2-Amino-5-oxo-4-(thio­phen-2-yl)-5,6,7,8-tetra­hydro-4H-chromene-3-carbo­nitrile

Nyapola, C.; Zamisa, S.J.; Njogu, E.M.; Omondi, B.

doi:10.1107/S2414314624010496

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 11| November 2024| x241049

https://doi.org/10.1107/S2414314624010496

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2-Amino-5-oxo-4-(thiophen-2-yl)-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile

Carren Nyapola,^a Sizwe J. Zamisa,^a ^* Eric M. Njogu ^b and Bernard Omondi ^a

^aSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville campus, Private bag X54001, Durban, 4000, South Africa, and ^bMultimedia University of Kenya, PO Box 15653-00503, Nairobi, Kenya
^*Correspondence e-mail: Zamisas@ukzn.ac.za

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 27 September 2024; accepted 30 October 2024; online 8 November 2024)

The crystal structure of the title compound, C₁₄H₁₂N₂O₂S, reveals two symmetrically independent molecules within the asymmetric unit. Each molecule contains a chromenone core attached to a 2-thiophene ring, cyano, and amino groups. The 2-thiophene ring of one of the two molecules in the asymmetric unit was found to be disordered over two positions, with the major component having a site occupancy factor of 0.837 (2). The 2-thiophene ring is nearly orthogonal to the fused 4H-pyran ring, with dihedral angles between the two sets of planes being 89.5 (5) and 89.63 (8)°. Intermolecular hydrogen bonding, involving N—H⋯N and N—H⋯O interactions, creates two distinct motifs leading to the formation of a two-dimensional supramolecular network along the crystallographic ac plane.

Keywords: crystal structure; pyran; chromenone; hydrogen bond.

CCDC reference: 2394700

Structure description

Pyran-based 2-amino-3-carbonitrile derivatives are known to possess interesting pharmacological properties, which enable them to be explored as potential anticancer (Braga et al., 2022 ), antioxidant (Symeonidis et al., 2009 ), antibacterial (Kathrotiya & Patel, 2012 ), antifungal (Alvey et al., 2009 ), hypotensive (Cai et al., 2009 ) and antileishmanial (Narender et al., 2004 ) agents. In our previous work, we surveyed the Cambridge Structural Database (CSD) and categorized the diverse intermolecular hydrogen-bonding patterns that emerge in the crystal structures of aryl-based rac-2-amino-3-carbonitrile derivatives (Zamisa et al., 2022 ). The study revealed that the propensity of intermolecular hydrogen bonds that involve the compounds amino functional group could be linked to their binding affinity towards calf thymus deoxyribonucleic acid, which aligned with our quest for developing potential anticancer agents (Adeleke et al., 2022 , 2023 ; Zamisa et al., 2023 ).

The crystal structure of the title compound consists of two symmetrically independent molecules in the asymmetric unit. Each molecule consists of a chromenone moiety with a 2-thiophene, cyano and amino groups attached to it, as shown in Fig. 1. The 2-thiophene rings are orthogonal to the fused 4H-pyran rings, with measured dihedral angles of 89.5 (5) and 89.63 (8)°, which is slightly wider than that of 2-amino-7,7-dimethyl-5-oxo-4-(thiophen-2-yl)-5,6,7,8-tetrahydro-4H-1-benzopyran-3-carbonitrile [85.80 (8)°; Zamisa et al., 2022]. In the crystal packing of the title compound, intermolecular hydrogen-bonding patterns engendered by the amino functional group were found (Fig. 2). One of amino functional group's hydrogen atoms (H1A or H3A) interacts with the nitrogen atom (N2 or N4) of the cyano group in a neighbouring molecule, via N—H⋯N hydrogen bonds (Table 1), with graph-set descriptor R₂²(12). The other hydrogen atom of the amino functional group (H1B or H3B) forms N—H⋯O hydrogen bonds [graph-set descriptor C(8)] with the carbonyl oxygen atom (O4 or O2) of a neighbouring molecule (Table 1). The intermolecular N—H⋯N and N—H⋯O hydrogen bonding patterns are categorized as motif I and II, respectively, according to the literature (Zamisa et al., 2022). The combination of the two hydrogen-bonding motifs results in the formation of a two-dimensional supramolecular structure that extends along the crystallographic ac plane as shown in Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N4ⁱ	0.86 (1)	2.25 (1)	3.089 (3)	164 (2)
N3—H3B⋯O2ⁱⁱ	0.86 (1)	2.10 (2)	2.794 (2)	138 (2)
N1—H1A⋯N2ⁱⁱⁱ	0.86 (1)	2.25 (1)	3.105 (2)	174 (2)
N1—H1B⋯O4^iv	0.86 (1)	2.13 (1)	2.984 (2)	176 (2)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 1
Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Only one of the two molecules in the asymmetric unit is shown for clarity.

Figure 2
Representation of intermolecular N—H⋯N (blue dotted bonds) and N—H⋯O (red dotted bonds) hydrogen-bonding patterns which are categorized as motifs I and II, respectively.

Figure 3
Representation of the two-dimensional supramolecular architecture that results from intermolecular N—H⋯N and N—H⋯O hydrogen bonds.

Synthesis and crystallization

A mixture of malononitrile (0.01515 mmol), 2-thiophenecarboxaldehyde (0.01515 mmol), 1,3-cyclohexanedione (0.01515 mmol), and two drops of triethylamine added as a catalyst, was poured in a 35 ml microwave reaction vessel, which was closed using a snap-on cap. The same microwave radiation-assisted synthesis protocol described in the literature was followed (Zamisa et al., 2022). This reaction was closely monitored by thin-layer chromatography with a solvent mixture of ethyl acetate:hexane (1:1 ratio, v/v). A brown solid mass precipitated from the reaction mixture and was filtered off in vacuo. The crude product was then purified by recrystallization from an ethanolic solution, to give brown block-shaped crystals.

Refinement

Crystallographic data and structure refinement details are summarized in Table 2. The 2-thiophene ring of one of the two molecules of the title compound in the asymmetric unit was found to be disordered over two positions. PART instructions were used to model the disorder (Sheldrick, 2015b ), with the major component having a site occupancy factor of 0.837 (2). Furthermore, the refinement of the disordered 2-thiophene ring was kept stable with SADI, SIMU and DELU restraints in SHELXL. The displacement parameters of the equivalent atoms of the disordered components were kept the same using an EADP instruction (Sheldrick, 2015b). Finally, the hydrogen atoms of the amino functional group were located and assigned from a difference map, but the N—H bond lengths were restrained to 0.860 (1) Å using DFIX instructions.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₂S
M_r	272.32
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.6822 (2), 10.0623 (2), 16.5504 (4)
α, β, γ (°)	77.201 (1), 84.053 (1), 73.839 (1)
V (Å³)	1352.89 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.22 × 0.18 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.710, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	31629, 5315, 3991
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.05
No. of reflections	5315
No. of parameters	368
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.37
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2394700

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624010496/bh4090sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624010496/bh4090Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624010496/bh4090Isup3.cml

checkCIF report

Computing details top

2-Amino-5-oxo-4-(thiophen-2-yl)-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile top

Crystal data top

C₁₄H₁₂N₂O₂S	Z = 4
M_r = 272.32	F(000) = 568
Triclinic, P1	D_x = 1.337 Mg m⁻³
a = 8.6822 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0623 (2) Å	Cell parameters from 9904 reflections
c = 16.5504 (4) Å	θ = 2.3–27.2°
α = 77.201 (1)°	µ = 0.24 mm⁻¹
β = 84.053 (1)°	T = 296 K
γ = 73.839 (1)°	Needle, yellow
V = 1352.89 (5) Å³	0.22 × 0.18 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	5315 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	3991 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 7.9 pixels mm^-1	θ_max = 26.0°, θ_min = 1.3°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −12→12
T_min = 0.710, T_max = 0.746	l = −20→20
31629 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: mixed
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0601P)² + 0.4153P] where P = (F_o² + 2F_c²)/3
5315 reflections	(Δ/σ)_max = 0.001
368 parameters	Δρ_max = 0.36 e Å⁻³
14 restraints	Δρ_min = −0.37 e Å⁻³

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S2	0.10201 (8)	0.94938 (7)	0.60311 (4)	0.0711 (2)
O3	0.42624 (18)	0.71195 (16)	0.48925 (8)	0.0573 (4)
O4	0.49178 (17)	0.66307 (15)	0.77429 (8)	0.0510 (3)
N3	0.2673 (3)	0.6174 (2)	0.43486 (12)	0.0666 (5)
H3A	0.1778 (15)	0.597 (3)	0.4339 (16)	0.080*
H3B	0.321 (3)	0.640 (3)	0.3895 (8)	0.080*
N4	0.0220 (3)	0.4797 (2)	0.60077 (13)	0.0712 (6)
C15	0.1180 (3)	0.5409 (2)	0.59319 (12)	0.0498 (5)
C16	0.2381 (2)	0.6149 (2)	0.58188 (11)	0.0438 (4)
C17	0.3050 (3)	0.6454 (2)	0.50498 (12)	0.0485 (5)
C18	0.4997 (2)	0.7261 (2)	0.55589 (12)	0.0478 (5)
C19	0.4398 (2)	0.70019 (19)	0.63378 (11)	0.0418 (4)
C20	0.2793 (2)	0.66725 (19)	0.65438 (11)	0.0395 (4)
H20	0.290103	0.590437	0.703329	0.047*
C21	0.6484 (3)	0.7723 (3)	0.52901 (14)	0.0622 (6)
H21A	0.630047	0.844621	0.478774	0.075*
H21B	0.733930	0.692872	0.516795	0.075*
C22	0.6987 (3)	0.8305 (3)	0.59647 (16)	0.0734 (7)
H22A	0.806529	0.841406	0.583168	0.088*
H22B	0.627145	0.922980	0.598604	0.088*
C23	0.6942 (3)	0.7334 (3)	0.68045 (15)	0.0683 (7)
H23A	0.778320	0.646518	0.680706	0.082*
H23B	0.716365	0.778096	0.722603	0.082*
C24	0.5369 (2)	0.6985 (2)	0.70210 (12)	0.0446 (4)
C25	0.1501 (2)	0.7936 (2)	0.67445 (11)	0.0436 (4)
C26	0.0545 (3)	0.8058 (3)	0.74616 (14)	0.0595 (5)
H26	0.062218	0.734092	0.793156	0.071*
C27	−0.0554 (3)	0.9393 (3)	0.7394 (2)	0.0844 (8)
H27	−0.129952	0.964223	0.781700	0.101*
C28	−0.0440 (3)	1.0265 (3)	0.6680 (2)	0.0856 (9)
H28	−0.107778	1.118749	0.654771	0.103*
O1	0.56105 (15)	0.28654 (14)	1.02275 (7)	0.0454 (3)
O2	0.7051 (2)	0.3316 (2)	0.73827 (9)	0.0738 (5)
N1	0.3186 (2)	0.3670 (2)	1.07922 (10)	0.0531 (4)
H1A	0.2157 (3)	0.398 (2)	1.0812 (14)	0.064*
H1B	0.372 (2)	0.354 (2)	1.1226 (8)	0.064*
N2	0.0503 (2)	0.5075 (2)	0.90516 (11)	0.0595 (5)
C1	0.1816 (2)	0.4476 (2)	0.91835 (11)	0.0432 (4)
C2	0.3455 (2)	0.37569 (18)	0.93099 (11)	0.0382 (4)
C3	0.4013 (2)	0.34601 (19)	1.00834 (11)	0.0389 (4)
C4	0.6690 (2)	0.27370 (19)	0.95603 (11)	0.0401 (4)
C5	0.6239 (2)	0.29850 (19)	0.87822 (11)	0.0400 (4)
C6	0.4509 (2)	0.33547 (19)	0.85652 (10)	0.0384 (4)
H6	0.432398	0.419030	0.811480	0.046*
C7	0.7462 (3)	0.2988 (2)	0.80992 (13)	0.0515 (5)
C8	0.9179 (3)	0.2652 (3)	0.83094 (15)	0.0685 (7)
H8A	0.945730	0.352477	0.829798	0.082*
H8B	0.985389	0.219461	0.789125	0.082*
C9	0.9518 (3)	0.1697 (3)	0.91552 (16)	0.0704 (7)
H9A	1.061586	0.158856	0.928494	0.084*
H9B	0.940187	0.077074	0.914302	0.084*
C10	0.8381 (2)	0.2298 (2)	0.98259 (13)	0.0529 (5)
H10A	0.847670	0.159001	1.033546	0.064*
H10B	0.866823	0.310630	0.993272	0.064*
C11	0.4122 (2)	0.2179 (2)	0.82559 (11)	0.0415 (4)
S1	0.43755 (12)	0.05115 (8)	0.88552 (5)	0.0659 (3)	0.837 (2)
C12	0.3525 (6)	0.2187 (5)	0.7519 (3)	0.0724 (13)	0.837 (2)
H12	0.326137	0.298965	0.710130	0.087*	0.837 (2)
C13	0.3351 (17)	0.0874 (8)	0.7456 (5)	0.0737 (13)	0.837 (2)
H13	0.299889	0.070523	0.698581	0.088*	0.837 (2)
C14	0.3736 (11)	−0.0099 (5)	0.8132 (5)	0.0655 (10)	0.837 (2)
H14	0.366076	−0.102135	0.819845	0.079*	0.837 (2)
S1A	0.3589 (11)	0.2484 (7)	0.7296 (4)	0.0659 (3)	0.163 (2)
C12A	0.409 (3)	0.0840 (17)	0.8574 (12)	0.0724 (13)	0.163 (2)
H12A	0.438376	0.041108	0.911508	0.087*	0.163 (2)
C13A	0.361 (7)	0.010 (3)	0.805 (2)	0.0737 (13)	0.163 (2)
H13A	0.361086	−0.084666	0.818619	0.088*	0.163 (2)
C14A	0.314 (10)	0.097 (4)	0.735 (3)	0.0737 (13)	0.163 (2)
H14A	0.264412	0.075658	0.693790	0.088*	0.163 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0787 (4)	0.0567 (4)	0.0716 (4)	−0.0080 (3)	−0.0210 (3)	−0.0044 (3)
O3	0.0665 (9)	0.0756 (10)	0.0363 (7)	−0.0287 (8)	−0.0050 (6)	−0.0105 (7)
O4	0.0540 (8)	0.0610 (9)	0.0424 (8)	−0.0152 (7)	−0.0133 (6)	−0.0144 (6)
N3	0.0837 (15)	0.0846 (14)	0.0418 (10)	−0.0311 (12)	−0.0117 (10)	−0.0189 (10)
N4	0.0732 (13)	0.0932 (15)	0.0646 (12)	−0.0411 (12)	−0.0085 (10)	−0.0248 (11)
C15	0.0513 (12)	0.0588 (12)	0.0443 (11)	−0.0127 (10)	−0.0106 (9)	−0.0192 (9)
C16	0.0474 (11)	0.0473 (11)	0.0400 (10)	−0.0114 (9)	−0.0109 (8)	−0.0128 (8)
C17	0.0550 (12)	0.0521 (11)	0.0407 (10)	−0.0112 (10)	−0.0129 (9)	−0.0129 (9)
C18	0.0490 (11)	0.0523 (11)	0.0425 (10)	−0.0113 (9)	−0.0072 (9)	−0.0108 (9)
C19	0.0412 (10)	0.0449 (10)	0.0402 (10)	−0.0086 (8)	−0.0081 (8)	−0.0113 (8)
C20	0.0440 (10)	0.0433 (10)	0.0335 (9)	−0.0128 (8)	−0.0088 (7)	−0.0074 (7)
C21	0.0573 (13)	0.0757 (15)	0.0560 (13)	−0.0259 (12)	0.0033 (10)	−0.0100 (11)
C22	0.0640 (15)	0.0934 (19)	0.0765 (17)	−0.0420 (14)	0.0017 (13)	−0.0204 (14)
C23	0.0501 (13)	0.1007 (19)	0.0635 (14)	−0.0301 (13)	−0.0080 (11)	−0.0204 (13)
C24	0.0439 (11)	0.0447 (10)	0.0472 (11)	−0.0077 (9)	−0.0100 (9)	−0.0148 (8)
C25	0.0432 (10)	0.0497 (11)	0.0447 (10)	−0.0167 (9)	−0.0085 (8)	−0.0149 (8)
C26	0.0599 (13)	0.0687 (12)	0.0583 (13)	−0.0253 (9)	0.0061 (10)	−0.0236 (11)
C27	0.0637 (16)	0.0900 (17)	0.111 (2)	−0.0130 (12)	0.0103 (15)	−0.0593 (19)
C28	0.0677 (17)	0.0618 (16)	0.130 (3)	0.0017 (13)	−0.0277 (17)	−0.0390 (17)
O1	0.0371 (7)	0.0586 (8)	0.0357 (7)	−0.0034 (6)	−0.0062 (5)	−0.0093 (6)
O2	0.0749 (11)	0.1056 (14)	0.0436 (9)	−0.0294 (10)	0.0117 (8)	−0.0201 (8)
N1	0.0405 (9)	0.0784 (12)	0.0378 (9)	−0.0036 (9)	−0.0051 (7)	−0.0203 (8)
N2	0.0423 (10)	0.0775 (13)	0.0546 (11)	−0.0028 (9)	−0.0102 (8)	−0.0177 (9)
C1	0.0462 (12)	0.0486 (11)	0.0372 (10)	−0.0097 (9)	−0.0054 (8)	−0.0153 (8)
C2	0.0376 (10)	0.0385 (9)	0.0383 (9)	−0.0056 (8)	−0.0057 (7)	−0.0110 (7)
C3	0.0369 (10)	0.0410 (10)	0.0386 (9)	−0.0060 (8)	−0.0050 (7)	−0.0118 (8)
C4	0.0386 (10)	0.0396 (10)	0.0431 (10)	−0.0089 (8)	−0.0016 (8)	−0.0121 (8)
C5	0.0416 (10)	0.0392 (9)	0.0409 (10)	−0.0109 (8)	−0.0007 (8)	−0.0118 (8)
C6	0.0429 (10)	0.0388 (9)	0.0325 (9)	−0.0077 (8)	−0.0050 (7)	−0.0077 (7)
C7	0.0549 (12)	0.0567 (12)	0.0492 (12)	−0.0196 (10)	0.0082 (9)	−0.0222 (10)
C8	0.0513 (13)	0.0968 (19)	0.0706 (15)	−0.0288 (13)	0.0161 (11)	−0.0413 (14)
C9	0.0391 (12)	0.0877 (18)	0.0875 (18)	−0.0058 (12)	−0.0023 (11)	−0.0384 (15)
C10	0.0409 (11)	0.0601 (13)	0.0588 (12)	−0.0091 (9)	−0.0089 (9)	−0.0162 (10)
C11	0.0398 (10)	0.0481 (11)	0.0374 (9)	−0.0080 (8)	−0.0034 (8)	−0.0139 (8)
S1	0.0967 (7)	0.0480 (4)	0.0577 (5)	−0.0199 (4)	−0.0220 (4)	−0.0107 (3)
C12	0.087 (2)	0.065 (3)	0.068 (3)	−0.025 (2)	−0.034 (2)	0.0009 (19)
C13	0.081 (5)	0.096 (2)	0.065 (3)	−0.031 (3)	−0.018 (2)	−0.0414 (19)
C14	0.073 (3)	0.0532 (18)	0.077 (2)	−0.017 (2)	0.0004 (19)	−0.0270 (17)
S1A	0.0967 (7)	0.0480 (4)	0.0577 (5)	−0.0199 (4)	−0.0220 (4)	−0.0107 (3)
C12A	0.087 (2)	0.065 (3)	0.068 (3)	−0.025 (2)	−0.034 (2)	0.0009 (19)
C13A	0.081 (5)	0.096 (2)	0.065 (3)	−0.031 (3)	−0.018 (2)	−0.0414 (19)
C14A	0.081 (5)	0.096 (2)	0.065 (3)	−0.031 (3)	−0.018 (2)	−0.0414 (19)

Geometric parameters (Å, º) top

S2—C25	1.716 (2)	N1—H1B	0.8600 (10)
S2—C28	1.704 (3)	N1—C3	1.337 (2)
O3—C17	1.373 (3)	N2—C1	1.149 (2)
O3—C18	1.382 (2)	C1—C2	1.419 (3)
O4—C24	1.225 (2)	C2—C3	1.357 (2)
N3—H3A	0.8600 (10)	C2—C6	1.517 (2)
N3—H3B	0.8600 (10)	C4—C5	1.335 (3)
N3—C17	1.344 (2)	C4—C10	1.493 (3)
N4—C15	1.149 (3)	C5—C6	1.505 (3)
C15—C16	1.416 (3)	C5—C7	1.468 (3)
C16—C17	1.351 (3)	C6—H6	0.9800
C16—C20	1.523 (2)	C6—C11	1.517 (3)
C18—C19	1.337 (3)	C7—C8	1.494 (3)
C18—C21	1.485 (3)	C8—H8A	0.9700
C19—C20	1.509 (3)	C8—H8B	0.9700
C19—C24	1.473 (3)	C8—C9	1.517 (4)
C20—H20	0.9800	C9—H9A	0.9700
C20—C25	1.517 (3)	C9—H9B	0.9700
C21—H21A	0.9700	C9—C10	1.520 (3)
C21—H21B	0.9700	C10—H10A	0.9700
C21—C22	1.521 (3)	C10—H10B	0.9700
C22—H22A	0.9700	C11—S1	1.717 (2)
C22—H22B	0.9700	C11—C12	1.371 (5)
C22—C23	1.515 (3)	C11—S1A	1.639 (6)
C23—H23A	0.9700	C11—C12A	1.340 (14)
C23—H23B	0.9700	S1—C14	1.664 (6)
C23—C24	1.493 (3)	C12—H12	0.9300
C25—C26	1.384 (3)	C12—C13	1.399 (7)
C26—H26	0.9300	C13—H13	0.9300
C26—C27	1.404 (4)	C13—C14	1.316 (5)
C27—H27	0.9300	C14—H14	0.9300
C27—C28	1.319 (4)	S1A—C14A	1.66 (2)
C28—H28	0.9300	C12A—H12A	0.9300
O1—C3	1.372 (2)	C12A—C13A	1.42 (2)
O1—C4	1.377 (2)	C13A—H13A	0.9300
O2—C7	1.221 (3)	C13A—C14A	1.315 (17)
N1—H1A	0.8600 (10)	C14A—H14A	0.9300

C28—S2—C25	92.21 (14)	C3—C2—C6	122.88 (16)
C17—O3—C18	118.29 (15)	N1—C3—O1	110.24 (15)
H3A—N3—H3B	121 (2)	N1—C3—C2	128.33 (17)
C17—N3—H3A	118.8 (18)	C2—C3—O1	121.42 (16)
C17—N3—H3B	118.9 (18)	O1—C4—C10	111.39 (15)
N4—C15—C16	178.5 (2)	C5—C4—O1	122.87 (16)
C15—C16—C20	119.63 (17)	C5—C4—C10	125.73 (17)
C17—C16—C15	118.39 (17)	C4—C5—C6	122.77 (16)
C17—C16—C20	121.82 (17)	C4—C5—C7	119.17 (18)
N3—C17—O3	110.55 (18)	C7—C5—C6	117.95 (16)
N3—C17—C16	127.3 (2)	C2—C6—H6	107.6
C16—C17—O3	122.10 (16)	C5—C6—C2	108.66 (14)
O3—C18—C21	111.46 (17)	C5—C6—H6	107.6
C19—C18—O3	122.36 (18)	C5—C6—C11	111.93 (15)
C19—C18—C21	126.18 (18)	C11—C6—C2	113.07 (15)
C18—C19—C20	122.39 (16)	C11—C6—H6	107.6
C18—C19—C24	118.72 (18)	O2—C7—C5	119.7 (2)
C24—C19—C20	118.84 (16)	O2—C7—C8	122.03 (19)
C16—C20—H20	108.2	C5—C7—C8	118.24 (19)
C19—C20—C16	108.00 (15)	C7—C8—H8A	109.1
C19—C20—H20	108.2	C7—C8—H8B	109.1
C19—C20—C25	111.81 (15)	C7—C8—C9	112.65 (19)
C25—C20—C16	112.35 (15)	H8A—C8—H8B	107.8
C25—C20—H20	108.2	C9—C8—H8A	109.1
C18—C21—H21A	109.5	C9—C8—H8B	109.1
C18—C21—H21B	109.5	C8—C9—H9A	109.4
C18—C21—C22	110.55 (18)	C8—C9—H9B	109.4
H21A—C21—H21B	108.1	C8—C9—C10	111.3 (2)
C22—C21—H21A	109.5	H9A—C9—H9B	108.0
C22—C21—H21B	109.5	C10—C9—H9A	109.4
C21—C22—H22A	109.4	C10—C9—H9B	109.4
C21—C22—H22B	109.4	C4—C10—C9	110.25 (17)
H22A—C22—H22B	108.0	C4—C10—H10A	109.6
C23—C22—C21	111.2 (2)	C4—C10—H10B	109.6
C23—C22—H22A	109.4	C9—C10—H10A	109.6
C23—C22—H22B	109.4	C9—C10—H10B	109.6
C22—C23—H23A	109.0	H10A—C10—H10B	108.1
C22—C23—H23B	109.0	C6—C11—S1	121.78 (13)
H23A—C23—H23B	107.8	C6—C11—S1A	118.6 (3)
C24—C23—C22	113.06 (19)	C12—C11—C6	130.4 (2)
C24—C23—H23A	109.0	C12—C11—S1	107.9 (2)
C24—C23—H23B	109.0	C12A—C11—C6	136.1 (8)
O4—C24—C19	120.29 (18)	C12A—C11—S1A	105.3 (8)
O4—C24—C23	121.58 (18)	C14—S1—C11	93.38 (18)
C19—C24—C23	118.05 (18)	C11—C12—H12	123.2
C20—C25—S2	120.92 (14)	C11—C12—C13	113.5 (4)
C26—C25—S2	109.92 (16)	C13—C12—H12	123.2
C26—C25—C20	129.15 (19)	C12—C13—H13	123.5
C25—C26—H26	124.1	C14—C13—C12	113.0 (4)
C25—C26—C27	111.9 (2)	C14—C13—H13	123.5
C27—C26—H26	124.1	S1—C14—H14	123.9
C26—C27—H27	122.8	C13—C14—S1	112.2 (4)
C28—C27—C26	114.3 (3)	C13—C14—H14	123.9
C28—C27—H27	122.8	C11—S1A—C14A	97.3 (12)
S2—C28—H28	124.2	C11—C12A—H12A	121.4
C27—C28—S2	111.7 (2)	C11—C12A—C13A	117.1 (15)
C27—C28—H28	124.2	C13A—C12A—H12A	121.4
C3—O1—C4	118.88 (13)	C12A—C13A—H13A	125.2
H1A—N1—H1B	120 (2)	C14A—C13A—C12A	110 (2)
C3—N1—H1A	121.5 (16)	C14A—C13A—H13A	125.2
C3—N1—H1B	117.9 (15)	S1A—C14A—H14A	125.1
N2—C1—C2	177.5 (2)	C13A—C14A—S1A	109.8 (19)
C1—C2—C6	117.98 (15)	C13A—C14A—H14A	125.1
C3—C2—C1	119.15 (16)

S2—C25—C26—C27	1.3 (2)	C1—C2—C6—C5	164.50 (16)
O3—C18—C19—C20	−6.0 (3)	C1—C2—C6—C11	−70.6 (2)
O3—C18—C19—C24	171.55 (17)	C2—C6—C11—S1	−63.9 (2)
O3—C18—C21—C22	162.46 (19)	C2—C6—C11—C12	115.0 (4)
C15—C16—C17—O3	−177.49 (18)	C2—C6—C11—S1A	121.2 (4)
C15—C16—C17—N3	2.3 (3)	C2—C6—C11—C12A	−59.1 (16)
C15—C16—C20—C19	162.83 (17)	C3—O1—C4—C5	−9.4 (3)
C15—C16—C20—C25	−73.4 (2)	C3—O1—C4—C10	170.46 (16)
C16—C20—C25—S2	−62.0 (2)	C3—C2—C6—C5	−15.4 (2)
C16—C20—C25—C26	117.1 (2)	C3—C2—C6—C11	109.5 (2)
C17—O3—C18—C19	−11.9 (3)	C4—O1—C3—N1	−171.63 (16)
C17—O3—C18—C21	168.12 (18)	C4—O1—C3—C2	8.4 (3)
C17—C16—C20—C19	−21.9 (2)	C4—C5—C6—C2	14.6 (2)
C17—C16—C20—C25	101.9 (2)	C4—C5—C6—C11	−111.03 (19)
C18—O3—C17—N3	−168.63 (18)	C4—C5—C7—O2	−174.59 (19)
C18—O3—C17—C16	11.2 (3)	C4—C5—C7—C8	2.5 (3)
C18—C19—C20—C16	21.4 (2)	C5—C4—C10—C9	−18.9 (3)
C18—C19—C20—C25	−102.7 (2)	C5—C6—C11—S1	59.2 (2)
C18—C19—C24—O4	−173.63 (18)	C5—C6—C11—C12	−121.9 (4)
C18—C19—C24—C23	3.2 (3)	C5—C6—C11—S1A	−115.7 (4)
C18—C21—C22—C23	47.1 (3)	C5—C6—C11—C12A	64.1 (15)
C19—C18—C21—C22	−17.5 (3)	C5—C7—C8—C9	27.9 (3)
C19—C20—C25—S2	59.58 (19)	C6—C2—C3—O1	5.0 (3)
C19—C20—C25—C26	−121.3 (2)	C6—C2—C3—N1	−174.93 (19)
C20—C16—C17—O3	7.2 (3)	C6—C5—C7—O2	1.7 (3)
C20—C16—C17—N3	−173.0 (2)	C6—C5—C7—C8	178.74 (19)
C20—C19—C24—O4	4.1 (3)	C6—C11—S1—C14	179.9 (4)
C20—C19—C24—C23	−179.11 (19)	C6—C11—C12—C13	179.0 (7)
C20—C25—C26—C27	−177.9 (2)	C6—C11—S1A—C14A	−174 (3)
C21—C18—C19—C20	173.9 (2)	C6—C11—C12A—C13A	179 (3)
C21—C18—C19—C24	−8.5 (3)	C7—C5—C6—C2	−161.54 (16)
C21—C22—C23—C24	−53.0 (3)	C7—C5—C6—C11	72.9 (2)
C22—C23—C24—O4	−155.5 (2)	C7—C8—C9—C10	−53.4 (3)
C22—C23—C24—C19	27.7 (3)	C8—C9—C10—C4	48.0 (3)
C24—C19—C20—C16	−156.23 (16)	C10—C4—C5—C6	176.85 (18)
C24—C19—C20—C25	79.7 (2)	C10—C4—C5—C7	−7.1 (3)
C25—S2—C28—C27	0.0 (2)	C11—S1—C14—C13	0.6 (10)
C25—C26—C27—C28	−1.4 (3)	C11—C12—C13—C14	2.5 (14)
C26—C27—C28—S2	0.8 (3)	C11—S1A—C14A—C13A	−9 (7)
C28—S2—C25—C20	178.51 (16)	C11—C12A—C13A—C14A	−5 (7)
C28—S2—C25—C26	−0.78 (17)	S1—C11—C12—C13	−2.0 (8)
O1—C4—C5—C6	−3.3 (3)	C12—C11—S1—C14	0.8 (4)
O1—C4—C5—C7	172.76 (16)	C12—C13—C14—S1	−1.8 (15)
O1—C4—C10—C9	161.20 (18)	S1A—C11—C12A—C13A	−2 (3)
O2—C7—C8—C9	−155.1 (2)	C12A—C11—S1A—C14A	6 (3)
C1—C2—C3—O1	−174.91 (17)	C12A—C13A—C14A—S1A	9 (8)
C1—C2—C3—N1	5.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N4ⁱ	0.86 (1)	2.25 (1)	3.089 (3)	164 (2)
N3—H3B···O2ⁱⁱ	0.86 (1)	2.10 (2)	2.794 (2)	138 (2)
N1—H1A···N2ⁱⁱⁱ	0.86 (1)	2.25 (1)	3.105 (2)	174 (2)
N1—H1B···O4^iv	0.86 (1)	2.13 (1)	2.984 (2)	176 (2)

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

Funding information

The authors acknowledge the University of KwaZulu-Natal for financial support.

References

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