Crystal structure and Hirshfeld surface analysis of 4-[4-(1H-benzo[d]imidazol-2-yl)phen­oxy]phthalo­nitrile dimethyl sulfoxide monosolvate

Demir Kanmazalp, S.; Şen, P.; Dege, N.; Yildiz, S.Z.; Ozdemir, N.; Golenya, I.A.

doi:10.1107/S2056989019006510

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Volume 75| Part 6| June 2019| Pages 780-784

https://doi.org/10.1107/S2056989019006510

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Crystal structure and Hirshfeld surface analysis of 4-[4-(1H-benzo[d]imidazol-2-yl)phenoxy]phthalonitrile dimethyl sulfoxide monosolvate

Sibel Demir Kanmazalp,^a ^* Pınar Şen,^b Necmi Dege,^c ^* Salih Zeki Yildiz,^d Namık Ozdemir ^e and Irina A. Golenya ^f ^*

^aGaziantep University, Technical Sciences, 27310, Gaziantep, Turkey, ^bCentre for Nanotechnology Innovation, Department of Chemistry, Rhodes University, Grahamstown, South Africa, ^cOndokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics, 55139 Samsun, Turkey, ^dSakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, Sakarya, Turkey, ^eDepartment of Mathematics and Science Education, Faculty of Education, Ondokuz Mayıs University, Samsun, Turkey, and ^fTaras Shevchenko National University of Kyiv, Department of Chemistry, 64, Vladimirska Str., Kiev 01601, Ukraine
^*Correspondence e-mail: sibeld@gantep.edu.tr, necmid@omu.edu.tr, igolenya@ua.fm

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 March 2019; accepted 7 May 2019; online 10 May 2019)

This work presents the synthesis and structural characterization of [4-(1H-benzo[d]imidazol-2-yl)phenoxy]phthalonitrile, a phthalonitrile derivative carrying a benzimidazole moiety. The compound crystallizes as its dimethyl sulfoxide monosolvate, C₂₁H₁₂N₄O·(CH₃)₂SO. The dihedral angle between the two fused rings in the heterocyclic ring system is 2.11 (1)°, while the phenyl ring attached to the imidazole moiety is inclined by 20.7 (1)° to the latter. In the crystal structure, adjacent molecules are connected by pairs of weak intermolecular C—H⋯N hydrogen bonds into inversion dimers. N—H⋯O and C—H⋯O hydrogen bonds with R₂¹(7) graph-set motifs are also formed between the organic molecule and the disordered dimethyl sulfoxide solvent [occupancy ratio of 0.623 (5):0.377 (5) for the two sites of the sulfur atom]. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the crystalline state.

Keywords: crystal structure; phthalonitrile; imidazole; Hirshfeld analysis; hydrogen bonds.

CCDC reference: 1846754

1. Chemical context

Benzimidazole and its derivatives are some of the oldest and chemically most-studied nitrogen-containing aromatic heterocyclic compounds (Srestha et al., 2014 ). They have a wide range of applications in medicinal chemistry and in biological processes including as anticancer, antiulcer, antifungal and anti-inflammatory agents, and exhibit antimycobacterial and antioxidant activities (El Rashedy & Aboul-Enein, 2013 ; Gaba et al., 2014 ; Kathiravan et al., 2012 ). They are also used as ligands with fluorescent properties. The fluorescent characteristic of these compounds can be changed by substitution or derivatization of different groups at the NH position of the benzimidazole skeleton.

Phthalonitrile derivatives are some of the most widely used precursors for the preparation of phthalocyanines (Pc). The preparation of phthalocyanines is frequently carried out by a cyclotetramerization reaction of phthalonitriles. The synthesis of the latter compound family, carrying different functional groups, leads to functionalized phthalocyanines that are of great importance with respect to new molecular materials and targeted applications such as catalysis, liquid crystals, photosensitizers for photodynamic therapy (PDT), non-linear optics, nanotechnology or dye-sensitized solar cells (Torre et al., 2004 ; Martínez-Díaz et al., 2011 ). In this context, we have recently described a model study, i.e. the synthesis, characterization and Hirshfeld surface analysis of zinc phthalocyanines carrying benzimidazole groups through oxygen bridges to a Zn–Pc core (Sen et al., 2018b ). Here we report the synthesis, structural characterization and Hirshfeld surface analysis of a related ligand that crystallizes as its dimethylsulfoxide monosolvate, C₂₁H₁₂N₄O·(CH₃)₂SO.

2. Structural commentary

The molecular components of the title compound are shown in Fig. 1. The molecular structure of the phthalonitrile derivative is constructed from three ring systems, viz. a central phenoxy ring, a terminal phthalonitrile system and a terminal benzimidazole ring. The bond lengths of the cyano groups, 1.132 (6) and 1.137 (6) Å, for C21≡N4 and C20≡N3, respectively, conform well with literature values (Saraçoğlu et al., 2011 ). The corresponding C—C≡N angles [179.4 (6) and 177.9 (7)°] are almost linear and are also in good agreement with literature values (Saraçoğlu et al., 2011; Sen et al., 2018a ). The C—C bond lengths of the phenyl rings are in the normal range of 1.356 (5)–1.395 (6) Å, i.e. characteristic of a delocalized system. The dihedral angle of 2.11 (1)° between the fused C1–C6 and C5/N2/C7/N1/C6 rings in the heterocycle indicate a minute deviation from planarity, whereas the attached C8–C13 ring is inclined by 20.7 (1)° to the C5/N2/C7/N1/C6 ring plane.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds (Table 1

) are shown as dashed lines.

3. Supramolecular features

In the crystal structure, N2—H2⋯O2 and C9—H9⋯O2 intermolecular hydrogen bonding interactions with an R₂¹(7) graph-set motif are present, whereby the O2 atom acts as an acceptor in both cases (Fig. 1). There are also weak intermolecular N2—H2⋯S1A interactions between the the N—H group of the imidazole ring and the disordered dimethyl sulfate solvent, and a C23—H23D⋯N4 interaction between one of the methyl groups of the dimethyl sulfoxide solvent and one of the nitrile N atoms (Table 1, Fig. 2). These interactions lead to the formation of a three-dimensional supramolecular network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	1.94	2.794 (5)	172
N2—H2⋯S1A	0.86	2.83	3.614 (4)	152
C9—H9⋯O2	0.93	2.40	3.175 (5)	141
C23—H23D⋯N4ⁱ	0.96	2.63	3.500 (9)	151
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
A view of the crystal packing of the title compound. Dashed lines denote the N2—H2⋯S1A, N2—H2⋯O2 and C23—H23D⋯N4 intermolecular hydrogen-bonding interactions.

4. Database survey

A search of the Cambridge Structural database (CSD, version 5.40, update November 2018; Groom et al., 2016 ) for the 4-[4-(1H-benzo[d]imidazole-2yl)phenoxy]phthalonitrile moiety revealed two hits. Distinctive bond lengths (N4≡C21, N3≡C20, C7—N2, C5—N2) in the title structure are the same within standard uncertainties as the corresponding bond lengths in the structures of 4-[4-(1H-benzimidazol-2-yl)phenoxy]benzene-1,2-dicarbonitrile monohydrate (HIDHEK; Sen et al., 2018b) or 4-{4-[1-(prop-2-en-1-yl)-1H-benzimidazol-2-yl]phenoxy}benzene-1,2-dicarbonitrile (RELBUI; Sen et al., 2018a). In these structures, the C—O bond lengths vary from 1.363–1.407 Å. In the title molecule, the corresponding bond lengths are 1.367 (5) and 1.406 (4) Å, respectively. In all these structures, the molecules are linked into chains by C—H⋯N hydrogen bonds.

5. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed with CrystalExplorer17 (Turner et al., 2017 ). The Hirshfeld surfaces were generated using a standard (high) surface resolution with the three-dimensional surfaces mapped over d_norm (Fig. 3). For the title molecule, the H⋯H interactions appear in the middle of the scattered points in the fingerprint plots with a contribution to the overall Hirshfeld surface of 36.1% (Fig. 4). The contribution from the N⋯H/H⋯N contacts, corresponding to the C—H⋯N interactions, is represented by a pair of sharp spikes characteristic of a rather strong hydrogen-bonding interaction (23.6%). The whole fingerprint region and all other interactions are displayed in Fig. 4. In particular, the O⋯H/H⋯O contacts indicate the presence of intermolecular C—H⋯O and N—H⋯O interactions.

Figure 3
The Hirshfeld surface of the title compound mapped with d_norm in the range −0.6328 to 1.3784 a.u.

Figure 4
Two-dimensional fingerprint plots with a d_norm view of all interactions in the title compound, and subdivided into H⋯H (36.1%), N⋯H/H⋯N(23.6%), C⋯H/H⋯C (15.1%), C⋯C/C⋯C (12.4%), O⋯H/H⋯O (5.0%), C⋯N/N⋯C (3.7%), C⋯O/O⋯C (1.8%) and S⋯H/H⋯S (1.6%) contacts.

A view of the molecular electrostatic potential for the title compound, using the STO-3G basis set at the Hartree–Fock level of theory, is shown in Fig. 5. The N—H⋯N and C—H⋯N hydrogen-bond donor and acceptor groups are shown as blue and red areas around the atoms related with positive (hydrogen-bond donors) and negative (hydrogen-bond acceptors) electrostatic potentials, respectively.

Figure 5
A view of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potentials in the range −0.0893 to 0.1930 a.u.

6. Synthesis and crystallization

2-(4-Hydroxy-phenyl)-benzimidazole (1.2 g, 5.71 mmol), which was synthesized by the reaction of o-phenylenediamine and 4-hydroxybenzaldehyde, and 4-nitrophthalonitrile (0.989 g, 5.71 mmol) were dissolved in DMF (15 ml) and degassed by argon in a dual-bank vacuum-gas manifold system. After stirring for 15 min, finely ground anhydrous K₂CO₃ (0.790 g, 5.71 mmol) was added portion-wise over 2 h under stirring. The suspension solution was maintained at 333 K for 24 h. After completion of the reaction, the crude product was precipitated by pouring into ice–water. The precipitate was collected by filtration, washed with hot water, ethanol, diethyl ether and was finally dried in vacuo. The desired compound was obtained in sufficient purity. The obtained spectroscopic data are accordance with the literature (Khan et al., 2009 ). Single crystals for structure analysis were obtained from slow evaporation of a DMSO solution.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å for aromatic groups, with N—H = 0.86 Å for the imidazole moiety and with 0.96 Å for methyl groups. U_iso(H) values were constrained to 1.2–1.5 U_eq of their carrier atoms. The sulfur atom of the dimethylsulfate solvent is disordered over two sites (S1A and S1B), with an occupancy ratio of 0.623 (5):0.377 (5).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₁₂N₄O·C₂H₆OS
M_r	414.47
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	20.9154 (11), 11.4208 (6), 8.8938 (6)
V (Å³)	2124.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.18
Crystal size (mm)	0.65 × 0.56 × 0.47

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.966, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	15225, 4660, 2281
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.098, 0.83
No. of reflections	4660
No. of parameters	281
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.12
Absolute structure	Flack x determined using 771 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.02 (8)
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2006 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1846754

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006510/wm5496sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006510/wm5496Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019006510/wm5496Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

4-[4-(1H-Benzo[d]imidazol-2-yl)phenoxy]phthalonitrile dimethyl sulfoxide monosolvate top

Crystal data top

C₂₁H₁₂N₄O·C₂H₆OS	D_x = 1.296 Mg m⁻³
M_r = 414.47	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 9474 reflections
a = 20.9154 (11) Å	θ = 1.8–27.0°
b = 11.4208 (6) Å	µ = 0.18 mm⁻¹
c = 8.8938 (6) Å	T = 296 K
V = 2124.5 (2) Å³	Prism, yellow
Z = 4	0.65 × 0.56 × 0.47 mm
F(000) = 864

Data collection top

Stoe IPDS 2 diffractometer	4660 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2281 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.058
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.1°, θ_min = 2.0°
rotation method scans	h = −26→22
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −14→14
T_min = 0.966, T_max = 0.977	l = −11→11
15225 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0409P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 0.83	Δρ_max = 0.20 e Å⁻³
4660 reflections	Δρ_min = −0.12 e Å⁻³
281 parameters	Absolute structure: Flack x determined using 771 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.02 (8)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1A	0.55296 (11)	0.14556 (16)	0.7814 (2)	0.0869 (9)	0.623 (5)
S1B	0.4957 (2)	0.1452 (4)	0.7420 (4)	0.114 (2)	0.377 (5)
O1	0.39958 (15)	0.4586 (3)	0.0943 (3)	0.0925 (8)
O2	0.53727 (19)	0.1838 (3)	0.6323 (4)	0.1425 (15)
N1	0.69349 (16)	0.3756 (2)	0.2997 (4)	0.0751 (8)
N2	0.64212 (17)	0.2699 (2)	0.4721 (3)	0.0720 (8)
H2	0.611036	0.236598	0.518771	0.086*
N3	0.1249 (2)	0.4056 (4)	0.1258 (7)	0.1429 (19)
N4	0.1428 (2)	0.5716 (5)	0.5187 (7)	0.156 (2)
C1	0.8034 (2)	0.3391 (4)	0.4030 (6)	0.0968 (13)
H1	0.824993	0.380986	0.329242	0.116*
C2	0.8361 (3)	0.2860 (5)	0.5198 (7)	0.1100 (17)
H2A	0.880352	0.293117	0.526112	0.132*
C3	0.8032 (3)	0.2223 (5)	0.6272 (7)	0.1098 (16)
H3	0.826349	0.187242	0.704234	0.132*
C4	0.7380 (3)	0.2085 (4)	0.6256 (6)	0.0957 (13)
H4	0.716824	0.165147	0.698781	0.115*
C5	0.7054 (2)	0.2630 (3)	0.5081 (4)	0.0724 (10)
C6	0.7375 (2)	0.3280 (3)	0.3992 (5)	0.0748 (10)
C7	0.6375 (2)	0.3395 (3)	0.3484 (4)	0.0652 (10)
C8	0.57530 (16)	0.3683 (3)	0.2821 (4)	0.0605 (8)
C9	0.52110 (19)	0.3027 (3)	0.3118 (4)	0.0679 (10)
H9	0.523936	0.237162	0.373482	0.081*
C10	0.46302 (19)	0.3338 (3)	0.2509 (4)	0.0785 (11)
H10	0.427035	0.288323	0.270114	0.094*
C11	0.45811 (19)	0.4303 (4)	0.1630 (4)	0.0716 (10)
C12	0.5104 (2)	0.4970 (4)	0.1317 (5)	0.0783 (11)
H12	0.506725	0.562819	0.070782	0.094*
C13	0.5690 (2)	0.4659 (3)	0.1912 (4)	0.0752 (11)
H13	0.604801	0.511332	0.169824	0.090*
C14	0.3486 (2)	0.4793 (3)	0.1868 (5)	0.0734 (11)
C15	0.2890 (2)	0.4466 (3)	0.1358 (5)	0.0804 (11)
H15	0.284932	0.408992	0.043566	0.096*
C16	0.2358 (2)	0.4694 (4)	0.2210 (6)	0.0827 (12)
C17	0.2414 (2)	0.5253 (4)	0.3584 (5)	0.0845 (12)
C18	0.3018 (2)	0.5574 (4)	0.4094 (5)	0.0890 (12)
H18	0.306198	0.594294	0.502000	0.107*
C19	0.3549 (2)	0.5347 (4)	0.3231 (5)	0.0820 (11)
H19	0.395119	0.556988	0.357067	0.098*
C20	0.1739 (3)	0.4332 (4)	0.1682 (6)	0.1069 (17)
C21	0.1857 (3)	0.5498 (5)	0.4466 (6)	0.1113 (17)
C22	0.5253 (2)	0.0068 (4)	0.8099 (6)	0.1185 (17)
H22A	0.536012	−0.018040	0.909946	0.178*	0.623 (5)
H22B	0.479713	0.005567	0.797600	0.178*	0.623 (5)
H22C	0.544633	−0.045215	0.738362	0.178*	0.623 (5)
H22D	0.497256	−0.022369	0.886737	0.178*	0.377 (5)
H22E	0.527035	−0.048198	0.728417	0.178*	0.377 (5)
H22F	0.567387	0.017228	0.850914	0.178*	0.377 (5)
C23	0.4951 (4)	0.2180 (5)	0.8988 (7)	0.151 (2)
H23A	0.502326	0.196930	1.001908	0.227*	0.623 (5)
H23B	0.499347	0.301270	0.887593	0.227*	0.623 (5)
H23C	0.452845	0.194538	0.869547	0.227*	0.623 (5)
H23D	0.464660	0.183633	0.966396	0.227*	0.377 (5)
H23E	0.536893	0.215626	0.943443	0.227*	0.377 (5)
H23F	0.483454	0.297886	0.879270	0.227*	0.377 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0892 (19)	0.1040 (13)	0.0676 (11)	−0.0240 (11)	−0.0011 (11)	0.0104 (10)
S1B	0.124 (5)	0.131 (3)	0.087 (3)	0.016 (3)	−0.017 (2)	0.002 (2)
O1	0.081 (2)	0.135 (2)	0.0614 (15)	0.0085 (18)	0.0017 (16)	0.0154 (17)
O2	0.159 (4)	0.159 (3)	0.109 (3)	0.021 (3)	0.056 (3)	0.056 (2)
N1	0.068 (2)	0.0793 (19)	0.078 (2)	−0.0039 (17)	0.0160 (19)	−0.0036 (19)
N2	0.078 (2)	0.0676 (19)	0.070 (2)	−0.0024 (17)	0.0048 (19)	−0.0014 (16)
N3	0.097 (3)	0.166 (4)	0.165 (4)	−0.038 (3)	−0.028 (3)	0.051 (4)
N4	0.102 (4)	0.230 (6)	0.135 (4)	0.061 (4)	0.025 (3)	0.029 (4)
C1	0.080 (3)	0.110 (3)	0.100 (3)	0.005 (3)	0.014 (3)	−0.028 (3)
C2	0.079 (3)	0.138 (5)	0.113 (4)	0.030 (3)	−0.003 (4)	−0.042 (4)
C3	0.111 (5)	0.112 (4)	0.106 (4)	0.052 (3)	−0.008 (4)	−0.028 (3)
C4	0.103 (4)	0.083 (3)	0.101 (3)	0.023 (3)	−0.001 (3)	−0.010 (3)
C5	0.084 (3)	0.062 (2)	0.072 (3)	0.014 (2)	0.001 (3)	−0.011 (2)
C6	0.068 (3)	0.078 (3)	0.078 (3)	0.006 (2)	0.009 (2)	−0.019 (2)
C7	0.079 (3)	0.0538 (19)	0.063 (2)	−0.001 (2)	0.011 (2)	−0.0006 (19)
C8	0.070 (2)	0.0558 (19)	0.0556 (19)	−0.0026 (18)	0.010 (2)	−0.0016 (19)
C9	0.079 (3)	0.064 (2)	0.061 (2)	−0.009 (2)	0.008 (2)	0.0118 (18)
C10	0.075 (3)	0.085 (3)	0.076 (3)	−0.013 (2)	0.008 (2)	0.010 (2)
C11	0.071 (3)	0.087 (3)	0.057 (2)	0.007 (2)	0.006 (2)	0.010 (2)
C12	0.084 (3)	0.076 (3)	0.075 (3)	0.002 (2)	0.007 (2)	0.020 (2)
C13	0.081 (3)	0.067 (2)	0.077 (3)	−0.008 (2)	0.011 (2)	0.007 (2)
C14	0.074 (3)	0.085 (3)	0.062 (2)	0.003 (2)	−0.004 (2)	0.022 (2)
C15	0.084 (3)	0.086 (3)	0.071 (3)	−0.005 (2)	−0.013 (2)	0.020 (2)
C16	0.067 (3)	0.087 (3)	0.094 (3)	−0.004 (2)	−0.007 (3)	0.037 (3)
C17	0.075 (3)	0.099 (3)	0.079 (3)	0.016 (2)	0.000 (3)	0.029 (3)
C18	0.088 (4)	0.106 (3)	0.073 (3)	0.021 (3)	−0.007 (3)	0.007 (3)
C19	0.073 (3)	0.103 (3)	0.071 (3)	0.004 (2)	−0.009 (2)	0.007 (2)
C20	0.085 (3)	0.117 (4)	0.119 (4)	−0.012 (3)	−0.012 (3)	0.050 (3)
C21	0.089 (4)	0.139 (4)	0.106 (4)	0.034 (3)	0.008 (3)	0.034 (3)
C22	0.150 (5)	0.096 (3)	0.110 (4)	−0.009 (3)	0.006 (3)	0.021 (3)
C23	0.231 (7)	0.101 (4)	0.122 (4)	0.003 (4)	0.046 (5)	−0.007 (4)

Geometric parameters (Å, º) top

S1A—O2	1.434 (4)	C10—C11	1.356 (5)
S1A—C22	1.706 (5)	C10—H10	0.9300
S1A—C23	1.800 (6)	C11—C12	1.362 (5)
S1B—O2	1.379 (5)	C12—C13	1.381 (5)
S1B—C23	1.624 (7)	C12—H12	0.9300
S1B—C22	1.801 (6)	C13—H13	0.9300
O1—C14	1.367 (5)	C14—C19	1.374 (5)
O1—C11	1.406 (4)	C14—C15	1.378 (5)
N1—C7	1.314 (4)	C15—C16	1.372 (6)
N1—C6	1.388 (5)	C15—H15	0.9300
N2—C7	1.361 (4)	C16—C17	1.384 (6)
N2—C5	1.365 (5)	C16—C20	1.437 (7)
N2—H2	0.8600	C17—C18	1.390 (6)
N3—C20	1.137 (6)	C17—C21	1.433 (7)
N4—C21	1.132 (6)	C18—C19	1.375 (5)
C1—C6	1.384 (6)	C18—H18	0.9300
C1—C2	1.384 (7)	C19—H19	0.9300
C1—H1	0.9300	C22—H22A	0.9600
C2—C3	1.384 (7)	C22—H22B	0.9600
C2—H2A	0.9300	C22—H22C	0.9600
C3—C4	1.372 (7)	C22—H22D	0.9600
C3—H3	0.9300	C22—H22E	0.9600
C4—C5	1.395 (6)	C22—H22F	0.9600
C4—H4	0.9300	C23—H23A	0.9600
C5—C6	1.392 (5)	C23—H23B	0.9600
C7—C8	1.466 (5)	C23—H23C	0.9600
C8—C9	1.384 (5)	C23—H23D	0.9600
C8—C13	1.384 (5)	C23—H23E	0.9600
C9—C10	1.376 (5)	C23—H23F	0.9600
C9—H9	0.9300

O2—S1A—C22	110.0 (3)	C12—C13—C8	121.0 (4)
O2—S1A—C23	104.1 (3)	C12—C13—H13	119.5
C22—S1A—C23	96.5 (3)	C8—C13—H13	119.5
O2—S1B—C23	116.7 (4)	O1—C14—C19	122.5 (4)
O2—S1B—C22	107.6 (4)	O1—C14—C15	117.4 (4)
C23—S1B—C22	99.4 (3)	C19—C14—C15	120.1 (4)
C14—O1—C11	117.2 (3)	C16—C15—C14	120.1 (4)
C7—N1—C6	104.9 (3)	C16—C15—H15	120.0
C7—N2—C5	106.9 (3)	C14—C15—H15	120.0
C7—N2—H2	126.5	C15—C16—C17	120.3 (4)
C5—N2—H2	126.5	C15—C16—C20	119.8 (5)
C6—C1—C2	118.1 (5)	C17—C16—C20	119.9 (5)
C6—C1—H1	120.9	C16—C17—C18	119.2 (5)
C2—C1—H1	120.9	C16—C17—C21	120.3 (5)
C1—C2—C3	120.1 (5)	C18—C17—C21	120.6 (5)
C1—C2—H2A	120.0	C19—C18—C17	120.1 (4)
C3—C2—H2A	120.0	C19—C18—H18	119.9
C4—C3—C2	123.3 (5)	C17—C18—H18	119.9
C4—C3—H3	118.4	C14—C19—C18	120.2 (4)
C2—C3—H3	118.4	C14—C19—H19	119.9
C3—C4—C5	116.2 (5)	C18—C19—H19	119.9
C3—C4—H4	121.9	N3—C20—C16	179.4 (6)
C5—C4—H4	121.9	N4—C21—C17	177.9 (7)
N2—C5—C6	105.9 (4)	S1A—C22—H22A	109.5
N2—C5—C4	132.5 (4)	S1A—C22—H22B	109.5
C6—C5—C4	121.6 (5)	H22A—C22—H22B	109.5
C1—C6—N1	129.8 (4)	S1A—C22—H22C	109.5
C1—C6—C5	120.7 (4)	H22A—C22—H22C	109.5
N1—C6—C5	109.4 (4)	H22B—C22—H22C	109.5
N1—C7—N2	112.8 (4)	S1B—C22—H22D	109.5
N1—C7—C8	126.0 (3)	S1B—C22—H22E	109.5
N2—C7—C8	121.2 (3)	H22D—C22—H22E	109.5
C9—C8—C13	118.0 (4)	S1B—C22—H22F	109.5
C9—C8—C7	122.0 (3)	H22D—C22—H22F	109.5
C13—C8—C7	120.0 (3)	H22E—C22—H22F	109.5
C10—C9—C8	120.6 (4)	S1A—C23—H23A	109.5
C10—C9—H9	119.7	S1A—C23—H23B	109.5
C8—C9—H9	119.7	H23A—C23—H23B	109.5
C11—C10—C9	120.2 (4)	S1A—C23—H23C	109.5
C11—C10—H10	119.9	H23A—C23—H23C	109.5
C9—C10—H10	119.9	H23B—C23—H23C	109.5
C10—C11—C12	120.8 (4)	S1B—C23—H23D	109.5
C10—C11—O1	120.3 (4)	S1B—C23—H23E	109.5
C12—C11—O1	118.8 (4)	H23D—C23—H23E	109.5
C11—C12—C13	119.4 (4)	S1B—C23—H23F	109.5
C11—C12—H12	120.3	H23D—C23—H23F	109.5
C13—C12—H12	120.3	H23E—C23—H23F	109.5

C6—C1—C2—C3	1.1 (7)	C8—C9—C10—C11	−1.2 (6)
C1—C2—C3—C4	−0.3 (7)	C9—C10—C11—C12	1.0 (6)
C2—C3—C4—C5	−0.2 (7)	C9—C10—C11—O1	176.6 (3)
C7—N2—C5—C6	−1.6 (4)	C14—O1—C11—C10	60.5 (5)
C7—N2—C5—C4	177.2 (4)	C14—O1—C11—C12	−123.7 (4)
C3—C4—C5—N2	−178.8 (4)	C10—C11—C12—C13	−0.4 (6)
C3—C4—C5—C6	−0.1 (6)	O1—C11—C12—C13	−176.1 (4)
C2—C1—C6—N1	177.1 (4)	C11—C12—C13—C8	−0.1 (6)
C2—C1—C6—C5	−1.4 (6)	C9—C8—C13—C12	−0.1 (5)
C7—N1—C6—C1	−178.8 (4)	C7—C8—C13—C12	−177.8 (4)
C7—N1—C6—C5	−0.2 (4)	C11—O1—C14—C19	36.2 (5)
N2—C5—C6—C1	179.9 (3)	C11—O1—C14—C15	−146.4 (3)
C4—C5—C6—C1	0.9 (6)	O1—C14—C15—C16	−177.3 (3)
N2—C5—C6—N1	1.1 (4)	C19—C14—C15—C16	0.1 (6)
C4—C5—C6—N1	−177.9 (3)	C14—C15—C16—C17	0.0 (6)
C6—N1—C7—N2	−0.9 (4)	C14—C15—C16—C20	−178.9 (4)
C6—N1—C7—C8	178.9 (3)	C15—C16—C17—C18	−0.3 (6)
C5—N2—C7—N1	1.6 (4)	C20—C16—C17—C18	178.6 (4)
C5—N2—C7—C8	−178.1 (3)	C15—C16—C17—C21	179.5 (4)
N1—C7—C8—C9	161.5 (3)	C20—C16—C17—C21	−1.6 (6)
N2—C7—C8—C9	−18.8 (5)	C16—C17—C18—C19	0.6 (6)
N1—C7—C8—C13	−20.9 (5)	C21—C17—C18—C19	−179.2 (4)
N2—C7—C8—C13	158.9 (3)	O1—C14—C19—C18	177.5 (4)
C13—C8—C9—C10	0.7 (5)	C15—C14—C19—C18	0.2 (5)
C7—C8—C9—C10	178.3 (3)	C17—C18—C19—C14	−0.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.94	2.794 (5)	172
N2—H2···S1A	0.86	2.83	3.614 (4)	152
C9—H9···O2	0.93	2.40	3.175 (5)	141
C23—H23D···N4ⁱ	0.96	2.63	3.500 (9)	151

Symmetry code: (i) −x+1/2, y−1/2, z+1/2.

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

Funding information

This study was supported by Ondokuz Mayıs University under project No. PYOFEN.1906.19.001 (contract No. PYOFEN.1906.19.001).

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