Synthesis and structure of ethyl 2-[(4-oxo-3-phenyl-3,4-di­hydro­quinazolin-2-yl)sulfan­yl]acetate

Nguyen Tien, C.; Nguyen Tan, Q.; Pham Duc, D.; Tran Hoang, P.; Nguyen Dang, D.; Truong Minh, L.; Van Meervelt, L.

doi:10.1107/S2056989020005071

research communications

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ISSN: 2056-9890

Volume 76| Part 5| May 2020| Pages 668-672

https://doi.org/10.1107/S2056989020005071

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Synthesis and structure of ethyl 2-[(4-oxo-3-phenyl-3,4-dihydroquinazolin-2-yl)sulfanyl]acetate

Cong Nguyen Tien,^a ^* Quang Nguyen Tan,^a,^b Dung Pham Duc,^a Phuong Tran Hoang,^c Dat Nguyen Dang,^d Luong Truong Minh ^d and Luc Van Meervelt ^e ^*

^aFaculty of Chemistry, Ho Chi Minh City University of Education, 280 An Duong Vuong Street, Ho Chi Minh City, 700000, Vietnam, ^bPhan Boi Chau High School, 70 Le Hong Phong Street, Binh Thuan Province, 77000, Vietnam, ^cFaculty of Chemistry, University of Science, 227 Nguyen Van Cu Street, Ho Chi Minh City, 721337, Vietnam, ^dFaculty of Chemistry, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam, and ^eDepartment of Chemistry, KU Leuven, Biomolecular Architecture, Celestijnenlaan 200F, Leuven (Heverlee), B-3001, Belgium
^*Correspondence e-mail: congnt@hcmue.edu.vn, luc.vanmeervelt@kuleuven.be

(Received 23 March 2020; accepted 10 April 2020; online 17 April 2020)

The title compound, C₁₈H₁₆N₂O₃S, was synthesized by reaction of 2-mercapto-3-phenylquinazolin-4(3H)-one with ethyl chloroacetate. The quinazoline ring forms a dihedral angle of 86.83 (5)° with the phenyl ring. The terminal methyl group is disordered by a rotation of about 60° in a 0.531 (13): 0.469 (13) ratio. In the crystal, C—H⋯O hydrogen-bonding interactions result in the formation of columns running in the [010] direction. Two parallel columns further interact by C—H⋯O hydrogen bonds. The most important contributions to the surface contacts are from H⋯H (48.4%), C⋯H/H⋯C (21.5%) and O⋯H/H⋯O (18.7%) interactions, as concluded from a Hirshfeld analysis.

Keywords: crystal structure; quinazolin-4-one; hydrogen bonding; Hirshfeld analysis.

CCDC reference: 1996127

1. Chemical context

Hybrid derivatives, where quinazolin-4-one is incorporated with different heterocycles, possess a variety of biological effects including anticancer (Khalil et al., 2003 ; Gursoy & Karal, 2003 ; Gawad et al., 2010 ; Elfekki et al., 2014 ; Alanazi et al., 2016 ; El-Sayed et al., 2017 ; Nguyen et al., 2019 ), anticonvulsant (El-Azab et al., 2013 ) and antimicrobial (Pandey et al., 2009 ; Al-Khuzaie & Al-Majidi, 2014 ; Al-Majidi & Al-Khuzaie, 2015 ; Lv et al., 2018 ; Godhani et al., 2016 ) activities. Some derivatives of 2-mercapto-3-(4-methoxyphenyl)quinazolin-4(3H)-one containing the thiazolidine-4-one moiety have been found to have good antituberculosis activity (Godhani et al., 2016). In addition, many amide and N-substituted hydrazide compounds derived from 2-mercapto-3-phenylquinazolin-4-one have been demonstrated to have valuable biological activities such as antitumor (Al-Suwaidan et al., 2016 , 2017 ; Mohamed et al., 2016 ), anticonvulsant (El-Helby & Wahab, 2003 ) and antibacterial (Lfta et al., 2016 ) activity. The capacity to increase the HDL cholesterol activity of some N-substituted compounds containing a quinazolin-4-one moiety has also been investigated (Deshmukh & Dhongade, 2004 ).

Ethyl 2-[(4-oxo-3-phenyl-3,4-dihydroquinazolin-2-yl)sulfanyl]acetate is an intermediate compound in the synthesis process of both N-substituted and heterocyclic compounds containing a quinazolin-4-one moiety. The synthesis and properties of ethyl 2-[(4-oxo-3-phenyl-3,4-dihydroquinazolin-2-yl)thio]acetate have therefore attracted much attention.

As shown in Fig. 1, 2-mercapto-3-phenylquinazolin-4(3H)-one (3) was obtained by the reaction of anthranilic acid (1) and phenyl isothiocyanate (2) (Nguyen et al., 2019). The IR spectrum of (3) shows the stretching vibrations of N—H (3217 and 3134 cm⁻¹) and C=O (1659 cm⁻¹) bonds, indicating that (3) exists in the thione form (Al-Majidi & Al-Khuzaie, 2015). In the ¹H NMR spectrum, besides signals of nine protons in the aromatic area, there is a singlet signal with the intensity of 1H at δ 13.05 ppm attributed to the proton of the thiol group. In an alkaline medium, (3) exists in the thiolate form and reacts easily with ethyl chloroacetate to yield (4). In the IR spectrum of (4), the disappearance of the NH stretching and the presence of a strong C=O absorption at 1732 cm⁻¹ indicate the existence of an ester compound. In the ¹H NMR spectrum of (4), the signal at δ 13.05 ppm disappears and three new signals in the aliphatic area [singlet signal at δ 3.99 (2H), quartet signal at δ 4.15 (2H) and triplet signal at δ 1.23 ppm (3H)] are consistent with the presence of the –CH₂COOCH₂CH₃ moiety in (4).

Figure 1
Reaction scheme for the synthesis of the title compound (4).

As no X-ray crystallographic information is available for this ester, we have determined the crystal structure by single-crystal X-ray diffraction and a Hirshfeld surface analysis has been performed to gain further insight into the intermolecular interactions.

2. Structural commentary

The title compound crystallizes in the space group P2₁/n with four molecules in the unit cell. The asymmetric unit of the title compound is illustrated in Fig. 2. The C17 methyl group is disordered over two orientations by a rotation of about 60° about the O15—C16 bond in a 0.531 (13): 0.469 (13) ratio. The quinazoline ring system is almost planar (r.m.s. deviation = 0.0207 Å). The angle between the two fused six-membered rings is 2.05 (9)°. The substituents S11, C18 and O23 deviating by −0.0951 (17), −0.140 (2) and 0.108 (2) Å, respectively, from the best plane through the quinazoline ring system. This plane makes an angle of 86.83 (5)° with the plane of the C18–C23 phenyl ring (r.m.s. deviation = 0.0052 Å). The dihedral angle between the best planes through the acetate atoms (C12, C13, O14 and O15) and the quinazoline ring system is 75.21 (5)°. A short intramolecular C16—H16B⋯O14 contact is observed [C16—H16B = 0.97 Å, H16B⋯O14 = 2.28 Å, C16⋯O14 = 2.655 (4) Å, C16—H16B⋯O14 = 102°].

Figure 2
The molecular structure of the title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Methyl group C17B [occupancy 0.469 (13)] is shown in green.

Theoretically, compound (3) may exist in the thione form, namely 3-phenyl-2-thioxo-2,3-dihydroquinazolin-4(1H)-one. Therefore, it could react with ethyl chloroacetate to give ethyl 2-(4-oxo-3-phenyl-2-thioxo-3,4-dihydroquinazolin-1(2H)-yl)acetate as illustrated in Fig. 3. However, our current structure determination indicates that the final product is ethyl 2-[(4-oxo-3-phenyl-3,4-dihydroquinazolin-2-yl)sulfanyl]acetate (4), which proves that in the alkaline environment, (3) converts into the thiolate form and then reacts with ethyl chloroacetate to yield the title compound (4).

Figure 3
Reaction scheme for the thione tautomer of (3) with ethyl chloroacetate resulting in ethyl 2-(4-oxo-3-phenyl-2-thioxo-3,4-dihydroquinazolin-1(2H)-yl)acetate as reaction product.

3. Supramolecular features and Hirshfeld surface analysis

The crystal packing is mainly characterized by C—H⋯O hydrogen-bonding interactions (Table 1, Figs. 4 and 5). Columns running in the [010] direction are formed by C12—H12B⋯O14ⁱⁱ and C19—H19⋯O23ⁱⁱ interactions, which results also in a short S11⋯H23ⁱⁱ contact of 3.020 Å [symmetry code: (ii) x, y + 1, z]. Two parallel columns interact via C7—H7⋯O23ⁱ hydrogen-bonding interactions [symmetry code: (i) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. No voids, C—H⋯π interactions or π–π stackings are observed in the crystal packing.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O23ⁱ	0.93	2.59	3.452 (3)	155
C12—H12B⋯O14ⁱⁱ	0.97	2.42	3.311 (3)	153
C19—H19⋯O23ⁱⁱ	0.93	2.41	3.236 (2)	148
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Figure 4
View of the crystal packing of the title compound along the [010] direction. Only the major component of the disordered C17 methyl group is shown.

Figure 5
Partial crystal packing of the title compound showing two parallel columns running in the [010] direction. Intermolecular C—H⋯O interactions are shown as red dashed lines (see Table 1

for details), C—H⋯S interactions as yellow dashed lines. Only the major component of the disordered C17 methyl group is shown.

In order to gain further insight into the intermolecular interactions, a Hirshfeld surface and two-dimensional fingerprint plots were calculated using CrystalExplorer (Turner et al., 2017 ). The Hirshfeld surface mapped over d_norm (Fig. 6) shows the expected bright-red spots near atoms O14, O23, H7, H12B and H19 involved in the C—H⋯O hydrogen-bonding interactions described above. In addition, the faint-red spots near atoms S11 and O14 indicate a short S⋯O contact [3.2128 (16) Å]. Small faint-red spots appear near atoms H8 and H17E are due to a short H8⋯H17E contact (2.352 Å). The S11⋯H23 contact mentioned is only visible as a white spot, while a white region above the C18–C23 phenyl ring is present because of the proximity of atom H20. The distance between H20 and the centroid of this phenyl ring of 3.204 Å, however, is too long for a C—H⋯π interaction. The fingerprint plots (Fig. 7) illustrate that the largest contributions to the Hirshfeld surface come from H⋯H contacts (48.4%), followed by significant contributions by reciprocal C⋯H/H⋯C (21.5%) and O⋯H/H⋯O (18.7%) contacts. Smaller contributions are from S⋯H/H⋯S (4.0%), N⋯C/C⋯N (1.6%), C⋯C (1.6%), C⋯S/S⋯C (1.4%), N⋯H/H⋯N (1.3%), S⋯O/O⋯S (1.0%), N⋯S/S⋯N (1.0%) and O⋯O contacts (0.1%).

Figure 6
The Hirshfeld surface of (4) mapped over d_norm for the title compound in the range −0.2419 to 1.2857 a.u.

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

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.41, update of November 2019; Groom et al., 2016 ) for 4-oxo-3,4-dihydroquinazoline gave 645 hits, of which 141 have a phenyl group at position N3 and 27 have a sulfur atom at position C2. A combination of both substitutions (without a link between the two) results in a set of 10 hits, which was used for further analysis. The dihedral angle between the least-squares planes through the quinazoline and phenyl rings varies between 71.99° (CSD refcode MUDGID; Saeed et al., 2014 ) and 86.46° (CSD refcode GUWDIM; Rimaz et al., 2009 ) with an average of 81.63°. The dihedral angle does not depend on eventual ortho subsitution of the phenyl ring, as illustrated by the structures MUDGID (71.99°) and MUDNAC (85.90°; Saeed et al., 2014), which both have an o-toluidine substituent at position N3. The almost perpendicular mutual orientation of both rings is also observed for the title compound.

5. Synthesis and crystallization

Anthranilic acid, phenyl isothiocyanate and ethyl chloroacetate were purchased from Acros and used without purification. Melting points were measured in open capillary tubes on a Gallenkamp melting point apparatus. IR spectra (ν, cm⁻¹) were recorded on FTIR-8400S-SHIMADZU spectrometer using KBr pellets. The NMR spectra were recorded on a Bruker Avance III spectrometer (500 MHz for ¹H NMR) using residual solvent DMSO-d₆ signals as internal reference. The spin–spin coupling constants (J) are given in Hz. Peak multiplicity is reported as s (singlet), d (doublet), dd (doublet-doublet), t (triplet), q (quartet), m (multiplet). The synthetic protocol for title compound (4) is shown in Fig. 1 (Nguyen et al., 2019).

Synthesis of 2-mercapto-3-phenylquinazolin-4-one (3):

Phenyl isothiocyanate (2) (0.1 mol) was added to the solution of anthranilic acid (1) (0.1 mol) and triethylamine (3.0 mL) in absolute ethanol (200 mL). The reaction mixture then was refluxed for 4 h. After cooling to room temperature, the reaction mixture was poured into cold water. The resulting solid was filtered and recrystallized from a mixture of DMF and water, then washed with cold ethanol to give the product (3). M.p. 569 K; yield 80%. IR (KBr, cm⁻¹): 3217, 3134 (N—H), 3028 (C—H aromatic), 1659 (C=O), 1618, 1524, 1485 (C=N, C=C aromatic). ¹H NMR [Bruker XL-500, 500 MHz, d₆-DMSO, δ (ppm), J (Hz)]: 13.05 (s, 1H, H^2a), 7.96 (d, 1H, ³J = 8.0 Hz, H⁵), 7.80 (dd, 1H, ³J₁ = ³J₂ = 8.0 Hz, H⁷), 7.50–7.40 (m, 3H, H^8,3c,3e), 7.42 (dd, 1H, ³J₁ = ³J₂ = 7.5 Hz, H⁶), 7.36 (dd, 1H, ³J₁ = ³J₂ = 7.5 Hz, H^3d), 7.29 (d, 2H, ³J = 7.5 Hz, H^3b,3f).

Synthesis of ethyl 2-[(4-oxo-3-phenyl-3,4-dihydroquinazolin-2-yl) sulfanyl]acetate (4):

A mixture of (3) (20 mmol) and anhydrous potassium carbonate (20 mmol) in dry DMF (30 mL) was stirred for 30 min, ethyl chloroacetate (20 mmol) was then added. After refluxing for 5 h, the reaction mixture was cooled to room temperature and poured into ice-cold water. The white precipitate was filtered off and recrystallized from ethanol to afford crystals of (4). Colourless crystals, m.p. 485 K, yield 65%. IR (KBr, cm⁻¹): 3059 (C—H aromatic), 2976, 2906 (C—H aliphatic), 1732 (C=O ester), 1680 (C=O ketone), 1607, 1598, 1468 (C=N, C=C aromatic). ¹H NMR [Bruker XL-500, 500 MHz, d₆-DMSO, δ (ppm), J (Hz)]: 8.09 (d, 1H, ³J = 8.0 Hz, H⁵), 7.84 (d, 1H, ³J = 7.5 Hz, H⁸), 7.61-7.48 (m, 7H, H^{6,7,3b,3c,3d,3e,3f}), 4.15 (q, 2H, ³J = 7.0 Hz, H^2c), 3.99 (s, 2H, H^2a), 1.23 (t, 3H, ³J = 7.0 Hz, H^2d).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The methyl group C17 is disordered over two positions with population parameters 0.531 (13) and 0.469 (13)]. The H atoms were placed in idealized positions and included as riding contributions with U_iso(H) values of 1.2U_eq or 1.5U_eq of the parent atoms, with C—H distances of 0.93 (aromatic), 0.97 (CH₂) and 0.96 Å (CH₃). In the final cycles of refinement, two outliers were omitted.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₂O₃S
M_r	340.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.8865 (6), 5.1298 (3), 28.2942 (14)
β (°)	93.667 (4)
V (Å³)	1721.72 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.5 × 0.15 × 0.15

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, single source at offset/far, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, UK.]$ )
T_min, T_max	0.715, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18522, 3533, 2875
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.111, 1.08
No. of reflections	3533
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.22
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, UK.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1996127

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020005071/dj2002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020005071/dj2002Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020005071/dj2002Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Ethyl 2-[(4-oxo-3-phenyl-3,4-dihydroquinazolin-2-yl)sulfanyl]acetate top

Crystal data top

C₁₈H₁₆N₂O₃S	F(000) = 712
M_r = 340.39	D_x = 1.313 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.8865 (6) Å	Cell parameters from 7343 reflections
b = 5.1298 (3) Å	θ = 2.9–26.9°
c = 28.2942 (14) Å	µ = 0.21 mm⁻¹
β = 93.667 (4)°	T = 293 K
V = 1721.72 (16) Å³	Needle, colourless
Z = 4	0.5 × 0.15 × 0.15 mm

Data collection top

Rigaku Oxford Diffraction SuperNova, Single source at offset/far, Eos diffractometer	3533 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2875 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 15.9631 pixels mm^-1	θ_max = 26.4°, θ_min = 2.7°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −6→6
T_min = 0.715, T_max = 1.000	l = −35→35
18522 measured reflections

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0409P)² + 0.5306P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3533 reflections	Δρ_max = 0.14 e Å⁻³
229 parameters	Δρ_min = −0.22 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	Occ. (<1)
N1	0.68674 (11)	0.7908 (3)	0.38689 (5)	0.0521 (4)
C2	0.58088 (13)	0.8340 (3)	0.37790 (6)	0.0453 (4)
N3	0.51456 (10)	0.7160 (3)	0.34201 (5)	0.0438 (3)
C4	0.55985 (14)	0.5351 (3)	0.31132 (6)	0.0456 (4)
C5	0.67846 (13)	0.4761 (3)	0.32214 (6)	0.0450 (4)
C6	0.73246 (16)	0.2867 (4)	0.29607 (7)	0.0577 (5)
H6	0.692325	0.197199	0.271885	0.069*
C7	0.84377 (17)	0.2334 (4)	0.30609 (8)	0.0702 (6)
H7	0.879740	0.107617	0.288799	0.084*
C8	0.90293 (17)	0.3672 (5)	0.34210 (9)	0.0794 (7)
H8	0.979020	0.331142	0.348609	0.095*
C9	0.85182 (16)	0.5518 (5)	0.36837 (8)	0.0709 (6)
H9	0.893080	0.639601	0.392451	0.085*
C10	0.73754 (14)	0.6078 (4)	0.35893 (6)	0.0489 (4)
S11	0.50921 (4)	1.05531 (10)	0.41245 (2)	0.06194 (18)
C12	0.62397 (16)	1.1534 (4)	0.45253 (7)	0.0564 (5)
H12A	0.686170	1.209133	0.434376	0.068*
H12B	0.600486	1.301892	0.470701	0.068*
C13	0.66465 (17)	0.9421 (4)	0.48617 (7)	0.0563 (5)
O14	0.61472 (13)	0.7513 (3)	0.49620 (5)	0.0728 (4)
O15	0.76681 (14)	1.0046 (3)	0.50483 (6)	0.0907 (5)
C16	0.8156 (3)	0.8266 (9)	0.54064 (14)	0.1386 (14)
H16A	0.856216	0.924744	0.565576	0.166*	0.531 (13)
H16B	0.756086	0.729319	0.554614	0.166*	0.531 (13)
H16C	0.780435	0.857679	0.570144	0.166*	0.469 (13)
H16D	0.798109	0.649159	0.530875	0.166*	0.469 (13)
C17A	0.8872 (9)	0.6589 (19)	0.5203 (4)	0.129 (4)	0.531 (13)
H17A	0.844520	0.538073	0.500469	0.194*	0.531 (13)
H17B	0.930264	0.565109	0.544649	0.194*	0.531 (13)
H17C	0.937310	0.755551	0.501607	0.194*	0.531 (13)
C17B	0.9293 (6)	0.850 (3)	0.5485 (4)	0.152 (7)	0.469 (13)
H17D	0.964924	0.820026	0.519528	0.228*	0.469 (13)
H17E	0.955908	0.724381	0.571772	0.228*	0.469 (13)
H17F	0.947221	1.022473	0.559888	0.228*	0.469 (13)
C18	0.39382 (13)	0.7640 (3)	0.33627 (6)	0.0454 (4)
C19	0.35129 (17)	0.9418 (4)	0.30424 (7)	0.0620 (5)
H19	0.399266	1.040013	0.286589	0.074*
C20	0.23496 (18)	0.9749 (5)	0.29822 (9)	0.0763 (6)
H20	0.205352	1.096917	0.276528	0.092*
C21	0.16481 (17)	0.8324 (5)	0.32340 (9)	0.0773 (6)
H21	0.087168	0.852870	0.318649	0.093*
C22	0.20844 (17)	0.6590 (6)	0.35575 (11)	0.0981 (9)
H22	0.160210	0.563733	0.373781	0.118*
O23	0.50149 (10)	0.4422 (3)	0.27855 (5)	0.0628 (4)
C23	0.32353 (16)	0.6215 (5)	0.36235 (9)	0.0804 (7)
H23	0.352638	0.500489	0.384337	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0442 (8)	0.0581 (9)	0.0531 (9)	0.0025 (7)	−0.0027 (6)	−0.0094 (7)
C2	0.0450 (9)	0.0470 (9)	0.0436 (9)	0.0019 (7)	0.0000 (7)	−0.0009 (7)
N3	0.0390 (7)	0.0495 (8)	0.0429 (7)	−0.0008 (6)	0.0014 (6)	−0.0007 (6)
C4	0.0448 (9)	0.0500 (10)	0.0426 (9)	−0.0079 (7)	0.0059 (7)	−0.0003 (7)
C5	0.0436 (8)	0.0490 (9)	0.0432 (9)	−0.0020 (7)	0.0087 (7)	0.0011 (7)
C6	0.0592 (11)	0.0621 (12)	0.0530 (10)	0.0015 (9)	0.0133 (9)	−0.0057 (9)
C7	0.0640 (12)	0.0763 (14)	0.0722 (14)	0.0156 (11)	0.0198 (10)	−0.0067 (11)
C8	0.0448 (10)	0.1025 (18)	0.0911 (16)	0.0192 (11)	0.0054 (10)	−0.0125 (14)
C9	0.0454 (10)	0.0877 (15)	0.0784 (14)	0.0082 (10)	−0.0050 (9)	−0.0172 (12)
C10	0.0415 (9)	0.0551 (10)	0.0503 (10)	0.0012 (8)	0.0051 (7)	−0.0006 (8)
S11	0.0562 (3)	0.0648 (3)	0.0638 (3)	0.0166 (2)	−0.0040 (2)	−0.0173 (2)
C12	0.0662 (11)	0.0442 (10)	0.0583 (11)	0.0019 (9)	−0.0007 (9)	−0.0083 (8)
C13	0.0682 (12)	0.0521 (11)	0.0486 (10)	0.0027 (9)	0.0039 (9)	−0.0064 (9)
O14	0.0954 (11)	0.0510 (8)	0.0736 (10)	−0.0013 (8)	0.0189 (8)	−0.0009 (7)
O15	0.0849 (11)	0.0986 (12)	0.0845 (11)	−0.0084 (9)	−0.0259 (9)	0.0233 (10)
C16	0.130 (3)	0.164 (3)	0.115 (3)	0.017 (3)	−0.037 (2)	0.058 (3)
C17A	0.131 (7)	0.112 (6)	0.143 (7)	0.033 (5)	0.006 (5)	0.020 (5)
C17B	0.093 (5)	0.221 (15)	0.137 (9)	0.000 (6)	−0.030 (5)	0.083 (10)
C18	0.0390 (8)	0.0472 (9)	0.0495 (9)	0.0018 (7)	−0.0019 (7)	0.0005 (7)
C19	0.0591 (11)	0.0629 (12)	0.0625 (12)	−0.0047 (9)	−0.0084 (9)	0.0135 (10)
C20	0.0663 (13)	0.0759 (14)	0.0830 (15)	0.0141 (11)	−0.0229 (12)	0.0171 (12)
C21	0.0445 (10)	0.0862 (16)	0.0997 (17)	0.0125 (11)	−0.0074 (11)	0.0044 (14)
C22	0.0431 (11)	0.113 (2)	0.139 (2)	0.0074 (12)	0.0148 (13)	0.0576 (19)
O23	0.0525 (7)	0.0796 (9)	0.0558 (8)	−0.0115 (7)	0.0002 (6)	−0.0174 (7)
C23	0.0441 (10)	0.0888 (16)	0.1085 (18)	0.0097 (10)	0.0063 (11)	0.0494 (14)

Geometric parameters (Å, º) top

N1—C2	1.287 (2)	S11—C12	1.7896 (19)
N1—C10	1.390 (2)	C12—H12A	0.9700
C17Aa—H17A	0.9600	C12—H12B	0.9700
C17Aa—H17B	0.9600	C12—C13	1.502 (3)
C17Aa—H17C	0.9600	C13—O14	1.188 (2)
C17Bb—H17D	0.9600	C13—O15	1.332 (2)
C17Bb—H17E	0.9600	O15—C16	1.456 (3)
C17Bb—H17F	0.9600	C16—H16A	0.9700
C2—N3	1.384 (2)	C16—H16B	0.9700
C2—S11	1.7541 (17)	C16—H16C	0.9700
N3—C4	1.402 (2)	C16—H16D	0.9700
N3—C18	1.4550 (19)	C16—C17A	1.363 (8)
C4—C5	1.455 (2)	C16—C17B	1.361 (9)
C4—O23	1.219 (2)	C18—C19	1.360 (2)
C5—C6	1.400 (2)	C18—C23	1.362 (3)
C5—C10	1.393 (2)	C19—H19	0.9300
C6—H6	0.9300	C19—C20	1.393 (3)
C6—C7	1.363 (3)	C20—H20	0.9300
C7—H7	0.9300	C20—C21	1.346 (3)
C7—C8	1.383 (3)	C21—H21	0.9300
C8—H8	0.9300	C21—C22	1.356 (3)
C8—C9	1.370 (3)	C22—H22	0.9300
C9—H9	0.9300	C22—C23	1.382 (3)
C9—C10	1.397 (2)	C23—H23	0.9300

C2—N1—C10	117.28 (15)	H16Aa—C16—H16B	108.2
N1—C2—N3	124.99 (15)	C17Bb—C16—H16C	108.8
N1—C2—S11	120.31 (13)	C17Bb—C16—H16D	108.8
H17Aa—C17Aa—H17B	109.5	H16Cb—C16—H16D	107.7
H17Aa—C17Aa—H17C	109.5	H12A—C12—H12B	107.7
N3—C2—S11	114.70 (11)	C13—C12—S11	113.59 (13)
C2—N3—C4	121.38 (13)	C13—C12—H12A	108.8
C2—N3—C18	121.27 (13)	C13—C12—H12B	108.8
C4—N3—C18	117.26 (13)	O14—C13—C12	126.89 (19)
N3—C4—C5	114.37 (14)	O14—C13—O15	124.07 (19)
O23—C4—N3	120.51 (15)	O15—C13—C12	109.01 (17)
H17Ba—C17Aa—H17C	109.5	C13—O15—C16	115.9 (2)
H17Db—C17Bb—H17E	109.5	O15—C16—H16A	109.8
H17Db—C17Bb—H17F	109.5	O15—C16—H16B	109.8
H17Eb—C17Bb—H17F	109.5	O15—C16—H16C	108.8
O23—C4—C5	125.12 (16)	O15—C16—H16D	108.8
C6—C5—C4	120.27 (16)	C16—C17Aa—H17A	109.5
C10—C5—C4	119.46 (15)	C19—C18—N3	120.65 (16)
C10—C5—C6	120.27 (16)	C16—C17Aa—H17B	109.5
C5—C6—H6	120.0	C19—C18—C23	120.39 (17)
C7—C6—C5	120.09 (19)	C23—C18—N3	118.92 (15)
C7—C6—H6	120.0	C16—C17Aa—H17C	109.5
C6—C7—H7	120.2	C16—C17Bb—H17D	109.5
C6—C7—C8	119.64 (19)	C18—C19—H19	120.4
C8—C7—H7	120.2	C18—C19—C20	119.14 (19)
C7—C8—H8	119.3	C16—C17Bb—H17E	109.5
C9—C8—C7	121.39 (19)	C16—C17Bb—H17F	109.5
C9—C8—H8	119.3	C20—C19—H19	120.4
C8—C9—H9	120.1	C19—C20—H20	119.6
C8—C9—C10	119.9 (2)	C21—C20—C19	120.9 (2)
C10—C9—H9	120.1	C21—C20—H20	119.6
N1—C10—C5	122.43 (15)	C20—C21—H21	120.3
N1—C10—C9	118.83 (17)	C20—C21—C22	119.37 (19)
C17Aa—C16—O15	109.5 (5)	C22—C21—H21	120.3
C5—C10—C9	118.73 (17)	C21—C22—H22	119.5
C2—S11—C12	99.06 (8)	C21—C22—C23	121.0 (2)
C17Bb—C16—O15	113.9 (5)	C23—C22—H22	119.5
S11—C12—H12A	108.8	C18—C23—C22	119.24 (19)
C17Aa—C16—H16A	109.8	C18—C23—H23	120.4
S11—C12—H12B	108.8	C22—C23—H23	120.4
C17Aa—C16—H16B	109.8

N1—C2—N3—C4	−0.6 (3)	C7—C8—C9—C10	0.0 (4)
N1—C2—N3—C18	176.02 (16)	C8—C9—C10—N1	178.3 (2)
N1—C2—S11—C12	0.18 (17)	C8—C9—C10—C5	−1.0 (3)
C2—N1—C10—C5	0.7 (3)	C10—N1—C2—N3	−1.3 (3)
C2—N1—C10—C9	−178.59 (18)	C10—N1—C2—S11	178.30 (13)
C2—N3—C4—C5	2.9 (2)	C10—C5—C6—C7	−1.1 (3)
C2—N3—C4—O23	−176.56 (16)	S11—C2—N3—C4	179.77 (12)
C2—N3—C18—C19	97.9 (2)	S11—C2—N3—C18	−3.6 (2)
C2—N3—C18—C23	−84.4 (2)	S11—C12—C13—O14	−19.1 (3)
C2—S11—C12—C13	−68.94 (15)	S11—C12—C13—O15	162.70 (14)
N3—C2—S11—C12	179.82 (13)	C12—C13—O15—C16	176.3 (3)
N3—C4—C5—C6	176.06 (15)	O14—C13—O15—C16	−1.9 (4)
N3—C4—C5—C10	−3.3 (2)	C13—O15—C16—C17Bb	161.5 (9)
N3—C18—C19—C20	177.27 (18)	C13—O15—C16—C17Aa	97.7 (7)
N3—C18—C23—C22	−177.5 (2)	C18—N3—C4—C5	−173.88 (14)
C4—N3—C18—C19	−85.4 (2)	C18—N3—C4—O23	6.7 (2)
C4—N3—C18—C23	92.4 (2)	C18—C19—C20—C21	−0.4 (4)
C4—C5—C6—C7	179.52 (18)	C19—C18—C23—C22	0.3 (4)
C4—C5—C10—N1	1.7 (3)	C19—C20—C21—C22	1.5 (4)
C4—C5—C10—C9	−179.01 (18)	C20—C21—C22—C23	−1.7 (5)
C5—C6—C7—C8	0.0 (3)	C21—C22—C23—C18	0.8 (5)
C6—C5—C10—N1	−177.70 (16)	O23—C4—C5—C6	−4.5 (3)
C6—C5—C10—C9	1.6 (3)	O23—C4—C5—C10	176.07 (17)
C6—C7—C8—C9	0.6 (4)	C23—C18—C19—C20	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O23ⁱ	0.93	2.59	3.452 (3)	155
C12—H12B···O14ⁱⁱ	0.97	2.42	3.311 (3)	153
C19—H19···O23ⁱⁱ	0.93	2.41	3.236 (2)	148

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x, y+1, z.

Funding information

We are grateful to The Ministry of Education and Training of Vietnam for supporting this research (grant No. B2019-SPS-02). LVM thanks the Hercules Foundation for supporting the purchase of the diffractometer through project AKUL/09/0035.

References

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