Three aryl-substituted tetrahydro-1,4-epoxy-1-benzazepines: hydrogen-bonded structures in two or three dimensions

In (2SR,4RS)-7-chloro-2-exo-(4-chloro­phenyl)-2,3,4,5-tetra­hy­dro-1H-1,4-epoxy-1-benzazepine, C₁₆H₁₃Cl₂NO, (I), the mol­ecules are linked by a combination of C—H...O and C—H...N hydrogen bonds into a chain of edge-fused R₃³(12) rings. The isomeric compound (2S,4R)-7-chloro-2-exo-(2-chloro­phenyl)-2,3,4,5-tetra­hydro-1H-1,4-epoxy-1-benzazepine, (II), crystallizes as a single 2S,4R enantio­mer and the mol­ecules are linked into a three-dimensional framework structure by two C—H...O hydrogen bonds and one C—H...π(arene) hydrogen bond. The mol­ecules of (2S,4R)-7-chloro-2-exo-(1-naphthyl)-2,3,4,5-tetra­hydro-1H-1,4-epoxy-1-benzazepine, C₂₀H₁₆ClNO, (III), are also linked into a three-dimensional framework structure, here by one C—H...O hydrogen bond and two C—H...π(arene) hydrogen bonds. The significance of this study lies in its observation of the variations in mol­ecular configuration and conformation, and in the variation in the patterns of supra­molecular aggregation, consequent upon modest changes in the peripheral substituents.

S1. Comment

In a continuation of our structural study of 2-substituted 1,4-epoxy-tetrahydro-1-benzazepines (Acosta et al., 2008), itself part of a programme to identify structurally novel anti-parasitic compounds with new modes of action to combat both Trypanosoma cruzi and Leishmania chagasi parasites (Gómez et al., 2006; Yépez et al., 2006), we now report the structures of three aryl-substituted examples, compounds (I)–(III) (Figs. 1–3).

Compounds (I)–(III) were prepared by reaction of an appropriately substituted 2-allyl-N-benzylaniline or 2-allyl-N-(1-naphthylmethyl) aniline with an excess of hydrogen peroxide solution in the presence of catalytic amounts of sodium tungstate, with subsequent internal 1,3-dipolar cycloaddition of the resulting nitrones across the terminal C═C bond of the pendant allylic fragment.

Compound (I) crystallizes as a racemic mixture in space group Pna2₁, while the positional isomers, (II) and (III), were both refined as single enantiomorphs with the R configuration at atom C4, as indicated by the Flack x parameters (Flack, 1983). Accordingly, the reference molecule for the racemic compound, (I), was selected to have the R configuration at C4. On this basis, the reference molecules in compounds (I)–(III) all have the S configuration at atom C2.

The shapes of the heterobicyclic ring systems in (I)–(III), as defined by the ring-puckering parameters (Cremer & Pople, 1975), are all very similar (Table 1). For the five-membered rings, those in (I) and (II) adopt half-chair conformations, for which the ideal puckering angle ϕ is (36k + 18)°, where k represents an integer. For the corresponding ring in (III), the conformation is intermediate between an envelope form, where the ideal value of ϕ is 36k°, and the half-chair form observed in the other examples. The conformations of the six-membered heterocyclic rings are intermediate between a half-chair form, where the idealized values of the ring-puckering angles are θ = 50.8° and ϕ = (60k + 30)°, and an envelope form, where the idealized values are θ = 54.7° and ϕ = 60k°. The values of the torsion angle N1—C2—C21—C22 in (I)–(III), which defines the orientation of the pendent aryl group [94.3 (3), -12.4 (7) and 5.9 (4)°, respectively], are almost certainly dominated by steric factors.

In compound (I), molecules related by the 2₁ screw axis along (1/2, 1/2, z) are linked by one each of C—H···O and C—H···N hydrogen bonds (Table 2). Acting individually, these hydrogen bonds both generate C(4) (Bernstein et al., 1995) chains and in combination they generate a chain of edge-fused R₃³(12) rings (Fig. 4). A C—H···π(arene) hydrogen bond is also present, but this lies within the chain and hence the dimensionality of the hydrogen-bonded structure is unaffected.

In compound (II), on the other hand, where there are again three hydrogen bonds present in the structure, now one of the C—H···O type and two of the C—H···π(arene) type, the hydrogen bonds give rise to a three-dimensional hydrogen-bonded framework. The formation of this framework is readily analysed in terms of three one-dimensional substructures, each constructed using just one hydrogen bond. The C—H···O hydrogen bond, acting alone, generates a C(6) chain running parallel to the [010] direction, linking molecules related by the 2₁ screw axis along (1/2, y, 1/4). The shorter of the two C—H···π(arene) hydrogen bonds, involving the fused aryl ring as acceptor, forms a chain running parallel to the [100] direction, which consists of molecules related by the 2₁ screw axis along (x, 1/4, 1/2). The longer of the C—H···π(arene) hydrogen bonds utilizes the pendent aryl ring as the acceptor, and it generates a chain running parallel to the [001] direction and consisting of molecules related by the 2₁ screw axis along (3/4, 1/2, z). The combination of the chains along [100], [010] and [001] suffices to generate a continuous three-dimensional framework structure. The crystal structure of compound (II) also contains a short intermolecular C—H···Cl contact (Table 2). However, this contact is not likely to be structurally significant, firstly because the C—H bond concerned is of low acidity, and secondly because Cl bonded to C is known to be an extremely poor acceptor of hydrogen bonds, even from O or N (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001).

As in compound (II), the structure of (III) contains one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds and, again, these link the molecules into a three-dimensional framework. However, the detailed construction of this framework differs from that in (II), and there are two readily identified substructures in the structure of (III), one of which is one-dimensional and the other two-dimensional. The two-dimensional substructure is built from the two C—H···π(arene) interactions. The hydrogen bond in which the pendent naphthyl substituent is the acceptor generates a chain along (3/4, 1/2, z), while that having the fused aryl ring as acceptor forms a chain along (1/4, 1/2, z), and the combination of these two hydrogen bonds thus generates a sheet parallel to (010) (Fig. 5). Two sheets of this type, containing the 2₁ axes at y = 0 and y = 1/2, respectively, pass through each unit cell and they are linked by the one-dimensional substructure. This substructure is built using the C—H···O hydrogen bond, which links into a C(4) chain (Fig. 6) the molecules related by the 2₁ screw axis along (x, 3/4, 1/2). Atom C3 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O14 in the molecule at (1/2 + x, 3/2 - y, 1 - z). Since these two molecules are components of different (010) sheets, the effect of this C(4) chain is to link the sheets into a continuous three-dimensional framework structure.

S2. Experimental

For each of compounds (I)–(III), to a stirred solution of the appropriately substituted 2-allylaniline (0.10 mol) 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 ambient temperature for periods ranging from 48 to 72 h. Each mixture was then filtered and the solvent was removed under reduced pressure. Toluene (50 ml) was added to the solid residue and the resulting solution was heated under reflux for periods ranging from 3 to 7 h. After cooling the solution to ambient temperature, the solvent was removed under reduced pressure, and the crude product was purified by chromatography on silica using heptane–ethyl acetate (compositions ranged from 10:1 to 60:1 v/v) as eluent. Crystallization from heptane gave crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction.

For (I): colourless crystals, yield 46%, m.p. 406–407 K; MS (70 eV) m/z (%): 305 (M⁺, ³⁵Cl, 31), 288 (12), 276 (3), 262 (5), 164 (7), 138 (100), 125 (13), 111 (5). Analysis, found: C 63.0, H 4.5, N 4.7%; C₁₆H₁₃Cl₂NO requires: C 62.8, H 4.3, N 4.6%.

For (II): colourless crystals, yield 50%, m.p. 440–442 K; MS (70 eV) m/z (%): 305 (M⁺, ³⁵Cl, 21), 288 (7), 276 (1), 262 (1), 164 (6), 138 (100), 125 (13), 111 (4). Analysis, found: C 62.5, H 4.6, N 4.4%; C₁₆H₁₃Cl₂NO requires: C 62.8, H 4.3, N, 4.6%.

For (III): colourless crystals, yield 60%, m.p. 469–470 K; MS (70 eV) m/z (%): 321 (M⁺, ³⁵Cl, 20), 304 (10), 292 (6), 278 (6), 154 (100), 153 (75), 139 (33), 138 (35), 127 (20). Analysis, found: C 74.9, H 4.9, N 4.5%; C₂₀H₁₆ClNO requires: C 74.7, H 5.0, N 4.4%.

S3. Refinement

Unique assignments of space groups were made from the systematic absences for compounds (II) and (III), both P2₁2₁2₁. For compound (I), the systematic absences permitted Pna2₁ or Pnam (= Pnma, No. 62) as possible space groups; Pna2₁ was selected, and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic, heteroaromatic and alkene), 0.99 (CH₂) or 1.00 Å (aliphatic CH), and with U_iso(H) = 1.2U_eq(C). Compounds (II) and (III) were refined as single enantiomorphs, in each case having the R configuration at atom C4, as suggested by the values of the Flack x parameter (Flack, 1983; Flack & Bernardinelli, 1999). However, particularly for compound (II), the enantiomorph-discrimating power (Flack & Bernardinelli, 2000) is not high. The reference molecule in the racemic compound, (I), was chosen as that having the R configuration at atom C4; here the correct orientation of the structure with respect to the polar axis direction was established by means of the Flack x parameter. Compound (II) diffracted rather weakly, with only ca 49% of the reflections labelled `observed', even at 120 K.

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: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of compound (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular structure of compound (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded chain of R3^3(12) rings along [001]. For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of compound (III), showing the formation of a sheet parallel to (010) built from two C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of compound (III), showing the formation of a C(4) chain along [100] built from C—H···O hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted.

(I) (2SR,4RS)-7-chloro-2-exo-(4-chlorophenyl)-2,3,4,5-tetrahydro- 1H-1,4-epoxy-1-benzazepine

Crystal data

C16H13Cl2NO	F(000) = 632
Mr = 306.17	Dx = 1.487 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3116 reflections
a = 11.9348 (11) Å	θ = 3.3–27.5°
b = 21.617 (2) Å	µ = 0.47 mm^−1
c = 5.3024 (6) Å	T = 120 K
V = 1368.0 (2) Å^3	Plate, colourless
Z = 4	0.45 × 0.27 × 0.05 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3116 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2124 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ϕ and ω scans	h = −13→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −28→21
Tmin = 0.817, Tmax = 0.977	l = −6→6
12986 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) = 0.104	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 0.5401P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3116 reflections	Δρmax = 0.30 e Å^−3
181 parameters	Δρmin = −0.30 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1380 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (9)

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

	x	y	z	Uiso*/Ueq
Cl7	0.27978 (8)	0.27881 (4)	1.1092 (2)	0.0470 (3)
Cl24	0.99300 (7)	0.67574 (4)	0.8265 (2)	0.0371 (2)
O14	0.67229 (19)	0.42691 (10)	0.4982 (4)	0.0282 (6)
N1	0.6336 (2)	0.44608 (11)	0.7431 (5)	0.0251 (6)
C2	0.7363 (3)	0.43863 (14)	0.8972 (6)	0.0249 (7)
C3	0.7892 (3)	0.37935 (14)	0.7898 (6)	0.0272 (8)
C4	0.7265 (3)	0.36889 (13)	0.5454 (6)	0.0269 (8)
C5	0.6345 (3)	0.32047 (14)	0.5617 (7)	0.0304 (8)
C5a	0.5464 (3)	0.34263 (14)	0.7425 (6)	0.0266 (8)
C6	0.4627 (3)	0.30475 (14)	0.8304 (7)	0.0302 (8)
C7	0.3858 (3)	0.32706 (15)	0.9998 (7)	0.0305 (8)
C8	0.3887 (3)	0.38686 (14)	1.0844 (7)	0.0321 (8)
C9	0.4708 (3)	0.42498 (15)	0.9935 (7)	0.0299 (8)
C9a	0.5490 (3)	0.40341 (14)	0.8243 (7)	0.0255 (7)
C21	0.8054 (3)	0.49636 (14)	0.8811 (6)	0.0258 (8)
C22	0.7931 (3)	0.54124 (14)	1.0647 (7)	0.0282 (8)
C23	0.8500 (3)	0.59673 (15)	1.0509 (7)	0.0313 (8)
C24	0.9209 (3)	0.60655 (14)	0.8503 (7)	0.0282 (8)
C25	0.9356 (3)	0.56266 (14)	0.6660 (7)	0.0300 (8)
C26	0.8784 (3)	0.50758 (15)	0.6819 (6)	0.0280 (8)
H2	0.7146	0.4313	1.0770	0.030*
H3A	0.8703	0.3852	0.7583	0.033*
H3B	0.7789	0.3441	0.9065	0.033*
H4	0.7799	0.3587	0.4060	0.032*
H5A	0.6011	0.3138	0.3930	0.036*
H5B	0.6661	0.2807	0.6211	0.036*
H6	0.4580	0.2631	0.7739	0.036*
H8	0.3352	0.4015	1.2028	0.038*
H9	0.4738	0.4668	1.0478	0.036*
H22	0.7444	0.5337	1.2032	0.034*
H23	0.8404	0.6275	1.1771	0.038*
H25	0.9849	0.5703	0.5289	0.036*
H26	0.8888	0.4769	0.5556	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl7	0.0446 (5)	0.0307 (4)	0.0658 (7)	−0.0058 (4)	0.0225 (6)	−0.0055 (5)
Cl24	0.0320 (4)	0.0306 (4)	0.0486 (5)	−0.0033 (4)	−0.0055 (5)	0.0011 (5)
O14	0.0335 (13)	0.0321 (12)	0.0189 (12)	0.0047 (10)	0.0024 (11)	0.0014 (10)
N1	0.0312 (15)	0.0267 (14)	0.0174 (15)	0.0026 (12)	0.0025 (12)	0.0021 (12)
C2	0.0305 (18)	0.0258 (16)	0.0184 (17)	0.0041 (14)	−0.0013 (14)	0.0021 (14)
C3	0.0336 (18)	0.0227 (16)	0.025 (2)	0.0058 (14)	−0.0004 (16)	0.0024 (14)
C4	0.0296 (17)	0.0272 (17)	0.024 (2)	0.0055 (14)	0.0040 (16)	−0.0043 (15)
C5	0.0325 (19)	0.0289 (17)	0.030 (2)	0.0037 (15)	0.0053 (16)	−0.0071 (16)
C5a	0.0279 (18)	0.0244 (16)	0.0276 (19)	0.0046 (14)	0.0035 (15)	−0.0014 (14)
C6	0.0354 (18)	0.0199 (15)	0.035 (2)	0.0016 (13)	0.0037 (19)	−0.0054 (17)
C7	0.0323 (19)	0.0255 (17)	0.034 (2)	0.0034 (15)	0.0050 (17)	0.0011 (16)
C8	0.0343 (19)	0.0273 (17)	0.035 (2)	0.0074 (14)	0.0090 (18)	0.0000 (17)
C9	0.035 (2)	0.0212 (17)	0.033 (2)	0.0045 (15)	0.0028 (17)	−0.0009 (15)
C9a	0.0269 (16)	0.0234 (15)	0.0261 (18)	0.0033 (13)	0.0029 (17)	0.0009 (15)
C21	0.0327 (19)	0.0229 (16)	0.0216 (19)	0.0053 (14)	−0.0016 (15)	0.0039 (14)
C22	0.0318 (18)	0.0320 (17)	0.0206 (18)	0.0034 (15)	0.0025 (16)	0.0008 (15)
C23	0.0349 (19)	0.0313 (18)	0.028 (2)	0.0039 (15)	−0.0035 (17)	−0.0042 (15)
C24	0.0250 (17)	0.0247 (16)	0.035 (2)	0.0044 (13)	−0.0093 (18)	0.0020 (17)
C25	0.0337 (19)	0.0277 (17)	0.029 (2)	0.0026 (15)	0.0007 (16)	0.0027 (15)
C26	0.0319 (19)	0.0285 (17)	0.0236 (19)	0.0063 (15)	0.0000 (16)	−0.0017 (15)

Geometric parameters (Å, º)

Cl7—C7	1.740 (3)	C5a—C9a	1.384 (4)
Cl24—C24	1.730 (3)	C6—C7	1.372 (5)
O14—C4	1.433 (4)	C6—H6	0.95
O14—N1	1.439 (3)	C7—C8	1.369 (4)
N1—C9a	1.433 (4)	C8—C9	1.368 (5)
N1—C2	1.482 (4)	C8—H8	0.95
C2—C21	1.499 (4)	C9—C9a	1.377 (5)
C2—C3	1.538 (4)	C9—H9	0.95
C2—H2	1.00	C21—C22	1.383 (4)
C3—C4	1.513 (5)	C21—C26	1.390 (5)
C3—H3A	0.99	C22—C23	1.380 (5)
C3—H3B	0.99	C22—H22	0.95
C4—C5	1.519 (4)	C23—C24	1.376 (5)
C4—H4	1.00	C23—H23	0.95
C5—C5a	1.502 (5)	C24—C25	1.373 (5)
C5—H5A	0.99	C25—C26	1.375 (4)
C5—H5B	0.99	C25—H25	0.95
C5a—C6	1.373 (4)	C26—H26	0.95
C4—O14—N1	103.8 (2)	C7—C6—H6	120.0
C9a—N1—O14	108.2 (2)	C5a—C6—H6	120.0
C9a—N1—C2	110.3 (2)	C8—C7—C6	122.0 (3)
O14—N1—C2	101.6 (2)	C8—C7—Cl7	118.4 (3)
N1—C2—C21	109.5 (2)	C6—C7—Cl7	119.6 (3)
N1—C2—C3	103.1 (2)	C9—C8—C7	118.1 (3)
C21—C2—C3	116.5 (3)	C9—C8—H8	120.9
N1—C2—H2	109.2	C7—C8—H8	120.9
C21—C2—H2	109.2	C8—C9—C9a	120.8 (3)
C3—C2—H2	109.2	C8—C9—H9	119.6
C4—C3—C2	103.8 (3)	C9a—C9—H9	119.6
C4—C3—H3A	111.0	C9—C9a—C5a	120.7 (3)
C2—C3—H3A	111.0	C9—C9a—N1	117.1 (3)
C4—C3—H3B	111.0	C5a—C9a—N1	122.2 (3)
C2—C3—H3B	111.0	C22—C21—C26	118.7 (3)
H3A—C3—H3B	109.0	C22—C21—C2	119.0 (3)
O14—C4—C3	104.0 (2)	C26—C21—C2	122.3 (3)
O14—C4—C5	106.6 (3)	C23—C22—C21	121.3 (3)
C3—C4—C5	114.3 (3)	C23—C22—H22	119.3
O14—C4—H4	110.5	C21—C22—H22	119.3
C3—C4—H4	110.5	C24—C23—C22	118.5 (3)
C5—C4—H4	110.5	C24—C23—H23	120.7
C5a—C5—C4	108.8 (3)	C22—C23—H23	120.7
C5a—C5—H5A	109.9	C25—C24—C23	121.5 (3)
C4—C5—H5A	109.9	C25—C24—Cl24	118.8 (3)
C5a—C5—H5B	109.9	C23—C24—Cl24	119.7 (3)
C4—C5—H5B	109.9	C24—C25—C26	119.4 (3)
H5A—C5—H5B	108.3	C24—C25—H25	120.3
C6—C5a—C9a	118.5 (3)	C26—C25—H25	120.3
C6—C5a—C5	122.4 (3)	C25—C26—C21	120.6 (3)
C9a—C5a—C5	119.1 (3)	C25—C26—H26	119.7
C7—C6—C5a	119.9 (3)	C21—C26—H26	119.7
C4—O14—N1—C9a	−66.2 (3)	C8—C9—C9a—N1	−178.6 (3)
C4—O14—N1—C2	49.9 (3)	C6—C5a—C9a—C9	1.2 (5)
C9a—N1—C2—C21	−158.9 (3)	C5—C5a—C9a—C9	−178.8 (3)
O14—N1—C2—C21	86.6 (3)	C6—C5a—C9a—N1	179.7 (3)
C9a—N1—C2—C3	76.5 (3)	C5—C5a—C9a—N1	−0.3 (5)
O14—N1—C2—C3	−38.1 (3)	O14—N1—C9a—C9	−154.2 (3)
N1—C2—C3—C4	13.8 (3)	C2—N1—C9a—C9	95.6 (3)
C21—C2—C3—C4	−106.1 (3)	O14—N1—C9a—C5a	27.2 (4)
N1—O14—C4—C3	−40.7 (3)	C2—N1—C9a—C5a	−83.0 (4)
N1—O14—C4—C5	80.5 (3)	N1—C2—C21—C22	94.3 (3)
C2—C3—C4—O14	15.6 (3)	C3—C2—C21—C22	−149.3 (3)
C2—C3—C4—C5	−100.3 (3)	N1—C2—C21—C26	−83.0 (4)
O14—C4—C5—C5a	−50.5 (3)	C3—C2—C21—C26	33.4 (4)
C3—C4—C5—C5a	63.8 (4)	C26—C21—C22—C23	1.1 (5)
C4—C5—C5a—C6	−168.4 (3)	C2—C21—C22—C23	−176.3 (3)
C4—C5—C5a—C9a	11.6 (4)	C21—C22—C23—C24	−0.6 (5)
C9a—C5a—C6—C7	−1.5 (5)	C22—C23—C24—C25	0.1 (5)
C5—C5a—C6—C7	178.5 (3)	C22—C23—C24—Cl24	179.7 (2)
C5a—C6—C7—C8	0.7 (6)	C23—C24—C25—C26	0.0 (5)
C5a—C6—C7—Cl7	179.8 (3)	Cl24—C24—C25—C26	−179.7 (3)
C6—C7—C8—C9	0.5 (5)	C24—C25—C26—C21	0.5 (5)
Cl7—C7—C8—C9	−178.6 (3)	C22—C21—C26—C25	−1.1 (5)
C7—C8—C9—C9a	−0.8 (5)	C2—C21—C26—C25	176.2 (3)
C8—C9—C9a—C5a	0.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O14^i	1.00	2.29	3.287 (4)	173
C9—H9···N1^ii	0.95	2.50	3.328 (4)	145
C8—H8···Cg1^ii	0.95	2.72	3.615 (4)	157

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

(II) (2S,4R)-7-chloro-2-exo-(2-chlorophenyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C16H13Cl2NO	F(000) = 632
Mr = 306.17	Dx = 1.482 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3131 reflections
a = 7.4328 (11) Å	θ = 2.7–27.5°
b = 12.3746 (16) Å	µ = 0.47 mm^−1
c = 14.9187 (19) Å	T = 120 K
V = 1372.2 (3) Å^3	Lath, colourless
Z = 4	0.27 × 0.10 × 0.07 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3131 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1541 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.147
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→14
Tmin = 0.926, Tmax = 0.968	l = −19→17
12048 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)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.056P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3131 reflections	Δρmax = 0.38 e Å^−3
181 parameters	Δρmin = −0.48 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1316 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (15)

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

	x	y	z	Uiso*/Ueq
Cl7	0.91147 (19)	0.25680 (13)	0.04857 (8)	0.0380 (4)
Cl26	0.63144 (17)	0.25582 (13)	0.60354 (9)	0.0357 (4)
O14	0.5843 (5)	0.5547 (3)	0.3685 (2)	0.0350 (10)
N1	0.5225 (6)	0.4453 (3)	0.3547 (3)	0.0286 (11)
C2	0.5803 (7)	0.3925 (4)	0.4394 (3)	0.0271 (13)
C3	0.7614 (7)	0.4474 (5)	0.4614 (4)	0.0351 (15)
C4	0.7677 (8)	0.5423 (5)	0.3987 (4)	0.0359 (15)
C5	0.8810 (8)	0.5241 (5)	0.3167 (4)	0.0391 (15)
C5a	0.7934 (8)	0.4375 (4)	0.2601 (4)	0.0292 (14)
C6	0.8795 (8)	0.3929 (4)	0.1873 (4)	0.0297 (14)
C7	0.7959 (8)	0.3148 (4)	0.1384 (3)	0.0298 (14)
C8	0.6297 (7)	0.2757 (4)	0.1590 (3)	0.0278 (14)
C9	0.5405 (8)	0.3220 (4)	0.2312 (3)	0.0263 (14)
C9a	0.6214 (8)	0.4020 (4)	0.2804 (3)	0.0256 (13)
C21	0.4438 (7)	0.4070 (4)	0.5123 (4)	0.0254 (13)
C22	0.3029 (7)	0.4784 (4)	0.5061 (4)	0.0294 (14)
C23	0.1792 (8)	0.4895 (4)	0.5747 (4)	0.0317 (14)
C24	0.1922 (7)	0.4259 (4)	0.6492 (4)	0.0310 (14)
C25	0.3322 (8)	0.3542 (4)	0.6575 (4)	0.0287 (14)
C26	0.4547 (7)	0.3460 (4)	0.5903 (4)	0.0282 (13)
H2	0.6003	0.3137	0.4285	0.032*
H3A	0.7649	0.4715	0.5247	0.042*
H3B	0.8633	0.3977	0.4503	0.042*
H4	0.8082	0.6086	0.4312	0.043*
H5A	1.0035	0.5011	0.3344	0.047*
H5B	0.8909	0.5920	0.2819	0.047*
H6	0.9967	0.4165	0.1713	0.036*
H8	0.5768	0.2189	0.1253	0.033*
H9	0.4229	0.2981	0.2465	0.032*
H22	0.2901	0.5211	0.4536	0.035*
H23	0.0854	0.5414	0.5700	0.038*
H24	0.1044	0.4313	0.6952	0.037*
H25	0.3433	0.3107	0.7097	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl7	0.0468 (8)	0.0406 (8)	0.0264 (7)	0.0092 (9)	0.0072 (6)	−0.0012 (7)
Cl26	0.0329 (8)	0.0372 (8)	0.0369 (8)	0.0074 (8)	0.0008 (6)	0.0033 (8)
O14	0.038 (2)	0.027 (2)	0.039 (2)	−0.0019 (19)	0.008 (2)	−0.0034 (19)
N1	0.031 (3)	0.024 (3)	0.031 (3)	−0.004 (2)	0.006 (2)	−0.001 (2)
C2	0.026 (3)	0.030 (3)	0.025 (3)	0.001 (3)	0.002 (3)	0.000 (3)
C3	0.027 (3)	0.049 (4)	0.029 (3)	−0.004 (3)	0.004 (3)	−0.008 (3)
C4	0.035 (4)	0.027 (3)	0.046 (4)	−0.010 (3)	0.004 (3)	−0.009 (3)
C5	0.043 (4)	0.037 (4)	0.037 (3)	−0.002 (3)	0.013 (3)	−0.008 (3)
C5a	0.029 (4)	0.028 (3)	0.031 (3)	0.004 (3)	0.005 (3)	0.000 (3)
C6	0.033 (3)	0.029 (3)	0.028 (3)	0.001 (3)	0.008 (3)	0.003 (3)
C7	0.044 (4)	0.028 (3)	0.017 (3)	0.006 (3)	0.003 (3)	0.002 (3)
C8	0.030 (3)	0.029 (3)	0.025 (3)	0.000 (3)	−0.003 (2)	0.000 (2)
C9	0.025 (3)	0.034 (3)	0.021 (3)	−0.001 (3)	−0.001 (3)	0.007 (3)
C9a	0.024 (3)	0.029 (3)	0.023 (3)	0.008 (3)	0.000 (3)	−0.001 (3)
C21	0.019 (3)	0.026 (3)	0.031 (3)	0.003 (3)	−0.001 (3)	−0.005 (3)
C22	0.031 (3)	0.026 (3)	0.031 (3)	−0.003 (3)	−0.006 (3)	−0.002 (3)
C23	0.024 (3)	0.032 (3)	0.039 (3)	0.004 (3)	0.001 (3)	−0.005 (3)
C24	0.024 (3)	0.036 (3)	0.033 (3)	−0.006 (3)	0.003 (3)	−0.003 (3)
C25	0.035 (4)	0.027 (3)	0.024 (3)	−0.003 (3)	−0.004 (3)	−0.002 (3)
C26	0.026 (3)	0.026 (3)	0.032 (3)	0.003 (3)	0.002 (3)	−0.002 (3)

Geometric parameters (Å, º)

Cl7—C7	1.747 (6)	C5a—C6	1.376 (7)
Cl26—C26	1.735 (5)	C6—C7	1.361 (7)
O14—N1	1.444 (5)	C6—H6	0.95
O14—C4	1.443 (7)	C7—C8	1.362 (8)
N1—C9a	1.434 (6)	C8—C9	1.388 (7)
N1—C2	1.486 (7)	C8—H8	0.95
C2—C21	1.498 (7)	C9—C9a	1.372 (7)
C2—C3	1.543 (7)	C9—H9	0.95
C2—H2	1.00	C21—C22	1.374 (7)
C3—C4	1.502 (8)	C21—C26	1.389 (7)
C3—H3A	0.99	C22—C23	1.382 (7)
C3—H3B	0.99	C22—H22	0.95
C4—C5	1.502 (8)	C23—C24	1.365 (8)
C4—H4	1.00	C23—H23	0.95
C5—C5a	1.511 (8)	C24—C25	1.374 (8)
C5—H5A	0.99	C24—H24	0.95
C5—H5B	0.99	C25—C26	1.357 (8)
C5a—C9a	1.385 (8)	C25—H25	0.95
N1—O14—C4	104.2 (4)	C7—C6—H6	120.1
C9a—N1—O14	107.3 (4)	C5a—C6—H6	120.1
C9a—N1—C2	110.2 (4)	C6—C7—C8	123.1 (5)
O14—N1—C2	101.5 (4)	C6—C7—Cl7	118.6 (4)
N1—C2—C21	111.7 (4)	C8—C7—Cl7	118.2 (4)
N1—C2—C3	103.8 (4)	C7—C8—C9	117.5 (5)
C21—C2—C3	112.6 (4)	C7—C8—H8	121.3
N1—C2—H2	109.5	C9—C8—H8	121.3
C21—C2—H2	109.5	C8—C9—C9a	120.2 (5)
C3—C2—H2	109.5	C8—C9—H9	119.9
C4—C3—C2	103.8 (5)	C9a—C9—H9	119.9
C4—C3—H3A	111.0	C5a—C9a—C9	121.1 (5)
C2—C3—H3A	111.0	C5a—C9a—N1	121.6 (5)
C4—C3—H3B	111.0	C9—C9a—N1	117.3 (5)
C2—C3—H3B	111.0	C22—C21—C26	116.8 (5)
H3A—C3—H3B	109.0	C22—C21—C2	123.0 (5)
O14—C4—C3	104.3 (4)	C26—C21—C2	120.3 (5)
O14—C4—C5	107.0 (5)	C21—C22—C23	121.4 (5)
C3—C4—C5	114.1 (5)	C21—C22—H22	119.3
O14—C4—H4	110.4	C23—C22—H22	119.3
C3—C4—H4	110.4	C24—C23—C22	119.9 (5)
C5—C4—H4	110.4	C24—C23—H23	120.1
C4—C5—C5a	108.6 (5)	C22—C23—H23	120.1
C4—C5—H5A	110.0	C23—C24—C25	120.0 (5)
C5a—C5—H5A	110.0	C23—C24—H24	120.0
C4—C5—H5B	110.0	C25—C24—H24	120.0
C5a—C5—H5B	110.0	C26—C25—C24	119.3 (5)
H5A—C5—H5B	108.3	C26—C25—H25	120.3
C9a—C5a—C6	118.3 (5)	C24—C25—H25	120.3
C9a—C5a—C5	120.0 (5)	C25—C26—C21	122.6 (5)
C6—C5a—C5	121.7 (5)	C25—C26—Cl26	118.1 (4)
C7—C6—C5a	119.7 (5)	C21—C26—Cl26	119.3 (4)
C4—O14—N1—C9a	−67.4 (5)	C5—C5a—C9a—C9	−178.7 (5)
C4—O14—N1—C2	48.2 (4)	C6—C5a—C9a—N1	−179.4 (5)
C9a—N1—C2—C21	−161.2 (5)	C5—C5a—C9a—N1	−0.2 (8)
O14—N1—C2—C21	85.4 (5)	C8—C9—C9a—C5a	−0.7 (8)
C9a—N1—C2—C3	77.3 (5)	C8—C9—C9a—N1	−179.3 (4)
O14—N1—C2—C3	−36.2 (5)	O14—N1—C9a—C5a	28.4 (6)
N1—C2—C3—C4	12.2 (5)	C2—N1—C9a—C5a	−81.2 (6)
C21—C2—C3—C4	−108.8 (5)	O14—N1—C9a—C9	−153.0 (4)
N1—O14—C4—C3	−40.5 (5)	C2—N1—C9a—C9	97.3 (5)
N1—O14—C4—C5	80.7 (5)	N1—C2—C21—C22	−12.4 (7)
C2—C3—C4—O14	16.4 (5)	C3—C2—C21—C22	104.0 (6)
C2—C3—C4—C5	−99.9 (5)	N1—C2—C21—C26	166.9 (5)
O14—C4—C5—C5a	−48.7 (6)	C3—C2—C21—C26	−76.7 (7)
C3—C4—C5—C5a	66.1 (6)	C26—C21—C22—C23	0.6 (8)
C4—C5—C5a—C9a	10.1 (7)	C2—C21—C22—C23	179.9 (5)
C4—C5—C5a—C6	−170.6 (5)	C21—C22—C23—C24	−2.4 (8)
C9a—C5a—C6—C7	−1.0 (8)	C22—C23—C24—C25	2.7 (8)
C5—C5a—C6—C7	179.8 (5)	C23—C24—C25—C26	−1.3 (8)
C5a—C6—C7—C8	−1.5 (8)	C24—C25—C26—C21	−0.5 (8)
C5a—C6—C7—Cl7	−178.0 (4)	C24—C25—C26—Cl26	179.2 (4)
C6—C7—C8—C9	2.9 (8)	C22—C21—C26—C25	0.9 (8)
Cl7—C7—C8—C9	179.4 (4)	C2—C21—C26—C25	−178.5 (5)
C7—C8—C9—C9a	−1.7 (7)	C22—C21—C26—Cl26	−178.9 (4)
C6—C5a—C9a—C9	2.0 (8)	C2—C21—C26—Cl26	1.8 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O14^i	0.95	2.36	3.190 (6)	146
C6—H6···Cg1^ii	0.95	2.82	3.619 (6)	143
C25—H25···Cg2^iii	0.95	2.60	3.410 (6)	143

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

(III) (2S,4R)-7-chloro-2-exo- (1-naphthyl)-2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C20H16ClNO	F(000) = 672
Mr = 321.79	Dx = 1.428 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab1	Cell parameters from 3418 reflections
a = 9.6174 (18) Å	θ = 2.8–27.5°
b = 11.558 (3) Å	µ = 0.26 mm^−1
c = 13.465 (4) Å	T = 120 K
V = 1496.7 (7) Å^3	Needle, colourless
Z = 4	0.32 × 0.08 × 0.06 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3418 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2460 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.956, Tmax = 0.985	l = −16→17
16825 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)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 0.5441P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3418 reflections	Δρmax = 0.30 e Å^−3
208 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1446 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (9)

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

	x	y	z	Uiso*/Ueq
Cl7	0.77897 (9)	0.56688 (7)	0.16877 (6)	0.0288 (2)
O14	0.3010 (2)	0.69865 (19)	0.49069 (17)	0.0244 (5)
N1	0.4112 (3)	0.6186 (2)	0.51586 (19)	0.0192 (6)
C2	0.4811 (3)	0.6777 (3)	0.5990 (2)	0.0166 (7)
C3	0.4663 (3)	0.8084 (3)	0.5746 (2)	0.0189 (7)
C4	0.3715 (3)	0.8096 (3)	0.4849 (2)	0.0203 (7)
C5	0.4438 (3)	0.8145 (3)	0.3855 (3)	0.0233 (8)
C5a	0.5172 (3)	0.7021 (3)	0.3653 (2)	0.0190 (7)
C6	0.6011 (3)	0.6863 (3)	0.2831 (2)	0.0193 (7)
C7	0.6704 (3)	0.5841 (3)	0.2712 (2)	0.0203 (7)
C8	0.6616 (3)	0.4950 (3)	0.3378 (2)	0.0195 (7)
C9	0.5733 (3)	0.5086 (3)	0.4179 (2)	0.0191 (7)
C9a	0.5030 (3)	0.6111 (3)	0.4312 (2)	0.0170 (7)
C21	0.4203 (3)	0.6408 (3)	0.6970 (2)	0.0182 (7)
C22	0.3068 (3)	0.5707 (3)	0.7003 (2)	0.0213 (7)
C23	0.2545 (4)	0.5310 (3)	0.7913 (3)	0.0277 (8)
C24	0.3160 (3)	0.5607 (3)	0.8776 (3)	0.0281 (8)
C25	0.4338 (3)	0.6327 (3)	0.8783 (2)	0.0227 (8)
C26	0.5013 (4)	0.6636 (3)	0.9654 (3)	0.0313 (9)
C27	0.6128 (4)	0.7343 (3)	0.9656 (3)	0.0352 (10)
C28	0.6630 (4)	0.7791 (3)	0.8762 (3)	0.0276 (8)
C29	0.6016 (3)	0.7507 (3)	0.7888 (3)	0.0218 (7)
C30	0.4858 (3)	0.6751 (3)	0.7867 (2)	0.0212 (7)
H2	0.5820	0.6568	0.5980	0.020*
H3A	0.4242	0.8509	0.6309	0.023*
H3B	0.5577	0.8431	0.5588	0.023*
H4	0.3027	0.8741	0.4906	0.024*
H5A	0.3747	0.8295	0.3325	0.028*
H5B	0.5120	0.8787	0.3853	0.028*
H6	0.6104	0.7462	0.2352	0.023*
H8	0.7144	0.4262	0.3293	0.023*
H9	0.5611	0.4470	0.4638	0.023*
H22	0.2625	0.5483	0.6403	0.026*
H23	0.1746	0.4826	0.7922	0.033*
H24	0.2794	0.5326	0.9385	0.034*
H26	0.4680	0.6340	1.0268	0.038*
H27	0.6571	0.7537	1.0264	0.042*
H28	0.7407	0.8299	0.8766	0.033*
H29	0.6366	0.7819	0.7285	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl7	0.0327 (4)	0.0275 (4)	0.0262 (4)	−0.0024 (4)	0.0093 (4)	−0.0047 (4)
O14	0.0132 (11)	0.0294 (12)	0.0308 (13)	0.0018 (10)	−0.0031 (10)	−0.0015 (10)
N1	0.0146 (13)	0.0217 (14)	0.0213 (14)	0.0005 (11)	−0.0016 (12)	−0.0011 (11)
C2	0.0130 (15)	0.0185 (17)	0.0182 (16)	0.0009 (13)	0.0013 (13)	−0.0006 (13)
C3	0.0139 (15)	0.0147 (15)	0.0279 (18)	0.0005 (13)	0.0030 (13)	0.0011 (14)
C4	0.0131 (15)	0.0201 (16)	0.0276 (19)	0.0053 (13)	−0.0013 (13)	−0.0007 (14)
C5	0.0220 (17)	0.0227 (18)	0.0252 (18)	0.0046 (15)	−0.0049 (15)	0.0017 (14)
C5a	0.0149 (15)	0.0190 (16)	0.0231 (18)	−0.0018 (13)	−0.0069 (13)	−0.0006 (13)
C6	0.0229 (16)	0.0186 (15)	0.0163 (16)	−0.0041 (14)	−0.0045 (14)	0.0019 (13)
C7	0.0200 (16)	0.0244 (18)	0.0164 (15)	−0.0050 (14)	0.0013 (13)	−0.0035 (14)
C8	0.0192 (15)	0.0185 (15)	0.0207 (16)	0.0018 (13)	−0.0023 (15)	−0.0034 (14)
C9	0.0213 (17)	0.0168 (16)	0.0193 (17)	−0.0053 (13)	−0.0065 (14)	0.0006 (13)
C9a	0.0128 (15)	0.0217 (17)	0.0166 (16)	−0.0018 (13)	−0.0056 (13)	−0.0020 (12)
C21	0.0175 (16)	0.0163 (15)	0.0206 (17)	0.0040 (13)	0.0013 (14)	0.0002 (13)
C22	0.0157 (16)	0.0189 (14)	0.0293 (17)	0.0025 (14)	0.0060 (13)	−0.0025 (14)
C23	0.0244 (19)	0.0233 (17)	0.035 (2)	0.0020 (14)	0.0132 (16)	0.0044 (14)
C24	0.035 (2)	0.0215 (17)	0.0275 (18)	0.0068 (17)	0.0141 (16)	0.0025 (16)
C25	0.0318 (19)	0.0142 (16)	0.0222 (17)	0.0071 (15)	0.0055 (16)	0.0006 (14)
C26	0.046 (2)	0.025 (2)	0.0221 (19)	0.0102 (18)	0.0056 (18)	0.0037 (15)
C27	0.051 (3)	0.025 (2)	0.029 (2)	0.0088 (18)	−0.007 (2)	−0.0045 (16)
C28	0.0324 (19)	0.0228 (18)	0.0276 (19)	0.0015 (15)	−0.0055 (17)	−0.0019 (15)
C29	0.0237 (18)	0.0209 (16)	0.0208 (18)	0.0041 (14)	0.0013 (16)	0.0006 (14)
C30	0.0232 (16)	0.0159 (16)	0.0246 (18)	0.0065 (14)	0.0002 (15)	−0.0009 (14)

Geometric parameters (Å, º)

Cl7—C7	1.742 (3)	C8—H8	0.95
O14—N1	1.447 (3)	C9—C9a	1.376 (4)
O14—C4	1.453 (4)	C9—H9	0.95
N1—C9a	1.444 (4)	C21—C22	1.360 (4)
N1—C2	1.473 (4)	C21—C30	1.419 (5)
C2—C21	1.505 (4)	C22—C23	1.401 (4)
C2—C3	1.552 (4)	C22—H22	0.95
C2—H2	1.00	C23—C24	1.348 (5)
C3—C4	1.513 (4)	C23—H23	0.95
C3—H3A	0.99	C24—C25	1.405 (5)
C3—H3B	0.99	C24—H24	0.95
C4—C5	1.510 (5)	C25—C26	1.388 (5)
C4—H4	1.00	C25—C30	1.419 (4)
C5—C5a	1.504 (5)	C26—C27	1.348 (6)
C5—H5A	0.99	C26—H26	0.95
C5—H5B	0.99	C27—C28	1.396 (5)
C5a—C6	1.382 (5)	C27—H27	0.95
C5a—C9a	1.383 (4)	C28—C29	1.357 (5)
C6—C7	1.366 (4)	C28—H28	0.95
C6—H6	0.95	C29—C30	1.416 (5)
C7—C8	1.368 (4)	C29—H29	0.95
C8—C9	1.382 (4)
N1—O14—C4	103.6 (2)	C7—C8—H8	121.2
C9a—N1—O14	107.6 (2)	C9—C8—H8	121.2
C9a—N1—C2	110.4 (2)	C9a—C9—C8	120.1 (3)
O14—N1—C2	102.5 (2)	C9a—C9—H9	119.9
N1—C2—C21	111.0 (2)	C8—C9—H9	119.9
N1—C2—C3	104.4 (2)	C9—C9a—C5a	121.5 (3)
C21—C2—C3	115.2 (3)	C9—C9a—N1	117.1 (3)
N1—C2—H2	108.7	C5a—C9a—N1	121.4 (3)
C21—C2—H2	108.7	C22—C21—C30	119.6 (3)
C3—C2—H2	108.7	C22—C21—C2	120.7 (3)
C4—C3—C2	103.5 (3)	C30—C21—C2	119.6 (3)
C4—C3—H3A	111.1	C21—C22—C23	120.8 (3)
C2—C3—H3A	111.1	C21—C22—H22	119.6
C4—C3—H3B	111.1	C23—C22—H22	119.6
C2—C3—H3B	111.1	C24—C23—C22	120.8 (3)
H3A—C3—H3B	109.0	C24—C23—H23	119.6
O14—C4—C5	107.2 (3)	C22—C23—H23	119.6
O14—C4—C3	103.3 (2)	C23—C24—C25	120.7 (3)
C5—C4—C3	115.5 (2)	C23—C24—H24	119.6
O14—C4—H4	110.2	C25—C24—H24	119.6
C5—C4—H4	110.2	C26—C25—C24	122.4 (3)
C3—C4—H4	110.2	C26—C25—C30	118.8 (3)
C5a—C5—C4	110.1 (3)	C24—C25—C30	118.9 (3)
C5a—C5—H5A	109.6	C27—C26—C25	122.0 (4)
C4—C5—H5A	109.6	C27—C26—H26	119.0
C5a—C5—H5B	109.6	C25—C26—H26	119.0
C4—C5—H5B	109.6	C26—C27—C28	119.9 (4)
H5A—C5—H5B	108.2	C26—C27—H27	120.1
C6—C5a—C9a	118.1 (3)	C28—C27—H27	120.1
C6—C5a—C5	122.2 (3)	C29—C28—C27	120.5 (3)
C9a—C5a—C5	119.7 (3)	C29—C28—H28	119.8
C7—C6—C5a	119.5 (3)	C27—C28—H28	119.8
C7—C6—H6	120.3	C28—C29—C30	120.6 (3)
C5a—C6—H6	120.3	C28—C29—H29	119.7
C6—C7—C8	123.0 (3)	C30—C29—H29	119.7
C6—C7—Cl7	119.0 (2)	C29—C30—C25	118.2 (3)
C8—C7—Cl7	118.0 (2)	C29—C30—C21	122.6 (3)
C7—C8—C9	117.6 (3)	C25—C30—C21	119.1 (3)
C4—O14—N1—C9a	−68.2 (3)	O14—N1—C9a—C9	−151.0 (3)
C4—O14—N1—C2	48.3 (3)	C2—N1—C9a—C9	97.9 (3)
C9a—N1—C2—C21	−154.1 (3)	O14—N1—C9a—C5a	27.7 (4)
O14—N1—C2—C21	91.5 (3)	C2—N1—C9a—C5a	−83.4 (3)
C9a—N1—C2—C3	81.2 (3)	N1—C2—C21—C22	−5.9 (4)
O14—N1—C2—C3	−33.1 (3)	C3—C2—C21—C22	112.4 (3)
N1—C2—C3—C4	7.1 (3)	N1—C2—C21—C30	171.1 (3)
C21—C2—C3—C4	−114.8 (3)	C3—C2—C21—C30	−70.6 (4)
N1—O14—C4—C5	79.1 (3)	C30—C21—C22—C23	−0.5 (4)
N1—O14—C4—C3	−43.3 (3)	C2—C21—C22—C23	176.5 (3)
C2—C3—C4—O14	21.4 (3)	C21—C22—C23—C24	−0.5 (5)
C2—C3—C4—C5	−95.4 (3)	C22—C23—C24—C25	0.4 (5)
O14—C4—C5—C5a	−44.9 (3)	C23—C24—C25—C26	−178.9 (3)
C3—C4—C5—C5a	69.6 (4)	C23—C24—C25—C30	0.8 (5)
C4—C5—C5a—C6	−174.7 (3)	C24—C25—C26—C27	−178.8 (3)
C4—C5—C5a—C9a	4.4 (4)	C30—C25—C26—C27	1.4 (5)
C9a—C5a—C6—C7	−2.2 (4)	C25—C26—C27—C28	0.3 (5)
C5—C5a—C6—C7	176.9 (3)	C26—C27—C28—C29	−0.9 (5)
C5a—C6—C7—C8	−0.3 (5)	C27—C28—C29—C30	−0.1 (5)
C5a—C6—C7—Cl7	−178.4 (2)	C28—C29—C30—C25	1.7 (5)
C6—C7—C8—C9	3.0 (5)	C28—C29—C30—C21	−178.5 (3)
Cl7—C7—C8—C9	−178.9 (2)	C26—C25—C30—C29	−2.4 (5)
C7—C8—C9—C9a	−3.1 (4)	C24—C25—C30—C29	177.9 (3)
C8—C9—C9a—C5a	0.6 (5)	C26—C25—C30—C21	177.9 (3)
C8—C9—C9a—N1	179.3 (3)	C24—C25—C30—C21	−1.9 (4)
C6—C5a—C9a—C9	2.1 (4)	C22—C21—C30—C29	−178.0 (3)
C5—C5a—C9a—C9	−177.0 (3)	C2—C21—C30—C29	5.0 (4)
C6—C5a—C9a—N1	−176.5 (3)	C22—C21—C30—C25	1.7 (4)
C5—C5a—C9a—N1	4.4 (4)	C2—C21—C30—C25	−175.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O14^i	0.99	2.48	3.338 (4)	145
C8—H8···Cg3^ii	0.95	2.81	3.658 (4)	149
C23—H23···Cg2^iii	0.95	2.80	3.702 (4)	158

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