Crystal structure of 3-(benzo[d]thia­zol-2-yl)-6-methyl-2H-chromen-2-one

Abdallah, A.E.M.; Elgemeie, G.H.; Jones, P.G.

doi:10.1107/S205698902300347X

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ISSN: 2056-9890

Volume 79| Part 5| May 2023| Pages 504-507

https://doi.org/10.1107/S205698902300347X

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Crystal structure of 3-(benzo[d]thiazol-2-yl)-6-methyl-2H-chromen-2-one

Amira E. M. Abdallah,^a Galal H. Elgemeie ^a and Peter G. Jones ^b ^*

^aChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, and ^bInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-braunschweig.de

Edited by C. Schulzke, Universität Greifswald, Germany (Received 29 March 2023; accepted 17 April 2023; online 25 April 2023)

This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.

The molecule of the title compound, C₁₇H₁₁NO₂S, is almost planar, with an interplanar angle of 3.01 (3)° between the benzothiazole and chromene ring systems. A short intramolecular S⋯O=C contact of 2.727 (2) Å is observed. The crystal packing involves a layer structure parallel to (211), containing dimeric inversion-symmetric units connected by a `weak' C—H⋯O=C hydrogen bond.

Keywords: benzothiazole; coumarin; crystal structure.

CCDC reference: 2256779

1. Chemical context

Benzothiazole and its derivatives are important heterocyclic aromatic compounds. Benzothiazole can be readily substituted at the C-2 position of the thiazole ring (Elgemeie et al., 2020 ). Compounds containing a benzothiazolyl group have found numerous applications in medicine and in nonlinear optics (Sigmundová et al., 2007 ). Benzothiazole derivatives can also display strong fluorescence and luminescence in the solid state and in solution (Wang et al., 2010 ). Benzothiazole compounds as incorporated in organic light-emitting diodes have attracted substantial attention because of their notable photovoltaic properties (Ghanavatkar et al., 2020 ). Recently, we have synthesized novel heterocyclic derivatives involving the benzothiazole moiety, many of which showed significant biological and fluorescence activities (Azzam et al., 2020 ; Khedr et al., 2022 ).

Coumarin is a natural product with the systematic name 2H-chromen-2-one. Its derivatives represent an important class of organic heterocycles. Thus, they are constituents of many intensively investigated and commercially important organic fluorescent materials; they also display important biological activities and are found in synthetic drugs (Curini et al., 2006 ). Furthermore, many coumarin compounds are current photosensitizers with valuable applications in medicinal chemistry (Bansal et al., 2013 ). Because of their photochemical properties, coumarin compounds have found applications in nonlinear optical materials, solar energy collectors and charge-transfer agents (Kim et al., 2011 ), and also as daylight fluorescent pigments, tunable dye lasers, fluorescent probes and components of organic light-emitting diodes (Christie & Lui, 2000 ). The emission intensities of coumarin chromophores depend on the nature of their substituents at various sites (Żamojć et al., 2014 ).

In two recent papers (Abdallah et al., 2022 , 2023 ), we have given a more extensive list of references concerning the properties of benzothiazoles and coumarins, including many of our own publications in these fields.

Some decades ago, we reported the syntheses and characterizations of novel coumarin derivatives that have found applications as laser dyes (Elgemeie, 1989 ); these included 3-(benzo[d]thiazol-2-yl)-2H-chromen-2-one, the desmethyl analogue of title compound 4, a benzothiazole-based coumarin derivative which was synthesized by the reaction of 2-(cyanomethyl)benzothiazole with salicyaldehyde. Afterwards, other research groups utilized essentially the same reaction to synthesize different derivatives of the same heterocyclic framework, including compound 4 (Chao et al., 2010 ; Makowska et al., 2019 ).

Recently, we attempted to synthesize N-[3-(benzo[d]thiazol-2-yl)-6-methyl-2-oxoquinolin-1(2H)-yl]benzamide (5) by the reaction of N-[2-(benzo[d]thiazol-2-yl)acetyl]benzohydrazide (1) (Azzam et al., 2021 ) with 5-methylsalicylaldehyde (2) (Fig. 1). However, the product gave a mass spectrum that was inconsistent with the proposed structure. Therefore, the X-ray crystal structure was determined, indicating the formation of 3-(benzo[d]thiazol-2-yl)-6-methyl-2H-chromen-2-one (4) as the sole product, presumably arising via the initial formation of adduct 3 and the subsequent elimination of benzohydrazide rather than water. This is consistent with our recent observation that the desmethyl compound mentioned above is also formed as an unintended product by an exactly analogous reaction (Abdallah et al., 2022). The products thus represent, by coincidence, a continuation of our research on developing new benzothiazole and coumarin derivatives as organic fluorescent constituents (Elgemeie et al., 2015 ).

Figure 1
Reaction scheme showing the the attempted synthesis of compound 5, which led instead to the product 4.

2. Structural commentary

The structure of compound 4 is shown in Fig. 2. Its bond lengths and angles may be regarded as normal; a selection is presented in Table 1. The chromene and benzothiazole ring systems are planar as expected, with respective r.m.s. deviations of 0.020 and 0.015 Å; the angle between these planes is only 3.01 (3)°, so that the whole molecule almost planar. A short intramolecular S11⋯O2 contact of 2.792 (1) Å is observed. The desmethyl analogue (Abdallah et al., 2022) has, as expected, a closely similar molecular structure, with an S⋯O=C contact of 2.727 (2) Å and an interplanar angle of 6.47 (6)°, but is not isotypic to 4.

Table 1
Selected geometric parameters (Å, °)

O1—C2	1.3723 (17)	S11—C17A	1.7343 (14)
O1—C8A	1.3765 (18)	S11—C12	1.7515 (15)
O2—C2	1.2077 (19)	C12—N13	1.3076 (18)
C3—C12	1.4698 (19)	N13—C13A	1.3836 (18)

C2—O1—C8A	122.52 (11)	N13—C12—S11	115.94 (11)
O2—C2—O1	116.99 (12)	C3—C12—S11	123.35 (10)
O2—C2—C3	125.69 (14)	N13—C13A—C14	124.90 (13)
O1—C2—C3	117.32 (13)	N13—C13A—C17A	115.23 (12)
C17A—S11—C12	88.94 (7)	C17—C17A—S11	129.05 (12)
N13—C12—C3	120.72 (13)	C13A—C17A—S11	109.42 (11)

Figure 2
The molecule of compound 4 in the crystal. Displacement ellipsoids represent 50% probability levels.

3. Supramolecular features

The short contact H17⋯O2 (at −x + 2, −y, −z + 1; see Table 2) may be regarded as a `weak' hydrogen bond. It links the molecules to form inversion-symmetric dimers (Fig. 3) in which the S⋯S distance is 3.678 (1) Å. Adjacent dimers are related by translation to give an extended structure consisting of layers parallel to (211). The intercentroid distances (in Å) between rings of neighbouring layers, defining rings A–D as thiazole, the arene ring of benzothiazole, pyran and the arene ring of chromene, respectively, are A⋯C = 3.64, A⋯D = 3.70 and B⋯D = 3.61 [all with the symmetry code (−x + 1, −y + 1, −z + 1)], B⋯C = 3.51 and B⋯D = 3.66 Å [both with the symmetry code (−x + 2, −y + 1, −z + 1)]. The ring offsets (in the same order) are 1.44, 1.32, 0.80, 0.86 and 1.39 Å.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O2ⁱ	0.95	2.43	3.3235 (19)	157
Symmetry code: (i) .

Figure 3
Packing diagram of compound 4, viewed perpendicular to (211). Dashed lines indicate `weak' hydrogen bonds. Atom labels indicate the asymmetric unit. H atoms other than H17 have been omitted.

4. Database survey

The searches employed the routine ConQuest (Bruno et al., 2002 ), part of Version 2022.3.0 of the Cambridge Structural Database (Groom et al., 2016 ). A search for structures containing both a coumarin and a benzothiazole ring system in the same residue gave 16 hits. After excluding ring systems with more extended annelation and molecules where the ring systems were not directly bonded to each other, 7 hits remained. In all of these, the benzothiazole was bonded via its 2-position. The structure with refcode AKUCUG (Bakthadoss & Selvakumar, 2016 ) involved a linkage via the 8-position of the coumarin; the other 6 hits [VIVWEF and VIWDOX (Shi et al., 2019 ); WINZAU (Jasinski & Paight, 1995 ); SECSEC (Abdallah et al., 2022); PEGMEX and PEGMIB (Singh et al., 2022 )] all had this linkage at the 3-position, as in compound 4. In all cases, a short intramolecular S⋯O=C contact was observed, with distances in the range 2.681–2.786 Å.

5. Synthesis and crystallization

5-Methylsalicylaldehyde, 2 (1.36 g, 0.01 mol) and ammonium acetate (0.77 g, 0.01 mol) were added to a solution of N-[2-(benzo[d]thiazol-2-yl)acetyl]benzohydrazide, 1 (3.11 g, 0.01 mol), in ethanol (10 mL). The reaction mixture was refluxed for ca 3 h and the resulting precipitate was collected by filtration and recrystallized from ethanol.

Pale-yellow crystals; yield: 96% (2.82 g); m.p. 495–497 K; IR (KBr, cm⁻¹): ν 3062, (CH-aromatic), 2918 (CH₃), 1710 (C=O), 1582 (C=N) and 1619, 1485 (C=C). ¹H NMR (400 MHz, DMSO-d₆): δ 2.40 (s, 3H, CH₃), 7.42–8.18 (m, 7H, C₆H₄, C₆H₃), 9.19 (s, 1H, CH-pyran). ¹³C NMR (100 MHz, DMSO-d₆): δ 20.8 (CH₃), 116.5, 119.0, 120.0, 122.7, 123.0, 124.5, 125.9, 127.2, 128.6, 130.2, 135.2, 136.4, 142.4, 152.4 (aromatic C atoms, pyran ring), 160.0 (C=N), 160.4 (C=O). MS (EI): m/z (%) 293 [M⁺] (100.00). Analysis calculated (%) for C₁₇H₁₁NO₂S: C 69.61, H 3.78, N 4.77, S 10.93; found: C 69.42, H 3.90, N 4.66, S 10.99.

6. Refinement

The title crystal was a non-merohedral two-component twin. The orientations are related by a 180° rotation around the reciprocal axis c*. The structure was refined using the HKLF5 method, whereby the relative volume of the smaller twin component refined to 0.387 (1). For non-merohedral twins thus refined, R_int is not a valid concept, and the number of reflections should be interpreted with caution, because the equivalent reflections in the intensity file have already been merged.

Crystal data, data collection and structure refinement details are summarized in Table 3. The methyl group was included as an idealized rigid group allowed to rotate but not tip (C—H = 0.98 Å and H—C—H = 109.5°). Other H atoms were included using a riding model starting from calculated positions (aromatic C—H = 0.95 Å). The U_iso(H) values were fixed at 1.5 times U_eq of the parent C atoms for methyl groups and at 1.2 times U_eq for the other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₇H₁₁NO₂S
M_r	293.33
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.1592 (2), 9.0048 (2), 10.8678 (3)
α, β, γ (°)	82.779 (2), 76.016 (2), 75.078 (2)
V (Å³)	655.42 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.22
Crystal size (mm)	0.2 × 0.08 × 0.03

Data collection
Diffractometer	Rigaku XtaLAB Synergy
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd Inc., Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.391, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4408, 4408, 4313
R_int	See Refinement
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.102, 1.07
No. of reflections	4408
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd Inc., Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and XP (Siemens, 1994 ).

Supporting information

CCDC reference: 2256779

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698902300347X/yz2033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300347X/yz2033Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

3-(Benzo[d]thiazol-2-yl)-6-methyl-2H-chromen-2-one top

Crystal data top

C₁₇H₁₁NO₂S	Z = 2
M_r = 293.33	F(000) = 304
Triclinic, P1	D_x = 1.486 Mg m⁻³
a = 7.1592 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.0048 (2) Å	Cell parameters from 15669 reflections
c = 10.8678 (3) Å	θ = 5.1–76.9°
α = 82.779 (2)°	µ = 2.22 mm⁻¹
β = 76.016 (2)°	T = 100 K
γ = 75.078 (2)°	Lath, yellow
V = 655.42 (3) Å³	0.2 × 0.08 × 0.03 mm

Data collection top

Rigaku XtaLAB Synergy diffractometer	4408 measured reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	4408 independent reflections
Mirror monochromator	4313 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.7°, θ_min = 4.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	k = −11→11
T_min = 0.391, T_max = 1.000	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.069P)² + 0.1477P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4408 reflections	Δρ_max = 0.36 e Å⁻³
192 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints

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
O1	0.51103 (16)	0.48246 (12)	0.81168 (9)	0.0190 (2)
O2	0.6896 (2)	0.26471 (13)	0.73105 (10)	0.0284 (3)
C2	0.6325 (2)	0.40210 (18)	0.71141 (13)	0.0193 (3)
C3	0.6808 (2)	0.48993 (17)	0.58998 (12)	0.0165 (3)
C4	0.6030 (2)	0.64361 (17)	0.57955 (12)	0.0167 (3)
H4	0.632732	0.699040	0.499800	0.020*
C4A	0.4771 (2)	0.72457 (17)	0.68581 (13)	0.0163 (3)
C5	0.3967 (2)	0.88415 (17)	0.68151 (13)	0.0180 (3)
H5	0.421660	0.943350	0.603163	0.022*
C6	0.2821 (2)	0.95747 (18)	0.78852 (13)	0.0186 (3)
C7	0.2475 (2)	0.86682 (17)	0.90335 (13)	0.0179 (3)
H7	0.169855	0.915469	0.977831	0.022*
C8A	0.4369 (2)	0.63944 (17)	0.80150 (13)	0.0163 (3)
C8	0.3231 (2)	0.70939 (17)	0.91095 (13)	0.0185 (3)
H8	0.297826	0.650194	0.989268	0.022*
C9	0.1992 (3)	1.12900 (19)	0.78301 (15)	0.0253 (3)
H9A	0.109385	1.158236	0.864314	0.038*
H9B	0.126469	1.159123	0.714667	0.038*
H9C	0.307944	1.181373	0.766476	0.038*
S11	0.92276 (5)	0.21156 (4)	0.48745 (3)	0.01826 (13)
C12	0.8130 (2)	0.40930 (16)	0.48039 (13)	0.0163 (3)
N13	0.85618 (18)	0.48415 (14)	0.37018 (11)	0.0170 (3)
C13A	0.9840 (2)	0.38535 (17)	0.28225 (13)	0.0167 (3)
C14	1.0636 (2)	0.42978 (18)	0.15610 (13)	0.0189 (3)
H14	1.029684	0.533983	0.123985	0.023*
C15	1.1927 (2)	0.31842 (18)	0.07949 (13)	0.0200 (3)
H15	1.249720	0.347072	−0.005730	0.024*
C16	1.2408 (2)	0.16354 (18)	0.12571 (14)	0.0205 (3)
H16	1.327948	0.089102	0.070564	0.025*
C17A	1.0364 (2)	0.23021 (17)	0.32803 (13)	0.0177 (3)
C17	1.1641 (2)	0.11734 (18)	0.24965 (14)	0.0198 (3)
H17	1.196910	0.012568	0.280584	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0238 (6)	0.0148 (5)	0.0158 (5)	−0.0030 (4)	−0.0012 (4)	−0.0006 (4)
O2	0.0399 (7)	0.0162 (6)	0.0212 (5)	−0.0006 (5)	0.0006 (5)	0.0007 (4)
C2	0.0228 (7)	0.0171 (7)	0.0174 (6)	−0.0044 (6)	−0.0029 (5)	−0.0018 (5)
C3	0.0178 (7)	0.0169 (7)	0.0151 (6)	−0.0046 (5)	−0.0036 (5)	−0.0016 (5)
C4	0.0188 (7)	0.0177 (7)	0.0141 (6)	−0.0050 (6)	−0.0036 (5)	−0.0008 (5)
C4A	0.0165 (7)	0.0178 (7)	0.0153 (6)	−0.0044 (6)	−0.0037 (5)	−0.0021 (5)
C5	0.0196 (7)	0.0173 (7)	0.0163 (6)	−0.0043 (6)	−0.0034 (5)	0.0009 (5)
C6	0.0179 (7)	0.0181 (7)	0.0198 (6)	−0.0034 (6)	−0.0046 (5)	−0.0024 (5)
C7	0.0157 (7)	0.0205 (7)	0.0167 (6)	−0.0029 (5)	−0.0017 (5)	−0.0041 (5)
C8A	0.0170 (7)	0.0149 (7)	0.0174 (6)	−0.0047 (5)	−0.0039 (5)	−0.0004 (5)
C8	0.0198 (7)	0.0197 (7)	0.0158 (6)	−0.0060 (6)	−0.0024 (5)	0.0002 (5)
C9	0.0317 (8)	0.0180 (8)	0.0217 (7)	−0.0002 (6)	−0.0027 (6)	−0.0034 (5)
S11	0.0232 (2)	0.01407 (19)	0.01565 (19)	−0.00208 (14)	−0.00330 (13)	−0.00092 (13)
C12	0.0172 (6)	0.0160 (7)	0.0162 (6)	−0.0040 (5)	−0.0046 (5)	−0.0011 (5)
N13	0.0174 (6)	0.0172 (6)	0.0160 (5)	−0.0038 (5)	−0.0031 (4)	−0.0018 (4)
C13A	0.0157 (7)	0.0168 (7)	0.0180 (6)	−0.0038 (5)	−0.0037 (5)	−0.0027 (5)
C14	0.0190 (7)	0.0190 (7)	0.0184 (6)	−0.0047 (6)	−0.0038 (5)	−0.0003 (5)
C15	0.0186 (7)	0.0240 (8)	0.0175 (6)	−0.0067 (6)	−0.0017 (5)	−0.0028 (5)
C16	0.0185 (7)	0.0227 (8)	0.0211 (7)	−0.0041 (6)	−0.0036 (5)	−0.0076 (6)
C17A	0.0186 (7)	0.0171 (7)	0.0186 (6)	−0.0052 (6)	−0.0051 (5)	−0.0016 (5)
C17	0.0206 (7)	0.0176 (7)	0.0216 (7)	−0.0036 (6)	−0.0054 (5)	−0.0039 (5)

Geometric parameters (Å, º) top

O1—C2	1.3723 (17)	C13A—C14	1.4022 (19)
O1—C8A	1.3765 (18)	C13A—C17A	1.409 (2)
O2—C2	1.2077 (19)	C14—C15	1.383 (2)
C2—C3	1.4645 (19)	C15—C16	1.406 (2)
C3—C4	1.354 (2)	C16—C17	1.381 (2)
C3—C12	1.4698 (19)	C17A—C17	1.399 (2)
C4—C4A	1.4310 (19)	C4—H4	0.9500
C4A—C8A	1.3956 (19)	C5—H5	0.9500
C4A—C5	1.403 (2)	C7—H7	0.9500
C5—C6	1.384 (2)	C8—H8	0.9500
C6—C7	1.4083 (19)	C9—H9A	0.9800
C6—C9	1.504 (2)	C9—H9B	0.9800
C7—C8	1.381 (2)	C9—H9C	0.9800
C8A—C8	1.3897 (19)	C14—H14	0.9500
S11—C17A	1.7343 (14)	C15—H15	0.9500
S11—C12	1.7515 (15)	C16—H16	0.9500
C12—N13	1.3076 (18)	C17—H17	0.9500
N13—C13A	1.3836 (18)

C2—O1—C8A	122.52 (11)	C14—C15—C16	121.07 (13)
O2—C2—O1	116.99 (12)	C17—C16—C15	121.37 (14)
O2—C2—C3	125.69 (14)	C17—C17A—C13A	121.53 (13)
O1—C2—C3	117.32 (13)	C17—C17A—S11	129.05 (12)
C4—C3—C2	119.91 (13)	C13A—C17A—S11	109.42 (11)
C4—C3—C12	120.78 (12)	C16—C17—C17A	117.68 (14)
C2—C3—C12	119.31 (13)	C3—C4—H4	119.2
C3—C4—C4A	121.57 (12)	C4A—C4—H4	119.2
C8A—C4A—C5	118.28 (13)	C6—C5—H5	119.2
C8A—C4A—C4	117.62 (13)	C4A—C5—H5	119.2
C5—C4A—C4	124.07 (12)	C8—C7—H7	119.0
C6—C5—C4A	121.65 (13)	C6—C7—H7	119.0
C5—C6—C7	117.94 (14)	C7—C8—H8	120.7
C5—C6—C9	121.11 (13)	C8A—C8—H8	120.7
C7—C6—C9	120.94 (13)	C6—C9—H9A	109.5
C8—C7—C6	122.00 (13)	C6—C9—H9B	109.5
O1—C8A—C8	117.40 (12)	H9A—C9—H9B	109.5
O1—C8A—C4A	121.01 (13)	C6—C9—H9C	109.5
C8—C8A—C4A	121.59 (14)	H9A—C9—H9C	109.5
C7—C8—C8A	118.53 (13)	H9B—C9—H9C	109.5
C17A—S11—C12	88.94 (7)	C15—C14—H14	120.8
N13—C12—C3	120.72 (13)	C13A—C14—H14	120.8
N13—C12—S11	115.94 (11)	C14—C15—H15	119.5
C3—C12—S11	123.35 (10)	C16—C15—H15	119.5
C12—N13—C13A	110.47 (12)	C17—C16—H16	119.3
N13—C13A—C14	124.90 (13)	C15—C16—H16	119.3
N13—C13A—C17A	115.23 (12)	C16—C17—H17	121.2
C14—C13A—C17A	119.86 (13)	C17A—C17—H17	121.2
C15—C14—C13A	118.48 (14)

C8A—O1—C2—O2	179.74 (13)	C4A—C8A—C8—C7	0.5 (2)
C8A—O1—C2—C3	−0.6 (2)	C4—C3—C12—N13	−0.9 (2)
O2—C2—C3—C4	178.35 (15)	C2—C3—C12—N13	178.82 (13)
O1—C2—C3—C4	−1.3 (2)	C4—C3—C12—S11	178.79 (11)
O2—C2—C3—C12	−1.3 (2)	C2—C3—C12—S11	−1.53 (19)
O1—C2—C3—C12	178.98 (12)	C17A—S11—C12—N13	−0.22 (11)
C2—C3—C4—C4A	1.5 (2)	C17A—S11—C12—C3	−179.88 (12)
C12—C3—C4—C4A	−178.79 (13)	C3—C12—N13—C13A	179.37 (12)
C3—C4—C4A—C8A	0.1 (2)	S11—C12—N13—C13A	−0.31 (15)
C3—C4—C4A—C5	178.18 (13)	C12—N13—C13A—C14	−178.01 (13)
C8A—C4A—C5—C6	0.7 (2)	C12—N13—C13A—C17A	0.85 (17)
C4—C4A—C5—C6	−177.38 (13)	N13—C13A—C14—C15	178.86 (13)
C4A—C5—C6—C7	0.0 (2)	C17A—C13A—C14—C15	0.1 (2)
C4A—C5—C6—C9	179.11 (13)	C13A—C14—C15—C16	1.1 (2)
C5—C6—C7—C8	−0.4 (2)	C14—C15—C16—C17	−1.2 (2)
C9—C6—C7—C8	−179.54 (14)	N13—C13A—C17A—C17	179.81 (13)
C2—O1—C8A—C8	−177.01 (13)	C14—C13A—C17A—C17	−1.3 (2)
C2—O1—C8A—C4A	2.3 (2)	N13—C13A—C17A—S11	−1.00 (16)
C5—C4A—C8A—O1	179.81 (12)	C14—C13A—C17A—S11	177.92 (11)
C4—C4A—C8A—O1	−2.0 (2)	C12—S11—C17A—C17	179.76 (15)
C5—C4A—C8A—C8	−1.0 (2)	C12—S11—C17A—C13A	0.66 (11)
C4—C4A—C8A—C8	177.23 (13)	C15—C16—C17—C17A	0.0 (2)
C6—C7—C8—C8A	0.2 (2)	C13A—C17A—C17—C16	1.2 (2)
O1—C8A—C8—C7	179.80 (12)	S11—C17A—C17—C16	−177.78 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O2ⁱ	0.95	2.43	3.3235 (19)	157

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

The authors acknowledge support by the Open Access Publication Funds of the Technical University of Braunschweig.

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