A concise and efficient concurrent synthesis of 6,11-di­hydro­dibenzo[b,e]azepines and 5,6,11,12-tetra­hydro­dibenzo[b,f]azocines and their conversion to 4-oxo-8,13-di­hydro-4H-benzo[5,6]azepino[3,2,1-ij]quinoline-5-carboxyl­ates and N-acetyl-5,6,11,12-tetra­hydro­dibenzo[b,f]azocines: synthetic sequence, spectroscopic characterization and the structures of two products

Reaction of 2-allyl-N-benzyl-4-fluoro­aniline or 2-allyl-N-benzyl-4-chloro­aniline with 98% sulfuric acid leads to the concurrent formation of halogeno-sub­stituted 11-ethyl-6,11-di­hydro­dibenzo[b,e]azepines, (II), and halogeno-substituted 11-methyl-5,6,11,12-tetra­hydro­dibenzo[b,f]azocines, (III), in each case in (II):(III) molar ratios of ca 2:1. Further reaction of (II) leads to ethyl 13-ethyl-2-halogeno-4-oxo-8,13-di­hydro-4H-benzo[5,6]azepino[3,2,1-ij]quinoline-5-car­box­yl­ate, while acetyl­ation of (III) gives the corresponding N-acetyl derivatives. The dibenzo[b,e]azepine and dibenzo[b,f]azocine ring systems are of importance in forming the core of a variety of bioactive compounds. In ethyl 13-ethyl-2-fluoro-4-oxo-8,13-di­hydro-4H-benzo[5,6]azepino[3,2,1-ij]quinoline-5-carboxyl­ate, C₂₂H₂₀FNO₃, (IVa), the azepine ring adopts a conformation close to the twist-boat form, and the mol­ecules are linked into a three-dimensional framework structure by a combination of C—H...O and C—H...π(arene) hydrogen bonds. The azocine ring in 5-acetyl-2-chloro-11-methyl-5,6,11,12-tetra­hydro­benzo[b,f]azocine, C₁₈H₁₈ClNO, (Vb), adopts the boat–boat conformation and the mol­ecules are again linked by C—H...O and C—H...π(arene) hydrogen bonds, but this time form a sheet structure.

Computing details

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Ethyl (RS)-13-ethyl-2-fluoro-4-oxo-8,13-dihydro-4H-benzo[5,6]azepino[3,2,1-ij]quinoline-5-carboxylate (IVa)

Crystal data

C22H20FNO3	F(000) = 768
Mr = 365.39	Dx = 1.361 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5920 (6) Å	Cell parameters from 4414 reflections
b = 13.4325 (7) Å	θ = 2.2–28.3°
c = 14.2186 (8) Å	µ = 0.10 mm^−1
β = 103.290 (2)°	T = 100 K
V = 1782.93 (18) Å^3	Needle, colourless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Bruker D8 Venture diffractometer	4414 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3808 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.037
φ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −12→12
Tmin = 0.962, Tmax = 0.990	k = −17→17
33534 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 0.9921P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4414 reflections	Δρmax = 0.52 e Å^−3
246 parameters	Δρmin = −0.32 e Å^−3
0 restraints

Special details

Experimental. Spectroscopic data for compounds (IIIa), (IIIb), (IVa), (Va) and (Vb).

IR spectra were recorded in KBr disks using a Bruker Tensor 27 spectrophotometer NMR spectra were recorded at 400 MHz (¹H) and 100 MHz (¹³C) at 298 K, using the signals of the residual non-deuterated (7.26 ppm) and the ¹³C (77.16 ppm) signals of the solvent, respectively, as the internal references. The subscripts A and B applied to the diastereotopic protons are labels without further significance. The ¹³C NMR spectra were fully and unambiguously assigned using the DEPT spectra. Mass spectra were recorded using a Thermo model DSQ-II spectrometer, equipped with a direct inlet probe and operating at 70 eV.

Compound (IIIa). IR (ATR, cm^-1) 3385 (N—H), 2954 [C—H (arom.)], 1481 [C═C (arom.)], 1242 (C—N). NMR (CDCl₃): δ(¹H) 1.46 (d, J = 6.7 Hz, 3H, 11-CH₃), 2.81–2.89 (m, 1H, 12-H_B), 3.25–3.35 (m, 2H, 11-H, 12-H_A), 4.01 (d, J = 14.7 Hz, 1H, 6-H_B), 4.05 (br s, 1H, N—H), 4.88 (d, J = 14.7 Hz, 1H, 6-H_A), 6.35 (dd, J = 8.8, 5.2 Hz, 1H, 4-H), 6.54 (td, J = 8.4, 3.0 Hz, 1H, 3-H), 6.69 (dd, J = 9.2, 3.0 Hz, 1H, 1-H), 7.00-7.05 (m, 2H, 7-H, 10-H), 7.06-7.11 (m, 2H, 8-H, 9-H); δ(¹³C) 24.8 (11-CH₃), 40.5 (12-C), 44.5 (11-C), 51.4 (6-C), 113.3 (d, J = 22.4 Hz, 3-C), 114.1 (d, J = 22.1 Hz, 1-C), 119.6 (d, J = 8.9 Hz, 4-C), 126.9 (8-C), 128.0 (9-C), 130.3 (7-C, 10-C), 130.8 (d, J = 8.4 Hz, 12a-C), 135.3 (6a-C), 142.3 (10a-C), 144.8 (d, J = 2.7 Hz, 4a-C), 157.2 (d, J = 247.8 Hz, 2-C). GC-MS (70 eV) m/z (%) 241 (M⁺, 26), 226 (100), 211 (17), 150 (13), 117 (28), 91 (16).

Compound (IIIb). IR (ATR, cm^-1) 3383 (N—H), 2951 [C—H (arom.)], 1478 [C═C (arom.)], 1305 (C—N). NMR (CDCl₃): δ(¹H) 1.45 (d, J = 6.7 Hz, 3H, 11-CH₃), 2.80–2.89 (m, 1H, 12-H_B), 3.25-3.36 (m, 2H, 11-H, 12-H_A), 3.98 (d, J = 14.8 Hz, 1H, 6-H_B), 4.06 (br s, 1H, N—H), 4.93 (d, J = 14.8 Hz, 1H, 6-H_A), 6.32 (d, J = 8.4 Hz, 1H, 4-H), 6.79 (dd, J = 8.4, 2.5 Hz, 1H, 3-H), 6.94 (d, J = 2.5 Hz, 1H, 1-H), 7.00–7.03 (m, 1H, 10-H), 7.04–7.06 (m, 1H, 7-H), 7.08–7.12 (m, 2H, 8-H, 9-H); δ(¹³C) 25.1 (11-CH₃), 40.2 (12-C), 44.9 (11-C), 51.0 (6-C), 119.6 (4-C), 123.8 (2-C), 126.7 (3-C), 126.9 (8-C), 127.9 (9-C), 129.7 (12a-C), 130.4 (1-C, 10-C), 130.7 (7-C), 135.2 (6a-C), 144.7 (10a-C), 145.1 (4a-C). GC-MS (70 eV) m/z (%) 257 (M⁺, ³⁵Cl, 46), 242 (³⁵Cl, 100), 207 (43), 166 (15), 140 (13), 117 (59), 91 (25).

Compound (IVa). IR (ATR, cm^-1) 2935-2971 (C—H), 1723 [C═O (ester)], 1613 [C═O (ketone)], 1483 (C═C), 1142 (C-O). NMR (CDCl₃): δ(¹H) 1.03 (t, J = 7.2 Hz, 3H, 13-CH₂-CH₃), 1.41 (t, J = 7.1 Hz, 3H, O-CH₂-CH₃), 2.25–2.34 (m, 2H, 13-CH₂-CH₃), 4.15 (br s, 1H, 13-H), 4.39 (q, J = 7.1 Hz, 2H, O-CH₂-), 5.00 (br s, 1H, 8-H_B), 5.83 (br s, 1H, 8-H_A), 7.23 (dd, J = 7.4, 1.1 Hz, 1H, 12-H), 7.28-7.38 (m, 3H, 1-H, 10-H, 11-H), 7.41 (dd, J = 7.0, 1.7 Hz, 1H, 9-H), 8.09 (dd, J = 8.4, 3.1 Hz, 1H, 3-H), 8.56 (s, 1H, 6-H); δ¹³C) 13.1 (13-CH₂-CH₃), 14.5 (O-CH₂-CH₃), 31.5 (13-CH₂-CH₃), 52.2 (13-C), 61.1 (O-CH₂-), 61.2 (8-C), 109.1 (5-C), 111.9 (d, J = 22.5 Hz, 3-C), 128.0 (d, J = 22.9 Hz, 1-C), 128.1 (10-C), 129.1 (9-C), 129.2 (12-C), 129.8 (11-C), 131.8 (8a-C), 133.3 (d, J = 7.0 Hz, 3a-C), 135.1 (13a-C), 135.2 (d, J = 1.1 Hz, 3b-C), 140.5 (12a-C), 149.9 (6-C), 159.4 (d, J = 247.7 Hz, 2-C), 165.9 (COO), 173.1 (4-C).; GC-MS (70 eV) m/z (%) 365 (M⁺, 13), 337 (11), 336 (48), 293 (100), 264 (32). HRMS (Q-TOF-ESI) m/z found 366.1500; for C₂₂H₂₁FNO₃ [M + H]⁺ requires 366.1505.

Compound (Va). IR (ATR, cm^-1) 2979 [C—H (arom.)], 1648 [C═O (amide)], 1461 [C═C (arom.)], 1382 (C—N). NMR (CDCl₃): δ(¹H) 1.44 (d, J = 6.7 Hz, 3H, 11-CH₃), 1.83 (s, 3H, CO-CH₃), 2.34 (dd, J = 15.4, 10.9 Hz, 1H, 12-H_B), 3.36 (dd, J = 15.4, 7.2 Hz, 1H, 12-H_A), 3.59 (dp, J = 11.4, 6.9 Hz, 1H, 11-H), 4.05 (d, J = 14.7 Hz, 1H, 6-H_B), 5.87 (d, J = 14.7 Hz, 1H, 6-H_A), 6.60 (dd, J = 9.2, 2.8 Hz, 1H, 1-H), 6.78 (td, J = 8.2, 2.8 Hz, 1H, 3-H), 6.90 (d, J = 7.5 Hz, 1H, 7-H ), 6.95–6.98 (m, 2H, 4-H, 8-H), 7.13–7.19 (m, 2H, 9-H, 10-H); δ(¹³C) 20.0 (11-CH₃), 23.0 (CO-CH₃), 32.1 (11-C), 44.9 (12-C), 52.3 (6-C), 114.5 (d, J = 22.2 Hz, 3-C), 117.9 (d, J = 22.1 Hz, 1-C), 124.4 (10-C), 126.3 (8-C), 128.3 (9-C), 129.6 (7-C), 130.2 (d, J = 8.9 Hz, 4-C), 134.0 (6a-C), 135.5 (d, J = 2.9 Hz, 4a-C), 142.0 (d, J = 8.1 Hz, 12a-C), 143.6 (10a-C), 161.8 (d, J = 248.1 Hz, 2-C), 170.1 (C═O). GC-MS (70 eV) m/z (%) 283 (M⁺, 80), 268 (33), 240 (85), 226 (100), 117 (60). HRMS (Q-TOF-ESI) m/z found 284.1445; for C₁₈H₁₉FNO [M + H]⁺ requires 284.1445.

Compound (Vb). IR (ATR, cm^-1) 2962 [C—H (arom.)], 1650 [C═O (amide)], 1488 [C═C (arom.)], 1386 (C—N), 764 (C-Cl). NMR (CDCl₃): δ(¹H) 1.44 (d, J = 6.8 Hz, 3H, 11-CH₃), 1.82 (s, 3H, CO-CH₃), 2.33 (dd, J = 15.4, 10.9 Hz, 1H, 12-H_B), 3.34 (dd, J = 15.4, 7.3 Hz, 1H, 12-H_A), 3.58 (dp, J = 10.9, 6.9 Hz, 1H, 11-H), 4.05 (d, J = 14.8 Hz, 1H, 6-H_B), 5.87 (d, J = 14.8 Hz, 1H, 6-H_A), 6.89 (d, J = 2.4 Hz, 1H, 1-H), 6.90 (d, J = 7.8 Hz, 1H, 7-H), 6.93 (d, J = 8.3 Hz, 1H, 4-H), 6.95–6.99 (m, 1H, 8-H), 7.07 (dd, J = 8.3, 2.4 Hz, 1H, 3-H), 7.13–7.19 (m, 2H, 9-H, 10-H); δ(¹³C) 20.0 (11-CH₃), 23.0 (CO-CH₃), 32.2 (11-C), 44.7 (12-C), 52.3 (6-C), 124.5 (10-C), 126.3 (8-C), 127.8 (3-C), 128.4 (9-C), 129.6 (7-C), 130.0 (4-C), 131.2 (1-C), 133.8 (2-C), 133.9 (6a-C), 138.1 (4a-C), 141.5 (12a-C), 143.5 (10a-C), 169.8 (C═O). GC-MS (70 eV) m/z (%) 299 (M⁺, ³⁵Cl, 89), 284 (44), 256 (³⁵Cl, 39), 242 (³⁵Cl, 100), 117 (81). HRMS (Q-TOF-ESI) m/z found 300.1146, for C₁₈H₁₉ClNO [M + H]⁺ requires 300.1150.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.76704 (13)	0.48880 (9)	0.50675 (9)	0.0170 (2)
H1	0.8254	0.4940	0.4613	0.020*
C2	0.68911 (13)	0.57064 (9)	0.52398 (9)	0.0168 (2)
F2	0.69784 (9)	0.65521 (6)	0.47303 (6)	0.02351 (18)
C3	0.60800 (13)	0.57020 (9)	0.59120 (9)	0.0157 (2)
H3	0.5601	0.6286	0.6044	0.019*
C3A	0.59749 (12)	0.48102 (9)	0.64018 (8)	0.0141 (2)
C4	0.50994 (13)	0.48376 (9)	0.71382 (9)	0.0158 (2)
O4	0.45295 (11)	0.56264 (7)	0.73021 (7)	0.0233 (2)
C5	0.50193 (13)	0.39018 (9)	0.76189 (9)	0.0151 (2)
C6	0.56364 (12)	0.30668 (9)	0.73232 (8)	0.0149 (2)
H6	0.5510	0.2453	0.7624	0.018*
N7	0.64019 (11)	0.30533 (7)	0.66429 (7)	0.0145 (2)
C8	0.67867 (13)	0.20682 (9)	0.63070 (9)	0.0157 (2)
H8A	0.6443	0.2026	0.5596	0.019*
H8B	0.6304	0.1539	0.6599	0.019*
C8A	0.83772 (13)	0.18999 (9)	0.65748 (8)	0.0155 (2)
C9	0.89680 (13)	0.11852 (9)	0.72634 (9)	0.0183 (2)
H9	0.8361	0.0784	0.7548	0.022*
C10	1.04463 (14)	0.10595 (10)	0.75334 (10)	0.0226 (3)
H10	1.0847	0.0561	0.7990	0.027*
C11	1.13337 (14)	0.16613 (11)	0.71357 (10)	0.0251 (3)
H11	1.2344	0.1589	0.7334	0.030*
C12	1.07456 (14)	0.23711 (10)	0.64464 (10)	0.0228 (3)
H12	1.1359	0.2781	0.6176	0.027*
C12A	0.92672 (13)	0.24873 (9)	0.61487 (9)	0.0179 (2)
C13	0.86567 (13)	0.32007 (10)	0.53351 (9)	0.0187 (2)
H13	0.9500	0.3584	0.5226	0.022*
C13A	0.76172 (13)	0.39905 (9)	0.55466 (9)	0.0159 (2)
C13B	0.66797 (12)	0.39382 (9)	0.61947 (8)	0.0143 (2)
C51	0.42757 (13)	0.37255 (9)	0.84088 (9)	0.0161 (2)
O51	0.45359 (11)	0.30113 (7)	0.89481 (7)	0.0212 (2)
O52	0.32784 (10)	0.44026 (7)	0.84682 (7)	0.0205 (2)
C52	0.24441 (14)	0.41982 (10)	0.91868 (10)	0.0232 (3)
H52B	0.2357	0.3469	0.9258	0.028*
H52A	0.1468	0.4475	0.8960	0.028*
C53	0.31294 (17)	0.46448 (11)	1.01541 (11)	0.0291 (3)
H53B	0.3261	0.5362	1.0080	0.044*
H53C	0.4062	0.4331	1.0407	0.044*
H53A	0.2511	0.4533	1.0605	0.044*
C131	0.80444 (14)	0.26574 (10)	0.43672 (9)	0.0215 (3)
H31A	0.7204	0.2257	0.4430	0.026*
H31B	0.7712	0.3159	0.3854	0.026*
C132	0.91372 (16)	0.19764 (11)	0.40648 (10)	0.0276 (3)
H32A	0.9404	0.1440	0.4540	0.041*
H32B	0.9992	0.2362	0.4031	0.041*
H32C	0.8718	0.1689	0.3429	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0159 (5)	0.0211 (6)	0.0143 (5)	−0.0012 (4)	0.0038 (4)	0.0017 (4)
C2	0.0189 (5)	0.0145 (5)	0.0162 (6)	−0.0035 (4)	0.0025 (4)	0.0029 (4)
F2	0.0312 (4)	0.0169 (4)	0.0253 (4)	−0.0015 (3)	0.0123 (3)	0.0063 (3)
C3	0.0162 (5)	0.0142 (5)	0.0158 (5)	−0.0019 (4)	0.0022 (4)	−0.0011 (4)
C3A	0.0138 (5)	0.0148 (5)	0.0134 (5)	−0.0015 (4)	0.0024 (4)	−0.0006 (4)
C4	0.0166 (5)	0.0151 (5)	0.0157 (5)	−0.0004 (4)	0.0037 (4)	−0.0004 (4)
O4	0.0324 (5)	0.0149 (4)	0.0270 (5)	0.0051 (4)	0.0158 (4)	0.0018 (4)
C5	0.0168 (5)	0.0148 (5)	0.0142 (5)	−0.0003 (4)	0.0046 (4)	−0.0002 (4)
C6	0.0153 (5)	0.0148 (5)	0.0146 (5)	0.0002 (4)	0.0034 (4)	0.0009 (4)
N7	0.0159 (5)	0.0136 (5)	0.0144 (5)	0.0013 (4)	0.0044 (4)	0.0005 (4)
C8	0.0164 (5)	0.0146 (5)	0.0164 (5)	0.0011 (4)	0.0041 (4)	−0.0018 (4)
C8A	0.0165 (5)	0.0158 (5)	0.0139 (5)	0.0013 (4)	0.0029 (4)	−0.0010 (4)
C9	0.0207 (6)	0.0172 (6)	0.0172 (6)	0.0009 (4)	0.0045 (5)	0.0015 (4)
C10	0.0221 (6)	0.0245 (6)	0.0192 (6)	0.0048 (5)	0.0006 (5)	0.0051 (5)
C11	0.0166 (6)	0.0321 (7)	0.0251 (7)	0.0035 (5)	0.0014 (5)	0.0043 (5)
C12	0.0188 (6)	0.0263 (7)	0.0243 (6)	0.0006 (5)	0.0070 (5)	0.0054 (5)
C12A	0.0187 (6)	0.0196 (6)	0.0161 (6)	0.0036 (4)	0.0056 (4)	0.0024 (4)
C13	0.0179 (6)	0.0215 (6)	0.0181 (6)	0.0031 (4)	0.0068 (5)	0.0045 (5)
C13A	0.0154 (5)	0.0178 (6)	0.0142 (5)	0.0010 (4)	0.0025 (4)	0.0014 (4)
C13B	0.0141 (5)	0.0150 (5)	0.0131 (5)	−0.0002 (4)	0.0020 (4)	0.0008 (4)
C51	0.0176 (5)	0.0135 (5)	0.0178 (6)	−0.0010 (4)	0.0052 (4)	−0.0020 (4)
O51	0.0289 (5)	0.0160 (4)	0.0218 (5)	0.0029 (4)	0.0120 (4)	0.0037 (3)
O52	0.0208 (4)	0.0199 (4)	0.0246 (5)	0.0043 (3)	0.0127 (4)	0.0046 (3)
C52	0.0206 (6)	0.0231 (6)	0.0306 (7)	0.0017 (5)	0.0157 (5)	0.0055 (5)
C53	0.0349 (8)	0.0291 (7)	0.0284 (7)	0.0013 (6)	0.0182 (6)	0.0024 (6)
C131	0.0235 (6)	0.0249 (6)	0.0172 (6)	0.0052 (5)	0.0065 (5)	0.0022 (5)
C132	0.0310 (7)	0.0310 (7)	0.0224 (7)	0.0128 (6)	0.0090 (6)	0.0014 (5)

Geometric parameters (Å, º)

C1—C2	1.3826 (17)	C10—H10	0.9500
C1—C13A	1.3915 (17)	C11—C12	1.3905 (19)
C1—H1	0.9500	C11—H11	0.9500
C2—F2	1.3602 (13)	C12—C12A	1.3922 (18)
C2—C3	1.3641 (17)	C12—H12	0.9500
C3—C3A	1.4009 (16)	C12A—C13	1.5126 (17)
C3—H3	0.9500	C13—C13A	1.5323 (17)
C3A—C13B	1.4168 (16)	C13—C131	1.5492 (18)
C3A—C4	1.4856 (16)	C13—H13	1.0000
C4—O4	1.2387 (15)	C13A—C13B	1.4296 (16)
C4—C5	1.4413 (16)	C51—O51	1.2177 (15)
C5—C6	1.3783 (16)	C51—O52	1.3366 (15)
C5—C51	1.4813 (17)	O52—C52	1.4615 (15)
C6—N7	1.3422 (15)	C52—C53	1.506 (2)
C6—H6	0.9500	C52—H52B	0.9900
N7—C13B	1.4029 (15)	C52—H52A	0.9900
N7—C8	1.4819 (15)	C53—H53B	0.9800
C8—C8A	1.5022 (16)	C53—H53C	0.9800
C8—H8A	0.9900	C53—H53A	0.9800
C8—H8B	0.9900	C131—C132	1.5257 (18)
C8A—C9	1.3951 (17)	C131—H31A	0.9900
C8A—C12A	1.3987 (17)	C131—H31B	0.9900
C9—C10	1.3915 (18)	C132—H32A	0.9800
C9—H9	0.9500	C132—H32B	0.9800
C10—C11	1.385 (2)	C132—H32C	0.9800
C2—C1—C13A	121.33 (11)	C12A—C12—H12	119.6
C2—C1—H1	119.3	C12—C12A—C8A	119.04 (11)
C13A—C1—H1	119.3	C12—C12A—C13	119.46 (11)
F2—C2—C3	119.45 (11)	C8A—C12A—C13	121.41 (11)
F2—C2—C1	117.88 (11)	C12A—C13—C13A	116.33 (10)
C3—C2—C1	122.64 (11)	C12A—C13—C131	112.46 (11)
C2—C3—C3A	118.03 (11)	C13A—C13—C131	111.69 (10)
C2—C3—H3	121.0	C12A—C13—H13	105.1
C3A—C3—H3	121.0	C13A—C13—H13	105.1
C3—C3A—C13B	120.75 (11)	C131—C13—H13	105.1
C3—C3A—C4	116.50 (10)	C1—C13A—C13B	117.22 (11)
C13B—C3A—C4	122.75 (10)	C1—C13A—C13	113.89 (10)
O4—C4—C5	125.65 (11)	C13B—C13A—C13	128.80 (11)
O4—C4—C3A	119.94 (11)	N7—C13B—C3A	117.17 (10)
C5—C4—C3A	114.40 (10)	N7—C13B—C13A	123.21 (10)
C6—C5—C4	119.45 (11)	C3A—C13B—C13A	119.62 (11)
C6—C5—C51	114.62 (10)	O51—C51—O52	122.84 (11)
C4—C5—C51	125.90 (11)	O51—C51—C5	122.59 (11)
N7—C6—C5	125.12 (11)	O52—C51—C5	114.55 (10)
N7—C6—H6	117.4	C51—O52—C52	115.54 (10)
C5—C6—H6	117.4	O52—C52—C53	111.68 (11)
C6—N7—C13B	120.56 (10)	O52—C52—H52B	109.3
C6—N7—C8	117.54 (10)	C53—C52—H52B	109.3
C13B—N7—C8	121.52 (10)	O52—C52—H52A	109.3
N7—C8—C8A	111.49 (10)	C53—C52—H52A	109.3
N7—C8—H8A	109.3	H52B—C52—H52A	107.9
C8A—C8—H8A	109.3	C52—C53—H53B	109.5
N7—C8—H8B	109.3	C52—C53—H53C	109.5
C8A—C8—H8B	109.3	H53B—C53—H53C	109.5
H8A—C8—H8B	108.0	C52—C53—H53A	109.5
C9—C8A—C12A	120.15 (11)	H53B—C53—H53A	109.5
C9—C8A—C8	120.43 (11)	H53C—C53—H53A	109.5
C12A—C8A—C8	119.39 (11)	C132—C131—C13	112.84 (11)
C10—C9—C8A	120.06 (12)	C132—C131—H31A	109.0
C10—C9—H9	120.0	C13—C131—H31A	109.0
C8A—C9—H9	120.0	C132—C131—H31B	109.0
C11—C10—C9	119.96 (12)	C13—C131—H31B	109.0
C11—C10—H10	120.0	H31A—C131—H31B	107.8
C9—C10—H10	120.0	C131—C132—H32A	109.5
C10—C11—C12	120.00 (12)	C131—C132—H32B	109.5
C10—C11—H11	120.0	H32A—C132—H32B	109.5
C12—C11—H11	120.0	C131—C132—H32C	109.5
C11—C12—C12A	120.73 (12)	H32A—C132—H32C	109.5
C11—C12—H12	119.6	H32B—C132—H32C	109.5
C13A—C1—C2—F2	−178.82 (11)	C8—C8A—C12A—C13	−7.65 (18)
C13A—C1—C2—C3	2.94 (19)	C12—C12A—C13—C13A	−126.40 (13)
F2—C2—C3—C3A	177.96 (10)	C8A—C12A—C13—C13A	57.14 (16)
C1—C2—C3—C3A	−3.83 (18)	C12—C12A—C13—C131	103.00 (14)
C2—C3—C3A—C13B	−0.68 (17)	C8A—C12A—C13—C131	−73.46 (15)
C2—C3—C3A—C4	179.16 (10)	C2—C1—C13A—C13B	2.45 (18)
C3—C3A—C4—O4	−1.21 (17)	C2—C1—C13A—C13	−174.51 (11)
C13B—C3A—C4—O4	178.62 (11)	C12A—C13—C13A—C1	147.66 (11)
C3—C3A—C4—C5	179.75 (10)	C131—C13—C13A—C1	−81.38 (13)
C13B—C3A—C4—C5	−0.41 (16)	C12A—C13—C13A—C13B	−28.86 (18)
O4—C4—C5—C6	176.15 (12)	C131—C13—C13A—C13B	102.10 (14)
C3A—C4—C5—C6	−4.87 (16)	C6—N7—C13B—C3A	−7.68 (16)
O4—C4—C5—C51	−1.7 (2)	C8—N7—C13B—C3A	164.99 (10)
C3A—C4—C5—C51	177.25 (11)	C6—N7—C13B—C13A	172.78 (11)
C4—C5—C6—N7	4.14 (19)	C8—N7—C13B—C13A	−14.55 (17)
C51—C5—C6—N7	−177.75 (11)	C3—C3A—C13B—N7	−173.58 (10)
C5—C6—N7—C13B	2.53 (18)	C4—C3A—C13B—N7	6.59 (16)
C5—C6—N7—C8	−170.43 (11)	C3—C3A—C13B—C13A	5.97 (17)
C6—N7—C8—C8A	−114.48 (12)	C4—C3A—C13B—C13A	−173.85 (11)
C13B—N7—C8—C8A	72.64 (13)	C1—C13A—C13B—N7	172.81 (11)
N7—C8—C8A—C9	111.47 (12)	C13—C13A—C13B—N7	−10.76 (19)
N7—C8—C8A—C12A	−66.61 (14)	C1—C13A—C13B—C3A	−6.72 (17)
C12A—C8A—C9—C10	0.45 (19)	C13—C13A—C13B—C3A	169.71 (12)
C8—C8A—C9—C10	−177.62 (12)	C6—C5—C51—O51	21.28 (17)
C8A—C9—C10—C11	1.6 (2)	C4—C5—C51—O51	−160.76 (12)
C9—C10—C11—C12	−1.9 (2)	C6—C5—C51—O52	−157.46 (11)
C10—C11—C12—C12A	0.1 (2)	C4—C5—C51—O52	20.51 (17)
C11—C12—C12A—C8A	2.0 (2)	O51—C51—O52—C52	−3.85 (18)
C11—C12—C12A—C13	−174.58 (13)	C5—C51—O52—C52	174.88 (10)
C9—C8A—C12A—C12	−2.21 (18)	C51—O52—C52—C53	90.07 (14)
C8—C8A—C12A—C12	175.88 (12)	C12A—C13—C131—C132	−55.46 (15)
C9—C8A—C12A—C13	174.27 (11)	C13A—C13—C131—C132	171.62 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O51^i	0.95	2.32	3.1725 (16)	149
C6—H6···O4^ii	0.95	2.46	3.3308 (15)	153
C8—H8B···O4^ii	0.99	2.27	3.2255 (16)	162
C131—H31A···O51^iii	0.99	2.52	3.4008 (17)	148
C10—H10···Cg1^iv	0.95	2.72	3.5641 (15)	148

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

(RS)-5-Acetyl-2-chloro-11-methyl-5,6,11,12-tetrahydrobenzo[b,f]azocine (Vb)

Crystal data

C18H18ClNO	F(000) = 632
Mr = 299.78	Dx = 1.314 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.333 (5) Å	Cell parameters from 3774 reflections
b = 20.800 (14) Å	θ = 2.5–28.4°
c = 9.186 (6) Å	µ = 0.25 mm^−1
β = 107.857 (17)°	T = 100 K
V = 1515.5 (17) Å^3	Plate, colourless
Z = 4	0.30 × 0.25 × 0.12 mm

Data collection

Bruker D8 Venture diffractometer	3774 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3337 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.066
φ and ω scans	θmax = 28.4°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −10→11
Tmin = 0.947, Tmax = 0.970	k = −27→27
50802 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 1.1112P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3774 reflections	Δρmax = 0.43 e Å^−3
192 parameters	Δρmin = −0.33 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.13803 (17)	0.29721 (6)	0.23168 (15)	0.0147 (3)
H1	0.1058	0.2611	0.1658	0.018*
C2	0.04139 (16)	0.31511 (6)	0.32372 (15)	0.0146 (3)
Cl2	−0.13541 (5)	0.26920 (2)	0.31914 (4)	0.02543 (11)
C3	0.08007 (16)	0.36819 (6)	0.41892 (14)	0.0144 (2)
H3	0.0112	0.3802	0.4799	0.017*
C4	0.22308 (16)	0.40329 (6)	0.42235 (14)	0.0128 (2)
H4	0.2522	0.4402	0.4860	0.015*
C4A	0.32430 (15)	0.38505 (6)	0.33375 (14)	0.0110 (2)
N5	0.47415 (13)	0.42145 (5)	0.34511 (12)	0.0111 (2)
C6	0.46467 (17)	0.47747 (6)	0.24434 (15)	0.0146 (3)
H6A	0.5779	0.4854	0.2341	0.017*
H6B	0.4331	0.5158	0.2933	0.017*
C6A	0.33958 (16)	0.46960 (6)	0.08616 (14)	0.0132 (2)
C7	0.22746 (17)	0.51960 (7)	0.02940 (16)	0.0176 (3)
H7	0.2278	0.5559	0.0923	0.021*
C8	0.11457 (18)	0.51757 (8)	−0.11792 (17)	0.0235 (3)
H8	0.0407	0.5527	−0.1561	0.028*
C9	0.11079 (19)	0.46416 (8)	−0.20808 (16)	0.0258 (3)
H9	0.0328	0.4619	−0.3081	0.031*
C10	0.22197 (19)	0.41372 (7)	−0.15153 (16)	0.0215 (3)
H10	0.2179	0.3768	−0.2136	0.026*
C10A	0.33952 (17)	0.41598 (7)	−0.00563 (15)	0.0158 (3)
C11	0.46351 (17)	0.36170 (6)	0.05585 (15)	0.0159 (3)
H11	0.5644	0.3804	0.1337	0.019*
C12	0.38781 (18)	0.30976 (6)	0.13671 (16)	0.0161 (3)
H12A	0.3172	0.2808	0.0570	0.019*
H12B	0.4821	0.2837	0.2016	0.019*
C12A	0.28266 (16)	0.33200 (6)	0.23513 (14)	0.0126 (2)
C51	0.62253 (16)	0.41006 (6)	0.45647 (14)	0.0119 (2)
O51	0.74656 (12)	0.44425 (5)	0.47193 (11)	0.0172 (2)
C52	0.62918 (18)	0.35294 (7)	0.55875 (16)	0.0197 (3)
H52C	0.7403	0.3508	0.6360	0.030*
H52A	0.6095	0.3135	0.4973	0.030*
H52B	0.5420	0.3573	0.6095	0.030*
C111	0.5244 (2)	0.32899 (7)	−0.06712 (18)	0.0245 (3)
H11A	0.4301	0.3061	−0.1389	0.037*
H11B	0.6143	0.2984	−0.0187	0.037*
H11C	0.5676	0.3616	−0.1225	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0176 (6)	0.0134 (6)	0.0128 (6)	−0.0030 (5)	0.0043 (5)	−0.0013 (5)
C2	0.0121 (6)	0.0169 (6)	0.0146 (6)	−0.0038 (5)	0.0036 (5)	0.0019 (5)
Cl2	0.01983 (18)	0.0314 (2)	0.02774 (19)	−0.01413 (14)	0.01116 (14)	−0.00721 (15)
C3	0.0130 (6)	0.0182 (6)	0.0129 (6)	0.0006 (5)	0.0055 (5)	0.0010 (5)
C4	0.0140 (6)	0.0129 (6)	0.0111 (5)	0.0001 (5)	0.0031 (4)	−0.0002 (4)
C4A	0.0113 (5)	0.0110 (5)	0.0100 (5)	−0.0009 (4)	0.0023 (4)	0.0025 (4)
N5	0.0110 (5)	0.0114 (5)	0.0103 (5)	−0.0016 (4)	0.0026 (4)	0.0015 (4)
C6	0.0177 (6)	0.0113 (6)	0.0132 (6)	−0.0025 (5)	0.0024 (5)	0.0013 (5)
C6A	0.0124 (6)	0.0154 (6)	0.0118 (6)	−0.0036 (5)	0.0038 (5)	0.0037 (5)
C7	0.0172 (6)	0.0170 (6)	0.0190 (6)	−0.0011 (5)	0.0060 (5)	0.0045 (5)
C8	0.0164 (7)	0.0306 (8)	0.0221 (7)	0.0020 (6)	0.0038 (5)	0.0132 (6)
C9	0.0200 (7)	0.0405 (9)	0.0132 (6)	−0.0096 (6)	−0.0004 (5)	0.0065 (6)
C10	0.0260 (7)	0.0258 (7)	0.0127 (6)	−0.0094 (6)	0.0061 (5)	−0.0019 (5)
C10A	0.0187 (6)	0.0171 (6)	0.0131 (6)	−0.0043 (5)	0.0072 (5)	0.0013 (5)
C11	0.0202 (6)	0.0146 (6)	0.0159 (6)	−0.0028 (5)	0.0102 (5)	−0.0017 (5)
C12	0.0218 (7)	0.0111 (6)	0.0192 (6)	−0.0015 (5)	0.0119 (5)	−0.0014 (5)
C12A	0.0153 (6)	0.0119 (6)	0.0110 (5)	0.0008 (4)	0.0046 (5)	0.0017 (4)
C51	0.0138 (6)	0.0125 (6)	0.0092 (5)	0.0018 (4)	0.0034 (4)	−0.0022 (4)
O51	0.0134 (4)	0.0178 (5)	0.0177 (5)	−0.0026 (4)	0.0008 (4)	−0.0008 (4)
C52	0.0222 (7)	0.0187 (7)	0.0159 (6)	0.0018 (5)	0.0026 (5)	0.0047 (5)
C111	0.0372 (8)	0.0185 (7)	0.0268 (7)	−0.0051 (6)	0.0229 (7)	−0.0056 (6)

Geometric parameters (Å, º)

C1—C2	1.3855 (19)	C8—H8	0.9500
C1—C12A	1.3977 (19)	C9—C10	1.391 (2)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.384 (2)	C10—C10A	1.397 (2)
C2—Cl2	1.7453 (15)	C10—H10	0.9500
C3—C4	1.3896 (19)	C10A—C11	1.518 (2)
C3—H3	0.9500	C11—C111	1.532 (2)
C4—C4A	1.3923 (18)	C11—C12	1.5505 (19)
C4—H4	0.9500	C11—H11	1.0000
C4A—C12A	1.4022 (18)	C12—C12A	1.5115 (18)
C4A—N5	1.4365 (17)	C12—H12A	0.9900
N5—C51	1.3622 (17)	C12—H12B	0.9900
N5—C6	1.4751 (17)	C51—O51	1.2264 (17)
C6—C6A	1.5152 (19)	C51—C52	1.5052 (19)
C6—H6A	0.9900	C52—H52C	0.9800
C6—H6B	0.9900	C52—H52A	0.9800
C6A—C7	1.3884 (19)	C52—H52B	0.9800
C6A—C10A	1.398 (2)	C111—H11A	0.9800
C7—C8	1.392 (2)	C111—H11B	0.9800
C7—H7	0.9500	C111—H11C	0.9800
C8—C9	1.380 (2)
C2—C1—C12A	120.37 (12)	C9—C10—C10A	121.58 (14)
C2—C1—H1	119.8	C9—C10—H10	119.2
C12A—C1—H1	119.8	C10A—C10—H10	119.2
C3—C2—C1	122.25 (12)	C10—C10A—C6A	118.40 (13)
C3—C2—Cl2	118.89 (10)	C10—C10A—C11	121.93 (13)
C1—C2—Cl2	118.86 (11)	C6A—C10A—C11	119.66 (12)
C2—C3—C4	117.74 (12)	C10A—C11—C111	113.42 (12)
C2—C3—H3	121.1	C10A—C11—C12	111.47 (12)
C4—C3—H3	121.1	C111—C11—C12	108.62 (12)
C3—C4—C4A	120.84 (12)	C10A—C11—H11	107.7
C3—C4—H4	119.6	C111—C11—H11	107.7
C4A—C4—H4	119.6	C12—C11—H11	107.7
C4—C4A—C12A	121.19 (12)	C12A—C12—C11	117.97 (11)
C4—C4A—N5	118.87 (11)	C12A—C12—H12A	107.8
C12A—C4A—N5	119.94 (11)	C11—C12—H12A	107.8
C51—N5—C4A	122.11 (11)	C12A—C12—H12B	107.8
C51—N5—C6	118.05 (11)	C11—C12—H12B	107.8
C4A—N5—C6	119.52 (10)	H12A—C12—H12B	107.2
N5—C6—C6A	113.90 (11)	C1—C12A—C4A	117.57 (12)
N5—C6—H6A	108.8	C1—C12A—C12	118.81 (12)
C6A—C6—H6A	108.8	C4A—C12A—C12	123.59 (12)
N5—C6—H6B	108.8	O51—C51—N5	121.65 (12)
C6A—C6—H6B	108.8	O51—C51—C52	121.13 (12)
H6A—C6—H6B	107.7	N5—C51—C52	117.21 (11)
C7—C6A—C10A	119.69 (13)	C51—C52—H52C	109.5
C7—C6A—C6	117.71 (12)	C51—C52—H52A	109.5
C10A—C6A—C6	122.51 (12)	H52C—C52—H52A	109.5
C6A—C7—C8	121.24 (14)	C51—C52—H52B	109.5
C6A—C7—H7	119.4	H52C—C52—H52B	109.5
C8—C7—H7	119.4	H52A—C52—H52B	109.5
C9—C8—C7	119.48 (14)	C11—C111—H11A	109.5
C9—C8—H8	120.3	C11—C111—H11B	109.5
C7—C8—H8	120.3	H11A—C111—H11B	109.5
C8—C9—C10	119.54 (14)	C11—C111—H11C	109.5
C8—C9—H9	120.2	H11A—C111—H11C	109.5
C10—C9—H9	120.2	H11B—C111—H11C	109.5
C12A—C1—C2—C3	1.6 (2)	C7—C6A—C10A—C10	−1.80 (19)
C12A—C1—C2—Cl2	−178.50 (10)	C6—C6A—C10A—C10	−178.39 (12)
C1—C2—C3—C4	−1.19 (19)	C7—C6A—C10A—C11	179.29 (12)
Cl2—C2—C3—C4	178.94 (10)	C6—C6A—C10A—C11	2.70 (18)
C2—C3—C4—C4A	−0.56 (19)	C10—C10A—C11—C111	34.86 (18)
C3—C4—C4A—C12A	1.90 (19)	C6A—C10A—C11—C111	−146.27 (12)
C3—C4—C4A—N5	−177.81 (11)	C10—C10A—C11—C12	−88.11 (16)
C4—C4A—N5—C51	84.18 (16)	C6A—C10A—C11—C12	90.76 (15)
C12A—C4A—N5—C51	−95.53 (15)	C10A—C11—C12—C12A	−39.95 (16)
C4—C4A—N5—C6	−89.12 (15)	C111—C11—C12—C12A	−165.63 (12)
C12A—C4A—N5—C6	91.16 (15)	C2—C1—C12A—C4A	−0.27 (19)
C51—N5—C6—C6A	151.63 (11)	C2—C1—C12A—C12	178.12 (12)
C4A—N5—C6—C6A	−34.80 (16)	C4—C4A—C12A—C1	−1.45 (18)
N5—C6—C6A—C7	131.79 (13)	N5—C4A—C12A—C1	178.26 (11)
N5—C6—C6A—C10A	−51.56 (17)	C4—C4A—C12A—C12	−179.75 (12)
C10A—C6A—C7—C8	−0.2 (2)	N5—C4A—C12A—C12	−0.05 (18)
C6—C6A—C7—C8	176.60 (12)	C11—C12—C12A—C1	140.65 (13)
C6A—C7—C8—C9	1.7 (2)	C11—C12—C12A—C4A	−41.07 (18)
C7—C8—C9—C10	−1.2 (2)	C4A—N5—C51—O51	−174.78 (11)
C8—C9—C10—C10A	−0.8 (2)	C6—N5—C51—O51	−1.39 (18)
C9—C10—C10A—C6A	2.3 (2)	C4A—N5—C51—C52	6.19 (17)
C9—C10—C10A—C11	−178.83 (13)	C6—N5—C51—C52	179.59 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O51^i	0.95	2.56	3.361 (3)	142
C4—H4···O51^ii	0.95	2.43	3.303 (3)	152
C6—H6A···Cg3^iii	0.99	2.70	3.673 (3)	149
C8—H8···Cg2^iv	0.95	2.86	3.802 (3)	169

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