Crystal structure, Hirshfeld surface analysis and computational studies of 5-[(prop-2-en-1-yl)sulfan­yl]-1-[2-(tri­fluoro­meth­yl)phen­yl]-1H-tetra­zole

Slyvka, Y.; Goreshnik, E.; Pokhodylo, N.; Mys`kiv, M.

doi:10.1107/S2056989019011459

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ISSN: 2056-9890

Volume 75| Part 9| September 2019| Pages 1331-1335

https://doi.org/10.1107/S2056989019011459

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Crystal structure, Hirshfeld surface analysis and computational studies of 5-[(prop-2-en-1-yl)sulfanyl]-1-[2-(trifluoromethyl)phenyl]-1H-tetrazole

Yurii Slyvka,^a ^* Evgeny Goreshnik,^b Nazariy Pokhodylo ^a and Marian Mys`kiv ^a

^aFaculty of Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodia Str, 6, 79005 L'viv, Ukraine, and ^bDepartment of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: yurii.slyvka@lnu.edu.ua

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 July 2019; accepted 14 August 2019; online 23 August 2019)

The title compound, C₁₁H₉F₃N₄S, was synthesized from 2-(trifluoromethyl)aniline by a multi-step reaction. It crystallizes in the non-centrosymmetric space group Pna2₁, with one molecule in the asymmetric unit, and is constructed from a pair of aromatic rings [2-(trifluoromethyl)phenyl and tetrazole], which are twisted by 76.8 (1)° relative to each other because of significant steric hindrance of the trifluoromethyl group at the ortho position of the benzene ring. In the crystal, very weak C—H⋯N and C—H⋯F hydrogen bonds and aromatic π–π stacking interactions link the molecules into a three-dimensional network. To further analyse the intermolecular interactions, a Hirshfeld surface analysis, as well as interaction energy calculations, were performed.

Keywords: crystal structure; tetrazole derivative; DFT calculation; Hirshfeld surface analysis.

CCDC reference: 1947200

1. Chemical context

Tetrazoles are a well-known class of aromatic five-membered heterocycles, which have been investigated since the end of the 19th century. Their biological properties, including antiviral, anticancer, anti-tuberculosis, antifungal and antioxidant activities have been shown by numerous studies (see, for example, Ostrovskii et al., 2017 ). They also are increasingly regarded as efficient and selective inhibitors of enzymes governing the metabolic processes in the human body (Pegklidou et al., 2010 ; Al-Hourani et al., 2012 ; Aggarwal et al., 2016 ).

Tetrazoles are well established as suitable precursors for the construction of other nitrogen-containing heterocycles such as pyrimidines (Shyyka et al., 2018 ; Pokhodylo et al., 2015 ), as well as being widely used as ligands in their own right to generate coordination compounds (Gaponik et al., 2006 ; Aromí et al., 2011 ). For example, allyl derivatives of 1H-tetrazole-5-thiols have been used for the preparation of copper(I) π,σ-complexes possessing non-linear optical properties (Slyvka et al., 2018 , 2019 ). Among these, three copper(I) π,σ-coordination compounds, [Cu₂(C₁₁H₉F₃N₄S)₂(CF₃SO₃)₂] (Slyvka, 2015 ), [Cu(C₁₁H₉F₃N₄S)₂]BF₄ and [Cu(C₁₁H₉F₃N₄S)(NH₂SO₃)(MeOH)] based on 5-[(prop-2-en-1-yl)sulfanyl]-1-[2-(trifluoromethyl)phenyl]-1H-tetrazole (I) (C₁₁H₉F₃N₄S) have been reported recently (Slyvka et al., 2019). As part of our ongoing studies in this area, the synthesis and structure of the title compound, (I), are reported here.

2. Structural commentary

The title compound crystallizes in the non-centrosymmetric space group Pna2₁, with one molecule in the asymmetric unit. As shown in Fig. 1, it is constructed from two aromatic rings [2-(trifluoromethyl)phenyl and tetrazole rings], which are twisted relative to each other by 76.8 (1)° because of the significant steric hindrance of the trifluoromethyl group attached to C10. This dihedral angle is comparable with the analogous parameter in the same ligand when it is π,σ-coordinated to a copper atom in [Cu(C₁₁H₉F₃N₄S)₂]BF₄ [dihedral angle = 78.0 (1)°] and [Cu(C₁₁H₉F₃N₄S)(NH₂SO₃)(MeOH)] [85.5 (1)°] (Slyvka et al., 2019). The (prop-2-en-1-yl)sulfanyl group in (I) has an anticlinal conformation relative to the C2—C3 bond and a synclinal conformation relative to the S1—C2 bond. The S1—C2—C3—C4 and C1— S1—C2—C3 torsion angles are 117.0 (3) and 75.0 (2)°, respectively.

Figure 1
The molecular structure of (I)

with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

As shown in Fig. 2 and listed in Table 1, the crystal structure of (I) features several weak intermolecular interactions. The hydrogen atoms of the (prop-2-en-1-yl)sulfanyl group are involved in C—H⋯N bonding with the tetrazole ring of an adjacent molecule; these bonds link independent molecules into layers (Fig. 3). The layers are interconnected by C—H⋯F contacts into a three-dimensional network (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N3ⁱ	0.99	2.58	3.464 (3)	148
C2—H2B⋯N2ⁱⁱ	0.99	2.69	3.666 (4)	169
C3—H3⋯F3ⁱⁱⁱ	0.95	2.71	3.351 (3)	125
C4—H4A⋯N3ⁱ	0.95	2.67	3.491 (3)	145
C4—H4B⋯F1^iv	0.95	2.47	3.355 (3)	155
C6—H6⋯N4ⁱⁱⁱ	0.95	2.76	3.601 (3)	148
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
The hydrogen-bonding of molecules in (I)

. Hydrogen bonds are shown as dashed lines. The symmetry codes are as in Table 1.

Figure 3
A C—H⋯N-bonded layer in the structure of compound (I)

Figure 4
A view along the a axis of the crystal packing of the title compound.

4. Hirshfeld surface analysis and computational study

To further analyse the intermolecular interactions between the molecules of (I), Hirshfeld surface analysis through the mapping of the normalized contact distance (d_norm) as well as calculation of the interaction energies were performed using CrystalExplorer (Turner et al., 2017 ; Spackman & Jayatilaka, 2009 ). The most prominent interactions among the allyl group H atoms and tetrazole N atoms as well as among allylic H atoms and F atoms of neighbouring molecules can be seen in the Hirshfeld surface plot as the red areas (Fig. 5a). Fingerprint plots were produced to show the intermolecular surface bond distances with the regions highlighted for C—H⋯F (Fig. 5b) and C—H⋯N (Fig. 5c) interactions. The contribution to the surface area for H⋯H contacts is 19.8%.

Figure 5
(a) Hirshfeld surface for molecule of (I)

mapped with d_norm over the range −0.15 to 1.2 showing C—H⋯N and C—H⋯F hydrogen-bonded contacts. Fingerprint plots for molecule resolved into (b) F⋯H/H⋯F and (c) N⋯H/H⋯N contacts. Neighbouring molecules associated with close contacts are also shown.

The interaction energies in (I) were calculated using a dispersion-corrected CE-B3LYP/6-31G(d,p) quantum level of theory, as available in CrystalExplorer. The total intermolecular energy is the sum of energies of four main components, viz. electrostatic, polarization, dispersion and exchange-repulsion factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie et al., 2017 ). The total calculated energy of the intermolecular interactions of (I) is −115.9 kJ mol⁻. From Table 2, one can see the highest energy value (–36.2 kJ mol⁻) covers C—H⋯N and C—H⋯F interactions with the neighbouring molecule generated by the symmetry code −x + 1, −y + 1, z − $[{1\over 2}]$ . The interactions between the neighbouring 2-(trifluoromethyl)phenyl rings stacked along [100] cover −25.7 kJ mol⁻¹ and are mainly dispersive in nature.

Table 2
Interaction energies (kJ mol⁻¹) for selected close contacts in the crystal of (I)

Contact	E_{electrostatic}	E_polarization	E_dispersion	E_{exchange-repulsion}	E_total	Symmetry operation
C4—H4B⋯F1	−1.4	−0.3	−5.2	5.7	−2.6	-x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$
C4—H4A⋯N3/C2—H2A⋯N3	−12.0	−4.1	−13.4	16.6	−17.1	x + 1, y, z
C2—H2B⋯N2/C3—H3⋯F3/C4—H4B⋯F3	−14.6	−5.3	−31.0	16.4	−36.2	-x + 1, −y + 1, z − $[{1\over 2}]$
(CF₃C₆H₄–)⋯(CF₃C₆H₄–)	−5.0	−1.9	−31.8	14.1	−25.7	x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z

5. Database survey

A survey of the Cambridge Structural Database (CSD version 5.39, last update August 2018; Groom et al., 2016 ) confirmed that 1-aryl substituted 5-[(prop-2-en-1-yl)sulfanyl]-1H-tetrazoles are known only as ligands in the structures of copper(I) and silver(I) π-complexes. In the crystal structures of bis[μ²-η²-5-(allylsulfanyl)-1-phenyl-1H-tetrazole]diaquadisilver bis(tetrafluoroborate) (refcode HAHTIV; Slyvka et al., 2011 ), bis{μ-η²-1-phenyl-5-[(prop-2-en-1-yl)sulfanyl]-1H-tetrazole}diaquadicopper bis(tetrafluoroborate) (JAHCON; Slyvka et al., 2010 ), bis{μ-η²-1-(4-chlorophenyl)-5-[(prop-2-en-1-yl)sulfanyl]-1H-tetrazole}diaquadicopper bis(tetrafluoroborate) ethanol solvate (JAHCUT; Slyvka et al., 2010) and bis{μ-5-[(prop-2-en-1-yl)sulfanyl]-1-[2-(trifluoromethyl)phenyl]-1H-tetrazole}bis(trifluoromethanesulfonato)dicopper (JADHII; Slyvka, 2015), the tetrazole moieties are bonded to the metal ions through two heterocyclic nitrogen atoms and the allylic C=C bond in the chelate-bridging mode. In catena-{(μ-sulfamato){η²-1-(3,5-dimethylphenyl)-5-[(prop-2-en-1-yl)sulfanyl]-1H-tetrazole}copper(I)} (ZEYRUT; Slyvka et al., 2018) (VI), the organic molecule is coordinated to the copper atom by the allylic C=C bond and the only tetrazole nitrogen atom. As a result of the presence of back-donation from an occupied 3d metal orbital to a low-lying empty π* orbital of the olefin, in all these compounds the double bond of the (prop-2-en-1-yl)sulfanyl group is slightly elongated to 1.35–1.38 Å, in comparison with noncoordinated olefin bond value. The other S-substituted 1-phenyl-1H-tetrazole-5-thiol structures in the Cambridge Structural Database have different alkyl substituents, such as 2-naphthyl (TICRAY; Alves et al., 1996 ), 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl (GIJRAU; Bodrov et al., 2013 ) and benzoyl (BAZVAA; Kim et al., 2003 ).

6. Synthesis and crystallization

The title compound was synthesized from 2-(trifluoromethyl)aniline by a multi-step reaction. Commercially available 2-(trifluoromethyl)aniline (1.611 g, 0.010 mol) was dissolved in the minimum amount of benzene and treated with carbon disulfide (0.7 ml, 0.01 mol) and triethylamine (1.4 ml, 0.010 mol). The solution was cooled to 273 K and left for 5 d. After complete precipitation of the triethylammonium dithiocarbamate salt, the solution was filtered. The solid was washed with anhydrous ether and air-dried for about 10 min. The salt was then dissolved in about 7.5 ml of chloroform, treated with 1.4 ml of triethylamine and cooled to 273 K. To this solution was added ethyl chloroformate (1.02 ml, 0.01 mol) dropwise over a 15 min period under intensive stirring. The resulting solution was stirred at 273 K for 10 min and allowed to warm to room temperature over 1 h. The chloroform solution was washed with 3 M HCI and twice with water and dried over Na₂SO₄. The chloroform was evaporated and the 1-isothiocyanato-2-(trifluoromethyl)benzene was distilled in vacuo.

The obtained isothiocyanate (1.016 g, 5.0 mmol) was mixed with water (10 ml) and NaN₃ (0.71 g, 0.011 mol) and refluxed under intensive stirring until the suspension disappeared. The solution was cooled to room temperature and washed with TBME. The water fraction was separated and acidified with 3 M HCl (Caution! During the acidification beware of toxic HN₃ gas). The sediment of 1-[2-(trifluoromethyl)phenyl]-1H-tetrazole-5-thiol was separated by filtration and used for alkylation without further purification.

1-[2-(Trifluoromethyl)phenyl]-1H-tetrazole-5-thiol (0.985g, 0.004 mol) was dissolved in a solution of KOH (0.22 g, 0.004 mol) in ethanol (10 ml). To the solution allyl bromide (0.43 ml, 0.005 mole) was added and the mixture was heated at 323 K for 1 h. The solvent was removed in vacuo and to the residue was added water (5 ml) and dichloromethane (10 ml). The dichloromethane was separated and removed to give the title compound. Colourless blocks of (I) were obtained by recrystallization from an ethanol solution, m.p. 336 K.

NMR ¹H (400 MHz, DMSO-d₆), δ, p.p.m. 8.03 (d, J = 7.3 Hz, 1H, H_Ph-3), 7.98–7.88 (m, 2H, H_Ph-4,5), 7.71 (d, J = 7.3 Hz, 1H, H_Ph-6), 5.94 (td, J = 16.8, 7.2Hz, 1H, =CH), 5.36 (d, J = 16.8 Hz, 1H, =CH₂), 5.18 (d, J = 9.9 Hz, 1H, =CH₂), 3.98 (d, J = 6.9 Hz, 2H, CH₂). Analysis calculated for C₁₁H₉F₃N₄S: C, 46.15; H, 3.17; N, 19.57; S, 11.20; found: C, 45.97; H, 3.04; N, 19.49; S, 11.27.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were positioned geometrically and refined using riding model, with C—H = 0.95 or 0.99 Å and U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₁H₉F₃N₄S
M_r	286.28
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	7.6595 (3), 20.9841 (7), 7.8641 (3)
V (Å³)	1263.98 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.35 × 0.24 × 0.15

Data collection
Diffractometer	Rigaku Oxford Diffraction New Gemini, Dual, Cu at home/near, Atlas
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.929, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	28170, 3094, 2730
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.079, 1.07
No. of reflections	3094
No. of parameters	172
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.22
Absolute structure	Flack x determined using 1094 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.07 (4)
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1947200

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019011459/hb7842sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019011459/hb7842Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019011459/hb7842Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2056989019011459/hb7842Isup4.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).

5-[(Prop-2-en-1-yl)sulfanyl]-1-[2-(trifluoromethyl)phenyl]-1H-tetrazole top

Crystal data top

C₁₁H₉F₃N₄S	D_x = 1.504 Mg m⁻³
M_r = 286.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 9726 reflections
a = 7.6595 (3) Å	θ = 3.9–28.4°
b = 20.9841 (7) Å	µ = 0.28 mm⁻¹
c = 7.8641 (3) Å	T = 150 K
V = 1263.98 (8) Å³	Block, colourless
Z = 4	0.35 × 0.24 × 0.15 mm
F(000) = 584

Data collection top

Rigaku Oxford Diffraction New Gemini, Dual, Cu at home/near, Atlas diffractometer	2730 reflections with I > 2σ(I)
Detector resolution: 10.6426 pixels mm^-1	R_int = 0.059
ω scans	θ_max = 28.9°, θ_min = 2.8°
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2018)	h = −10→10
T_min = 0.929, T_max = 0.969	k = −28→28
28170 measured reflections	l = −10→10
3094 independent 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)] = 0.035	w = 1/[σ²(F_o²) + (0.0298P)² + 0.4395P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.23 e Å⁻³
3094 reflections	Δρ_min = −0.22 e Å⁻³
172 parameters	Absolute structure: Flack x determined using 1094 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.07 (4)

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.

Refinement. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups 2.a Secondary CH2 refined with riding coordinates: C2(H2A,H2B) 2.b Aromatic/amide H refined with riding coordinates: C3(H3), C6(H6), C7(H7), C8(H8), C9(H9) 2.c X=CH2 refined with riding coordinates: C4(H4A,H4B)

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

	x	y	z	U_iso*/U_eq
S1	0.82933 (7)	0.43951 (3)	0.47114 (11)	0.02848 (15)
F1	0.4353 (3)	0.24877 (9)	0.1989 (3)	0.0619 (6)
F2	0.5490 (3)	0.34169 (11)	0.2020 (2)	0.0590 (6)
F3	0.2811 (3)	0.32951 (12)	0.2643 (3)	0.0614 (6)
N1	0.4878 (3)	0.41022 (10)	0.5110 (3)	0.0263 (5)
N2	0.3257 (3)	0.43591 (10)	0.4866 (5)	0.0357 (6)
N3	0.3518 (3)	0.49149 (11)	0.4245 (4)	0.0406 (7)
N4	0.5253 (3)	0.50465 (11)	0.4058 (3)	0.0348 (6)
C1	0.6066 (3)	0.45334 (10)	0.4616 (4)	0.0252 (5)
C2	0.9068 (3)	0.51253 (12)	0.3701 (3)	0.0264 (5)
H2A	1.030061	0.506647	0.335573	0.032*
H2B	0.837482	0.520356	0.265975	0.032*
C3	0.8943 (3)	0.56925 (10)	0.4825 (5)	0.0301 (5)
H3	0.781849	0.582487	0.519235	0.036*
C4	1.0299 (4)	0.60194 (13)	0.5336 (4)	0.0378 (7)
H4A	1.143885	0.589750	0.498837	0.045*
H4B	1.014415	0.637872	0.605561	0.045*
C5	0.5129 (3)	0.34687 (11)	0.5739 (3)	0.0253 (5)
C6	0.5647 (4)	0.33874 (16)	0.7405 (4)	0.0363 (7)
H6	0.580710	0.374616	0.812478	0.044*
C7	0.5933 (5)	0.27776 (17)	0.8017 (4)	0.0436 (8)
H7	0.631875	0.271828	0.915363	0.052*
C8	0.5662 (4)	0.22597 (15)	0.6992 (5)	0.0427 (8)
H8	0.583610	0.184288	0.743224	0.051*
C9	0.5136 (4)	0.23375 (13)	0.5317 (4)	0.0370 (7)
H9	0.495146	0.197514	0.461602	0.044*
C10	0.4879 (3)	0.29472 (11)	0.4665 (4)	0.0278 (5)
C11	0.4394 (4)	0.30342 (14)	0.2845 (4)	0.0373 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0220 (3)	0.0207 (2)	0.0428 (3)	0.0028 (2)	−0.0018 (3)	0.0025 (4)
F1	0.1032 (19)	0.0361 (10)	0.0464 (12)	−0.0050 (11)	−0.0153 (12)	−0.0163 (10)
F2	0.0844 (16)	0.0638 (14)	0.0287 (10)	−0.0314 (12)	0.0085 (10)	0.0003 (10)
F3	0.0620 (13)	0.0750 (15)	0.0472 (11)	0.0155 (11)	−0.0163 (10)	−0.0005 (11)
N1	0.0222 (10)	0.0226 (10)	0.0341 (14)	0.0019 (8)	0.0027 (9)	−0.0039 (9)
N2	0.0222 (9)	0.0327 (11)	0.0522 (16)	0.0065 (8)	0.0027 (12)	−0.0053 (13)
N3	0.0282 (12)	0.0328 (13)	0.0607 (19)	0.0074 (9)	−0.0022 (11)	−0.0004 (11)
N4	0.0269 (12)	0.0265 (11)	0.0511 (15)	0.0058 (9)	−0.0015 (11)	0.0045 (11)
C1	0.0223 (10)	0.0218 (10)	0.0317 (13)	0.0029 (8)	0.0014 (14)	−0.0030 (13)
C2	0.0260 (13)	0.0243 (13)	0.0290 (14)	−0.0003 (10)	0.0015 (11)	0.0011 (10)
C3	0.0306 (12)	0.0228 (11)	0.0368 (14)	0.0022 (9)	0.0041 (15)	0.0025 (14)
C4	0.0427 (16)	0.0251 (13)	0.0456 (18)	−0.0011 (12)	0.0008 (13)	−0.0017 (12)
C5	0.0232 (12)	0.0229 (12)	0.0297 (14)	−0.0001 (10)	0.0053 (11)	0.0001 (11)
C6	0.0404 (17)	0.0397 (17)	0.0288 (16)	0.0005 (14)	0.0036 (13)	−0.0043 (13)
C7	0.049 (2)	0.051 (2)	0.0311 (16)	0.0076 (15)	0.0049 (14)	0.0108 (14)
C8	0.0466 (18)	0.0338 (15)	0.0477 (19)	0.0052 (13)	0.0142 (15)	0.0146 (15)
C9	0.0415 (16)	0.0257 (13)	0.0440 (17)	−0.0033 (12)	0.0099 (13)	0.0025 (12)
C10	0.0279 (11)	0.0237 (11)	0.0318 (13)	−0.0034 (9)	0.0055 (14)	−0.0005 (13)
C11	0.0489 (19)	0.0294 (15)	0.0337 (16)	−0.0053 (13)	−0.0017 (13)	−0.0046 (12)

Geometric parameters (Å, º) top

S1—C1	1.732 (2)	C3—C4	1.308 (4)
S1—C2	1.825 (3)	C4—H4A	0.9500
F1—C11	1.330 (3)	C4—H4B	0.9500
F2—C11	1.331 (4)	C5—C6	1.380 (4)
F3—C11	1.340 (4)	C5—C10	1.396 (4)
N1—N2	1.367 (3)	C6—H6	0.9500
N1—C1	1.341 (3)	C6—C7	1.384 (5)
N1—C5	1.431 (3)	C7—H7	0.9500
N2—N3	1.280 (3)	C7—C8	1.369 (5)
N3—N4	1.365 (3)	C8—H8	0.9500
N4—C1	1.319 (3)	C8—C9	1.387 (5)
C2—H2A	0.9900	C9—H9	0.9500
C2—H2B	0.9900	C9—C10	1.392 (4)
C2—C3	1.486 (4)	C10—C11	1.490 (4)
C3—H3	0.9500

C1—S1—C2	99.24 (12)	C6—C5—C10	121.1 (2)
N2—N1—C5	122.5 (2)	C10—C5—N1	120.0 (2)
C1—N1—N2	108.0 (2)	C5—C6—H6	120.3
C1—N1—C5	129.5 (2)	C5—C6—C7	119.3 (3)
N3—N2—N1	105.7 (2)	C7—C6—H6	120.3
N2—N3—N4	112.2 (2)	C6—C7—H7	119.8
C1—N4—N3	105.0 (2)	C8—C7—C6	120.4 (3)
N1—C1—S1	122.86 (17)	C8—C7—H7	119.8
N4—C1—S1	128.06 (19)	C7—C8—H8	119.7
N4—C1—N1	109.1 (2)	C7—C8—C9	120.6 (3)
S1—C2—H2A	109.0	C9—C8—H8	119.7
S1—C2—H2B	109.0	C8—C9—H9	120.0
H2A—C2—H2B	107.8	C8—C9—C10	120.0 (3)
C3—C2—S1	113.13 (19)	C10—C9—H9	120.0
C3—C2—H2A	109.0	C5—C10—C11	121.3 (2)
C3—C2—H2B	109.0	C9—C10—C5	118.5 (3)
C2—C3—H3	118.3	C9—C10—C11	120.1 (3)
C4—C3—C2	123.5 (2)	F1—C11—F2	106.8 (3)
C4—C3—H3	118.3	F1—C11—F3	105.7 (3)
C3—C4—H4A	120.0	F1—C11—C10	112.7 (2)
C3—C4—H4B	120.0	F2—C11—F3	105.5 (3)
H4A—C4—H4B	120.0	F2—C11—C10	112.6 (2)
C6—C5—N1	118.8 (2)	F3—C11—C10	112.9 (2)

S1—C2—C3—C4	117.0 (3)	C5—N1—N2—N3	−177.7 (2)
N1—N2—N3—N4	0.0 (4)	C5—N1—C1—S1	−1.9 (4)
N1—C5—C6—C7	−178.5 (3)	C5—N1—C1—N4	177.3 (2)
N1—C5—C10—C9	179.9 (2)	C5—C6—C7—C8	−1.6 (5)
N1—C5—C10—C11	1.5 (4)	C5—C10—C11—F1	174.8 (2)
N2—N1—C1—S1	−179.8 (3)	C5—C10—C11—F2	53.9 (4)
N2—N1—C1—N4	−0.6 (3)	C5—C10—C11—F3	−65.4 (3)
N2—N1—C5—C6	−104.5 (3)	C6—C5—C10—C9	1.1 (4)
N2—N1—C5—C10	76.6 (3)	C6—C5—C10—C11	−177.3 (3)
N2—N3—N4—C1	−0.3 (4)	C6—C7—C8—C9	1.4 (5)
N3—N4—C1—S1	179.7 (2)	C7—C8—C9—C10	0.0 (5)
N3—N4—C1—N1	0.6 (3)	C8—C9—C10—C5	−1.2 (4)
C1—S1—C2—C3	75.0 (2)	C8—C9—C10—C11	177.2 (3)
C1—N1—N2—N3	0.4 (4)	C9—C10—C11—F1	−3.6 (4)
C1—N1—C5—C6	77.8 (4)	C9—C10—C11—F2	−124.5 (3)
C1—N1—C5—C10	−101.1 (3)	C9—C10—C11—F3	116.2 (3)
C2—S1—C1—N1	175.3 (2)	C10—C5—C6—C7	0.3 (4)
C2—S1—C1—N4	−3.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N3ⁱ	0.99	2.58	3.464 (3)	148
C2—H2B···N2ⁱⁱ	0.99	2.69	3.666 (4)	169
C3—H3···F3ⁱⁱⁱ	0.95	2.71	3.351 (3)	125
C4—H4A···N3ⁱ	0.95	2.67	3.491 (3)	145
C4—H4B···F1^iv	0.95	2.47	3.355 (3)	155
C6—H6···N4ⁱⁱⁱ	0.95	2.76	3.601 (3)	148

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

Interaction energies (kJ mol^-1) for selected close contacts in the crystal of (I) top

Contact	E_{electrostatic}	E_polarization	E_dispersion	E_{exchange-repulsion}	E_total	Symmetry operation
C4—H4B···F1	-1.4	-0.3	-5.2	5.7	-2.6	-x + 3/2, y + 1/2, z + 1/2
C4—H4A···N3/C2—H2A···N3	-12.0	-4.1	-13.4	16.6	-17.1	x + 1, y, z
C2—H2B···N2/C3—H3···F3/C4—H4B···F3	-14.6	-5.3	-31.0	16.4	-36.2	-x + 1, -y + 1, z - 1/2
(CF₃C₆H₄–)···(CF₃C₆H₄–)	-5.0	-1.9	-31.8	14.1	-25.7	x - 1/2, -y + 1/2, z

Funding information

EG gratefully acknowledges financial support from the Slovenian Research Agency (ARRS).

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