Three tetra­cyclic dibenzoazepine derivatives exhibiting different mol­ecular conformations, different patterns of inter­molecular hydrogen bonding and different modes of supra­molecular aggregation

Mateus-Ruíz, J.B.; Acosta Quintero, L.M.; Palma, A.; Macías, M.A.; Cobo, J.; Glidewell, C.

doi:10.1107/S2053229616018143

Three tetracyclic dibenzoazepine derivatives exhibiting different molecular conformations, different patterns of intermolecular hydrogen bonding and different modes of supramolecular aggregation

J. B. Mateus-Ruíz, L. M. Acosta Quintero, A. Palma, M. A. Macías, J. Cobo and C. Glidewell

The biological potential of compounds of the tricyclic dibenzo[b,e]azepine system has resulted in considerable synthetic efforts to develop efficient methods for the synthesis of new derivatives of this kind. (9RS,15RS)-9-Ethyl-11-methyl-9,13b-dihydrodibenzo[c,f]thiazolo[3,2-a]azepin-3(2H)-one, C₁₉H₁₉NOS, (I), crystallizes as a kryptoracemate with Z′ = 2 in the space group P2₁, with one molecule each of the (9R,15R) and (9S,15S) configurations in the asymmetric unit, while (9RS,15RS)-9-ethyl-7,12-dimethyl-9,13b-dihydrodibenzo[c,f]thiazolo[3,2-a]azepin-3(2H)-one, C₂₀H₂₁NOS, (II), crystallizes with Z′ = 1 in the space group C2/c. Ethyl (13RS)-2-chloro-13-ethyl-4-oxo-8,13-dihydro-4H-benzo[5,6]azepino[3,2,1-ij]quinoline-5-carboxylate, C₂₂H₂₀ClNO₃, (III), exhibits enantiomeric disorder in the space group P $\overline{1}$ such that the reference site is occupied by the 13R and 13S enantiomers, with occupancies of 0.900 (6) and 0.100 (6). In each of the two independent molecules in (I), the five-membered ring adopts an envelope conformation, but the corresponding ring in (II) adopts a half-chair conformation, while the six-membered ring in the major form of (III) adopts a twist-boat conformation. The conformation of the seven-membered ring in each of (I), (II) and the major form of (III) approximates to the twist-boat form. The molecules of compound (I) are linked by two C—H

O hydrogen bonds to form two independent antiparallel C(5) chains, with each type containing only one enantiomer. These chains are linked into sheets by two C—H

π(arene) hydrogen bonds, in which the two donors are both provided by the (9R,15R) enantiomer and the two acceptor arene rings form part of a molecule of (9S,15S) configuration, precluding any additional crystallographic symmetry. The molecules of compound (II) are linked by inversion-related C—H

π(arene) hydrogen bonds to form isolated cyclic centrosymmetric dimers. The molecules of compound (III) are linked into cyclic centrosymmetric dimers by C—H

O hydrogen bonds and these dimers are linked into chains by a π–π stacking interaction. Comparisons are made with some related structures.

Keywords: synthesis; kryptoracemate; fused-ring systems; dibenzoazepines; crystal structure; enantiomeric disorder; molecular structure; molecular conformation; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616018143/sk3643sup1.cif Contains datablocks global, I, II, III
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616018143/sk3643Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616018143/sk3643IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616018143/sk3643IIIsup4.hkl Contains datablock III
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229616018143/sk3643Isup5.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229616018143/sk3643IIsup6.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229616018143/sk3643IIIsup7.cml Supplementary material

CCDC references: 1516770; 1516769; 1516768

Computing details top

Data collection: APEX2 (Bruker, 2006) for (I), (II); COLLECT (Nonius, 1998) for (III). Cell refinement: SAINT (Bruker, 2006) for (I), (II); DIRAX/LSQ (Duisenberg et al., 2000) for (III). Data reduction: SAINT (Bruker, 2006) for (I), (II); EVALCCD (Duisenberg et al., 2003) for (III). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I), (II); SIR2014 (Burla et al., 2015) for (III). For all compounds, 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).

(I) (9RS,15RS)-9-Ethyl-11-methyl-9,13b-dihydrodibenzo[c,f]thiazolo[3,2-a]azepin-3(2H)-one top

Crystal data top

C₁₉H₁₉NOS	F(000) = 656
M_r = 309.41	D_x = 1.308 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 11.4261 (5) Å	Cell parameters from 11002 reflections
b = 8.1847 (3) Å	θ = 1.8–32.5°
c = 16.8243 (6) Å	µ = 0.21 mm⁻¹
β = 93.067 (2)°	T = 100 K
V = 1571.14 (11) Å³	Block, colourless
Z = 4	0.40 × 0.35 × 0.22 mm

Data collection top

Bruker Kappa APEXII diffractometer	10697 reflections with I > 2σ(I)
Radiation source: high brilliance microfocus sealed tube	R_int = 0.025
φ and ω scans	θ_max = 32.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −17→16
T_min = 0.823, T_max = 0.955	k = −12→12
61785 measured reflections	l = −25→25
11002 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0527P)² + 0.1585P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.37 e Å⁻³
11002 reflections	Δρ_min = −0.21 e Å⁻³
401 parameters	Absolute structure: Flack x determined using 4787 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.007 (6)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S11	0.04257 (3)	0.64856 (4)	0.31677 (2)	0.02072 (7)
C12	−0.06240 (11)	0.6542 (2)	0.39359 (8)	0.0221 (2)
H12A	−0.0975	0.7643	0.3973	0.026*
H12B	−0.1258	0.5737	0.3825	0.026*
C13	0.00808 (11)	0.61139 (17)	0.46981 (8)	0.0198 (2)
O13	−0.03273 (10)	0.55030 (17)	0.52867 (7)	0.0298 (2)
N14	0.12297 (9)	0.65093 (16)	0.46388 (6)	0.01701 (19)
C14A	0.20563 (11)	0.63483 (17)	0.52973 (7)	0.0170 (2)
C15	0.19005 (13)	0.72209 (19)	0.59932 (8)	0.0221 (2)
H15	0.1246	0.7927	0.6032	0.027*
C16	0.27158 (15)	0.7045 (2)	0.66311 (8)	0.0256 (3)
H16	0.2618	0.7623	0.7113	0.031*
C17	0.36731 (14)	0.6021 (2)	0.65618 (8)	0.0243 (3)
H17	0.4241	0.5927	0.6993	0.029*
C18	0.38124 (11)	0.51298 (19)	0.58668 (7)	0.0195 (2)
H18	0.4466	0.4422	0.5832	0.023*
C18A	0.29966 (11)	0.52719 (16)	0.52223 (7)	0.0158 (2)
C19	0.30872 (10)	0.43915 (16)	0.44299 (7)	0.0151 (2)
H19	0.2274	0.4054	0.4252	0.018*
C19A	0.34743 (11)	0.56585 (16)	0.38285 (7)	0.0148 (2)
C110	0.45748 (11)	0.55481 (17)	0.35032 (7)	0.0164 (2)
H110	0.5071	0.4655	0.3650	0.020*
C111	0.49666 (11)	0.67094 (17)	0.29695 (7)	0.0173 (2)
C112	0.42386 (11)	0.80170 (18)	0.27585 (7)	0.0185 (2)
H112	0.4482	0.8808	0.2388	0.022*
C113	0.31535 (11)	0.81690 (17)	0.30887 (7)	0.0177 (2)
H113	0.2672	0.9083	0.2951	0.021*
C114	0.27587 (10)	0.70040 (16)	0.36181 (7)	0.0155 (2)
C115	0.15382 (11)	0.72903 (16)	0.38914 (7)	0.0160 (2)
H115	0.1415	0.8495	0.3942	0.019*
C116	0.61535 (12)	0.6532 (2)	0.26305 (8)	0.0246 (3)
H16A	0.6057	0.6325	0.2057	0.037*
H16B	0.6572	0.5615	0.2890	0.037*
H16C	0.6603	0.7539	0.2724	0.037*
C191	0.38285 (11)	0.28333 (17)	0.44701 (7)	0.0178 (2)
H19A	0.3929	0.2431	0.3923	0.021*
H19B	0.4615	0.3093	0.4713	0.021*
C192	0.32763 (11)	0.14856 (19)	0.49539 (8)	0.0211 (2)
H19C	0.3245	0.1837	0.5509	0.032*
H19D	0.3749	0.0490	0.4929	0.032*
H19E	0.2480	0.1265	0.4734	0.032*
S21	0.22593 (3)	0.00063 (5)	−0.08726 (2)	0.02161 (7)
C22	0.06874 (13)	0.02911 (19)	−0.08922 (8)	0.0224 (3)
H22A	0.0435	0.1113	−0.1298	0.027*
H22B	0.0276	−0.0750	−0.1016	0.027*
C23	0.04285 (12)	0.08804 (18)	−0.00633 (8)	0.0205 (2)
O23	−0.04535 (10)	0.16254 (18)	0.00951 (7)	0.0317 (3)
N24	0.13069 (9)	0.04697 (14)	0.04793 (6)	0.01589 (19)
C24A	0.12426 (10)	0.08689 (16)	0.13011 (7)	0.0151 (2)
C25	0.03501 (11)	0.02280 (18)	0.17405 (8)	0.0196 (2)
H25	−0.0202	−0.0517	0.1503	0.024*
C26	0.02786 (12)	0.06939 (18)	0.25329 (9)	0.0219 (2)
H26	−0.0332	0.0281	0.2838	0.026*
C27	0.11024 (12)	0.17634 (18)	0.28750 (8)	0.0207 (2)
H27	0.1057	0.2075	0.3416	0.025*
C28	0.19976 (11)	0.23845 (17)	0.24303 (7)	0.0175 (2)
H28	0.2562	0.3104	0.2674	0.021*
C28A	0.20726 (10)	0.19610 (15)	0.16314 (7)	0.0141 (2)
C29	0.30020 (10)	0.26061 (15)	0.10960 (7)	0.0140 (2)
H29	0.2589	0.2824	0.0567	0.017*
C29A	0.38728 (10)	0.12397 (15)	0.09590 (7)	0.0140 (2)
C210	0.50569 (10)	0.13608 (17)	0.12168 (7)	0.0157 (2)
H210	0.5318	0.2316	0.1494	0.019*
C211	0.58688 (10)	0.01222 (18)	0.10797 (7)	0.0170 (2)
C212	0.54650 (11)	−0.12996 (18)	0.06995 (7)	0.0183 (2)
H212	0.5995	−0.2166	0.0609	0.022*
C213	0.42911 (11)	−0.14551 (17)	0.04519 (7)	0.0167 (2)
H213	0.4027	−0.2437	0.0201	0.020*
C214	0.34913 (10)	−0.01951 (16)	0.05650 (7)	0.01384 (19)
C215	0.22787 (10)	−0.04930 (15)	0.01916 (7)	0.0144 (2)
H215	0.2088	−0.1678	0.0248	0.017*
C216	0.71526 (11)	0.0308 (2)	0.13229 (8)	0.0233 (3)
H26A	0.7347	0.1472	0.1370	0.035*
H26B	0.7625	−0.0195	0.0920	0.035*
H26C	0.7319	−0.0230	0.1837	0.035*
C291	0.35367 (11)	0.42370 (16)	0.13740 (8)	0.0172 (2)
H29A	0.3887	0.4117	0.1922	0.021*
H29B	0.4168	0.4547	0.1023	0.021*
C292	0.26090 (13)	0.55806 (18)	0.13589 (8)	0.0222 (2)
H29C	0.2227	0.5652	0.0824	0.033*
H29D	0.2982	0.6628	0.1498	0.033*
H29E	0.2023	0.5324	0.1745	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S11	0.01711 (13)	0.02520 (16)	0.01967 (13)	0.00113 (12)	−0.00079 (10)	−0.00009 (12)
C12	0.0153 (5)	0.0253 (7)	0.0256 (6)	0.0012 (5)	0.0011 (4)	0.0039 (5)
C13	0.0151 (5)	0.0196 (6)	0.0251 (6)	0.0016 (4)	0.0046 (4)	0.0031 (4)
O13	0.0208 (5)	0.0394 (7)	0.0298 (5)	−0.0007 (5)	0.0080 (4)	0.0110 (5)
N14	0.0143 (4)	0.0211 (5)	0.0160 (4)	0.0011 (4)	0.0037 (3)	0.0025 (4)
C14A	0.0177 (5)	0.0183 (6)	0.0153 (4)	−0.0010 (4)	0.0030 (4)	0.0013 (4)
C15	0.0276 (6)	0.0210 (6)	0.0183 (5)	0.0014 (5)	0.0063 (5)	−0.0008 (5)
C16	0.0371 (8)	0.0240 (7)	0.0159 (5)	−0.0034 (6)	0.0032 (5)	−0.0014 (5)
C17	0.0291 (7)	0.0283 (7)	0.0151 (5)	−0.0049 (5)	−0.0018 (5)	0.0008 (5)
C18	0.0183 (5)	0.0243 (6)	0.0159 (5)	−0.0018 (5)	0.0004 (4)	0.0033 (4)
C18A	0.0158 (5)	0.0179 (6)	0.0139 (4)	−0.0018 (4)	0.0026 (4)	0.0019 (4)
C19	0.0138 (5)	0.0174 (5)	0.0142 (4)	0.0006 (4)	0.0015 (4)	0.0014 (4)
C19A	0.0147 (5)	0.0173 (5)	0.0126 (4)	−0.0003 (4)	0.0019 (4)	0.0004 (4)
C110	0.0152 (5)	0.0205 (6)	0.0137 (4)	0.0000 (4)	0.0020 (4)	0.0001 (4)
C111	0.0160 (5)	0.0225 (6)	0.0136 (4)	−0.0019 (4)	0.0028 (4)	0.0001 (4)
C112	0.0192 (5)	0.0220 (6)	0.0145 (5)	−0.0024 (5)	0.0020 (4)	0.0028 (4)
C113	0.0182 (5)	0.0186 (6)	0.0162 (5)	−0.0007 (4)	0.0013 (4)	0.0028 (4)
C114	0.0143 (5)	0.0180 (5)	0.0143 (4)	−0.0004 (4)	0.0021 (4)	0.0003 (4)
C115	0.0153 (5)	0.0169 (5)	0.0159 (5)	0.0003 (4)	0.0026 (4)	0.0014 (4)
C116	0.0188 (5)	0.0323 (7)	0.0234 (6)	0.0010 (6)	0.0087 (4)	0.0042 (5)
C191	0.0158 (5)	0.0195 (6)	0.0181 (5)	0.0020 (4)	0.0025 (4)	0.0030 (4)
C192	0.0181 (5)	0.0204 (6)	0.0250 (5)	0.0006 (5)	0.0023 (4)	0.0051 (5)
S21	0.02265 (14)	0.02804 (18)	0.01408 (12)	−0.00534 (12)	0.00057 (10)	−0.00045 (11)
C22	0.0241 (6)	0.0233 (7)	0.0189 (5)	0.0003 (5)	−0.0065 (4)	−0.0005 (5)
C23	0.0192 (5)	0.0192 (6)	0.0223 (5)	0.0020 (5)	−0.0061 (4)	−0.0026 (5)
O23	0.0241 (5)	0.0360 (6)	0.0339 (5)	0.0138 (5)	−0.0088 (4)	−0.0078 (5)
N24	0.0131 (4)	0.0182 (5)	0.0162 (4)	0.0020 (4)	−0.0013 (3)	−0.0022 (4)
C24A	0.0133 (5)	0.0158 (5)	0.0164 (5)	0.0011 (4)	0.0010 (4)	−0.0006 (4)
C25	0.0141 (5)	0.0205 (6)	0.0245 (5)	−0.0009 (4)	0.0041 (4)	−0.0009 (5)
C26	0.0197 (6)	0.0215 (6)	0.0253 (6)	0.0009 (5)	0.0093 (5)	0.0024 (5)
C27	0.0238 (6)	0.0210 (6)	0.0180 (5)	0.0034 (5)	0.0062 (4)	0.0004 (4)
C28	0.0199 (5)	0.0174 (6)	0.0155 (5)	0.0009 (4)	0.0016 (4)	−0.0006 (4)
C28A	0.0133 (4)	0.0142 (5)	0.0150 (4)	0.0012 (4)	0.0014 (4)	−0.0002 (4)
C29	0.0149 (5)	0.0132 (5)	0.0140 (4)	−0.0013 (4)	0.0012 (4)	−0.0002 (4)
C29A	0.0132 (4)	0.0152 (5)	0.0138 (4)	−0.0006 (4)	0.0021 (3)	0.0012 (4)
C210	0.0149 (4)	0.0183 (5)	0.0140 (4)	−0.0023 (4)	0.0016 (3)	0.0014 (4)
C211	0.0134 (4)	0.0232 (6)	0.0145 (4)	0.0002 (4)	0.0023 (4)	0.0034 (4)
C212	0.0159 (5)	0.0226 (6)	0.0167 (5)	0.0034 (4)	0.0037 (4)	0.0007 (4)
C213	0.0171 (5)	0.0175 (6)	0.0159 (5)	0.0013 (4)	0.0032 (4)	−0.0010 (4)
C214	0.0133 (4)	0.0148 (5)	0.0136 (4)	−0.0005 (4)	0.0019 (3)	0.0000 (4)
C215	0.0139 (5)	0.0149 (5)	0.0144 (4)	0.0001 (4)	0.0008 (4)	−0.0009 (4)
C216	0.0131 (5)	0.0336 (8)	0.0231 (6)	0.0003 (5)	0.0002 (4)	0.0015 (5)
C291	0.0190 (5)	0.0149 (5)	0.0178 (5)	−0.0027 (4)	−0.0001 (4)	−0.0013 (4)
C292	0.0274 (6)	0.0155 (6)	0.0235 (6)	0.0006 (5)	0.0005 (5)	−0.0005 (4)

Geometric parameters (Å, º) top

S11—C12	1.8102 (14)	S21—C22	1.8096 (15)
S11—C115	1.8348 (13)	S21—C215	1.8354 (12)
C12—C13	1.5184 (19)	C22—C23	1.520 (2)
C12—H12A	0.9900	C22—H22A	0.9900
C12—H12B	0.9900	C22—H22B	0.9900
C13—O13	1.2238 (16)	C23—O23	1.2196 (17)
C13—N14	1.3609 (16)	C23—N24	1.3623 (16)
N14—C14A	1.4229 (15)	N24—C24A	1.4264 (16)
N14—C115	1.4702 (16)	N24—C215	1.4648 (16)
C14A—C15	1.3911 (18)	C24A—C25	1.3937 (17)
C14A—C18A	1.4003 (18)	C24A—C28A	1.3968 (17)
C15—C16	1.390 (2)	C25—C26	1.3933 (19)
C15—H15	0.9500	C25—H25	0.9500
C16—C17	1.387 (2)	C26—C27	1.388 (2)
C16—H16	0.9500	C26—H26	0.9500
C17—C18	1.3947 (19)	C27—C28	1.3951 (18)
C17—H17	0.9500	C27—H27	0.9500
C18—C18A	1.3964 (17)	C28—C28A	1.3951 (16)
C18—H18	0.9500	C28—H28	0.9500
C18A—C19	1.5238 (17)	C28A—C29	1.5232 (17)
C19—C191	1.5305 (18)	C29—C29A	1.5226 (17)
C19—C19A	1.5306 (17)	C29—C291	1.5308 (17)
C19—H19	1.0000	C29—H29	1.0000
C19A—C110	1.4009 (16)	C29A—C210	1.4020 (16)
C19A—C114	1.4056 (18)	C29A—C214	1.4063 (17)
C110—C111	1.3975 (17)	C210—C211	1.4015 (18)
C110—H110	0.9500	C210—H210	0.9500
C111—C112	1.3899 (19)	C211—C212	1.3946 (19)
C111—C116	1.5061 (18)	C211—C216	1.5094 (17)
C112—C113	1.3911 (17)	C212—C213	1.3890 (18)
C112—H112	0.9500	C212—H212	0.9500
C113—C114	1.3960 (17)	C213—C214	1.3976 (17)
C113—H113	0.9500	C213—H213	0.9500
C114—C115	1.5098 (17)	C214—C215	1.5102 (16)
C115—H115	1.0000	C215—H215	1.0000
C116—H16A	0.9800	C216—H26A	0.9800
C116—H16B	0.9800	C216—H26B	0.9800
C116—H16C	0.9800	C216—H26C	0.9800
C191—C192	1.5271 (19)	C291—C292	1.527 (2)
C191—H19A	0.9900	C291—H29A	0.9900
C191—H19B	0.9900	C291—H29B	0.9900
C192—H19C	0.9800	C292—H29C	0.9800
C192—H19D	0.9800	C292—H29D	0.9800
C192—H19E	0.9800	C292—H29E	0.9800

C12—S11—C115	88.80 (6)	C22—S21—C215	90.38 (6)
C13—C12—S11	104.79 (9)	C23—C22—S21	105.42 (9)
C13—C12—H12A	110.8	C23—C22—H22A	110.7
S11—C12—H12A	110.8	S21—C22—H22A	110.7
C13—C12—H12B	110.8	C23—C22—H22B	110.7
S11—C12—H12B	110.8	S21—C22—H22B	110.7
H12A—C12—H12B	108.9	H22A—C22—H22B	108.8
O13—C13—N14	124.56 (13)	O23—C23—N24	124.38 (13)
O13—C13—C12	124.74 (12)	O23—C23—C22	124.26 (12)
N14—C13—C12	110.69 (11)	N24—C23—C22	111.36 (12)
C13—N14—C14A	121.57 (11)	C23—N24—C24A	121.25 (11)
C13—N14—C115	116.26 (10)	C23—N24—C215	117.10 (10)
C14A—N14—C115	121.78 (10)	C24A—N24—C215	121.52 (10)
C15—C14A—C18A	122.15 (12)	C25—C24A—C28A	122.04 (11)
C15—C14A—N14	119.88 (12)	C25—C24A—N24	120.33 (11)
C18A—C14A—N14	117.95 (11)	C28A—C24A—N24	117.59 (11)
C16—C15—C14A	119.06 (14)	C26—C25—C24A	119.11 (12)
C16—C15—H15	120.5	C26—C25—H25	120.4
C14A—C15—H15	120.5	C24A—C25—H25	120.4
C17—C16—C15	119.77 (13)	C27—C26—C25	119.76 (12)
C17—C16—H16	120.1	C27—C26—H26	120.1
C15—C16—H16	120.1	C25—C26—H26	120.1
C16—C17—C18	120.80 (13)	C26—C27—C28	120.53 (12)
C16—C17—H17	119.6	C26—C27—H27	119.7
C18—C17—H17	119.6	C28—C27—H27	119.7
C17—C18—C18A	120.40 (13)	C27—C28—C28A	120.72 (12)
C17—C18—H18	119.8	C27—C28—H28	119.6
C18A—C18—H18	119.8	C28A—C28—H28	119.6
C18—C18A—C14A	117.78 (12)	C28—C28A—C24A	117.83 (11)
C18—C18A—C19	124.48 (12)	C28—C28A—C29	124.36 (11)
C14A—C18A—C19	117.69 (11)	C24A—C28A—C29	117.81 (10)
C18A—C19—C191	114.75 (10)	C29A—C29—C28A	108.47 (10)
C18A—C19—C19A	107.07 (10)	C29A—C29—C291	115.68 (10)
C191—C19—C19A	114.52 (10)	C28A—C29—C291	113.64 (10)
C18A—C19—H19	106.6	C29A—C29—H29	106.1
C191—C19—H19	106.6	C28A—C29—H29	106.1
C19A—C19—H19	106.6	C291—C29—H29	106.1
C110—C19A—C114	118.32 (11)	C210—C29A—C214	118.33 (11)
C110—C19A—C19	120.78 (11)	C210—C29A—C29	121.93 (11)
C114—C19A—C19	120.83 (10)	C214—C29A—C29	119.74 (10)
C111—C110—C19A	122.16 (12)	C211—C210—C29A	122.29 (12)
C111—C110—H110	118.9	C211—C210—H210	118.9
C19A—C110—H110	118.9	C29A—C210—H210	118.9
C112—C111—C110	118.68 (11)	C212—C211—C210	118.26 (11)
C112—C111—C116	121.09 (12)	C212—C211—C216	120.09 (12)
C110—C111—C116	120.23 (12)	C210—C211—C216	121.64 (12)
C111—C112—C113	120.06 (12)	C213—C212—C211	120.30 (12)
C111—C112—H112	120.0	C213—C212—H212	119.9
C113—C112—H112	120.0	C211—C212—H212	119.9
C112—C113—C114	121.27 (12)	C212—C213—C214	121.30 (12)
C112—C113—H113	119.4	C212—C213—H213	119.3
C114—C113—H113	119.4	C214—C213—H213	119.3
C113—C114—C19A	119.49 (11)	C213—C214—C29A	119.47 (11)
C113—C114—C115	115.06 (11)	C213—C214—C215	114.60 (11)
C19A—C114—C115	125.39 (11)	C29A—C214—C215	125.82 (11)
N14—C115—C114	117.43 (10)	N24—C215—C214	118.07 (10)
N14—C115—S11	102.84 (8)	N24—C215—S21	103.46 (8)
C114—C115—S11	111.14 (8)	C214—C215—S21	109.44 (8)
N14—C115—H115	108.4	N24—C215—H215	108.5
C114—C115—H115	108.4	C214—C215—H215	108.5
S11—C115—H115	108.4	S21—C215—H215	108.5
C111—C116—H16A	109.5	C211—C216—H26A	109.5
C111—C116—H16B	109.5	C211—C216—H26B	109.5
H16A—C116—H16B	109.5	H26A—C216—H26B	109.5
C111—C116—H16C	109.5	C211—C216—H26C	109.5
H16A—C116—H16C	109.5	H26A—C216—H26C	109.5
H16B—C116—H16C	109.5	H26B—C216—H26C	109.5
C192—C191—C19	112.46 (10)	C292—C291—C29	110.95 (10)
C192—C191—H19A	109.1	C292—C291—H29A	109.4
C19—C191—H19A	109.1	C29—C291—H29A	109.4
C192—C191—H19B	109.1	C292—C291—H29B	109.4
C19—C191—H19B	109.1	C29—C291—H29B	109.4
H19A—C191—H19B	107.8	H29A—C291—H29B	108.0
C191—C192—H19C	109.5	C291—C292—H29C	109.5
C191—C192—H19D	109.5	C291—C292—H29D	109.5
H19C—C192—H19D	109.5	H29C—C292—H29D	109.5
C191—C192—H19E	109.5	C291—C292—H29E	109.5
H19C—C192—H19E	109.5	H29C—C292—H29E	109.5
H19D—C192—H19E	109.5	H29D—C292—H29E	109.5

C115—S11—C12—C13	−35.23 (10)	C215—S21—C22—C23	30.15 (10)
S11—C12—C13—O13	−154.57 (14)	S21—C22—C23—O23	158.58 (14)
S11—C12—C13—N14	25.70 (15)	S21—C22—C23—N24	−21.43 (15)
O13—C13—N14—C14A	−4.8 (2)	O23—C23—N24—C24A	1.3 (2)
C12—C13—N14—C14A	174.94 (13)	C22—C23—N24—C24A	−178.71 (12)
O13—C13—N14—C115	−177.78 (14)	O23—C23—N24—C215	177.26 (14)
C12—C13—N14—C115	1.96 (18)	C22—C23—N24—C215	−2.73 (17)
C13—N14—C14A—C15	−60.13 (19)	C23—N24—C24A—C25	61.92 (18)
C115—N14—C14A—C15	112.47 (15)	C215—N24—C24A—C25	−113.89 (13)
C13—N14—C14A—C18A	118.52 (14)	C23—N24—C24A—C28A	−115.71 (14)
C115—N14—C14A—C18A	−68.89 (17)	C215—N24—C24A—C28A	68.49 (16)
C18A—C14A—C15—C16	1.2 (2)	C28A—C24A—C25—C26	0.3 (2)
N14—C14A—C15—C16	179.83 (13)	N24—C24A—C25—C26	−177.25 (12)
C14A—C15—C16—C17	0.7 (2)	C24A—C25—C26—C27	−1.0 (2)
C15—C16—C17—C18	−1.8 (2)	C25—C26—C27—C28	0.4 (2)
C16—C17—C18—C18A	1.0 (2)	C26—C27—C28—C28A	0.9 (2)
C17—C18—C18A—C14A	0.90 (19)	C27—C28—C28A—C24A	−1.56 (19)
C17—C18—C18A—C19	178.15 (13)	C27—C28—C28A—C29	178.65 (12)
C15—C14A—C18A—C18	−2.03 (19)	C25—C24A—C28A—C28	1.00 (19)
N14—C14A—C18A—C18	179.36 (12)	N24—C24A—C28A—C28	178.58 (11)
C15—C14A—C18A—C19	−179.46 (12)	C25—C24A—C28A—C29	−179.20 (12)
N14—C14A—C18A—C19	1.92 (17)	N24—C24A—C28A—C29	−1.62 (17)
C18—C18A—C19—C191	23.65 (17)	C28—C28A—C29—C29A	106.61 (13)
C14A—C18A—C19—C191	−159.10 (11)	C24A—C28A—C29—C29A	−73.18 (13)
C18—C18A—C19—C19A	−104.63 (14)	C28—C28A—C29—C291	−23.55 (17)
C14A—C18A—C19—C19A	72.62 (13)	C24A—C28A—C29—C291	156.66 (11)
C18A—C19—C19A—C110	113.42 (12)	C28A—C29—C29A—C210	−117.02 (12)
C191—C19—C19A—C110	−15.00 (16)	C291—C29—C29A—C210	12.01 (16)
C18A—C19—C19A—C114	−63.48 (14)	C28A—C29—C29A—C214	62.82 (13)
C191—C19—C19A—C114	168.09 (11)	C291—C29—C29A—C214	−168.16 (10)
C114—C19A—C110—C111	−1.25 (18)	C214—C29A—C210—C211	1.41 (17)
C19—C19A—C110—C111	−178.23 (11)	C29—C29A—C210—C211	−178.75 (11)
C19A—C110—C111—C112	0.21 (19)	C29A—C210—C211—C212	−2.46 (18)
C19A—C110—C111—C116	−179.52 (12)	C29A—C210—C211—C216	176.74 (11)
C110—C111—C112—C113	1.25 (19)	C210—C211—C212—C213	1.27 (18)
C116—C111—C112—C113	−179.02 (13)	C216—C211—C212—C213	−177.94 (12)
C111—C112—C113—C114	−1.7 (2)	C211—C212—C213—C214	0.92 (18)
C112—C113—C114—C19A	0.62 (19)	C212—C213—C214—C29A	−1.98 (18)
C112—C113—C114—C115	−176.88 (12)	C212—C213—C214—C215	174.33 (11)
C110—C19A—C114—C113	0.82 (18)	C210—C29A—C214—C213	0.81 (16)
C19—C19A—C114—C113	177.80 (11)	C29—C29A—C214—C213	−179.03 (11)
C110—C19A—C114—C115	178.04 (11)	C210—C29A—C214—C215	−175.05 (11)
C19—C19A—C114—C115	−4.98 (19)	C29—C29A—C214—C215	5.11 (17)
C13—N14—C115—C114	−150.37 (12)	C23—N24—C215—C214	146.00 (12)
C14A—N14—C115—C114	36.66 (18)	C24A—N24—C215—C214	−38.03 (17)
C13—N14—C115—S11	−28.03 (14)	C23—N24—C215—S21	24.98 (13)
C14A—N14—C115—S11	159.00 (11)	C24A—N24—C215—S21	−159.05 (10)
C113—C114—C115—N14	−158.47 (12)	C213—C214—C215—N24	161.04 (10)
C19A—C114—C115—N14	24.20 (18)	C29A—C214—C215—N24	−22.92 (17)
C113—C114—C115—S11	83.55 (12)	C213—C214—C215—S21	−81.06 (12)
C19A—C114—C115—S11	−93.77 (13)	C29A—C214—C215—S21	94.98 (12)
C12—S11—C115—N14	35.54 (9)	C22—S21—C215—N24	−30.96 (9)
C12—S11—C115—C114	162.03 (10)	C22—S21—C215—C214	−157.65 (10)
C18A—C19—C191—C192	66.55 (14)	C29A—C29—C291—C292	170.60 (10)
C19A—C19—C191—C192	−169.01 (11)	C28A—C29—C291—C292	−62.94 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C115—H115···O13ⁱ	1.00	2.47	3.3084 (18)	141
C215—H215···O23ⁱⁱ	1.00	2.37	3.1681 (18)	136
C112—H112···Cg1ⁱⁱⁱ	0.95	2.81	3.6738 (13)	152
C113—H113···Cg2ⁱⁱⁱ	0.95	2.85	3.7676 (14)	163

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

(II) (9RS,15RS)-9-Ethyl-7,12-dimethyl-9,13b-dihydrodibenzo[c,f]thiazolo[3,2-a]azepin-3(2H)-one top

Crystal data top

C₂₀H₂₁NOS	F(000) = 1376
M_r = 323.44	D_x = 1.297 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.1021 (12) Å	Cell parameters from 3402 reflections
b = 12.4436 (8) Å	θ = 2.0–26.4°
c = 14.8429 (9) Å	µ = 0.20 mm⁻¹
β = 97.645 (3)°	T = 298 K
V = 3313.7 (4) Å³	Block, colourless
Z = 8	0.23 × 0.22 × 0.20 mm

Data collection top

Bruker Kappa APEXII diffractometer	2307 reflections with I > 2σ(I)
Radiation source: high brilliance microfocus sealed tube	R_int = 0.048
φ and ω scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −22→22
T_min = 0.818, T_max = 0.961	k = −15→13
30952 measured reflections	l = −14→18
3402 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.168	w = 1/[σ²(F_o²) + (0.070P)² + 4.8478P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3402 reflections	Δρ_max = 0.57 e Å⁻³
211 parameters	Δρ_min = −0.45 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.40943 (5)	0.29645 (9)	0.65893 (6)	0.0801 (4)
C2	0.32187 (17)	0.2270 (3)	0.6390 (2)	0.0610 (8)
H2A	0.3186	0.1744	0.6866	0.073*
H2B	0.2811	0.2776	0.6391	0.073*
C3	0.31728 (16)	0.1719 (2)	0.5480 (2)	0.0524 (7)
O3	0.26206 (12)	0.12615 (19)	0.51154 (16)	0.0669 (6)
N4	0.38267 (12)	0.18081 (18)	0.51161 (15)	0.0466 (6)
C4A	0.38797 (15)	0.1538 (2)	0.41955 (18)	0.0453 (6)
C5	0.37768 (18)	0.0494 (2)	0.3880 (2)	0.0589 (8)
H5	0.3673	−0.0052	0.4272	0.071*
C6	0.38296 (18)	0.0273 (2)	0.2984 (2)	0.0612 (8)
H6	0.3754	−0.0429	0.2775	0.073*
C7	0.39919 (15)	0.1061 (2)	0.23845 (19)	0.0488 (7)
C8	0.40901 (14)	0.2104 (2)	0.27151 (17)	0.0421 (6)
H8	0.4194	0.2648	0.2320	0.051*
C8A	0.40380 (13)	0.23624 (19)	0.36146 (17)	0.0392 (6)
C9	0.41873 (14)	0.34878 (19)	0.40082 (17)	0.0403 (6)
H9	0.3821	0.3619	0.4427	0.048*
C9A	0.49525 (14)	0.34356 (19)	0.45798 (17)	0.0405 (6)
C10	0.55658 (16)	0.4003 (2)	0.43479 (19)	0.0486 (7)
H170	0.5497	0.4480	0.3862	0.058*
C11	0.62705 (16)	0.3875 (3)	0.4820 (2)	0.0571 (8)
H11	0.6664	0.4268	0.4645	0.069*
C12	0.64037 (16)	0.3175 (3)	0.5547 (2)	0.0548 (8)
C13	0.57916 (15)	0.2630 (2)	0.57933 (19)	0.0494 (7)
H13	0.5863	0.2162	0.6286	0.059*
C14	0.50769 (14)	0.2758 (2)	0.53333 (17)	0.0425 (6)
C15	0.44750 (15)	0.2154 (2)	0.57304 (18)	0.0484 (7)
H15	0.4703	0.1512	0.6034	0.058*
C71	0.40746 (18)	0.0815 (3)	0.1414 (2)	0.0613 (8)
H71A	0.3721	0.0272	0.1187	0.092*
H71B	0.4571	0.0560	0.1379	0.092*
H71C	0.3985	0.1455	0.1055	0.092*
C91	0.40972 (15)	0.4383 (2)	0.33031 (18)	0.0475 (7)
H91A	0.4249	0.5058	0.3598	0.057*
H91B	0.4426	0.4243	0.2851	0.057*
C92	0.33049 (18)	0.4491 (3)	0.2831 (2)	0.0630 (8)
H92A	0.3276	0.5085	0.2415	0.095*
H92B	0.2975	0.4614	0.3276	0.095*
H92C	0.3162	0.3842	0.2503	0.095*
C121	0.71688 (18)	0.3000 (3)	0.6059 (3)	0.0804 (11)
H12A	0.7308	0.2260	0.6009	0.121*
H12B	0.7166	0.3179	0.6687	0.121*
H12C	0.7521	0.3449	0.5807	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0711 (6)	0.1163 (8)	0.0586 (5)	−0.0213 (5)	0.0302 (4)	−0.0193 (5)
C2	0.0511 (17)	0.081 (2)	0.0540 (17)	0.0063 (16)	0.0195 (14)	0.0199 (16)
C3	0.0453 (16)	0.0565 (17)	0.0574 (17)	0.0010 (14)	0.0140 (13)	0.0231 (14)
O3	0.0440 (12)	0.0749 (15)	0.0830 (15)	−0.0105 (11)	0.0124 (11)	0.0168 (12)
N4	0.0427 (13)	0.0499 (13)	0.0489 (13)	−0.0057 (10)	0.0120 (10)	0.0065 (10)
C4A	0.0408 (14)	0.0438 (14)	0.0523 (15)	−0.0048 (11)	0.0094 (12)	0.0030 (12)
C5	0.067 (2)	0.0446 (16)	0.0644 (19)	−0.0152 (14)	0.0072 (15)	0.0090 (14)
C6	0.073 (2)	0.0397 (15)	0.068 (2)	−0.0096 (14)	−0.0006 (16)	−0.0059 (14)
C7	0.0444 (15)	0.0468 (15)	0.0538 (16)	0.0003 (12)	0.0012 (12)	−0.0047 (13)
C8	0.0377 (14)	0.0407 (14)	0.0488 (15)	−0.0003 (11)	0.0090 (11)	0.0026 (12)
C8A	0.0317 (12)	0.0362 (13)	0.0509 (15)	−0.0005 (10)	0.0099 (11)	0.0021 (11)
C9	0.0430 (14)	0.0376 (13)	0.0441 (14)	0.0001 (11)	0.0192 (11)	−0.0010 (11)
C9A	0.0410 (14)	0.0358 (13)	0.0474 (15)	−0.0020 (11)	0.0159 (11)	−0.0077 (11)
C10	0.0544 (17)	0.0455 (15)	0.0497 (15)	−0.0087 (13)	0.0211 (13)	−0.0082 (12)
C11	0.0441 (17)	0.0680 (19)	0.0632 (19)	−0.0156 (14)	0.0218 (14)	−0.0191 (16)
C12	0.0428 (16)	0.0672 (19)	0.0559 (17)	−0.0022 (13)	0.0125 (13)	−0.0187 (15)
C13	0.0475 (16)	0.0523 (16)	0.0488 (15)	0.0031 (13)	0.0084 (13)	−0.0083 (13)
C14	0.0425 (15)	0.0416 (14)	0.0456 (14)	−0.0004 (11)	0.0145 (12)	−0.0058 (11)
C15	0.0471 (16)	0.0520 (16)	0.0470 (15)	−0.0037 (13)	0.0097 (12)	0.0064 (13)
C71	0.064 (2)	0.0570 (18)	0.0623 (19)	0.0020 (15)	0.0050 (15)	−0.0142 (15)
C91	0.0530 (16)	0.0403 (14)	0.0530 (16)	0.0013 (12)	0.0208 (13)	0.0024 (12)
C92	0.063 (2)	0.0562 (18)	0.071 (2)	0.0113 (15)	0.0147 (16)	0.0179 (15)
C121	0.0466 (19)	0.111 (3)	0.082 (2)	−0.0024 (19)	0.0051 (17)	−0.022 (2)

Geometric parameters (Å, º) top

S1—C2	1.795 (3)	C9A—C10	1.397 (4)
S1—C15	1.831 (3)	C10—C11	1.381 (4)
C2—C3	1.508 (4)	C10—H170	0.9300
C2—H2A	0.9700	C11—C12	1.382 (4)
C2—H2B	0.9700	C11—H11	0.9300
C3—O3	1.214 (4)	C12—C13	1.389 (4)
C3—N4	1.369 (3)	C12—C121	1.504 (4)
N4—C4A	1.423 (3)	C13—C14	1.389 (4)
N4—C15	1.452 (3)	C13—H13	0.9300
C4A—C5	1.385 (4)	C14—C15	1.507 (4)
C4A—C8A	1.394 (3)	C15—H15	0.9800
C5—C6	1.374 (4)	C71—H71A	0.9600
C5—H5	0.9300	C71—H71B	0.9600
C6—C7	1.382 (4)	C71—H71C	0.9600
C6—H6	0.9300	C91—C92	1.516 (4)
C7—C8	1.391 (4)	C91—H91A	0.9700
C7—C71	1.499 (4)	C91—H91B	0.9700
C8—C8A	1.389 (3)	C92—H92A	0.9600
C8—H8	0.9300	C92—H92B	0.9600
C8A—C9	1.528 (3)	C92—H92C	0.9600
C9—C91	1.522 (3)	C121—H12A	0.9600
C9—C9A	1.527 (4)	C121—H12B	0.9600
C9—H9	0.9800	C121—H12C	0.9600
C9A—C14	1.395 (4)

C2—S1—C15	91.50 (14)	C10—C11—C12	121.5 (3)
C3—C2—S1	107.97 (19)	C10—C11—H11	119.3
C3—C2—H2A	110.1	C12—C11—H11	119.3
S1—C2—H2A	110.1	C11—C12—C13	116.8 (3)
C3—C2—H2B	110.1	C11—C12—C121	122.6 (3)
S1—C2—H2B	110.1	C13—C12—C121	120.6 (3)
H2A—C2—H2B	108.4	C12—C13—C14	122.6 (3)
O3—C3—N4	124.5 (3)	C12—C13—H13	118.7
O3—C3—C2	123.8 (3)	C14—C13—H13	118.7
N4—C3—C2	111.7 (3)	C13—C14—C9A	120.2 (2)
C3—N4—C4A	122.1 (2)	C13—C14—C15	115.2 (2)
C3—N4—C15	116.4 (2)	C9A—C14—C15	124.6 (2)
C4A—N4—C15	121.4 (2)	N4—C15—C14	117.9 (2)
C5—C4A—C8A	120.7 (3)	N4—C15—S1	104.64 (18)
C5—C4A—N4	121.5 (2)	C14—C15—S1	110.88 (19)
C8A—C4A—N4	117.8 (2)	N4—C15—H15	107.7
C6—C5—C4A	119.5 (3)	C14—C15—H15	107.7
C6—C5—H5	120.3	S1—C15—H15	107.7
C4A—C5—H5	120.3	C7—C71—H71A	109.5
C5—C6—C7	121.9 (3)	C7—C71—H71B	109.5
C5—C6—H6	119.0	H71A—C71—H71B	109.5
C7—C6—H6	119.0	C7—C71—H71C	109.5
C6—C7—C8	117.6 (3)	H71A—C71—H71C	109.5
C6—C7—C71	122.0 (3)	H71B—C71—H71C	109.5
C8—C7—C71	120.3 (3)	C92—C91—C9	113.0 (2)
C8A—C8—C7	122.2 (2)	C92—C91—H91A	109.0
C8A—C8—H8	118.9	C9—C91—H91A	109.0
C7—C8—H8	118.9	C92—C91—H91B	109.0
C8—C8A—C4A	118.1 (2)	C9—C91—H91B	109.0
C8—C8A—C9	123.3 (2)	H91A—C91—H91B	107.8
C4A—C8A—C9	118.6 (2)	C91—C92—H92A	109.5
C91—C9—C9A	114.8 (2)	C91—C92—H92B	109.5
C91—C9—C8A	114.2 (2)	H92A—C92—H92B	109.5
C9A—C9—C8A	106.0 (2)	C91—C92—H92C	109.5
C91—C9—H9	107.1	H92A—C92—H92C	109.5
C9A—C9—H9	107.1	H92B—C92—H92C	109.5
C8A—C9—H9	107.1	C12—C121—H12A	109.5
C14—C9A—C10	117.0 (2)	C12—C121—H12B	109.5
C14—C9A—C9	120.6 (2)	H12A—C121—H12B	109.5
C10—C9A—C9	122.3 (2)	C12—C121—H12C	109.5
C11—C10—C9A	121.9 (3)	H12A—C121—H12C	109.5
C11—C10—H170	119.1	H12B—C121—H12C	109.5
C9A—C10—H170	119.1

C15—S1—C2—C3	−18.5 (2)	C8A—C9—C9A—C14	−62.2 (3)
S1—C2—C3—O3	−173.3 (2)	C91—C9—C9A—C10	−13.3 (3)
S1—C2—C3—N4	6.3 (3)	C8A—C9—C9A—C10	113.8 (2)
O3—C3—N4—C4A	11.8 (4)	C14—C9A—C10—C11	2.2 (4)
C2—C3—N4—C4A	−167.8 (2)	C9—C9A—C10—C11	−173.9 (2)
O3—C3—N4—C15	−165.9 (3)	C9A—C10—C11—C12	0.1 (4)
C2—C3—N4—C15	14.6 (3)	C10—C11—C12—C13	−1.7 (4)
C3—N4—C4A—C5	−65.0 (4)	C10—C11—C12—C121	178.5 (3)
C15—N4—C4A—C5	112.5 (3)	C11—C12—C13—C14	0.9 (4)
C3—N4—C4A—C8A	114.9 (3)	C121—C12—C13—C14	−179.2 (3)
C15—N4—C4A—C8A	−67.6 (3)	C12—C13—C14—C9A	1.4 (4)
C8A—C4A—C5—C6	−0.2 (4)	C12—C13—C14—C15	−176.5 (2)
N4—C4A—C5—C6	179.7 (3)	C10—C9A—C14—C13	−2.9 (3)
C4A—C5—C6—C7	0.8 (5)	C9—C9A—C14—C13	173.3 (2)
C5—C6—C7—C8	−1.0 (4)	C10—C9A—C14—C15	174.8 (2)
C5—C6—C7—C71	178.0 (3)	C9—C9A—C14—C15	−9.0 (4)
C6—C7—C8—C8A	0.7 (4)	C3—N4—C15—C14	−151.3 (2)
C71—C7—C8—C8A	−178.3 (3)	C4A—N4—C15—C14	31.0 (4)
C7—C8—C8A—C4A	−0.2 (4)	C3—N4—C15—S1	−27.6 (3)
C7—C8—C8A—C9	176.4 (2)	C4A—N4—C15—S1	154.7 (2)
C5—C4A—C8A—C8	−0.1 (4)	C13—C14—C15—N4	−150.7 (2)
N4—C4A—C8A—C8	−180.0 (2)	C9A—C14—C15—N4	31.5 (4)
C5—C4A—C8A—C9	−176.8 (2)	C13—C14—C15—S1	88.7 (3)
N4—C4A—C8A—C9	3.3 (4)	C9A—C14—C15—S1	−89.0 (3)
C8—C8A—C9—C91	22.9 (3)	C2—S1—C15—N4	25.27 (19)
C4A—C8A—C9—C91	−160.6 (2)	C2—S1—C15—C14	153.4 (2)
C8—C8A—C9—C9A	−104.5 (3)	C9A—C9—C91—C92	−173.0 (2)
C4A—C8A—C9—C9A	72.0 (3)	C8A—C9—C91—C92	64.3 (3)
C91—C9—C9A—C14	170.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O3ⁱ	0.97	2.57	3.120 (4)	116
C91—H91A···Cg3ⁱⁱ	0.97	2.82	3.736 (3)	157

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

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

Crystal data top

C₂₂H₂₀ClNO₃	Z = 2
M_r = 381.84	F(000) = 400
Triclinic, P1	D_x = 1.394 Mg m⁻³
a = 6.8533 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.612 (5) Å	Cell parameters from 4176 reflections
c = 13.561 (3) Å	θ = 2.9–27.5°
α = 72.45 (4)°	µ = 0.23 mm⁻¹
β = 75.840 (19)°	T = 120 K
γ = 82.46 (2)°	Needle, colourless
V = 910.0 (6) Å³	0.26 × 0.15 × 0.13 mm

Data collection top

Nonius KappaCCD diffractometer	3776 independent reflections
Radiation source: fine focus sealed tube	2195 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.154
φ and ω scans	θ_max = 26.6°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
T_min = 0.845, T_max = 0.970	k = −13→13
20183 measured reflections	l = −16→17

Refinement top

Refinement on F²	74 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0192P)² + 1.1423P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3776 reflections	Δρ_max = 0.29 e Å⁻³
322 parameters	Δρ_min = −0.31 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C11	0.8032 (8)	0.3061 (4)	0.6534 (3)	0.0131 (8)	0.900 (6)
H11	0.8219	0.2338	0.7126	0.016*	0.900 (6)
C12	0.8306 (11)	0.2830 (4)	0.5549 (3)	0.0131 (8)	0.900 (6)
Cl12	0.9006 (7)	0.1222 (2)	0.5455 (3)	0.0224 (4)	0.900 (6)
C13	0.8071 (8)	0.3838 (4)	0.4674 (3)	0.0134 (10)	0.900 (6)
H13	0.8313	0.3677	0.4001	0.016*	0.900 (6)
C13A	0.7467 (12)	0.5117 (5)	0.4780 (3)	0.0138 (10)	0.900 (6)
C14	0.7273 (10)	0.6182 (5)	0.3794 (3)	0.0128 (11)	0.900 (6)
O14	0.750 (2)	0.5900 (6)	0.2952 (3)	0.0201 (10)	0.900 (6)
C15	0.675 (2)	0.7488 (5)	0.3946 (4)	0.0154 (9)	0.900 (6)
C16	0.623 (2)	0.7619 (4)	0.4956 (4)	0.0146 (12)	0.900 (6)
H16	0.5786	0.8476	0.5036	0.018*	0.900 (6)
N17	0.6312 (15)	0.6629 (4)	0.5838 (3)	0.0129 (7)	0.900 (6)
C18	0.5458 (9)	0.6900 (5)	0.6874 (4)	0.0151 (8)	0.900 (6)
H18A	0.4500	0.6222	0.7318	0.018*	0.900 (6)
H18B	0.4708	0.7777	0.6761	0.018*	0.900 (6)
C18A	0.7098 (10)	0.6883 (4)	0.7436 (5)	0.0147 (9)	0.900 (6)
C19	0.7676 (9)	0.8073 (4)	0.7489 (6)	0.0198 (14)	0.900 (6)
H19	0.6997	0.8888	0.7191	0.024*	0.900 (6)
C110	0.9232 (11)	0.8066 (5)	0.7972 (7)	0.0250 (13)	0.900 (6)
H110	0.9668	0.8877	0.7979	0.030*	0.900 (6)
C111	1.0156 (8)	0.6872 (5)	0.8449 (5)	0.0244 (12)	0.900 (6)
H111	1.1171	0.6862	0.8819	0.029*	0.900 (6)
C112	0.9603 (7)	0.5682 (5)	0.8387 (4)	0.0201 (11)	0.900 (6)
H112	1.0274	0.4871	0.8697	0.024*	0.900 (6)
C12A	0.8079 (6)	0.5675 (4)	0.7876 (3)	0.0155 (10)	0.900 (6)
C113	0.7482 (7)	0.4385 (4)	0.7797 (3)	0.0164 (9)	0.900 (6)
H113	0.8579	0.3720	0.8023	0.020*	0.900 (6)
C13C	0.7491 (7)	0.4319 (4)	0.6683 (3)	0.0132 (10)	0.900 (6)
C131	0.5547 (6)	0.3870 (4)	0.8619 (3)	0.0206 (10)	0.900 (6)
H13A	0.4468	0.4590	0.8571	0.025*	0.900 (6)
H13B	0.5095	0.3134	0.8439	0.025*	0.900 (6)
C132	0.5838 (8)	0.3386 (6)	0.9751 (3)	0.0223 (14)	0.900 (6)
H13C	0.6297	0.4106	0.9935	0.033*	0.900 (6)
H13D	0.6849	0.2638	0.9816	0.033*	0.900 (6)
H13E	0.4556	0.3101	1.0234	0.033*	0.900 (6)
C13B	0.7097 (12)	0.5356 (5)	0.5784 (3)	0.0137 (11)	0.900 (6)
C151	0.662 (2)	0.8739 (5)	0.3103 (4)	0.0181 (9)	0.900 (6)
O151	0.6227 (17)	0.9825 (6)	0.3249 (5)	0.0256 (15)	0.900 (6)
O152	0.707 (4)	0.8574 (8)	0.2120 (4)	0.0237 (10)	0.900 (6)
C152	0.6960 (10)	0.9782 (7)	0.1264 (4)	0.0234 (16)	0.900 (6)
H15A	0.7887	1.0424	0.1262	0.028*	0.900 (6)
H15B	0.5571	1.0197	0.1342	0.028*	0.900 (6)
C153	0.757 (3)	0.9364 (13)	0.0249 (5)	0.029 (2)	0.900 (6)
H15C	0.7525	1.0143	−0.0359	0.043*	0.900 (6)
H15D	0.8948	0.8953	0.0186	0.043*	0.900 (6)
H15E	0.6645	0.8727	0.0265	0.043*	0.900 (6)
C21	0.822 (8)	0.330 (3)	0.645 (2)	0.0131 (8)	0.100 (6)
H21	0.8866	0.2706	0.6970	0.016*	0.100 (6)
C22	0.844 (11)	0.307 (2)	0.546 (2)	0.0131 (8)	0.100 (6)
Cl22	0.889 (7)	0.146 (2)	0.536 (3)	0.0224 (4)	0.100 (6)
C23	0.830 (9)	0.410 (3)	0.459 (2)	0.0134 (10)	0.100 (6)
H23	0.8925	0.4039	0.3896	0.016*	0.100 (6)
C23A	0.720 (12)	0.527 (3)	0.474 (2)	0.0138 (10)	0.100 (6)
C24	0.694 (12)	0.634 (4)	0.377 (2)	0.0128 (11)	0.100 (6)
O24	0.73 (2)	0.607 (5)	0.291 (3)	0.0201 (10)	0.100 (6)
C25	0.68 (2)	0.766 (3)	0.390 (3)	0.0154 (9)	0.100 (6)
C26	0.64 (2)	0.780 (3)	0.490 (3)	0.0146 (12)	0.100 (6)
H26	0.6103	0.8675	0.4974	0.018*	0.100 (6)
N27	0.630 (14)	0.680 (3)	0.579 (2)	0.0129 (7)	0.100 (6)
C28	0.536 (7)	0.710 (4)	0.681 (3)	0.0151 (8)	0.100 (6)
H28A	0.4242	0.6517	0.7199	0.018*	0.100 (6)
H28B	0.4789	0.8031	0.6667	0.018*	0.100 (6)
C28A	0.689 (9)	0.691 (2)	0.748 (5)	0.0147 (9)	0.100 (6)
C29	0.800 (10)	0.797 (3)	0.739 (6)	0.0198 (14)	0.100 (6)
H29	0.7762	0.8816	0.6922	0.024*	0.100 (6)
C210	0.945 (11)	0.778 (4)	0.798 (7)	0.0250 (13)	0.100 (6)
H210	0.9976	0.8513	0.8064	0.030*	0.100 (6)
C211	1.013 (8)	0.650 (5)	0.844 (6)	0.0244 (12)	0.100 (6)
H211	1.1323	0.6345	0.8710	0.029*	0.100 (6)
C212	0.908 (7)	0.543 (4)	0.850 (4)	0.0201 (11)	0.100 (6)
H212	0.9427	0.4563	0.8910	0.024*	0.100 (6)
C22A	0.752 (6)	0.561 (2)	0.798 (3)	0.0155 (10)	0.100 (6)
C213	0.664 (5)	0.446 (2)	0.7812 (17)	0.0164 (9)	0.100 (6)
H223	0.5160	0.4694	0.7970	0.020*	0.100 (6)
C23C	0.704 (8)	0.441 (3)	0.6666 (17)	0.0132 (10)	0.100 (6)
C231	0.684 (5)	0.314 (2)	0.8666 (19)	0.0206 (10)	0.100 (6)
H23A	0.5920	0.2518	0.8633	0.025*	0.100 (6)
H23B	0.8238	0.2748	0.8512	0.025*	0.100 (6)
C232	0.636 (11)	0.330 (5)	0.9781 (19)	0.0223 (14)	0.100 (6)
H23C	0.6340	0.2425	1.0298	0.033*	0.100 (6)
H23D	0.5043	0.3775	0.9910	0.033*	0.100 (6)
H23E	0.7398	0.3803	0.9851	0.033*	0.100 (6)
C23B	0.679 (13)	0.549 (3)	0.576 (2)	0.0137 (11)	0.100 (6)
C251	0.66 (2)	0.891 (4)	0.305 (3)	0.0181 (9)	0.100 (6)
O251	0.592 (18)	0.996 (5)	0.320 (5)	0.0256 (15)	0.100 (6)
O252	0.70 (4)	0.871 (7)	0.208 (4)	0.0237 (10)	0.100 (6)
C252	0.649 (14)	0.985 (7)	0.124 (4)	0.0234 (16)	0.100 (6)
H25A	0.7156	1.0637	0.1225	0.028*	0.100 (6)
H25B	0.5016	1.0068	0.1354	0.028*	0.100 (6)
C253	0.73 (3)	0.947 (12)	0.022 (4)	0.029 (2)	0.100 (6)
H25C	0.7002	1.0204	−0.0378	0.043*	0.100 (6)
H25D	0.8737	0.9256	0.0125	0.043*	0.100 (6)
H25E	0.6609	0.8689	0.0254	0.043*	0.100 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.0130 (16)	0.0069 (15)	0.0188 (14)	−0.0051 (16)	−0.0023 (12)	−0.0017 (11)
C12	0.0130 (16)	0.0069 (15)	0.0188 (14)	−0.0051 (16)	−0.0023 (12)	−0.0017 (11)
Cl12	0.0303 (8)	0.0107 (10)	0.0255 (9)	0.0016 (10)	−0.0043 (6)	−0.0069 (9)
C13	0.008 (2)	0.017 (2)	0.0168 (19)	−0.0060 (19)	0.0014 (15)	−0.0073 (16)
C13A	0.010 (3)	0.016 (2)	0.0157 (18)	−0.0007 (16)	−0.0053 (14)	−0.0035 (15)
C14	0.008 (4)	0.018 (2)	0.0136 (17)	0.0013 (16)	−0.0052 (14)	−0.0046 (15)
O14	0.024 (3)	0.021 (2)	0.0164 (13)	0.003 (3)	−0.0057 (12)	−0.0078 (13)
C15	0.0154 (19)	0.017 (2)	0.0115 (17)	0.000 (3)	−0.0043 (16)	−0.0001 (15)
C16	0.015 (3)	0.012 (2)	0.0172 (18)	−0.001 (3)	−0.0053 (17)	−0.0032 (16)
N17	0.0182 (16)	0.0090 (18)	0.0106 (14)	0.0009 (19)	−0.0040 (13)	−0.0014 (12)
C18	0.0159 (19)	0.017 (2)	0.0121 (18)	0.0032 (17)	−0.0020 (14)	−0.0060 (17)
C18A	0.014 (2)	0.0192 (18)	0.0096 (17)	0.0003 (14)	0.0009 (17)	−0.0049 (14)
C19	0.026 (3)	0.0171 (19)	0.015 (3)	−0.0041 (18)	0.001 (2)	−0.0049 (17)
C110	0.028 (3)	0.026 (3)	0.024 (2)	−0.010 (3)	−0.006 (2)	−0.009 (3)
C111	0.020 (2)	0.036 (3)	0.025 (2)	−0.007 (2)	−0.0062 (17)	−0.018 (3)
C112	0.013 (3)	0.027 (3)	0.018 (2)	0.0031 (19)	−0.002 (2)	−0.0055 (19)
C12A	0.015 (3)	0.0191 (18)	0.0097 (18)	−0.0027 (16)	0.0046 (19)	−0.0055 (15)
C113	0.020 (2)	0.0177 (19)	0.0114 (18)	0.0014 (17)	−0.0055 (17)	−0.0029 (14)
C13C	0.012 (3)	0.0152 (18)	0.0138 (17)	−0.0004 (15)	−0.0044 (15)	−0.0042 (14)
C131	0.026 (2)	0.018 (2)	0.017 (2)	−0.0053 (17)	−0.0030 (17)	−0.0037 (17)
C132	0.027 (4)	0.022 (2)	0.0172 (19)	0.000 (2)	−0.0055 (18)	−0.0029 (16)
C13B	0.008 (4)	0.0157 (19)	0.0180 (17)	−0.0012 (15)	−0.0036 (15)	−0.0046 (15)
C151	0.0148 (18)	0.021 (2)	0.0184 (19)	−0.004 (3)	−0.0043 (17)	−0.0037 (17)
O151	0.040 (5)	0.0151 (18)	0.0198 (15)	0.0079 (17)	−0.0102 (16)	−0.0028 (14)
O152	0.039 (4)	0.018 (2)	0.0124 (13)	−0.001 (3)	−0.0069 (15)	−0.0001 (13)
C152	0.030 (5)	0.021 (2)	0.0154 (18)	0.000 (3)	−0.008 (2)	0.0024 (16)
C153	0.039 (7)	0.030 (3)	0.0157 (19)	−0.016 (3)	−0.0037 (18)	0.0014 (18)
C21	0.0130 (16)	0.0069 (15)	0.0188 (14)	−0.0051 (16)	−0.0023 (12)	−0.0017 (11)
C22	0.0130 (16)	0.0069 (15)	0.0188 (14)	−0.0051 (16)	−0.0023 (12)	−0.0017 (11)
Cl22	0.0303 (8)	0.0107 (10)	0.0255 (9)	0.0016 (10)	−0.0043 (6)	−0.0069 (9)
C23	0.008 (2)	0.017 (2)	0.0168 (19)	−0.0060 (19)	0.0014 (15)	−0.0073 (16)
C23A	0.010 (3)	0.016 (2)	0.0157 (18)	−0.0007 (16)	−0.0053 (14)	−0.0035 (15)
C24	0.008 (4)	0.018 (2)	0.0136 (17)	0.0013 (16)	−0.0052 (14)	−0.0046 (15)
O24	0.024 (3)	0.021 (2)	0.0164 (13)	0.003 (3)	−0.0057 (12)	−0.0078 (13)
C25	0.0154 (19)	0.017 (2)	0.0115 (17)	0.000 (3)	−0.0043 (16)	−0.0001 (15)
C26	0.015 (3)	0.012 (2)	0.0172 (18)	−0.001 (3)	−0.0053 (17)	−0.0032 (16)
N27	0.0182 (16)	0.0090 (18)	0.0106 (14)	0.0009 (19)	−0.0040 (13)	−0.0014 (12)
C28	0.0159 (19)	0.017 (2)	0.0121 (18)	0.0032 (17)	−0.0020 (14)	−0.0060 (17)
C28A	0.014 (2)	0.0192 (18)	0.0096 (17)	0.0003 (14)	0.0009 (17)	−0.0049 (14)
C29	0.026 (3)	0.0171 (19)	0.015 (3)	−0.0041 (18)	0.001 (2)	−0.0049 (17)
C210	0.028 (3)	0.026 (3)	0.024 (2)	−0.010 (3)	−0.006 (2)	−0.009 (3)
C211	0.020 (2)	0.036 (3)	0.025 (2)	−0.007 (2)	−0.0062 (17)	−0.018 (3)
C212	0.013 (3)	0.027 (3)	0.018 (2)	0.0031 (19)	−0.002 (2)	−0.0055 (19)
C22A	0.015 (3)	0.0191 (18)	0.0097 (18)	−0.0027 (16)	0.0046 (19)	−0.0055 (15)
C213	0.020 (2)	0.0177 (19)	0.0114 (18)	0.0014 (17)	−0.0055 (17)	−0.0029 (14)
C23C	0.012 (3)	0.0152 (18)	0.0138 (17)	−0.0004 (15)	−0.0044 (15)	−0.0042 (14)
C231	0.026 (2)	0.018 (2)	0.017 (2)	−0.0053 (17)	−0.0030 (17)	−0.0037 (17)
C232	0.027 (4)	0.022 (2)	0.0172 (19)	0.000 (2)	−0.0055 (18)	−0.0029 (16)
C23B	0.008 (4)	0.0157 (19)	0.0180 (17)	−0.0012 (15)	−0.0036 (15)	−0.0046 (15)
C251	0.0148 (18)	0.021 (2)	0.0184 (19)	−0.004 (3)	−0.0043 (17)	−0.0037 (17)
O251	0.040 (5)	0.0151 (18)	0.0198 (15)	0.0079 (17)	−0.0102 (16)	−0.0028 (14)
O252	0.039 (4)	0.018 (2)	0.0124 (13)	−0.001 (3)	−0.0069 (15)	−0.0001 (13)
C252	0.030 (5)	0.021 (2)	0.0154 (18)	0.000 (3)	−0.008 (2)	0.0024 (16)
C253	0.039 (7)	0.030 (3)	0.0157 (19)	−0.016 (3)	−0.0037 (18)	0.0014 (18)

Geometric parameters (Å, º) top

C11—C12	1.393 (5)	C21—C23C	1.401 (11)
C11—C13C	1.399 (5)	C21—C22	1.402 (10)
C11—H11	0.9500	C21—H21	0.9500
C12—C13	1.364 (5)	C22—C23	1.364 (10)
C12—Cl12	1.746 (4)	C22—Cl22	1.740 (10)
C13—C13A	1.405 (5)	C23—C23A	1.406 (11)
C13—H13	0.9500	C23—H23	0.9500
C13A—C13B	1.416 (5)	C23A—C23B	1.417 (9)
C13A—C14	1.489 (5)	C23A—C24	1.490 (10)
C14—O14	1.236 (4)	C24—O24	1.239 (10)
C14—C15	1.448 (5)	C24—C25	1.450 (11)
C15—C16	1.374 (5)	C25—C26	1.374 (10)
C15—C151	1.477 (5)	C25—C251	1.478 (10)
C16—N17	1.340 (5)	C26—N27	1.341 (9)
C16—H16	0.9500	C26—H26	0.9500
N17—C13B	1.403 (4)	N27—C23B	1.403 (10)
N17—C18	1.482 (4)	N27—C28	1.484 (10)
C18—C18A	1.500 (5)	C28—C28A	1.502 (10)
C18—H18A	0.9900	C28—H28A	0.9900
C18—H18B	0.9900	C28—H28B	0.9900
C18A—C19	1.399 (5)	C28A—C29	1.400 (11)
C18A—C12A	1.400 (5)	C28A—C22A	1.405 (9)
C19—C110	1.380 (5)	C29—C210	1.381 (10)
C19—H19	0.9500	C29—H29	0.9500
C110—C111	1.386 (6)	C210—C211	1.387 (11)
C110—H110	0.9500	C210—H210	0.9500
C111—C112	1.396 (6)	C211—C212	1.396 (11)
C111—H111	0.9500	C211—H211	0.9500
C112—C12A	1.389 (5)	C212—C22A	1.387 (10)
C112—H112	0.9500	C212—H212	0.9500
C12A—C113	1.519 (5)	C22A—C213	1.521 (10)
C113—C13C	1.531 (5)	C213—C23C	1.527 (9)
C113—C131	1.550 (5)	C213—C231	1.540 (10)
C113—H113	1.0000	C213—H223	1.0000
C13C—C13B	1.430 (5)	C23C—C23B	1.438 (9)
C131—C132	1.519 (5)	C231—C232	1.523 (11)
C131—H13A	0.9900	C231—H23A	0.9900
C131—H13B	0.9900	C231—H23B	0.9900
C132—H13C	0.9800	C232—H23C	0.9800
C132—H13D	0.9800	C232—H23D	0.9800
C132—H13E	0.9800	C232—H23E	0.9800
C151—O151	1.213 (5)	C251—O251	1.214 (11)
C151—O152	1.352 (4)	C251—O252	1.354 (11)
O152—C152	1.455 (6)	O252—C252	1.455 (12)
C152—C153	1.517 (5)	C252—C253	1.518 (11)
C152—H15A	0.9900	C252—H25A	0.9900
C152—H15B	0.9900	C252—H25B	0.9900
C153—H15C	0.9800	C253—H25C	0.9800
C153—H15D	0.9800	C253—H25D	0.9800
C153—H15E	0.9800	C253—H25E	0.9800

C12—C11—C13C	122.4 (3)	H15D—C153—H15E	109.5
C12—C11—H11	118.8	C23C—C21—C22	119.8 (13)
C13C—C11—H11	118.8	C23C—C21—H21	120.1
C13—C12—C11	121.0 (3)	C22—C21—H21	120.1
C13—C12—Cl12	120.6 (3)	C23—C22—C21	120.2 (12)
C11—C12—Cl12	118.4 (3)	C23—C22—Cl22	120.5 (12)
C12—C13—C13A	119.3 (3)	C21—C22—Cl22	119.3 (12)
C12—C13—H13	120.4	C22—C23—C23A	118.0 (14)
C13A—C13—H13	120.4	C22—C23—H23	121.0
C13—C13A—C13B	120.4 (3)	C23A—C23—H23	121.0
C13—C13A—C14	116.9 (3)	C23—C23A—C23B	119.3 (16)
C13B—C13A—C14	122.7 (3)	C23—C23A—C24	116.5 (14)
O14—C14—C15	126.0 (3)	C23B—C23A—C24	122.7 (10)
O14—C14—C13A	119.8 (3)	O24—C24—C25	125 (2)
C15—C14—C13A	114.2 (3)	O24—C24—C23A	118.9 (17)
C16—C15—C14	119.3 (3)	C25—C24—C23A	113.5 (13)
C16—C15—C151	114.5 (3)	C26—C25—C24	118.8 (16)
C14—C15—C151	126.0 (3)	C26—C25—C251	114.7 (14)
N17—C16—C15	124.8 (4)	C24—C25—C251	125.3 (18)
N17—C16—H16	117.6	N27—C26—C25	124.9 (13)
C15—C16—H16	117.6	N27—C26—H26	117.5
C16—N17—C13B	121.1 (3)	C25—C26—H26	117.5
C16—N17—C18	118.0 (3)	C26—N27—C23B	121.3 (11)
C13B—N17—C18	120.8 (3)	C26—N27—C28	117.1 (14)
N17—C18—C18A	110.7 (3)	C23B—N27—C28	120.8 (16)
N17—C18—H18A	109.5	N27—C28—C28A	110.5 (15)
C18A—C18—H18A	109.5	N27—C28—H28A	109.5
N17—C18—H18B	109.5	C28A—C28—H28A	109.5
C18A—C18—H18B	109.5	N27—C28—H28B	109.5
H18A—C18—H18B	108.1	C28A—C28—H28B	109.5
C19—C18A—C12A	120.6 (3)	H28A—C28—H28B	108.1
C19—C18A—C18	119.9 (3)	C29—C28A—C22A	120.2 (14)
C12A—C18A—C18	119.5 (3)	C29—C28A—C28	119.8 (15)
C110—C19—C18A	120.1 (4)	C22A—C28A—C28	118.2 (12)
C110—C19—H19	120.0	C210—C29—C28A	119.7 (15)
C18A—C19—H19	120.0	C210—C29—H29	120.2
C19—C110—C111	119.8 (4)	C28A—C29—H29	120.2
C19—C110—H110	120.1	C29—C210—C211	119.0 (15)
C111—C110—H110	120.1	C29—C210—H210	120.5
C110—C111—C112	120.3 (4)	C211—C210—H210	120.5
C110—C111—H111	119.8	C210—C211—C212	120.0 (14)
C112—C111—H111	119.8	C210—C211—H211	120.0
C12A—C112—C111	120.6 (4)	C212—C211—H211	120.0
C12A—C112—H112	119.7	C22A—C212—C211	120.6 (13)
C111—C112—H112	119.7	C22A—C212—H212	119.7
C112—C12A—C18A	118.6 (3)	C211—C212—H212	119.7
C112—C12A—C113	120.8 (3)	C212—C22A—C28A	118.3 (11)
C18A—C12A—C113	120.6 (3)	C212—C22A—C213	122.4 (13)
C12A—C113—C13C	116.4 (3)	C28A—C22A—C213	118.9 (11)
C12A—C113—C131	113.0 (3)	C22A—C213—C23C	115.5 (14)
C13C—C113—C131	112.9 (3)	C22A—C213—C231	113.8 (13)
C12A—C113—H113	104.3	C23C—C213—C231	117.1 (12)
C13C—C113—H113	104.3	C22A—C213—H223	102.5
C131—C113—H113	104.3	C23C—C213—H223	102.5
C11—C13C—C13B	116.6 (3)	C231—C213—H223	102.5
C11—C13C—C113	114.0 (3)	C21—C23C—C23B	115.6 (14)
C13B—C13C—C113	129.4 (3)	C21—C23C—C213	115.6 (12)
C132—C131—C113	113.4 (3)	C23B—C23C—C213	126.8 (11)
C132—C131—H13A	108.9	C232—C231—C213	112.8 (15)
C113—C131—H13A	108.9	C232—C231—H23A	109.0
C132—C131—H13B	108.9	C213—C231—H23A	109.0
C113—C131—H13B	108.9	C232—C231—H23B	109.0
H13A—C131—H13B	107.7	C213—C231—H23B	109.0
C131—C132—H13C	109.5	H23A—C231—H23B	107.8
C131—C132—H13D	109.5	C231—C232—H23C	109.5
H13C—C132—H13D	109.5	C231—C232—H23D	109.5
C131—C132—H13E	109.5	H23C—C232—H23D	109.5
H13C—C132—H13E	109.5	C231—C232—H23E	109.5
H13D—C132—H13E	109.5	H23C—C232—H23E	109.5
N17—C13B—C13A	116.7 (3)	H23D—C232—H23E	109.5
N17—C13B—C13C	123.2 (3)	N27—C23B—C23A	116.5 (11)
C13A—C13B—C13C	120.1 (3)	N27—C23B—C23C	123.4 (13)
O151—C151—O152	121.9 (4)	C23A—C23B—C23C	119.9 (10)
O151—C151—C15	124.7 (4)	O251—C251—O252	121 (2)
O152—C151—C15	113.3 (3)	O251—C251—C25	125 (2)
C151—O152—C152	115.2 (4)	O252—C251—C25	112.5 (15)
O152—C152—C153	105.8 (4)	C251—O252—C252	115.3 (17)
O152—C152—H15A	110.6	O252—C252—C253	105.7 (14)
C153—C152—H15A	110.6	O252—C252—H25A	110.6
O152—C152—H15B	110.6	C253—C252—H25A	110.6
C153—C152—H15B	110.6	H25A—C252—H25B	108.7
H15A—C152—H15B	108.7	C252—C253—H25C	109.5
C152—C153—H15C	109.5	C252—C253—H25D	109.5
C152—C153—H15D	109.5	H25C—C253—H25D	109.5
H15C—C153—H15D	109.5	C252—C253—H25E	109.5
C152—C153—H15E	109.5	H25D—C253—H25E	109.5
H15C—C153—H15E	109.5

C13C—C11—C12—C13	0.6 (7)	C15—C151—O152—C152	179.9 (16)
C13C—C11—C12—Cl12	179.3 (5)	C151—O152—C152—C153	178.5 (16)
C11—C12—C13—C13A	−2.5 (8)	C23C—C21—C22—C23	28 (6)
Cl12—C12—C13—C13A	178.7 (6)	C23C—C21—C22—Cl22	−152 (6)
C12—C13—C13A—C13B	−0.3 (9)	C21—C22—C23—C23A	−24 (7)
C12—C13—C13A—C14	178.9 (6)	Cl22—C22—C23—C23A	155 (6)
C13—C13A—C14—O14	5.3 (11)	C22—C23—C23A—C23B	18 (8)
C13B—C13A—C14—O14	−175.6 (10)	C22—C23—C23A—C24	−175 (6)
C13—C13A—C14—C15	−176.8 (9)	C23—C23A—C24—O24	14 (11)
C13B—C13A—C14—C15	2.3 (9)	C23B—C23A—C24—O24	180 (9)
O14—C14—C15—C16	169.4 (12)	C23—C23A—C24—C25	−150 (8)
C13A—C14—C15—C16	−8.4 (13)	C23B—C23A—C24—C25	16 (8)
O14—C14—C15—C151	−7.4 (16)	O24—C24—C25—C26	−179 (12)
C13A—C14—C15—C151	174.8 (10)	C23A—C24—C25—C26	−17 (12)
C14—C15—C16—N17	5.4 (18)	O24—C24—C25—C251	14 (15)
C151—C15—C16—N17	−177.5 (11)	C23A—C24—C25—C251	176 (9)
C15—C16—N17—C13B	4.8 (16)	C251—C25—C26—N27	176 (11)
C15—C16—N17—C18	−172.5 (11)	C25—C26—N27—C23B	4 (16)
C16—N17—C18—C18A	−110.9 (9)	C25—C26—N27—C28	−166 (10)
C13B—N17—C18—C18A	71.9 (8)	C26—N27—C28—C28A	−116 (8)
N17—C18—C18A—C19	105.6 (7)	C23B—N27—C28—C28A	74 (6)
N17—C18—C18A—C12A	−72.5 (6)	N27—C28—C28A—C29	90 (7)
C12A—C18A—C19—C110	0.4 (10)	N27—C28—C28A—C22A	−74 (4)
C18—C18A—C19—C110	−177.7 (7)	C22A—C28A—C29—C210	−14 (10)
C18A—C19—C110—C111	−3.0 (11)	C28—C28A—C29—C210	−178 (7)
C19—C110—C111—C112	3.8 (11)	C28A—C29—C210—C211	16 (12)
C110—C111—C112—C12A	−2.0 (9)	C29—C210—C211—C212	−14 (12)
C111—C112—C12A—C18A	−0.7 (7)	C210—C211—C212—C22A	9 (10)
C111—C112—C12A—C113	179.4 (5)	C211—C212—C22A—C28A	−7 (8)
C19—C18A—C12A—C112	1.5 (8)	C211—C212—C22A—C213	166 (5)
C18—C18A—C12A—C112	179.6 (5)	C29—C28A—C22A—C212	9 (8)
C19—C18A—C12A—C113	−178.6 (5)	C28—C28A—C22A—C212	174 (5)
C18—C18A—C12A—C113	−0.5 (8)	C29—C28A—C22A—C213	−164 (5)
C112—C12A—C113—C13C	−126.3 (4)	C28—C28A—C22A—C213	1 (7)
C18A—C12A—C113—C13C	53.8 (6)	C212—C22A—C213—C23C	−112 (5)
C112—C12A—C113—C131	100.6 (4)	C28A—C22A—C213—C23C	60 (4)
C18A—C12A—C113—C131	−79.3 (6)	C212—C22A—C213—C231	27 (5)
C12—C11—C13C—C13B	4.0 (7)	C28A—C22A—C213—C231	−160 (4)
C12—C11—C13C—C113	−173.9 (4)	C22—C21—C23C—C23B	−23 (6)
C12A—C113—C13C—C11	146.8 (4)	C22—C21—C23C—C213	171 (3)
C131—C113—C13C—C11	−80.1 (5)	C22A—C213—C23C—C21	116 (4)
C12A—C113—C13C—C13B	−30.8 (7)	C231—C213—C23C—C21	−22 (5)
C131—C113—C13C—C13B	102.3 (6)	C22A—C213—C23C—C23B	−47 (6)
C12A—C113—C131—C132	−69.4 (5)	C231—C213—C23C—C23B	175 (5)
C13C—C113—C131—C132	155.8 (4)	C22A—C213—C231—C232	42 (5)
C16—N17—C13B—C13A	−10.6 (12)	C23C—C213—C231—C232	−179 (4)
C18—N17—C13B—C13A	166.5 (7)	C26—N27—C23B—C23A	−5 (11)
C16—N17—C13B—C13C	170.4 (10)	C28—N27—C23B—C23A	165 (6)
C18—N17—C13B—C13C	−12.4 (11)	C26—N27—C23B—C23C	170 (10)
C13—C13A—C13B—N17	−174.0 (8)	C28—N27—C23B—C23C	−20 (11)
C14—C13A—C13B—N17	6.9 (10)	C23—C23A—C23B—N27	160 (7)
C13—C13A—C13B—C13C	5.0 (10)	C24—C23A—C23B—N27	−6 (10)
C14—C13A—C13B—C13C	−174.1 (7)	C23—C23A—C23B—C23C	−15 (9)
C11—C13C—C13B—N17	172.2 (7)	C24—C23A—C23B—C23C	179 (7)
C113—C13C—C13B—N17	−10.2 (10)	C21—C23C—C23B—N27	−157 (7)
C11—C13C—C13B—C13A	−6.7 (9)	C213—C23C—C23B—N27	6 (10)
C113—C13C—C13B—C13A	170.9 (6)	C21—C23C—C23B—C23A	18 (8)
C16—C15—C151—O151	4.8 (16)	C213—C23C—C23B—C23A	−179 (5)
C14—C15—C151—O151	−178.3 (15)	C24—C25—C251—O251	157 (14)
C16—C15—C151—O152	−177.8 (16)	C26—C25—C251—O252	−177 (15)
C14—C15—C151—O152	−0.9 (16)	C25—C251—O252—C252	170 (16)
O151—C151—O152—C152	−3 (2)	C251—O252—C252—C253	171 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18B···O151ⁱ	0.99	2.54	3.483 (9)	159
C19—H19···O151ⁱ	0.95	2.54	3.396 (12)	149
C28—H28B···O251ⁱ	0.99	2.10	3.13 (7)	159
C29—H29···O251ⁱ	0.95	2.75	3.38 (13)	124

Symmetry code: (i) −x+1, −y+2, −z+1.

Selected geometric parameters (Å, °) top

Ring-puckering parameters	(Å, °)
(a)	Five-membered ring
	(I), molecule 1	(I), molecule 2	(II)	(III), major	(III), minor
Q₂	0.4627 (12)	0.3979 (12)	0.300)3)
φ₂	359.12 (17)	178.1 (2)	339.0 (5)

(b)	Six-membered ring
Q				0.107 (8)	0.16 (7)
θ				87 (4)	112 (26)
φ				39 (4)	2(30)

(c)	Seven-membered rings
Q	0.9540 (13)	0.942 (2)	0.981 (3)	0.843 (6)	0.85 (5)
φ₂	38.32 (8)	217.47 (8)	40.16 (16)	271.8 (4)	267 (4)
φ₃	286.0 (3)	107.8 (3)	281.6 (7)	9.6 (10)	17 (7)

Dihedral angles
	(I), molecule 1	(I), molecule 2	(II)	(III), major	(III), minor
	70.84 (4)	65.44 (4)	76.67 (9)	52.8 (2)	66 (3)

Torsion angles
	(I), molecule 1	(I), molecule 2	(II)	(III), major	(III), minor
Cx9—Cx9—Cx91—Cx92	-169.01 (11)	170.60 (10)	-173.0 (2)
Cy2A—Cy13—Cy31—Cy32				-69.4 (5)	42 (5)

Notes: (i) x = 1 or 2 for molecules 1 and 2, respectively, in (I) and x = nul for (II); y = 1 or 2 for the major- and minor-disorder forms, respectively, in (III);

(ii) the ring-puckering angles are calculated for the following atom sequences: five-membered rings Sx1–Cx2–Cx3–Nx4–Cx1, six-membered rings Ny7–Cy3B–Cy3A–Cy4–Cy5–Cy6, and seven-membered rings Nx4–Cx4A–Cx8A–Cx9–Cx9A–Cx14–Cx15 in (I) and (II), and Ny7–Cy3B–Cy3C–Cy13–Cy2A–Cy8A–Cy8 in (III);

(iii) the dihedral angles are those between the mean planes of the two aryl rings in each of (I)–(III).

Parameters (Å, °) for hydrogen bonds and short intermolecular contacts top

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(I)	C115—H115···O13ⁱ	1.00	2.47	3.3084 (18)	141
	C215—H215···O23ⁱⁱ	1.00	2.37	3.1681 (18)	136
	C112—H112···Cg1ⁱⁱⁱ	0.95	2.81	3.6738 (13)	152
	C113—H113···Cg2ⁱⁱⁱ	0.95	2.85	3.7676 (14)	163
(II)	C2—H2B···O3^iv	0.97	2.57	3.120 (4)	116
	C91—H91A···Cg3^v	0.97	2.82	3.736 (3)	157
(III)	C18—H18B···O151^vi	0.99	2.54	3.483 (9)	159
	C19—H19···O151^vi	0.95	2.54	3.396 (12)	149
	C28—H28B···O251^vi	0.99	2.18	3.13 (7)	159
	C29—H29···O251^vi	0.95	2.70	3.34 (12)	125

Cg1–Cg3 represent the centroids of the C29A/C210–C214, C24A/C25–C28/C28A and C9A/C10–C14 rings, respectively.

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

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Three tetra­cyclic dibenzoazepine derivatives exhibiting different mol­ecular conformations, different patterns of inter­molecular hydrogen bonding and different modes of supra­molecular aggregation

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Three tetracyclic dibenzoazepine derivatives exhibiting different molecular conformations, different patterns of intermolecular hydrogen bonding and different modes of supramolecular aggregation