(2R,4S)-7-Bromo-2-phenyl-2,3,4,5-tetra­hydro-1,4-epoxy­naphtho[1,2-b]azepine, (2RS,4SR)-7-bromo-2-(4-chloro­phenyl-2,3,4,5-tetra­hydro-1,4-epoxy­naphtho[1,2-b]azepine and (2RS,4SR)-2-(4-fluoro­phen­yl)-2,3,4,5-tetra­hydro-1,4-epoxy­naphtho[1,2-b]azepine: hydrogen-bonded structures in two and three dimensions

(2R,4S)-7-Bromo-2-phenyl-2,3,4,5-tetra­hydro-1,4-epoxy­naphtho[1,2-b]azepine, C₂₀H₁₆BrNO, (I), exhibits evidence of a modest degree (ca 10%) of inversion twinning, while both (2RS,4SR)-7-bromo-2-(4-chloro­phenyl)-2,3,4,5-tetra­hydro-1,4-epoxy­naphtho[1,2-b]azepine, C₂₀H₁₅BrClNO, (II), and (2RS,4SR)-2-(4-fluoro­phen­yl)-2,3,4,5-tetra­hydro-1,4-epoxy­naphtho[1,2-b]azepine, C₂₀H₁₆FNO, (III), crystallize as genuine racemic mixtures. The mol­ecules of (I) are linked into sheets by a combination of one C-H...O hydrogen bond and two C-H...[pi](arene) hydrogen bonds, while those of (II) are linked into sheets of [pi]-stacked hydrogen-bonded chains. A combination of one C-H...O hydrogen bond and four independent C-H...[pi](arene) hydrogen bonds links the mol­ecules of (III) into a three-dimensional framework. The significance of this study lies in its finding, via comparison with the structures of some closely-related epoxybenzazepine analogues, of significant changes in crystal structures consequent upon small changes in the peripheral substituents.

S1. Comment

As part of a wider programme aimed at the synthesis and characterization of novel fused azepines, as potential antiprotozoal agents (Gómez et al., 2006; Yépez et al., 2006), we have recently reported on the molecular structures and supramolecular aggregation in several different types of substituted tetrahydro-1,4-epoxy-1-benzazepines (Acosta et al., 2008; Blanco et al., 2008; Gómez et al., 2008;). We have now extended this study to encompass analogues containing the tetrahydro-1,4-epoxy-naphth[2,1-b]azepine framework, and here we report the structure of three such compounds, (2R,4S)-7-bromo-2-exo-4-phenyl-2,3,4,5-tetrahydro-1H-1,4-epoxy naphtho[2,1-b]azepine, (I), (2RS,4SR)-7-bromo-2-exo-4- (4-chlorophenyl-2,3,4,5-tetrahydro-1H-1,4-epoxynaphtho[2,1-b]azepine, (II), and (2RS,4SR)-2-exo-4-(4-fluorophenyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxynaphtho[2,1-b]azepine, (III) (Figs. 1–3).

While compounds (II) and (III) crystallize as racemic mixtures in space groups Pbca and P2₁/c, respectively, compound (I) crystallizes in space group P2₁, and it was handled as an inversion twin, giving twin fractions for the crystal selected for data collection of 0.901 (15) for the (2R,4S) enantiomer and 0.099 (15) for the (2S,4R) enantiomer. Accordingly, the reference molecule in the racemic compounds (II) and (III) were each selected as having the (2R,4S) configuration. This behaviour in (I)–(III) may be contrasted with the behaviour (Gómez et al., 2008) of the aryl-substituted tetrahydro-1,4-epoxy-1-benzazepines (IV)–(VI). Compound (IV) crystallizes as a racemic mixture in space group Pna2₁, while each of (V) and (VI) crystallize as a single enantiomorph, both in space group P2₁2₁2₁, having the opposite configuration (2S,4R), as shown by the values of the Flack (1983) x parameter. Since the majority of the other substituted tetrahydro-1,4-epoxy-1-benzazepines that we have studied recently have been found to crystallize either as true racemic mixtures (Blanco et al., 2008) or as inversion twins containing unequal numbers of the two enantiomers (Acosta et al., 2008), it seems likely that all such species are, in fact, synthesized as racemic mixtures, particularly since their syntheses offer no obvious scope for enantiospecific discrimination. It is surprising, however, that of the 12 fused epoxyazepines of this type studied to date by us, including the three reported here, only six crystallize in space groups containing reflection or inversion operators; the other six all crystallize either in P2₁ or in P2₁2₁2₁, three as inversion twins and only three as single enantiomers.

The conformations of the fused heterocyclic systems in (I)–(III) are extremely similar, as shown by the values (Table 1) of the ring-puckering parameters (Cremer & Pople, 1975). The five-membered ring components adopt envelope conformations, folded across the line N1···C4 (Figs. 1–3), while the six-membered rings have conformations intermediate between envelope and half-chair forms, where the idealized values of the ring-puckering angles are θ = 54.7° and ϕ = 60n°, and θ = 50.8° and ϕ = (60n + 30)°, respectively, where n represents an integer. The N1—C2—C21—C22 torsion angles describing the orientation of the pendent aryl ring relative to the azepine ring are also fairly similar: -177.3 (4)° in (I), 172.4 (3)° in (II) and -171.98 (17)° in (III).

Despite the rather similar conformations, and the overall similarity in the molecular shapes in (I)–(III), the patterns of their supramolecular aggregation are significantly different. The hydrogen-bonded structure of (I) is dominated by one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds (Table 2). There is a short C—H···Br contact in this structure, but this involves an aliphatic C—H bond of fairly low acidity and, more importantly, it has been shown that Br bonded to C is an extremely poor acceptor of hydrogen bonds (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001); accordingly, this contact must be regarded as being not structurally significant. The C—H···O hydrogen bonds links molecules related by the 2₁ screw axis along (0, y, 1) into a C(7) (Bernstein et al., 1995) chain running parallel to the [010] direction. At the same time, the C—H···π(arene) hydrogen bond having the aryl atom C23 as the donor links molecules related by translation along [010]. The combination of these two interactions then generates a chain of rings running parallel to the [010] direction (Fig. 3). The other C—H···π(arene) hydrogen bond has an aliphatic C atom as the donor and the pendent phenyl ring as the acceptor, and its effect is to link molecules related by the 2₁ screw axis along (1/2, y, 1) into a second chain running parallel to the [010] direction (Fig. 4). The combined action of the two independent [010] chains is to link the molecules into a sheet parallel to (001). There are no direction-specific interactions between adjacent sheets, so that the hydrogen-bonded structure in (I) is two-dimensional.

Molecules of compound (II) related by the b-glide plane at x = 1/4 are linked by a single, rather weak C—H···O hydrogen bond (Table 2) into a C(4) chain running parallel to the [010] direction. Chains of this type are linked into sheets by a single aromatic π–π stacking interaction. The chlorinated aryl rings of the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel with an interplanar spacing of 3.500 (2) Å. The ring-centroid separation is 3.833 (2) Å, corresponding to a ring-centroid offset of 1.563 (2) Å. The effect of this interaction is to link the C(4) chain involving the glide plane at x = 0.25 to the two chains involving glide planes at x = 0.75 and x = -0.25, respectively, so generating a sheet of π-stacked hydrogen-bonded chains lying parallel to (001) (Fig. 6).

The hydrogen-bonded structure of (III) is three-dimensional and it is determined by a combination of one C—H···O hydrogen bond and four independent C—H···π(arene) hydrogen bonds; in the event, just three of these interactions suffice to demonstrate the three-dimensional nature of the hydrogen-bonded structure. The C—H···π(arene) interaction having atom C3 as the donor links molecules related by the c-glide plane at y = 3/4 into a chain running parallel to the [001] direction (Fig. 7), while that having atom C5 as the donor links molecules related by the 2₁ screw axis along (1/2, y, 1/4) into a chain running parallel to the [010] direction (Fig. 8). The combination of these two chains generates a sheet parallel to (100), and a third hydrogen bond links adjacent sheets to form a continuous three-dimensional framework via a cyclic centrosymmetric motif (Fig. 9). The C—H···O hydrogen bond lies within the (100) sheet, while the final C—H···π(arene) interaction reinforces, albeit weakly, the linking of adjacent (100) sheets.

It is of interest briefly to compare the hydrogen-bonded structures of compounds (I)–(III) with those of the benzazepine analogues (IV)–(VI) (Gómez et al., 2008). In the monohalogented compound (VI), a combination of one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds generates a three-dimensional structure in space group P2₁2₁2₁. Two substructures can readily be identified, one of them one-dimensional and the other two-dimensional. Not only do the two isomeric dichloro compounds (IV) and (V) exhibit different space groups (Pna2₁ and P2₁2₁2₁, respectively) with very different unit-cell dimensions, but their hydrogen-bonded structures also differ considerably. In (IV), a combination of C—H···O and C—H···N hydrogen bonds generates a chain of edge-fused R³₃(12) rings; this is the only example so far studied whose structure both contains a C—H···N hydrogen bond and does not contain a C—H···π(arene) hydrogen bond. In the structure of (IV), one C—H···O and two C—H···π(arene) hydrogen bonds acting individually generate three orthogonal chains of molecules related by different 2₁ screw axes which, in combination, give rise to a three-dimensional framework structure. Thus, although the hydrogen-bonded structures in (III), (V) and (VI) are all three-dimensional, there are few if any similarities in the detailed construction of the frameworks involved. The differences in crystal structures observed for (I)–(VI) are all consequent upon rather modest changes in the substituents.

Related literature

For related literature, see: Aakeröy et al. (1999); Acosta et al. (2008); Bernstein et al. (1995); Blanco et al. (2008); Brammer et al. (2001); Cremer & Pople (1975); Flack (1983); Gómez et al. (2006, 2008); Hooft et al. (2008); Sheldrick (2008); Thallapally & Nangia (2001); Yépez et al. (2006).

S2. Experimental

To a stirred solution of 0.10 mol of the appropriately substituted 2-allyl-N-benzyl-1-naphthylamine in methanol (40 ml) was added sodium tungstate dihydrate, Na₂WO₄.2H₂O (5 mol %), followed by 30% aqueous hydrogen peroxide solution (0.30 mol). The resulting mixtures were then stirred at room temperature for 45–50 h. Each mixture was filtered and then evaporated to dryness. The crude products were purified by column chromatography on silica gel using heptane/ethyl acetate (30:1 v/v) as eluant. Finally, the resulting 2-exo-aryl-1,4-epoxycycloadducts were recrystallized from heptane, providing crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction. For (I), colourless crystals, yield 52%, m.p. 412–413 K; MS (70 eV) m/z (%): 365 (M⁺, ⁷⁹Br, 10), 336 (5), 286 (2), 257 (9), 243 (22), 220 (100), 180 (4), 139 (28), 128 (14), 115 (6); analysis found: C 65.7, H 4.4, N, 3.8%; C₂₀H₁₆BrNO requires: C 65.6, H 4.4, N 3.8%. For (II), colourless crystals, yield 48%, m.p. 459–460 K; MS (70 eV) m/z (%): 399 (M⁺, ⁷⁹Br, ³⁵Cl, 5), 370 (3), 291 (6), 277 (14), 220 (100), 180 (5), 152 (5), 139 (33), 128 (19), 115 (5); analysis found: C 59.9, H 3.8, N 3.6%; C₂₀H₁₅BrClNO requires: C 59.95, H 3.8, N 3.5%. For (III), pale-yellow crystals, yield 49%, m.p. 401–402 K; MS (70 eV) m/z (%): 305 (M⁺, 10), 276 (5), 262 (14), 142 (100), 115 (17); analysis found: C 78.5, H 5.3, N 4.6%; C₂₀H₁₆FNO requires: C 78.7, H 5.3, N, 4.6%.

S3. Refinement

For (I) the systematic absences permitted P2₁ and P2₁/m as possible space groups; P2₁ was selected and confirmed by the successful structure analysis. For (II) and (III), the space groups were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances 0.95 Å (aromatic), 0.99 Å (CH₂) or 1.00 Å (aliphatic C—H) and with U_iso(H) = 1.2U_eq(C). A straightforward (`hole-in-one') calculation of the Flack (1983) x parameter for (I) gave a value of 0.089 (14), with a Hooft y parameter (Hooft et al., 2008) of 0.186 (12). In the presence of a Br atom, the deviation from zero of the Flack x parameter was significant and it seemed rather large, possibly suggesting a modest degree of inversion twinning. Calculation of the twin fractions using the TWIN/BASF procedure in SHELXL (Sheldrick, 2008) gave, for the crystal under study, twin fractions of 0.901 (15) for the (2R,4S) enantiomer and 0.099 (15) for the (2S,4R) form. Accordingly, the (2R,4S) configuration was selected for the reference molecules in the racemic compounds (II) and (III).

Computing details

For all compounds, data collection: COLLECT (Hooft, 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: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of (I), with configuration (2R,4S), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of the (2R,4S) enantiomer in the racemic compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The molecular structure of the (2R,4S) enantiomer in the racemic compound (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a chain of rings along (0, y, 1) formed by the two hydrogen bonds having aryl C atoms as the donors. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a chain along (1/2, y, 1) formed by the single hydrogen bond having an aliphatic C atom as the donor. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (II), showing two of the C(4) hydrogen-bonded chains, those based on the glide planes at x = 1/4 and x = 3/4, which form part of the (001) sheet of π-stacked chains For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a chain running parallel to [001]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 8. A stereoview of part of the crystal structure of compound (III), showing the formation of a chain running parallel to [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 9. Part of the crystal structure of (III), showing the formation of a cyclic centrosymmetric motif which links adjacent (100) sheets. For the sake of clarity, H atoms not involved in the motif shown have been omitted. The atom marked with an asterisk (*) is at the symmetry position (-x + 2, -y + 1, -z + 1).

(I) (2R,4S)-7-Bromo-2-phenyl-2,3,4,5-tetrahydro-1,4- epoxynaphtho[1,2-b]azepine

Crystal data

C20H16BrNO	F(000) = 372
Mr = 366.24	Dx = 1.567 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3132 reflections
a = 7.8444 (3) Å	θ = 3.2–27.5°
b = 9.8146 (4) Å	µ = 2.65 mm^−1
c = 10.0871 (4) Å	T = 120 K
β = 92.103 (3)°	Lath, colourless
V = 776.08 (5) Å^3	0.20 × 0.04 × 0.01 mm
Z = 2

Data collection

Bruker–Nonius KappaCCD diffractometer	3132 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2810 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ & ω scans	h = −8→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.619, Tmax = 0.974	l = −12→13
7511 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) = 0.102	w = 1/[σ^2(Fo^2) + (0.P)^2 + 1.3066P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3132 reflections	Δρmax = 0.44 e Å^−3
209 parameters	Δρmin = −0.53 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1237 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.099 (15)

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

	x	y	z	Uiso*/Ueq
N1	0.3120 (4)	0.4045 (5)	0.8557 (3)	0.0199 (10)
C2	0.3417 (6)	0.5346 (5)	0.7883 (5)	0.0201 (11)
H2	0.3459	0.5180	0.6906	0.024*
C3	0.5203 (6)	0.5823 (6)	0.8414 (6)	0.0242 (12)
H31	0.6046	0.5802	0.7707	0.029*
H32	0.5155	0.6755	0.8786	0.029*
C4	0.5639 (5)	0.4762 (5)	0.9507 (5)	0.0209 (9)
H4	0.6201	0.5210	1.0299	0.025*
C5	0.6708 (6)	0.3582 (5)	0.9037 (5)	0.0213 (10)
H51	0.7693	0.3935	0.8557	0.026*
H52	0.7151	0.3054	0.9812	0.026*
C5A	0.5655 (6)	0.2670 (6)	0.8136 (5)	0.0184 (10)
C6	0.6385 (6)	0.1533 (5)	0.7509 (5)	0.0214 (10)
H6	0.7536	0.1292	0.7721	0.026*
C7	0.5455 (6)	0.0775 (5)	0.6600 (5)	0.0237 (10)
Br7	0.65110 (6)	−0.07516 (7)	0.58212 (4)	0.03017 (14)
C7A	0.3737 (6)	0.1107 (5)	0.6227 (4)	0.0206 (10)
C8	0.2790 (6)	0.0455 (5)	0.5184 (5)	0.0248 (10)
H8	0.3299	−0.0258	0.4700	0.030*
C9	0.1138 (6)	0.0846 (5)	0.4863 (5)	0.0251 (10)
H9	0.0525	0.0416	0.4149	0.030*
C10	0.0358 (6)	0.1881 (5)	0.5591 (5)	0.0248 (10)
H10	−0.0788	0.2131	0.5374	0.030*
C11	0.1222 (6)	0.2534 (5)	0.6606 (5)	0.0242 (10)
H11	0.0670	0.3220	0.7098	0.029*
C11A	0.2961 (6)	0.2181 (5)	0.6925 (4)	0.0183 (9)
C11B	0.3954 (6)	0.2940 (5)	0.7873 (5)	0.0186 (11)
O14	0.3988 (3)	0.4218 (6)	0.9831 (2)	0.0201 (6)
C21	0.1990 (5)	0.6365 (5)	0.8145 (4)	0.0185 (9)
C22	0.2026 (6)	0.7628 (5)	0.7539 (5)	0.0218 (10)
H22	0.2936	0.7854	0.6984	0.026*
C23	0.0735 (6)	0.8565 (5)	0.7741 (5)	0.0253 (10)
H23	0.0748	0.9424	0.7307	0.030*
C24	−0.0574 (6)	0.8248 (5)	0.8576 (5)	0.0244 (10)
H24	−0.1459	0.8888	0.8716	0.029*
C25	−0.0585 (6)	0.7003 (5)	0.9200 (5)	0.0247 (10)
H25	−0.1466	0.6789	0.9787	0.030*
C26	0.0675 (6)	0.6065 (5)	0.8978 (5)	0.0217 (10)
H26	0.0644	0.5201	0.9401	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0195 (16)	0.022 (3)	0.0183 (16)	0.0027 (17)	−0.0010 (13)	−0.0014 (19)
C2	0.025 (3)	0.015 (3)	0.020 (2)	0.001 (2)	0.0019 (19)	0.001 (2)
C3	0.022 (3)	0.016 (3)	0.034 (3)	−0.0010 (19)	0.003 (2)	0.001 (2)
C4	0.014 (2)	0.020 (2)	0.028 (2)	−0.0022 (16)	0.0016 (18)	−0.0001 (18)
C5	0.021 (2)	0.021 (2)	0.022 (2)	0.0003 (18)	−0.0072 (18)	0.001 (2)
C5A	0.020 (2)	0.018 (3)	0.017 (2)	−0.0017 (19)	−0.0016 (18)	−0.0003 (19)
C6	0.015 (2)	0.022 (3)	0.026 (2)	0.0017 (18)	−0.0016 (17)	−0.002 (2)
C7	0.027 (2)	0.023 (3)	0.022 (2)	0.006 (2)	0.0039 (19)	0.002 (2)
Br7	0.0374 (2)	0.0256 (2)	0.0276 (2)	0.0118 (3)	0.00207 (16)	−0.0042 (3)
C7A	0.031 (2)	0.015 (2)	0.016 (2)	0.0028 (19)	0.0005 (18)	0.0024 (18)
C8	0.030 (3)	0.024 (3)	0.021 (2)	0.000 (2)	0.0014 (19)	−0.001 (2)
C9	0.033 (3)	0.019 (3)	0.023 (2)	−0.005 (2)	−0.006 (2)	0.000 (2)
C10	0.023 (2)	0.020 (3)	0.031 (3)	−0.0011 (19)	−0.0038 (19)	0.007 (2)
C11	0.027 (2)	0.019 (2)	0.027 (2)	−0.0015 (19)	0.0014 (19)	0.002 (2)
C11A	0.020 (2)	0.019 (2)	0.016 (2)	0.0009 (18)	0.0037 (17)	0.0058 (18)
C11B	0.026 (3)	0.010 (2)	0.020 (2)	−0.0031 (19)	0.003 (2)	0.0024 (19)
O14	0.0199 (13)	0.0250 (15)	0.0153 (12)	−0.005 (2)	0.0000 (10)	0.000 (2)
C21	0.014 (2)	0.021 (2)	0.020 (2)	−0.0001 (17)	−0.0023 (16)	−0.0044 (19)
C22	0.026 (2)	0.019 (2)	0.020 (2)	0.0017 (19)	0.0008 (18)	0.0005 (19)
C23	0.031 (3)	0.020 (3)	0.024 (2)	0.0037 (19)	−0.0018 (19)	0.002 (2)
C24	0.020 (2)	0.031 (3)	0.022 (2)	0.008 (2)	−0.0046 (18)	−0.002 (2)
C25	0.020 (2)	0.027 (3)	0.028 (3)	0.0001 (19)	0.0036 (18)	0.002 (2)
C26	0.023 (2)	0.018 (2)	0.024 (2)	0.0005 (18)	0.0023 (18)	−0.0018 (19)

Geometric parameters (Å, º)

N1—O14	1.442 (4)	C7A—C8	1.418 (7)
N1—C11B	1.454 (6)	C8—C9	1.378 (7)
N1—C2	1.469 (7)	C8—H8	0.9500
C2—C21	1.532 (7)	C9—C10	1.407 (7)
C2—C3	1.554 (7)	C9—H9	0.9500
C2—H2	1.0000	C10—C11	1.366 (7)
C3—C4	1.545 (7)	C10—H10	0.9500
C3—H31	0.9900	C11—C11A	1.433 (6)
C3—H32	0.9900	C11—H11	0.9500
C4—O14	1.449 (5)	C11A—C11B	1.421 (7)
C4—C5	1.516 (6)	C21—C22	1.382 (7)
C4—H4	1.0000	C21—C26	1.386 (6)
C5—C5A	1.501 (7)	C22—C23	1.389 (7)
C5—H51	0.9900	C22—H22	0.9500
C5—H52	0.9900	C23—C24	1.387 (7)
C5A—C11B	1.377 (7)	C23—H23	0.9500
C5A—C6	1.414 (7)	C24—C25	1.375 (7)
C6—C7	1.370 (7)	C24—H24	0.9500
C6—H6	0.9500	C25—C26	1.375 (7)
C7—C7A	1.424 (6)	C25—H25	0.9500
C7—Br7	1.896 (5)	C26—H26	0.9500
C7A—C11A	1.418 (6)
O14—N1—C11B	107.8 (4)	C8—C7A—C7	123.9 (4)
O14—N1—C2	103.5 (4)	C9—C8—C7A	120.7 (5)
C11B—N1—C2	110.3 (3)	C9—C8—H8	119.6
N1—C2—C21	111.0 (4)	C7A—C8—H8	119.6
N1—C2—C3	105.0 (4)	C8—C9—C10	120.1 (4)
C21—C2—C3	113.5 (4)	C8—C9—H9	120.0
N1—C2—H2	109.1	C10—C9—H9	120.0
C21—C2—H2	109.1	C11—C10—C9	121.1 (5)
C3—C2—H2	109.1	C11—C10—H10	119.4
C4—C3—C2	102.5 (4)	C9—C10—H10	119.4
C4—C3—H31	111.3	C10—C11—C11A	119.8 (5)
C2—C3—H31	111.3	C10—C11—H11	120.1
C4—C3—H32	111.3	C11A—C11—H11	120.1
C2—C3—H32	111.3	C7A—C11A—C11B	119.3 (4)
H31—C3—H32	109.2	C7A—C11A—C11	119.4 (4)
O14—C4—C5	107.3 (4)	C11B—C11A—C11	121.3 (4)
O14—C4—C3	103.5 (4)	C5A—C11B—C11A	122.2 (5)
C5—C4—C3	113.7 (4)	C5A—C11B—N1	120.1 (5)
O14—C4—H4	110.7	C11A—C11B—N1	117.7 (4)
C5—C4—H4	110.7	N1—O14—C4	103.8 (3)
C3—C4—H4	110.7	C22—C21—C26	119.1 (4)
C5A—C5—C4	110.3 (4)	C22—C21—C2	118.8 (4)
C5A—C5—H51	109.6	C26—C21—C2	122.0 (4)
C4—C5—H51	109.6	C21—C22—C23	120.1 (4)
C5A—C5—H52	109.6	C21—C22—H22	119.9
C4—C5—H52	109.6	C23—C22—H22	119.9
H51—C5—H52	108.1	C24—C23—C22	120.0 (5)
C11B—C5A—C6	118.1 (5)	C24—C23—H23	120.0
C11B—C5A—C5	120.7 (5)	C22—C23—H23	120.0
C6—C5A—C5	121.2 (4)	C25—C24—C23	119.6 (4)
C7—C6—C5A	120.9 (4)	C25—C24—H24	120.2
C7—C6—H6	119.6	C23—C24—H24	120.2
C5A—C6—H6	119.6	C26—C25—C24	120.3 (4)
C6—C7—C7A	121.9 (4)	C26—C25—H25	119.9
C6—C7—Br7	118.4 (3)	C24—C25—H25	119.9
C7A—C7—Br7	119.7 (4)	C25—C26—C21	120.8 (5)
C11A—C7A—C8	118.8 (4)	C25—C26—H26	119.6
C11A—C7A—C7	117.3 (4)	C21—C26—H26	119.6
O14—N1—C2—C21	−90.7 (4)	C10—C11—C11A—C11B	172.9 (5)
C11B—N1—C2—C21	154.4 (4)	C6—C5A—C11B—C11A	−4.8 (7)
O14—N1—C2—C3	32.4 (4)	C5—C5A—C11B—C11A	173.6 (4)
C11B—N1—C2—C3	−82.6 (5)	C6—C5A—C11B—N1	176.1 (4)
N1—C2—C3—C4	−6.6 (5)	C5—C5A—C11B—N1	−5.4 (7)
C21—C2—C3—C4	114.8 (5)	C7A—C11A—C11B—C5A	0.2 (7)
C2—C3—C4—O14	−21.2 (5)	C11—C11A—C11B—C5A	−176.0 (5)
C2—C3—C4—C5	94.9 (5)	C7A—C11A—C11B—N1	179.3 (4)
O14—C4—C5—C5A	42.3 (5)	C11—C11A—C11B—N1	3.0 (7)
C3—C4—C5—C5A	−71.5 (5)	O14—N1—C11B—C5A	−28.3 (6)
C4—C5—C5A—C11B	−1.8 (6)	C2—N1—C11B—C5A	83.9 (5)
C4—C5—C5A—C6	176.6 (4)	O14—N1—C11B—C11A	152.6 (4)
C11B—C5A—C6—C7	4.2 (7)	C2—N1—C11B—C11A	−95.2 (5)
C5—C5A—C6—C7	−174.3 (5)	C11B—N1—O14—C4	69.3 (4)
C5A—C6—C7—C7A	1.2 (7)	C2—N1—O14—C4	−47.4 (4)
C5A—C6—C7—Br7	−179.0 (4)	C5—C4—O14—N1	−78.1 (4)
C6—C7—C7A—C11A	−5.8 (7)	C3—C4—O14—N1	42.4 (5)
Br7—C7—C7A—C11A	174.4 (3)	N1—C2—C21—C22	−177.3 (4)
C6—C7—C7A—C8	172.3 (5)	C3—C2—C21—C22	64.7 (6)
Br7—C7—C7A—C8	−7.5 (6)	N1—C2—C21—C26	3.3 (6)
C11A—C7A—C8—C9	−0.8 (7)	C3—C2—C21—C26	−114.7 (5)
C7—C7A—C8—C9	−178.9 (4)	C26—C21—C22—C23	−1.6 (7)
C7A—C8—C9—C10	−1.4 (7)	C2—C21—C22—C23	179.0 (4)
C8—C9—C10—C11	1.3 (7)	C21—C22—C23—C24	1.5 (7)
C9—C10—C11—C11A	1.1 (7)	C22—C23—C24—C25	0.0 (7)
C8—C7A—C11A—C11B	−173.2 (4)	C23—C24—C25—C26	−1.3 (7)
C7—C7A—C11A—C11B	5.0 (6)	C24—C25—C26—C21	1.2 (7)
C8—C7A—C11A—C11	3.1 (6)	C22—C21—C26—C25	0.3 (7)
C7—C7A—C11A—C11	−178.7 (4)	C2—C21—C26—C25	179.7 (4)
C10—C11—C11A—C7A	−3.3 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br7^i	1.00	2.90	3.891 (5)	171
C5—H52···Cg1^ii	0.99	2.55	3.484 (5)	157
C23—H23···Cg2^iii	0.95	2.70	3.596 (5)	157
C24—H24···O14^iv	0.95	2.53	3.313 (6)	140

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

(II) (2RS,4SR)-7-bromo-2-(4-chlorophenyl-2,3,4,5-tetrahydro- 1,4-epoxynaphtho[1,2-b]azepine

Crystal data

C20H15BrClNO	F(000) = 1616
Mr = 400.69	Dx = 1.671 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3658 reflections
a = 9.7758 (16) Å	θ = 3.2–27.5°
b = 9.8211 (14) Å	µ = 2.76 mm^−1
c = 33.174 (3) Å	T = 120 K
V = 3185.0 (7) Å^3	Block, colourless
Z = 8	0.32 × 0.12 × 0.04 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	3658 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2574 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ & ω scans	h = −12→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→12
Tmin = 0.551, Tmax = 0.896	l = −42→42
28541 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0262P)^2 + 5.3752P] where P = (Fo^2 + 2Fc^2)/3
3658 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.4336 (3)	0.5489 (3)	0.37768 (7)	0.0152 (5)
C2	0.3734 (3)	0.4859 (3)	0.41377 (9)	0.0161 (7)
H2	0.4193	0.3968	0.4192	0.019*
C3	0.2232 (3)	0.4606 (3)	0.40147 (9)	0.0189 (7)
H31	0.2063	0.3627	0.3965	0.023*
H32	0.1595	0.4931	0.4226	0.023*
C4	0.2072 (3)	0.5427 (3)	0.36305 (9)	0.0184 (7)
H4	0.1196	0.5954	0.3633	0.022*
C5	0.2181 (3)	0.4565 (3)	0.32548 (9)	0.0175 (7)
H51	0.1518	0.3805	0.3268	0.021*
H52	0.1965	0.5122	0.3015	0.021*
C5A	0.3599 (3)	0.4015 (3)	0.32217 (9)	0.0153 (6)
C6	0.3921 (3)	0.3014 (3)	0.29326 (9)	0.0172 (7)
H6	0.3234	0.2704	0.2752	0.021*
C7	0.5195 (3)	0.2493 (3)	0.29095 (9)	0.0174 (7)
Br7	0.55294 (3)	0.11186 (3)	0.251972 (10)	0.02465 (10)
C7A	0.6265 (3)	0.2930 (3)	0.31632 (9)	0.0155 (7)
C8	0.7600 (3)	0.2415 (3)	0.31442 (9)	0.0197 (7)
H8	0.7812	0.1709	0.2959	0.024*
C9	0.8594 (3)	0.2916 (3)	0.33882 (10)	0.0206 (7)
H9	0.9493	0.2553	0.3374	0.025*
C10	0.8305 (3)	0.3963 (3)	0.36610 (10)	0.0208 (7)
H10	0.9014	0.4321	0.3825	0.025*
C11	0.7015 (3)	0.4473 (3)	0.36930 (9)	0.0186 (7)
H11	0.6828	0.5176	0.3882	0.022*
C11A	0.5959 (3)	0.3970 (3)	0.34491 (9)	0.0149 (6)
C11B	0.4605 (3)	0.4467 (3)	0.34744 (9)	0.0146 (6)
O14	0.3237 (2)	0.6333 (2)	0.36334 (6)	0.0174 (5)
C21	0.3881 (3)	0.5770 (3)	0.44995 (9)	0.0151 (7)
C22	0.3230 (3)	0.5412 (3)	0.48554 (9)	0.0200 (7)
H22	0.2710	0.4596	0.4866	0.024*
C23	0.3323 (3)	0.6222 (3)	0.51960 (10)	0.0216 (7)
H23	0.2873	0.5970	0.5439	0.026*
C24	0.4077 (3)	0.7393 (3)	0.51753 (9)	0.0184 (7)
Cl24	0.41575 (9)	0.84425 (9)	0.55984 (2)	0.0279 (2)
C25	0.4763 (3)	0.7764 (3)	0.48327 (10)	0.0206 (7)
H25	0.5304	0.8568	0.4827	0.025*
C26	0.4652 (3)	0.6943 (3)	0.44955 (9)	0.0192 (7)
H26	0.5118	0.7194	0.4256	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0147 (13)	0.0147 (13)	0.0162 (13)	0.0064 (11)	0.0008 (10)	0.0000 (10)
C2	0.0173 (16)	0.0132 (16)	0.0178 (16)	0.0004 (13)	0.0037 (13)	0.0008 (13)
C3	0.0202 (18)	0.0160 (17)	0.0206 (17)	−0.0013 (14)	0.0020 (13)	−0.0036 (13)
C4	0.0124 (15)	0.0188 (17)	0.0241 (17)	0.0000 (14)	0.0029 (13)	0.0015 (14)
C5	0.0130 (16)	0.0173 (17)	0.0223 (17)	−0.0006 (13)	0.0007 (13)	0.0001 (13)
C5A	0.0157 (15)	0.0126 (16)	0.0175 (15)	−0.0012 (13)	0.0020 (12)	0.0044 (13)
C6	0.0172 (16)	0.0177 (17)	0.0166 (16)	−0.0022 (13)	−0.0017 (13)	−0.0001 (13)
C7	0.0229 (17)	0.0134 (15)	0.0158 (16)	0.0005 (14)	0.0041 (13)	−0.0034 (13)
Br7	0.02227 (16)	0.02535 (17)	0.02632 (18)	0.00087 (15)	0.00264 (15)	−0.01117 (15)
C7A	0.0187 (17)	0.0145 (16)	0.0133 (15)	0.0009 (13)	0.0038 (12)	0.0040 (12)
C8	0.0190 (16)	0.0183 (17)	0.0219 (17)	0.0017 (15)	0.0036 (14)	0.0018 (14)
C9	0.0166 (16)	0.0225 (18)	0.0228 (18)	0.0041 (15)	0.0003 (13)	0.0015 (15)
C10	0.0197 (17)	0.0214 (18)	0.0214 (17)	−0.0021 (15)	−0.0065 (13)	−0.0010 (15)
C11	0.0193 (16)	0.0163 (16)	0.0201 (17)	−0.0026 (15)	0.0001 (13)	0.0007 (13)
C11A	0.0142 (14)	0.0152 (16)	0.0154 (15)	−0.0017 (14)	0.0032 (12)	0.0056 (13)
C11B	0.0165 (16)	0.0117 (15)	0.0157 (15)	−0.0001 (14)	0.0029 (13)	0.0019 (12)
O14	0.0147 (11)	0.0133 (12)	0.0243 (12)	0.0025 (9)	0.0011 (9)	0.0016 (9)
C21	0.0141 (15)	0.0123 (16)	0.0188 (16)	0.0028 (12)	−0.0003 (12)	−0.0007 (12)
C22	0.0190 (17)	0.0204 (18)	0.0206 (17)	−0.0035 (14)	0.0009 (13)	0.0019 (14)
C23	0.0201 (17)	0.0257 (19)	0.0190 (16)	−0.0009 (15)	0.0010 (13)	0.0001 (15)
C24	0.0187 (16)	0.0162 (17)	0.0203 (16)	0.0051 (14)	−0.0036 (13)	−0.0044 (13)
Cl24	0.0353 (5)	0.0248 (4)	0.0237 (4)	0.0017 (4)	−0.0041 (4)	−0.0085 (4)
C25	0.0206 (17)	0.0150 (17)	0.0263 (18)	−0.0004 (14)	−0.0015 (14)	−0.0018 (13)
C26	0.0186 (17)	0.0196 (17)	0.0195 (16)	−0.0012 (14)	0.0021 (13)	0.0028 (13)

Geometric parameters (Å, º)

N1—O14	1.438 (3)	C7A—C11A	1.425 (4)
N1—C11B	1.443 (4)	C8—C9	1.357 (4)
N1—C2	1.471 (4)	C8—H8	0.9500
C2—C21	1.504 (4)	C9—C10	1.398 (5)
C2—C3	1.544 (4)	C9—H9	0.9500
C2—H2	1.0000	C10—C11	1.361 (4)
C3—C4	1.516 (4)	C10—H10	0.9500
C3—H31	0.9900	C11—C11A	1.402 (4)
C3—H32	0.9900	C11—H11	0.9500
C4—O14	1.445 (4)	C11A—C11B	1.414 (4)
C4—C5	1.511 (4)	C21—C26	1.377 (4)
C4—H4	1.0000	C21—C22	1.386 (4)
C5—C5A	1.492 (4)	C22—C23	1.385 (5)
C5—H51	0.9900	C22—H22	0.9500
C5—H52	0.9900	C23—C24	1.368 (5)
C5A—C11B	1.366 (4)	C23—H23	0.9500
C5A—C6	1.408 (4)	C24—C25	1.369 (4)
C6—C7	1.349 (4)	C24—Cl24	1.743 (3)
C6—H6	0.9500	C25—C26	1.383 (4)
C7—C7A	1.410 (4)	C25—H25	0.9500
C7—Br7	1.897 (3)	C26—H26	0.9500
C7A—C8	1.401 (4)
O14—N1—C11B	107.9 (2)	C7—C7A—C11A	117.4 (3)
O14—N1—C2	102.3 (2)	C9—C8—C7A	120.6 (3)
C11B—N1—C2	110.3 (2)	C9—C8—H8	119.7
N1—C2—C21	111.2 (3)	C7A—C8—H8	119.7
N1—C2—C3	103.5 (2)	C8—C9—C10	120.5 (3)
C21—C2—C3	113.4 (3)	C8—C9—H9	119.7
N1—C2—H2	109.5	C10—C9—H9	119.7
C21—C2—H2	109.5	C11—C10—C9	120.6 (3)
C3—C2—H2	109.5	C11—C10—H10	119.7
C4—C3—C2	103.6 (2)	C9—C10—H10	119.7
C4—C3—H31	111.0	C10—C11—C11A	120.5 (3)
C2—C3—H31	111.0	C10—C11—H11	119.8
C4—C3—H32	111.0	C11A—C11—H11	119.8
C2—C3—H32	111.0	C11—C11A—C11B	122.2 (3)
H31—C3—H32	109.0	C11—C11A—C7A	118.8 (3)
O14—C4—C5	107.1 (2)	C11B—C11A—C7A	118.9 (3)
O14—C4—C3	103.9 (2)	C5A—C11B—C11A	121.7 (3)
C5—C4—C3	112.8 (3)	C5A—C11B—N1	121.4 (3)
O14—C4—H4	110.9	C11A—C11B—N1	116.9 (3)
C5—C4—H4	110.9	N1—O14—C4	103.7 (2)
C3—C4—H4	110.9	C26—C21—C22	118.1 (3)
C5A—C5—C4	109.2 (3)	C26—C21—C2	122.9 (3)
C5A—C5—H51	109.8	C22—C21—C2	119.0 (3)
C4—C5—H51	109.8	C23—C22—C21	121.3 (3)
C5A—C5—H52	109.8	C23—C22—H22	119.4
C4—C5—H52	109.8	C21—C22—H22	119.4
H51—C5—H52	108.3	C24—C23—C22	118.5 (3)
C11B—C5A—C6	119.0 (3)	C24—C23—H23	120.7
C11B—C5A—C5	120.4 (3)	C22—C23—H23	120.7
C6—C5A—C5	120.7 (3)	C23—C24—C25	122.0 (3)
C7—C6—C5A	120.6 (3)	C23—C24—Cl24	118.7 (3)
C7—C6—H6	119.7	C25—C24—Cl24	119.3 (3)
C5A—C6—H6	119.7	C24—C25—C26	118.5 (3)
C6—C7—C7A	122.4 (3)	C24—C25—H25	120.7
C6—C7—Br7	117.9 (2)	C26—C25—H25	120.7
C7A—C7—Br7	119.7 (2)	C21—C26—C25	121.6 (3)
C8—C7A—C7	123.7 (3)	C21—C26—H26	119.2
C8—C7A—C11A	119.0 (3)	C25—C26—H26	119.2
O14—N1—C2—C21	−84.7 (3)	C6—C5A—C11B—C11A	0.8 (4)
C11B—N1—C2—C21	160.8 (2)	C5—C5A—C11B—C11A	−179.7 (3)
O14—N1—C2—C3	37.4 (3)	C6—C5A—C11B—N1	−179.9 (3)
C11B—N1—C2—C3	−77.1 (3)	C5—C5A—C11B—N1	−0.4 (4)
N1—C2—C3—C4	−12.9 (3)	C11—C11A—C11B—C5A	176.8 (3)
C21—C2—C3—C4	107.7 (3)	C7A—C11A—C11B—C5A	−2.6 (4)
C2—C3—C4—O14	−16.1 (3)	C11—C11A—C11B—N1	−2.5 (4)
C2—C3—C4—C5	99.6 (3)	C7A—C11A—C11B—N1	178.1 (3)
O14—C4—C5—C5A	47.8 (3)	O14—N1—C11B—C5A	−28.6 (4)
C3—C4—C5—C5A	−66.0 (3)	C2—N1—C11B—C5A	82.4 (3)
C4—C5—C5A—C11B	−9.1 (4)	O14—N1—C11B—C11A	150.7 (2)
C4—C5—C5A—C6	170.3 (3)	C2—N1—C11B—C11A	−98.3 (3)
C11B—C5A—C6—C7	1.1 (5)	C11B—N1—O14—C4	67.0 (3)
C5—C5A—C6—C7	−178.4 (3)	C2—N1—O14—C4	−49.3 (3)
C5A—C6—C7—C7A	−1.3 (5)	C5—C4—O14—N1	−79.3 (3)
C5A—C6—C7—Br7	178.5 (2)	C3—C4—O14—N1	40.4 (3)
C6—C7—C7A—C8	−179.5 (3)	N1—C2—C21—C26	−8.4 (4)
Br7—C7—C7A—C8	0.7 (4)	C3—C2—C21—C26	−124.5 (3)
C6—C7—C7A—C11A	−0.5 (5)	N1—C2—C21—C22	172.4 (3)
Br7—C7—C7A—C11A	179.7 (2)	C3—C2—C21—C22	56.3 (4)
C7—C7A—C8—C9	177.7 (3)	C26—C21—C22—C23	1.4 (5)
C11A—C7A—C8—C9	−1.3 (5)	C2—C21—C22—C23	−179.4 (3)
C7A—C8—C9—C10	−0.5 (5)	C21—C22—C23—C24	−0.1 (5)
C8—C9—C10—C11	1.6 (5)	C22—C23—C24—C25	−1.6 (5)
C9—C10—C11—C11A	−0.9 (5)	C22—C23—C24—Cl24	178.1 (2)
C10—C11—C11A—C11B	179.7 (3)	C23—C24—C25—C26	1.8 (5)
C10—C11—C11A—C7A	−1.0 (5)	Cl24—C24—C25—C26	−177.9 (2)
C8—C7A—C11A—C11	2.0 (4)	C22—C21—C26—C25	−1.1 (5)
C7—C7A—C11A—C11	−177.0 (3)	C2—C21—C26—C25	179.7 (3)
C8—C7A—C11A—C11B	−178.6 (3)	C24—C25—C26—C21	−0.4 (5)
C7—C7A—C11A—C11B	2.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H31···O14^i	0.99	2.52	3.485 (4)	164

Symmetry code: (i) −x+1/2, y−1/2, z.

(III) (2RS,4SR)-2-(4-fluorophenyl)-2,3,4,5-tetrahydro-1,4- epoxynaphtho[1,2-b]azepine

Crystal data

C20H16FNO	F(000) = 640
Mr = 305.34	Dx = 1.332 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3467 reflections
a = 11.3036 (4) Å	θ = 3.2–27.5°
b = 12.7585 (5) Å	µ = 0.09 mm^−1
c = 11.1730 (3) Å	T = 120 K
β = 109.137 (2)°	Plate, pale yellow
V = 1522.29 (9) Å^3	0.09 × 0.08 × 0.03 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	3467 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2667 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ & ω scans	h = −14→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→16
Tmin = 0.986, Tmax = 0.997	l = −14→14
15443 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.018P)^2 + 1.6124P] where P = (Fo^2 + 2Fc^2)/3
3467 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.66621 (14)	0.62564 (13)	0.43066 (15)	0.0209 (4)
C2	0.73297 (19)	0.55233 (15)	0.37140 (18)	0.0221 (4)
H2	0.8188	0.5802	0.3837	0.027*
C3	0.6548 (2)	0.55638 (17)	0.22753 (19)	0.0275 (5)
H31	0.7020	0.5918	0.1785	0.033*
H32	0.6316	0.4850	0.1930	0.033*
C4	0.53856 (19)	0.61970 (17)	0.22436 (19)	0.0260 (4)
H4	0.4615	0.5879	0.1632	0.031*
C5	0.5454 (2)	0.73585 (17)	0.19739 (19)	0.0268 (5)
H51	0.5671	0.7452	0.1191	0.032*
H52	0.4628	0.7688	0.1842	0.032*
C5A	0.64302 (19)	0.78813 (16)	0.30709 (18)	0.0236 (4)
C6	0.67807 (19)	0.89389 (16)	0.29931 (19)	0.0256 (4)
H6	0.6362	0.9336	0.2257	0.031*
C7	0.7710 (2)	0.93982 (16)	0.3958 (2)	0.0271 (5)
H7	0.7940	1.0104	0.3875	0.033*
C7A	0.83385 (18)	0.88344 (16)	0.50856 (19)	0.0230 (4)
C8	0.92798 (19)	0.92934 (17)	0.6122 (2)	0.0271 (5)
H8	0.9543	0.9992	0.6055	0.033*
C9	0.98160 (19)	0.87396 (18)	0.7221 (2)	0.0293 (5)
H9	1.0442	0.9058	0.7911	0.035*
C10	0.94407 (19)	0.77008 (17)	0.73300 (19)	0.0275 (5)
H10	0.9806	0.7327	0.8098	0.033*
C11	0.85535 (18)	0.72270 (16)	0.63372 (18)	0.0241 (4)
H11	0.8326	0.6520	0.6415	0.029*
C11A	0.79700 (18)	0.77790 (15)	0.51930 (18)	0.0206 (4)
C11B	0.70082 (18)	0.73298 (15)	0.41552 (18)	0.0205 (4)
O14	0.53635 (12)	0.61056 (11)	0.35326 (13)	0.0249 (3)
C21	0.74384 (18)	0.44406 (15)	0.42875 (18)	0.0207 (4)
C22	0.81765 (19)	0.36951 (17)	0.39509 (19)	0.0263 (4)
H22	0.8598	0.3879	0.3372	0.032*
C23	0.8303 (2)	0.26892 (17)	0.44504 (19)	0.0278 (5)
H23	0.8803	0.2181	0.4220	0.033*
C24	0.76834 (19)	0.24505 (16)	0.52867 (19)	0.0245 (4)
F24	0.77986 (13)	0.14603 (9)	0.57801 (12)	0.0346 (3)
C25	0.69542 (18)	0.31562 (16)	0.56540 (18)	0.0228 (4)
H25	0.6547	0.2965	0.6243	0.027*
C26	0.68271 (18)	0.41599 (15)	0.51395 (18)	0.0214 (4)
H26	0.6318	0.4659	0.5372	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0179 (8)	0.0214 (8)	0.0231 (8)	−0.0002 (7)	0.0065 (7)	−0.0006 (7)
C2	0.0226 (10)	0.0225 (10)	0.0234 (10)	0.0006 (8)	0.0105 (8)	−0.0007 (8)
C3	0.0351 (12)	0.0260 (11)	0.0228 (10)	0.0019 (9)	0.0114 (9)	0.0016 (8)
C4	0.0248 (10)	0.0293 (11)	0.0221 (10)	−0.0030 (9)	0.0053 (8)	0.0000 (9)
C5	0.0257 (11)	0.0294 (11)	0.0231 (10)	0.0030 (9)	0.0050 (8)	0.0038 (8)
C5A	0.0239 (10)	0.0243 (10)	0.0244 (10)	0.0036 (8)	0.0104 (8)	0.0015 (8)
C6	0.0295 (11)	0.0225 (10)	0.0269 (10)	0.0060 (9)	0.0120 (9)	0.0051 (8)
C7	0.0341 (12)	0.0187 (10)	0.0333 (11)	0.0027 (9)	0.0176 (10)	0.0019 (9)
C7A	0.0230 (10)	0.0218 (10)	0.0283 (10)	0.0019 (8)	0.0139 (8)	−0.0010 (8)
C8	0.0235 (10)	0.0234 (11)	0.0374 (12)	0.0004 (8)	0.0140 (9)	−0.0057 (9)
C9	0.0214 (10)	0.0339 (12)	0.0315 (11)	−0.0004 (9)	0.0075 (9)	−0.0095 (9)
C10	0.0246 (10)	0.0330 (12)	0.0230 (10)	0.0034 (9)	0.0051 (8)	0.0007 (9)
C11	0.0247 (10)	0.0236 (11)	0.0259 (10)	0.0020 (8)	0.0109 (8)	0.0007 (8)
C11A	0.0204 (9)	0.0201 (10)	0.0233 (10)	0.0027 (8)	0.0099 (8)	−0.0007 (8)
C11B	0.0214 (9)	0.0193 (10)	0.0234 (10)	0.0023 (8)	0.0108 (8)	0.0009 (8)
O14	0.0186 (7)	0.0300 (8)	0.0266 (7)	−0.0015 (6)	0.0080 (6)	0.0016 (6)
C21	0.0192 (9)	0.0217 (10)	0.0196 (9)	−0.0002 (8)	0.0040 (8)	−0.0019 (8)
C22	0.0281 (11)	0.0288 (11)	0.0247 (10)	0.0036 (9)	0.0123 (9)	0.0009 (9)
C23	0.0315 (11)	0.0256 (11)	0.0273 (11)	0.0086 (9)	0.0111 (9)	−0.0012 (9)
C24	0.0282 (11)	0.0189 (10)	0.0225 (10)	0.0006 (8)	0.0029 (8)	0.0015 (8)
F24	0.0452 (8)	0.0226 (7)	0.0365 (7)	0.0072 (6)	0.0141 (6)	0.0053 (5)
C25	0.0228 (10)	0.0239 (10)	0.0211 (10)	−0.0008 (8)	0.0063 (8)	0.0000 (8)
C26	0.0214 (10)	0.0204 (10)	0.0228 (10)	0.0007 (8)	0.0077 (8)	−0.0028 (8)

Geometric parameters (Å, º)

N1—C11B	1.449 (2)	C7A—C11A	1.426 (3)
N1—O14	1.452 (2)	C8—C9	1.374 (3)
N1—C2	1.487 (2)	C8—H8	0.9500
C2—C21	1.511 (3)	C9—C10	1.409 (3)
C2—C3	1.561 (3)	C9—H9	0.9500
C2—H2	1.0000	C10—C11	1.368 (3)
C3—C4	1.533 (3)	C10—H10	0.9500
C3—H31	0.9900	C11—C11A	1.419 (3)
C3—H32	0.9900	C11—H11	0.9500
C4—O14	1.453 (2)	C11A—C11B	1.424 (3)
C4—C5	1.519 (3)	C21—C26	1.394 (3)
C4—H4	1.0000	C21—C22	1.396 (3)
C5—C5A	1.509 (3)	C22—C23	1.388 (3)
C5—H51	0.9900	C22—H22	0.9500
C5—H52	0.9900	C23—C24	1.373 (3)
C5A—C11B	1.368 (3)	C23—H23	0.9500
C5A—C6	1.417 (3)	C24—F24	1.367 (2)
C6—C7	1.366 (3)	C24—C25	1.371 (3)
C6—H6	0.9500	C25—C26	1.392 (3)
C7—C7A	1.422 (3)	C25—H25	0.9500
C7—H7	0.9500	C26—H26	0.9500
C7A—C8	1.417 (3)
C11B—N1—O14	108.34 (14)	C7—C7A—C11A	118.51 (19)
C11B—N1—C2	110.28 (15)	C9—C8—C7A	120.7 (2)
O14—N1—C2	102.30 (14)	C9—C8—H8	119.6
N1—C2—C21	111.65 (15)	C7A—C8—H8	119.6
N1—C2—C3	103.85 (15)	C8—C9—C10	120.3 (2)
C21—C2—C3	114.02 (16)	C8—C9—H9	119.9
N1—C2—H2	109.0	C10—C9—H9	119.9
C21—C2—H2	109.0	C11—C10—C9	120.5 (2)
C3—C2—H2	109.0	C11—C10—H10	119.8
C4—C3—C2	103.45 (16)	C9—C10—H10	119.8
C4—C3—H31	111.1	C10—C11—C11A	120.79 (19)
C2—C3—H31	111.1	C10—C11—H11	119.6
C4—C3—H32	111.1	C11A—C11—H11	119.6
C2—C3—H32	111.1	C11—C11A—C11B	122.63 (18)
H31—C3—H32	109.0	C11—C11A—C7A	118.83 (18)
O14—C4—C5	107.05 (16)	C11B—C11A—C7A	118.52 (18)
O14—C4—C3	103.18 (15)	C5A—C11B—C11A	121.98 (18)
C5—C4—C3	114.81 (17)	C5A—C11B—N1	121.38 (18)
O14—C4—H4	110.5	C11A—C11B—N1	116.64 (17)
C5—C4—H4	110.5	N1—O14—C4	103.72 (13)
C3—C4—H4	110.5	C26—C21—C22	118.87 (18)
C5A—C5—C4	109.95 (17)	C26—C21—C2	122.34 (17)
C5A—C5—H51	109.7	C22—C21—C2	118.79 (17)
C4—C5—H51	109.7	C23—C22—C21	120.90 (19)
C5A—C5—H52	109.7	C23—C22—H22	119.6
C4—C5—H52	109.7	C21—C22—H22	119.6
H51—C5—H52	108.2	C24—C23—C22	118.08 (19)
C11B—C5A—C6	118.84 (19)	C24—C23—H23	121.0
C11B—C5A—C5	120.11 (18)	C22—C23—H23	121.0
C6—C5A—C5	121.05 (18)	F24—C24—C25	118.24 (18)
C7—C6—C5A	121.20 (19)	F24—C24—C23	118.49 (18)
C7—C6—H6	119.4	C25—C24—C23	123.27 (19)
C5A—C6—H6	119.4	C24—C25—C26	118.12 (18)
C6—C7—C7A	120.91 (19)	C24—C25—H25	120.9
C6—C7—H7	119.5	C26—C25—H25	120.9
C7A—C7—H7	119.5	C25—C26—C21	120.75 (18)
C8—C7A—C7	122.54 (19)	C25—C26—H26	119.6
C8—C7A—C11A	118.90 (19)	C21—C26—H26	119.6
C11B—N1—C2—C21	156.26 (16)	C5—C5A—C11B—C11A	177.41 (18)
O14—N1—C2—C21	−88.66 (17)	C6—C5A—C11B—N1	178.02 (17)
C11B—N1—C2—C3	−80.44 (18)	C5—C5A—C11B—N1	−3.0 (3)
O14—N1—C2—C3	34.64 (17)	C11—C11A—C11B—C5A	178.18 (18)
N1—C2—C3—C4	−8.7 (2)	C7A—C11A—C11B—C5A	−0.3 (3)
C21—C2—C3—C4	112.98 (18)	C11—C11A—C11B—N1	−1.4 (3)
C2—C3—C4—O14	−20.2 (2)	C7A—C11A—C11B—N1	−179.89 (16)
C2—C3—C4—C5	95.89 (19)	O14—N1—C11B—C5A	−27.4 (2)
O14—C4—C5—C5A	46.0 (2)	C2—N1—C11B—C5A	83.8 (2)
C3—C4—C5—C5A	−67.8 (2)	O14—N1—C11B—C11A	152.15 (15)
C4—C5—C5A—C11B	−6.4 (3)	C2—N1—C11B—C11A	−96.64 (19)
C4—C5—C5A—C6	172.52 (18)	C11B—N1—O14—C4	67.08 (17)
C11B—C5A—C6—C7	2.4 (3)	C2—N1—O14—C4	−49.41 (17)
C5—C5A—C6—C7	−176.54 (18)	C5—C4—O14—N1	−78.33 (18)
C5A—C6—C7—C7A	−1.3 (3)	C3—C4—O14—N1	43.18 (18)
C6—C7—C7A—C8	−178.03 (19)	N1—C2—C21—C26	8.1 (3)
C6—C7—C7A—C11A	−0.6 (3)	C3—C2—C21—C26	−109.2 (2)
C7—C7A—C8—C9	176.39 (19)	N1—C2—C21—C22	−171.98 (17)
C11A—C7A—C8—C9	−1.1 (3)	C3—C2—C21—C22	70.7 (2)
C7A—C8—C9—C10	0.4 (3)	C26—C21—C22—C23	0.1 (3)
C8—C9—C10—C11	1.0 (3)	C2—C21—C22—C23	−179.84 (19)
C9—C10—C11—C11A	−1.7 (3)	C21—C22—C23—C24	−0.2 (3)
C10—C11—C11A—C11B	−177.49 (18)	C22—C23—C24—F24	179.76 (18)
C10—C11—C11A—C7A	1.0 (3)	C22—C23—C24—C25	−0.3 (3)
C8—C7A—C11A—C11	0.4 (3)	F24—C24—C25—C26	−179.29 (17)
C7—C7A—C11A—C11	−177.20 (18)	C23—C24—C25—C26	0.8 (3)
C8—C7A—C11A—C11B	178.95 (17)	C24—C25—C26—C21	−0.8 (3)
C7—C7A—C11A—C11B	1.4 (3)	C22—C21—C26—C25	0.4 (3)
C6—C5A—C11B—C11A	−1.5 (3)	C2—C21—C26—C25	−179.67 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H31···Cg2^i	0.99	2.63	3.575 (2)	160
C5—H52···Cg1^ii	0.99	2.72	3.605 (2)	149
C9—H9···Cg1^iii	0.95	2.92	3.684 (2)	139
C23—H23···Cg2^iv	0.95	2.85	3.683 (3)	147
C25—H25···O14^v	0.95	2.55	3.184 (3)	125

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