Synthesis, crystal structure and Hirshfeld surface analysis of 5-oxo-N-phenyl-3-(thio­phen-2-yl)-2,3,4,5-tetra­hydro-[1,1′-biphen­yl]-4-carboxamide

Aliyeva, K.N.; Hökelek, T.; Khrustalev, V.N.; Rzayev, R.M.; Bhattarai, A.; Maharramov, A.M.; Shikhaliyev, N.G.

doi:10.1107/S205698902500057X

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ISSN: 2056-9890

Volume 81| Part 2| February 2025| Pages 177-182

https://doi.org/10.1107/S205698902500057X

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Synthesis, crystal structure and Hirshfeld surface analysis of 5-oxo-N-phenyl-3-(thiophen-2-yl)-2,3,4,5-tetrahydro-[1,1′-biphenyl]-4-carboxamide

Khatira N. Aliyeva,^a Tuncer Hökelek,^b Victor N. Khrustalev,^c,^d Rovnag M. Rzayev,^e Ajaya Bhattarai,^f ^* Abel M. Maharramov ^a and Namig G. Shikhaliyev ^g

^aDepartment of Chemistry, Baku State University, Z. Xalilov Str. 23, AZ 1148 Baku, Azerbaijan, ^bHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, ^cFriendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow 117198, Russian Federation, ^dN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow 119991, Russian Federation, ^e`Composite materials' Scientific Research Center, Azerbaijan State Economic University (UNEC), Murtuza Mukhtarov Str. 194, AZ 1065, Baku, Azerbaijan, ^fDepartment of Chemistry, M. M. A. M. C. (Tribhuvan University), Biratnagar, Nepal, and ^gDepartment of Chemical Engineering, Baku Engineering University, Hasan Aliyev Str. 120, AZ 0101 Baku, Azerbaijan
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 December 2024; accepted 21 January 2025; online 28 January 2025)

The asymmetric unit of the title compound, C₂₃H₁₉NO₂S, contains two molecules that differ in the conformation of the two carboxamide moieties. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into chains propagating parallel to the c-axis direction. Between the molecules, weak C—H⋯π(ring) interactions are present, whereas π–π interactions are not observed. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (47.6%), H⋯C/C⋯H (33.4%) and H⋯O/O⋯H (11.6%) interactions. Orientational disorder is observed for both thiophene rings.

Keywords: crystal structure; carboxamide; hydrogen bond; thiophene disorder; biphenyl-4-carboxamide.

CCDC reference: 2418655

1. Chemical context

The syntheses and structural characterization of heterocyclic compounds continue to be of interest in organic and medicinal chemistry due to the various applications of these compounds in pharmaceuticals, materials science and catalysis (Askerov et al., 2020 ; Karimli et al., 2023 ; Khalilov, 2021 ; Khalilov et al., 2024 ). Among these, biphenyl derivatives containing thiophene and amide functional groups are particularly notable for their biological activities, including anti-inflammatory, anticancer and antimicrobial properties (Tas et al., 2023 ; Rzayev & Khalilov, 2024 ). Furthermore, the structural features of these compounds suggest their potential relevance in coordination chemistry (Mahmoudi et al., 2021 ; Gurbanov et al., 2021 ). In particular, when other functional groups are present, like the amide group, the thiophene moiety and the biphenyl skeleton, multiple coordination sites are available, enabling the formation of stable metal complexes (Khalilov et al., 2018a ,b ; Naghiyev et al., 2021a ,b ; Akkurt et al., 2018 ).

Natural products with a tetrahydro-[1,1′-biphenyl] core are rare, but many contain biphenyl-like or partially hydrogenated systems. Examples include flavonoids, stilbenoids and lignans, which often function as biosynthetic intermediates or exhibit significant biological activities (Nenajdenko et al., 2023 ; Niesen et al., 2013 ). Thiophene-containing fragments appear in natural products such as biotin and thiocillins, the latter of which exhibit antibiotic activity. The amide functionality is a common feature in bioactive molecules such as capsaicin, which has pain-relieving properties, and β-lactam antibiotics, which are critical in medicinal treatments. These structural motifs contribute to the rigidity, conjugation and hydrogen-bonding potential, influencing its interactions in biological and chemical environments (Nagiyev et al., 2022 ; Mamedov et al., 2020 ).

In the context given above, we report here the synthesis, molecular and crystal structures, as well as Hirshfeld surface analysis, of 5-oxo-N-phenyl-3-(thiophen-2-yl)-2,3,4,5-tetrahydro-[1,1′-biphenyl]-4-carboxamide. The results provide comprehensive insights into its molecular shape, hydrogen-bonding interactions and crystal packing features, contributing valuable information to the growing database of functionalized carbo- and heterocyclic compounds.

2. Structural commentary

The asymmetric unit of the title compound comprises two molecules (Fig. 1). The A (C1—C6) and E (C24—C29) rings are in envelope conformations (Fig. 2), with puckering parameters (Cremer & Pople, 1975 ) of Q_T = 0.496 (3) Å, θ = 126.0 (3)° and φ = 289.2 (4)° for ring A, and Q_T = 0.443 (3) Å, θ = 126.2 (4)° and φ = 299.2 (4)° for ring E, where atoms C3 and C26, respectively, are at the flap positions and are 0.6894 (16) and 0.6191 (16) Å away from the least-squares planes of the other five atoms. The coplanar B (C8—C13), C (S1/C14—C17) and D (C18—C23) rings, and coplanar F (C31—C36), G (S2/C37—C40) and H (C41—C46) rings are oriented at dihedral angles of B/C = 58.93 (7)°, B/D = 87.08 (8)° and C/D = 41.61 (8)°, and F/G = 62.65 (5)°, F/H = 89.30 (7)° and G/H = 80.57 (6)°. Thus, the B/D and F/H rings are almost perpendicularly oriented. Both thiophene rings (C and G) are disordered over two sets of sites. For a more compherensible and visual comparison of the two molecules present in the asymmetric unit, an overlay plot is given in Fig. 3. The differences between the two molecules are clearly seen in the conformations about the carboxamide moieties, with torsion angles of 71.4 (3)° for C1—C2—C7—O2 and −60.9 (3)° for C24—C25—C30—O4, so that the N—H and C=O groups in the two molecules are oppositely oriented. The C and D, and G and H rings overlap exactly, whereas the A and B, and E and F rings do not. There are no unusual bond distances or interbond angles in the molecules.

Figure 1
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level and with the labelling scheme for the rings. Only the major parts of the disordered thiophene rings are shown for clarity.

Figure 2
Conformations of the central (a) A (C1–C6) ring and (b) E (C24–C29) ring.

Figure 3
An overlay plot of the two molecules present in the asymmetric unit.

3. Supramolecular features

In the crystal, intermolecular N—H⋯O hydrogen bonds between neighbouring carboxamide moieties (Table 1) link the molecules into supramolecular chains propagating parallel to the c-axis direction (Fig. 4). Weak C—H⋯π(ring) interactions are observed (Table 1), whereas notable π–π interactions are not present.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg7 and Cg10 are the centroids of the S1/C14–C17, S2/C37–C49, C18–C23 and C41–C46 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O4ⁱⁱⁱ	0.85 (4)	2.07 (4)	2.921 (3)	173 (4)
N2—H2N⋯O2	0.94 (4)	1.95 (4)	2.871 (3)	167 (3)
C11—H11⋯Cg1^v	0.95	2.71	3.468 (3)	137
C12—H12⋯Cg10^vi	0.95	2.87	3.772 (3)	159
C34—H34⋯Cg2ⁱ	0.95	2.78	3.546 (3)	139
C38—H38⋯Cg7^v	0.95	2.81	3.603 (5)	142
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vi) $[x, -y+2, z-{\script{1\over 2}}]$ .

Figure 4
A partial packing diagram showing intermolecular N—H⋯O hydrogen bonds as dashed lines. Only the major parts of the disordered thiophene rings are shown for clarity.

4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out using CrystalExplorer (Spackman et al., 2021 ). It is noted that only the major components of the disordered part of the thiophene rings were taken into account for the analysis. In the HS plotted over d_norm (Fig. 5), the white surface indicates contacts with distances equal to the sum of the van der Waals radii, and the red and blue colours indicate distances shorter or longer than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The present bright-red spots indicate their roles as the respective donors and/or acceptors in hydrogen bonding, as discussed. In addition, shape index was used to identify possible π–π stacking and C—H⋯π interactions, where π–π stacking is indicated by the presence of adjacent red and blue triangles, and C—H⋯π interactions as ‘red p-holes’ which are related to the electron ring interactions between the C—H groups with the centroid of the aromatic rings of neighbouring molecules. Fig. 6 clearly suggests that there are C—H⋯π interactions in the title compound but no π–π interactions.

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm.

Figure 6
Hirshfeld surface of the title compound plotted over shape index for two orientations.

The overall two-dimensional fingerprint plot (McKinnon et al., 2007 ) is ahown in Fig. 7(a) and those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, H⋯S/S⋯H, C⋯S/S⋯C and H⋯N/N⋯H interactions are illustrated in Figs. 7(b)–(g), respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H (Table 2), contributing 47.6% to the overall crystal packing, which is reflected in Fig. 7(b), with the tip at d_e = d_i = 1.10 Å. Due to C—H⋯π interactions (Table 1), the characteristic wings of the H⋯C/C⋯H contacts (Table 2) are reflected in Fig. 7(c), with the tips at d_e + d_i = 2.64 Å and d_e + d_i = 2.66 Å for the sharper and wider ones, respectively. The symmetrical pairs of spikes of the H⋯O/O⋯H [Table 2 and Fig. 7(d)] and H⋯S/S⋯H [Table 2 and Fig. 7(e)] contacts are viewed with the tips at d_e + d_i = 1.94 Å and d_e + d_i = 3.00 Å, respectively. The C⋯S/S⋯C [Fig. 7(f)] contacts have an arrow-shaped distribution of points, and they are viewed with the tip at d_e = d_i = 1.72 Å. Finally, the H⋯N/N⋯H [Fig. 7(g)] contacts contribute only marginally to the HS.

Table 2
Selected interatomic distances (Å)

S1⋯H2	2.95	C23⋯H4B	2.57
S2⋯H25	2.96	C27⋯H42	2.54
S2⋯H27B	2.93	C27⋯H38A	2.97
O2⋯C13	2.920 (3)	C29⋯H46	2.65
O4⋯C36	2.900 (3)	C30⋯H36	2.79
H16⋯O1ⁱ	2.71	C30⋯H43ⁱ	2.88
H17A⋯O1ⁱ	2.72	C40⋯H44^iv	2.84
H22⋯O1ⁱⁱ	2.35	C42⋯H27A	2.61
O2⋯H3	2.68	C46⋯H29	2.59
O2⋯H13	2.37	H1N⋯H9	2.32
O2⋯H2N	1.95 (4)	H1N⋯H2	2.10
O3⋯H43ⁱ	2.42	H2N⋯H25	2.03
O4⋯H26	2.67	H4B⋯H23	1.96
O4⋯H36	2.38	H6⋯H19	2.06
H1N⋯O4ⁱⁱⁱ	2.07 (4)	H27A⋯H42	2.11
C4⋯H23	2.61	H27B⋯H38A	2.37
C6⋯H19	2.62	H29⋯H46	2.05
C7⋯H13	2.84	H40⋯H44^iv	2.36
C19⋯H6	2.58
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) .

Figure 7
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) H⋯S/S⋯H, (f) C⋯S/S⋯C and (g) H⋯N/N⋯H interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

The nearest neighbour environment of a molecule can be determined from the colour patches on the HS based on how close to other molecules they are. The Hirshfeld surface representations of contact patches plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions in Figs. 8(a)–(c), respectively.

Figure 8
The Hirshfeld surface representations of contact patches plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H and (c) H⋯O/O⋯H interactions.

In summary, the HS analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that corresponding van der Waals interactions, as well as hydrogen bonding, play the major roles in the crystal packing (Hathwar et al., 2015 ).

5. Synthesis and crystallization

A solution of acetoacetanilide (5.20 mmol) and 1-phenyl-3-(thiophen-2-yl)prop-2-en-1-one (5.10 mmol) in methanol (10 ml) was stirred for 1 h. 3 drops of methylpiperazine were then added to the solution. The resulting mixture was refluxed for 3 h. When the reaction was complete, it was kept for 5 d for the formation of crystals, which were separated by filtration and recrystallized from an ethanol–water solution (m.p. 568–569 K; yield: 72%). ¹H NMR (300 MHz, DMSO-d₆): δ 3.19 (dd, 2H, CH₂), 3.86 (d, 1H, CH), 4.16 (k, 1H, CH) [q, 6.59 (s, 1H, =CH), 6.95–7.74 (m, 13H, 10CH_ar + 3CH_thien), 10.23 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d₆): δ 36.20 (CH₂), 38.47 (CH), 61.44 (CH), 119.50 (CH=), 119.60 (CH_ar), 123.91 (CH_thien), 124.11 (CH_ar), 124.69 (CH_ar), 125.19 (CH_thien), 126.99 (2CH_ar), 127.29 (CH_thien), 129.19 (2CH_ar), 129.34 (2CH_ar), 131.01 (CH_ar), 137.82 (C_thien), 139.14 (C_tert), 145.82 (C_ar), 159.18 (C_ar), 167.72 (–N—C=O), 195.19 (C=O).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The N—H hydrogens were located in a difference Fourier map and refined freely. The C-bound H-atom positions were calculated geometrically at distances of 1.00 (for methine CH), 0.95 (for aromatic CH) and 0.99 Å (for CH₂), and refined using a riding model with U_iso(H) = 1.2U_eq(C). Both thiophene rings are found to be disordered over two sets of sites. They were refined with a fixed occupancy ratio of 0.7:0.3 for the major and minor parts.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₃H₁₉NO₂S
M_r	373.45
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	16.1416 (5), 12.8991 (4), 19.0656 (5)
β (°)	107.416 (1)
V (Å³)	3787.71 (19)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.19
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III area-detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.666, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	44070, 13781, 12646
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.129, 1.03
No. of reflections	13781
No. of parameters	494
No. of restraints	34
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.65
Absolute structure	Refined as an inversion twin; Flack x determined using 5763 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons & Flack, 2004 )
Absolute structure parameter	0.37 (8)
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2018), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2418655

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698902500057X/wm5747sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902500057X/wm5747Isup2.hkl

cover letter. DOI: https://doi.org/10.1107/S205698902500057X/wm5747sup3.txt

Supporting information file. DOI: https://doi.org/10.1107/S205698902500057X/wm5747Isup4.cml

checkCIF report

Computing details top

5-Oxo-N-phenyl-3-(thiophen-2-yl)-2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-carboxamide top

Crystal data top

C₂₃H₁₉NO₂S	F(000) = 1568
M_r = 373.45	D_x = 1.310 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 16.1416 (5) Å	Cell parameters from 9482 reflections
b = 12.8991 (4) Å	θ = 2.2–32.5°
c = 19.0656 (5) Å	µ = 0.19 mm⁻¹
β = 107.416 (1)°	T = 100 K
V = 3787.71 (19) Å³	Prism, colourless
Z = 8	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker D8 QUEST PHOTON-III area-detector diffractometer	12646 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.031
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 32.6°, θ_min = 2.2°
T_min = 0.666, T_max = 0.746	h = −24→24
44070 measured reflections	k = −19→19
13781 independent reflections	l = −28→28

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.0623P)² + 3.960P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
13781 reflections	Δρ_max = 0.62 e Å⁻³
494 parameters	Δρ_min = −0.65 e Å⁻³
34 restraints	Absolute structure: Refined as an inversion twin; Flack x determined using 5763 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
Primary atom site location: difference Fourier map	Absolute structure parameter: 0.37 (8)

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.

Refinement. Refined as a 2-component inversion twin

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.73160 (7)	0.42886 (8)	0.71887 (6)	0.02445 (19)	0.7
S1'	0.73378 (16)	0.38641 (19)	0.57558 (16)	0.0263 (5)	0.3
O1	0.40433 (13)	0.60901 (15)	0.57901 (13)	0.0270 (4)
O2	0.49029 (13)	0.39952 (15)	0.53972 (10)	0.0221 (3)
N1	0.48998 (14)	0.37371 (15)	0.65812 (11)	0.0165 (3)
C1	0.48285 (15)	0.62230 (18)	0.59522 (13)	0.0173 (4)
C2	0.54702 (15)	0.53526 (17)	0.62719 (13)	0.0163 (4)
H2	0.564164	0.539595	0.682040	0.020*
C3	0.62924 (13)	0.54764 (17)	0.60251 (13)	0.0174 (4)
H3	0.610628	0.545920	0.547561	0.021*
C4	0.66919 (15)	0.65469 (18)	0.62661 (15)	0.0208 (4)
H4A	0.693229	0.655867	0.680852	0.025*
H4B	0.717865	0.665911	0.605888	0.025*
C5	0.60495 (15)	0.74233 (17)	0.60257 (13)	0.0162 (4)
C6	0.51878 (15)	0.72339 (17)	0.58679 (13)	0.0168 (4)
H6	0.479630	0.779177	0.569254	0.020*
C7	0.50540 (14)	0.42931 (17)	0.60344 (13)	0.0155 (4)
C8	0.46246 (15)	0.26899 (17)	0.65529 (13)	0.0159 (4)
C9	0.47950 (19)	0.21882 (19)	0.72294 (14)	0.0232 (5)
H9	0.508457	0.254912	0.766873	0.028*
C10	0.4544 (2)	0.1165 (2)	0.72647 (16)	0.0263 (5)
H10	0.466516	0.082856	0.772774	0.032*
C11	0.41199 (17)	0.06340 (19)	0.66302 (15)	0.0218 (4)
H11	0.394683	−0.006549	0.665548	0.026*
C12	0.39466 (18)	0.1132 (2)	0.59509 (15)	0.0232 (5)
H12	0.365616	0.076614	0.551390	0.028*
C13	0.41951 (16)	0.21586 (19)	0.59071 (14)	0.0198 (4)
H13	0.407405	0.249391	0.544372	0.024*
C14	0.69198 (9)	0.46161 (14)	0.62909 (10)	0.0199 (4)
C15	0.7246 (2)	0.3998 (3)	0.5853 (3)	0.02445 (19)	0.7
H15	0.709503	0.406978	0.533395	0.029*	0.7
C16	0.7843 (2)	0.3228 (3)	0.62621 (18)	0.02445 (19)	0.7
H16	0.813366	0.273307	0.605154	0.029*	0.7
C17	0.79315 (18)	0.3309 (2)	0.69932 (19)	0.02445 (19)	0.7
H17	0.829553	0.286942	0.735642	0.029*	0.7
C15'	0.7301 (4)	0.4225 (5)	0.6987 (3)	0.0263 (5)	0.3
H15A	0.715137	0.454323	0.738197	0.032*	0.3
C16'	0.7904 (4)	0.3381 (5)	0.7164 (4)	0.0263 (5)	0.3
H16A	0.819170	0.307482	0.762600	0.032*	0.3
C17'	0.7948 (3)	0.3143 (5)	0.6480 (3)	0.0263 (5)	0.3
H17A	0.830639	0.259395	0.640767	0.032*	0.3
C18	0.63757 (16)	0.84809 (18)	0.59696 (13)	0.0179 (4)
C19	0.58505 (17)	0.9349 (2)	0.59560 (17)	0.0252 (5)
H19	0.528169	0.925720	0.599421	0.030*
C20	0.6148 (2)	1.0343 (2)	0.58875 (19)	0.0313 (6)
H20	0.578244	1.092451	0.587643	0.038*
C21	0.6980 (2)	1.0486 (2)	0.58352 (17)	0.0304 (6)
H21	0.718368	1.116423	0.578379	0.037*
C22	0.75120 (19)	0.9639 (2)	0.58582 (18)	0.0300 (6)
H22	0.808301	0.973681	0.582633	0.036*
C23	0.72128 (18)	0.8642 (2)	0.59279 (17)	0.0251 (5)
H23	0.758482	0.806550	0.594727	0.030*
S2	0.28115 (7)	0.47394 (8)	0.41495 (7)	0.02627 (18)	0.7
S2'	0.25927 (18)	0.4669 (2)	0.26876 (14)	0.0280 (5)	0.3
O3	0.59672 (12)	0.67727 (16)	0.42626 (12)	0.0250 (4)
O4	0.50311 (13)	0.52390 (14)	0.29766 (10)	0.0215 (3)
N2	0.50923 (14)	0.41810 (15)	0.39523 (11)	0.0163 (3)
C24	0.51761 (15)	0.68815 (19)	0.41100 (13)	0.0178 (4)
C25	0.45807 (15)	0.59458 (17)	0.39697 (13)	0.0163 (4)
H25	0.455743	0.567333	0.445444	0.020*
C26	0.36501 (13)	0.62122 (17)	0.35019 (13)	0.0181 (4)
H26	0.366513	0.639001	0.299534	0.022*
C27	0.33101 (16)	0.71636 (19)	0.38174 (15)	0.0204 (4)
H27A	0.275071	0.738234	0.346700	0.024*
H27B	0.319819	0.696322	0.428205	0.024*
C28	0.39277 (15)	0.80691 (18)	0.39644 (13)	0.0166 (4)
C29	0.47893 (15)	0.79046 (18)	0.40955 (13)	0.0177 (4)
H29	0.516314	0.849028	0.418306	0.021*
C30	0.49336 (15)	0.50904 (17)	0.35838 (13)	0.0165 (4)
C31	0.53480 (14)	0.32350 (17)	0.36947 (13)	0.0153 (4)
C32	0.57754 (16)	0.25144 (18)	0.42214 (14)	0.0188 (4)
H32	0.589395	0.267025	0.472893	0.023*
C33	0.60284 (17)	0.15704 (19)	0.40074 (15)	0.0221 (4)
H33	0.632745	0.108574	0.437023	0.026*
C34	0.58502 (18)	0.13252 (19)	0.32701 (16)	0.0238 (5)
H34	0.603118	0.067987	0.312537	0.029*
C35	0.5403 (2)	0.2036 (2)	0.27440 (15)	0.0267 (5)
H35	0.526614	0.186576	0.223729	0.032*
C36	0.51516 (19)	0.29968 (19)	0.29508 (14)	0.0226 (5)
H36	0.485079	0.348121	0.258852	0.027*
C37	0.30635 (9)	0.53143 (15)	0.34455 (11)	0.0236 (5)
C38	0.2622 (2)	0.4790 (3)	0.2804 (3)	0.02627 (18)	0.7
H38	0.267720	0.498578	0.233975	0.032*	0.7
C39	0.2081 (2)	0.3941 (3)	0.2878 (2)	0.02627 (18)	0.7
H39	0.174131	0.351909	0.248964	0.032*	0.7
C40	0.21388 (18)	0.3843 (2)	0.36005 (19)	0.02627 (18)	0.7
H40	0.183584	0.332886	0.378302	0.032*	0.7
C38'	0.2831 (4)	0.4893 (5)	0.4023 (4)	0.0280 (5)	0.3
H38A	0.304677	0.517381	0.450437	0.034*	0.3
C39'	0.2257 (4)	0.4022 (5)	0.3880 (4)	0.0280 (5)	0.3
H39A	0.204087	0.365049	0.421800	0.034*	0.3
C40'	0.2093 (3)	0.3847 (4)	0.3147 (3)	0.0280 (5)	0.3
H40A	0.172328	0.330200	0.290280	0.034*	0.3
C41	0.35706 (15)	0.91145 (18)	0.39858 (13)	0.0175 (4)
C42	0.27141 (16)	0.92410 (19)	0.40067 (15)	0.0211 (4)
H42	0.236348	0.864781	0.400146	0.025*
C43	0.23728 (17)	1.0228 (2)	0.40349 (16)	0.0234 (5)
H43	0.179575	1.030114	0.405746	0.028*
C44	0.28699 (18)	1.1103 (2)	0.40302 (15)	0.0241 (5)
H44	0.263395	1.177438	0.404512	0.029*
C45	0.37189 (18)	1.0989 (2)	0.40036 (15)	0.0230 (4)
H45	0.406196	1.158652	0.399970	0.028*
C46	0.40657 (16)	1.00110 (19)	0.39827 (14)	0.0202 (4)
H46	0.464568	0.994496	0.396597	0.024*
H1N	0.498 (2)	0.406 (3)	0.699 (2)	0.024*
H2N	0.496 (2)	0.419 (3)	0.440 (2)	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0270 (4)	0.0249 (4)	0.0211 (4)	0.0066 (3)	0.0066 (3)	0.0059 (3)
S1'	0.0214 (9)	0.0245 (10)	0.0325 (12)	−0.0058 (8)	0.0073 (7)	−0.0081 (8)
O1	0.0174 (8)	0.0195 (8)	0.0452 (12)	−0.0051 (7)	0.0108 (8)	0.0005 (8)
O2	0.0310 (9)	0.0207 (8)	0.0159 (7)	−0.0068 (7)	0.0091 (7)	−0.0013 (6)
N1	0.0216 (8)	0.0131 (8)	0.0157 (8)	−0.0019 (7)	0.0070 (7)	−0.0006 (6)
C1	0.0171 (9)	0.0155 (9)	0.0210 (10)	−0.0037 (7)	0.0081 (8)	−0.0018 (8)
C2	0.0185 (9)	0.0135 (9)	0.0185 (9)	−0.0042 (7)	0.0081 (7)	−0.0013 (7)
C3	0.0176 (9)	0.0141 (9)	0.0225 (10)	−0.0018 (7)	0.0089 (8)	0.0008 (7)
C4	0.0164 (9)	0.0132 (9)	0.0329 (12)	−0.0026 (7)	0.0076 (9)	0.0010 (8)
C5	0.0167 (9)	0.0138 (9)	0.0199 (9)	−0.0039 (7)	0.0079 (7)	0.0000 (7)
C6	0.0152 (9)	0.0135 (9)	0.0223 (10)	−0.0030 (7)	0.0065 (7)	−0.0005 (8)
C7	0.0164 (9)	0.0129 (8)	0.0188 (9)	−0.0017 (7)	0.0078 (7)	0.0004 (7)
C8	0.0175 (9)	0.0125 (8)	0.0194 (9)	−0.0023 (7)	0.0082 (7)	−0.0018 (7)
C9	0.0344 (13)	0.0166 (10)	0.0190 (10)	−0.0030 (9)	0.0086 (9)	−0.0002 (8)
C10	0.0388 (14)	0.0178 (10)	0.0235 (11)	−0.0029 (10)	0.0109 (10)	0.0026 (9)
C11	0.0259 (11)	0.0141 (9)	0.0269 (11)	−0.0050 (8)	0.0101 (9)	0.0000 (8)
C12	0.0257 (11)	0.0183 (10)	0.0250 (11)	−0.0085 (9)	0.0067 (9)	−0.0039 (8)
C13	0.0234 (10)	0.0159 (9)	0.0188 (10)	−0.0053 (8)	0.0046 (8)	0.0000 (8)
C14	0.0186 (9)	0.0142 (9)	0.0274 (11)	−0.0018 (8)	0.0078 (8)	0.0001 (8)
C15	0.0270 (4)	0.0249 (4)	0.0211 (4)	0.0066 (3)	0.0066 (3)	0.0059 (3)
C16	0.0270 (4)	0.0249 (4)	0.0211 (4)	0.0066 (3)	0.0066 (3)	0.0059 (3)
C17	0.0270 (4)	0.0249 (4)	0.0211 (4)	0.0066 (3)	0.0066 (3)	0.0059 (3)
C15'	0.0214 (9)	0.0245 (10)	0.0325 (12)	−0.0058 (8)	0.0073 (7)	−0.0081 (8)
C16'	0.0214 (9)	0.0245 (10)	0.0325 (12)	−0.0058 (8)	0.0073 (7)	−0.0081 (8)
C17'	0.0214 (9)	0.0245 (10)	0.0325 (12)	−0.0058 (8)	0.0073 (7)	−0.0081 (8)
C18	0.0178 (9)	0.0148 (9)	0.0215 (10)	−0.0044 (8)	0.0066 (8)	0.0010 (8)
C19	0.0215 (11)	0.0147 (10)	0.0372 (14)	−0.0047 (8)	0.0054 (10)	0.0034 (9)
C20	0.0296 (13)	0.0156 (10)	0.0440 (16)	−0.0043 (10)	0.0038 (11)	0.0061 (10)
C21	0.0369 (14)	0.0214 (12)	0.0292 (13)	−0.0146 (11)	0.0041 (11)	0.0044 (10)
C22	0.0267 (12)	0.0266 (12)	0.0391 (15)	−0.0135 (10)	0.0135 (11)	0.0022 (11)
C23	0.0222 (11)	0.0198 (11)	0.0358 (13)	−0.0079 (9)	0.0126 (10)	−0.0013 (10)
S2	0.0239 (4)	0.0226 (4)	0.0338 (5)	0.0018 (3)	0.0109 (3)	0.0058 (3)
S2'	0.0325 (11)	0.0291 (11)	0.0197 (10)	−0.0075 (8)	0.0035 (7)	−0.0159 (7)
O3	0.0177 (8)	0.0237 (9)	0.0335 (10)	0.0064 (7)	0.0074 (7)	−0.0025 (7)
O4	0.0310 (9)	0.0171 (7)	0.0198 (8)	0.0051 (7)	0.0129 (7)	0.0038 (6)
N2	0.0216 (9)	0.0114 (7)	0.0178 (8)	0.0034 (6)	0.0086 (7)	0.0019 (6)
C24	0.0183 (9)	0.0168 (9)	0.0196 (10)	0.0057 (8)	0.0074 (8)	0.0000 (7)
C25	0.0189 (9)	0.0126 (8)	0.0194 (9)	0.0050 (7)	0.0086 (7)	0.0025 (7)
C26	0.0180 (9)	0.0141 (9)	0.0233 (10)	0.0019 (7)	0.0076 (8)	0.0012 (8)
C27	0.0161 (9)	0.0154 (9)	0.0316 (12)	0.0032 (8)	0.0098 (8)	0.0007 (8)
C28	0.0178 (9)	0.0138 (9)	0.0195 (9)	0.0032 (7)	0.0076 (8)	0.0011 (7)
C29	0.0164 (9)	0.0152 (9)	0.0223 (10)	0.0039 (7)	0.0072 (8)	0.0005 (8)
C30	0.0169 (9)	0.0137 (9)	0.0196 (9)	0.0039 (7)	0.0067 (7)	0.0013 (7)
C31	0.0160 (9)	0.0117 (8)	0.0195 (9)	0.0003 (7)	0.0073 (7)	0.0011 (7)
C32	0.0201 (10)	0.0160 (9)	0.0191 (9)	0.0013 (8)	0.0038 (8)	0.0001 (8)
C33	0.0210 (10)	0.0160 (10)	0.0279 (12)	0.0045 (8)	0.0054 (9)	0.0035 (8)
C34	0.0273 (11)	0.0148 (9)	0.0327 (13)	0.0024 (8)	0.0144 (10)	−0.0040 (9)
C35	0.0425 (15)	0.0198 (11)	0.0200 (11)	0.0008 (10)	0.0128 (10)	−0.0032 (9)
C36	0.0336 (13)	0.0169 (10)	0.0177 (10)	0.0029 (9)	0.0083 (9)	0.0017 (8)
C37	0.0196 (10)	0.0173 (10)	0.0349 (13)	0.0037 (8)	0.0096 (9)	0.0011 (9)
C38	0.0239 (4)	0.0226 (4)	0.0338 (5)	0.0018 (3)	0.0109 (3)	0.0058 (3)
C39	0.0239 (4)	0.0226 (4)	0.0338 (5)	0.0018 (3)	0.0109 (3)	0.0058 (3)
C40	0.0239 (4)	0.0226 (4)	0.0338 (5)	0.0018 (3)	0.0109 (3)	0.0058 (3)
C38'	0.0325 (11)	0.0291 (11)	0.0197 (10)	−0.0075 (8)	0.0035 (7)	−0.0159 (7)
C39'	0.0325 (11)	0.0291 (11)	0.0197 (10)	−0.0075 (8)	0.0035 (7)	−0.0159 (7)
C40'	0.0325 (11)	0.0291 (11)	0.0197 (10)	−0.0075 (8)	0.0035 (7)	−0.0159 (7)
C41	0.0174 (9)	0.0158 (9)	0.0198 (9)	0.0052 (7)	0.0062 (8)	−0.0002 (7)
C42	0.0186 (10)	0.0152 (9)	0.0323 (12)	0.0043 (8)	0.0118 (9)	0.0023 (9)
C43	0.0215 (10)	0.0193 (10)	0.0309 (12)	0.0082 (9)	0.0102 (9)	0.0004 (9)
C44	0.0267 (11)	0.0175 (10)	0.0255 (12)	0.0079 (9)	0.0041 (9)	−0.0012 (9)
C45	0.0266 (11)	0.0145 (9)	0.0268 (11)	0.0011 (8)	0.0065 (9)	0.0000 (8)
C46	0.0187 (10)	0.0177 (10)	0.0249 (11)	0.0020 (8)	0.0075 (8)	−0.0006 (8)

Geometric parameters (Å, º) top

S1—C14	1.692 (2)	S2—C37	1.686 (2)
S1—C17	1.716 (3)	S2—C40	1.712 (3)
S1'—C14	1.688 (3)	S2'—C37	1.644 (3)
S1'—C17'	1.712 (4)	S2'—C40'	1.722 (4)
O1—C1	1.223 (3)	O3—C24	1.230 (3)
O2—C7	1.227 (3)	O4—C30	1.229 (3)
N1—C7	1.349 (3)	N2—C30	1.352 (3)
N1—C8	1.418 (3)	N2—C31	1.422 (3)
N1—H1N	0.85 (4)	N2—H2N	0.94 (4)
C1—C6	1.455 (3)	C24—C29	1.457 (3)
C1—C2	1.526 (3)	C24—C25	1.516 (3)
C2—C7	1.530 (3)	C25—C30	1.528 (3)
C2—C3	1.543 (3)	C25—C26	1.539 (3)
C2—H2	1.0000	C25—H25	1.0000
C3—C14	1.486 (3)	C26—C37	1.479 (3)
C3—C4	1.535 (3)	C26—C27	1.538 (3)
C3—H3	1.0000	C26—H26	1.0000
C4—C5	1.510 (3)	C27—C28	1.507 (3)
C4—H4A	0.9900	C27—H27A	0.9900
C4—H4B	0.9900	C27—H27B	0.9900
C5—C6	1.354 (3)	C28—C29	1.354 (3)
C5—C18	1.478 (3)	C28—C41	1.472 (3)
C6—H6	0.9500	C29—H29	0.9500
C8—C9	1.395 (3)	C31—C32	1.391 (3)
C8—C13	1.398 (3)	C31—C36	1.392 (3)
C9—C10	1.388 (4)	C32—C33	1.384 (3)
C9—H9	0.9500	C32—H32	0.9500
C10—C11	1.380 (4)	C33—C34	1.385 (4)
C10—H10	0.9500	C33—H33	0.9500
C11—C12	1.397 (4)	C34—C35	1.391 (4)
C11—H11	0.9500	C34—H34	0.9500
C12—C13	1.394 (3)	C35—C36	1.397 (4)
C12—H12	0.9500	C35—H35	0.9500
C13—H13	0.9500	C36—H36	0.9500
C14—C15	1.369 (4)	C37—C38'	1.377 (4)
C14—C15'	1.381 (4)	C37—C38	1.392 (4)
C15—C16	1.440 (4)	C38—C39	1.435 (4)
C15—H15	0.9500	C38—H38	0.9500
C16—C17	1.362 (3)	C39—C40	1.358 (3)
C16—H16	0.9500	C39—H39	0.9500
C17—H17	0.9500	C40—H40	0.9500
C15'—C16'	1.432 (4)	C38'—C39'	1.430 (4)
C15'—H15A	0.9500	C38'—H38A	0.9500
C16'—C17'	1.361 (4)	C39'—C40'	1.360 (4)
C16'—H16A	0.9500	C39'—H39A	0.9500
C17'—H17A	0.9500	C40'—H40A	0.9500
C18—C23	1.393 (3)	C41—C42	1.404 (3)
C18—C19	1.401 (4)	C41—C46	1.407 (3)
C19—C20	1.389 (4)	C42—C43	1.395 (3)
C19—H19	0.9500	C42—H42	0.9500
C20—C21	1.389 (4)	C43—C44	1.386 (4)
C20—H20	0.9500	C43—H43	0.9500
C21—C22	1.381 (5)	C44—C45	1.394 (4)
C21—H21	0.9500	C44—H44	0.9500
C22—C23	1.394 (4)	C45—C46	1.386 (3)
C22—H22	0.9500	C45—H45	0.9500
C23—H23	0.9500	C46—H46	0.9500

S1···H2	2.95	C23···H4B	2.57
S2···H25	2.96	C27···H42	2.54
S2···H27B	2.93	C27···H38A	2.97
O2···C13	2.920 (3)	C29···H46	2.65
O4···C36	2.900 (3)	C30···H36	2.79
H16···O1ⁱ	2.71	C30···H43ⁱ	2.88
H17A···O1ⁱ	2.72	C40···H44^iv	2.84
H22···O1ⁱⁱ	2.35	C42···H27A	2.61
O2···H3	2.68	C46···H29	2.59
O2···H13	2.37	H1N···H9	2.32
O2···H2N	1.95 (4)	H1N···H2	2.10
O3···H43ⁱ	2.42	H2N···H25	2.03
O4···H26	2.67	H4B···H23	1.96
O4···H36	2.38	H6···H19	2.06
H1N···O4ⁱⁱⁱ	2.07 (4)	H27A···H42	2.11
C4···H23	2.61	H27B···H38A	2.37
C6···H19	2.62	H29···H46	2.05
C7···H13	2.84	H40···H44^iv	2.36
C19···H6	2.58

C14—S1—C17	91.85 (14)	C37—S2—C40	94.03 (16)
C14—S1'—C17'	93.6 (3)	C37—S2'—C40'	91.6 (3)
C7—N1—C8	127.3 (2)	C30—N2—C31	126.5 (2)
C7—N1—H1N	115 (3)	C30—N2—H2N	114 (2)
C8—N1—H1N	118 (3)	C31—N2—H2N	119 (2)
O1—C1—C6	121.0 (2)	O3—C24—C29	121.1 (2)
O1—C1—C2	121.7 (2)	O3—C24—C25	120.6 (2)
C6—C1—C2	117.26 (19)	C29—C24—C25	118.20 (19)
C1—C2—C7	110.71 (19)	C24—C25—C30	110.62 (18)
C1—C2—C3	110.18 (18)	C24—C25—C26	112.44 (18)
C7—C2—C3	110.10 (18)	C30—C25—C26	108.80 (19)
C1—C2—H2	108.6	C24—C25—H25	108.3
C7—C2—H2	108.6	C30—C25—H25	108.3
C3—C2—H2	108.6	C26—C25—H25	108.3
C14—C3—C4	112.79 (15)	C37—C26—C27	110.94 (16)
C14—C3—C2	112.29 (16)	C37—C26—C25	111.09 (15)
C4—C3—C2	108.93 (19)	C27—C26—C25	110.6 (2)
C14—C3—H3	107.5	C37—C26—H26	108.0
C4—C3—H3	107.5	C27—C26—H26	108.0
C2—C3—H3	107.5	C25—C26—H26	108.0
C5—C4—C3	113.19 (19)	C28—C27—C26	113.43 (19)
C5—C4—H4A	108.9	C28—C27—H27A	108.9
C3—C4—H4A	108.9	C26—C27—H27A	108.9
C5—C4—H4B	108.9	C28—C27—H27B	108.9
C3—C4—H4B	108.9	C26—C27—H27B	108.9
H4A—C4—H4B	107.8	H27A—C27—H27B	107.7
C6—C5—C18	121.0 (2)	C29—C28—C41	121.8 (2)
C6—C5—C4	119.9 (2)	C29—C28—C27	119.9 (2)
C18—C5—C4	119.08 (19)	C41—C28—C27	118.21 (19)
C5—C6—C1	123.6 (2)	C28—C29—C24	123.8 (2)
C5—C6—H6	118.2	C28—C29—H29	118.1
C1—C6—H6	118.2	C24—C29—H29	118.1
O2—C7—N1	124.8 (2)	O4—C30—N2	124.5 (2)
O2—C7—C2	120.8 (2)	O4—C30—C25	120.8 (2)
N1—C7—C2	114.36 (19)	N2—C30—C25	114.6 (2)
C9—C8—C13	119.7 (2)	C32—C31—C36	120.0 (2)
C9—C8—N1	115.7 (2)	C32—C31—N2	117.2 (2)
C13—C8—N1	124.6 (2)	C36—C31—N2	122.7 (2)
C10—C9—C8	120.4 (2)	C33—C32—C31	120.1 (2)
C10—C9—H9	119.8	C33—C32—H32	119.9
C8—C9—H9	119.8	C31—C32—H32	119.9
C11—C10—C9	120.3 (2)	C32—C33—C34	120.7 (2)
C11—C10—H10	119.8	C32—C33—H33	119.7
C9—C10—H10	119.8	C34—C33—H33	119.7
C10—C11—C12	119.6 (2)	C33—C34—C35	119.1 (2)
C10—C11—H11	120.2	C33—C34—H34	120.4
C12—C11—H11	120.2	C35—C34—H34	120.4
C13—C12—C11	120.7 (2)	C34—C35—C36	120.9 (2)
C13—C12—H12	119.6	C34—C35—H35	119.6
C11—C12—H12	119.6	C36—C35—H35	119.6
C12—C13—C8	119.3 (2)	C31—C36—C35	119.1 (2)
C12—C13—H13	120.4	C31—C36—H36	120.4
C8—C13—H13	120.4	C35—C36—H36	120.4
C15—C14—C3	125.1 (3)	C38'—C37—C26	124.9 (4)
C15'—C14—C3	131.5 (4)	C38—C37—C26	126.3 (3)
C15'—C14—S1'	103.1 (4)	C38'—C37—S2'	109.8 (4)
C3—C14—S1'	125.3 (2)	C26—C37—S2'	125.3 (2)
C15—C14—S1	112.0 (3)	C38—C37—S2	107.7 (3)
C3—C14—S1	122.98 (16)	C26—C37—S2	126.02 (18)
C14—C15—C16	112.8 (4)	C37—C38—C39	116.8 (4)
C14—C15—H15	123.6	C37—C38—H38	121.6
C16—C15—H15	123.6	C39—C38—H38	121.6
C17—C16—C15	110.5 (4)	C40—C39—C38	108.2 (4)
C17—C16—H16	124.7	C40—C39—H39	125.9
C15—C16—H16	124.7	C38—C39—H39	125.9
C16—C17—S1	112.8 (3)	C39—C40—S2	113.3 (3)
C16—C17—H17	123.6	C39—C40—H40	123.3
S1—C17—H17	123.6	S2—C40—H40	123.3
C14—C15'—C16'	125.5 (8)	C37—C38'—C39'	118.2 (7)
C14—C15'—H15A	117.3	C37—C38'—H38A	120.9
C16'—C15'—H15A	117.3	C39'—C38'—H38A	120.9
C17'—C16'—C15'	99.9 (8)	C40'—C39'—C38'	104.0 (8)
C17'—C16'—H16A	130.0	C40'—C39'—H39A	128.0
C15'—C16'—H16A	130.0	C38'—C39'—H39A	128.0
C16'—C17'—S1'	117.9 (7)	C39'—C40'—S2'	116.4 (6)
C16'—C17'—H17A	121.1	C39'—C40'—H40A	121.8
S1'—C17'—H17A	121.1	S2'—C40'—H40A	121.8
C23—C18—C19	118.1 (2)	C42—C41—C46	118.0 (2)
C23—C18—C5	121.0 (2)	C42—C41—C28	120.3 (2)
C19—C18—C5	120.9 (2)	C46—C41—C28	121.7 (2)
C20—C19—C18	121.1 (3)	C43—C42—C41	120.7 (2)
C20—C19—H19	119.5	C43—C42—H42	119.6
C18—C19—H19	119.5	C41—C42—H42	119.6
C19—C20—C21	119.8 (3)	C44—C43—C42	120.5 (2)
C19—C20—H20	120.1	C44—C43—H43	119.8
C21—C20—H20	120.1	C42—C43—H43	119.8
C22—C21—C20	119.9 (2)	C43—C44—C45	119.5 (2)
C22—C21—H21	120.1	C43—C44—H44	120.3
C20—C21—H21	120.1	C45—C44—H44	120.3
C21—C22—C23	120.2 (3)	C46—C45—C44	120.4 (2)
C21—C22—H22	119.9	C46—C45—H45	119.8
C23—C22—H22	119.9	C44—C45—H45	119.8
C18—C23—C22	120.9 (3)	C45—C46—C41	120.9 (2)
C18—C23—H23	119.6	C45—C46—H46	119.6
C22—C23—H23	119.6	C41—C46—H46	119.6

O1—C1—C2—C7	25.9 (3)	O3—C24—C25—C30	−35.2 (3)
C6—C1—C2—C7	−156.0 (2)	C29—C24—C25—C30	147.8 (2)
O1—C1—C2—C3	147.9 (2)	O3—C24—C25—C26	−157.1 (2)
C6—C1—C2—C3	−34.0 (3)	C29—C24—C25—C26	26.0 (3)
C1—C2—C3—C14	−177.06 (17)	C24—C25—C26—C37	−173.58 (18)
C7—C2—C3—C14	−54.7 (2)	C30—C25—C26—C37	63.5 (2)
C1—C2—C3—C4	57.3 (2)	C24—C25—C26—C27	−49.9 (3)
C7—C2—C3—C4	179.64 (19)	C30—C25—C26—C27	−172.79 (19)
C14—C3—C4—C5	−177.59 (19)	C37—C26—C27—C28	173.80 (19)
C2—C3—C4—C5	−52.2 (3)	C25—C26—C27—C28	50.0 (3)
C3—C4—C5—C6	22.4 (3)	C26—C27—C28—C29	−25.5 (3)
C3—C4—C5—C18	−157.9 (2)	C26—C27—C28—C41	156.6 (2)
C18—C5—C6—C1	−176.4 (2)	C41—C28—C29—C24	177.4 (2)
C4—C5—C6—C1	3.3 (4)	C27—C28—C29—C24	−0.4 (4)
O1—C1—C6—C5	−178.8 (2)	O3—C24—C29—C28	−176.9 (2)
C2—C1—C6—C5	3.1 (3)	C25—C24—C29—C28	0.1 (3)
C8—N1—C7—O2	6.8 (4)	C31—N2—C30—O4	−3.7 (4)
C8—N1—C7—C2	−171.5 (2)	C31—N2—C30—C25	174.1 (2)
C1—C2—C7—O2	71.4 (3)	C24—C25—C30—O4	−60.9 (3)
C3—C2—C7—O2	−50.7 (3)	C26—C25—C30—O4	63.1 (3)
C1—C2—C7—N1	−110.2 (2)	C24—C25—C30—N2	121.2 (2)
C3—C2—C7—N1	127.7 (2)	C26—C25—C30—N2	−114.8 (2)
C7—N1—C8—C9	158.7 (2)	C30—N2—C31—C32	157.3 (2)
C7—N1—C8—C13	−22.4 (4)	C30—N2—C31—C36	−25.8 (4)
C13—C8—C9—C10	0.3 (4)	C36—C31—C32—C33	1.8 (4)
N1—C8—C9—C10	179.3 (2)	N2—C31—C32—C33	178.9 (2)
C8—C9—C10—C11	−0.3 (4)	C31—C32—C33—C34	−0.9 (4)
C9—C10—C11—C12	0.2 (4)	C32—C33—C34—C35	−0.8 (4)
C10—C11—C12—C13	−0.2 (4)	C33—C34—C35—C36	1.5 (4)
C11—C12—C13—C8	0.2 (4)	C32—C31—C36—C35	−1.1 (4)
C9—C8—C13—C12	−0.2 (4)	N2—C31—C36—C35	−178.0 (2)
N1—C8—C13—C12	−179.2 (2)	C34—C35—C36—C31	−0.6 (4)
C4—C3—C14—C15	−111.8 (2)	C27—C26—C37—C38'	−57.0 (2)
C2—C3—C14—C15	124.67 (19)	C25—C26—C37—C38'	66.5 (2)
C4—C3—C14—C15'	69.4 (2)	C27—C26—C37—C38	119.5 (2)
C2—C3—C14—C15'	−54.2 (2)	C25—C26—C37—C38	−117.0 (2)
C4—C3—C14—S1'	−110.7 (2)	C27—C26—C37—S2'	123.1 (2)
C2—C3—C14—S1'	125.8 (2)	C25—C26—C37—S2'	−113.4 (2)
C4—C3—C14—S1	68.23 (18)	C27—C26—C37—S2	−60.68 (18)
C2—C3—C14—S1	−55.32 (17)	C25—C26—C37—S2	62.81 (17)
C17'—S1'—C14—C15'	−0.03 (12)	C40'—S2'—C37—C38'	0.00 (12)
C17'—S1'—C14—C3	−179.97 (7)	C40'—S2'—C37—C26	179.91 (7)
C17—S1—C14—C15	−0.02 (11)	C40—S2—C37—C38	−0.36 (11)
C17—S1—C14—C3	179.97 (6)	C40—S2—C37—C26	179.79 (7)
C3—C14—C15—C16	179.94 (10)	C26—C37—C38—C39	−179.62 (11)
S1—C14—C15—C16	−0.07 (18)	S2—C37—C38—C39	0.54 (18)
C14—C15—C16—C17	0.1 (2)	C37—C38—C39—C40	−0.5 (2)
C15—C16—C17—S1	−0.2 (2)	C38—C39—C40—S2	0.2 (2)
C14—S1—C17—C16	0.11 (14)	C37—S2—C40—C39	0.12 (15)
C3—C14—C15'—C16'	−179.92 (14)	C26—C37—C38'—C39'	−179.91 (13)
S1'—C14—C15'—C16'	0.2 (2)	S2'—C37—C38'—C39'	0.0 (2)
C14—C15'—C16'—C17'	−0.2 (3)	C37—C38'—C39'—C40'	0.0 (3)
C15'—C16'—C17'—S1'	0.2 (2)	C38'—C39'—C40'—S2'	0.0 (2)
C14—S1'—C17'—C16'	−0.08 (17)	C37—S2'—C40'—C39'	0.00 (17)
C6—C5—C18—C23	−161.9 (2)	C29—C28—C41—C42	−166.2 (2)
C4—C5—C18—C23	18.4 (3)	C27—C28—C41—C42	11.7 (3)
C6—C5—C18—C19	18.0 (4)	C29—C28—C41—C46	14.1 (4)
C4—C5—C18—C19	−161.7 (2)	C27—C28—C41—C46	−168.0 (2)
C23—C18—C19—C20	1.3 (4)	C46—C41—C42—C43	−1.0 (4)
C5—C18—C19—C20	−178.6 (3)	C28—C41—C42—C43	179.3 (2)
C18—C19—C20—C21	−0.3 (5)	C41—C42—C43—C44	1.1 (4)
C19—C20—C21—C22	−0.6 (5)	C42—C43—C44—C45	−0.6 (4)
C20—C21—C22—C23	0.5 (5)	C43—C44—C45—C46	−0.1 (4)
C19—C18—C23—C22	−1.4 (4)	C44—C45—C46—C41	0.2 (4)
C5—C18—C23—C22	178.5 (3)	C42—C41—C46—C45	0.3 (4)
C21—C22—C23—C18	0.5 (5)	C28—C41—C46—C45	−180.0 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg7 and Cg10 are the centroids of the S1/C14···C17, S2/C37···C49, C18···C23 and C41···C46 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4ⁱⁱⁱ	0.85 (4)	2.07 (4)	2.921 (3)	173 (4)
N2—H2N···O2	0.94 (4)	1.95 (4)	2.871 (3)	167 (3)
C11—H11···Cg1^v	0.95	2.71	3.468 (3)	137
C12—H12···Cg10^vi	0.95	2.87	3.772 (3)	159
C34—H34···Cg2ⁱ	0.95	2.78	3.546 (3)	139
C38—H38···Cg7^v	0.95	2.81	3.603 (5)	142

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

Acknowledgements

This work has been supported by the Baku State University and RUDN University Strategic Academic Leadership Program. TH is also grateful to Hacettepe University Scientific Research Project Unit. The authors contributions are as follows: conceptualizations KNA and TH; methodology AMM and NGS; investigation VNK and KNA; writing (original draft) TH, AB and AMM; writing (review and editing of the manuscript) TH and NGS; visualization TH and AB; funding acquisition VNK, TH and NGS; resources TH, VNK and RMR; supervision AMM and TH.

Funding information

Funding for this research was provided by: Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004 to T. Hökelek).

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