Four 1-naphthyl-substituted tetra­hydro-1,4-ep­oxy-1-benzazepines: hydrogen-bonded structures in one, two and three dimensions

(2S*,4R*)-2-exo-(1-Naphthyl)-2,3,4,5-tetra­hydro-1H-1,4-epoxy-1-benzazepine, C₂₀H₁₇NO, (I), crystallizes with Z′ = 2 in the space group P2₁; the two independent mol­ecules have the same absolute configuration, although this configuration is indeterminate. The mol­ecules of each type are linked by a combination of C—H...O and C—H...π(arene) hydrogen bonds to form two independent sheets, each containing only one type of mol­ecule. (2SR,4RS)-7-Methyl-2-exo-(1-naphthyl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₂₁H₁₉NO, (II), crystallizes as a true racemate in the space group P2₁/c, and a combination of C—H...N, C—H...O and C—H...π(arene) hydrogen bonds links the mol­ecules into sheets, each containing equal numbers of the two enantio­morphs. (2S*,4R*)-2-exo-(1-Naphthyl)-7-trifluoro­methyl-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₂₁H₁₆F₃NO₂, (III), crystallizes as a single enantio­morph, as for (I), but now with Z′ = 1 in the space group P2₁2₁2₁; again, the absolute configuration is indeterminate. A single C—H...π(arene) hydrogen bond links the mol­ecules of (III) into simple chains. (2S,4R)-8-Chloro-9-methyl-2-exo-(1-naphthyl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₂₁H₁₈ClNO, (IV), crystallizes as a single enanti­omorph of well defined configuration, in the space group P2₁2₁2₁, where two independent C—H...π(arene) hydrogen bonds link the mol­ecules into a single three-dimensional framework structure.

S1. Comment

We report here the structures of four substituted 2-exo-(1-naphthyl)-2,3,4,5-tetrahydro-1H-1,4-epoxy-1- benzazepines, compounds (I)-(IV), carrying different simple substituents in the fused aryl ring (Figs. 1–4), and we compare these with the 7-chloro analogue compound, (V) (Gómez et al., 2008). The work reported here is a continuation of an extensive study of benzazepine derivatives of this general type, involving wide variations in both the aromatic moiety fused to the azepine ring and the substituent present at position 2 (Acosta et al., 2008, 2010a,b; Gómez et al., 2008, 2009, 2010; Blanco et al., 2008, 2009; Palma et al., 2009).

The compounds reported here were all prepared using appropriate variations of the synthetic method described previously (Acosta et al., 2008), in which an N-substituted 2-allylaniline is oxidized with aqueous hydrogen peroxide solution in the presence of sodium tungstate as catalyst, yielding the fused tricyclic product in a one-pot process. Although the products all contain two stereogenic C atoms, there are no reagents employed in the synthetic procedure which are capable of inducing stereoselectivity or enantioselectivity in the final products. Despite this, only (II) crystallizes as a racemic mixture of (2S,4R) and (2R,4S) enantiomers, in space group P2₁/c. In contrast, (IV) crystallizes as a single enantiomer in space group P2₁2₁2₁, with the configuration (2S,4R) in the crystal selected for data collection, as shown by the values of the Flack x parameter (Flack, 1983) and the Hooft y parameter (Hooft et al., 2008), 0.02 (7) and 0.01 (3), respectively. Compounds (I), where Z' = 2, and (III) crystallize in the Sohnke space groups P2₁ and P2₁2₁2₁, respectively, indicating the presence of only a single enantiomer in a given crystal, provided that inversion twinning is absent. However, in the absence of significant resonant scattering, the absolute stereochemistry of (I) and (III) remains unknown, although the relative stereochemistry at C2 and C4 is unambiguous.

The analogous compound, (V) (Gómez et al., 2008), which differs from (II) only in the notional replacement of the 7-methyl substituent in (II) by a 7-chloro substituent in (V), is neither isomorphous nor isostructural with the racemic compound, (II). Instead, (V) crystallizes as a single enantiomorph in space group P2₁2₁2₁, having the (2S,4R) configuration in the crystal selected for data collection, just as for (IV).

These observations on (IV) and (V) prompted us to review briefly the crystallization characteristics of other compounds of this general type. Including the four compounds reported here, we have now determined the structures of 35 examples, and of these, 21 crystallize as genuine racemates in space groups containing reflection and/or inversion operators. A further five examples crystallize as inversion twins. In two of these, both in space group P2₁2₁2₁, the twin fractions are equal to 0.5 within experimental uncertainly, indicating that these two compounds are also racemic, but in three other examples of inversion twins, all of them in space group P2₁, one enantiomorph predominates in the crystals selected for data collection. However, in addition to (II) and (V), there are three other examples, namely compounds (VI) (Gómez et al., 2009), (VII) (Gómez et al., 2008) and (VIII) (Blanco et al., 2008), which all crystallize as single enantiomorphs, in space group P2₁ for compounds (VI) and (VIII) and in P2₁2₁2₁ for compound (VII), and which all have the (2S,4R) configuration in the crystals used for data collection. Finally, there are four examples, including (I) and (III) reported here, for which the absolute configuration could not be established because of insignificant resonant scattering. Hence, overall, we have 21 true racemates, five single enantiomers, five inversion twins and four structures where the configuration is indeterminate. To be sure, five examples crystallizing as single enantiomorphs from a total population of 35 compounds is only a small sample, but it is interesting that the absolute configuration was unambiguously established as (2S,4R) in each of these five examples.

The molecular conformations of (I), (II) and (IV) are fully defined by the shapes of the fused ring system and the orientation of the 2-(1-naphthyl) substituent relative to the fused system. In (III), full definition of the conformation also requires specification of the orientation of the CF₃O– substituent. The shapes of the fused ring systems are conveniently defined in terms of the ring-puckering parameters (Cremer & Pople, 1975) for the fused five-and six-membered heterocyclic rings, which are compared in Table 1 with the corresponding values for the related compound, (V) (Gómez et al., 2008). These parameters not only confirm that the reference molecules selected for (I)-(IV) all have the same absolute configuration, as do the two independent molecules in (I), but, when compared with those of the previously reported analogues, they show that the shape of the fused heterocyclic ring system is essentially invariant to the nature of the peripheral substituents. On the other hand, the naphthyl group appears to adopt one of two quite distinct orientations, with the naphthyl group in (II) having an orientation which is almost orthogonal to those in (I) and (III)–(V) (Table 1). In all of (I)–(V), one or other of the rings in the naphthyl substituent acts as an acceptor in C—H···π hydrogen bonds (see below), and these interactions may be influential in determining the orientation of this substituent. In (III), the dihedral angle between the planes C5a/C6–C9/C9a and C7/O7/C71 is 86.9 (2)°.

Just as (I)–(IV) all exhibit different crystallization characteristics, so too they all adopt different modes of supramolecular aggregation, with hydrogen-bonded systems which are one-dimensional in (II), two-dimensional in (I) and (II), and three-dimensional in (IV). The dominant intermolecular interactions (Table 2) are of C—H···O and C—H···π(arene) types, with a single occurrence of a C—H···N hydrogen bond in (II). However, aromatic π–π stacking interactions are absent from the structures of (I)–(V). We have excluded from consideration as being structurally significant those C—H···π(arene) contacts having an H···Cg distance greater than 2.85 Å, a C···Cg distance greater than 3.70 Å or a C—H···Cg angle less than 130° (Cg represents a ring centroid). This last is consistent with a recent recommendation for intermolecular hydrogen bonds, based on database analysis and intermolecular energy calculations (Wood et al., 2009) for conventional hydrogen bonds of the general type D—H···A, where D represents C, N or O and A represents N or O.

In (I), each of the two independent molecules forms a hydrogen-bonded sheet. These two sheets are similar in overall architecture but different in detail, although there are no significant direction-specific interactions between adjacent sheets. Molecules of type 1, containing atom N11 (Fig. 1a), are linked by a combination of one C—H···O hydrogen bond and one C—H···π(arene) hydrogen bond, having atoms C14 and C18 as the donors, into a sheet lying parallel to (001) in the domain -0.3 < z < 0.3 and containing the 2₁ screw axes at z = 0 (Fig. 5). Molecules of type 2, containing atom N21, are also linked into sheets, but now by means of three hydrogen bonds, one of C—H···O type and two of C—H···π(arene) type having atoms C24, C26 and C28 as the donors. This sheet also lies parallel to (001), in the domain 0.2 < z < 0.8, and it contains the 2₁ screw axes at z = 1/2 (Fig. 6). The corresponding pairs of intermolecular interactions involving atoms C14 and C24 on the one hand, and atoms C18 and C28 on the other, both have recognisably similar sets of dimensions, although with differences which are sufficient to preclude the possibility of any additional crystallographic symmetry. However, the corresponding pair of contacts involving atoms C16 and C26 has very different dimensions, such that while the contact involving C26 must be regarded as a structurally significant hydrogen bond, that involving C16, by contrast, is probably no more than an adventitious short contact.

The aggregation in (II) is determined by a combination of C—H···N, C—H···O and C—H···π(arene) hydrogen bonds which link molecules related by the 2₁ screw axis along (1/2, y, 3/4) into a complex chain running parallel to the [010] direction (Fig. 7). Chains of this type are linked via a centrosymmetric motif containing inversion-related pairs of a second, weaker, C—H···π(arene) hydrogen bond, so forming a sheet parallel to (100) (Fig. 7).

The hydrogen-bonded structure of (III) is very simple, as a single C—H···π(arene) hydrogen bond links molecules related by the 2₁ screw axis along (1/4, 1/2, z) into simple chains parallel to [001] (Fig. 8). There are no direction-specific interactions between adjacent chains so that, unlike the hydrogen-bonded structures of (I) and (II), that of (III) is only one-dimensional.

In the crystal structure of (IV), just two independent C—H···π(arene) hydrogen bonds link the molecules into a continuous three-dimensional framework structure. It is convenient to analyse the formation of this structure in terms of the actions of the individual hydrogen bonds, firstly when each is acting alone and then when they act in combination. Acting alone, the hydrogen bond having atom C6 as the donor links molecules related by the 2₁ screw axis along (3/4, 1/2, z) into a chain running parallel to [001] (Fig. 9), and that having atom C27 as the donor links molecules related by the 2₁ screw axis along (x, 3/4, 1/2) into a second chain, this time running parallel to [100] (Fig. 10). Finally, the combination of these two hydrogen bonds, acting alternately, generates a chain running parallel to the [010] direction (Fig. 11). The combination of these distinct chain motifs parallel to [100], [010] and [001], respectively, suffices to generate a continuous three-dimensional structure.

Although different donor atoms and acceptor rings are involved in the hydrogen bonding in (III) and (IV), nevertheless the overall architectures of the chains parallel to [001] in these two compounds are strikingly similar, as shown in Figs. 8 and 9, which also illustrate the rather different values of the cell-vector ratio c/b in (III) and (IV).

In (V) (Gómez et al., 2008), a combination of one C—H···O and two C—H···π(arene) hydrogen bonds links the molecules into a continuous three-dimensional structure which is significantly different from that formed by (IV). Whereas the three-dimensional structure of (IV) is best analysed in terms of three separate one-dimensional substructures, in the hydrogen-bonded structure of (V) two substructures can be identified. The C—H···O hydrogen bond in (V) forms a one-dimensional substructure, while the two C—H···π(arene) hydrogen bonds form a two-dimensional substructure.

S2. Experimental

For the preparation of (I)–(IV), 30% aqueous hydrogen peroxide solution (0.30 mol) was added dropwise to sodium tungstate dihydrate (7 mol%), and then this mixture was added to a stirred solution of the appropriately substituted 2-allyl-N-(naphth-1-ylmethyl)aniline (0.10 mol) in methanol (20 ml). The resulting mixtures were then stirred at ambient temperature for 72 h. Each mixture was filtered and the solvent removed under reduced pressure. Toluene (25 ml) was added to the organic residue and the resulting solution was heated at 333 K for periods ranging from 6 to 24 h. After cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified by chromatography on silica gel using heptane–ethyl acetate as eluent (compositions ranged from 40:1 to 15:1 v/v). Crystallization from heptane gave colourless crystals of (I)–(IV) suitable for single-crystal X-ray diffraction. Analysis for (I): m.p. 402–403 K, yield 67%; MS (70 eV) m/z (%): 287 (M+, 61), 270 (38), 258 (18), 244 (22), 154 (100), 153 (80), 127 (18), 105 (38), 104 (55). Analysis for (II): m.p. 463–464 K, yield 65%; MS (70 eV) m/z (%): 301 (M+, 56), 284 (25), 272 (16), 258 (16), 154 (60), 153 (64), 127 (16), 119 (81), 118 (100). Analysis for (III): m.p. 397–398 K, yield 70%; MS (70 eV) m/z (%): 371 (M+, 24), 354 (14), 342 (7), 328 (7), 189 (33), 188 (51), 154 (100), 153 (70), 127 (14). Analysis for (IV): m.p. 453–454 K, yield 63%; MS (70 eV) m/z (%): 335 (M+, 35Cl, 13), 318 (7), 306 (3), 292 (3), 154 (100), 153 (64), 152 (25), 127 (11).

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (aliphatic CH) and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. Compound (IV) crystallized as a single enantiomorph in space group P2₁2₁2₁ and, for the crystal selected for data collection, the (2S,4R) configuration was established by means of the Flack x parameter (Flack, 1983) of 0.02 (7) and the Hooft y parameter (Hooft et al., 2008) of 0.01 (3), calculated for 1581 Bijvoet pairs (99% coverage). Compound (II) crystallized as a racemic mixture in the centrosymmetric space group P2₁/c and the reference molecule was selected as one having the (2S,4R) configuration, to be consistent with (IV). In the absence of significant resonant scattering for (I) and (III), Friedel-equivalent reflections were merged prior to the final refinements and again the reference molecules were specified as having the (2S,4R) configuration. The two independent molecules of (I) have the same configuration.

Computing details

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The two independent molecules of (I), showing the atom-labelling scheme. (a) A type 1 molecule and (b) a type 2 molecule, both shown as the (2S,4R) enantiomorph. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The (2S,4R) enantiomorph of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The molecular structure of (III), showing the atom-labelling scheme. The (2S,4R) enantiomorph is shown and the displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. The molecular structure of (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (001) and containing only type 1 molecules. All molecules are shown in the (2S,4R) configuration and H atoms not involved in the motifs shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (001) and containing only type 2 molecules. All molecules are shown in the (2S,4R) configuration and H atoms not involved in the motifs shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (100). H atoms not involved in the motifs shown have been omitted.
	Fig. 8. Part of the crystal structure of (III), showing the formation of a hydrogen-bonded chain parallel to [001]. H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1/2 - x, 1 - y, 1/2 + z), (x, y, 1 + z), (1/2 - x, 1 - y, -1/2 + z) and (x, y, -1 + z), respectively.
	Fig. 9. Part of the crystal structure of (IV), showing the formation of a hydrogen-bonded chain parallel to [001] and containing only one type of hydrogen bond. H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (3/2 - x, 1 - y, 1/2 + z), (x, y, 1 + z), (3/2 - x, 1 - y, -1/2 + z) and (x, y, -1 + z), respectively.
	Fig. 10. Part of the crystal structure of (IV), showing the formation of a hydrogen-bonded chain parallel to [100] and containing only one type of hydrogen bond. H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1/2 + x, 3/2 - y, 1 - z), (1 + x, y, z), (-1/2 + x, 3/2 - y, 1 - z) and (- 1 + x, y, z), respectively.
	Fig. 11. A stereoview of part of the crystal structure of (IV), showing the formation of a hydrogen-bonded chain parallel to [010] and containing two types of hydrogen bond. H atoms not involved in the motifs shown have been omitted.

(I) (2S*,4R*)-2-exo-(1-Naphthyl)-2,3,4,5-tetrahydro- 1H-1,4-epoxy-1-benzazepine

Crystal data

C20H17NO	F(000) = 608
Mr = 287.35	Dx = 1.309 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3589 reflections
a = 8.974 (4) Å	θ = 3.4–27.5°
b = 7.1817 (8) Å	µ = 0.08 mm^−1
c = 22.718 (9) Å	T = 120 K
β = 95.39 (3)°	Block, colourless
V = 1457.7 (9) Å^3	0.38 × 0.21 × 0.14 mm
Z = 4

Data collection

Bruker-Nonius KappaCCD area-detector diffractometer	3589 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3064 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.961, Tmax = 0.989	l = −29→29
20821 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0359P)^2 + 0.5587P] where P = (Fo^2 + 2Fc^2)/3
3589 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 0.22 e Å^−3
1 restraint	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.3423 (2)	0.4475 (3)	0.07890 (9)	0.0166 (5)
C12	0.4368 (3)	0.4073 (4)	0.13436 (11)	0.0150 (5)
H12	0.3735	0.4095	0.1683	0.018*
C13	0.4935 (3)	0.2063 (4)	0.12554 (12)	0.0179 (6)
H13A	0.6033	0.1980	0.1349	0.021*
H13B	0.4441	0.1167	0.1505	0.021*
C14	0.4495 (3)	0.1705 (4)	0.05996 (11)	0.0183 (6)
H14	0.5334	0.1086	0.0415	0.022*
C15	0.3058 (3)	0.0619 (4)	0.04667 (12)	0.0190 (6)
H15A	0.2955	0.0234	0.0046	0.023*
H15B	0.3085	−0.0518	0.0714	0.023*
C15a	0.1745 (3)	0.1798 (4)	0.05915 (11)	0.0174 (6)
C16	0.0292 (3)	0.1124 (4)	0.05410 (12)	0.0200 (6)
H16	0.0100	−0.0106	0.0399	0.024*
C17	−0.0879 (3)	0.2206 (4)	0.06929 (12)	0.0228 (6)
H17	−0.1869	0.1725	0.0652	0.027*
C18	−0.0612 (3)	0.3999 (4)	0.09057 (12)	0.0220 (6)
H18	−0.1410	0.4726	0.1030	0.026*
C19	0.0808 (3)	0.4714 (4)	0.09355 (11)	0.0200 (6)
H19	0.0990	0.5956	0.1067	0.024*
C19a	0.1970 (3)	0.3633 (4)	0.07757 (11)	0.0157 (5)
O114	0.4234 (2)	0.3547 (3)	0.03570 (8)	0.0181 (4)
C121	0.5591 (3)	0.5510 (4)	0.14434 (11)	0.0160 (5)
C122	0.5836 (3)	0.6756 (4)	0.10117 (12)	0.0174 (6)
H122	0.5221	0.6716	0.0648	0.021*
C123	0.6970 (3)	0.8094 (4)	0.10896 (12)	0.0194 (6)
H123	0.7140	0.8916	0.0775	0.023*
C124	0.7827 (3)	0.8224 (4)	0.16129 (12)	0.0211 (6)
H124	0.8568	0.9169	0.1668	0.025*
C125	0.7626 (3)	0.6972 (4)	0.20730 (12)	0.0184 (6)
C126	0.8508 (3)	0.7083 (4)	0.26199 (13)	0.0247 (7)
H126	0.9249	0.8026	0.2678	0.030*
C127	0.8318 (3)	0.5866 (5)	0.30637 (12)	0.0257 (7)
H127	0.8931	0.5950	0.3427	0.031*
C128	0.7216 (3)	0.4489 (5)	0.29844 (12)	0.0234 (6)
H128	0.7081	0.3646	0.3297	0.028*
C129	0.6334 (3)	0.4340 (4)	0.24654 (12)	0.0201 (6)
H129	0.5594	0.3391	0.2420	0.024*
C130	0.6506 (3)	0.5582 (4)	0.19935 (11)	0.0157 (5)
N21	0.6826 (2)	0.0780 (3)	0.41048 (9)	0.0179 (5)
C22	0.5817 (3)	−0.0150 (4)	0.36486 (11)	0.0170 (6)
H22	0.6403	−0.0583	0.3321	0.020*
C23	0.5237 (3)	−0.1866 (4)	0.39770 (12)	0.0202 (6)
H23A	0.4136	−0.1983	0.3903	0.024*
H23B	0.5709	−0.3029	0.3852	0.024*
C24	0.5703 (3)	−0.1441 (5)	0.46245 (12)	0.0227 (6)
H24	0.4864	−0.1699	0.4873	0.027*
C25	0.7106 (3)	−0.2452 (5)	0.48618 (13)	0.0239 (6)
H25A	0.7293	−0.2243	0.5293	0.029*
H25B	0.6983	−0.3806	0.4792	0.029*
C25a	0.8409 (3)	−0.1743 (4)	0.45562 (11)	0.0198 (6)
C26	0.9804 (3)	−0.2585 (4)	0.46314 (12)	0.0215 (6)
H26	0.9949	−0.3634	0.4885	0.026*
C27	1.0980 (3)	−0.1927 (5)	0.43451 (12)	0.0245 (7)
H27	1.1933	−0.2510	0.4405	0.029*
C28	1.0775 (3)	−0.0422 (5)	0.39710 (12)	0.0243 (6)
H28	1.1582	0.0020	0.3767	0.029*
C29	0.9405 (3)	0.0444 (4)	0.38918 (12)	0.0224 (6)
H29	0.9265	0.1482	0.3633	0.027*
C29a	0.8234 (3)	−0.0196 (4)	0.41879 (11)	0.0185 (6)
O214	0.6063 (2)	0.0523 (3)	0.46288 (8)	0.0216 (4)
C221	0.4559 (3)	0.1097 (4)	0.33997 (12)	0.0168 (6)
C222	0.4260 (3)	0.2766 (4)	0.36491 (12)	0.0202 (6)
H222	0.4867	0.3176	0.3989	0.024*
C223	0.3072 (3)	0.3891 (4)	0.34129 (13)	0.0227 (6)
H223	0.2878	0.5040	0.3598	0.027*
C224	0.2202 (3)	0.3358 (4)	0.29256 (12)	0.0222 (6)
H224	0.1416	0.4146	0.2765	0.027*
C225	0.2453 (3)	0.1635 (4)	0.26527 (12)	0.0180 (6)
C226	0.1544 (3)	0.1027 (4)	0.21496 (12)	0.0204 (6)
H226	0.0756	0.1802	0.1983	0.024*
C227	0.1780 (3)	−0.0653 (4)	0.18995 (12)	0.0218 (6)
H227	0.1153	−0.1051	0.1563	0.026*
C228	0.2941 (3)	−0.1793 (5)	0.21368 (12)	0.0249 (6)
H228	0.3098	−0.2967	0.1960	0.030*
C229	0.3854 (3)	−0.1248 (4)	0.26182 (12)	0.0205 (6)
H229	0.4642	−0.2043	0.2772	0.025*
C230	0.3644 (3)	0.0483 (4)	0.28916 (11)	0.0164 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0142 (11)	0.0192 (12)	0.0160 (10)	0.0004 (10)	−0.0002 (8)	−0.0013 (9)
C12	0.0148 (12)	0.0139 (13)	0.0162 (12)	−0.0003 (11)	0.0011 (10)	0.0014 (10)
C13	0.0161 (13)	0.0147 (14)	0.0228 (14)	−0.0010 (11)	0.0011 (11)	−0.0003 (11)
C14	0.0173 (13)	0.0181 (14)	0.0193 (13)	0.0021 (12)	0.0009 (10)	−0.0012 (11)
C15	0.0195 (13)	0.0158 (13)	0.0216 (13)	−0.0006 (12)	0.0012 (10)	−0.0033 (12)
C15a	0.0177 (13)	0.0184 (14)	0.0151 (12)	−0.0014 (12)	−0.0032 (10)	0.0006 (11)
C16	0.0203 (14)	0.0170 (14)	0.0219 (13)	−0.0048 (12)	−0.0023 (11)	0.0011 (11)
C17	0.0161 (14)	0.0255 (17)	0.0262 (15)	−0.0037 (13)	−0.0016 (11)	0.0067 (13)
C18	0.0162 (13)	0.0240 (16)	0.0253 (14)	0.0037 (12)	−0.0012 (10)	0.0013 (12)
C19	0.0210 (14)	0.0175 (14)	0.0207 (13)	0.0017 (12)	−0.0024 (11)	−0.0014 (12)
C19a	0.0144 (13)	0.0177 (14)	0.0144 (12)	−0.0003 (11)	−0.0019 (9)	0.0018 (11)
O114	0.0188 (9)	0.0185 (10)	0.0173 (9)	0.0007 (8)	0.0028 (7)	0.0014 (8)
C121	0.0138 (12)	0.0152 (13)	0.0192 (13)	0.0020 (11)	0.0029 (10)	−0.0023 (11)
C122	0.0154 (13)	0.0155 (13)	0.0205 (13)	0.0027 (11)	−0.0016 (10)	−0.0003 (11)
C123	0.0194 (14)	0.0128 (13)	0.0258 (14)	0.0009 (11)	0.0011 (11)	0.0038 (11)
C124	0.0186 (14)	0.0130 (13)	0.0318 (15)	−0.0017 (12)	0.0035 (11)	−0.0021 (12)
C125	0.0158 (13)	0.0182 (14)	0.0213 (13)	0.0019 (12)	0.0018 (10)	−0.0045 (11)
C126	0.0195 (14)	0.0282 (17)	0.0263 (15)	−0.0041 (13)	0.0012 (11)	−0.0072 (13)
C127	0.0197 (14)	0.0375 (19)	0.0191 (14)	−0.0014 (14)	−0.0031 (11)	−0.0042 (13)
C128	0.0225 (14)	0.0290 (16)	0.0185 (13)	0.0009 (14)	0.0013 (11)	0.0024 (13)
C129	0.0166 (13)	0.0221 (15)	0.0217 (13)	−0.0024 (12)	0.0030 (10)	−0.0007 (12)
C130	0.0140 (12)	0.0151 (13)	0.0181 (12)	0.0017 (11)	0.0022 (10)	−0.0039 (11)
N21	0.0169 (11)	0.0209 (12)	0.0160 (11)	0.0006 (10)	0.0016 (9)	−0.0013 (10)
C22	0.0155 (12)	0.0176 (14)	0.0176 (12)	−0.0008 (11)	−0.0004 (10)	−0.0012 (11)
C23	0.0163 (13)	0.0169 (14)	0.0268 (14)	0.0012 (12)	−0.0019 (11)	0.0031 (12)
C24	0.0186 (14)	0.0268 (16)	0.0235 (14)	0.0005 (13)	0.0053 (11)	0.0070 (13)
C25	0.0205 (14)	0.0289 (16)	0.0223 (14)	−0.0012 (13)	0.0016 (11)	0.0082 (12)
C25a	0.0209 (14)	0.0228 (15)	0.0153 (12)	−0.0002 (12)	−0.0003 (10)	−0.0027 (12)
C26	0.0235 (14)	0.0224 (15)	0.0178 (13)	0.0028 (13)	−0.0033 (11)	0.0013 (11)
C27	0.0179 (14)	0.0326 (17)	0.0220 (14)	0.0038 (13)	−0.0024 (11)	−0.0029 (13)
C28	0.0160 (13)	0.0341 (17)	0.0227 (14)	−0.0058 (13)	0.0019 (11)	−0.0026 (13)
C29	0.0204 (14)	0.0251 (15)	0.0212 (14)	−0.0039 (13)	−0.0012 (11)	0.0012 (12)
C29a	0.0165 (13)	0.0214 (15)	0.0169 (12)	−0.0015 (12)	−0.0016 (10)	−0.0042 (12)
O214	0.0227 (10)	0.0242 (11)	0.0185 (9)	0.0016 (9)	0.0048 (8)	−0.0021 (8)
C221	0.0149 (13)	0.0153 (14)	0.0205 (13)	−0.0006 (11)	0.0039 (10)	0.0008 (11)
C222	0.0188 (14)	0.0214 (15)	0.0204 (14)	−0.0055 (12)	0.0014 (11)	−0.0017 (11)
C223	0.0240 (15)	0.0150 (14)	0.0292 (15)	0.0034 (12)	0.0038 (11)	−0.0038 (12)
C224	0.0175 (14)	0.0175 (14)	0.0315 (15)	0.0027 (12)	0.0011 (11)	0.0027 (13)
C225	0.0176 (13)	0.0171 (14)	0.0199 (13)	−0.0002 (11)	0.0041 (10)	0.0031 (11)
C226	0.0167 (13)	0.0208 (15)	0.0229 (14)	0.0000 (12)	−0.0019 (11)	0.0048 (12)
C227	0.0214 (14)	0.0263 (16)	0.0169 (12)	−0.0046 (13)	−0.0018 (11)	−0.0027 (12)
C228	0.0255 (15)	0.0250 (16)	0.0244 (14)	0.0013 (14)	0.0031 (12)	−0.0054 (13)
C229	0.0179 (13)	0.0216 (15)	0.0214 (13)	0.0045 (12)	−0.0002 (10)	−0.0023 (12)
C230	0.0143 (12)	0.0166 (13)	0.0186 (13)	−0.0042 (11)	0.0032 (10)	0.0017 (11)

Geometric parameters (Å, º)

N11—C19a	1.434 (3)	N21—O214	1.440 (3)
N11—O114	1.439 (3)	N21—C29a	1.442 (3)
N11—C12	1.480 (3)	N21—C22	1.471 (3)
C12—C121	1.508 (4)	C22—C221	1.509 (4)
C12—C13	1.549 (4)	C22—C23	1.555 (4)
C12—H12	1.0000	C22—H22	1.0000
C13—C14	1.527 (4)	C23—C24	1.522 (4)
C13—H13A	0.9900	C23—H23A	0.9900
C13—H13B	0.9900	C23—H23B	0.9900
C14—O114	1.444 (3)	C24—O214	1.447 (4)
C14—C15	1.513 (4)	C24—C25	1.509 (4)
C14—H14	1.0000	C24—H24	1.0000
C15—C15a	1.500 (4)	C25—C25a	1.504 (4)
C15—H15A	0.9900	C25—H25A	0.9900
C15—H15B	0.9900	C25—H25B	0.9900
C15a—C16	1.386 (4)	C25a—C26	1.386 (4)
C15a—C19a	1.392 (4)	C25a—C29a	1.391 (4)
C16—C17	1.376 (4)	C26—C27	1.375 (4)
C16—H16	0.9500	C26—H26	0.9500
C17—C18	1.388 (4)	C27—C28	1.377 (4)
C17—H17	0.9500	C27—H27	0.9500
C18—C19	1.370 (4)	C28—C29	1.375 (4)
C18—H18	0.9500	C28—H28	0.9500
C19—C19a	1.376 (4)	C29—C29a	1.379 (4)
C19—H19	0.9500	C29—H29	0.9500
C121—C122	1.361 (4)	C221—C222	1.364 (4)
C121—C130	1.430 (4)	C221—C230	1.422 (4)
C122—C123	1.399 (4)	C222—C223	1.403 (4)
C122—H122	0.9500	C222—H222	0.9500
C123—C124	1.357 (4)	C223—C224	1.349 (4)
C123—H123	0.9500	C223—H223	0.9500
C124—C125	1.403 (4)	C224—C225	1.411 (4)
C124—H124	0.9500	C224—H224	0.9500
C125—C126	1.411 (4)	C225—C226	1.409 (4)
C125—C130	1.416 (4)	C225—C230	1.419 (4)
C126—C127	1.357 (4)	C226—C227	1.359 (4)
C126—H126	0.9500	C226—H226	0.9500
C127—C128	1.398 (4)	C227—C228	1.393 (4)
C127—H127	0.9500	C227—H227	0.9500
C128—C129	1.361 (4)	C228—C229	1.361 (4)
C128—H128	0.9500	C228—H228	0.9500
C129—C130	1.414 (4)	C229—C230	1.410 (4)
C129—H129	0.9500	C229—H229	0.9500
C19a—N11—O114	107.9 (2)	O214—N21—C29a	107.9 (2)
C19a—N11—C12	112.5 (2)	O214—N21—C22	102.43 (19)
O114—N11—C12	101.75 (18)	C29a—N21—C22	110.2 (2)
N11—C12—C121	110.2 (2)	N21—C22—C221	112.6 (2)
N11—C12—C13	103.9 (2)	N21—C22—C23	103.5 (2)
C121—C12—C13	114.4 (2)	C221—C22—C23	112.2 (2)
N11—C12—H12	109.4	N21—C22—H22	109.5
C121—C12—H12	109.4	C221—C22—H22	109.5
C13—C12—H12	109.4	C23—C22—H22	109.5
C14—C13—C12	103.0 (2)	C24—C23—C22	103.4 (2)
C14—C13—H13A	111.2	C24—C23—H23A	111.1
C12—C13—H13A	111.2	C22—C23—H23A	111.1
C14—C13—H13B	111.2	C24—C23—H23B	111.1
C12—C13—H13B	111.2	C22—C23—H23B	111.1
H13A—C13—H13B	109.1	H23A—C23—H23B	109.1
O114—C14—C15	106.9 (2)	O214—C24—C25	106.7 (2)
O114—C14—C13	103.6 (2)	O214—C24—C23	104.1 (2)
C15—C14—C13	114.8 (2)	C25—C24—C23	113.1 (3)
O114—C14—H14	110.4	O214—C24—H24	110.9
C15—C14—H14	110.4	C25—C24—H24	110.9
C13—C14—H14	110.4	C23—C24—H24	110.9
C15a—C15—C14	110.0 (2)	C25a—C25—C24	109.3 (2)
C15a—C15—H15A	109.7	C25a—C25—H25A	109.8
C14—C15—H15A	109.7	C24—C25—H25A	109.8
C15a—C15—H15B	109.7	C25a—C25—H25B	109.8
C14—C15—H15B	109.7	C24—C25—H25B	109.8
H15A—C15—H15B	108.2	H25A—C25—H25B	108.3
C16—C15a—C19a	117.7 (3)	C26—C25a—C29a	118.2 (3)
C16—C15a—C15	122.5 (3)	C26—C25a—C25	121.8 (3)
C19a—C15a—C15	119.8 (2)	C29a—C25a—C25	120.0 (2)
C17—C16—C15a	121.1 (3)	C27—C26—C25a	121.1 (3)
C17—C16—H16	119.5	C27—C26—H26	119.5
C15a—C16—H16	119.5	C25a—C26—H26	119.5
C16—C17—C18	120.0 (3)	C26—C27—C28	119.8 (3)
C16—C17—H17	120.0	C26—C27—H27	120.1
C18—C17—H17	120.0	C28—C27—H27	120.1
C19—C18—C17	119.6 (3)	C29—C28—C27	120.1 (3)
C19—C18—H18	120.2	C29—C28—H28	119.9
C17—C18—H18	120.2	C27—C28—H28	119.9
C18—C19—C19a	120.1 (3)	C28—C29—C29a	119.9 (3)
C18—C19—H19	120.0	C28—C29—H29	120.0
C19a—C19—H19	120.0	C29a—C29—H29	120.0
C19—C19a—C15a	121.4 (3)	C29—C29a—C25a	120.8 (3)
C19—C19a—N11	117.8 (3)	C29—C29a—N21	118.2 (3)
C15a—C19a—N11	120.8 (2)	C25a—C29a—N21	121.0 (2)
N11—O114—C14	103.81 (18)	N21—O214—C24	104.1 (2)
C122—C121—C130	119.2 (2)	C222—C221—C230	119.2 (3)
C122—C121—C12	120.4 (2)	C222—C221—C22	122.4 (2)
C130—C121—C12	120.4 (2)	C230—C221—C22	118.3 (2)
C121—C122—C123	121.7 (2)	C221—C222—C223	121.3 (3)
C121—C122—H122	119.1	C221—C222—H222	119.4
C123—C122—H122	119.1	C223—C222—H222	119.4
C124—C123—C122	120.2 (3)	C224—C223—C222	120.7 (3)
C124—C123—H123	119.9	C224—C223—H223	119.6
C122—C123—H123	119.9	C222—C223—H223	119.6
C123—C124—C125	120.4 (3)	C223—C224—C225	120.4 (3)
C123—C124—H124	119.8	C223—C224—H224	119.8
C125—C124—H124	119.8	C225—C224—H224	119.8
C124—C125—C126	121.3 (3)	C226—C225—C224	121.6 (3)
C124—C125—C130	119.7 (2)	C226—C225—C230	119.2 (3)
C126—C125—C130	119.0 (3)	C224—C225—C230	119.3 (2)
C127—C126—C125	121.2 (3)	C227—C226—C225	120.9 (3)
C127—C126—H126	119.4	C227—C226—H226	119.6
C125—C126—H126	119.4	C225—C226—H226	119.6
C126—C127—C128	119.8 (3)	C226—C227—C228	120.0 (3)
C126—C127—H127	120.1	C226—C227—H227	120.0
C128—C127—H127	120.1	C228—C227—H227	120.0
C129—C128—C127	120.9 (3)	C229—C228—C227	120.9 (3)
C129—C128—H128	119.5	C229—C228—H228	119.5
C127—C128—H128	119.5	C227—C228—H228	119.5
C128—C129—C130	120.7 (3)	C228—C229—C230	120.8 (3)
C128—C129—H129	119.6	C228—C229—H229	119.6
C130—C129—H129	119.6	C230—C229—H229	119.6
C129—C130—C125	118.4 (2)	C229—C230—C225	118.2 (2)
C129—C130—C121	123.0 (2)	C229—C230—C221	122.7 (2)
C125—C130—C121	118.6 (2)	C225—C230—C221	119.1 (3)
C19a—N11—C12—C121	−158.4 (2)	O214—N21—C22—C221	84.0 (2)
O114—N11—C12—C121	86.4 (2)	C29a—N21—C22—C221	−161.3 (2)
C19a—N11—C12—C13	78.5 (2)	O214—N21—C22—C23	−37.3 (2)
O114—N11—C12—C13	−36.7 (2)	C29a—N21—C22—C23	77.3 (3)
N11—C12—C13—C14	11.4 (2)	N21—C22—C23—C24	13.3 (3)
C121—C12—C13—C14	−108.9 (2)	C221—C22—C23—C24	−108.4 (2)
C12—C13—C14—O114	18.0 (2)	C22—C23—C24—O214	15.4 (3)
C12—C13—C14—C15	−98.3 (3)	C22—C23—C24—C25	−100.0 (3)
O114—C14—C15—C15a	−44.0 (3)	O214—C24—C25—C25a	−47.9 (3)
C13—C14—C15—C15a	70.3 (3)	C23—C24—C25—C25a	65.9 (3)
C14—C15—C15a—C16	−176.2 (2)	C24—C25—C25a—C26	−171.6 (3)
C14—C15—C15a—C19a	2.6 (3)	C24—C25—C25a—C29a	8.6 (4)
C19a—C15a—C16—C17	−2.8 (4)	C29a—C25a—C26—C27	−0.8 (4)
C15—C15a—C16—C17	176.0 (2)	C25—C25a—C26—C27	179.5 (3)
C15a—C16—C17—C18	−0.6 (4)	C25a—C26—C27—C28	−0.8 (4)
C16—C17—C18—C19	3.2 (4)	C26—C27—C28—C29	1.2 (4)
C17—C18—C19—C19a	−2.4 (4)	C27—C28—C29—C29a	0.0 (4)
C18—C19—C19a—C15a	−1.1 (4)	C28—C29—C29a—C25a	−1.6 (4)
C18—C19—C19a—N11	177.2 (2)	C28—C29—C29a—N21	178.4 (3)
C16—C15a—C19a—C19	3.7 (4)	C26—C25a—C29a—C29	2.0 (4)
C15—C15a—C19a—C19	−175.2 (2)	C25—C25a—C29a—C29	−178.3 (3)
C16—C15a—C19a—N11	−174.6 (2)	C26—C25a—C29a—N21	−178.1 (2)
C15—C15a—C19a—N11	6.6 (4)	C25—C25a—C29a—N21	1.7 (4)
O114—N11—C19a—C19	−151.9 (2)	O214—N21—C29a—C29	−152.5 (2)
C12—N11—C19a—C19	96.7 (3)	C22—N21—C29a—C29	96.3 (3)
O114—N11—C19a—C15a	26.4 (3)	O214—N21—C29a—C25a	27.5 (3)
C12—N11—C19a—C15a	−85.0 (3)	C22—N21—C29a—C25a	−83.6 (3)
C19a—N11—O114—C14	−68.6 (2)	C29a—N21—O214—C24	−67.4 (2)
C12—N11—O114—C14	49.9 (2)	C22—N21—O214—C24	48.9 (2)
C15—C14—O114—N11	79.4 (2)	C25—C24—O214—N21	80.2 (2)
C13—C14—O114—N11	−42.2 (2)	C23—C24—O214—N21	−39.7 (2)
N11—C12—C121—C122	−9.4 (3)	N21—C22—C221—C222	−10.9 (4)
C13—C12—C121—C122	107.2 (3)	C23—C22—C221—C222	105.4 (3)
N11—C12—C121—C130	170.4 (2)	N21—C22—C221—C230	170.0 (2)
C13—C12—C121—C130	−72.9 (3)	C23—C22—C221—C230	−73.7 (3)
C130—C121—C122—C123	0.7 (4)	C230—C221—C222—C223	−0.2 (4)
C12—C121—C122—C123	−179.5 (2)	C22—C221—C222—C223	−179.3 (3)
C121—C122—C123—C124	−2.4 (4)	C221—C222—C223—C224	−0.9 (4)
C122—C123—C124—C125	2.5 (4)	C222—C223—C224—C225	1.4 (4)
C123—C124—C125—C126	179.9 (3)	C223—C224—C225—C226	178.8 (3)
C123—C124—C125—C130	−0.9 (4)	C223—C224—C225—C230	−0.9 (4)
C124—C125—C126—C127	−179.7 (3)	C224—C225—C226—C227	−178.6 (3)
C130—C125—C126—C127	1.1 (4)	C230—C225—C226—C227	1.2 (4)
C125—C126—C127—C128	−0.9 (5)	C225—C226—C227—C228	−0.6 (4)
C126—C127—C128—C129	0.4 (5)	C226—C227—C228—C229	−0.1 (4)
C127—C128—C129—C130	−0.3 (4)	C227—C228—C229—C230	0.3 (4)
C128—C129—C130—C125	0.5 (4)	C228—C229—C230—C225	0.3 (4)
C128—C129—C130—C121	−178.8 (3)	C228—C229—C230—C221	179.1 (3)
C124—C125—C130—C129	179.9 (3)	C226—C225—C230—C229	−1.0 (4)
C126—C125—C130—C129	−0.9 (4)	C224—C225—C230—C229	178.8 (2)
C124—C125—C130—C121	−0.8 (4)	C226—C225—C230—C221	−179.9 (2)
C126—C125—C130—C121	178.4 (2)	C224—C225—C230—C221	−0.1 (4)
C122—C121—C130—C129	−179.8 (2)	C222—C221—C230—C229	−178.1 (2)
C12—C121—C130—C129	0.3 (4)	C22—C221—C230—C229	0.9 (4)
C122—C121—C130—C125	0.9 (4)	C222—C221—C230—C225	0.7 (4)
C12—C121—C130—C125	−179.0 (2)	C22—C221—C230—C225	179.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O114^i	1.00	2.58	3.411 (4)	140
C24—H24···O214^ii	1.00	2.48	3.263 (4)	135
C16—H16···Cg1^iii	0.95	2.96	3.736 (3)	139
C26—H26···Cg2^iv	0.95	2.61	3.550 (3)	170
C18—H18···Cg3^v	0.95	2.61	3.553 (3)	170
C28—H28···Cg4^vi	0.95	2.72	3.634 (4)	163

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

(II) (2SR,4RS)-7-Methyl-2-exo-(1-naphthyl)-2,3,4,5-tetrahydro- 1H-1,4-epoxy-1-benzazepine

Crystal data

C21H19NO	F(000) = 640
Mr = 301.37	Dx = 1.354 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3390 reflections
a = 10.7760 (13) Å	θ = 3.0–27.5°
b = 8.9612 (11) Å	µ = 0.08 mm^−1
c = 15.4241 (15) Å	T = 120 K
β = 96.799 (10)°	Block, colourless
V = 1479.0 (3) Å^3	0.30 × 0.28 × 0.24 mm
Z = 4

Data collection

Bruker-Nonius KappaCCD area-detector diffractometer	2744 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1737 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 3.0°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.965, Tmax = 0.980	l = −18→18
19719 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0804P)^2 + 0.8442P] where P = (Fo^2 + 2Fc^2)/3
2744 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.54567 (19)	0.6701 (2)	0.65191 (13)	0.0225 (5)
C2	0.4638 (2)	0.5357 (3)	0.63922 (16)	0.0241 (6)
H2	0.4332	0.5247	0.5758	0.029*
C3	0.5528 (2)	0.4056 (3)	0.66801 (17)	0.0265 (6)
H3A	0.5140	0.3357	0.7066	0.032*
H3B	0.5763	0.3501	0.6169	0.032*
C4	0.6657 (2)	0.4831 (3)	0.71704 (17)	0.0266 (6)
H4	0.6927	0.4315	0.7736	0.032*
C5	0.7730 (2)	0.4966 (3)	0.66300 (16)	0.0272 (6)
H5A	0.8477	0.5354	0.6996	0.033*
H5B	0.7936	0.3971	0.6407	0.033*
C5a	0.7372 (2)	0.6006 (3)	0.58776 (16)	0.0234 (6)
C6	0.8110 (2)	0.6207 (3)	0.52150 (16)	0.0266 (6)
H6	0.8864	0.5652	0.5231	0.032*
C7	0.7798 (3)	0.7185 (3)	0.45266 (17)	0.0279 (6)
C71	0.8622 (3)	0.7363 (3)	0.38225 (18)	0.0350 (7)
H71A	0.9419	0.6857	0.3993	0.052*
H71B	0.8773	0.8427	0.3731	0.052*
H71C	0.8214	0.6923	0.3280	0.052*
C8	0.6699 (3)	0.7984 (3)	0.45219 (17)	0.0289 (6)
H8	0.6462	0.8662	0.4058	0.035*
C9	0.5942 (2)	0.7822 (3)	0.51721 (16)	0.0257 (6)
H9	0.5195	0.8389	0.5159	0.031*
C9a	0.6274 (2)	0.6826 (3)	0.58492 (16)	0.0220 (6)
O14	0.62210 (16)	0.63238 (19)	0.73193 (10)	0.0277 (5)
C21	0.3542 (2)	0.5588 (3)	0.68948 (16)	0.0228 (6)
C22	0.3486 (2)	0.4965 (3)	0.76946 (16)	0.0256 (6)
H22	0.4160	0.4362	0.7945	0.031*
C23	0.2458 (3)	0.5189 (3)	0.81588 (17)	0.0292 (6)
H23	0.2439	0.4725	0.8711	0.035*
C24	0.1493 (2)	0.6063 (3)	0.78264 (17)	0.0280 (6)
H24	0.0798	0.6198	0.8144	0.034*
C25	0.1510 (2)	0.6776 (3)	0.70114 (16)	0.0253 (6)
C26	0.0540 (2)	0.7732 (3)	0.66774 (17)	0.0285 (6)
H26	−0.0150	0.7883	0.6997	0.034*
C27	0.0573 (3)	0.8444 (3)	0.59035 (17)	0.0304 (7)
H27	−0.0090	0.9091	0.5684	0.036*
C28	0.1589 (3)	0.8218 (3)	0.54326 (17)	0.0296 (6)
H28	0.1614	0.8722	0.4893	0.036*
C29	0.2539 (2)	0.7291 (3)	0.57335 (17)	0.0268 (6)
H29	0.3211	0.7143	0.5396	0.032*
C210	0.2545 (2)	0.6543 (3)	0.65400 (16)	0.0224 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0253 (12)	0.0233 (11)	0.0188 (11)	−0.0003 (9)	0.0018 (9)	0.0010 (9)
C2	0.0265 (14)	0.0213 (14)	0.0253 (14)	−0.0032 (11)	0.0063 (11)	−0.0015 (11)
C3	0.0275 (14)	0.0239 (14)	0.0290 (14)	0.0003 (11)	0.0075 (11)	−0.0009 (11)
C4	0.0316 (15)	0.0227 (14)	0.0256 (14)	0.0023 (11)	0.0038 (12)	0.0007 (11)
C5	0.0285 (15)	0.0256 (14)	0.0272 (14)	0.0026 (11)	0.0024 (12)	0.0016 (11)
C5a	0.0234 (14)	0.0229 (14)	0.0238 (14)	−0.0041 (11)	0.0018 (11)	−0.0023 (11)
C6	0.0255 (14)	0.0259 (14)	0.0285 (14)	−0.0023 (11)	0.0038 (11)	−0.0035 (12)
C7	0.0299 (15)	0.0296 (15)	0.0250 (14)	−0.0091 (12)	0.0060 (12)	−0.0038 (11)
C71	0.0356 (17)	0.0396 (17)	0.0310 (16)	−0.0099 (13)	0.0093 (13)	0.0000 (13)
C8	0.0338 (16)	0.0303 (15)	0.0220 (14)	−0.0074 (12)	0.0012 (12)	0.0016 (11)
C9	0.0266 (14)	0.0225 (14)	0.0275 (14)	−0.0026 (11)	0.0015 (11)	−0.0007 (11)
C9a	0.0228 (14)	0.0210 (13)	0.0227 (13)	−0.0047 (11)	0.0046 (11)	−0.0017 (10)
O14	0.0319 (11)	0.0273 (10)	0.0232 (10)	0.0020 (8)	0.0006 (8)	0.0000 (8)
C21	0.0247 (14)	0.0197 (13)	0.0242 (14)	−0.0021 (11)	0.0035 (11)	−0.0030 (11)
C22	0.0273 (15)	0.0244 (14)	0.0254 (14)	0.0017 (11)	0.0039 (12)	0.0013 (11)
C23	0.0328 (16)	0.0292 (15)	0.0269 (14)	0.0021 (12)	0.0093 (12)	0.0035 (12)
C24	0.0280 (14)	0.0267 (14)	0.0310 (15)	−0.0010 (12)	0.0106 (12)	−0.0030 (12)
C25	0.0282 (15)	0.0209 (13)	0.0275 (14)	−0.0031 (11)	0.0064 (12)	−0.0034 (11)
C26	0.0249 (15)	0.0273 (15)	0.0338 (15)	0.0003 (12)	0.0056 (12)	−0.0026 (12)
C27	0.0296 (15)	0.0272 (15)	0.0331 (16)	0.0025 (12)	−0.0015 (12)	−0.0005 (12)
C28	0.0351 (16)	0.0286 (15)	0.0248 (14)	0.0003 (12)	0.0015 (12)	0.0023 (12)
C29	0.0274 (15)	0.0262 (14)	0.0269 (14)	−0.0012 (12)	0.0037 (11)	−0.0012 (11)
C210	0.0250 (14)	0.0191 (13)	0.0225 (13)	−0.0036 (11)	0.0005 (11)	−0.0026 (10)

Geometric parameters (Å, º)

N1—C9a	1.440 (3)	C71—H71C	0.9800
N1—O14	1.441 (3)	C8—C9	1.373 (4)
N1—C2	1.492 (3)	C8—H8	0.9500
C2—C21	1.503 (3)	C9—C9a	1.388 (3)
C2—C3	1.541 (4)	C9—H9	0.9500
C2—H2	1.0000	C21—C22	1.362 (3)
C3—C4	1.522 (4)	C21—C210	1.430 (3)
C3—H3A	0.9900	C22—C23	1.403 (4)
C3—H3B	0.9900	C22—H22	0.9500
C4—O14	1.445 (3)	C23—C24	1.353 (4)
C4—C5	1.508 (4)	C23—H23	0.9500
C4—H4	1.0000	C24—C25	1.412 (4)
C5—C5a	1.503 (3)	C24—H24	0.9500
C5—H5A	0.9900	C25—C26	1.401 (4)
C5—H5B	0.9900	C25—C210	1.418 (3)
C5a—C6	1.379 (3)	C26—C27	1.358 (4)
C5a—C9a	1.389 (3)	C26—H26	0.9500
C6—C7	1.387 (4)	C27—C28	1.399 (4)
C6—H6	0.9500	C27—H27	0.9500
C7—C8	1.384 (4)	C28—C29	1.357 (4)
C7—C71	1.490 (4)	C28—H28	0.9500
C71—H71A	0.9800	C29—C210	1.413 (3)
C71—H71B	0.9800	C29—H29	0.9500
C9a—N1—O14	107.27 (18)	H71B—C71—H71C	109.5
C9a—N1—C2	111.79 (18)	C9—C8—C7	121.6 (2)
O14—N1—C2	101.07 (17)	C9—C8—H8	119.2
N1—C2—C21	108.06 (19)	C7—C8—H8	119.2
N1—C2—C3	103.61 (19)	C8—C9—C9a	119.7 (2)
C21—C2—C3	117.1 (2)	C8—C9—H9	120.2
N1—C2—H2	109.2	C9a—C9—H9	120.2
C21—C2—H2	109.2	C9—C9a—C5a	120.5 (2)
C3—C2—H2	109.2	C9—C9a—N1	117.7 (2)
C4—C3—C2	103.4 (2)	C5a—C9a—N1	121.8 (2)
C4—C3—H3A	111.1	N1—O14—C4	104.16 (17)
C2—C3—H3A	111.1	C22—C21—C210	118.7 (2)
C4—C3—H3B	111.1	C22—C21—C2	122.2 (2)
C2—C3—H3B	111.1	C210—C21—C2	119.1 (2)
H3A—C3—H3B	109.1	C21—C22—C23	121.7 (2)
O14—C4—C5	107.4 (2)	C21—C22—H22	119.1
O14—C4—C3	104.2 (2)	C23—C22—H22	119.1
C5—C4—C3	112.5 (2)	C24—C23—C22	120.5 (2)
O14—C4—H4	110.8	C24—C23—H23	119.8
C5—C4—H4	110.8	C22—C23—H23	119.8
C3—C4—H4	110.8	C23—C24—C25	120.6 (2)
C5a—C5—C4	109.4 (2)	C23—C24—H24	119.7
C5a—C5—H5A	109.8	C25—C24—H24	119.7
C4—C5—H5A	109.8	C26—C25—C24	121.1 (2)
C5a—C5—H5B	109.8	C26—C25—C210	120.0 (2)
C4—C5—H5B	109.8	C24—C25—C210	118.9 (2)
H5A—C5—H5B	108.2	C27—C26—C25	121.0 (2)
C6—C5a—C9a	118.1 (2)	C27—C26—H26	119.5
C6—C5a—C5	122.4 (2)	C25—C26—H26	119.5
C9a—C5a—C5	119.5 (2)	C26—C27—C28	119.5 (3)
C5a—C6—C7	122.7 (2)	C26—C27—H27	120.3
C5a—C6—H6	118.6	C28—C27—H27	120.3
C7—C6—H6	118.6	C29—C28—C27	121.1 (2)
C8—C7—C6	117.4 (2)	C29—C28—H28	119.4
C8—C7—C71	121.6 (2)	C27—C28—H28	119.5
C6—C7—C71	120.9 (2)	C28—C29—C210	121.1 (3)
C7—C71—H71A	109.5	C28—C29—H29	119.4
C7—C71—H71B	109.5	C210—C29—H29	119.4
H71A—C71—H71B	109.5	C29—C210—C25	117.4 (2)
C7—C71—H71C	109.5	C29—C210—C21	123.1 (2)
H71A—C71—H71C	109.5	C25—C210—C21	119.5 (2)
C9a—N1—C2—C21	−160.1 (2)	C9a—N1—O14—C4	−67.6 (2)
O14—N1—C2—C21	86.0 (2)	C2—N1—O14—C4	49.6 (2)
C9a—N1—C2—C3	75.0 (2)	C5—C4—O14—N1	79.6 (2)
O14—N1—C2—C3	−38.9 (2)	C3—C4—O14—N1	−39.9 (2)
N1—C2—C3—C4	15.0 (2)	N1—C2—C21—C22	−99.7 (3)
C21—C2—C3—C4	−103.8 (2)	C3—C2—C21—C22	16.7 (3)
C2—C3—C4—O14	14.2 (2)	N1—C2—C21—C210	77.6 (3)
C2—C3—C4—C5	−101.8 (2)	C3—C2—C21—C210	−165.9 (2)
O14—C4—C5—C5a	−47.4 (3)	C210—C21—C22—C23	2.5 (4)
C3—C4—C5—C5a	66.7 (3)	C2—C21—C22—C23	179.9 (2)
C4—C5—C5a—C6	−172.1 (2)	C21—C22—C23—C24	−1.2 (4)
C4—C5—C5a—C9a	9.3 (3)	C22—C23—C24—C25	−0.7 (4)
C9a—C5a—C6—C7	−0.2 (4)	C23—C24—C25—C26	−177.4 (2)
C5—C5a—C6—C7	−178.8 (2)	C23—C24—C25—C210	1.0 (4)
C5a—C6—C7—C8	0.3 (4)	C24—C25—C26—C27	178.4 (2)
C5a—C6—C7—C71	−179.8 (2)	C210—C25—C26—C27	0.0 (4)
C6—C7—C8—C9	0.0 (4)	C25—C26—C27—C28	0.1 (4)
C71—C7—C8—C9	−179.8 (2)	C26—C27—C28—C29	0.4 (4)
C7—C8—C9—C9a	−0.5 (4)	C27—C28—C29—C210	−1.1 (4)
C8—C9—C9a—C5a	0.7 (4)	C28—C29—C210—C25	1.2 (4)
C8—C9—C9a—N1	179.6 (2)	C28—C29—C210—C21	−178.2 (2)
C6—C5a—C9a—C9	−0.3 (4)	C26—C25—C210—C29	−0.7 (4)
C5—C5a—C9a—C9	178.4 (2)	C24—C25—C210—C29	−179.1 (2)
C6—C5a—C9a—N1	−179.2 (2)	C26—C25—C210—C21	178.8 (2)
C5—C5a—C9a—N1	−0.5 (4)	C24—C25—C210—C21	0.4 (3)
O14—N1—C9a—C9	−149.4 (2)	C22—C21—C210—C29	177.3 (2)
C2—N1—C9a—C9	100.6 (3)	C2—C21—C210—C29	−0.1 (4)
O14—N1—C9a—C5a	29.5 (3)	C22—C21—C210—C25	−2.1 (4)
C2—N1—C9a—C5a	−80.5 (3)	C2—C21—C210—C25	−179.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O14^i	0.99	2.59	3.552 (3)	164
C22—H22···N1^i	0.95	2.54	3.316 (3)	139
C2—H2···Cg5^ii	1.00	2.81	3.558 (3)	132
C4—H4···Cg6^i	1.00	2.71	3.626 (3)	153

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

(III) (2S*,4R*)-2-exo-(1-Naphthyl)-7-trifluoromethyl-2,3,4,5- tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C21H16F3NO2	F(000) = 768
Mr = 371.35	Dx = 1.480 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2193 reflections
a = 7.2209 (5) Å	θ = 3.1–27.5°
b = 13.140 (2) Å	µ = 0.12 mm^−1
c = 17.559 (2) Å	T = 120 K
V = 1666.0 (3) Å^3	Block, colourless
Z = 4	0.21 × 0.20 × 0.14 mm

Data collection

Bruker-Nonius KappaCCD area-detector diffractometer	2193 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1899 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→17
Tmin = 0.957, Tmax = 0.984	l = −22→22
20342 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0334P)^2 + 0.5461P] where P = (Fo^2 + 2Fc^2)/3
2193 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.4649 (3)	0.53538 (15)	0.65449 (11)	0.0223 (4)
C2	0.5316 (3)	0.58817 (18)	0.58600 (12)	0.0207 (5)
H2	0.5534	0.6617	0.5977	0.025*
C3	0.7178 (3)	0.5351 (2)	0.56863 (14)	0.0272 (6)
H3A	0.7301	0.5200	0.5136	0.033*
H3B	0.8238	0.5776	0.5850	0.033*
C4	0.7060 (4)	0.4379 (2)	0.61518 (15)	0.0327 (6)
H4	0.7414	0.3777	0.5836	0.039*
C5	0.8168 (4)	0.4404 (2)	0.68826 (15)	0.0342 (7)
H5A	0.8160	0.3724	0.7125	0.041*
H5B	0.9468	0.4592	0.6772	0.041*
C5a	0.7312 (4)	0.51751 (18)	0.74093 (13)	0.0235 (5)
C6	0.8150 (4)	0.54313 (18)	0.80913 (13)	0.0227 (5)
H6	0.9230	0.5082	0.8256	0.027*
C7	0.7408 (3)	0.61918 (18)	0.85249 (12)	0.0209 (5)
O7	0.8235 (2)	0.64146 (13)	0.92370 (8)	0.0242 (4)
C71	0.9577 (4)	0.71102 (19)	0.92242 (13)	0.0260 (6)
F71	1.0164 (3)	0.72417 (13)	0.99247 (8)	0.0445 (5)
F72	1.1013 (2)	0.68440 (13)	0.88031 (9)	0.0367 (4)
F73	0.9012 (2)	0.80003 (11)	0.89604 (9)	0.0389 (4)
C8	0.5827 (4)	0.67079 (18)	0.83186 (13)	0.0237 (5)
H8	0.5360	0.7248	0.8622	0.028*
C9	0.4946 (4)	0.64182 (18)	0.76608 (12)	0.0224 (5)
H9	0.3832	0.6748	0.7513	0.027*
C9a	0.5667 (3)	0.56517 (17)	0.72132 (12)	0.0205 (5)
O14	0.5137 (3)	0.43151 (13)	0.63794 (10)	0.0294 (4)
C21	0.3953 (3)	0.57850 (17)	0.52122 (12)	0.0197 (5)
C22	0.2493 (4)	0.5131 (2)	0.52548 (13)	0.0248 (5)
H22	0.2309	0.4746	0.5706	0.030*
C23	0.1255 (4)	0.5014 (2)	0.46459 (14)	0.0291 (6)
H23	0.0254	0.4548	0.4688	0.035*
C24	0.1475 (4)	0.5560 (2)	0.39974 (14)	0.0281 (6)
H24	0.0623	0.5478	0.3589	0.034*
C25	0.2949 (3)	0.62437 (19)	0.39263 (13)	0.0239 (5)
C26	0.3213 (4)	0.6812 (2)	0.32503 (14)	0.0300 (6)
H26	0.2371	0.6731	0.2839	0.036*
C27	0.4646 (4)	0.7468 (2)	0.31808 (15)	0.0330 (6)
H27	0.4804	0.7842	0.2722	0.040*
C28	0.5894 (4)	0.7596 (2)	0.37814 (15)	0.0318 (6)
H28	0.6893	0.8062	0.3729	0.038*
C29	0.5695 (4)	0.70616 (19)	0.44418 (14)	0.0263 (5)
H29	0.6558	0.7157	0.4844	0.032*
C210	0.4226 (3)	0.63695 (17)	0.45338 (13)	0.0204 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0256 (11)	0.0200 (9)	0.0212 (10)	−0.0022 (9)	−0.0004 (9)	−0.0009 (8)
C2	0.0211 (11)	0.0221 (11)	0.0188 (10)	−0.0012 (10)	0.0031 (9)	−0.0044 (9)
C3	0.0186 (12)	0.0415 (15)	0.0215 (12)	0.0022 (11)	−0.0026 (10)	−0.0095 (11)
C4	0.0372 (15)	0.0311 (14)	0.0297 (13)	0.0114 (12)	−0.0110 (12)	−0.0133 (12)
C5	0.0404 (16)	0.0329 (15)	0.0292 (13)	0.0126 (13)	−0.0119 (12)	−0.0108 (12)
C5a	0.0278 (13)	0.0204 (11)	0.0225 (11)	0.0003 (11)	−0.0022 (11)	−0.0021 (9)
C6	0.0257 (12)	0.0217 (12)	0.0208 (11)	0.0011 (10)	−0.0012 (10)	0.0023 (9)
C7	0.0285 (12)	0.0208 (11)	0.0135 (10)	−0.0050 (10)	0.0013 (10)	0.0012 (9)
O7	0.0322 (9)	0.0265 (9)	0.0138 (8)	−0.0071 (8)	−0.0009 (7)	0.0022 (7)
C71	0.0346 (14)	0.0259 (12)	0.0175 (11)	−0.0042 (11)	0.0005 (11)	0.0006 (10)
F71	0.0605 (12)	0.0527 (11)	0.0203 (7)	−0.0228 (10)	−0.0078 (8)	−0.0059 (7)
F72	0.0268 (8)	0.0473 (9)	0.0361 (8)	−0.0025 (8)	0.0036 (7)	−0.0060 (8)
F73	0.0457 (10)	0.0218 (7)	0.0493 (10)	−0.0029 (8)	−0.0009 (9)	0.0030 (7)
C8	0.0293 (13)	0.0238 (11)	0.0181 (11)	0.0028 (11)	0.0077 (11)	0.0014 (9)
C9	0.0226 (12)	0.0259 (11)	0.0187 (11)	0.0035 (11)	0.0038 (11)	0.0031 (9)
C9a	0.0234 (12)	0.0194 (11)	0.0187 (11)	−0.0036 (10)	0.0001 (9)	0.0019 (9)
O14	0.0377 (10)	0.0186 (8)	0.0320 (9)	−0.0009 (8)	−0.0083 (8)	−0.0043 (7)
C21	0.0180 (10)	0.0228 (11)	0.0183 (10)	0.0018 (10)	0.0005 (9)	−0.0064 (9)
C22	0.0256 (12)	0.0295 (13)	0.0191 (11)	−0.0016 (11)	0.0005 (11)	−0.0044 (10)
C23	0.0212 (12)	0.0365 (15)	0.0294 (13)	−0.0023 (11)	−0.0001 (11)	−0.0100 (11)
C24	0.0213 (12)	0.0373 (14)	0.0258 (12)	0.0046 (11)	−0.0080 (10)	−0.0092 (11)
C25	0.0238 (12)	0.0257 (12)	0.0221 (11)	0.0091 (10)	−0.0006 (10)	−0.0069 (10)
C26	0.0367 (15)	0.0303 (13)	0.0231 (12)	0.0113 (13)	−0.0064 (12)	−0.0023 (11)
C27	0.0506 (17)	0.0272 (12)	0.0211 (12)	0.0075 (14)	0.0036 (12)	0.0036 (10)
C28	0.0407 (16)	0.0281 (13)	0.0268 (13)	−0.0047 (13)	0.0049 (13)	−0.0023 (11)
C29	0.0311 (14)	0.0274 (12)	0.0204 (11)	−0.0021 (11)	0.0005 (11)	−0.0055 (10)
C210	0.0199 (11)	0.0219 (11)	0.0193 (11)	0.0037 (10)	−0.0003 (9)	−0.0057 (9)

Geometric parameters (Å, º)

N1—C9a	1.439 (3)	C71—F73	1.322 (3)
N1—O14	1.439 (3)	C8—C9	1.373 (3)
N1—C2	1.469 (3)	C8—H8	0.9500
C2—C21	1.509 (3)	C9—C9a	1.379 (3)
C2—C3	1.545 (3)	C9—H9	0.9500
C2—H2	1.0000	C21—C22	1.363 (3)
C3—C4	1.519 (4)	C21—C210	1.431 (3)
C3—H3A	0.9900	C22—C23	1.402 (3)
C3—H3B	0.9900	C22—H22	0.9500
C4—O14	1.447 (3)	C23—C24	1.355 (4)
C4—C5	1.513 (4)	C23—H23	0.9500
C4—H4	1.0000	C24—C25	1.399 (4)
C5—C5a	1.505 (3)	C24—H24	0.9500
C5—H5A	0.9900	C25—C26	1.415 (4)
C5—H5B	0.9900	C25—C210	1.419 (3)
C5a—C6	1.383 (3)	C26—C27	1.352 (4)
C5a—C9a	1.386 (3)	C26—H26	0.9500
C6—C7	1.366 (3)	C27—C28	1.398 (4)
C6—H6	0.9500	C27—H27	0.9500
C7—C8	1.376 (4)	C28—C29	1.364 (4)
C7—O7	1.416 (3)	C28—H28	0.9500
O7—C71	1.332 (3)	C29—C210	1.407 (3)
C71—F71	1.312 (3)	C29—H29	0.9500
C71—F72	1.321 (3)
C9a—N1—O14	107.33 (18)	F73—C71—O7	112.9 (2)
C9a—N1—C2	111.83 (18)	C9—C8—C7	118.0 (2)
O14—N1—C2	101.68 (17)	C9—C8—H8	121.0
N1—C2—C21	111.32 (19)	C7—C8—H8	121.0
N1—C2—C3	103.50 (19)	C8—C9—C9a	120.5 (2)
C21—C2—C3	112.36 (18)	C8—C9—H9	119.8
N1—C2—H2	109.8	C9a—C9—H9	119.8
C21—C2—H2	109.8	C9—C9a—C5a	120.8 (2)
C3—C2—H2	109.8	C9—C9a—N1	118.1 (2)
C4—C3—C2	103.0 (2)	C5a—C9a—N1	121.1 (2)
C4—C3—H3A	111.2	N1—O14—C4	103.59 (18)
C2—C3—H3A	111.2	C22—C21—C210	119.4 (2)
C4—C3—H3B	111.2	C22—C21—C2	121.1 (2)
C2—C3—H3B	111.2	C210—C21—C2	119.5 (2)
H3A—C3—H3B	109.1	C21—C22—C23	121.4 (2)
O14—C4—C5	105.9 (2)	C21—C22—H22	119.3
O14—C4—C3	104.6 (2)	C23—C22—H22	119.3
C5—C4—C3	114.1 (2)	C24—C23—C22	120.6 (2)
O14—C4—H4	110.6	C24—C23—H23	119.7
C5—C4—H4	110.6	C22—C23—H23	119.7
C3—C4—H4	110.6	C23—C24—C25	120.3 (2)
C5a—C5—C4	108.6 (2)	C23—C24—H24	119.9
C5a—C5—H5A	110.0	C25—C24—H24	119.9
C4—C5—H5A	110.0	C24—C25—C26	121.1 (2)
C5a—C5—H5B	110.0	C24—C25—C210	120.1 (2)
C4—C5—H5B	110.0	C26—C25—C210	118.8 (2)
H5A—C5—H5B	108.4	C27—C26—C25	121.0 (2)
C6—C5a—C9a	118.7 (2)	C27—C26—H26	119.5
C6—C5a—C5	121.1 (2)	C25—C26—H26	119.5
C9a—C5a—C5	120.2 (2)	C26—C27—C28	120.2 (2)
C7—C6—C5a	119.3 (2)	C26—C27—H27	119.9
C7—C6—H6	120.4	C28—C27—H27	119.9
C5a—C6—H6	120.4	C29—C28—C27	120.7 (3)
C6—C7—C8	122.6 (2)	C29—C28—H28	119.6
C6—C7—O7	118.6 (2)	C27—C28—H28	119.6
C8—C7—O7	118.7 (2)	C28—C29—C210	120.7 (2)
C71—O7—C7	115.70 (17)	C28—C29—H29	119.7
F71—C71—F72	107.8 (2)	C210—C29—H29	119.7
F71—C71—F73	108.1 (2)	C29—C210—C25	118.6 (2)
F72—C71—F73	106.3 (2)	C29—C210—C21	123.1 (2)
F71—C71—O7	108.03 (19)	C25—C210—C21	118.3 (2)
F72—C71—O7	113.5 (2)
C9a—N1—C2—C21	−164.99 (19)	O14—N1—C9a—C5a	24.8 (3)
O14—N1—C2—C21	80.8 (2)	C2—N1—C9a—C5a	−85.9 (3)
C9a—N1—C2—C3	74.1 (2)	C9a—N1—O14—C4	−67.8 (2)
O14—N1—C2—C3	−40.1 (2)	C2—N1—O14—C4	49.7 (2)
N1—C2—C3—C4	16.6 (2)	C5—C4—O14—N1	82.2 (2)
C21—C2—C3—C4	−103.7 (2)	C3—C4—O14—N1	−38.7 (2)
C2—C3—C4—O14	12.9 (2)	N1—C2—C21—C22	−10.7 (3)
C2—C3—C4—C5	−102.4 (3)	C3—C2—C21—C22	104.9 (3)
O14—C4—C5—C5a	−47.8 (3)	N1—C2—C21—C210	170.98 (19)
C3—C4—C5—C5a	66.7 (3)	C3—C2—C21—C210	−73.4 (3)
C4—C5—C5a—C6	−173.5 (3)	C210—C21—C22—C23	0.3 (3)
C4—C5—C5a—C9a	5.8 (3)	C2—C21—C22—C23	−178.0 (2)
C9a—C5a—C6—C7	−4.5 (4)	C21—C22—C23—C24	−0.6 (4)
C5—C5a—C6—C7	174.8 (2)	C22—C23—C24—C25	0.4 (4)
C5a—C6—C7—C8	1.3 (4)	C23—C24—C25—C26	179.3 (2)
C5a—C6—C7—O7	177.3 (2)	C23—C24—C25—C210	0.0 (4)
C6—C7—O7—C71	90.0 (3)	C24—C25—C26—C27	−179.6 (2)
C8—C7—O7—C71	−93.8 (3)	C210—C25—C26—C27	−0.3 (4)
C7—O7—C71—F71	178.7 (2)	C25—C26—C27—C28	−0.1 (4)
C7—O7—C71—F72	−61.8 (3)	C26—C27—C28—C29	0.4 (4)
C7—O7—C71—F73	59.2 (3)	C27—C28—C29—C210	−0.1 (4)
C6—C7—C8—C9	2.0 (4)	C28—C29—C210—C25	−0.3 (3)
O7—C7—C8—C9	−174.1 (2)	C28—C29—C210—C21	179.7 (2)
C7—C8—C9—C9a	−1.9 (3)	C24—C25—C210—C29	179.8 (2)
C8—C9—C9a—C5a	−1.4 (4)	C26—C25—C210—C29	0.5 (3)
C8—C9—C9a—N1	177.7 (2)	C24—C25—C210—C21	−0.2 (3)
C6—C5a—C9a—C9	4.6 (4)	C26—C25—C210—C21	−179.5 (2)
C5—C5a—C9a—C9	−174.7 (2)	C22—C21—C210—C29	−180.0 (2)
C6—C5a—C9a—N1	−174.5 (2)	C2—C21—C210—C29	−1.7 (3)
C5—C5a—C9a—N1	6.1 (3)	C22—C21—C210—C25	0.1 (3)
O14—N1—C9a—C9	−154.4 (2)	C2—C21—C210—C25	178.4 (2)
C2—N1—C9a—C9	94.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C24—H24···Cg5^i	0.95	2.74	3.539 (3)	143

Symmetry code: (i) −x+1/2, −y+1, z−1/2.

(IV) (2S,4R)-8-Chloro-9-methyl-2-exo-(1-naphthyl)-2,3,4,5- tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C21H18ClNO	F(000) = 704
Mr = 335.81	Dx = 1.366 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3731 reflections
a = 7.4394 (7) Å	θ = 2.8–27.5°
b = 14.498 (3) Å	µ = 0.24 mm^−1
c = 15.136 (3) Å	T = 120 K
V = 1632.5 (5) Å^3	Block, colourless
Z = 4	0.24 × 0.17 × 0.16 mm

Data collection

Bruker-Nonius KappaCCD area-detector diffractometer	3731 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3028 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→18
Tmin = 0.935, Tmax = 0.963	l = −19→17
16529 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 0.5177P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3731 reflections	Δρmax = 0.21 e Å^−3
218 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1581 Bijvoet pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (7)

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

	x	y	z	Uiso*/Ueq
N1	0.5192 (2)	0.52750 (12)	0.69290 (12)	0.0200 (4)
C2	0.5617 (3)	0.57593 (14)	0.60970 (13)	0.0183 (5)
H2	0.5882	0.6422	0.6228	0.022*
C3	0.7352 (3)	0.52799 (15)	0.57749 (14)	0.0224 (5)
H3A	0.7283	0.5135	0.5137	0.027*
H3B	0.8420	0.5671	0.5884	0.027*
C4	0.7419 (3)	0.44006 (16)	0.63295 (15)	0.0251 (5)
H4	0.7679	0.3850	0.5953	0.030*
C5	0.8709 (3)	0.44584 (16)	0.70933 (15)	0.0279 (5)
H5A	0.8757	0.3858	0.7405	0.033*
H5B	0.9930	0.4604	0.6874	0.033*
C5a	0.8090 (3)	0.51987 (15)	0.77174 (14)	0.0201 (5)
C6	0.9179 (3)	0.55212 (16)	0.83783 (14)	0.0232 (5)
H6	1.0327	0.5249	0.8465	0.028*
C7	0.8641 (3)	0.62276 (16)	0.89147 (15)	0.0248 (5)
H7	0.9407	0.6448	0.9370	0.030*
C8	0.6971 (3)	0.66155 (15)	0.87851 (15)	0.0217 (5)
Cl8	0.63590 (9)	0.75263 (4)	0.94652 (4)	0.03721 (17)
C9	0.5796 (3)	0.63166 (15)	0.81420 (13)	0.0190 (5)
C91	0.3981 (3)	0.67419 (16)	0.80117 (15)	0.0259 (5)
H91A	0.3403	0.6832	0.8587	0.039*
H91B	0.3238	0.6333	0.7648	0.039*
H91C	0.4114	0.7339	0.7715	0.039*
C9a	0.6396 (3)	0.55917 (14)	0.76138 (13)	0.0184 (4)
O14	0.5653 (2)	0.43378 (10)	0.67212 (10)	0.0263 (4)
C21	0.4128 (3)	0.57041 (14)	0.54312 (14)	0.0186 (5)
C22	0.2809 (3)	0.50465 (15)	0.54812 (15)	0.0219 (5)
H22	0.2796	0.4630	0.5965	0.026*
C23	0.1483 (3)	0.49801 (15)	0.48300 (16)	0.0262 (5)
H23	0.0595	0.4511	0.4871	0.031*
C24	0.1447 (3)	0.55753 (16)	0.41417 (16)	0.0262 (5)
H24	0.0520	0.5530	0.3712	0.031*
C25	0.2777 (3)	0.62603 (15)	0.40581 (14)	0.0215 (5)
C26	0.2803 (3)	0.68700 (16)	0.33314 (15)	0.0265 (6)
H26	0.1891	0.6826	0.2894	0.032*
C27	0.4105 (3)	0.75167 (17)	0.32454 (14)	0.0279 (5)
H27	0.4103	0.7920	0.2751	0.034*
C28	0.5453 (3)	0.75888 (16)	0.38853 (14)	0.0250 (5)
H28	0.6359	0.8046	0.3825	0.030*
C29	0.5480 (3)	0.70087 (14)	0.45955 (14)	0.0218 (5)
H29	0.6410	0.7065	0.5022	0.026*
C210	0.4147 (3)	0.63280 (14)	0.47045 (13)	0.0185 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0233 (10)	0.0157 (9)	0.0209 (9)	−0.0009 (8)	−0.0007 (8)	−0.0004 (7)
C2	0.0191 (11)	0.0164 (11)	0.0193 (10)	−0.0016 (9)	0.0017 (10)	−0.0007 (8)
C3	0.0209 (12)	0.0266 (12)	0.0198 (11)	0.0012 (10)	0.0001 (10)	−0.0048 (9)
C4	0.0239 (13)	0.0232 (12)	0.0282 (12)	0.0066 (10)	−0.0008 (10)	−0.0056 (10)
C5	0.0288 (13)	0.0241 (12)	0.0308 (12)	0.0099 (11)	−0.0041 (11)	0.0007 (10)
C5a	0.0217 (12)	0.0189 (11)	0.0197 (11)	0.0033 (9)	0.0012 (9)	0.0058 (9)
C6	0.0203 (12)	0.0261 (12)	0.0232 (11)	0.0031 (10)	−0.0017 (10)	0.0093 (10)
C7	0.0282 (13)	0.0268 (12)	0.0195 (11)	−0.0046 (11)	−0.0035 (11)	0.0060 (9)
C8	0.0277 (13)	0.0198 (11)	0.0177 (11)	−0.0009 (9)	0.0017 (10)	0.0024 (9)
Cl8	0.0470 (4)	0.0363 (3)	0.0283 (3)	0.0087 (3)	−0.0045 (3)	−0.0120 (3)
C9	0.0204 (12)	0.0204 (11)	0.0163 (10)	−0.0014 (9)	0.0037 (9)	0.0065 (9)
C91	0.0222 (13)	0.0290 (12)	0.0265 (12)	0.0033 (10)	0.0040 (10)	−0.0015 (10)
C9a	0.0218 (11)	0.0192 (10)	0.0142 (10)	−0.0045 (10)	0.0008 (9)	0.0054 (8)
O14	0.0310 (9)	0.0158 (8)	0.0323 (9)	−0.0018 (7)	−0.0009 (8)	−0.0011 (7)
C21	0.0171 (11)	0.0173 (10)	0.0213 (11)	0.0017 (8)	−0.0005 (9)	−0.0056 (9)
C22	0.0192 (11)	0.0228 (11)	0.0236 (11)	0.0002 (9)	0.0017 (10)	−0.0046 (10)
C23	0.0166 (11)	0.0254 (12)	0.0367 (13)	−0.0035 (10)	0.0000 (11)	−0.0108 (10)
C24	0.0171 (11)	0.0294 (12)	0.0321 (12)	0.0045 (11)	−0.0058 (11)	−0.0129 (10)
C25	0.0171 (11)	0.0214 (11)	0.0260 (12)	0.0080 (9)	−0.0009 (10)	−0.0102 (9)
C26	0.0285 (13)	0.0293 (13)	0.0216 (11)	0.0109 (11)	−0.0068 (10)	−0.0072 (10)
C27	0.0376 (14)	0.0259 (12)	0.0203 (10)	0.0125 (12)	−0.0023 (10)	0.0003 (10)
C28	0.0303 (13)	0.0191 (11)	0.0256 (11)	0.0008 (10)	0.0003 (10)	−0.0014 (10)
C29	0.0231 (12)	0.0209 (11)	0.0213 (11)	0.0002 (9)	−0.0046 (10)	−0.0027 (9)
C210	0.0188 (12)	0.0191 (10)	0.0176 (10)	0.0055 (9)	−0.0001 (9)	−0.0064 (8)

Geometric parameters (Å, º)

N1—O14	1.436 (2)	C9—C9a	1.394 (3)
N1—C9a	1.445 (3)	C9—C91	1.497 (3)
N1—C2	1.476 (3)	C91—H91A	0.9800
C2—C21	1.500 (3)	C91—H91B	0.9800
C2—C3	1.545 (3)	C91—H91C	0.9800
C2—H2	1.0000	C21—C22	1.370 (3)
C3—C4	1.527 (3)	C21—C210	1.424 (3)
C3—H3A	0.9900	C22—C23	1.398 (3)
C3—H3B	0.9900	C22—H22	0.9500
C4—O14	1.445 (3)	C23—C24	1.353 (3)
C4—C5	1.505 (3)	C23—H23	0.9500
C4—H4	1.0000	C24—C25	1.407 (3)
C5—C5a	1.502 (3)	C24—H24	0.9500
C5—H5A	0.9900	C25—C26	1.411 (3)
C5—H5B	0.9900	C25—C210	1.417 (3)
C5a—C6	1.369 (3)	C26—C27	1.354 (4)
C5a—C9a	1.392 (3)	C26—H26	0.9500
C6—C7	1.367 (3)	C27—C28	1.398 (3)
C6—H6	0.9500	C27—H27	0.9500
C7—C8	1.377 (3)	C28—C29	1.365 (3)
C7—H7	0.9500	C28—H28	0.9500
C8—C9	1.378 (3)	C29—C210	1.408 (3)
C8—Cl8	1.735 (2)	C29—H29	0.9500
O14—N1—C9a	108.06 (16)	C9a—C9—C91	121.6 (2)
O14—N1—C2	102.25 (16)	C9—C91—H91A	109.5
C9a—N1—C2	109.15 (16)	C9—C91—H91B	109.5
N1—C2—C21	112.92 (17)	H91A—C91—H91B	109.5
N1—C2—C3	103.54 (17)	C9—C91—H91C	109.5
C21—C2—C3	112.41 (17)	H91A—C91—H91C	109.5
N1—C2—H2	109.3	H91B—C91—H91C	109.5
C21—C2—H2	109.3	C5a—C9a—C9	122.3 (2)
C3—C2—H2	109.3	C5a—C9a—N1	120.79 (19)
C4—C3—C2	103.26 (18)	C9—C9a—N1	116.9 (2)
C4—C3—H3A	111.1	N1—O14—C4	104.32 (16)
C2—C3—H3A	111.1	C22—C21—C210	119.5 (2)
C4—C3—H3B	111.1	C22—C21—C2	121.9 (2)
C2—C3—H3B	111.1	C210—C21—C2	118.53 (18)
H3A—C3—H3B	109.1	C21—C22—C23	121.0 (2)
O14—C4—C5	105.56 (18)	C21—C22—H22	119.5
O14—C4—C3	104.39 (18)	C23—C22—H22	119.5
C5—C4—C3	113.4 (2)	C24—C23—C22	120.8 (2)
O14—C4—H4	111.1	C24—C23—H23	119.6
C5—C4—H4	111.1	C22—C23—H23	119.6
C3—C4—H4	111.1	C23—C24—C25	120.4 (2)
C5a—C5—C4	109.12 (19)	C23—C24—H24	119.8
C5a—C5—H5A	109.9	C25—C24—H24	119.8
C4—C5—H5A	109.9	C24—C25—C26	121.5 (2)
C5a—C5—H5B	109.9	C24—C25—C210	119.5 (2)
C4—C5—H5B	109.9	C26—C25—C210	119.0 (2)
H5A—C5—H5B	108.3	C27—C26—C25	121.2 (2)
C6—C5a—C9a	118.6 (2)	C27—C26—H26	119.4
C6—C5a—C5	121.5 (2)	C25—C26—H26	119.4
C9a—C5a—C5	120.0 (2)	C26—C27—C28	119.9 (2)
C7—C6—C5a	121.1 (2)	C26—C27—H27	120.1
C7—C6—H6	119.4	C28—C27—H27	120.1
C5a—C6—H6	119.4	C29—C28—C27	120.7 (2)
C6—C7—C8	119.0 (2)	C29—C28—H28	119.7
C6—C7—H7	120.5	C27—C28—H28	119.7
C8—C7—H7	120.5	C28—C29—C210	120.9 (2)
C7—C8—C9	123.0 (2)	C28—C29—H29	119.5
C7—C8—Cl8	117.58 (18)	C210—C29—H29	119.5
C9—C8—Cl8	119.45 (18)	C29—C210—C25	118.3 (2)
C8—C9—C9a	116.0 (2)	C29—C210—C21	122.9 (2)
C8—C9—C91	122.4 (2)	C25—C210—C21	118.8 (2)
O14—N1—C2—C21	83.36 (19)	O14—N1—C9a—C9	−156.09 (17)
C9a—N1—C2—C21	−162.36 (17)	C2—N1—C9a—C9	93.5 (2)
O14—N1—C2—C3	−38.48 (19)	C9a—N1—O14—C4	−66.58 (19)
C9a—N1—C2—C3	75.8 (2)	C2—N1—O14—C4	48.49 (19)
N1—C2—C3—C4	15.3 (2)	C5—C4—O14—N1	81.67 (19)
C21—C2—C3—C4	−106.9 (2)	C3—C4—O14—N1	−38.1 (2)
C2—C3—C4—O14	13.1 (2)	N1—C2—C21—C22	−19.3 (3)
C2—C3—C4—C5	−101.2 (2)	C3—C2—C21—C22	97.4 (2)
O14—C4—C5—C5a	−50.4 (2)	N1—C2—C21—C210	163.82 (18)
C3—C4—C5—C5a	63.2 (3)	C3—C2—C21—C210	−79.5 (2)
C4—C5—C5a—C6	−167.4 (2)	C210—C21—C22—C23	−0.1 (3)
C4—C5—C5a—C9a	10.7 (3)	C2—C21—C22—C23	−176.90 (19)
C9a—C5a—C6—C7	−1.5 (3)	C21—C22—C23—C24	−1.3 (3)
C5—C5a—C6—C7	176.6 (2)	C22—C23—C24—C25	1.5 (3)
C5a—C6—C7—C8	0.2 (3)	C23—C24—C25—C26	177.9 (2)
C6—C7—C8—C9	0.8 (3)	C23—C24—C25—C210	−0.5 (3)
C6—C7—C8—Cl8	−178.68 (17)	C24—C25—C26—C27	−178.7 (2)
C7—C8—C9—C9a	−0.5 (3)	C210—C25—C26—C27	−0.3 (3)
Cl8—C8—C9—C9a	179.04 (15)	C25—C26—C27—C28	−0.1 (3)
C7—C8—C9—C91	179.7 (2)	C26—C27—C28—C29	0.5 (3)
Cl8—C8—C9—C91	−0.8 (3)	C27—C28—C29—C210	−0.4 (3)
C6—C5a—C9a—C9	1.8 (3)	C28—C29—C210—C25	0.0 (3)
C5—C5a—C9a—C9	−176.24 (19)	C28—C29—C210—C21	179.6 (2)
C6—C5a—C9a—N1	−179.80 (19)	C24—C25—C210—C29	178.8 (2)
C5—C5a—C9a—N1	2.1 (3)	C26—C25—C210—C29	0.3 (3)
C8—C9—C9a—C5a	−0.9 (3)	C24—C25—C210—C21	−0.8 (3)
C91—C9—C9a—C5a	179.0 (2)	C26—C25—C210—C21	−179.3 (2)
C8—C9—C9a—N1	−179.31 (18)	C22—C21—C210—C29	−178.5 (2)
C91—C9—C9a—N1	0.6 (3)	C2—C21—C210—C29	−1.6 (3)
O14—N1—C9a—C5a	25.5 (3)	C22—C21—C210—C25	1.1 (3)
C2—N1—C9a—C5a	−85.0 (2)	C2—C21—C210—C25	178.00 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cg7^i	0.95	2.75	3.522 (2)	139
C27—H27···Cg5^ii	0.95	2.57	3.432 (3)	151

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