	0.0631 (7)
H81	0.4593	−0.0937	0.1797	0.076*
H82	0.5842	−0.0741	0.1087	0.076*
C9	0.6029 (3)	−0.0520 (2)	0.2546 (2)	0.0624 (8)
H91	0.5446	−0.0278	0.3115	0.075*
H92	0.6417	−0.1358	0.2713	0.075*
C10	0.6551 (2)	0.1497 (2)	0.21039 (16)	0.0411 (5)
H10	0.7309	0.1905	0.1897	0.049*
C11	0.5839 (2)	0.2090 (2)	0.29950 (16)	0.0368 (5)
C12	0.6242 (2)	0.1741 (2)	0.39497 (17)	0.0466 (6)
H12	0.6922	0.1111	0.4049	0.056*
C13	0.4482 (2)	0.33888 (19)	0.00965 (15)	0.0351 (5)
C14	0.3154 (2)	0.3528 (2)	0.01000 (17)	0.0459 (6)
H14	0.2652	0.3414	0.0705	0.055*
C15	0.2565 (2)	0.3835 (2)	−0.07812 (19)	0.0532 (6)
H15	0.1670	0.3933	−0.0765	0.064*
C16	0.3289 (3)	0.3996 (2)	−0.16818 (18)	0.0518 (6)
H16	0.2888	0.4206	−0.2274	0.062*
C17	0.4607 (2)	0.3844 (2)	−0.17021 (17)	0.0514 (6)
H17	0.5104	0.3940	−0.2311	0.062*
C18	0.5196 (2)	0.3551 (2)	−0.08227 (17)	0.0441 (6)
H18	0.6091	0.3459	−0.0845	0.053*
Cl1'	0.12764 (8)	0.08374 (8)	1.11111 (5)	0.0714 (2)
F1'	−0.07605 (16)	0.29479 (16)	1.11800 (10)	0.0712 (5)
O1'	−0.19761 (16)	0.47460 (15)	0.77456 (12)	0.0511 (4)
N1'	0.05158 (19)	0.15115 (17)	0.74056 (13)	0.0433 (5)
H1A'	0.0638	0.0693	0.7466	0.052*
C1'	−0.0474 (2)	0.2583 (2)	1.02500 (17)	0.0476 (6)
C2'	0.0474 (2)	0.1606 (2)	1.01076 (17)	0.0470 (6)
C3'	0.0786 (2)	0.1241 (2)	0.91682 (17)	0.0441 (6)
H3'	0.1423	0.0578	0.9076	0.053*
C4'	0.0156 (2)	0.1857 (2)	0.83509 (15)	0.0370 (5)
C5'	−0.0319 (2)	0.19373 (19)	0.65985 (16)	0.0376 (5)
H5'	−0.1076	0.1514	0.6727	0.045*
C6'	−0.0778 (2)	0.3307 (2)	0.66291 (16)	0.0381 (5)
H6'	−0.1358	0.3585	0.6098	0.046*
C7'	0.0312 (2)	0.4067 (2)	0.64576 (17)	0.0447 (6)
H71'	0.0719	0.4024	0.5781	0.054*
H72'	0.0957	0.3743	0.6922	0.054*
C8'	−0.0191 (3)	0.5386 (2)	0.6606 (2)	0.0599 (7)
H81'	0.0527	0.5841	0.6561	0.072*
H82'	−0.0742	0.5745	0.6081	0.072*
C9'	−0.0945 (3)	0.5467 (2)	0.7616 (2)	0.0582 (7)
H91'	−0.0369	0.5189	0.8140	0.070*
H92'	−0.1300	0.6310	0.7680	0.070*
C10'	−0.1553 (2)	0.3490 (2)	0.76359 (16)	0.0399 (5)
H10'	−0.2330	0.3108	0.7647	0.048*
C11'	−0.0816 (2)	0.2840 (2)	0.85074 (16)	0.0365 (5)
C12'	−0.1108 (2)	0.3196 (2)	0.94652 (17)	0.0441 (6)
H12'	−0.1740	0.3858	0.9571	0.053*
C13'	0.0357 (2)	0.16573 (18)	0.55893 (15)	0.0359 (5)
C14'	0.1683 (2)	0.1485 (2)	0.53974 (17)	0.0447 (6)
H14'	0.2198	0.1527	0.5907	0.054*
C15'	0.2255 (3)	0.1250 (2)	0.44585 (18)	0.0529 (6)
H15'	0.3149	0.1128	0.4342	0.063*
C16'	0.1512 (3)	0.1197 (2)	0.37018 (18)	0.0568 (7)
H16'	0.1899	0.1034	0.3072	0.068*
C17'	0.0193 (3)	0.1383 (2)	0.38715 (18)	0.0558 (7)
H17'	−0.0314	0.1359	0.3353	0.067*
C18'	−0.0382 (2)	0.1604 (2)	0.48091 (17)	0.0446 (6)
H18'	−0.1276	0.1720	0.4920	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0773 (5)	0.0966 (6)	0.0376 (4)	−0.0122 (4)	0.0063 (3)	−0.0291 (3)
F1	0.0863 (12)	0.1060 (13)	0.0356 (8)	−0.0004 (10)	−0.0236 (8)	−0.0055 (8)
O1	0.0528 (10)	0.0475 (10)	0.0540 (10)	0.0173 (8)	−0.0170 (8)	−0.0095 (8)
N1	0.0491 (11)	0.0371 (10)	0.0290 (9)	0.0084 (8)	−0.0047 (8)	−0.0066 (8)
C1	0.0544 (15)	0.0635 (16)	0.0326 (12)	−0.0096 (13)	−0.0144 (11)	−0.0032 (11)
C2	0.0519 (14)	0.0560 (15)	0.0311 (12)	−0.0149 (12)	0.0007 (10)	−0.0135 (10)
C3	0.0438 (13)	0.0429 (13)	0.0360 (12)	−0.0017 (10)	−0.0028 (10)	−0.0095 (10)
C4	0.0390 (12)	0.0360 (12)	0.0319 (11)	−0.0043 (9)	−0.0050 (9)	−0.0058 (9)
C5	0.0374 (12)	0.0424 (13)	0.0298 (11)	−0.0021 (10)	−0.0031 (9)	−0.0061 (9)
C6	0.0382 (12)	0.0448 (13)	0.0302 (11)	0.0034 (10)	−0.0017 (9)	−0.0105 (9)
C7	0.0527 (14)	0.0457 (14)	0.0475 (14)	−0.0008 (11)	−0.0176 (11)	−0.0095 (11)
C8	0.083 (2)	0.0431 (15)	0.0662 (18)	−0.0017 (13)	−0.0263 (15)	−0.0120 (13)
C9	0.086 (2)	0.0357 (14)	0.0659 (18)	0.0034 (13)	−0.0279 (15)	−0.0037 (12)
C10	0.0358 (12)	0.0446 (13)	0.0412 (13)	0.0024 (10)	−0.0060 (10)	−0.0063 (10)
C11	0.0363 (12)	0.0407 (12)	0.0344 (12)	−0.0048 (9)	−0.0075 (9)	−0.0055 (9)
C12	0.0443 (13)	0.0534 (15)	0.0421 (13)	0.0000 (11)	−0.0139 (11)	−0.0053 (11)
C13	0.0416 (12)	0.0328 (11)	0.0308 (11)	−0.0032 (9)	−0.0038 (9)	−0.0050 (9)
C14	0.0421 (13)	0.0583 (15)	0.0349 (12)	−0.0038 (11)	−0.0003 (10)	−0.0039 (11)
C15	0.0416 (14)	0.0693 (17)	0.0484 (15)	−0.0031 (12)	−0.0107 (11)	−0.0065 (13)
C16	0.0624 (17)	0.0614 (16)	0.0340 (13)	−0.0097 (13)	−0.0168 (11)	−0.0026 (11)
C17	0.0570 (16)	0.0687 (17)	0.0292 (12)	−0.0160 (13)	−0.0009 (11)	−0.0023 (11)
C18	0.0403 (13)	0.0564 (15)	0.0364 (12)	−0.0093 (11)	−0.0023 (10)	−0.0062 (11)
Cl1'	0.0869 (5)	0.0923 (6)	0.0386 (4)	−0.0259 (4)	−0.0261 (3)	0.0121 (3)
F1'	0.0833 (11)	0.1026 (13)	0.0334 (8)	−0.0258 (10)	0.0073 (7)	−0.0250 (8)
O1'	0.0480 (10)	0.0471 (10)	0.0519 (10)	0.0130 (8)	−0.0002 (8)	−0.0102 (8)
N1'	0.0583 (12)	0.0372 (10)	0.0294 (10)	0.0099 (9)	−0.0065 (8)	−0.0033 (8)
C1'	0.0512 (14)	0.0661 (17)	0.0303 (12)	−0.0222 (13)	0.0044 (10)	−0.0128 (11)
C2'	0.0534 (14)	0.0611 (16)	0.0299 (12)	−0.0226 (12)	−0.0086 (10)	0.0044 (11)
C3'	0.0501 (14)	0.0438 (13)	0.0363 (13)	−0.0036 (11)	−0.0060 (10)	0.0017 (10)
C4'	0.0406 (12)	0.0391 (12)	0.0298 (11)	−0.0050 (10)	−0.0026 (9)	0.0002 (9)
C5'	0.0420 (12)	0.0375 (12)	0.0328 (12)	−0.0034 (9)	−0.0046 (9)	−0.0041 (9)
C6'	0.0392 (12)	0.0422 (12)	0.0305 (11)	0.0040 (10)	−0.0090 (9)	−0.0022 (9)
C7'	0.0497 (14)	0.0429 (13)	0.0372 (12)	−0.0003 (11)	0.0041 (10)	−0.0026 (10)
C8'	0.0780 (19)	0.0411 (14)	0.0560 (16)	−0.0057 (13)	0.0069 (14)	−0.0027 (12)
C9'	0.0778 (19)	0.0361 (13)	0.0561 (16)	0.0021 (13)	0.0041 (14)	−0.0091 (12)
C10'	0.0328 (12)	0.0436 (13)	0.0417 (13)	0.0020 (10)	−0.0032 (9)	−0.0079 (10)
C11'	0.0339 (11)	0.0414 (12)	0.0338 (12)	−0.0065 (9)	0.0019 (9)	−0.0051 (9)
C12'	0.0387 (13)	0.0530 (14)	0.0415 (13)	−0.0096 (11)	0.0049 (10)	−0.0125 (11)
C13'	0.0477 (13)	0.0283 (11)	0.0316 (11)	−0.0044 (9)	−0.0060 (9)	−0.0024 (9)
C14'	0.0499 (14)	0.0495 (14)	0.0353 (12)	−0.0048 (11)	−0.0069 (10)	−0.0076 (10)
C15'	0.0577 (16)	0.0567 (16)	0.0422 (14)	−0.0062 (12)	0.0055 (12)	−0.0087 (12)
C16'	0.084 (2)	0.0533 (16)	0.0324 (13)	−0.0111 (14)	0.0052 (13)	−0.0096 (11)
C17'	0.088 (2)	0.0508 (15)	0.0332 (13)	−0.0136 (14)	−0.0196 (13)	−0.0067 (11)
C18'	0.0529 (14)	0.0420 (13)	0.0409 (13)	−0.0080 (11)	−0.0125 (11)	−0.0044 (10)

Geometric parameters (Å, º)

Cl1—C2	1.734 (2)	Cl1'—C2'	1.733 (2)
F1—C1	1.361 (3)	F1'—C1'	1.359 (3)
O1—C10	1.426 (3)	O1'—C10'	1.429 (3)
O1—C9	1.432 (3)	O1'—C9'	1.437 (3)
N1—C4	1.386 (3)	N1'—C4'	1.378 (3)
N1—C5	1.460 (3)	N1'—C5'	1.458 (3)
N1—H1A	0.9000	N1'—H1A'	0.9000
C1—C12	1.367 (3)	C1'—C12'	1.363 (3)
C1—C2	1.372 (4)	C1'—C2'	1.377 (4)
C2—C3	1.377 (3)	C2'—C3'	1.373 (3)
C3—C4	1.392 (3)	C3'—C4'	1.396 (3)
C3—H3	0.9300	C3'—H3'	0.9300
C4—C11	1.400 (3)	C4'—C11'	1.401 (3)
C5—C13	1.515 (3)	C5'—C13'	1.514 (3)
C5—C6	1.538 (3)	C5'—C6'	1.538 (3)
C5—H5	0.9800	C5'—H5'	0.9800
C6—C7	1.517 (3)	C6'—C7'	1.517 (3)
C6—C10	1.534 (3)	C6'—C10'	1.529 (3)
C6—H6	0.9800	C6'—H6'	0.9800
C7—C8	1.521 (3)	C7'—C8'	1.520 (3)
C7—H71	0.9700	C7'—H71'	0.9700
C7—H72	0.9700	C7'—H72'	0.9700
C8—C9	1.508 (4)	C8'—C9'	1.507 (4)
C8—H81	0.9700	C8'—H81'	0.9700
C8—H82	0.9700	C8'—H82'	0.9700
C9—H91	0.9700	C9'—H91'	0.9700
C9—H92	0.9700	C9'—H92'	0.9700
C10—C11	1.519 (3)	C10'—C11'	1.521 (3)
C10—H10	0.9800	C10'—H10'	0.9800
C11—C12	1.388 (3)	C11'—C12'	1.391 (3)
C12—H12	0.9300	C12'—H12'	0.9300
C13—C14	1.383 (3)	C13'—C14'	1.382 (3)
C13—C18	1.387 (3)	C13'—C18'	1.387 (3)
C14—C15	1.379 (3)	C14'—C15'	1.382 (3)
C14—H14	0.9300	C14'—H14'	0.9300
C15—C16	1.372 (3)	C15'—C16'	1.364 (4)
C15—H15	0.9300	C15'—H15'	0.9300
C16—C17	1.371 (4)	C16'—C17'	1.372 (4)
C16—H16	0.9300	C16'—H16'	0.9300
C17—C18	1.376 (3)	C17'—C18'	1.378 (3)
C17—H17	0.9300	C17'—H17'	0.9300
C18—H18	0.9300	C18'—H18'	0.9300
C10—O1—C9	113.90 (17)	C10'—O1'—C9'	113.55 (17)
C4—N1—C5	118.23 (17)	C4'—N1'—C5'	120.02 (18)
C4—N1—H1A	107.8	C4'—N1'—H1A'	107.3
C5—N1—H1A	107.8	C5'—N1'—H1A'	107.3
F1—C1—C12	119.6 (2)	F1'—C1'—C12'	119.9 (2)
F1—C1—C2	119.6 (2)	F1'—C1'—C2'	119.5 (2)
C12—C1—C2	120.9 (2)	C12'—C1'—C2'	120.7 (2)
C1—C2—C3	119.8 (2)	C3'—C2'—C1'	120.0 (2)
C1—C2—Cl1	120.33 (18)	C3'—C2'—Cl1'	119.8 (2)
C3—C2—Cl1	119.85 (19)	C1'—C2'—Cl1'	120.19 (18)
C2—C3—C4	120.4 (2)	C2'—C3'—C4'	120.5 (2)
C2—C3—H3	119.8	C2'—C3'—H3'	119.8
C4—C3—H3	119.8	C4'—C3'—H3'	119.8
N1—C4—C3	119.82 (19)	N1'—C4'—C3'	119.8 (2)
N1—C4—C11	120.89 (19)	N1'—C4'—C11'	121.17 (19)
C3—C4—C11	119.25 (19)	C3'—C4'—C11'	119.0 (2)
N1—C5—C13	111.03 (17)	N1'—C5'—C13'	111.50 (17)
N1—C5—C6	107.98 (17)	N1'—C5'—C6'	108.22 (17)
C13—C5—C6	112.69 (17)	C13'—C5'—C6'	112.25 (17)
N1—C5—H5	108.3	N1'—C5'—H5'	108.2
C13—C5—H5	108.3	C13'—C5'—H5'	108.2
C6—C5—H5	108.3	C6'—C5'—H5'	108.2
C7—C6—C10	111.17 (18)	C7'—C6'—C10'	110.79 (18)
C7—C6—C5	113.19 (18)	C7'—C6'—C5'	113.51 (18)
C10—C6—C5	108.34 (17)	C10'—C6'—C5'	108.52 (17)
C7—C6—H6	108.0	C7'—C6'—H6'	107.9
C10—C6—H6	108.0	C10'—C6'—H6'	107.9
C5—C6—H6	108.0	C5'—C6'—H6'	107.9
C6—C7—C8	111.0 (2)	C6'—C7'—C8'	110.7 (2)
C6—C7—H71	109.4	C6'—C7'—H71'	109.5
C8—C7—H71	109.4	C8'—C7'—H71'	109.5
C6—C7—H72	109.4	C6'—C7'—H72'	109.5
C8—C7—H72	109.4	C8'—C7'—H72'	109.5
H71—C7—H72	108.0	H71'—C7'—H72'	108.1
C9—C8—C7	109.7 (2)	C9'—C8'—C7'	110.5 (2)
C9—C8—H81	109.7	C9'—C8'—H81'	109.5
C7—C8—H81	109.7	C7'—C8'—H81'	109.5
C9—C8—H82	109.7	C9'—C8'—H82'	109.5
C7—C8—H82	109.7	C7'—C8'—H82'	109.5
H81—C8—H82	108.2	H81'—C8'—H82'	108.1
O1—C9—C8	111.6 (2)	O1'—C9'—C8'	111.8 (2)
O1—C9—H91	109.3	O1'—C9'—H91'	109.3
C8—C9—H91	109.3	C8'—C9'—H91'	109.3
O1—C9—H92	109.3	O1'—C9'—H92'	109.3
C8—C9—H92	109.3	C8'—C9'—H92'	109.3
H91—C9—H92	108.0	H91'—C9'—H92'	107.9
O1—C10—C11	112.11 (18)	O1'—C10'—C11'	112.06 (18)
O1—C10—C6	112.29 (18)	O1'—C10'—C6'	112.32 (18)
C11—C10—C6	111.66 (17)	C11'—C10'—C6'	111.35 (17)
O1—C10—H10	106.8	O1'—C10'—H10'	106.9
C11—C10—H10	106.8	C11'—C10'—H10'	106.9
C6—C10—H10	106.8	C6'—C10'—H10'	106.9
C12—C11—C4	119.3 (2)	C12'—C11'—C4'	119.4 (2)
C12—C11—C10	120.25 (19)	C12'—C11'—C10'	120.8 (2)
C4—C11—C10	120.44 (18)	C4'—C11'—C10'	119.82 (18)
C1—C12—C11	120.4 (2)	C1'—C12'—C11'	120.5 (2)
C1—C12—H12	119.8	C1'—C12'—H12'	119.7
C11—C12—H12	119.8	C11'—C12'—H12'	119.7
C14—C13—C18	117.7 (2)	C14'—C13'—C18'	118.0 (2)
C14—C13—C5	123.45 (19)	C14'—C13'—C5'	123.02 (19)
C18—C13—C5	118.86 (19)	C18'—C13'—C5'	118.9 (2)
C15—C14—C13	120.9 (2)	C13'—C14'—C15'	120.8 (2)
C15—C14—H14	119.6	C13'—C14'—H14'	119.6
C13—C14—H14	119.6	C15'—C14'—H14'	119.6
C16—C15—C14	120.5 (2)	C16'—C15'—C14'	120.2 (3)
C16—C15—H15	119.8	C16'—C15'—H15'	119.9
C14—C15—H15	119.8	C14'—C15'—H15'	119.9
C17—C16—C15	119.5 (2)	C15'—C16'—C17'	119.9 (2)
C17—C16—H16	120.2	C15'—C16'—H16'	120.1
C15—C16—H16	120.2	C17'—C16'—H16'	120.1
C16—C17—C18	120.1 (2)	C16'—C17'—C18'	120.1 (2)
C16—C17—H17	120.0	C16'—C17'—H17'	119.9
C18—C17—H17	120.0	C18'—C17'—H17'	119.9
C17—C18—C13	121.4 (2)	C17'—C18'—C13'	120.9 (2)
C17—C18—H18	119.3	C17'—C18'—H18'	119.6
C13—C18—H18	119.3	C13'—C18'—H18'	119.6
F1—C1—C2—C3	179.4 (2)	F1'—C1'—C2'—C3'	−179.0 (2)
C12—C1—C2—C3	−0.4 (4)	C12'—C1'—C2'—C3'	−0.1 (4)
F1—C1—C2—Cl1	−0.3 (3)	F1'—C1'—C2'—Cl1'	0.9 (3)
C12—C1—C2—Cl1	179.81 (19)	C12'—C1'—C2'—Cl1'	179.79 (18)
C1—C2—C3—C4	0.5 (4)	C1'—C2'—C3'—C4'	0.4 (4)
Cl1—C2—C3—C4	−179.80 (17)	Cl1'—C2'—C3'—C4'	−179.48 (17)
C5—N1—C4—C3	160.4 (2)	C5'—N1'—C4'—C3'	165.2 (2)
C5—N1—C4—C11	−21.7 (3)	C5'—N1'—C4'—C11'	−16.4 (3)
C2—C3—C4—N1	177.3 (2)	C2'—C3'—C4'—N1'	177.3 (2)
C2—C3—C4—C11	−0.6 (3)	C2'—C3'—C4'—C11'	−1.1 (3)
C4—N1—C5—C13	174.66 (18)	C4'—N1'—C5'—C13'	169.23 (19)
C4—N1—C5—C6	50.7 (2)	C4'—N1'—C5'—C6'	45.3 (3)
N1—C5—C6—C7	60.6 (2)	N1'—C5'—C6'—C7'	61.9 (2)
C13—C5—C6—C7	−62.4 (2)	C13'—C5'—C6'—C7'	−61.5 (2)
N1—C5—C6—C10	−63.2 (2)	N1'—C5'—C6'—C10'	−61.7 (2)
C13—C5—C6—C10	173.78 (17)	C13'—C5'—C6'—C10'	174.83 (18)
C10—C6—C7—C8	−50.8 (3)	C10'—C6'—C7'—C8'	−51.6 (2)
C5—C6—C7—C8	−172.97 (19)	C5'—C6'—C7'—C8'	−174.02 (19)
C6—C7—C8—C9	54.0 (3)	C6'—C7'—C8'—C9'	53.5 (3)
C10—O1—C9—C8	58.5 (3)	C10'—O1'—C9'—C8'	57.3 (3)
C7—C8—C9—O1	−57.1 (3)	C7'—C8'—C9'—O1'	−55.7 (3)
C9—O1—C10—C11	72.0 (2)	C9'—O1'—C10'—C11'	70.7 (2)
C9—O1—C10—C6	−54.7 (3)	C9'—O1'—C10'—C6'	−55.5 (2)
C7—C6—C10—O1	50.5 (2)	C7'—C6'—C10'—O1'	52.4 (2)
C5—C6—C10—O1	175.44 (17)	C5'—C6'—C10'—O1'	177.68 (17)
C7—C6—C10—C11	−76.5 (2)	C7'—C6'—C10'—C11'	−74.2 (2)
C5—C6—C10—C11	48.5 (2)	C5'—C6'—C10'—C11'	51.1 (2)
N1—C4—C11—C12	−177.1 (2)	N1'—C4'—C11'—C12'	−176.9 (2)
C3—C4—C11—C12	0.8 (3)	C3'—C4'—C11'—C12'	1.5 (3)
N1—C4—C11—C10	5.6 (3)	N1'—C4'—C11'—C10'	4.1 (3)
C3—C4—C11—C10	−176.6 (2)	C3'—C4'—C11'—C10'	−177.4 (2)
O1—C10—C11—C12	35.1 (3)	O1'—C10'—C11'—C12'	31.3 (3)
C6—C10—C11—C12	162.1 (2)	C6'—C10'—C11'—C12'	158.1 (2)
O1—C10—C11—C4	−147.5 (2)	O1'—C10'—C11'—C4'	−149.8 (2)
C6—C10—C11—C4	−20.5 (3)	C6'—C10'—C11'—C4'	−23.0 (3)
F1—C1—C12—C11	−179.2 (2)	F1'—C1'—C12'—C11'	179.4 (2)
C2—C1—C12—C11	0.6 (4)	C2'—C1'—C12'—C11'	0.5 (4)
C4—C11—C12—C1	−0.8 (3)	C4'—C11'—C12'—C1'	−1.2 (3)
C10—C11—C12—C1	176.6 (2)	C10'—C11'—C12'—C1'	177.7 (2)
N1—C5—C13—C14	−21.8 (3)	N1'—C5'—C13'—C14'	−23.9 (3)
C6—C5—C13—C14	99.5 (2)	C6'—C5'—C13'—C14'	97.8 (2)
N1—C5—C13—C18	158.8 (2)	N1'—C5'—C13'—C18'	158.05 (19)
C6—C5—C13—C18	−80.0 (2)	C6'—C5'—C13'—C18'	−80.3 (2)
C18—C13—C14—C15	−0.9 (3)	C18'—C13'—C14'—C15'	−0.8 (3)
C5—C13—C14—C15	179.6 (2)	C5'—C13'—C14'—C15'	−179.0 (2)
C13—C14—C15—C16	0.7 (4)	C13'—C14'—C15'—C16'	0.6 (4)
C14—C15—C16—C17	0.3 (4)	C14'—C15'—C16'—C17'	0.4 (4)
C15—C16—C17—C18	−1.0 (4)	C15'—C16'—C17'—C18'	−1.0 (4)
C16—C17—C18—C13	0.7 (4)	C16'—C17'—C18'—C13'	0.8 (4)
C14—C13—C18—C17	0.2 (3)	C14'—C13'—C18'—C17'	0.2 (3)
C5—C13—C18—C17	179.7 (2)	C5'—C13'—C18'—C17'	178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1′—H1A′···O1^i	0.90	2.55	3.016 (2)	113
N1—H1A···O1′^ii	0.90	2.41	3.034 (2)	127
C7—H72···N1	0.97	2.56	2.942 (3)	103
C7′—H72′···N1′	0.97	2.60	2.965 (3)	102
C3—H3···O1′^ii	0.93	2.60	3.368 (3)	140
C3′—H3′···O1^i	0.93	2.57	3.322 (3)	138
C10—H10···F1′^iii	0.98	2.55	3.523 (3)	174

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

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

Crystal data

C18H17ClFNO	Z = 4
Mr = 317.78	F(000) = 664
Triclinic, P1	Dx = 1.379 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3032 (8) Å	Cell parameters from 5061 reflections
b = 10.5190 (11) Å	θ = 2.8–26.4°
c = 18.1165 (18) Å	µ = 0.26 mm^−1
α = 104.234 (2)°	T = 273 K
β = 92.309 (2)°	Needle, pale yellow
γ = 91.783 (2)°	0.18 × 0.10 × 0.07 mm
V = 1531.1 (3) Å^3

Data collection

Bruker Smart APEX CCD Area Detector diffractometer	4502 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 25°, θmin = 1.2°
ω scans	h = −9→9
14616 measured reflections	k = −12→12
5373 independent reflections	l = −21→21

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.166	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0703P)^2 + 1.0004P] where P = (Fo^2 + 2Fc^2)/3
5373 reflections	(Δ/σ)max < 0.001
397 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.26 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
Cl1	0.92960 (10)	0.66010 (9)	0.84398 (5)	0.0566 (3)
F1	0.7347 (3)	0.87726 (19)	0.83181 (13)	0.0701 (6)
O1	0.7914 (2)	0.45674 (19)	0.94415 (11)	0.0415 (5)
N1	0.3750 (3)	0.4581 (3)	0.87967 (17)	0.0487 (7)
H1A	0.3042	0.4905	0.9151	0.058*
C1	0.6466 (4)	0.7737 (3)	0.84334 (19)	0.0479 (8)
C2	0.4838 (4)	0.7819 (3)	0.8493 (2)	0.0553 (9)
H2	0.4334	0.8577	0.8451	0.066*
C3	0.3949 (4)	0.6776 (3)	0.8616 (2)	0.0527 (8)
H3	0.2837	0.6829	0.8650	0.063*
C4	0.4687 (4)	0.5637 (3)	0.86923 (17)	0.0403 (7)
C5	0.4520 (3)	0.3496 (3)	0.90213 (17)	0.0366 (7)
H5	0.4892	0.3782	0.9559	0.044*
C6	0.5982 (3)	0.3147 (3)	0.85298 (16)	0.0338 (6)
H6	0.5604	0.2964	0.7993	0.041*
C7	0.6867 (4)	0.1955 (3)	0.8648 (2)	0.0482 (8)
H71	0.6090	0.1236	0.8621	0.058*
H72	0.7603	0.1681	0.8242	0.058*
C8	0.7805 (4)	0.2250 (3)	0.9408 (2)	0.0555 (9)
H81	0.7060	0.2360	0.9816	0.067*
H82	0.8470	0.1518	0.9432	0.067*
C9	0.8861 (4)	0.3482 (3)	0.9515 (2)	0.0543 (9)
H91	0.9410	0.3682	1.0015	0.065*
H92	0.9673	0.3341	0.9136	0.065*
C10	0.7167 (3)	0.4332 (3)	0.86925 (16)	0.0337 (6)
H10	0.8009	0.4159	0.8321	0.040*
C11	0.6354 (3)	0.5555 (3)	0.86298 (15)	0.0327 (6)
C12	0.7220 (4)	0.6634 (3)	0.85059 (17)	0.0392 (7)
C13	0.3314 (3)	0.2351 (3)	0.89197 (17)	0.0392 (7)
C14	0.2407 (4)	0.1882 (4)	0.8246 (2)	0.0567 (9)
H14	0.2505	0.2293	0.7850	0.068*
C15	0.1360 (5)	0.0808 (4)	0.8158 (3)	0.0753 (13)
H15	0.0753	0.0499	0.7703	0.090*
C16	0.1206 (5)	0.0195 (4)	0.8734 (4)	0.0861 (16)
H16	0.0500	−0.0532	0.8669	0.103*
C17	0.2091 (6)	0.0650 (4)	0.9410 (3)	0.0839 (14)
H17	0.1986	0.0235	0.9805	0.101*
C18	0.3142 (5)	0.1732 (4)	0.9500 (2)	0.0606 (10)
H18	0.3739	0.2043	0.9958	0.073*
Cl1'	0.04433 (10)	−0.29325 (9)	0.33136 (6)	0.0609 (3)
F1'	0.2427 (3)	−0.51631 (18)	0.32401 (12)	0.0660 (6)
O1'	0.1925 (2)	−0.0045 (2)	0.44105 (12)	0.0443 (5)
N1'	0.6000 (3)	−0.0489 (3)	0.38236 (16)	0.0462 (6)
H1A'	0.6753	−0.0509	0.4192	0.055*
C1'	0.3308 (4)	−0.4014 (3)	0.33710 (18)	0.0458 (8)
C2'	0.4946 (4)	−0.4018 (3)	0.34442 (19)	0.0513 (8)
H2'	0.5464	−0.4805	0.3388	0.062*
C3'	0.5825 (4)	−0.2847 (3)	0.36021 (19)	0.0475 (8)
H3'	0.6944	−0.2848	0.3656	0.057*
C4'	0.5076 (3)	−0.1658 (3)	0.36839 (16)	0.0374 (7)
C5'	0.5232 (3)	0.0770 (3)	0.40480 (17)	0.0366 (7)
H5'	0.4936	0.0913	0.4580	0.044*
C6'	0.3690 (3)	0.0691 (3)	0.35406 (16)	0.0357 (6)
H6'	0.3987	0.0451	0.3008	0.043*
C7'	0.2794 (4)	0.1970 (3)	0.3671 (2)	0.0494 (8)
H71'	0.3551	0.2687	0.3664	0.059*
H72'	0.1989	0.1904	0.3258	0.059*
C8'	0.1976 (4)	0.2266 (3)	0.4423 (2)	0.0569 (9)
H81'	0.2786	0.2502	0.4840	0.068*
H82'	0.1293	0.3007	0.4452	0.068*
C9'	0.0971 (4)	0.1089 (3)	0.4497 (2)	0.0554 (9)
H91'	0.0507	0.1278	0.4993	0.067*
H92'	0.0093	0.0911	0.4111	0.067*
C10'	0.2560 (3)	−0.0396 (3)	0.36702 (16)	0.0353 (6)
H10'	0.1660	−0.0540	0.3288	0.042*
C11'	0.3390 (3)	−0.1657 (3)	0.35975 (16)	0.0353 (6)
C12'	0.2532 (4)	−0.2864 (3)	0.34365 (16)	0.0395 (7)
C13'	0.6398 (3)	0.1867 (3)	0.39848 (18)	0.0411 (7)
C14'	0.7152 (4)	0.1836 (4)	0.3322 (2)	0.0608 (10)
H14'	0.6978	0.1114	0.2908	0.073*
C15'	0.8170 (5)	0.2868 (6)	0.3263 (3)	0.0822 (14)
H15'	0.8674	0.2842	0.2811	0.099*
C16'	0.8436 (5)	0.3942 (5)	0.3880 (4)	0.0899 (17)
H16'	0.9118	0.4640	0.3844	0.108*
C17'	0.7702 (6)	0.3965 (4)	0.4530 (3)	0.0847 (14)
H17'	0.7883	0.4684	0.4946	0.102*
C18'	0.6688 (5)	0.2942 (4)	0.4589 (2)	0.0625 (10)
H18'	0.6190	0.2977	0.5044	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0385 (4)	0.0563 (5)	0.0784 (6)	−0.0145 (4)	0.0045 (4)	0.0251 (4)
F1	0.0830 (15)	0.0433 (11)	0.0924 (16)	−0.0107 (10)	−0.0010 (12)	0.0353 (11)
O1	0.0347 (11)	0.0386 (11)	0.0486 (12)	0.0002 (9)	−0.0057 (9)	0.0073 (9)
N1	0.0320 (14)	0.0428 (15)	0.0722 (19)	0.0041 (11)	0.0135 (12)	0.0139 (13)
C1	0.060 (2)	0.0346 (17)	0.053 (2)	−0.0022 (15)	−0.0037 (16)	0.0181 (14)
C2	0.061 (2)	0.0387 (18)	0.069 (2)	0.0096 (16)	−0.0068 (18)	0.0211 (17)
C3	0.0374 (17)	0.053 (2)	0.068 (2)	0.0097 (15)	−0.0027 (15)	0.0146 (17)
C4	0.0353 (16)	0.0351 (16)	0.0488 (18)	−0.0019 (13)	−0.0008 (13)	0.0080 (13)
C5	0.0328 (15)	0.0337 (15)	0.0404 (16)	−0.0043 (12)	0.0036 (12)	0.0044 (12)
C6	0.0339 (15)	0.0300 (14)	0.0345 (15)	−0.0040 (12)	0.0031 (12)	0.0029 (12)
C7	0.0463 (18)	0.0314 (16)	0.066 (2)	0.0015 (14)	0.0124 (16)	0.0084 (15)
C8	0.057 (2)	0.0427 (19)	0.073 (2)	0.0154 (16)	0.0105 (18)	0.0243 (17)
C9	0.0420 (18)	0.056 (2)	0.068 (2)	0.0089 (16)	−0.0085 (16)	0.0206 (17)
C10	0.0278 (14)	0.0339 (15)	0.0390 (16)	−0.0013 (11)	0.0046 (11)	0.0080 (12)
C11	0.0319 (15)	0.0318 (15)	0.0328 (15)	−0.0010 (11)	0.0002 (11)	0.0055 (11)
C12	0.0374 (16)	0.0401 (16)	0.0390 (16)	−0.0075 (13)	−0.0004 (12)	0.0096 (13)
C13	0.0309 (15)	0.0365 (16)	0.0468 (18)	−0.0047 (12)	0.0096 (13)	0.0032 (13)
C14	0.0419 (19)	0.058 (2)	0.062 (2)	−0.0071 (16)	−0.0011 (16)	0.0009 (17)
C15	0.043 (2)	0.061 (3)	0.101 (3)	−0.0131 (19)	−0.002 (2)	−0.017 (2)
C16	0.046 (2)	0.040 (2)	0.159 (5)	−0.0150 (18)	0.024 (3)	−0.001 (3)
C17	0.073 (3)	0.061 (3)	0.128 (4)	−0.013 (2)	0.033 (3)	0.041 (3)
C18	0.059 (2)	0.058 (2)	0.065 (2)	−0.0111 (18)	0.0131 (18)	0.0164 (18)
Cl1'	0.0392 (5)	0.0492 (5)	0.0919 (7)	−0.0099 (4)	−0.0015 (4)	0.0153 (5)
F1'	0.0824 (15)	0.0336 (10)	0.0803 (15)	−0.0065 (10)	0.0008 (11)	0.0126 (9)
O1'	0.0379 (11)	0.0422 (12)	0.0552 (13)	0.0075 (9)	0.0124 (10)	0.0143 (10)
N1'	0.0319 (13)	0.0462 (15)	0.0635 (17)	−0.0002 (11)	−0.0055 (12)	0.0205 (13)
C1'	0.061 (2)	0.0319 (16)	0.0440 (18)	0.0000 (15)	0.0020 (15)	0.0089 (13)
C2'	0.063 (2)	0.0397 (18)	0.055 (2)	0.0183 (16)	0.0060 (16)	0.0154 (15)
C3'	0.0389 (17)	0.0506 (19)	0.057 (2)	0.0121 (15)	0.0055 (14)	0.0188 (16)
C4'	0.0343 (16)	0.0428 (17)	0.0371 (16)	0.0036 (13)	0.0019 (12)	0.0133 (13)
C5'	0.0349 (15)	0.0387 (16)	0.0394 (16)	−0.0023 (12)	0.0018 (12)	0.0161 (13)
C6'	0.0338 (15)	0.0392 (16)	0.0363 (15)	−0.0005 (12)	−0.0001 (12)	0.0139 (12)
C7'	0.0453 (19)	0.0373 (17)	0.069 (2)	−0.0004 (14)	−0.0086 (16)	0.0224 (16)
C8'	0.057 (2)	0.0350 (17)	0.075 (2)	0.0152 (16)	−0.0022 (18)	0.0052 (16)
C9'	0.0454 (19)	0.049 (2)	0.071 (2)	0.0161 (16)	0.0123 (17)	0.0090 (17)
C10'	0.0307 (15)	0.0361 (15)	0.0389 (16)	0.0014 (12)	−0.0017 (12)	0.0094 (12)
C11'	0.0347 (15)	0.0382 (16)	0.0338 (15)	0.0001 (12)	0.0029 (12)	0.0104 (12)
C12'	0.0416 (17)	0.0390 (17)	0.0374 (16)	−0.0014 (13)	0.0012 (13)	0.0089 (13)
C13'	0.0325 (15)	0.0464 (18)	0.0477 (18)	−0.0041 (13)	−0.0022 (13)	0.0195 (14)
C14'	0.048 (2)	0.077 (3)	0.063 (2)	−0.0046 (18)	0.0067 (17)	0.0266 (19)
C15'	0.049 (2)	0.121 (4)	0.101 (4)	−0.012 (3)	0.006 (2)	0.075 (3)
C16'	0.054 (3)	0.084 (3)	0.152 (5)	−0.028 (2)	−0.029 (3)	0.077 (4)
C17'	0.080 (3)	0.054 (2)	0.117 (4)	−0.026 (2)	−0.020 (3)	0.024 (3)
C18'	0.064 (2)	0.058 (2)	0.063 (2)	−0.0169 (19)	−0.0015 (18)	0.0118 (18)

Geometric parameters (Å, º)

Cl1—C12	1.734 (3)	Cl1'—C12'	1.736 (3)
F1—C1	1.357 (4)	F1'—C1'	1.357 (4)
O1—C10	1.430 (3)	O1'—C10'	1.428 (3)
O1—C9	1.436 (4)	O1'—C9'	1.433 (4)
N1—C4	1.392 (4)	N1'—C4'	1.391 (4)
N1—C5	1.459 (4)	N1'—C5'	1.461 (4)
N1—H1A	0.9000	N1'—H1A'	0.9000
C1—C2	1.365 (5)	C1'—C2'	1.361 (5)
C1—C12	1.366 (4)	C1'—C12'	1.370 (4)
C2—C3	1.371 (5)	C2'—C3'	1.373 (5)
C2—H2	0.9300	C2'—H2'	0.9300
C3—C4	1.397 (4)	C3'—C4'	1.392 (4)
C3—H3	0.9300	C3'—H3'	0.9300
C4—C11	1.397 (4)	C4'—C11'	1.403 (4)
C5—C13	1.512 (4)	C5'—C13'	1.513 (4)
C5—C6	1.535 (4)	C5'—C6'	1.533 (4)
C5—H5	0.9800	C5'—H5'	0.9800
C6—C10	1.526 (4)	C6'—C10'	1.525 (4)
C6—C7	1.528 (4)	C6'—C7'	1.529 (4)
C6—H6	0.9800	C6'—H6'	0.9800
C7—C8	1.512 (5)	C7'—C8'	1.514 (5)
C7—H71	0.9700	C7'—H71'	0.9700
C7—H72	0.9700	C7'—H72'	0.9700
C8—C9	1.509 (5)	C8'—C9'	1.509 (5)
C8—H81	0.9700	C8'—H81'	0.9700
C8—H82	0.9700	C8'—H82'	0.9700
C9—H91	0.9700	C9'—H91'	0.9700
C9—H92	0.9700	C9'—H92'	0.9700
C10—C11	1.497 (4)	C10'—C11'	1.494 (4)
C10—H10	0.9800	C10'—H10'	0.9800
C11—C12	1.394 (4)	C11'—C12'	1.396 (4)
C13—C18	1.376 (5)	C13'—C14'	1.370 (5)
C13—C14	1.381 (5)	C13'—C18'	1.374 (5)
C14—C15	1.377 (5)	C14'—C15'	1.382 (6)
C14—H14	0.9300	C14'—H14'	0.9300
C15—C16	1.362 (7)	C15'—C16'	1.384 (7)
C15—H15	0.9300	C15'—H15'	0.9300
C16—C17	1.374 (7)	C16'—C17'	1.344 (7)
C16—H16	0.9300	C16'—H16'	0.9300
C17—C18	1.385 (5)	C17'—C18'	1.373 (5)
C17—H17	0.9300	C17'—H17'	0.9300
C18—H18	0.9300	C18'—H18'	0.9300
C10—O1—C9	110.8 (2)	C10'—O1'—C9'	111.1 (2)
C4—N1—C5	120.0 (2)	C4'—N1'—C5'	120.2 (2)
C4—N1—H1A	107.3	C4'—N1'—H1A'	107.3
C5—N1—H1A	107.3	C5'—N1'—H1A'	107.3
F1—C1—C2	119.5 (3)	F1'—C1'—C2'	119.7 (3)
F1—C1—C12	119.8 (3)	F1'—C1'—C12'	119.4 (3)
C2—C1—C12	120.6 (3)	C2'—C1'—C12'	120.9 (3)
C1—C2—C3	119.6 (3)	C1'—C2'—C3'	119.3 (3)
C1—C2—H2	120.2	C1'—C2'—H2'	120.3
C3—C2—H2	120.2	C3'—C2'—H2'	120.3
C2—C3—C4	121.0 (3)	C2'—C3'—C4'	121.4 (3)
C2—C3—H3	119.5	C2'—C3'—H3'	119.3
C4—C3—H3	119.5	C4'—C3'—H3'	119.3
N1—C4—C3	119.8 (3)	N1'—C4'—C3'	120.1 (3)
N1—C4—C11	120.9 (3)	N1'—C4'—C11'	120.6 (3)
C3—C4—C11	119.3 (3)	C3'—C4'—C11'	119.3 (3)
N1—C5—C13	109.5 (2)	N1'—C5'—C13'	109.9 (2)
N1—C5—C6	107.5 (2)	N1'—C5'—C6'	107.9 (2)
C13—C5—C6	112.4 (2)	C13'—C5'—C6'	112.6 (2)
N1—C5—H5	109.1	N1'—C5'—H5'	108.8
C13—C5—H5	109.1	C13'—C5'—H5'	108.8
C6—C5—H5	109.1	C6'—C5'—H5'	108.8
C10—C6—C7	109.0 (2)	C10'—C6'—C7'	109.2 (2)
C10—C6—C5	108.9 (2)	C10'—C6'—C5'	108.8 (2)
C7—C6—C5	114.6 (2)	C7'—C6'—C5'	114.4 (2)
C10—C6—H6	108.0	C10'—C6'—H6'	108.1
C7—C6—H6	108.0	C7'—C6'—H6'	108.1
C5—C6—H6	108.0	C5'—C6'—H6'	108.1
C8—C7—C6	111.9 (3)	C8'—C7'—C6'	111.8 (3)
C8—C7—H71	109.2	C8'—C7'—H71'	109.3
C6—C7—H71	109.2	C6'—C7'—H71'	109.3
C8—C7—H72	109.2	C8'—C7'—H72'	109.3
C6—C7—H72	109.2	C6'—C7'—H72'	109.3
H71—C7—H72	107.9	H71'—C7'—H72'	107.9
C9—C8—C7	110.6 (3)	C9'—C8'—C7'	110.5 (3)
C9—C8—H81	109.5	C9'—C8'—H81'	109.6
C7—C8—H81	109.5	C7'—C8'—H81'	109.6
C9—C8—H82	109.5	C9'—C8'—H82'	109.6
C7—C8—H82	109.5	C7'—C8'—H82'	109.6
H81—C8—H82	108.1	H81'—C8'—H82'	108.1
O1—C9—C8	110.6 (3)	O1'—C9'—C8'	111.1 (3)
O1—C9—H91	109.5	O1'—C9'—H91'	109.4
C8—C9—H91	109.5	C8'—C9'—H91'	109.4
O1—C9—H92	109.5	O1'—C9'—H92'	109.4
C8—C9—H92	109.5	C8'—C9'—H92'	109.4
H91—C9—H92	108.1	H91'—C9'—H92'	108.0
O1—C10—C11	107.9 (2)	O1'—C10'—C11'	107.7 (2)
O1—C10—C6	111.3 (2)	O1'—C10'—C6'	111.3 (2)
C11—C10—C6	111.7 (2)	C11'—C10'—C6'	112.1 (2)
O1—C10—H10	108.6	O1'—C10'—H10'	108.6
C11—C10—H10	108.6	C11'—C10'—H10'	108.6
C6—C10—H10	108.6	C6'—C10'—H10'	108.6
C12—C11—C4	118.1 (3)	C12'—C11'—C4'	118.0 (3)
C12—C11—C10	121.6 (2)	C12'—C11'—C10'	121.8 (3)
C4—C11—C10	120.3 (2)	C4'—C11'—C10'	120.2 (3)
C1—C12—C11	121.4 (3)	C1'—C12'—C11'	121.2 (3)
C1—C12—Cl1	118.4 (2)	C1'—C12'—Cl1'	118.6 (2)
C11—C12—Cl1	120.2 (2)	C11'—C12'—Cl1'	120.2 (2)
C18—C13—C14	118.7 (3)	C14'—C13'—C18'	118.4 (3)
C18—C13—C5	119.7 (3)	C14'—C13'—C5'	121.2 (3)
C14—C13—C5	121.5 (3)	C18'—C13'—C5'	120.4 (3)
C15—C14—C13	120.4 (4)	C13'—C14'—C15'	120.6 (4)
C15—C14—H14	119.8	C13'—C14'—H14'	119.7
C13—C14—H14	119.8	C15'—C14'—H14'	119.7
C16—C15—C14	120.5 (4)	C14'—C15'—C16'	119.8 (4)
C16—C15—H15	119.8	C14'—C15'—H15'	120.1
C14—C15—H15	119.8	C16'—C15'—H15'	120.1
C15—C16—C17	120.1 (4)	C17'—C16'—C15'	119.4 (4)
C15—C16—H16	119.9	C17'—C16'—H16'	120.3
C17—C16—H16	119.9	C15'—C16'—H16'	120.3
C16—C17—C18	119.5 (4)	C16'—C17'—C18'	120.8 (5)
C16—C17—H17	120.3	C16'—C17'—H17'	119.6
C18—C17—H17	120.3	C18'—C17'—H17'	119.6
C13—C18—C17	120.8 (4)	C17'—C18'—C13'	121.0 (4)
C13—C18—H18	119.6	C17'—C18'—H18'	119.5
C17—C18—H18	119.6	C13'—C18'—H18'	119.5
F1—C1—C2—C3	−179.5 (3)	F1'—C1'—C2'—C3'	−177.8 (3)
C12—C1—C2—C3	−1.0 (5)	C12'—C1'—C2'—C3'	1.4 (5)
C1—C2—C3—C4	0.9 (5)	C1'—C2'—C3'—C4'	−0.4 (5)
C5—N1—C4—C3	−168.2 (3)	C5'—N1'—C4'—C3'	−168.7 (3)
C5—N1—C4—C11	14.5 (4)	C5'—N1'—C4'—C11'	13.5 (4)
C2—C3—C4—N1	−178.3 (3)	C2'—C3'—C4'—N1'	−178.3 (3)
C2—C3—C4—C11	−1.0 (5)	C2'—C3'—C4'—C11'	−0.5 (5)
C4—N1—C5—C13	−167.0 (3)	C4'—N1'—C5'—C13'	−166.7 (3)
C4—N1—C5—C6	−44.6 (4)	C4'—N1'—C5'—C6'	−43.6 (3)
N1—C5—C6—C10	61.9 (3)	N1'—C5'—C6'—C10'	61.2 (3)
C13—C5—C6—C10	−177.5 (2)	C13'—C5'—C6'—C10'	−177.4 (2)
N1—C5—C6—C7	−175.7 (2)	N1'—C5'—C6'—C7'	−176.3 (2)
C13—C5—C6—C7	−55.1 (3)	C13'—C5'—C6'—C7'	−54.9 (3)
C10—C6—C7—C8	50.4 (3)	C10'—C6'—C7'—C8'	50.4 (3)
C5—C6—C7—C8	−72.0 (3)	C5'—C6'—C7'—C8'	−71.8 (3)
C6—C7—C8—C9	−51.0 (4)	C6'—C7'—C8'—C9'	−50.8 (4)
C10—O1—C9—C8	−62.7 (3)	C10'—O1'—C9'—C8'	−62.1 (3)
C7—C8—C9—O1	56.2 (4)	C7'—C8'—C9'—O1'	55.8 (4)
C9—O1—C10—C11	−173.9 (2)	C9'—O1'—C10'—C11'	−174.2 (2)
C9—O1—C10—C6	63.2 (3)	C9'—O1'—C10'—C6'	62.6 (3)
C7—C6—C10—O1	−56.1 (3)	C7'—C6'—C10'—O1'	−55.9 (3)
C5—C6—C10—O1	69.6 (3)	C5'—C6'—C10'—O1'	69.7 (3)
C7—C6—C10—C11	−176.8 (2)	C7'—C6'—C10'—C11'	−176.6 (2)
C5—C6—C10—C11	−51.0 (3)	C5'—C6'—C10'—C11'	−51.0 (3)
N1—C4—C11—C12	178.4 (3)	N1'—C4'—C11'—C12'	178.2 (3)
C3—C4—C11—C12	1.1 (4)	C3'—C4'—C11'—C12'	0.4 (4)
N1—C4—C11—C10	−1.4 (4)	N1'—C4'—C11'—C10'	−1.2 (4)
C3—C4—C11—C10	−178.7 (3)	C3'—C4'—C11'—C10'	−179.0 (3)
O1—C10—C11—C12	78.7 (3)	O1'—C10'—C11'—C12'	79.2 (3)
C6—C10—C11—C12	−158.7 (3)	C6'—C10'—C11'—C12'	−158.0 (3)
O1—C10—C11—C4	−101.5 (3)	O1'—C10'—C11'—C4'	−101.3 (3)
C6—C10—C11—C4	21.1 (4)	C6'—C10'—C11'—C4'	21.4 (4)
F1—C1—C12—C11	179.6 (3)	F1'—C1'—C12'—C11'	177.7 (3)
C2—C1—C12—C11	1.1 (5)	C2'—C1'—C12'—C11'	−1.5 (5)
F1—C1—C12—Cl1	−0.5 (4)	F1'—C1'—C12'—Cl1'	−2.4 (4)
C2—C1—C12—Cl1	−178.9 (3)	C2'—C1'—C12'—Cl1'	178.4 (3)
C4—C11—C12—C1	−1.1 (4)	C4'—C11'—C12'—C1'	0.5 (4)
C10—C11—C12—C1	178.6 (3)	C10'—C11'—C12'—C1'	180.0 (3)
C4—C11—C12—Cl1	178.9 (2)	C4'—C11'—C12'—Cl1'	−179.4 (2)
C10—C11—C12—Cl1	−1.3 (4)	C10'—C11'—C12'—Cl1'	0.1 (4)
N1—C5—C13—C18	−131.6 (3)	N1'—C5'—C13'—C14'	53.6 (4)
C6—C5—C13—C18	109.0 (3)	C6'—C5'—C13'—C14'	−66.8 (4)
N1—C5—C13—C14	50.4 (4)	N1'—C5'—C13'—C18'	−128.4 (3)
C6—C5—C13—C14	−69.0 (4)	C6'—C5'—C13'—C18'	111.3 (3)
C18—C13—C14—C15	−0.4 (5)	C18'—C13'—C14'—C15'	−0.5 (5)
C5—C13—C14—C15	177.6 (3)	C5'—C13'—C14'—C15'	177.6 (3)
C13—C14—C15—C16	−0.1 (6)	C13'—C14'—C15'—C16'	0.3 (6)
C14—C15—C16—C17	0.4 (6)	C14'—C15'—C16'—C17'	0.1 (7)
C15—C16—C17—C18	−0.2 (7)	C15'—C16'—C17'—C18'	−0.3 (7)
C14—C13—C18—C17	0.6 (5)	C16'—C17'—C18'—C13'	0.1 (7)
C5—C13—C18—C17	−177.5 (3)	C14'—C13'—C18'—C17'	0.3 (6)
C16—C17—C18—C13	−0.3 (6)	C5'—C13'—C18'—C17'	−177.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cl1	0.98	2.71	3.061 (3)	102
C10′—H10′···Cl1′	0.98	2.70	3.065 (3)	103