Crystal structure, Hirshfeld surface and crystal void analysis, inter­molecular inter­action energies, DFT calculations and energy frameworks of 2H-benzo[b][1,4]thia­zin-3(4H)-one 1,1-dioxide

Irrou, E.; Ait Elmachkouri, Y.; Mazzah, A.; Hökelek, T.; Haoudi, A.; Mague, J.T.; Taha, M.L.; Sebbar, N.K.

doi:10.1107/S205698902300868X

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Volume 79| Part 11| November 2023| Pages 1037-1043

https://doi.org/10.1107/S205698902300868X

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Crystal structure, Hirshfeld surface and crystal void analysis, intermolecular interaction energies, DFT calculations and energy frameworks of 2H-benzo[b][1,4]thiazin-3(4H)-one 1,1-dioxide

Ezaddine Irrou,^a ^* Younesse Ait Elmachkouri,^a Ahmed Mazzah,^b Tuncer Hökelek,^c Amal Haoudi,^d Joel T. Mague,^e Mohamed Labd Taha ^a and Nada Kheira Sebbar ^a,^f

^aLaboratory of Organic and Physical Chemistry, Applied Bioorganic Chemistry Team, Faculty of Sciences, Ibn Zohr University, Agadir, Morocco, ^bUniversity of Lille, CNRS, UAR 3290, MSAP, Miniaturization for Synthesis, Analysis and Proteomics, F-59000 Lille, France, ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Türkiye, ^dLaboratory of Applied Organic Chemistry, Faculty of Science and Technology, University of Sidi Mohamed Ben Abdellah BP 2202, Fez, Morocco, ^eDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and ^fLaboratory of Heterocyclic Organic Chemistry, Medicines Science Research Center, Pharmacochemistry Competence Center, Mohammed V University in Rabat, Faculté des Sciences, Av. Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: ezaddine.irrou@edu.uiz.ac.ma

Edited by M. Weil, Vienna University of Technology, Austria (Received 13 September 2023; accepted 3 October 2023; online 19 October 2023)

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

In the title molecule, C₈H₇NO₃S, the nitrogen atom has a planar environment, and the thiazine ring exhibits a screw-boat conformation. In the crystal, corrugated layers of molecules parallel to the ab plane are formed by N—H⋯O and C—H⋯O hydrogen bonds together with C—H⋯π(ring) and S=O⋯π(ring) interactions. The layers are connected by additional C—H⋯O hydrogen bonds and π-stacking interactions. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯O/O⋯H (49.4%), H⋯H (23.0%) and H⋯C/C⋯H (14.1%) interactions. The volume of the crystal voids and the percentage of free space were calculated as 75.4 Å³ and 9.3%. Density functional theory (DFT) computations revealed N—H⋯O and C—H⋯O hydrogen-bonding energies of 43.3, 34.7 and 34.4 kJ mol⁻¹, respectively. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated via the electrostatic energy contribution. Moreover, the DFT-optimized structure at the B3LYP/ 6–311 G(d,p) level is compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

Keywords: Crystal structure; hydrogen bond; C—H⋯π(ring) interaction; π-stacking; sulfone; crystal structure.

CCDC reference: 2298958

1. Chemical context

Numerous heterocyclic compounds containing sulfur and nitrogen have been extensively studied because of their various biological applications (Gowda et al., 2011 ; Sebbar et al., 2020a ; Fringuelli et al., 2005 ). In this respect, 1,4-benzothiazine derivatives possess various pharmacological properties and have therapeutic applications such as antifungal (Kamila et al., 2006 ), anti-inflammatory (Gowda et al., 2011), antagonistic (Corelli et al., 1997 ), anti-tumour (Abbas & Farghaly, 2010 ), antioxidant (Bakavoli et al., 2008 ), antipyretic (Warren & Knaus, 1987 ), antihypertensive (Fringuelli et al., 2005) or antibacterial effects (Sebbar et al., 2016 , 2020a).

Continuing our research on the development of new 1,4-benzothiazine derivatives with potential pharmacological applications, we carried out the oxidation of 3,4-dihydro-2H-1,4-benzothiazin-3-one by potassium permanganate in order to obtain 2H-benzo[b][1,4]thiazin-3(4H)-one 1,1-dioxide (I) with good yield. We report herein the molecular and crystal structure of this compound, as well as Hirshfeld surface analysis and DFT-computational studies carried out at the B3LYP/6–31 G(d,p) and B3LYP/6–311 G(d,p) levels.

2. Structural commentary

A puckering analysis (Cremer & Pople, 1975 ) of the thiazine ring (C1, C6, N1, C7, C8, S1) gave the parameters Q = 0.5138 (6) Å, θ = 60.49 (7)° and φ = 326.72 (8)°. The distorted screw-boat conformation places O2 in an axial position and O3 in a pseudo-equatorial position (Fig. 1). The angles about N1 sum up to 360° within experimental error, indicating involvement of the lone pair in the C–N bond. This is reflected in the N1—C7 and N1—C6 distances of 1.3661 (9) and 1.4043 (9) Å, respectively.

Figure 1
The title molecule with atom labelling and displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal, N1—H1⋯O3 hydrogen bonds (Table 1) form chains of molecules extending parallel to the a axis. These chains are connected into corrugated layers parallel to the ab plane by C8—H8B⋯O2 hydrogen bonds together with C8—H8A⋯Cg2 and S1=O2⋯Cg2ⁱ interactions [O2⋯Cg2 = 3.6233 (7) Å, S1⋯Cg2 = 4.1655 (5) Å, S1=O2⋯Cg2ⁱ = 101.77 (3)°; symmetry code: (i) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; Fig. 2]. The layers are connected by C5—H5⋯O1 hydrogen bonds (Table 1) and slipped π–π stacking interactions between inversion-related C1–C6 rings [Cg2⋯Cg2(1 −x, 1 −y, 1 −z) = 3.7353 (5) Å, slippage = 1.55 Å] into a tri-periodic network structure (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.89 (1)	2.08 (1)	2.9472 (8)	165 (1)
C5—H5⋯O1ⁱⁱ	0.95	2.58	3.2330 (9)	126
C8—H8A⋯Cg2ⁱⁱⁱ	0.99	2.93	3.7933 (8)	146
C8—H8B⋯O2^iv	0.99	2.39	3.2126 (9)	140
Symmetry codes: (i) ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The crystal structure of (I)

viewed along the c axis with N—H⋯O and C—H⋯O hydrogen bonds depicted, respectively, by violet and black dashed lines. C—H⋯π(ring) and C=O⋯π(ring) interactions are depicted, respectively, by green and dark-pink dashed lines and non-interacting hydrogen atoms are omitted for clarity.

Figure 3
The crystal structure of (I)

viewed along the b axis with N—H⋯O and C—H⋯O hydrogen bonds depicted, respectively, by violet and black dashed lines. C—H⋯π(ring), C=O⋯π(ring) and slipped π-stacking interactions are depicted, respectively, by green, dark-pink and orange dashed lines. Non-interacting hydrogen atoms are omitted for clarity.

4. Hirshfeld surface analysis

To visualize the intermolecular interactions in the crystal of (I), a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ) was carried out with Crystal Explorer (Spackman et al., 2021 ). In the HS plotted over d_norm in the range −0.4976 to 1.2253 a.u. (Fig. 4), the white surface indicates contacts with distances equal to the sum of van der Waals radii and the red and blue colours indicate distances shorter (in close contact) or longer (distant contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) in the range −0.05 to 0.05 a.u., as shown in Fig. 5. The blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles. Fig. 6 clearly suggests that there are π–π interactions in (I). The overall two-dimensional fingerprint plot, Fig. 7a, and those delineated into H⋯O/O⋯H, H⋯H, H⋯C/C⋯H, C⋯O/O⋯C,C⋯C, H⋯N/N⋯H, O⋯O and C⋯N/N⋯C contacts (McKinnon et al., 2007 ) are illustrated in Fig. 7b–i, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯O/O⋯H, contributing 49.4% to the overall crystal packing, which is reflected in Fig. 7b, where the symmetric pair of spikes is observed with the tips at d_e + d_i = 1.98 Å. The H⋯H contacts contribute 23.0% to the overall crystal packing, which is reflected in Fig. 7c as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at d_e = d_i = 1.13 Å. In the presence of C—H⋯π interactions, the pair of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts, Fig. 7d, make a 14.1% contribution to the HS and viewed with the tips at d_e + d_i = 2.59 Å. The wing pair of C⋯O/O⋯C contacts (Fig. 7e) with 4.9% contribution to the HS is viewed at d_e + d_i = 3.30 Å. The C⋯C contacts (Fig. 7f) appearing as a bullet-shaped distribution of points make a contribution of 3.7% to the HS with the tip at d_e = d_i = 1.70 Å. The spikes of H⋯N/N⋯H contacts (Fig. 7g) with 3.2% contribution to the HS are viewed at d_e + d_i = 2.75 Å. Finally, the O⋯O (Fig. 7h) and C⋯N/N⋯C (Fig. 7i) contacts contribute 1.3% and 0.4%, respectively, to the HS. The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯O/O⋯H, H⋯H and H⋯C/C⋯H interactions in Fig. 8a–c, respectively. The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯O/O⋯H, H⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions play the major role in the crystal packing (Hathwar et al., 2015 ).

Figure 4
View of the three-dimensional Hirshfeld surface of (I)

plotted over d_norm.

Figure 5
View of the three-dimensional Hirshfeld surface of (I)

plotted over electrostatic potential energy using the STO-3 G basis set at the Hartree–Fock level of theory.

Figure 6
Hirshfeld surface of (I)

plotted over shape-index.

Figure 7
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, (b) H⋯O/O⋯H, (c) H⋯H, (d) H⋯C/C⋯H, (e) O⋯C/C⋯O, (f) C⋯C, (g) H⋯N/N⋯H, (h) O⋯O and (i) C⋯N/N⋯C 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.

Figure 8
Hirshfeld surface representations of (I)

with the function d_norm plotted onto the surface for (a) H⋯O/O⋯H, (b) H⋯H and (c) H⋯C/C⋯H interactions.

The strength of the crystal packing is important for determining the response to an applied mechanical force. If the crystal packing results in significant voids, then the molecules are not tightly packed and a small amount of applied external mechanical force may easily break the crystal. To check the mechanical stability of the crystal, a void analysis was performed by adding up the electron densities of the spherically symmetric atoms contained in the asymmetric unit (Turner et al., 2011 ). The void surface is defined as an isosurface of the procrystal electron density and is calculated for the whole unit cell where the void surface meets the boundary of the unit cell and capping faces are generated to create an enclosed volume. The volume of the crystal voids (Fig. 9a,b) and the percentage of free space in the unit cell are calculated as 75.4 Å³ and 9.3%, respectively. Thus, the crystal packing appears compact and the mechanical stability should be substantial.

Figure 9
Graphical views of voids in the crystal packing of (I)

, (a) along the a axis and (b) along the b axis.

5. Interaction energy calculations and energy frameworks

The intermolecular interaction energies were calculated using the CEB3LYP/631G(d,p) energy model available in CrystalExplorer (Spackman et al., 2021), where a cluster of molecules is generated by applying crystallographic symmetry operations with respect to a selected central molecule within the radius of 3.8 Å by default (Turner et al., 2014 ). The total intermolecular energy (E_tot) is the sum of electrostatic (E_ele), polarization (E_pol), dispersion (E_dis) and exchange-repulsion (E_rep) energies (Turner et al., 2015 ) with scale factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie et al., 2017 ). Hydrogen-bonding interaction energies (in kJ mol⁻¹) were calculated to be [−18.5 (E_ele), −5.2 (E_pol), −41.4 (E_dis), 26.2 (E_rep) and −43.3 (E_tot)] for N1—H1⋯O3, [−22.4 (E_ele), −4.8 (E_pol), −28.3 (E_dis), 27.9 (E_rep) and −34.7 (E_tot)] for C8—H8B⋯O2 and [−20.6 (E_ele), −5.8 (E_pol), −24.6 (E_dis), 21.2 (E_rep) and −34.4 (E_tot)] for C5—H5⋯O1.

Energy frameworks combine the calculation of intermolecular interaction energies with a graphical representation of their magnitude (Turner et al., 2015). Energies between molecular pairs are represented as cylinders joining the centroids of pairs of molecules with the cylinder radius proportional to the relative strength of the corresponding interaction energy. Energy frameworks were constructed for E_ele (shown in Fig. 10), E_dis and E_tot. The evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated via the electrostatic energy contribution in the crystal structure of (I).

Figure 10
The energy framework for the electrostatic energy, viewed down the b axis for a cluster of molecules, where the a axis is vertical and the c axis is horizontal. The cylindrical radius is proportional to the relative strength of the corresponding energy and adjusted to the scale factor of 80 with a cut-off value of 5 kJ mol⁻¹ within 2 × 2 × 2 unit cells.

6. DFT calculations

The optimized structure of (I) was computed in the gas phase using density functional theory (DFT) with the standard B3LYP functional and 6–311 G(d,p) basis-set calculations (Becke, 1993 ), employing the GAUSSIAN 09 software (Frisch et al., 2009 ). The theoretical and experimental results exhibit a good agreement, as summarized in Table 2.

Table 2
Comparison of the selected (X-ray and DFT) geometric data (Å, °)

Bonds/angles	X-ray	B3LYP/6–311G(d,p)
S1—O2	1.4450 (6)	1.50996
S1—O3	1.4464 (6)	1.59088
S1—C1	1.7478 (6)	1.78874
S1—C8	1.7649 (7)	1.80529
O1—C7	1.2203 (8)	1.21656
N1—C7	1.3661 (9)	1.37417
N1—C6	1.4043 (9)	1.39867
O2—S1—O3	117.64 (4)	118.09813
O2—S1—C1	109.21 (3)	109.40063
O3—S1—C1	109.56 (3)	109.84640
O2—S1—C8	108.59 (3)	109.10007
O3—S1—C8	109.59 (3)	109.62080
C1—S1—C8	100.95 (3)	99.96775
C7—N1—C6	127.24 (6)	127.88849
C7—N1—H1	116.1 (10)	115.98354

The highest-occupied molecular orbital (HOMO), functioning as an electron donor, and the lowest-unoccupied molecular orbital (LUMO), acting as an electron acceptor, serve as vital parameters in quantum chemistry. A small energy gap signifies high molecular polarizability and enhanced chemical reactivity. The DFT calculations provided crucial insights into the reactivity and site selectivity of the molecular framework. Parameters such as E_HOMO and E_LUMO, electronegativity (χ), hardness (η), dipole moment (μ), electrophilicity (ω) and softness (σ) are compiled in Table 3. Both η and σ are essential for assessing reactivity and stability. The electron transition from HOMO to LUMO energy levels is depicted in Fig. 11. Notably, both HOMO and LUMO are localized within the plane spanning the entire 2H-benzo[b][1,4]thiazin-3(4H)-one 1,1-dioxide ring. The energy band gap [ΔE = E_LUMO − E_HOMO] for the molecule is 11.7261 eV, and the energies of the frontier molecular orbitals, E_HOMO and E_LUMO, are −9.6740 eV and 2.0522 eV, respectively.

Table 3
Calculated energies

Molecular Energy (a.u.) (eV)	Compound (I)
Total Energy, TE (eV)	−26615,8936
E_HOMO (eV)	−9.6740
E_LUMO (eV)	2.0522
Gap, ΔE (eV)	11.7261
Dipole moment, μ (Debye)	7.583751
Ionization potential, I (eV)	9.6740
Electron affinity, A	2.0522
Electronegativity, χ	−3.8109
Hardness, η	−5.8631
Electrophilicity index, ω	−1.2385
Softness σ,	−0.1706
Fraction of electron transferred, ΔN	−0.9219

Figure 11
The energy band gap of (I)

7. Database survey

A search in the Cambridge Structural Database (CSD, updated March 2023; Groom et al., 2016 ) for compounds containing the fragment II (R1 = Ph or 2-ClC₆H₄, R2 = C; Fig. 12), gave 14 hits. With R1 = Ph, and with R2 = CH₂COOCH₂CH₃ (IIa; Sebbar et al., 2020b ), CH₂COOH (IIb; Sebbar et al., 2016), CH₂C≡CH (IIc; Sebbar et al., 2014 ) and C₅H₈NO2 (IId; Sebbar et al., 2016) (Fig. 12) are matching candidates. Other examples with R1 = 4-FC₆H₄ and R2 = CH₂C≡CH (Hni et al., 2019 ) and R1 = 2-ClC₆H₄, R2 = CH₂C≡CH (Sebbar et al., 2017 ) are also known.

Figure 12
The molecular moieties (II) used for the CSD database search.

8. Synthesis and crystallization

3,4-Dihydro-2H-1,4-benzothiazin-3-one (1.2 mmol) was dissolved in 3 ml of acetic acid and added dropwise into a solution of potassium permanganate (1.81 mmol) in 6 ml of water. After stirring for one h at room temperature, a solution of sodium thiosulfate pentahydrate (20%_wt) was added to react with excessive potassium permanganate. The precipitate obtained was filtered and recrystallized from ethanol to yield single-crystals suitable for X-ray structure analysis..

9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95–0.99 Å) and were included as riding contributions with isotropic displacement parameters 1.2 or 1.5 times those of the attached atoms. That attached to nitrogen was placed in a location derived from a difference map and refined with a DFIX 0.91 0.01 instruction. Two reflections affected by the beamstop were omitted from the final refinement.

Table 4
Experimental details

Crystal data
Chemical formula	C₈H₇NO₃S
M_r	197.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	125
a, b, c (Å)	7.2179 (6), 9.5043 (8), 11.9945 (9)
β (°)	97.584 (2)
V (Å³)	815.64 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.37
Crystal size (mm)	0.39 × 0.21 × 0.16

Data collection
Diffractometer	Bruker D8 QUEST PHOTON 3 diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.91, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	47688, 3957, 3739
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.074, 1.04
No. of reflections	3957
No. of parameters	122
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.36
Computer programs: APEX4 and SAINT (Bruker, 2021 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/1 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2298958

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S205698902300868X/wm5698sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300868X/wm5698Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902300868X/wm5698Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S205698902300868X/wm5698Isup4.cml

checkCIF report

Computing details top

2H-Benzo[b][1,4]thiazin-3(4H)-one 1,1-dioxide top

Crystal data top

C₈H₇NO₃S	F(000) = 408
M_r = 197.21	D_x = 1.606 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2179 (6) Å	Cell parameters from 9215 reflections
b = 9.5043 (8) Å	θ = 2.9–36.4°
c = 11.9945 (9) Å	µ = 0.37 mm⁻¹
β = 97.584 (2)°	T = 125 K
V = 815.64 (11) Å³	Prism, colourless
Z = 4	0.39 × 0.21 × 0.16 mm

Data collection top

Bruker D8 QUEST PHOTON 3 diffractometer	3957 independent reflections
Radiation source: fine-focus sealed tube	3739 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 7.3910 pixels mm^-1	θ_max = 36.4°, θ_min = 3.6°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −15→15
T_min = 0.91, T_max = 0.94	l = −19→20
47688 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)] = 0.025	Hydrogen site location: mixed
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0383P)² + 0.2724P] where P = (F_o² + 2F_c²)/3
3957 reflections	(Δ/σ)_max = 0.001
122 parameters	Δρ_max = 0.52 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Special details top

Experimental. The diffraction data were obtained from 9 sets of frames, each of width 0.5° in ω or φ, collected with scan parameters determined by the "strategy" routine in APEX4. The scan time was 15 sec/frame.

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	0.16068 (2)	0.52143 (2)	0.71754 (2)	0.01099 (4)
O1	0.61228 (8)	0.59530 (6)	0.90859 (5)	0.01991 (10)
O2	0.16268 (8)	0.66721 (6)	0.68352 (5)	0.01797 (10)
O3	−0.01882 (7)	0.45794 (7)	0.72667 (5)	0.01832 (10)
N1	0.57806 (8)	0.47975 (6)	0.74211 (5)	0.01411 (10)
H1	0.7001 (12)	0.4900 (15)	0.7398 (13)	0.027 (3)*
C1	0.27959 (8)	0.42044 (6)	0.62800 (5)	0.01059 (9)
C2	0.17997 (9)	0.35615 (7)	0.53412 (5)	0.01342 (10)
H2	0.047397	0.361237	0.521776	0.016*
C3	0.27651 (11)	0.28460 (7)	0.45882 (6)	0.01663 (11)
H3	0.210847	0.242727	0.393292	0.020*
C4	0.47092 (11)	0.27481 (8)	0.48036 (6)	0.01841 (12)
H4	0.536825	0.224837	0.429380	0.022*
C5	0.56985 (10)	0.33681 (8)	0.57499 (6)	0.01630 (11)
H5	0.701938	0.327605	0.588942	0.020*
C6	0.47486 (8)	0.41274 (7)	0.64966 (5)	0.01164 (10)
C7	0.51172 (9)	0.53288 (7)	0.83499 (5)	0.01315 (10)
C8	0.30863 (9)	0.50214 (7)	0.84603 (5)	0.01299 (10)
H8A	0.266578	0.566751	0.902374	0.016*
H8B	0.298167	0.404753	0.873825	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.00776 (7)	0.01295 (7)	0.01219 (7)	0.00109 (4)	0.00109 (4)	−0.00153 (4)
O1	0.0173 (2)	0.0236 (3)	0.0174 (2)	−0.00682 (19)	−0.00298 (17)	−0.00209 (18)
O2	0.0205 (2)	0.0129 (2)	0.0200 (2)	0.00460 (17)	0.00061 (18)	0.00015 (16)
O3	0.00783 (18)	0.0262 (3)	0.0214 (2)	−0.00199 (17)	0.00373 (16)	−0.00439 (19)
N1	0.0078 (2)	0.0195 (2)	0.0149 (2)	−0.00112 (17)	0.00092 (16)	0.00008 (18)
C1	0.0092 (2)	0.0114 (2)	0.0113 (2)	0.00061 (16)	0.00190 (16)	−0.00003 (16)
C2	0.0138 (2)	0.0137 (2)	0.0125 (2)	−0.00096 (19)	0.00073 (18)	−0.00101 (18)
C3	0.0212 (3)	0.0150 (3)	0.0140 (2)	−0.0010 (2)	0.0038 (2)	−0.00282 (19)
C4	0.0218 (3)	0.0166 (3)	0.0184 (3)	0.0025 (2)	0.0088 (2)	−0.0024 (2)
C5	0.0133 (2)	0.0177 (3)	0.0190 (3)	0.0033 (2)	0.0064 (2)	0.0004 (2)
C6	0.0093 (2)	0.0130 (2)	0.0130 (2)	0.00103 (17)	0.00242 (17)	0.00133 (17)
C7	0.0114 (2)	0.0143 (2)	0.0133 (2)	−0.00146 (18)	−0.00035 (18)	0.00154 (18)
C8	0.0115 (2)	0.0162 (2)	0.0113 (2)	−0.00114 (19)	0.00154 (18)	−0.00122 (18)

Geometric parameters (Å, º) top

S1—O2	1.4450 (6)	C2—H2	0.9500
S1—O3	1.4464 (6)	C3—C4	1.3960 (11)
S1—C1	1.7478 (6)	C3—H3	0.9500
S1—C8	1.7649 (7)	C4—C5	1.3898 (11)
O1—C7	1.2203 (8)	C4—H4	0.9500
N1—C7	1.3661 (9)	C5—C6	1.3982 (9)
N1—C6	1.4043 (9)	C5—H5	0.9500
N1—H1	0.890 (8)	C7—C8	1.5175 (9)
C1—C2	1.3945 (9)	C8—H8A	0.9900
C1—C6	1.4010 (9)	C8—H8B	0.9900
C2—C3	1.3892 (10)

O2—S1—O3	117.64 (4)	C5—C4—C3	121.22 (6)
O2—S1—C1	109.21 (3)	C5—C4—H4	119.4
O3—S1—C1	109.56 (3)	C3—C4—H4	119.4
O2—S1—C8	108.59 (3)	C4—C5—C6	119.96 (6)
O3—S1—C8	109.59 (3)	C4—C5—H5	120.0
C1—S1—C8	100.95 (3)	C6—C5—H5	120.0
C7—N1—C6	127.24 (6)	C5—C6—C1	118.33 (6)
C7—N1—H1	116.1 (10)	C5—C6—N1	119.08 (6)
C6—N1—H1	116.7 (10)	C1—C6—N1	122.58 (6)
C2—C1—C6	121.72 (6)	O1—C7—N1	122.05 (6)
C2—C1—S1	119.61 (5)	O1—C7—C8	121.31 (6)
C6—C1—S1	118.58 (5)	N1—C7—C8	116.53 (6)
C3—C2—C1	119.34 (6)	C7—C8—S1	112.57 (4)
C3—C2—H2	120.3	C7—C8—H8A	109.1
C1—C2—H2	120.3	S1—C8—H8A	109.1
C2—C3—C4	119.38 (6)	C7—C8—H8B	109.1
C2—C3—H3	120.3	S1—C8—H8B	109.1
C4—C3—H3	120.3	H8A—C8—H8B	107.8

O2—S1—C1—C2	−93.69 (6)	C2—C1—C6—C5	−0.74 (9)
O3—S1—C1—C2	36.48 (6)	S1—C1—C6—C5	−177.28 (5)
C8—S1—C1—C2	152.03 (5)	C2—C1—C6—N1	178.32 (6)
O2—S1—C1—C6	82.92 (6)	S1—C1—C6—N1	1.78 (8)
O3—S1—C1—C6	−146.91 (5)	C7—N1—C6—C5	−165.40 (7)
C8—S1—C1—C6	−31.36 (6)	C7—N1—C6—C1	15.55 (10)
C6—C1—C2—C3	−1.16 (10)	C6—N1—C7—O1	−176.50 (7)
S1—C1—C2—C3	175.34 (5)	C6—N1—C7—C8	7.37 (10)
C1—C2—C3—C4	1.92 (10)	O1—C7—C8—S1	141.26 (6)
C2—C3—C4—C5	−0.81 (11)	N1—C7—C8—S1	−42.58 (7)
C3—C4—C5—C6	−1.12 (11)	O2—S1—C8—C7	−64.45 (5)
C4—C5—C6—C1	1.86 (10)	O3—S1—C8—C7	165.81 (5)
C4—C5—C6—N1	−177.23 (6)	C1—S1—C8—C7	50.29 (5)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.89 (1)	2.08 (1)	2.9472 (8)	165 (1)
C5—H5···O1ⁱⁱ	0.95	2.58	3.2330 (9)	126
C8—H8A···Cg2ⁱⁱⁱ	0.99	2.93	3.7933 (8)	146
C8—H8B···O2^iv	0.99	2.39	3.2126 (9)	140

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

Comparison of the selected (X-ray and DFT) geometric data (Å, °) top

Bonds/angles	X-ray	B3LYP/6-311G(d,p)
S1—O2	1.4450 (6)	1.50996
S1—O3	1.4464 (6)	1.59088
S1—C1	1.7478 (6)	1.78874
S1—C8	1.7649 (7)	1.80529
O1—C7	1.2203 (8)	1.21656
N1—C7	1.3661 (9)	1.37417
N1—C6	1.4043 (9)	1.39867
O2—S1—O3	117.64 (4)	118.09813
O2—S1—C1	109.21 (3)	109.40063
O3—S1—C1	109.56 (3)	109.84640
O2—S1—C8	108.59 (3)	109.10007
O3—S1—C8	109.59 (3)	109.62080
C1—S1—C8	100.95 (3)	99.96775
C7—N1—C6	127.24 (6)	127.88849
C7—N1—H1	116.1 (10)	115.98354

Calculated energies top

Molecular Energy (a.u.) (eV)	Compound (I)
Total Energy, TE (eV)	-26615,8936
E_HOMO (eV)	-9.6740
E_LUMO (eV)	2.0522
Gap, ΔE (eV)	11.7261
Dipole moment, µ (Debye)	7.583751
Ionization potential, I (eV)	9.6740
Electron affinity, A	2.0522
Electronegativity, χ	-3.8109
Hardness, η	-5.8631
Electrophilicity index, ω	-1.2385
Softness σ,	-0.1706
Fraction of electron transferred, ΔN	-0.9219

Funding information

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory. TH is grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

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