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

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 73| Part 1| January 2017| Pages 28-35

https://doi.org/10.1107/S2053229616018143

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

Jeferson B. Mateus-Ruíz,^a Lina M. Acosta Quintero,^a Alirio Palma,^a Mario A. Macías,^b Justo Cobo ^c and Christopher Glidewell ^d ^*

^aLaboratorio de Síntesis Orgánica, Escuela de Química, Universidad Industrial de Santander, AA 678 Bucaramanga, Colombia, ^bDepartamento de Química, Universidad de los Andes, Carrera 1 No. 18A-12, Bogotá, Colombia, ^cDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

Edited by A. L. Spek, Utrecht University, The Netherlands (Received 7 November 2016; accepted 11 November 2016; online 1 January 2017)

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.

CCDC references: 1516770; 1516769; 1516768

1. Introduction

The tricyclic dibenzo[b,e]azepine system constitutes a class of nitrogen-containing heterocyclic compounds whose chemistry continues to be of interest, because of the action of compounds containing this system as analgesics and as anticancer, antidepressive, antihistaminic, antimuscarinic and antipsychotic agents (Al-Qawasmeh et al., 2009 ). Examples of such compounds in current clinical use include mianserin, racemic 2-methyl-1,2,3,4,10,14b-hexahydrodibenzo[c,f]pyrazino[1,2-a]azepine, which is a potent antidepressant (Dinesh et al., 2014 ), and epinastine, racemic 3-amino-9,13b-dihydro-1H-dibenz[c,f]imidazo[1,5-a]azepine, which is an antihistaminic used in the treatment of allergic conjunctivitis (Liu et al., 2004 ). The biological potential of these compounds has resulted in considerable synthetic efforts to develop efficient methods for the synthesis of new derivatives of this kind (Andrés et al., 2002 ; Stappers et al., 2002 ; Wikström et al., 2002 ).

In this context, and as part of our own interest in the identification of other molecular entities with pharmacological potential, we have for several years studied the chemistry of the synthetically available dihydrodibenzo[b,e]azepines (Palma et al., 2004 ) as building blocks for the construction of novel fused tetracyclic azepine systems. Accordingly, we have reported the synthesis of tetrahydrodibenzo[c,f]thiazolo[3,2-a]azepine derivatives, compounds in which the dibenzo[b,e]azepine nucleus is fused to a thiazolidin-4-one ring (Palma et al., 2010 ). We are now developing a simple and efficient synthetic methodology for the preparation of derivatives of the type alkyl 4-oxobenzo[5,6]azepino[3,2,1-ij]quinoline-5-carboxylate. This is a new heterocyclic system in which a benzazepine nucleus is fused to a 4-quinolone system, which is also of great interest for both the medicinal chemistry and pharmaceutical industries (Mugnaini et al., 2009 ), mainly because of their antibacterial activity, the best studied biological property of the so-called fluoroquinolone antibiotics.

We report here the molecular and supramolecular structures of three compounds containing fused tetracyclic azepine systems, namely 9-ethyl-11-methyl-9,13b-dihydrodibenzo[c,f]thiazolo[3,2-a]azepin-3(2H)-one, (I), 9-ethyl-7,12-dimethyl-9,13b-dihydrodibenzo[c,f]thiazolo[3,2-a]azepin-3(2H)-one, (II), and ethyl 2-chloro-13-ethyl-4-oxo-8,13-dihydro-4H-benzo[5,6]azepino[3,2,1-ij]quinoline-5-carboxylate, (III) (Figs. 1–3 ). Compounds (I) and (II) were synthesized from the corresponding dihydrodibenzo[b,e]azepines (A) and (B) (see Scheme 1) according to a previously described procedure (Palma et al., 2010), in which the tricyclic precursors (A) and (B) were first subjected to oxidation using pyridinium chlorochromate, followed by cyclocondensation with thioglycolic acid to give (I) and (II). Compound (III) was synthesized from dihydrodibenzo[b,e]azepine (C) employing the modified Gould–Jacobs reaction, in which an alkoxymethylenemalonate derivative, here diethyl 2-(methoxymethylene)malonate, reacts with the amino group of the precursor with displacement of the ethoxy unit by the N atom giving the intermediate (D), followed by benzannulation to give the quinolone derivative (III) (see Scheme 2).

Figure 1
The molecular structures of the two independent molecules of compound (I)

, showing (a) molecule 1, which has the (9R,15R) configuration, and (b) molecule 2, which has the (9S,15S) configuration. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The molecular structure of the (9R,15R) enantiomer of compound (II)

. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
The molecular structures of the disordered components of compound (III)

, showing (a) the major R enantiomer, (b) the minor S enantiomer and (c) the two disorder components together, with the bonds in the major form shown as full lines and those in the minor form shown as broken lines. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, the majority of the atom labels have been omitted from part (c).

2. Experimental

2.1. Synthesis and crystallization

Compounds (I) and (II) were prepared according to the method reported previously by Palma et al. (2010). For the synthesis of compound (III), a solution of 2-chloro-11-ethyl-6,11-dihydro-5H-dibenzo[b,e]azepine, (C) (0.10 mmol), and diethyl 2-(methoxymethylene)malonate (0.13 mmol) in toluene (10 ml) was heated under reflux for 15 h until the reaction was complete, as indicated by thin-layer chromatography (TLC). The solvent and the excess of diethyl 2-(methoxymethylene)malonate were removed from the reaction mixture under reduced pressure, and Eaton's reagent, i.e. a 7.7% solution of phosphorus(V) oxide in methanesulfonic acid (1.6 ml), was added to the remaining crude material. This mixture was heated at 343 K for 40 min, again with TLC monitoring, then cooled to ambient temperature and neutralized with saturated aqueous sodium carbonate solution. The neutralized mixture was extracted with ethyl acetate (3 × 50 ml) and the combined organic extracts were dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the crude product was purified by column chromatography on silica gel using heptane–ethyl acetate mixtures (10:1 to 1:3 v/v) to give compound (III) (yield 80%, m.p. 466–467 K). Colourless crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in heptane–ethyl acetate (2:1 v/v) for (I) and (II), and in ethanol–ethyl acetate (7:3 v/v) for (III).

2.2. Spectroscopic data

R_F = 0.27 (ethyl acetate–heptane, 1:1 v/v); IR (cm⁻¹): 2965–2926 (C—H), 1687 [C=O(ester)], 1605 [C=O(ketone)], 1482 (C=C), 1146 (C—O); NMR (CDCl₃): δ(¹H) 1.02 (t, J = 7.2 Hz, 3H, 13-CH₂—CH₃), 1.41 (t, J = 7.2 Hz, 3H, O—CH₂—CH₃), 2.36–2.24 (m, 2H, 13-CH₂—CH₃), 4.10 (br s, 1H, 13-H), 4.39 (q, J = 7.2 Hz, 2H, O—CH₂–), 4.88 (br s, 1H, 8-H_B), 5.88 (br s, 1H, 8-H_A), 7.22 (dd, J = 7.4, 1.4 Hz, 1H, 12-H), 7.31 (td, J = 7.4, 1.4 Hz, 1H, 10-H), 7.36 (td, J = 7.4, 1.4 Hz, 1H, 11-H), 7.40 (dd, J = 7.4, 1.4 Hz, 1H, 9-H), 7.51 (d, J = 2.4 Hz, 1H, 1-H), 8.34 (d, J = 2.4 Hz, 1H, 3-H), 8.53 (s, 1H, 6-H); δ(¹³C) 13.1 (13-CH₂—CH₃), 14.5 (O—CH₂—CH₃), 61.1 (O—CH₂–), 61.2 (8-C), 109.6 (5-C), 126.3 (3-C), 128.1 (10-C), 129.1 (9-C, 12-C), 129.8 (11-C), 131.2 (2-C), 131.8 (8a-C), 132.3 (3a-C), 134.2 (13a-C), 137.2 (3b-C), 140.5 (12a-C), 150.1 (6-C), 165.6 (COO), 172.8 (4-C); HRMS (EI–MS, 70 eV) m/z found 381.1132, C₂₂H₂₀³⁵ClNO₃ requires 381.1132.

2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For compounds (I) and (II), all H atoms were located in difference maps and subsequently treated as riding atoms in geometrically idealized positions, with C—H distances of 0.95 (aromatic), 0.98 (methyl), 0.99 (methylene) or 1.00 Å (methine) for (I), and 0.93, 0.96, 0.97 or 0.98 Å for the corresponding bond types in (II), and with, in each case, U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. The correct absolute configuration for compound (I) was established using both the Flack x parameter (Flack, 1983 ), x = 0.007 (6), calculated (Parsons et al., 2013 ) using 4787 quotients of the type [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)], and the Hooft y parameter (Hooft et al., 2010 ) y = 0.001 (7). It was apparent from an early stage in the refinement of compound (III) that the molecules exhibited configurational disorder, such that the reference site was occupied by partial-occupancy molecules of both R and S configuration having markedly unequal occupancies. For the minor component, having the S configuration, the bonded distances and the 1,3 nonbonded distances were restrained to be the same as the corresponding distances in the major component, having an R configuration, subject to s.u. values of 0.01 and 0.02 Å, respectively; in addition, the anisotropic displacement parameters for pairs of atoms occupying similar regions of physical space were constrained to be identical. The H atoms in the major component were all located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (alkenyl and aromatic), 0.98 (methyl), 0.99 (methylene) or 1.00 Å (methine), and with U_iso(H) defined as for (I) and (II). In the final analysis of variance for compound (II), there was a negative value, −0.346, of K = mean(F_o²)/mean(F_c²) for the group of 409 very weak reflections having F_c/F_c(max) in the range 0.000 < F_c/F_c(max) < 0.006, and for compound (III) there was a large value, 5.504, of K for the group of 382 very weak reflections having F_c/F_c(max) in the range 0.000 < F_c/F_c(max) < 0.015.

Table 1
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₉H₁₉NOS	C₂₀H₂₁NOS	C₂₂H₂₀ClNO₃
M_r	309.41	323.44	381.84
Crystal system, space group	Monoclinic, P2₁	Monoclinic, C2/c	Triclinic, P $[\overline{1}]$
Temperature (K)	100	298	120
a, b, c (Å)	11.4261 (5), 8.1847 (3), 16.8243 (6)	18.1021 (12), 12.4436 (8), 14.8429 (9)	6.8533 (16), 10.612 (5), 13.561 (3)
α, β, γ (°)	90, 93.067 (2), 90	90, 97.645 (3), 90	72.45 (4), 75.840 (19), 82.46 (2)
V (Å³)	1571.14 (11)	3313.7 (4)	910.0 (6)
Z	4	8	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.21	0.20	0.23
Crystal size (mm)	0.40 × 0.35 × 0.22	0.23 × 0.22 × 0.20	0.26 × 0.15 × 0.13

Data collection
Diffractometer	Bruker Kappa APEXII	Bruker Kappa APEXII	Nonius KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2006 )	Multi-scan (SADABS; Bruker, 2006)	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.823, 0.955	0.818, 0.961	0.845, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	61785, 11002, 10697	30952, 3402, 2307	20183, 3776, 2195
R_int	0.025	0.048	0.154
(sin θ/λ)_max (Å⁻¹)	0.757	0.626	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.079, 1.05	0.060, 0.168, 1.05	0.065, 0.118, 1.06
No. of reflections	11002	3402	3776
No. of parameters	401	211	322
No. of restraints	1	0	74
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.21	0.57, −0.45	0.29, −0.31
Absolute structure	See §2.3	–	–
Computer programs: APEX2 (Bruker, 2006), COLLECT (Nonius, 1998 ), SAINT (Bruker, 2006), DIRAX/LSQ (Duisenberg et al., 2000 ), EVALCCD (Duisenberg et al., 2003 ), SIR92 (Altomare et al., 1994 ), SIR2014 (Burla et al., 2015 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

3. Results and discussion

The constitutions of compounds (I) and (II) are rather similar, differing only in the number and location of the methyl substituents, which are at position 11 in (I) and at positions 7 and 12 in (II). Despite this close similarity, compound (I) crystallizes with Z′ = 2 in the Sohncke space group P2₁, while (II) crystallizes in the centrosymmetric space group C2/c. In molecule 1 of compound (I), containing atom S11 (Fig. 1a), there are stereogenic centres at atoms C19 and C115; the reference molecule 1 was selected as one having the R configuration at atom C19 and on this basis the configuration at atom C115 is also R, whereas the configurations at atoms C29 and C215 in molecule 2 (Fig. 1b) are both S. Thus, despite crystallizing in the space group P2₁, compound (I) is a racemic mixture of (9R,15R) and (9S,15S) enantiomers and it is therefore a kryptoracemate (Morales & Fronczek, 1996 ; Fábián & Brock, 2010 ; Bernal & Watkins, 2015 ); a search for possible additional crystallographic symmetry found none. Compound (III) has a stereogenic centre at position 13 and the reference molecule was selected as one having the R configuration at this site. However, it was apparent that the reference site was in fact occupied by partial-occupancy molecules of both R and S configurations (Figs. 3a and 3b), having occupancies of 0.900 (6) and 0.100 (6), respectively. These two enantiomeric forms occupy similar but not quite identical locations (Fig. 3c). The centrosymmetric space groups of compounds (II) and (III) confirm that these compounds have both crystallized as racemic mixtures. That compounds (I)–(III) are racemic is expected from the racemic nature of the precursors (A)–(C) (Palma et al., 2010), but it is interesting to note that for compounds (I) and (II), the stereochemistry at position 15 appears to be wholly controlled by that at position 9 and no evidence was found for the formation of the diastereoisomeric (9RS,15SR) forms.

In each of the two independent molecules of compound (I), the five-membered ring is slightly puckered out of planarity, and the ring-puckering parameters (Cremer & Pople, 1975 ) show that in each molecule this ring adopts an envelope (Evans & Boeyens, 1989 ) conformation (Table 2), with the ring folded across the line Cx2—Cx15, where x = 1 or 2 in molecules 1 and 2, respectively; the difference of ca 180° between the φ₂ values for the two molecules in (I) confirms their enantiomeric relationship. By contrast with (I), the five-membered ring in compound (II) adopts a half-chair conformation in which the ring is twisted about a line through atom C3 and the approximate mid-point of the S1—C15 bond. For idealized half-chair and envelope conformations, the values of φ₂ are (36k + 18)° and 36k°, respectively, where k represents an integer. Within the major disorder form of compound (III), the six-membered heterocyclic ring is slightly puckered into a twist-boat conformation; for an idealized twist-boat conformation; the ring-puckering angles are θ = 90° and φ = (60k + 30)°, where k represents an integer. For the seven-membered ring in each of (I), (II) and the major form of (III), the ring conformations are dominated by the twist-boat sin form 2 (Evans & Boeyens, 1989). By contrast, the most common conformation of the seven-membered ring in tricyclic dibenzazepines is one intermediate between the boat and twist-boat forms (Sanabría et al., 2014 ), while the most common form in benzopyrimidoazepines is the boat form (cos form 2) (Acosta et al., 2015 ; Acosta Quintero, Palma et al., 2016 ).

Table 2
Selected geometric parameters (Å, °)

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

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

Seven-membered rings
Q	0.9540 (13)	0.9418 (12)	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	70.84 (4)	65.44 (4)	76.67 (9)	52.8 (2)	66 (3)

Torsion angles
Cx9A—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).

In each of the five independent molecular entities reported here, the dihedral angle between the two aryl rings falls within a fairly narrow range of less than 25° (Table 2). The specification of the molecular conformations is completed by the orientation of the ethyl substituent relative to the seven-membered ring; the torsion angles defining this orientation are very similar in compounds (I) and (II), except for the difference in sign between the two independent molecules in (I) consistent with their enantiomeric relationship, whereas in (III) this orientation is entirely different (Table 2 and Figs. 1–3 ).

Despite the close similarity between the constitutions of compounds (I) and (II), the supramolecular assembly in these two compounds is entirely different. In compound (I), the molecules are linked into complex sheets by a combination of two C—H⋯O hydrogen bonds and two C—H⋯π(arene) hydrogen bonds (Table 3), but the formation of the sheet structure is readily analysed in terms of simple substructures (Ferguson et al., 1998a ,b ; Gregson et al., 2000 ). The molecules of type 1 which are related by the 2₁ screw axis along (0, y, $[1 \over 2]$ ) are linked by C—H⋯O hydrogen bonds to form a C(5) (Bernstein et al., 1995 ) chain running parallel to the [010] direction. A similar C(5) chain, antiparallel to the first chain is built from type 2 molecules which are related by the 2₁ screw axis along (0, y, 0); thus each type of C(5) chain contains only a single enantiomeric form. Two independent C—H⋯π(arene) hydrogen bonds, in which the donors are two adjacent C—H bonds in a type 1 molecule and the acceptors are the two aryl rings of a type 2 molecule, thus precluding the possibility of any additional crystallographic symmetry, link the type 1 chains along (0, y, n + $[1 \over 2]$ ) to the type 2 chains along (0, y, n), where n represents an integer in each case, to form a sheet lying parallel to (100) (Fig. 4); however, there are no direction-specific interactions between adjacent sheets.

Table 3
Parameters (Å, °) for hydrogen bonds and short intermolecular contacts

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

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	2.10	3.13 (7)	159
	C29—H29⋯O251^vi	0.95	2.75	3.34 (12)	124
Symmetry codes: (i) −x, y + $[{1\over 2}]$ , −z + 1; (ii) −x, y − $[{1\over 2}]$ , −z; (iii) x, y + 1, z; (iv) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (v) −x + 1, −y + 1, −z + 1; (vi) −x + 1, −y + 2, −z + 1.

Figure 4
A stereoview of part of the crystal structure of compound (I)

, showing the formation of a hydrogen-bonded sheet parallel to (100) in which chains built from C—H⋯O hydrogen bonds are linked by C—H⋯π(arene) hydrogen bonds. For the sake of clarity, H atoms which are not involved in the motifs shown have been omitted.

In contrast to the complex supramolecular assembly in compound (I), that in compound (II) is extremely simple. Inversion-related pairs of molecules are linked by paired C—H⋯π(arene) hydrogen bonds to form centrosymmetric dimers, each containing an enantiomeric pair (Fig. 5), but there are no direction-specific interactions between adjacent dimers, so that the supramolecular assembly is finite and zero-dimensional.

Figure 5
Part of the crystal structure of compound (II)

, showing the formation of a centrosymmetric hydrogen-bonded dimer. For the sake of clarity, the unit-cell outline and H atoms bonded to C atoms that are not involved in the motif shown have been omitted. The atom marked with an asterisk (*) is at the symmetry position (−x + 1, −y + 1, −z + 1).

The molecules of compound (III) are linked by C—H⋯O hydrogen bonds to form centrosymmetric dimers (Fig. 6). For the major-disorder form, the hydrogen bonds generate a dimer, centred at ( $[1 \over 2]$ 1, $[1 \over 2]$ ), characterized by an outer R₂²(18) ring, which encloses an inner R₂²(14) ring flanked by two inversion-related R₂¹(6) rings; for the minor-disorder component, only the R₂²(14) ring is present as the H29⋯O251ⁱ separation [symmetry code: (i) −x + 1, −y + 2, −z + 1] of 2.75 Å is above the sum of the van der Waals radii (Rowland & Taylor, 1996 ), so that the corresponding C—H⋯O contact cannot be regarded as a hydrogen bond. Dimers of this type are linked into a chain by a single π–π stacking interaction. The chlorinated aryl rings of the molecules at (x, y, z) and (−x + 2, −y + 1, −z + 1) are strictly parallel, with an interplanar spacing of 3.368 (3) Å; the ring-centroid separation is 3.649 (4) Å, corresponding to a ring-centroid offset of 1.404 (4) Å. This interaction links hydrogen-bonded dimers related by translation into a π-stacked chain running parallel to the [1 $[\overline{1}]$ 0] direction (Fig. 7).

Figure 6
Part of the crystal structure of compound (III)

, showing the formation by the major-disorder form of a cyclic centrosymmetric hydrogen-bonded dimer. For the sake of clarity, the unit-cell outline and H atoms bonded to C atoms that are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (−x + 1, −y + 2, −z + 1).

Figure 7
A stereoview of part of the crystal structure of compound (III)

, showing the formation of a π-stacked chain of hydrogen-bonded dimers running parallel to the [1 $[\overline{1}]$ 0] direction. For the sake of clarity, the minor-disorder component and H atoms bonded to C atoms that are not involved in the motif shown have been omitted.

It is interesting briefly to compare compounds (I)–(III) reported here with the related tetracyclic benzopyrimidoazepine derivatives (IV) and (V) (see Scheme 3). Firstly, the syntheses of (IV) and (V) utilized a completely different approach (Acosta Quintero et al., 2015 ; Acosta Quintero, Burgos et al., 2016 ) from that employed for the preparation of (I)–(III); the synthesis of compounds (I)–(III) appended an additional ring to a preformed dibenzazepine skeleton, while those for (IV) and (V) were based on the formation of the azepine ring as the final step using an N-pyrimidoindole precursor for (IV) and an N-pyrimidoquinoline precursor for (V). Secondly, the conformation of the azepine ring in compound (IV) differs from the twist-boat form which predominates in (I)–(III) and (V), as this ring contains a significant contribution from the twist-chair form. As a consequence of this, the C-methyl group occupies a quasi-equatorial position in (V), as expected, but a quasi-axial site in (IV) (Acosta Quintero, Palma et al., 2016). Thirdly, the supramolecular aggregation in the structures of (IV) and (V) differs from that in (I)–(III). The molecules of compound (IV) are linked into C(5) chains by C—H⋯N hydrogen bonds, although interactions of this type are wholly absent from the structures of (I)–(III), and inversion-related chains of this type are linked into pairs by a π–π stacking interaction involving the pyrimidine ring. The molecules of compound (V) are linked by C—H⋯π(pyrimidine) interactions into cyclic centrosymmetric dimers, somewhat similar to those in the structure of compound (II).

Finally, we note that although the racemic compound (IV) crystallizes in the Sohncke space group P2₁, it does so as a conglomerate rather than as a a kryptoracemate.

Supporting information

CCDC references: 1516770; 1516769; 1516768

Crystal structure: contains datablocks global, I, II, III. DOI: https://doi.org/10.1107/S2053229616018143/sk3643sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229616018143/sk3643Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2053229616018143/sk3643IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2053229616018143/sk3643IIIsup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229616018143/sk3643Isup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229616018143/sk3643IIsup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229616018143/sk3643IIIsup7.cml

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.

Acknowledgements

The authors thank `Centro de Instrumentación Científico-Técnica of Universidad de Jaén' and Professor Pascal Roussel (University of Lille, France) for data collection. They also thank Vicerrectoría de Investigación y Extensión of Universidad Industrial de Santander (grant No. 9310), the Consejerιa de Innovación, Ciencía y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support.

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ISSN: 2053-2296

Volume 73| Part 1| January 2017| Pages 28-35

https://doi.org/10.1107/S2053229616018143

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research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

2.2. Spectroscopic data

2.3. Refinement

3. Results and discussion

Supporting information

Acknowledgements

References

research papers

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