Crystal structure and Hirshfeld surface analysis of (Z)-3-methyl-4-(thio­phen-2-yl­methyl­idene)isoxazol-5(4H)-one

Laroum, R.; Benouatas, A.; Hamdouni, N.; Zemamouche, W.; Boudjada, A.; Debache, A.

doi:10.1107/S2056989021002632

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 4| April 2021| Pages 378-382

https://doi.org/10.1107/S2056989021002632

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Crystal structure and Hirshfeld surface analysis of (Z)-3-methyl-4-(thiophen-2-ylmethylidene)isoxazol-5(4H)-one

Rima Laroum,^a Assia Benouatas,^b Noudjoud Hamdouni,^b ^* Wissame Zemamouche,^b Ali Boudjada ^b and Abdelmadjid Debache ^a

^aLaboratoire de Synthèse de Molécules d'Intérêts Biologiques, Département de Chimie, Université Mentouri Constantine, 25000, Algeria, and ^bLaboratoire de Cristallographie, Département de Physique, Université Mentouri Constantine, 25000, Algeria
^*Correspondence e-mail: n_hamdouni@yahoo.fr

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 27 October 2020; accepted 9 March 2021; online 12 March 2021)

The title compound, C₉H₇NO₂S crystallizes with two independent molecules (A and B) in the asymmetric unit with Z = 8. Both molecules are almost planar with a dihedral angle between the isoxazole and thiophen rings of 3.67 (2)° in molecule A and 10.00 (1) ° in molecule B. The packing of molecules A and B is of an ABAB⋯ type along the b-axis direction, the configuration about the C=C bond is Z. In the crystal, the presence of C—H⋯O, C—H⋯ N and π–π interactions [centroid–centroid distances of 3.701 (2) and 3.766 (2) Å] link the molecules into a three-dimensional architecture. An analysis of Hirshfeld surfaces shows the importance of C—H⋯O and C—H⋯N hydrogen bonds in the packing mechanism of the crystalline structure.

Keywords: crystal structure; π–π interactions; isoxazole; Hirshfeld surface.

CCDC reference: 2069004

1. Chemical context

Isoxazolones show some interesting biological properties. They are inhibitors of the factorization of tumor necrosis alpha (TNF-α) (Laughlin et al., 2005 ) and antimicrobial (Mazimba et al., 2014 ). They are used for the treatment of cerebrovascular disorders and as muscle relaxants. They are also herbicides (Tomita et al., 1977 ) and fungicides (Miyake et al., 2012 ). On other hand, isoxazolone derivatives constitute excellent intermediates for the synthesis of various heterocycles such as pyridopyrimidines (Tu et al., 2006 ), quinolines (Abbiati et al., 2003 ) and undergo various chemical transformations (Batra & Bhaduri, 1994 ). Some cycloaddition reactions are also described and provide access to several types of polycycles (Badrey & Gomha, 2014 ). For these reasons, these compounds have been the subject of several investigations. The present method for their synthesis is a three-component polycondensation between an aromatic aldehyde, ethyl acetoacetate and hydroxylamine hydrochloride under different conditions and for our part we propose here the use of K₂CO₃, a food additive, tolerated in organic agriculture, very inexpensive, highly available and a safe catalyst, in an aqueous medium. In the present study, we report on the synthesis, molecular and crystal structure together with a Hirshfeld surface analysis of the title isoxazole derivative.

2. Structural commentary

The molecular structure of the title compound is shown in (Fig. 1). It crystallizes with two independent molecules (A and B) in the asymmetric unit. The molecular structure adopts a Z-configuration about the C=C [1.354 (3) Å in molecule A and 1.357 (3) Å in molecule B] double bonds.

Figure 1
The molecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 50% probability level.

The bond lengths in the two molecules are practically equal, while there are slight differences in bond angles; with for example C2—C3—C4 (molecule A) and C11—C12—C13 (molecule B) differing by 0.8 (2)°. Also, a slight difference of 0.3 (2)° is observed between the angles C2—C5—C6 and C11—C14—C15. In molecule A, the angle between the normal of the molecular plane (O2A/N1A/C1A–C3A) and the normal of the (S1A/C6A–C9A) plane is 3.67 (2)°. An important difference is observed in molecule B, where the angle between the normal of the molecular plane (O3B/N2B/C10B–C12B) and the normal of the (S2B/C15B–C18B) plane is 10.00 (1)°. In the molecular skeleton, the angle between the mean planes of the molecules A and B is 4.09 (1)°. Each of the two methyl groups, C4 and C13, has a C—H bond lying in the mean plane of the molecular skeleton, and they are oriented toward the thiophene group.

3. Supramolecular features

In the crystal, the structure consists of wavy layers containing molecules of the same type, forming an alternated packing described by an ABAB⋯ sequence (Fig. 2). The molecules form infinite chains along the b-axis direction. They are linked by offset π–π interactions: [Cg1⋯Cg2ⁱ = 3.701 (2) Å and Cg3⋯Cg4ⁱⁱ = 3.766 (2) Å where Cg1, Cg2, Cg3 and Cg4 are the centroids of the O2A/N1A/C1A–C3A, S2B/C15B–C18B, S1A/C6A–C9A and O3B/N2B/C10B–C12B rings, respectively; symmetry codes: (i) −x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (ii) −x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z]. The two molecules A and B are involved in intermolecular C—H⋯O and C—H⋯N hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O4ⁱ	0.93	2.51	3.387 (3)	156
C8—H8⋯N1ⁱⁱ	0.93	2.58	3.491 (5)	166
C13—H13c⋯N1ⁱⁱⁱ	0.96	2.57	3.487 (4)	160
Symmetry codes: (i) ; (ii) ; (iii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view along the b axis of the crystal packing of the title compound (molecule A in blue and molecule B in red).

4. Analysis of the Hirshfeld surfaces

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were generated with CrystalExplorer (Turner et al., 2017 ). The analysis of Hirshfeld surface mapped over d_norm is shown in (Fig. 3). The interactions between the corresponding donor and acceptor atoms are visualized as bright-red spots on both sides (zones 1, 2, 3 and 4) of the Hirshfeld surfaces (Fig. 3), corresponding to C17—H17⋯N2, C4—H4C⋯N2, C16—H16⋯O2 and C18—H18⋯O4 hydrogen bonds, respectively. Two other red spots exist, corresponding to C4—H4A⋯O interactions (Fig. 3, zone 5), are considered to be very weak interactions, comparing them to the van der Waals radii. The overall two-dimensional fingerprint plot of the structure and H⋯S/S⋯H, H⋯H, H⋯O/O⋯H, H⋯N/N⋯H and C⋯C contacts are illustrated in Fig. 4a–m). The H⋯H contacts, accounting for about 35.4% of the Hirshfeld surface (Fig. 4b) represent the largest contribution and are seen in the fingerprint plot as a pair of shorts pikes at d_e + d_i = 2.2 Å; comparing this to van der Waals radius, we find the difference between them is about 1 Å, which means it is a very powerful interaction. H⋯O/O⋯H contacts (Fig. 4c) make a contribution of 28.7%, with a distinctive peak in the fingerprint plot at d_e + d_i = 2.4 Å; the van der Waals radius sum for this interaction is about 2.7 Å.

Figure 3
Two views of the Hirshfeld surface mapped over d_norm.

Figure 4
Two-dimensional finger print plots: (a) overall, and delineated into contributions from different contacts: (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯S/S⋯H, (e) H⋯N/N⋯H and (f) C⋯C.

The pair of short peaks at d_e + d_i = 3.1, i.e. almost equal to the sum of the van der Waals radius, in the fingerprint plot delineated into H⋯S/S⋯H contacts are indicative of short interatomic contacts in the crystal (6% contribution, Fig. 4d). Although the H⋯N /N⋯H interactions have a notable contribution of 12% to the Hirshfeld surface (Fig. 4e), their interatomic distances (d_e + d_i = 2.4 Å) are less than their van der Waals radius (2.7 Å), which means that it is a very strong interaction in this structure. The presence of π–π stacking reflects the presence of C⋯C contacts (Fig. 4f), which account for 7.9% of the Hirshfeld surface with d_e + d_i = 3.4 Å; the van der Waals radius is 3.4 Å, so we can confirm the presence of π–π stacking. Two further views of the Hirshfeld surface are shown in Fig. 5.

Figure 5
Two views of the Hirshfeld surface mapped over d_norm, with interactions to neighbouring molecules shown as green dashed lines.

5. Database survey

A search of the Cambridge Structural Database (CSD, v5.40, last update May 2019; Groom et al., 2016 ) for the (Z)-4-(thiophen-2-ylmethylidene)isoxazol-5(4H)-one unit gave five hits: 4-(2-hydroxybenzylidene)-3-methylisoxazol-5(4H)-one (AJESAK; Cheng et al., 2009 ), 2-(naphthalen-1-yl)-4-(thiophen-2-ylmethylidene)-1,3-oxazol-5(4H)-one (ERIXIN; Gündoğdu et al., 2011 ), (Z)-4-benzylidene-3-methylisoxazol-5(4H)-one (MBYIOZ01; Chandra et al., 2012 ), 2-methyl-4-(thiophen-2-ylmethylidene)-1,3-oxazol-5(4H)-one (WOYPIL; Sharma et al., 2015 ) and (Z)-4-(4-hydroxybenzylidene)-3-methylisoxazol-5(4H)-one (VIDSAF; Zemamouche et al., 2018 ).

The asymmetric unit of the title compound contains two crystallographically independent molecules, as found for ERIXIN and WOYPIL while in AJESAK, MBYIOZ01 and VIDSAF, there is only one molecule per asymmetric unit. The configuration about the C=C bond is Z in all five compounds and in each molecule, the oxazol and thiophene rings are inclined to one another by 3.67 (2), 10.00 (1), 0.86 (9), 7.02 (8), 2.65 (16), 4.55 (15), 6.50 (1), 7.98 (8) and 3.18 (8)°, respectively.

In the crystal of WOYPIL, the individual molecules are linked via C—H⋯O hydrogen bonds, forming ABAB chains along the [10 $[\overline{1}]$ ] direction, similarly in the crystal of the title compound, the packing of molecules A and B is of an ABAB⋯ type along the [100] direction. In our compound, the cohesion of the crystal is ensured by interactions of the type C—H⋯O, C—H⋯π and π–π [intercentroid distances of 3.701 (2) and 3.766 (2) Å compared with 3.811 (2) and 3.889 (2) Å in ERIXIN and 3.767 (2) and 3.867 (2) Å in WOYPIL].

6. Synthesis and crystallization

Thiophene-2-carbaldehyde (C₅H₄OS, 1 mmol), hydroxylamine hydrochloride (ClH₄NO, 1 mmol), ethyl acetoacetate (C₆H₁₀O₃,1 mmol) and K₂CO₃ (5 mol%) were mixed in a 25 mL flask equipped with a magnetic stirrer. The mixture was refluxed in 5 mL of water for 3h (followed by TLC). When the reaction was judged to be finished, the mixture was gradually poured into ice-cold water. Stirring was maintained for a few minutes and the obtained solid was filtered and purified by crystallization from ethanol (yield 72%).

7. Refinement details

Crystal data, data collection and structure refinement details for the title compound are summarized in Table 2. H atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₇NO₂S
M_r	193.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	301
a, b, c (Å)	10.4660 (4), 12.1614 (5), 14.7636 (6)
β (°)	110.362 (1)
V (Å³)	1761.71 (12)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.33
Crystal size (mm)	0.31 × 0.20 × 0.10

Data collection
Diffractometer	Agilent Technologies Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 ))
T_min, T_max	0.758, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	72470, 6743, 4110
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.770

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.239, 1.07
No. of reflections	6743
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.54
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX publication routines (Farrugia, 2012 ) and Mercury (Macrae et al., 2020 ).

Supporting information

CCDC reference: 2069004

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002632/zn2002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002632/zn2002Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021002632/zn2002Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

(Z)-3-Methyl-4-(thiophen-2-ylmethylidene)isoxazol-5(4H)-one top

Crystal data top

C₉H₇NO₂S	F(000) = 800
M_r = 193.22	D_x = 1.457 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6745 reflections
a = 10.4660 (4) Å	θ = 2.2–33.2°
b = 12.1614 (5) Å	µ = 0.33 mm⁻¹
c = 14.7636 (6) Å	T = 301 K
β = 110.362 (1)°	Needle, white
V = 1761.71 (12) Å³	0.31 × 0.20 × 0.10 mm
Z = 8

Data collection top

Agilent Technologies Xcalibur, Eos diffractometer	6743 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4110 reflections with I > 2σ(I)
Detector resolution: 8.02 pixels mm^-1	R_int = 0.084
ω scans	θ_max = 33.2°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013))	h = −16→16
T_min = 0.758, T_max = 0.968	k = −18→18
72470 measured reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.239	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1035P)² + 1.1548P] where P = (F_o² + 2F_c²)/3
6743 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³
0 constraints

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
S1	0.50289 (8)	0.12735 (6)	0.55602 (6)	0.0497 (2)
S2	0.83062 (8)	0.29525 (7)	0.33090 (6)	0.0532 (2)
O4	0.6147 (3)	0.42483 (17)	0.34895 (19)	0.0640 (6)
O3	0.3944 (3)	0.40232 (18)	0.32977 (18)	0.0637 (6)
O2	0.9633 (2)	0.1945 (2)	0.58548 (19)	0.0614 (6)
O1	0.7799 (3)	0.09198 (18)	0.57358 (19)	0.0621 (6)
N1	0.9970 (3)	0.3094 (2)	0.5893 (2)	0.0568 (7)
C5	0.6521 (2)	0.32586 (19)	0.57740 (17)	0.0341 (5)
H5	0.644338	0.401627	0.582265	0.041*
C11	0.5024 (3)	0.2451 (2)	0.31621 (16)	0.0363 (5)
N2	0.2960 (3)	0.3124 (2)	0.3099 (2)	0.0592 (7)
C14	0.5970 (3)	0.1692 (2)	0.31523 (17)	0.0361 (5)
H14	0.563541	0.097687	0.305693	0.043*
C3	0.8908 (3)	0.3632 (2)	0.58677 (19)	0.0418 (6)
C16	0.8203 (3)	0.0795 (3)	0.3326 (2)	0.0465 (6)
H16	0.79039	0.007312	0.331323	0.056*
C15	0.7368 (3)	0.1771 (2)	0.32585 (17)	0.0364 (5)
C6	0.5301 (2)	0.2673 (2)	0.56833 (16)	0.0324 (4)
C9	0.3378 (3)	0.1419 (3)	0.5469 (2)	0.0550 (8)
H9	0.277609	0.083236	0.537456	0.066*
C10	0.5189 (3)	0.3637 (2)	0.3330 (2)	0.0465 (6)
C12	0.3616 (3)	0.2241 (2)	0.30278 (18)	0.0416 (6)
C7	0.4104 (3)	0.3206 (2)	0.56579 (19)	0.0418 (6)
H7	0.403306	0.39636	0.570886	0.05*
C2	0.7769 (2)	0.2927 (2)	0.58031 (17)	0.0355 (5)
C8	0.3026 (3)	0.2476 (3)	0.5548 (2)	0.0519 (7)
H8	0.216544	0.269318	0.553016	0.062*
C1	0.8307 (3)	0.1822 (2)	0.5786 (2)	0.0443 (6)
C13	0.2887 (3)	0.1175 (3)	0.2820 (2)	0.0532 (7)
H13A	0.350705	0.060565	0.279027	0.08*
H13B	0.253353	0.100902	0.332377	0.08*
H13C	0.214967	0.121852	0.221289	0.08*
C18	0.9717 (3)	0.2218 (3)	0.3399 (3)	0.0583 (8)
H18	1.053929	0.253953	0.343547	0.07*
C4	0.8928 (4)	0.4854 (3)	0.5881 (3)	0.0646 (9)
H4A	0.805554	0.512482	0.585866	0.097*
H4B	0.961917	0.510612	0.646195	0.097*
H4C	0.912103	0.512135	0.533023	0.097*
C17	0.9534 (3)	0.1117 (3)	0.3413 (3)	0.0566 (8)
H17	1.022934	0.061462	0.347417	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0513 (4)	0.0345 (3)	0.0660 (5)	−0.0054 (3)	0.0238 (3)	−0.0015 (3)
S2	0.0498 (4)	0.0494 (4)	0.0636 (5)	−0.0118 (3)	0.0237 (3)	−0.0100 (3)
O4	0.0809 (17)	0.0329 (10)	0.0859 (16)	−0.0047 (11)	0.0387 (14)	−0.0056 (10)
O3	0.0730 (16)	0.0448 (12)	0.0793 (15)	0.0232 (11)	0.0341 (13)	0.0034 (11)
O2	0.0423 (11)	0.0631 (14)	0.0834 (16)	0.0140 (10)	0.0278 (11)	−0.0066 (12)
O1	0.0627 (14)	0.0389 (11)	0.0916 (17)	0.0077 (10)	0.0354 (13)	−0.0033 (11)
N1	0.0374 (12)	0.0693 (18)	0.0679 (16)	−0.0039 (12)	0.0237 (11)	−0.0109 (13)
C5	0.0345 (11)	0.0299 (10)	0.0394 (11)	0.0009 (9)	0.0147 (9)	−0.0022 (8)
C11	0.0417 (12)	0.0362 (12)	0.0331 (11)	0.0051 (10)	0.0157 (9)	0.0013 (9)
N2	0.0530 (15)	0.0618 (17)	0.0671 (16)	0.0191 (13)	0.0263 (13)	0.0006 (13)
C14	0.0374 (12)	0.0318 (11)	0.0422 (12)	−0.0015 (9)	0.0176 (10)	−0.0020 (9)
C3	0.0337 (12)	0.0526 (15)	0.0426 (12)	−0.0043 (11)	0.0176 (10)	−0.0049 (11)
C16	0.0339 (12)	0.0606 (17)	0.0494 (14)	−0.0057 (12)	0.0203 (11)	−0.0100 (12)
C15	0.0354 (12)	0.0373 (12)	0.0385 (11)	−0.0018 (9)	0.0152 (9)	−0.0033 (9)
C6	0.0322 (11)	0.0333 (11)	0.0336 (10)	−0.0009 (8)	0.0139 (8)	−0.0031 (8)
C9	0.0515 (17)	0.0628 (19)	0.0546 (16)	−0.0228 (15)	0.0234 (14)	−0.0033 (14)
C10	0.0633 (18)	0.0370 (13)	0.0442 (13)	0.0105 (12)	0.0250 (13)	0.0043 (10)
C12	0.0399 (13)	0.0478 (14)	0.0395 (12)	0.0097 (11)	0.0168 (10)	0.0036 (10)
C7	0.0351 (12)	0.0447 (14)	0.0470 (13)	0.0004 (10)	0.0159 (10)	−0.0069 (11)
C2	0.0322 (11)	0.0377 (12)	0.0384 (11)	−0.0002 (9)	0.0147 (9)	−0.0011 (9)
C8	0.0327 (12)	0.072 (2)	0.0532 (15)	−0.0035 (13)	0.0182 (11)	−0.0082 (14)
C1	0.0399 (14)	0.0447 (14)	0.0525 (14)	0.0071 (11)	0.0212 (11)	−0.0010 (11)
C13	0.0348 (13)	0.0605 (18)	0.0669 (18)	0.0018 (12)	0.0209 (13)	−0.0016 (14)
C18	0.0392 (15)	0.068 (2)	0.070 (2)	−0.0122 (14)	0.0218 (14)	−0.0102 (16)
C4	0.0546 (19)	0.0530 (18)	0.093 (2)	−0.0161 (15)	0.0339 (18)	−0.0061 (17)
C17	0.0416 (15)	0.064 (2)	0.0678 (19)	0.0066 (14)	0.0238 (14)	−0.0052 (15)

Geometric parameters (Å, º) top

S1—C9	1.695 (3)	C3—C4	1.487 (4)
S1—C6	1.725 (2)	C16—C17	1.410 (4)
S2—C18	1.691 (4)	C16—C15	1.457 (4)
S2—C15	1.727 (3)	C16—H16	0.93
O4—C10	1.204 (4)	C6—C7	1.399 (3)
O3—C10	1.370 (4)	C9—C8	1.354 (5)
O3—N2	1.460 (4)	C9—H9	0.93
O2—C1	1.365 (4)	C12—C13	1.481 (4)
O2—N1	1.437 (4)	C7—C8	1.400 (4)
O1—C1	1.210 (4)	C7—H7	0.93
N1—C3	1.280 (4)	C2—C1	1.460 (4)
C5—C2	1.354 (3)	C8—H8	0.93
C5—C6	1.427 (3)	C13—H13A	0.96
C5—H5	0.93	C13—H13B	0.96
C11—C14	1.357 (3)	C13—H13C	0.96
C11—C12	1.440 (4)	C18—C17	1.354 (5)
C11—C10	1.463 (4)	C18—H18	0.93
N2—C12	1.299 (4)	C4—H4A	0.96
C14—C15	1.420 (3)	C4—H4B	0.96
C14—H14	0.93	C4—H4C	0.96
C3—C2	1.444 (4)	C17—H17	0.93

C9—S1—C6	91.80 (14)	N2—C12—C11	112.7 (3)
C18—S2—C15	91.80 (15)	N2—C12—C13	119.5 (3)
C10—O3—N2	110.2 (2)	C11—C12—C13	127.8 (2)
C1—O2—N1	109.8 (2)	C6—C7—C8	112.8 (3)
C3—N1—O2	107.3 (2)	C6—C7—H7	123.6
C2—C5—C6	132.6 (2)	C8—C7—H7	123.6
C2—C5—H5	113.7	C5—C2—C3	126.2 (2)
C6—C5—H5	113.7	C5—C2—C1	130.3 (2)
C14—C11—C12	126.4 (2)	C3—C2—C1	103.5 (2)
C14—C11—C10	129.0 (3)	C9—C8—C7	112.3 (3)
C12—C11—C10	104.6 (2)	C9—C8—H8	123.9
C12—N2—O3	106.3 (3)	C7—C8—H8	123.9
C11—C14—C15	132.9 (2)	O1—C1—O2	121.1 (3)
C11—C14—H14	113.6	O1—C1—C2	132.2 (3)
C15—C14—H14	113.6	O2—C1—C2	106.6 (2)
N1—C3—C2	112.8 (3)	C12—C13—H13A	109.5
N1—C3—C4	120.2 (3)	C12—C13—H13B	109.5
C2—C3—C4	127.0 (3)	H13A—C13—H13B	109.5
C17—C16—C15	109.3 (3)	C12—C13—H13C	109.5
C17—C16—H16	125.4	H13A—C13—H13C	109.5
C15—C16—H16	125.4	H13B—C13—H13C	109.5
C14—C15—C16	121.5 (2)	C17—C18—S2	113.6 (2)
C14—C15—S2	127.6 (2)	C17—C18—H18	123.2
C16—C15—S2	110.91 (19)	S2—C18—H18	123.2
C7—C6—C5	122.3 (2)	C3—C4—H4A	109.5
C7—C6—S1	109.93 (19)	C3—C4—H4B	109.5
C5—C6—S1	127.71 (18)	H4A—C4—H4B	109.5
C8—C9—S1	113.2 (2)	C3—C4—H4C	109.5
C8—C9—H9	123.4	H4A—C4—H4C	109.5
S1—C9—H9	123.4	H4B—C4—H4C	109.5
O4—C10—O3	120.8 (3)	C18—C17—C16	114.4 (3)
O4—C10—C11	133.0 (3)	C18—C17—H17	122.8
O3—C10—C11	106.1 (3)	C16—C17—H17	122.8

C1—O2—N1—C3	1.2 (3)	O3—N2—C12—C13	−179.7 (2)
C10—O3—N2—C12	0.6 (3)	C14—C11—C12—N2	178.3 (3)
C12—C11—C14—C15	179.0 (3)	C10—C11—C12—N2	−0.4 (3)
C10—C11—C14—C15	−2.7 (5)	C14—C11—C12—C13	−2.2 (4)
O2—N1—C3—C2	−0.5 (3)	C10—C11—C12—C13	179.2 (3)
O2—N1—C3—C4	−179.0 (3)	C5—C6—C7—C8	178.9 (2)
C11—C14—C15—C16	173.0 (3)	S1—C6—C7—C8	0.4 (3)
C11—C14—C15—S2	−8.0 (4)	C6—C5—C2—C3	177.9 (2)
C17—C16—C15—C14	179.2 (2)	C6—C5—C2—C1	−2.6 (5)
C17—C16—C15—S2	0.0 (3)	N1—C3—C2—C5	179.3 (3)
C18—S2—C15—C14	−178.4 (2)	C4—C3—C2—C5	−2.3 (5)
C18—S2—C15—C16	0.7 (2)	N1—C3—C2—C1	−0.3 (3)
C2—C5—C6—C7	−179.2 (3)	C4—C3—C2—C1	178.1 (3)
C2—C5—C6—S1	−0.9 (4)	S1—C9—C8—C7	1.8 (4)
C9—S1—C6—C7	0.5 (2)	C6—C7—C8—C9	−1.4 (4)
C9—S1—C6—C5	−177.9 (2)	N1—O2—C1—O1	179.3 (3)
C6—S1—C9—C8	−1.3 (3)	N1—O2—C1—C2	−1.4 (3)
N2—O3—C10—O4	−179.7 (3)	C5—C2—C1—O1	0.6 (6)
N2—O3—C10—C11	−0.8 (3)	C3—C2—C1—O1	−179.8 (3)
C14—C11—C10—O4	0.8 (5)	C5—C2—C1—O2	−178.6 (3)
C12—C11—C10—O4	179.4 (3)	C3—C2—C1—O2	1.0 (3)
C14—C11—C10—O3	−177.9 (2)	C15—S2—C18—C17	−1.2 (3)
C12—C11—C10—O3	0.7 (3)	S2—C18—C17—C16	1.5 (4)
O3—N2—C12—C11	−0.1 (3)	C15—C16—C17—C18	−0.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O4ⁱ	0.93	2.51	3.387 (3)	156
C8—H8···N1ⁱⁱ	0.93	2.58	3.491 (5)	166
C13—H13c···N1ⁱⁱⁱ	0.96	2.57	3.487 (4)	160

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

Acknowledgements

The authors gratefully acknowledge Ferhat Abbas University of Setif for assistance with the data collection.

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