Hydrogen-bonded dimers, chains and rings in six differently substituted 2-vinyl­tetra­hydro-1,4-ep­oxy-1-benz­azepines

In (2SR,4RS)-2-exo-vinyl-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₂H₁₃NO, (I), the mol­ecules are linked by two independent C-H...[pi](arene) hydrogen bonds to form sheets, such that all of the mol­ecules in a given sheet are of the same configuration. The mol­ecules of (2SR,4RS)-7-chloro-2-exo-(2-methyl­prop-1-en­yl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₄H₁₆ClNO, (II), are linked by a C-H...O hydrogen bond into C(4) chains, where all the mol­ecules in a given chain are of the same configuration, whereas the mol­ecules of (2SR,4RS)-8-chloro-9-methyl-2-exo-(2-methylprop-1-en­yl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₅H₁₈ClNO, (III), are linked into centrosymmetric dimers by pairs of symmetry-related C-H...[pi](arene) hydrogen bonds. (2RS,4RS)-8-Chloro-9-methyl-2-endo-(2-methyl­prop-1-en­yl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₅H₁₈ClNO, (IV), is a diastereoisomer of (III) and, as for (II), a single C-H...O hydrogen bond links the mol­ecules into C(4) chains, each containing mol­ecules of a single configuration. The struc­ture of (2SR,4RS)-8-chloro-9-methyl-2-exo-(prop-1-en-2-yl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₄H₁₆ClNO, (V), contains a C-H...O hydrogen bond which links pairs of mol­ecules into centrosymmetric R₂²(6) dimers. (2SR,4RS)-7,9-Dichloro-2-exo-(prop-1-en-2-yl)-2,3,4,5-tetrahydro-1H-1,4-ep­oxy-1-benzazepine, C₁₃H₁₃Cl₂NO, (VI), is an inversion twin containing both the (2S,4R) and (2R,4S) enantio­mers in the space group P2₁, and a C-H...O hydrogen bond links mol­ecules of a given configuration into simple C(3) chains.

S1. Comment

We report here the structures of six differently-substituted 2-vinyl-2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepines, (I)–(VI) (Fig. 1), which exhibit interesting variations in their intermolecular hydrogen-bonding arrangements. The work reported here is a continuation of a wider structural study of substituted tetrahydroepoxybenzazepines (Acosta et al., 2008, 2010; Blanco et al., 2008; Gómez et al., 2008, 2009, 2010), and the underlying synthetic rationale and the potential applications of these compounds have already been discussed (Acosta et al., 2008).

Compounds (I)–(V) (see scheme and Fig. 1) all crystallize as racemic mixtures in centrosymmetric space groups. In each of (I)–(V), the reference molecule was selected as having the R configuration at atom C4, and on this basis the reference molecules have the S configuration at atom C2 in (I)–(III) and (V), but in (IV) the reference molecule has the R configuration at C2, so that (III) and (IV) are, in fact, diastereoisomers. In addition, (II) and (V) are positional isomers. By contrast, (VI) crystallizes as an inversion twin in the Sohnke space group P2₁. For the crystal selected for data collection, the twin fractions were found to be unequal, 0.39 (7) for the (2S,4R) form and 0.61 (7) for the (2R,4S) form, although the deviations from 0.5 are not large compared with the experimental uncertainty. As the synthesis of these compounds involves no reagent or solvent capable of imparting any enantiomeric bias, it is to be expected that (V) [(VI)?], as well as (I)–(V), was synthesized as a true racemic mixture, and it is therefore possible that this compound crystallizes with somewhat different twin fractions in the various individual crystals.

The ring-puckering parameters (Cremer & Pople, 1975) for (I)–(VI) (Table 1) show that the overall shape of the fused heterocyclic system varies very little, regardless of the number and location of the methyl groups in the vinyl substituent or the configuration at atom C2. On the other hand, the orientation of the vinyl group relative to the fused bicyclic system, as defined by the values of the N1—C2—C21—C22 torsion angle (Table 1), shows considerable variation, in particular between the two diasteroisomers (III) and (IV), as expected from the different configurations at C2, but less expectedly for the two prop-1-en-2-yl derivatives, (V) and (VI).

The supramolecular aggregation in (I)–(VI) depends upon C—H···O and C—H···π(arene) hydrogen bonds (Table 2), but (I) is the only example in this group where the crystal structure contains two independent C—H···π(arene) hydrogen bonds.

In (I), the hydrogen bond having atom C6 as the donor links molecules related by the 2₁ screw axis along (1/4, y, 1/4), while the hydrogen bond in which atom C22 acts as the donor links molecules related by the 2₁ screw axis along (3/4, y, 1/2), so forming two chain motifs, both running parallel to the [010] direction but in opposite senses. The combination of these chains generates a sheet lying parallel to (001) in the domain 0 < z < 1/2 (Fig. 2) in which all of the molecules have the (2S,4R) configuration. A second sheet, lying in the domain 1/2 < z < 1.0, is related to the first sheet by inversion and contains only molecules with the (2R,4S) configuration. Within the sheet, each aryl ring accepts one hydrogen bond on each face and the angle subtended at the ring centroid Cg1 (ring C5a/C6–C9/C9a) of the reference molecule by the two H···Cg contacts, H6ⁱ···Cg1···H22ⁱⁱ, is 167° [symmetry codes: (i) 1/2 - x, 1/2 + y, 1/2 - z; (ii) 3/2 - x, -1/2 + y, 1/2 - z]. Between adjacent sheets, the only direction-specific interaction is a C—H···O contact (Table 2) with an H···O distance which is long and a C—H···O angle which is small, so that this contact cannot realistically be regarded as a structurally significant hydrogen bond. Aromatic π–π stacking interactions are absent from the structure of (I), because of the presence of C—H···π(arene) hydrogen bonds on each face of the aryl ring, so that the supramolecular aggregation in (I) is two-dimensional.

In contrast with the crystal structure of (I), those of (II)–(VI) each contain only a single hydrogen bond, all of the C—H···O type apart from (III), where the hydrogen bond is of the C—H···π(arene) type (Table 2). As found for (I), aromatic π–π stacking interactions are absent from the structures of all of (II)–(VI).

In each of (II) and (IV), molecules related by translation are linked by the C—H···O hydrogen bond to form simple C(4) chains (Bernstein et al., 1995) running parallel to the [100] direction (Fig. 3), but it is clear that, although the same donor and acceptor atoms are involved in these two structures, the mutual orientations of the molecules within the chains are different, as are the dimensions of the C—H···O hydrogen bonds. These differences may be associated with either or both of the differences in the molecular configurations, (2SR,4RS) for (II) and (2RS,4RS) for (IV), and in the space groups, P2₁/c for (II) and P1 for (IV). In the structure of (II) there are four chains passing through each unit cell, but in the structure of (IV) there are only two. In any specific chain, all of the molecules have the same configuration. As there are no direction-specific interactions between the chains in (II) and (IV), these hydrogen-bonded structures are both one-dimensional.

The hydrogen-bonded structures of (III) and (V), by contrast, both consist of centrosymmetric dimers, built from pairs of symmetry-related C—H···π(arene) hydrogen bonds in (III) (Fig. 4) and from pairs of symmetry-related C—H···O hydrogen bonds in (V), so forming an R₂²(6) ring having a chair-type conformation (Fig. 5). Within each of these dimers, the two molecules involved are of the opposite configuration and the hydrogen-bonded aggregation in (III) and (V) is thus finite, or zero-dimensional.

The single hydrogen bond in the structure of (VI) utilizes the same donor and acceptor atoms as that in (V), but rather than forming a cyclic dimer as in (V), in (VI) this hydrogen bond now generates a C(3) chain running parallel to the [010] direction and linking molecules related by the 2₁ screw axis along (1, y, 1/2) (Fig. 6). Again, therefore, the hydrogen-bonded structure is one-dimensional and all the molecules in a specific chain are of the same configuration.

In each of (I), (II), (IV) and (VI), the molecules within a given hydrogen-bonded aggregate, whether the sheet in (I) or the chains in (II), (IV) and (VI), all have the same configuration, whereas in (III) and (V) the hydrogen-bonded dimers both contain pairs of molecules having opposite configurations. Hence, the hydrogen bonding appears to mediate molecular-scale enantiomeric sorting in (I), (II) (IV) and (VI), but enantiomeric pairing in (III) and (V). Within the structure of each of (II)–(IV), atom C5 acts as the hydrogen-bond donor. However, in (II) and (IV), where C—H···O hydrogen bonds are present, these involve the bisectional H atom at C5, denoted H5B, and chain motifs result, but in (III), where a C—H···π(arene) hydrogen bond is present, this involves the axial H atom at C5, denoted H5A, and a ring motif results. Similarly, although the same combination of hydrogen-bond donor and acceptor are present in the structures of (V) and (VI), in (V) this interaction gives rise to a ring motif, whereas in (VI) a chain results, so that the hydrogen-bonded structures of (V) and (VI) are of different dimensionalities. These subtle differences in the hydrogen-bonding patterns do not appear to have any simple or readily-accessible explanations.

S2. Experimental

For the preparation of (I)–(VI), sodium tungstate dihydrate (5–10 mol%), followed by 30% aqueous hydrogen peroxide solution (0.30 mol), were added to a stirred solution of the appropriately substituted 2-allyl-N-alkenylaniline (0.10 mol) in methanol (30 ml). The resulting mixtures were then stirred at ambient temperature for either 8 h [for (I) and (II)] or 72 h [for each of (III)–(VI)]. Each mixture was then filtered and the solvent removed under reduced pressure. Toluene (30 ml) was added to the solid residue and the resulting solution was heated at 355–360 K for 5–7 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 (compositions in the range from 90:1 to 10:1 v/v) as eluent. Crystallization from methanol–dichloromethane (1:1 v/v) gave colourless crystals of (I)–(VI) suitable for single-crystal X-ray diffraction.

For (I), yield 58%, m.p. 335–336 K; MS (70 eV) m/z (%) 187 (M⁺, 31), 170 (18), 157 (10), 130 (22), 105 (38), 104 (100), 78 (36).

For (II), yield 49%, m.p. 350–351 K; MS (70 eV) m/z (%) 249 [M⁺ (³⁵Cl), 43], 232 (29), 164 (9), 139 (100), 104 (33), 77 (30).

For (III), yield 45%, m.p. 367–368 K; MS (70 eV) m/z (%) 263 [M⁺ (³⁵Cl), 45], 246 (27), 178 (12), 153 (100), 144 (39), 118 (36), 103 (18), 91 (36).

For (IV), yield 25%, m.p. 380–381 K; MS (70 eV) m/z (%) 263 [M⁺ (³⁵Cl), 64], 246 (33), 178 (15), 153 (100), 144 (39), 118 (36), 103 (18), 91 (39).

For (V), yield 65%, m.p. 375–376 K; MS (70 eV) m/z (%) 249 [M⁺ (³⁵Cl), 59], 166 (9), 153 (100), 141 (36), 118 (29), 91 (33), 77 (24).

For (VI), yield 63%, m.p. 370–371 K; MS (70 eV) m/z (%) 269 [M⁺ (³⁵Cl), 61], 172 (100), 151 (30), 138 (61), 123 (33), 102 (30), 75 (36).

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 or alkenyl H), 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. When the initial refinement for (VI) appeared to be complete, the value of the Flack x parameter (Flack, 1983), x = 0.59 (8), indicated that the refinement should be handled as an inversion twin, leading to twin fractions of 0.39 (7) for the (2S,4R) form and 0.61 (7) for the (2R,4S) form.

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 molecular structures of (I)–(VI), showing the atom-labelling schemes. (a) (I), (b) (II), (c) (III), (d) (IV), (e) (V) and (f) (VI). The (2R,4R) enantiomer is shown for (IV) and the (2S,4R) enantiomers for the remainder. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (001). Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 3. Parts of the crystal structures of (a) (II) and (b) (IV), showing the formation of C(4) chains along [100]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*) or a dollar sign ($) are at the symmetry positions (-1 + x, y, z) and (1 + x, y, z), respectively.
	Fig. 4. Part of the crystal structure of (III), showing the formation of a hydrogen-bonded dimer built from paired C—H···π(arene) hydrogen bonds (dashed lines). For the sake of clarity, the unit-cell outline and H atoms bonded to C atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (2 - x, 1 - y, 1 - z).
	Fig. 5. Part of the crystal structure of (IV), showing the formation of a hydrogen-bonded dimer built from paired C—H···O hydrogen bonds (dashed lines). For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).
	Fig. 6. Part of the crystal structure of (VI), showing the formation of a C(3) chain parallel to [010]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (2 - x, 1/2 + y, 1 - z), (2 - x, -1/2 + y, 1 - z), and (x, 1 + y, z), respectively.

(I) (2SR,4RS)-2-exo-vinyl-2,3,4,5-tetrahydro-1H- 1,4-epoxy-1-benzazepine

Crystal data

C12H13NO	F(000) = 400
Mr = 187.23	Dx = 1.294 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2200 reflections
a = 9.8070 (13) Å	θ = 3.0–27.5°
b = 7.3982 (7) Å	µ = 0.08 mm^−1
c = 13.738 (2) Å	T = 120 K
β = 105.441 (11)°	Block, colourless
V = 960.8 (2) Å^3	0.31 × 0.29 × 0.20 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2200 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1488 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.969, Tmax = 0.984	l = −15→17
13902 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 0.1879P] where P = (Fo^2 + 2Fc^2)/3
2200 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.17 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
O14	0.49055 (10)	0.45113 (14)	0.10465 (8)	0.0253 (3)
N1	0.57935 (12)	0.40949 (16)	0.20407 (9)	0.0207 (3)
C2	0.67762 (15)	0.2748 (2)	0.18020 (12)	0.0214 (3)
H2	0.7176	0.1959	0.2401	0.026*
C3	0.58270 (16)	0.1630 (2)	0.09360 (12)	0.0261 (4)
H3A	0.6278	0.1473	0.0377	0.031*
H3B	0.5624	0.0425	0.1178	0.031*
C4	0.44854 (16)	0.2754 (2)	0.06014 (12)	0.0262 (4)
H4	0.4170	0.2843	−0.0152	0.031*
C5	0.32915 (15)	0.2113 (2)	0.10149 (12)	0.0266 (4)
H5A	0.2420	0.2797	0.0696	0.032*
H5B	0.3107	0.0815	0.0857	0.032*
C5a	0.36800 (14)	0.2388 (2)	0.21397 (12)	0.0220 (3)
C6	0.28380 (15)	0.1747 (2)	0.27298 (12)	0.0254 (4)
H6	0.1982	0.1133	0.2417	0.031*
C7	0.32186 (16)	0.1984 (2)	0.37583 (13)	0.0286 (4)
H7	0.2625	0.1542	0.4150	0.034*
C8	0.44640 (16)	0.2864 (2)	0.42228 (12)	0.0285 (4)
H8	0.4738	0.3005	0.4936	0.034*
C9	0.53088 (15)	0.3537 (2)	0.36484 (12)	0.0242 (4)
H9	0.6160	0.4157	0.3963	0.029*
C9a	0.49104 (14)	0.33046 (19)	0.26153 (11)	0.0199 (3)
C21	0.79369 (16)	0.3709 (2)	0.15017 (12)	0.0255 (4)
H21	0.7684	0.4580	0.0977	0.031*
C22	0.92861 (16)	0.3425 (2)	0.19176 (13)	0.0312 (4)
H22A	0.9573	0.2562	0.2445	0.037*
H22B	0.9976	0.4082	0.1692	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O14	0.0301 (6)	0.0237 (6)	0.0199 (6)	−0.0008 (5)	0.0029 (4)	0.0037 (5)
N1	0.0213 (6)	0.0231 (7)	0.0170 (7)	0.0007 (5)	0.0038 (5)	0.0021 (5)
C2	0.0237 (7)	0.0196 (8)	0.0226 (8)	−0.0003 (6)	0.0091 (6)	−0.0016 (6)
C3	0.0292 (8)	0.0251 (8)	0.0263 (9)	−0.0048 (7)	0.0113 (7)	−0.0052 (7)
C4	0.0331 (9)	0.0242 (8)	0.0192 (8)	−0.0050 (7)	0.0032 (7)	−0.0023 (7)
C5	0.0247 (8)	0.0276 (9)	0.0244 (9)	−0.0035 (6)	0.0009 (6)	−0.0014 (7)
C5a	0.0207 (7)	0.0190 (8)	0.0258 (9)	0.0030 (6)	0.0054 (6)	0.0004 (7)
C6	0.0185 (7)	0.0219 (8)	0.0363 (10)	0.0005 (6)	0.0080 (7)	0.0008 (7)
C7	0.0293 (8)	0.0272 (9)	0.0351 (10)	0.0032 (7)	0.0187 (7)	0.0047 (7)
C8	0.0339 (9)	0.0309 (9)	0.0230 (9)	0.0057 (7)	0.0117 (7)	0.0013 (7)
C9	0.0227 (8)	0.0255 (8)	0.0245 (9)	0.0004 (6)	0.0067 (6)	−0.0017 (7)
C9a	0.0200 (7)	0.0184 (8)	0.0223 (8)	0.0031 (6)	0.0075 (6)	0.0019 (6)
C21	0.0314 (8)	0.0220 (8)	0.0271 (9)	−0.0024 (7)	0.0145 (7)	−0.0018 (7)
C22	0.0294 (9)	0.0268 (9)	0.0415 (11)	−0.0040 (7)	0.0168 (8)	−0.0050 (8)

Geometric parameters (Å, º)

O14—N1	1.4441 (15)	C5a—C6	1.386 (2)
O14—C4	1.4488 (18)	C5a—C9a	1.387 (2)
N1—C9a	1.4419 (18)	C6—C7	1.373 (2)
N1—C2	1.4822 (18)	C6—H6	0.9500
C2—C21	1.490 (2)	C7—C8	1.381 (2)
C2—C3	1.542 (2)	C7—H7	0.9500
C2—H2	1.0000	C8—C9	1.380 (2)
C3—C4	1.521 (2)	C8—H8	0.9500
C3—H3A	0.9900	C9—C9a	1.379 (2)
C3—H3B	0.9900	C9—H9	0.9500
C4—C5	1.508 (2)	C21—C22	1.311 (2)
C4—H4	1.0000	C21—H21	0.9500
C5—C5a	1.504 (2)	C22—H22A	0.9500
C5—H5A	0.9900	C22—H22B	0.9500
C5—H5B	0.9900
N1—O14—C4	103.88 (10)	C4—C5—H5B	109.8
C9a—N1—O14	107.78 (10)	H5A—C5—H5B	108.2
C9a—N1—C2	111.67 (11)	C6—C5a—C9a	118.10 (14)
O14—N1—C2	101.42 (10)	C6—C5a—C5	121.82 (13)
N1—C2—C21	109.30 (12)	C9a—C5a—C5	120.08 (13)
N1—C2—C3	103.70 (11)	C7—C6—C5a	121.15 (14)
C21—C2—C3	113.02 (12)	C7—C6—H6	119.4
N1—C2—H2	110.2	C5a—C6—H6	119.4
C21—C2—H2	110.2	C6—C7—C8	120.01 (14)
C3—C2—H2	110.2	C6—C7—H7	120.0
C4—C3—C2	103.64 (12)	C8—C7—H7	120.0
C4—C3—H3A	111.0	C9—C8—C7	119.83 (15)
C2—C3—H3A	111.0	C9—C8—H8	120.1
C4—C3—H3B	111.0	C7—C8—H8	120.1
C2—C3—H3B	111.0	C9a—C9—C8	119.66 (14)
H3A—C3—H3B	109.0	C9a—C9—H9	120.2
O14—C4—C5	106.59 (12)	C8—C9—H9	120.2
O14—C4—C3	103.72 (11)	C9—C9a—C5a	121.23 (14)
C5—C4—C3	114.21 (13)	C9—C9a—N1	117.78 (13)
O14—C4—H4	110.7	C5a—C9a—N1	120.96 (13)
C5—C4—H4	110.7	C22—C21—C2	124.03 (16)
C3—C4—H4	110.7	C22—C21—H21	118.0
C5a—C5—C4	109.56 (12)	C2—C21—H21	118.0
C5a—C5—H5A	109.8	C21—C22—H22A	120.0
C4—C5—H5A	109.8	C21—C22—H22B	120.0
C5a—C5—H5B	109.8	H22A—C22—H22B	120.0
C4—O14—N1—C9a	−67.70 (13)	C5—C5a—C6—C7	178.92 (14)
C4—O14—N1—C2	49.71 (12)	C5a—C6—C7—C8	−0.4 (2)
C9a—N1—C2—C21	−162.66 (12)	C6—C7—C8—C9	1.3 (2)
O14—N1—C2—C21	82.79 (13)	C7—C8—C9—C9a	−0.8 (2)
C9a—N1—C2—C3	76.55 (14)	C8—C9—C9a—C5a	−0.7 (2)
O14—N1—C2—C3	−38.00 (13)	C8—C9—C9a—N1	177.46 (13)
N1—C2—C3—C4	13.57 (15)	C6—C5a—C9a—C9	1.6 (2)
C21—C2—C3—C4	−104.67 (14)	C5—C5a—C9a—C9	−178.38 (14)
N1—O14—C4—C5	80.17 (13)	C6—C5a—C9a—N1	−176.48 (13)
N1—O14—C4—C3	−40.70 (13)	C5—C5a—C9a—N1	3.5 (2)
C2—C3—C4—O14	15.76 (15)	O14—N1—C9a—C9	−151.29 (12)
C2—C3—C4—C5	−99.84 (14)	C2—N1—C9a—C9	98.15 (15)
O14—C4—C5—C5a	−46.92 (16)	O14—N1—C9a—C5a	26.85 (17)
C3—C4—C5—C5a	66.99 (17)	C2—N1—C9a—C5a	−83.71 (16)
C4—C5—C5a—C6	−173.27 (14)	N1—C2—C21—C22	126.62 (16)
C4—C5—C5a—C9a	6.71 (19)	C3—C2—C21—C22	−118.46 (17)
C9a—C5a—C6—C7	−1.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O14^i	1.00	2.60	3.209 (2)	119
C6—H6···Cg1^ii	0.95	2.83	3.616 (2)	141
C22—H22B···Cg1^iii	0.95	2.78	3.529 (2)	136

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

(II) (2SR,4RS)-7-chloro-2-exo-(2-methylprop-1-enyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C14H16ClNO	F(000) = 528
Mr = 249.73	Dx = 1.366 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2783 reflections
a = 5.6445 (5) Å	θ = 2.9–27.5°
b = 25.744 (3) Å	µ = 0.30 mm^−1
c = 8.3894 (11) Å	T = 120 K
β = 95.124 (9)°	Block, colourless
V = 1214.2 (2) Å^3	0.44 × 0.24 × 0.20 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2783 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1929 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −31→33
Tmin = 0.895, Tmax = 0.943	l = −10→10
15979 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.6916P] where P = (Fo^2 + 2Fc^2)/3
2783 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl7	0.16222 (10)	0.32441 (2)	0.23221 (7)	0.03279 (19)
O14	0.6846 (3)	0.09756 (6)	0.24447 (18)	0.0245 (4)
N1	0.7332 (3)	0.13466 (7)	0.3718 (2)	0.0217 (4)
C2	0.6430 (4)	0.10686 (8)	0.5090 (3)	0.0222 (5)
H2	0.5999	0.1324	0.5915	0.027*
C3	0.4167 (4)	0.07945 (9)	0.4333 (3)	0.0272 (5)
H3A	0.4118	0.0428	0.4681	0.033*
H3B	0.2714	0.0973	0.4624	0.033*
C4	0.4392 (4)	0.08314 (9)	0.2551 (3)	0.0265 (5)
H4	0.4036	0.0489	0.2019	0.032*
C5	0.2867 (4)	0.12530 (9)	0.1758 (3)	0.0264 (5)
H5A	0.2946	0.1240	0.0585	0.032*
H5B	0.1191	0.1203	0.1984	0.032*
C5a	0.3753 (4)	0.17692 (8)	0.2393 (3)	0.0223 (5)
C6	0.2452 (4)	0.22204 (9)	0.2096 (3)	0.0240 (5)
H6	0.0970	0.2208	0.1465	0.029*
C7	0.3294 (4)	0.26844 (9)	0.2709 (3)	0.0245 (5)
C8	0.5437 (4)	0.27184 (9)	0.3622 (3)	0.0269 (5)
H8	0.6001	0.3043	0.4039	0.032*
C9	0.6748 (4)	0.22718 (9)	0.3921 (3)	0.0261 (5)
H9	0.8241	0.2288	0.4539	0.031*
C9a	0.5901 (4)	0.18016 (8)	0.3324 (3)	0.0214 (5)
C21	0.8280 (4)	0.07077 (8)	0.5795 (3)	0.0228 (5)
H21	0.9288	0.0554	0.5080	0.027*
C22	0.8670 (4)	0.05784 (8)	0.7323 (3)	0.0231 (5)
C23	1.0662 (4)	0.02214 (9)	0.7886 (3)	0.0293 (5)
H23A	1.1590	0.0136	0.6988	0.044*
H23B	1.0010	−0.0098	0.8308	0.044*
H23C	1.1692	0.0392	0.8731	0.044*
C24	0.7217 (4)	0.07689 (9)	0.8602 (3)	0.0303 (5)
H24A	0.5880	0.0975	0.8119	0.045*
H24B	0.8207	0.0985	0.9357	0.045*
H24C	0.6607	0.0472	0.9171	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl7	0.0318 (3)	0.0249 (3)	0.0410 (4)	0.0046 (2)	−0.0002 (3)	0.0038 (2)
O14	0.0234 (8)	0.0267 (8)	0.0236 (8)	0.0011 (6)	0.0031 (6)	−0.0062 (6)
N1	0.0253 (10)	0.0214 (9)	0.0184 (9)	−0.0004 (7)	0.0022 (7)	−0.0007 (7)
C2	0.0225 (11)	0.0224 (11)	0.0223 (11)	0.0000 (9)	0.0054 (9)	0.0008 (9)
C3	0.0210 (12)	0.0250 (12)	0.0359 (13)	−0.0019 (9)	0.0038 (10)	0.0050 (10)
C4	0.0240 (12)	0.0233 (12)	0.0317 (13)	−0.0032 (9)	−0.0007 (10)	−0.0055 (10)
C5	0.0249 (12)	0.0283 (12)	0.0253 (12)	−0.0010 (10)	−0.0016 (9)	−0.0023 (9)
C5a	0.0246 (11)	0.0245 (11)	0.0179 (11)	−0.0006 (9)	0.0028 (9)	0.0004 (9)
C6	0.0211 (11)	0.0279 (12)	0.0227 (12)	−0.0003 (9)	0.0007 (9)	0.0009 (9)
C7	0.0249 (12)	0.0237 (11)	0.0255 (12)	0.0034 (9)	0.0050 (9)	0.0064 (9)
C8	0.0304 (13)	0.0223 (11)	0.0279 (13)	−0.0033 (9)	0.0028 (10)	0.0011 (9)
C9	0.0257 (12)	0.0251 (11)	0.0269 (12)	−0.0040 (9)	−0.0009 (9)	0.0023 (9)
C9a	0.0235 (11)	0.0222 (11)	0.0193 (11)	−0.0003 (9)	0.0051 (9)	0.0015 (8)
C21	0.0232 (11)	0.0205 (11)	0.0252 (12)	−0.0006 (9)	0.0048 (9)	−0.0011 (9)
C22	0.0218 (11)	0.0195 (11)	0.0280 (12)	−0.0034 (9)	0.0019 (9)	−0.0003 (9)
C23	0.0305 (13)	0.0275 (12)	0.0294 (13)	0.0021 (10)	0.0004 (10)	0.0028 (10)
C24	0.0352 (14)	0.0317 (13)	0.0238 (12)	0.0052 (10)	0.0015 (10)	0.0004 (10)

Geometric parameters (Å, º)

Cl7—C7	1.737 (2)	C6—C7	1.369 (3)
O14—N1	1.441 (2)	C6—H6	0.9500
O14—C4	1.445 (3)	C7—C8	1.376 (3)
N1—C9a	1.444 (3)	C8—C9	1.378 (3)
N1—C2	1.483 (3)	C8—H8	0.9500
C2—C21	1.481 (3)	C9—C9a	1.379 (3)
C2—C3	1.545 (3)	C9—H9	0.9500
C2—H2	1.0000	C21—C22	1.324 (3)
C3—C4	1.514 (3)	C21—H21	0.9500
C3—H3A	0.9900	C22—C24	1.490 (3)
C3—H3B	0.9900	C22—C23	1.496 (3)
C4—C5	1.503 (3)	C23—H23A	0.9800
C4—H4	1.0000	C23—H23B	0.9800
C5—C5a	1.501 (3)	C23—H23C	0.9800
C5—H5A	0.9900	C24—H24A	0.9800
C5—H5B	0.9900	C24—H24B	0.9800
C5a—C6	1.385 (3)	C24—H24C	0.9800
C5a—C9a	1.385 (3)
N1—O14—C4	104.15 (15)	C7—C6—H6	119.9
O14—N1—C9a	107.59 (15)	C5a—C6—H6	119.9
O14—N1—C2	101.51 (15)	C6—C7—C8	121.5 (2)
C9a—N1—C2	110.19 (16)	C6—C7—Cl7	119.30 (17)
C21—C2—N1	109.52 (17)	C8—C7—Cl7	119.16 (18)
C21—C2—C3	113.90 (18)	C7—C8—C9	118.7 (2)
N1—C2—C3	103.30 (17)	C7—C8—H8	120.7
C21—C2—H2	110.0	C9—C8—H8	120.7
N1—C2—H2	110.0	C8—C9—C9a	120.2 (2)
C3—C2—H2	110.0	C8—C9—H9	119.9
C4—C3—C2	103.77 (17)	C9a—C9—H9	119.9
C4—C3—H3A	111.0	C9—C9a—C5a	121.0 (2)
C2—C3—H3A	111.0	C9—C9a—N1	117.40 (19)
C4—C3—H3B	111.0	C5a—C9a—N1	121.59 (19)
C2—C3—H3B	111.0	C22—C21—C2	126.5 (2)
H3A—C3—H3B	109.0	C22—C21—H21	116.7
O14—C4—C5	107.54 (18)	C2—C21—H21	116.7
O14—C4—C3	104.04 (17)	C21—C22—C24	124.0 (2)
C5—C4—C3	112.79 (19)	C21—C22—C23	121.0 (2)
O14—C4—H4	110.7	C24—C22—C23	114.9 (2)
C5—C4—H4	110.7	C22—C23—H23A	109.5
C3—C4—H4	110.7	C22—C23—H23B	109.5
C5a—C5—C4	108.83 (18)	H23A—C23—H23B	109.5
C5a—C5—H5A	109.9	C22—C23—H23C	109.5
C4—C5—H5A	109.9	H23A—C23—H23C	109.5
C5a—C5—H5B	109.9	H23B—C23—H23C	109.5
C4—C5—H5B	109.9	C22—C24—H24A	109.5
H5A—C5—H5B	108.3	C22—C24—H24B	109.5
C6—C5a—C9a	118.3 (2)	H24A—C24—H24B	109.5
C6—C5a—C5	121.62 (19)	C22—C24—H24C	109.5
C9a—C5a—C5	120.03 (19)	H24A—C24—H24C	109.5
C7—C6—C5a	120.2 (2)	H24B—C24—H24C	109.5
C4—O14—N1—C9a	−66.33 (19)	C5a—C6—C7—Cl7	−179.82 (16)
C4—O14—N1—C2	49.39 (18)	C6—C7—C8—C9	−0.1 (3)
O14—N1—C2—C21	83.46 (19)	Cl7—C7—C8—C9	−179.96 (17)
C9a—N1—C2—C21	−162.74 (18)	C7—C8—C9—C9a	−0.7 (3)
O14—N1—C2—C3	−38.25 (19)	C8—C9—C9a—C5a	1.3 (3)
C9a—N1—C2—C3	75.6 (2)	C8—C9—C9a—N1	−178.31 (19)
C21—C2—C3—C4	−104.3 (2)	C6—C5a—C9a—C9	−1.0 (3)
N1—C2—C3—C4	14.4 (2)	C5—C5a—C9a—C9	180.0 (2)
N1—O14—C4—C5	80.02 (19)	C6—C5a—C9a—N1	178.52 (18)
N1—O14—C4—C3	−39.8 (2)	C5—C5a—C9a—N1	−0.4 (3)
C2—C3—C4—O14	14.7 (2)	O14—N1—C9a—C9	−152.18 (18)
C2—C3—C4—C5	−101.6 (2)	C2—N1—C9a—C9	98.0 (2)
O14—C4—C5—C5a	−48.9 (2)	O14—N1—C9a—C5a	28.2 (3)
C3—C4—C5—C5a	65.2 (2)	C2—N1—C9a—C5a	−81.6 (2)
C4—C5—C5a—C6	−168.4 (2)	N1—C2—C21—C22	146.9 (2)
C4—C5—C5a—C9a	10.5 (3)	C3—C2—C21—C22	−98.0 (3)
C9a—C5a—C6—C7	0.3 (3)	C2—C21—C22—C24	2.0 (4)
C5—C5a—C6—C7	179.2 (2)	C2—C21—C22—C23	−177.9 (2)
C5a—C6—C7—C8	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O14^i	0.99	2.58	3.570 (3)	174

Symmetry code: (i) x−1, y, z.

(III) (2SR,4RS)-8-chloro-9-methyl-2-exo-(2-methylprop-1-enyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C15H18ClNO	F(000) = 560
Mr = 263.75	Dx = 1.338 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3013 reflections
a = 11.0631 (7) Å	θ = 3.1–27.5°
b = 5.7212 (5) Å	µ = 0.28 mm^−1
c = 21.203 (6) Å	T = 120 K
β = 102.587 (16)°	Prism, colourless
V = 1309.8 (4) Å^3	0.40 × 0.19 × 0.12 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2306 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1661 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.105
Detector resolution: 9.091 pixels mm^-1	θmax = 25.1°, θmin = 3.1°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −6→6
Tmin = 0.869, Tmax = 0.967	l = −25→25
16325 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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 1.9086P] where P = (Fo^2 + 2Fc^2)/3
2306 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl8	1.00257 (9)	0.68005 (19)	0.25837 (5)	0.0350 (3)
O14	0.7434 (2)	0.6716 (4)	0.49115 (11)	0.0227 (6)
N1	0.7273 (2)	0.7165 (5)	0.42340 (13)	0.0196 (7)
C2	0.6038 (3)	0.6127 (6)	0.39709 (17)	0.0193 (8)
H2	0.5947	0.5727	0.3504	0.023*
C3	0.6066 (3)	0.3878 (6)	0.43802 (18)	0.0249 (9)
H3A	0.5288	0.3698	0.4534	0.030*
H3B	0.6189	0.2476	0.4128	0.030*
C4	0.7161 (3)	0.4250 (6)	0.49432 (18)	0.0243 (9)
H4	0.6940	0.3848	0.5363	0.029*
C5	0.8310 (3)	0.2957 (6)	0.48660 (18)	0.0262 (9)
H5A	0.8951	0.3069	0.5271	0.031*
H5B	0.8111	0.1285	0.4780	0.031*
C5a	0.8797 (3)	0.3974 (6)	0.43209 (17)	0.0198 (8)
C6	0.9766 (3)	0.2972 (6)	0.40988 (18)	0.0250 (8)
H6	1.0169	0.1634	0.4313	0.030*
C7	1.0152 (3)	0.3863 (6)	0.35810 (18)	0.0269 (9)
H7	1.0830	0.3179	0.3441	0.032*
C8	0.9545 (3)	0.5773 (7)	0.32623 (18)	0.0252 (9)
C9	0.8578 (3)	0.6884 (6)	0.34598 (16)	0.0203 (8)
C9a	0.8237 (3)	0.5961 (6)	0.39995 (17)	0.0186 (8)
C21	0.5061 (3)	0.7815 (6)	0.40570 (17)	0.0196 (8)
H21	0.5234	0.8745	0.4437	0.024*
C22	0.3978 (3)	0.8148 (6)	0.36585 (17)	0.0198 (8)
C23	0.3536 (4)	0.6824 (7)	0.30516 (19)	0.0341 (10)
H23A	0.4235	0.6011	0.2934	0.051*
H23B	0.3166	0.7907	0.2705	0.051*
H23C	0.2913	0.5680	0.3114	0.051*
C24	0.3078 (3)	0.9934 (6)	0.37990 (19)	0.0265 (9)
H24A	0.3393	1.0603	0.4229	0.040*
H24B	0.2276	0.9187	0.3786	0.040*
H24C	0.2977	1.1178	0.3474	0.040*
C91	0.7918 (3)	0.8926 (6)	0.31029 (18)	0.0239 (8)
H91A	0.8521	0.9976	0.2974	0.036*
H91B	0.7470	0.9768	0.3383	0.036*
H91C	0.7330	0.8374	0.2717	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl8	0.0258 (5)	0.0425 (6)	0.0397 (6)	−0.0035 (5)	0.0136 (4)	0.0059 (5)
O14	0.0279 (13)	0.0155 (12)	0.0234 (13)	−0.0016 (10)	0.0030 (10)	−0.0020 (10)
N1	0.0191 (15)	0.0155 (14)	0.0238 (16)	−0.0009 (12)	0.0038 (12)	−0.0001 (12)
C2	0.0169 (17)	0.0147 (17)	0.025 (2)	−0.0026 (14)	0.0027 (14)	−0.0038 (14)
C3	0.0209 (19)	0.0137 (18)	0.041 (2)	−0.0017 (14)	0.0092 (16)	−0.0022 (16)
C4	0.032 (2)	0.0124 (17)	0.030 (2)	−0.0016 (16)	0.0091 (16)	0.0060 (15)
C5	0.0257 (19)	0.0176 (18)	0.032 (2)	−0.0002 (16)	−0.0017 (16)	0.0024 (17)
C5a	0.0176 (17)	0.0139 (17)	0.0248 (19)	−0.0021 (14)	−0.0023 (14)	−0.0020 (15)
C6	0.0212 (19)	0.0172 (18)	0.034 (2)	0.0045 (15)	−0.0005 (16)	0.0010 (17)
C7	0.0113 (17)	0.029 (2)	0.038 (2)	0.0015 (15)	0.0006 (16)	−0.0019 (18)
C8	0.0149 (17)	0.026 (2)	0.034 (2)	−0.0037 (15)	0.0035 (15)	−0.0023 (17)
C9	0.0159 (17)	0.0213 (18)	0.0224 (19)	−0.0051 (15)	0.0015 (14)	−0.0024 (16)
C9a	0.0134 (17)	0.0141 (17)	0.0259 (19)	−0.0007 (13)	−0.0014 (14)	−0.0058 (15)
C21	0.0239 (19)	0.0103 (16)	0.026 (2)	−0.0009 (14)	0.0095 (15)	−0.0018 (14)
C22	0.0206 (18)	0.0134 (16)	0.0269 (19)	−0.0038 (15)	0.0085 (14)	0.0007 (15)
C23	0.027 (2)	0.034 (2)	0.039 (2)	0.0059 (19)	0.0013 (17)	−0.005 (2)
C24	0.024 (2)	0.0175 (18)	0.039 (2)	0.0037 (16)	0.0091 (17)	0.0022 (17)
C91	0.0235 (19)	0.0196 (18)	0.029 (2)	−0.0007 (15)	0.0066 (16)	0.0011 (16)

Geometric parameters (Å, º)

Cl8—C8	1.741 (4)	C6—H6	0.9500
O14—N1	1.432 (4)	C7—C8	1.380 (5)
O14—C4	1.448 (4)	C7—H7	0.9500
N1—C9a	1.446 (4)	C8—C9	1.385 (5)
N1—C2	1.482 (4)	C9—C9a	1.385 (5)
C2—C21	1.491 (5)	C9—C91	1.493 (5)
C2—C3	1.548 (5)	C21—C22	1.320 (5)
C2—H2	1.0000	C21—H21	0.9500
C3—C4	1.519 (5)	C22—C23	1.481 (5)
C3—H3A	0.9900	C22—C24	1.501 (5)
C3—H3B	0.9900	C23—H23A	0.9800
C4—C5	1.510 (5)	C23—H23B	0.9800
C4—H4	1.0000	C23—H23C	0.9800
C5—C5a	1.495 (5)	C24—H24A	0.9800
C5—H5A	0.9900	C24—H24B	0.9800
C5—H5B	0.9900	C24—H24C	0.9800
C5a—C6	1.386 (5)	C91—H91A	0.9800
C5a—C9a	1.399 (5)	C91—H91B	0.9800
C6—C7	1.361 (5)	C91—H91C	0.9800
N1—O14—C4	103.9 (2)	C6—C7—H7	120.4
O14—N1—C9a	108.7 (2)	C8—C7—H7	120.4
O14—N1—C2	102.1 (2)	C7—C8—C9	122.7 (4)
C9a—N1—C2	111.6 (3)	C7—C8—Cl8	117.9 (3)
N1—C2—C21	109.1 (3)	C9—C8—Cl8	119.3 (3)
N1—C2—C3	102.6 (3)	C8—C9—C9a	116.2 (3)
C21—C2—C3	113.3 (3)	C8—C9—C91	122.0 (3)
N1—C2—H2	110.5	C9a—C9—C91	121.7 (3)
C21—C2—H2	110.5	C9—C9a—C5a	122.8 (3)
C3—C2—H2	110.5	C9—C9a—N1	117.2 (3)
C4—C3—C2	103.8 (3)	C5a—C9a—N1	120.1 (3)
C4—C3—H3A	111.0	C22—C21—C2	126.6 (3)
C2—C3—H3A	111.0	C22—C21—H21	116.7
C4—C3—H3B	111.0	C2—C21—H21	116.7
C2—C3—H3B	111.0	C21—C22—C23	124.3 (3)
H3A—C3—H3B	109.0	C21—C22—C24	121.3 (3)
O14—C4—C5	106.5 (3)	C23—C22—C24	114.3 (3)
O14—C4—C3	103.8 (3)	C22—C23—H23A	109.5
C5—C4—C3	113.1 (3)	C22—C23—H23B	109.5
O14—C4—H4	111.1	H23A—C23—H23B	109.5
C5—C4—H4	111.1	C22—C23—H23C	109.5
C3—C4—H4	111.1	H23A—C23—H23C	109.5
C5a—C5—C4	110.3 (3)	H23B—C23—H23C	109.5
C5a—C5—H5A	109.6	C22—C24—H24A	109.5
C4—C5—H5A	109.6	C22—C24—H24B	109.5
C5a—C5—H5B	109.6	H24A—C24—H24B	109.5
C4—C5—H5B	109.6	C22—C24—H24C	109.5
H5A—C5—H5B	108.1	H24A—C24—H24C	109.5
C6—C5a—C9a	117.6 (3)	H24B—C24—H24C	109.5
C6—C5a—C5	122.5 (3)	C9—C91—H91A	109.5
C9a—C5a—C5	119.8 (3)	C9—C91—H91B	109.5
C7—C6—C5a	121.4 (3)	H91A—C91—H91B	109.5
C7—C6—H6	119.3	C9—C91—H91C	109.5
C5a—C6—H6	119.3	H91A—C91—H91C	109.5
C6—C7—C8	119.2 (3)	H91B—C91—H91C	109.5
C4—O14—N1—C9a	−67.8 (3)	C7—C8—C9—C9a	−0.4 (5)
C4—O14—N1—C2	50.2 (3)	Cl8—C8—C9—C9a	179.4 (2)
O14—N1—C2—C21	81.3 (3)	C7—C8—C9—C91	−179.0 (3)
C9a—N1—C2—C21	−162.9 (3)	Cl8—C8—C9—C91	0.9 (5)
O14—N1—C2—C3	−39.2 (3)	C8—C9—C9a—C5a	−2.1 (5)
C9a—N1—C2—C3	76.7 (3)	C91—C9—C9a—C5a	176.4 (3)
N1—C2—C3—C4	14.9 (3)	C8—C9—C9a—N1	176.9 (3)
C21—C2—C3—C4	−102.6 (3)	C91—C9—C9a—N1	−4.5 (5)
N1—O14—C4—C5	79.8 (3)	C6—C5a—C9a—C9	2.8 (5)
N1—O14—C4—C3	−39.8 (3)	C5—C5a—C9a—C9	−174.8 (3)
C2—C3—C4—O14	14.2 (4)	C6—C5a—C9a—N1	−176.2 (3)
C2—C3—C4—C5	−100.7 (3)	C5—C5a—C9a—N1	6.1 (5)
O14—C4—C5—C5a	−45.8 (4)	O14—N1—C9a—C9	−153.5 (3)
C3—C4—C5—C5a	67.6 (4)	C2—N1—C9a—C9	94.7 (3)
C4—C5—C5a—C6	−173.0 (3)	O14—N1—C9a—C5a	25.6 (4)
C4—C5—C5a—C9a	4.5 (4)	C2—N1—C9a—C5a	−86.2 (4)
C9a—C5a—C6—C7	−0.9 (5)	N1—C2—C21—C22	144.9 (3)
C5—C5a—C6—C7	176.7 (3)	C3—C2—C21—C22	−101.5 (4)
C5a—C6—C7—C8	−1.5 (5)	C2—C21—C22—C23	1.5 (6)
C6—C7—C8—C9	2.2 (5)	C2—C21—C22—C24	−179.3 (3)
C6—C7—C8—Cl8	−177.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cg1^i	0.99	2.79	3.730 (4)	158

Symmetry code: (i) −x+2, −y+2, −z+1.

(IV) (2RS,4RS)-8-chloro-9-methyl-2-endo-(2-methylprop-1-enyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C15H18ClNO	Z = 2
Mr = 263.75	F(000) = 280
Triclinic, P1	Dx = 1.334 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2890 (9) Å	Cell parameters from 3005 reflections
b = 9.3076 (16) Å	θ = 2.8–27.5°
c = 13.551 (3) Å	µ = 0.28 mm^−1
α = 94.554 (15)°	T = 120 K
β = 94.684 (15)°	Plate, colourless
γ = 97.298 (14)°	0.32 × 0.26 × 0.11 mm
V = 656.7 (2) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3005 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2348 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.932, Tmax = 0.970	l = −17→17
16228 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 0.5092P] where P = (Fo^2 + 2Fc^2)/3
3005 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl8	0.73078 (12)	0.74226 (5)	0.21073 (4)	0.03620 (17)
O14	0.6146 (2)	0.07431 (14)	0.12657 (10)	0.0230 (3)
N1	0.6629 (3)	0.18689 (17)	0.20756 (12)	0.0191 (3)
C2	0.5250 (4)	0.1133 (2)	0.28500 (15)	0.0242 (4)
H2	0.6309	0.0404	0.3110	0.029*
C3	0.2807 (4)	0.0301 (2)	0.22771 (15)	0.0254 (4)
H3A	0.2483	−0.0706	0.2470	0.031*
H3B	0.1300	0.0800	0.2395	0.031*
C4	0.3402 (4)	0.0311 (2)	0.12007 (15)	0.0234 (4)
H4	0.2926	−0.0678	0.0840	0.028*
C5	0.2183 (4)	0.1429 (2)	0.06578 (15)	0.0228 (4)
H5A	0.2398	0.1281	−0.0061	0.027*
H5B	0.0327	0.1321	0.0739	0.027*
C5a	0.3407 (4)	0.2930 (2)	0.10635 (14)	0.0191 (4)
C6	0.2486 (4)	0.4150 (2)	0.07421 (16)	0.0274 (5)
H6	0.1016	0.4040	0.0277	0.033*
C7	0.3654 (4)	0.5516 (2)	0.10817 (16)	0.0297 (5)
H7	0.3005	0.6349	0.0855	0.036*
C8	0.5780 (4)	0.5666 (2)	0.17553 (15)	0.0246 (4)
C9	0.6787 (4)	0.4489 (2)	0.21219 (14)	0.0194 (4)
C9a	0.5537 (3)	0.31158 (19)	0.17540 (13)	0.0169 (4)
C21	0.4772 (4)	0.2126 (2)	0.37011 (15)	0.0260 (4)
H21	0.3520	0.2755	0.3584	0.031*
C22	0.5935 (4)	0.2218 (2)	0.46155 (16)	0.0297 (5)
C23	0.8029 (5)	0.1396 (3)	0.4932 (2)	0.0474 (7)
H23A	0.8582	0.0874	0.4348	0.071*
H23B	0.7418	0.0697	0.5392	0.071*
H23C	0.9474	0.2071	0.5266	0.071*
C24	0.5118 (5)	0.3198 (3)	0.54187 (18)	0.0465 (7)
H24A	0.3681	0.3665	0.5152	0.070*
H24B	0.6551	0.3945	0.5670	0.070*
H24C	0.4583	0.2629	0.5962	0.070*
C91	0.9103 (4)	0.4665 (2)	0.28569 (15)	0.0255 (4)
H91A	1.0328	0.5479	0.2703	0.038*
H91B	0.9901	0.3770	0.2820	0.038*
H91C	0.8595	0.4860	0.3529	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl8	0.0492 (4)	0.0189 (2)	0.0386 (3)	−0.0047 (2)	0.0108 (3)	−0.0011 (2)
O14	0.0171 (7)	0.0209 (7)	0.0292 (8)	0.0013 (5)	0.0032 (6)	−0.0088 (6)
N1	0.0174 (8)	0.0195 (7)	0.0192 (8)	0.0025 (6)	−0.0003 (6)	−0.0038 (6)
C2	0.0249 (10)	0.0244 (10)	0.0238 (10)	0.0030 (8)	0.0023 (8)	0.0055 (8)
C3	0.0234 (10)	0.0245 (10)	0.0270 (11)	−0.0019 (8)	0.0031 (8)	0.0013 (8)
C4	0.0189 (10)	0.0212 (9)	0.0272 (11)	−0.0027 (7)	0.0026 (8)	−0.0074 (8)
C5	0.0161 (9)	0.0304 (10)	0.0197 (10)	−0.0016 (8)	0.0012 (8)	−0.0047 (8)
C5a	0.0157 (9)	0.0250 (9)	0.0163 (9)	0.0021 (7)	0.0035 (7)	−0.0010 (7)
C6	0.0247 (11)	0.0327 (11)	0.0247 (11)	0.0062 (9)	−0.0035 (8)	0.0043 (9)
C7	0.0346 (12)	0.0259 (10)	0.0305 (12)	0.0091 (9)	0.0018 (9)	0.0066 (9)
C8	0.0293 (11)	0.0195 (9)	0.0242 (10)	−0.0016 (8)	0.0085 (9)	−0.0022 (8)
C9	0.0175 (9)	0.0225 (9)	0.0175 (9)	0.0004 (7)	0.0051 (7)	−0.0025 (7)
C9a	0.0143 (9)	0.0203 (9)	0.0165 (9)	0.0030 (7)	0.0048 (7)	−0.0008 (7)
C21	0.0268 (11)	0.0254 (10)	0.0261 (11)	0.0035 (8)	0.0034 (9)	0.0043 (8)
C22	0.0261 (11)	0.0358 (11)	0.0238 (11)	−0.0089 (9)	0.0024 (9)	0.0039 (9)
C23	0.0361 (14)	0.0610 (17)	0.0424 (15)	0.0000 (12)	−0.0087 (12)	0.0116 (13)
C24	0.0486 (16)	0.0589 (17)	0.0268 (12)	−0.0062 (13)	0.0027 (11)	−0.0066 (11)
C91	0.0200 (10)	0.0282 (10)	0.0250 (11)	−0.0032 (8)	−0.0006 (8)	−0.0044 (8)

Geometric parameters (Å, º)

Cl8—C8	1.741 (2)	C6—H6	0.9500
O14—N1	1.4392 (19)	C7—C8	1.375 (3)
O14—C4	1.450 (2)	C7—H7	0.9500
N1—C9a	1.442 (2)	C8—C9	1.387 (3)
N1—C2	1.488 (3)	C9—C9a	1.396 (2)
C2—C21	1.479 (3)	C9—C91	1.497 (3)
C2—C3	1.536 (3)	C21—C22	1.329 (3)
C2—H2	1.0000	C21—H21	0.9500
C3—C4	1.518 (3)	C22—C23	1.479 (3)
C3—H3A	0.9900	C22—C24	1.491 (3)
C3—H3B	0.9900	C23—H23A	0.9800
C4—C5	1.501 (3)	C23—H23B	0.9800
C4—H4	1.0000	C23—H23C	0.9800
C5—C5a	1.505 (3)	C24—H24A	0.9800
C5—H5A	0.9900	C24—H24B	0.9800
C5—H5B	0.9900	C24—H24C	0.9800
C5a—C6	1.378 (3)	C91—H91A	0.9800
C5a—C9a	1.388 (3)	C91—H91B	0.9800
C6—C7	1.368 (3)	C91—H91C	0.9800
N1—O14—C4	104.10 (13)	C6—C7—H7	120.4
O14—N1—C9a	107.54 (14)	C8—C7—H7	120.4
O14—N1—C2	100.29 (14)	C7—C8—C9	122.85 (18)
C9a—N1—C2	113.92 (15)	C7—C8—Cl8	117.31 (16)
C21—C2—N1	114.18 (16)	C9—C8—Cl8	119.78 (16)
C21—C2—C3	114.01 (17)	C8—C9—C9a	116.06 (18)
N1—C2—C3	104.22 (16)	C8—C9—C91	122.44 (17)
C21—C2—H2	108.0	C9a—C9—C91	121.50 (17)
N1—C2—H2	108.0	C5a—C9a—C9	122.34 (17)
C3—C2—H2	108.0	C5a—C9a—N1	120.22 (16)
C4—C3—C2	103.08 (16)	C9—C9a—N1	117.35 (16)
C4—C3—H3A	111.1	C22—C21—C2	125.9 (2)
C2—C3—H3A	111.1	C22—C21—H21	117.1
C4—C3—H3B	111.1	C2—C21—H21	117.0
C2—C3—H3B	111.1	C21—C22—C23	125.2 (2)
H3A—C3—H3B	109.1	C21—C22—C24	119.9 (2)
O14—C4—C5	106.92 (15)	C23—C22—C24	114.9 (2)
O14—C4—C3	103.98 (15)	C22—C23—H23A	109.5
C5—C4—C3	113.35 (16)	C22—C23—H23B	109.5
O14—C4—H4	110.8	H23A—C23—H23B	109.5
C5—C4—H4	110.8	C22—C23—H23C	109.5
C3—C4—H4	110.8	H23A—C23—H23C	109.5
C4—C5—C5a	109.79 (16)	H23B—C23—H23C	109.5
C4—C5—H5B	109.7	C22—C24—H24A	109.5
C5a—C5—H5B	109.7	C22—C24—H24B	109.5
C4—C5—H5A	109.7	H24A—C24—H24B	109.5
C5a—C5—H5A	109.7	C22—C24—H24C	109.5
H5B—C5—H5A	108.2	H24A—C24—H24C	109.5
C6—C5a—C9a	118.50 (18)	H24B—C24—H24C	109.5
C6—C5a—C5	121.01 (18)	C9—C91—H91A	109.5
C9a—C5a—C5	120.47 (17)	C9—C91—H91B	109.5
C7—C6—C5a	121.11 (19)	H91A—C91—H91B	109.5
C7—C6—H6	119.4	C9—C91—H91C	109.5
C5a—C6—H6	119.4	H91A—C91—H91C	109.5
C6—C7—C8	119.13 (19)	H91B—C91—H91C	109.5
C4—O14—N1—C9a	−69.19 (17)	C7—C8—C9—C9a	1.0 (3)
C4—O14—N1—C2	50.12 (16)	Cl8—C8—C9—C9a	−176.12 (14)
O14—N1—C2—C21	−164.40 (16)	C7—C8—C9—C91	−179.91 (19)
C9a—N1—C2—C21	−49.8 (2)	Cl8—C8—C9—C91	2.9 (3)
O14—N1—C2—C3	−39.38 (17)	C6—C5a—C9a—C9	−0.8 (3)
C9a—N1—C2—C3	75.18 (19)	C5—C5a—C9a—C9	177.59 (17)
C21—C2—C3—C4	140.31 (17)	C6—C5a—C9a—N1	−177.20 (17)
N1—C2—C3—C4	15.18 (19)	C5—C5a—C9a—N1	1.2 (3)
N1—O14—C4—C5	79.45 (17)	C8—C9—C9a—C5a	−0.1 (3)
N1—O14—C4—C3	−40.72 (17)	C91—C9—C9a—C5a	−179.21 (17)
C2—C3—C4—O14	14.57 (19)	C8—C9—C9a—N1	176.37 (17)
C2—C3—C4—C5	−101.17 (18)	C91—C9—C9a—N1	−2.7 (3)
O14—C4—C5—C5a	−45.5 (2)	O14—N1—C9a—C5a	29.7 (2)
C3—C4—C5—C5a	68.5 (2)	C2—N1—C9a—C5a	−80.5 (2)
C4—C5—C5a—C6	−174.80 (18)	O14—N1—C9a—C9	−146.86 (15)
C4—C5—C5a—C9a	6.9 (2)	C2—N1—C9a—C9	102.95 (19)
C9a—C5a—C6—C7	0.9 (3)	N1—C2—C21—C22	−108.4 (2)
C5—C5a—C6—C7	−177.50 (19)	C3—C2—C21—C22	132.0 (2)
C5a—C6—C7—C8	0.0 (3)	C2—C21—C22—C23	3.6 (4)
C6—C7—C8—C9	−1.0 (3)	C2—C21—C22—C24	−175.6 (2)
C6—C7—C8—Cl8	176.25 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O14^i	0.99	2.39	3.358 (3)	166

Symmetry code: (i) x−1, y, z.

(V) (2SR,4RS)-8-chloro-9-methyl-2-exo-(prop-1-en-2-yl)- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C14H16ClNO	F(000) = 528
Mr = 249.73	Dx = 1.382 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2759 reflections
a = 8.6828 (11) Å	θ = 3.0–27.5°
b = 10.1456 (6) Å	µ = 0.30 mm^−1
c = 14.2976 (16) Å	T = 120 K
β = 107.587 (9)°	Needle, colourless
V = 1200.6 (2) Å^3	0.50 × 0.17 × 0.14 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2759 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2083 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −11→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.844, Tmax = 0.959	l = −18→18
14152 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.033P)^2 + 0.6821P] where P = (Fo^2 + 2Fc^2)/3
2759 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl8	0.17493 (5)	0.51162 (5)	−0.04294 (3)	0.02313 (13)
O14	0.56116 (15)	0.44942 (12)	0.39932 (9)	0.0181 (3)
N1	0.56968 (17)	0.44244 (14)	0.30049 (10)	0.0154 (3)
C2	0.7240 (2)	0.50923 (18)	0.30829 (13)	0.0163 (4)
H2	0.7174	0.5504	0.2436	0.020*
C3	0.7334 (2)	0.61983 (18)	0.38466 (14)	0.0196 (4)
H3A	0.8390	0.6188	0.4365	0.024*
H3B	0.7167	0.7076	0.3530	0.024*
C4	0.5964 (2)	0.58590 (18)	0.42662 (14)	0.0186 (4)
H4	0.6323	0.5960	0.4996	0.022*
C5	0.4426 (2)	0.66211 (18)	0.38113 (13)	0.0200 (4)
H5A	0.3640	0.6436	0.4172	0.024*
H5B	0.4659	0.7578	0.3856	0.024*
C5a	0.3718 (2)	0.62281 (17)	0.27530 (13)	0.0167 (4)
C6	0.2428 (2)	0.69009 (18)	0.21303 (14)	0.0188 (4)
H6	0.1953	0.7611	0.2378	0.023*
C7	0.1822 (2)	0.65572 (18)	0.11573 (14)	0.0186 (4)
H7	0.0938	0.7025	0.0732	0.022*
C8	0.2519 (2)	0.55219 (18)	0.08087 (13)	0.0175 (4)
C9	0.3788 (2)	0.47884 (17)	0.13986 (13)	0.0163 (4)
C9a	0.4367 (2)	0.51727 (17)	0.23824 (13)	0.0154 (4)
C21	0.8665 (2)	0.41759 (18)	0.33704 (13)	0.0181 (4)
C22	0.8561 (2)	0.29420 (19)	0.36188 (14)	0.0239 (4)
H22A	0.9496	0.2399	0.3789	0.029*
H22B	0.7551	0.2592	0.3628	0.029*
C23	1.0216 (2)	0.4792 (2)	0.33394 (16)	0.0287 (5)
H23A	1.1069	0.4122	0.3484	0.043*
H23B	1.0519	0.5498	0.3829	0.043*
H23C	1.0076	0.5159	0.2685	0.043*
C91	0.4504 (2)	0.36465 (18)	0.10169 (14)	0.0207 (4)
H91A	0.3637	0.3112	0.0586	0.031*
H91B	0.5136	0.3107	0.1568	0.031*
H91C	0.5210	0.3972	0.0646	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl8	0.0201 (2)	0.0286 (3)	0.0186 (2)	−0.00090 (19)	0.00268 (17)	−0.0012 (2)
O14	0.0235 (7)	0.0183 (7)	0.0148 (6)	−0.0017 (5)	0.0089 (5)	0.0008 (5)
N1	0.0172 (8)	0.0166 (8)	0.0132 (7)	−0.0004 (6)	0.0056 (6)	0.0009 (6)
C2	0.0166 (9)	0.0157 (9)	0.0170 (9)	−0.0017 (7)	0.0058 (7)	0.0010 (7)
C3	0.0188 (9)	0.0180 (9)	0.0220 (10)	−0.0020 (7)	0.0062 (8)	−0.0022 (8)
C4	0.0221 (10)	0.0168 (9)	0.0171 (9)	−0.0024 (7)	0.0060 (7)	−0.0035 (7)
C5	0.0217 (10)	0.0182 (10)	0.0215 (10)	−0.0002 (7)	0.0087 (8)	−0.0036 (8)
C5a	0.0166 (9)	0.0157 (9)	0.0194 (9)	−0.0030 (7)	0.0079 (7)	−0.0006 (7)
C6	0.0179 (9)	0.0150 (9)	0.0255 (10)	−0.0006 (7)	0.0097 (8)	0.0001 (8)
C7	0.0136 (9)	0.0169 (9)	0.0249 (10)	−0.0007 (7)	0.0052 (7)	0.0029 (8)
C8	0.0168 (9)	0.0195 (9)	0.0159 (9)	−0.0042 (7)	0.0044 (7)	−0.0013 (7)
C9	0.0161 (8)	0.0150 (9)	0.0194 (9)	−0.0032 (7)	0.0078 (7)	−0.0002 (7)
C9a	0.0140 (8)	0.0142 (9)	0.0196 (9)	−0.0019 (7)	0.0073 (7)	0.0013 (7)
C21	0.0179 (9)	0.0214 (10)	0.0144 (9)	0.0024 (7)	0.0038 (7)	−0.0016 (7)
C22	0.0236 (10)	0.0235 (11)	0.0237 (10)	0.0045 (8)	0.0057 (8)	0.0007 (8)
C23	0.0181 (10)	0.0294 (12)	0.0382 (12)	0.0028 (8)	0.0077 (9)	0.0023 (9)
C91	0.0218 (10)	0.0204 (10)	0.0205 (10)	0.0013 (8)	0.0072 (8)	−0.0028 (8)

Geometric parameters (Å, º)

Cl8—C8	1.7420 (18)	C6—C7	1.375 (3)
O14—N1	1.4389 (18)	C6—H6	0.9500
O14—C4	1.446 (2)	C7—C8	1.379 (3)
N1—C9a	1.443 (2)	C7—H7	0.9500
N1—C2	1.476 (2)	C8—C9	1.385 (3)
C2—C21	1.502 (2)	C9—C9a	1.399 (2)
C2—C3	1.551 (2)	C9—C91	1.494 (2)
C2—H2	1.0000	C21—C22	1.312 (3)
C3—C4	1.524 (3)	C21—C23	1.498 (3)
C3—H3A	0.9900	C22—H22A	0.9500
C3—H3B	0.9900	C22—H22B	0.9500
C4—C5	1.510 (3)	C23—H23A	0.9800
C4—H4	1.0000	C23—H23B	0.9800
C5—C5a	1.505 (3)	C23—H23C	0.9800
C5—H5A	0.9900	C91—H91A	0.9800
C5—H5B	0.9900	C91—H91B	0.9800
C5a—C6	1.382 (3)	C91—H91C	0.9800
C5a—C9a	1.387 (2)
N1—O14—C4	104.04 (12)	C7—C6—H6	119.5
O14—N1—C9a	108.11 (13)	C5a—C6—H6	119.5
O14—N1—C2	102.60 (12)	C6—C7—C8	118.91 (17)
C9a—N1—C2	110.15 (14)	C6—C7—H7	120.5
N1—C2—C21	112.98 (15)	C8—C7—H7	120.5
N1—C2—C3	103.81 (14)	C7—C8—C9	123.00 (17)
C21—C2—C3	113.06 (14)	C7—C8—Cl8	118.15 (14)
N1—C2—H2	108.9	C9—C8—Cl8	118.84 (14)
C21—C2—H2	108.9	C8—C9—C9a	116.15 (16)
C3—C2—H2	108.9	C8—C9—C91	122.45 (16)
C4—C3—C2	103.45 (14)	C9a—C9—C91	121.40 (16)
C4—C3—H3A	111.1	C5a—C9a—C9	122.37 (16)
C2—C3—H3A	111.1	C5a—C9a—N1	120.81 (16)
C4—C3—H3B	111.1	C9—C9a—N1	116.82 (15)
C2—C3—H3B	111.1	C22—C21—C23	122.83 (18)
H3A—C3—H3B	109.0	C22—C21—C2	123.14 (17)
O14—C4—C5	106.64 (14)	C23—C21—C2	114.03 (16)
O14—C4—C3	103.70 (14)	C21—C22—H22A	120.0
C5—C4—C3	114.12 (16)	C21—C22—H22B	120.0
O14—C4—H4	110.7	H22A—C22—H22B	120.0
C5—C4—H4	110.7	C21—C23—H23A	109.5
C3—C4—H4	110.7	C21—C23—H23B	109.5
C5a—C5—C4	109.68 (15)	H23A—C23—H23B	109.5
C5a—C5—H5A	109.7	C21—C23—H23C	109.5
C4—C5—H5A	109.7	H23A—C23—H23C	109.5
C5a—C5—H5B	109.7	H23B—C23—H23C	109.5
C4—C5—H5B	109.7	C9—C91—H91A	109.5
H5A—C5—H5B	108.2	C9—C91—H91B	109.5
C6—C5a—C9a	118.60 (17)	H91A—C91—H91B	109.5
C6—C5a—C5	121.47 (16)	C9—C91—H91C	109.5
C9a—C5a—C5	119.93 (16)	H91A—C91—H91C	109.5
C7—C6—C5a	120.94 (17)	H91B—C91—H91C	109.5
C4—O14—N1—C9a	−67.83 (15)	C7—C8—C9—C9a	−1.4 (3)
C4—O14—N1—C2	48.57 (15)	Cl8—C8—C9—C9a	179.20 (13)
O14—N1—C2—C21	87.38 (16)	C7—C8—C9—C91	178.36 (17)
C9a—N1—C2—C21	−157.70 (14)	Cl8—C8—C9—C91	−1.1 (2)
O14—N1—C2—C3	−35.46 (16)	C6—C5a—C9a—C9	1.6 (3)
C9a—N1—C2—C3	79.46 (16)	C5—C5a—C9a—C9	−178.10 (16)
N1—C2—C3—C4	10.65 (18)	C6—C5a—C9a—N1	−179.01 (15)
C21—C2—C3—C4	−112.14 (16)	C5—C5a—C9a—N1	1.3 (3)
N1—O14—C4—C5	79.72 (16)	C8—C9—C9a—C5a	−0.1 (3)
N1—O14—C4—C3	−41.07 (16)	C91—C9—C9a—C5a	−179.88 (17)
C2—C3—C4—O14	17.77 (17)	C8—C9—C9a—N1	−179.53 (15)
C2—C3—C4—C5	−97.83 (17)	C91—C9—C9a—N1	0.7 (2)
O14—C4—C5—C5a	−47.42 (19)	O14—N1—C9a—C5a	28.2 (2)
C3—C4—C5—C5a	66.5 (2)	C2—N1—C9a—C5a	−83.20 (19)
C4—C5—C5a—C6	−171.23 (16)	O14—N1—C9a—C9	−152.41 (14)
C4—C5—C5a—C9a	8.5 (2)	C2—N1—C9a—C9	96.21 (18)
C9a—C5a—C6—C7	−1.7 (3)	N1—C2—C21—C22	−6.3 (2)
C5—C5a—C6—C7	178.05 (17)	C3—C2—C21—C22	111.2 (2)
C5a—C6—C7—C8	0.2 (3)	N1—C2—C21—C23	173.15 (15)
C6—C7—C8—C9	1.4 (3)	C3—C2—C21—C23	−69.3 (2)
C6—C7—C8—Cl8	−179.22 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O14^i	1.00	2.57	3.202 (2)	121

Symmetry code: (i) −x+1, −y+1, −z+1.

(VI) 7,9-dichloro-2-exo-(prop-1-en-2-yl)-2,3,4,5-tetrahydro- 1H-1,4-epoxy-1-benzazepine

Crystal data

C13H13Cl2NO	F(000) = 280
Mr = 270.14	Dx = 1.483 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2751 reflections
a = 10.4753 (13) Å	θ = 3.2–27.5°
b = 5.4759 (8) Å	µ = 0.52 mm^−1
c = 10.9632 (12) Å	T = 120 K
β = 105.791 (13)°	Block, colourless
V = 605.13 (13) Å^3	0.30 × 0.25 × 0.16 mm
Z = 2

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2751 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2385 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −13→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −7→7
Tmin = 0.826, Tmax = 0.922	l = −14→14
10313 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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0738P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2751 reflections	Δρmax = 0.42 e Å^−3
156 parameters	Δρmin = −0.56 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1223 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.61 (7)

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

	x	y	z	Uiso*/Ueq
Cl7	0.27068 (6)	0.76451 (14)	0.35134 (6)	0.0354 (2)
Cl9	0.51226 (6)	0.11718 (13)	0.12174 (6)	0.03107 (19)
O14	0.86993 (18)	0.3899 (4)	0.38211 (17)	0.0286 (5)
N1	0.7617 (2)	0.3387 (4)	0.2721 (2)	0.0235 (5)
C2	0.8024 (3)	0.4726 (5)	0.1711 (3)	0.0255 (6)
H2	0.7214	0.5193	0.1028	0.031*
C3	0.8690 (3)	0.7046 (5)	0.2378 (3)	0.0281 (6)
H3A	0.9553	0.7339	0.2198	0.034*
H3B	0.8115	0.8493	0.2112	0.034*
C4	0.8875 (3)	0.6476 (6)	0.3783 (3)	0.0299 (6)
H4	0.9785	0.6953	0.4296	0.036*
C5	0.7833 (3)	0.7637 (6)	0.4311 (2)	0.0295 (6)
H5A	0.8064	0.7395	0.5240	0.035*
H5B	0.7794	0.9414	0.4139	0.035*
C5a	0.6502 (3)	0.6495 (5)	0.3702 (2)	0.0243 (6)
C6	0.5347 (3)	0.7452 (7)	0.3892 (2)	0.0282 (6)
H6	0.5381	0.8804	0.4443	0.034*
C7	0.4142 (3)	0.6412 (6)	0.3269 (2)	0.0276 (6)
C8	0.4050 (3)	0.4469 (6)	0.2457 (3)	0.0265 (6)
H8	0.3214	0.3789	0.2027	0.032*
C9	0.5213 (3)	0.3541 (5)	0.2288 (2)	0.0256 (6)
C9a	0.6444 (2)	0.4477 (5)	0.2917 (2)	0.0224 (5)
C21	0.8904 (3)	0.3158 (5)	0.1152 (2)	0.0264 (6)
C22	0.8488 (3)	0.2504 (7)	−0.0042 (3)	0.0401 (7)
H22A	0.9043	0.1553	−0.0412	0.048*
H22B	0.7631	0.2981	−0.0536	0.048*
C23	1.0237 (3)	0.2459 (7)	0.1965 (3)	0.0338 (6)
H23A	1.0690	0.1443	0.1476	0.051*
H23B	1.0137	0.1537	0.2700	0.051*
H23C	1.0760	0.3935	0.2255	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl7	0.0247 (3)	0.0457 (5)	0.0394 (4)	0.0035 (3)	0.0150 (3)	−0.0051 (3)
Cl9	0.0239 (3)	0.0359 (4)	0.0342 (3)	−0.0041 (3)	0.0093 (2)	−0.0080 (3)
O14	0.0199 (9)	0.0371 (12)	0.0268 (10)	−0.0008 (8)	0.0030 (7)	0.0008 (8)
N1	0.0163 (10)	0.0292 (12)	0.0248 (10)	0.0019 (9)	0.0052 (8)	0.0023 (9)
C2	0.0185 (12)	0.0323 (16)	0.0273 (13)	−0.0006 (11)	0.0089 (10)	0.0055 (11)
C3	0.0245 (13)	0.0270 (15)	0.0365 (15)	−0.0020 (11)	0.0144 (11)	0.0019 (12)
C4	0.0210 (13)	0.0355 (18)	0.0323 (13)	−0.0022 (12)	0.0057 (10)	−0.0040 (13)
C5	0.0268 (13)	0.0341 (15)	0.0278 (13)	−0.0026 (13)	0.0077 (10)	−0.0067 (14)
C5a	0.0227 (12)	0.0273 (16)	0.0232 (12)	0.0016 (12)	0.0070 (9)	0.0035 (11)
C6	0.0286 (13)	0.0346 (16)	0.0232 (12)	0.0025 (13)	0.0101 (10)	0.0001 (12)
C7	0.0225 (12)	0.0359 (17)	0.0269 (13)	−0.0012 (13)	0.0110 (10)	0.0032 (13)
C8	0.0184 (12)	0.0344 (15)	0.0283 (13)	0.0000 (11)	0.0093 (11)	−0.0004 (11)
C9	0.0235 (13)	0.0310 (16)	0.0246 (13)	0.0016 (12)	0.0106 (10)	0.0010 (12)
C9a	0.0175 (12)	0.0265 (14)	0.0245 (13)	0.0012 (10)	0.0082 (9)	0.0032 (11)
C21	0.0182 (12)	0.0297 (17)	0.0338 (14)	−0.0027 (11)	0.0113 (11)	0.0028 (12)
C22	0.0323 (15)	0.055 (2)	0.0368 (15)	0.0029 (16)	0.0157 (12)	−0.0042 (17)
C23	0.0216 (13)	0.0347 (16)	0.0462 (16)	0.0006 (13)	0.0113 (12)	−0.0021 (15)

Geometric parameters (Å, º)

Cl7—C7	1.734 (3)	C5—H5B	0.9900
Cl9—C9	1.735 (3)	C5a—C6	1.386 (4)
O14—C4	1.425 (4)	C5a—C9a	1.391 (4)
O14—N1	1.441 (3)	C6—C7	1.383 (4)
N1—C9a	1.433 (3)	C6—H6	0.9500
N1—C2	1.483 (3)	C7—C8	1.374 (4)
C2—C21	1.508 (4)	C8—C9	1.378 (4)
C2—C3	1.536 (4)	C8—H8	0.9500
C2—H2	1.0000	C9—C9a	1.385 (4)
C3—C4	1.531 (4)	C21—C22	1.312 (4)
C3—H3A	0.9900	C21—C23	1.488 (4)
C3—H3B	0.9900	C22—H22A	0.9500
C4—C5	1.508 (4)	C22—H22B	0.9500
C4—H4	1.0000	C23—H23A	0.9800
C5—C5a	1.508 (4)	C23—H23B	0.9800
C5—H5A	0.9900	C23—H23C	0.9800
C4—O14—N1	104.29 (19)	C6—C5a—C5	121.1 (3)
C9a—N1—O14	107.7 (2)	C9a—C5a—C5	118.9 (2)
C9a—N1—C2	109.8 (2)	C7—C6—C5a	119.1 (3)
O14—N1—C2	102.02 (19)	C7—C6—H6	120.4
N1—C2—C21	110.7 (2)	C5a—C6—H6	120.4
N1—C2—C3	103.8 (2)	C8—C7—C6	122.2 (3)
C21—C2—C3	114.6 (2)	C8—C7—Cl7	119.4 (2)
N1—C2—H2	109.2	C6—C7—Cl7	118.4 (2)
C21—C2—H2	109.2	C7—C8—C9	117.6 (3)
C3—C2—H2	109.2	C7—C8—H8	121.2
C4—C3—C2	103.1 (2)	C9—C8—H8	121.2
C4—C3—H3A	111.1	C8—C9—C9a	122.3 (3)
C2—C3—H3A	111.1	C8—C9—Cl9	118.6 (2)
C4—C3—H3B	111.1	C9a—C9—Cl9	119.1 (2)
C2—C3—H3B	111.1	C9—C9a—C5a	118.7 (2)
H3A—C3—H3B	109.1	C9—C9a—N1	119.4 (2)
O14—C4—C5	107.1 (3)	C5a—C9a—N1	121.9 (2)
O14—C4—C3	104.4 (2)	C22—C21—C23	122.1 (3)
C5—C4—C3	113.1 (2)	C22—C21—C2	119.2 (3)
O14—C4—H4	110.7	C23—C21—C2	118.7 (2)
C5—C4—H4	110.7	C21—C22—H22A	120.0
C3—C4—H4	110.7	C21—C22—H22B	120.0
C5a—C5—C4	109.5 (2)	H22A—C22—H22B	120.0
C5a—C5—H5A	109.8	C21—C23—H23A	109.5
C4—C5—H5A	109.8	C21—C23—H23B	109.5
C5a—C5—H5B	109.8	H23A—C23—H23B	109.5
C4—C5—H5B	109.8	C21—C23—H23C	109.5
H5A—C5—H5B	108.2	H23A—C23—H23C	109.5
C6—C5a—C9a	120.0 (3)	H23B—C23—H23C	109.5
C4—O14—N1—C9a	−67.0 (2)	C6—C7—C8—C9	0.9 (4)
C4—O14—N1—C2	48.5 (2)	Cl7—C7—C8—C9	−180.0 (2)
C9a—N1—C2—C21	−159.2 (2)	C7—C8—C9—C9a	0.9 (4)
O14—N1—C2—C21	86.8 (2)	C7—C8—C9—Cl9	−177.3 (2)
C9a—N1—C2—C3	77.3 (3)	C8—C9—C9a—C5a	−3.0 (4)
O14—N1—C2—C3	−36.7 (2)	Cl9—C9—C9a—C5a	175.2 (2)
N1—C2—C3—C4	12.8 (3)	C8—C9—C9a—N1	178.5 (2)
C21—C2—C3—C4	−108.1 (3)	Cl9—C9—C9a—N1	−3.3 (4)
N1—O14—C4—C5	80.3 (2)	C6—C5a—C9a—C9	3.3 (4)
N1—O14—C4—C3	−39.9 (2)	C5—C5a—C9a—C9	−175.5 (2)
C2—C3—C4—O14	15.8 (3)	C6—C5a—C9a—N1	−178.3 (2)
C2—C3—C4—C5	−100.2 (3)	C5—C5a—C9a—N1	3.0 (4)
O14—C4—C5—C5a	−47.6 (3)	O14—N1—C9a—C9	−155.3 (2)
C3—C4—C5—C5a	66.8 (3)	C2—N1—C9a—C9	94.4 (3)
C4—C5—C5a—C6	−171.3 (3)	O14—N1—C9a—C5a	26.3 (3)
C4—C5—C5a—C9a	7.4 (4)	C2—N1—C9a—C5a	−84.0 (3)
C9a—C5a—C6—C7	−1.6 (4)	N1—C2—C21—C22	115.5 (3)
C5—C5a—C6—C7	177.1 (3)	C3—C2—C21—C22	−127.5 (3)
C5a—C6—C7—C8	−0.5 (4)	N1—C2—C21—C23	−66.1 (3)
C5a—C6—C7—Cl7	−179.7 (2)	C3—C2—C21—C23	50.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O14^i	1.00	2.48	3.389 (4)	151

Symmetry code: (i) −x+2, y+1/2, −z+1.