1,1′,3,3′-Tetra­mesitylquinobis(imidazole)-2,2′-di­thione

Selvakumar, J.; Arumugam, K.

doi:10.1107/S2414314619012689

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 9| September 2019| x191268

https://doi.org/10.1107/S2414314619012689

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1,1′,3,3′-Tetramesitylquinobis(imidazole)-2,2′-dithione

Jayaraman Selvakumar ^a and Kuppuswamy Arumugam ^a ^*

^aDepartment of Chemistry, Wright State University, 3640 Colonel Glenn Hwy, Dayton, OH 45435, USA
^*Correspondence e-mail: kuppuswamy.arumugam@wright.edu

Edited by O. Blacque, University of Zürich, Switzerland (Received 4 September 2019; accepted 11 September 2019; online 27 September 2019)

The solid-state structural analysis of the title compound [systematic name: 5,11-disulfanylidene-4,6,10,12-tetrakis(2,4,6-trimethylphenyl)-4,6,10,12-tetraazatricyclo[7.3.0.0^3,7]dodeca-1(9),3(7)-diene-2,8-dione], C₄₄H₄₄N₄O₂S₂ [+solvent], reveals that the molecule crystallizes in a highly symmetric cubic space group so that one quarter of the molecule is crystallographically unique, the molecule lying on special positions (two mirror planes, two twofold axes and a center of inversion). The crystal structure exhibits large cavities of 193 Å³ accounting for 7.3% of the total unit-cell volume. These cavities contain residual density peaks but it was not possible to unambiguously identify the solvent therein. The contribution of the disordered solvent molecules to the scattering was removed using a solvent mask and is not included in the reported molecular weight. No classical hydrogen bonds are observed between the main molecules.

Keywords: crystal structure; quinobis(imidazole); dithione; cubic symmetry.

CCDC reference: 1953052

Structure description

A variety of substituted imidazole-2-thiones have been synthesized and used as precursors for the generation of free N-heterocyclic carbenes (Kuhn & Kratz, 1993 ). Other uses for these types of molecules include the stabilization of gold nanoparticles (Moraes et al., 2017 ; Okamoto et al., 2006 ) and as ligands for metal coordination studies (Parveen et al., 2019 ). As part of our ongoing effort with bis(N-heterocyclic carbene) and its transition-metal complexes (Tennyson et al., 2010 ), the title compound (1,1′,3,3′-tetramesitylquinobis(imidazole)-2,2′-dithione) was synthesized and its single-crystal X-ray analysis is reported here.

The molecular structure of the title compound is presented in Fig. 1. The molecules crystallize in a rare cubic space group (Im $[\overline{3}]$ ) with Z = 6 and lie on special positions (two mirror planes, two twofold axes and a center of inversion). A search in the Cambridge Structural Database revealed that only 0.3% of the crystals were reported to crystallize in the Im $[\overline{3}]$ space group. Three imidazolidine-thione structures closely related to the title compound were reported: 1-methyl-3-phenylimidazolidine-2-thione (Nor et al., 2014 ), 1,3-dibenzylimidazolidine-2-thione (Mietlarek-Kropidłowska et al., 2012 ), and 7-amino-1,2,3,4-tetrahydroquinazoline-2,4-dithione, (Yang et al., 2006 ). The C1—S1 bond distance of 1.659 (3) Å falls well within the range observed for other reported thione-type compounds (1.653–1.686 Å). The N1—C1—N1′ bond angle of 105.3 (3)° is also very similar to those reported in other thione-type compounds (108–116°). The imidazole and mesityl rings are found to be perpendicular to each other. The two imidazole rings that are on the opposite side of the quino-bis(imidazolidine)dithione share the same plane with the mesityl units oriented perpendicular to it.

Figure 1
Molecular structure of the title compound with atom labeling. Displacement ellipsoids are drawn at the 50% probability level and all hydrogen atoms are omitted for clarity. Unlabeled atoms are generated by the symmetry operation (−x, −y, z), (−x, y, −z and (x, −y, −z).

The crystal structure exhibits large cavities of 193 Å³ accounting for 7.3% of the total unit-cell volume of 5933.5 (11) Å³ (Fig. 2) These cavities contain residual density peaks but it was not possible to unambiguously identify the solvent therein. The contribution of the disordered solvent molecules to the scattering was removed using the solvent mask in OLEX2 (Dolomanov et al., 2009 ) and was not included in the reported molecular weight. No classical hydrogen bonds are observed between the main molecules.

Figure 2
A three-dimensional packing diagram of the title compound viewed along the b axis.

Synthesis and crystallization

To the stirred solution of 1,1′,3,3′-tetramesitylquinobis(imidazole) dichloride (73 mg, 1 mmol) (Tennyson et al., 2010) in THF (10 mL), NaN(Si(CH₃)₃)₂ (40 mg, 2.2 mmol) in THF (2 mL) was added drop wise at 25°C. After stirring for 60 min, elemental sulfur (76 mg, 2.4 mmol) was added as a solid and the solution was stirred for another 60 min. The resulting reaction mixture was filtered through a celite plug and the volatiles were removed under vacuum. The resulting residue was dissolved in a minimum amount of dichloromethane (3 ml) and precipitated with hexane (15 mL) to yield 1,1′,3,3′-tetramesitylquinobis(imidazole)-2,2′-dithione as a fine yellow solid: 62 mg, 85% yield. Black-colored diffraction-quality single crystals were obtained by diffusing hexane into a saturated solution of the title compound in 1,2-dichloroethane. FT–IR (NaCl): 3027, 2974, 2917, 2850, 1672, 1546, 1397, 1321, 1286, 1042, 1033, 849, 612; ¹H NMR (CDCl₃, 300 MHz): δ 6.98 (s, 8H), 2.31 (s, 12H), 2.07 (s, 24H); ¹³C NMR (CDCl₃, 75 MHz): δ 169.31, 163.93, 139.70, 134.59, 131.24, 129.77, 126.78, 21.33, 21.97.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. A solvent mask was generated revealing voids at (0, 0, 0) and (½, ½, ½) with a volume of 192.6 Å³ and containing about 43 electrons. The solvent could not be unambiguously identified.

Table 1
Experimental details

Crystal data
Chemical formula	C₄₄H₄₄N₄O₂S₂
M_r	724.98
Crystal system, space group	Cubic, Im $[\overline{3}]$
Temperature (K)	100
a (Å)	18.1038 (11)
V (Å³)	5933.5 (11)
Z	6
Radiation type	Mo Kα
μ (mm⁻¹)	0.18
Crystal size (mm)	0.25 × 0.15 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.969, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	82590, 1249, 1074
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.122, 1.11
No. of reflections	1246
No. of parameters	76
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.33
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009).

Structural data

CCDC reference: 1953052

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619012689/zq4037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619012689/zq4037Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); 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).

5,11-Disulfanylidene-4,6,10,12-tetrakis(2,4,6-trimethylphenyl)-4,6,10,12-\ tetraazatricyclo[7.3.0.0^{{3,7}]dodeca-1(9),3(7)-diene-2,8-dione [+solvent] top}

Crystal data top

C₄₄H₄₄N₄O₂S₂	Mo Kα radiation, λ = 0.71073 Å
M_r = 724.98	Cell parameters from 9582 reflections
Cubic, Im3	θ = 2.8–27.5°
a = 18.1038 (11) Å	µ = 0.18 mm⁻¹
V = 5933.5 (11) Å³	T = 100 K
Z = 6	Needle, black
F(000) = 2304	0.25 × 0.15 × 0.1 mm
D_x = 1.217 Mg m⁻³

Data collection top

Bruker APEXII CCD diffractometer	1074 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 27.5°, θ_min = 3.2°
T_min = 0.969, T_max = 0.983	h = −23→23
82590 measured reflections	k = −23→23
1249 independent reflections	l = −23→23

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)] = 0.049	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0406P)² + 16.2491P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1246 reflections	Δρ_max = 0.49 e Å⁻³
76 parameters	Δρ_min = −0.33 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.

Refinement. Aromatic C–H hydrogen atoms were added as riding-model approximation with C–H bond length 0.95 Å. Methyl (CH₃) H atoms were treated as a rotating group and added as riding-model approximation to the carbon atom to which they are attached, the methyl H atoms were fixed at a distance of 0.98 Å with U_iso (H) = 1.5U_eq(CH₃).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.500000	1.000000	0.77751 (5)	0.0225 (2)
O1	0.500000	0.84916 (13)	0.500000	0.0217 (5)
N1	0.500000	0.93936 (10)	0.63961 (10)	0.0155 (4)
C2	0.500000	0.96233 (12)	0.56706 (12)	0.0152 (4)
C3	0.500000	0.91602 (17)	0.500000	0.0160 (6)
C4	0.500000	0.86372 (12)	0.66431 (12)	0.0154 (4)
C1	0.500000	1.000000	0.68589 (18)	0.0170 (6)
C5	0.43245 (9)	0.82885 (9)	0.67454 (9)	0.0191 (4)
C6	0.43410 (10)	0.75514 (10)	0.69637 (10)	0.0231 (4)
H6	0.389700	0.730325	0.703546	0.028*
C7	0.500000	0.71749 (14)	0.70777 (15)	0.0262 (6)
C8	0.36117 (9)	0.86931 (10)	0.66228 (11)	0.0273 (4)
H8B	0.358366	0.910622	0.695412	0.041*
H8A	0.320463	0.836567	0.671379	0.041*
H8C	0.359060	0.886643	0.612208	0.041*
C9	0.500000	0.63900 (17)	0.7330 (2)	0.0495 (9)
H9B	0.485357	0.636818	0.783948	0.074*	0.5
H9A	0.548719	0.618737	0.727763	0.074*	0.5
H9C	0.465923	0.610968	0.703621	0.074*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0309 (5)	0.0219 (4)	0.0146 (4)	0.000	0.000	0.000
O1	0.0315 (13)	0.0132 (11)	0.0203 (12)	0.000	0.000	0.000
N1	0.0183 (9)	0.0148 (9)	0.0135 (9)	0.000	0.000	0.0005 (7)
C2	0.0154 (10)	0.0146 (11)	0.0155 (10)	0.000	0.000	0.0013 (8)
C3	0.0148 (14)	0.0163 (15)	0.0168 (14)	0.000	0.000	0.000
C4	0.0189 (10)	0.0148 (10)	0.0125 (10)	0.000	0.000	0.0019 (8)
C1	0.0177 (15)	0.0156 (14)	0.0177 (15)	0.000	0.000	0.000
C5	0.0196 (8)	0.0229 (8)	0.0149 (7)	0.0002 (6)	−0.0011 (6)	0.0023 (6)
C6	0.0225 (8)	0.0219 (8)	0.0250 (8)	−0.0051 (7)	−0.0004 (7)	0.0058 (7)
C7	0.0293 (13)	0.0202 (12)	0.0292 (13)	0.000	0.000	0.0082 (10)
C8	0.0179 (8)	0.0306 (9)	0.0334 (10)	0.0003 (7)	−0.0021 (7)	0.0081 (8)
C9	0.0341 (16)	0.0296 (15)	0.085 (3)	0.000	0.000	0.0253 (17)

Geometric parameters (Å, º) top

S1—C1	1.659 (3)	C5—C8	1.500 (2)
O1—C3	1.210 (4)	C6—H6	0.9300
N1—C2	1.378 (3)	C6—C7	1.389 (2)
N1—C4	1.440 (3)	C7—C9	1.493 (4)
N1—C1	1.381 (3)	C8—H8B	0.9600
C2—C2ⁱ	1.364 (4)	C8—H8A	0.9600
C2—C3	1.475 (3)	C8—H8C	0.9600
C4—C5	1.3886 (19)	C9—H9B	0.9600
C4—C5ⁱⁱ	1.3886 (19)	C9—H9A	0.9600
C5—C6	1.392 (2)	C9—H9C	0.9600

C2—N1—C4	125.65 (18)	C5—C6—H6	119.0
C2—N1—C1	109.79 (19)	C7—C6—C5	122.06 (17)
C1—N1—C4	124.57 (19)	C7—C6—H6	119.0
N1—C2—C3	127.8 (2)	C6—C7—C6ⁱⁱ	118.3 (2)
C2ⁱ—C2—N1	107.56 (12)	C6ⁱⁱ—C7—C9	120.83 (11)
C2ⁱ—C2—C3	124.63 (13)	C6—C7—C9	120.83 (11)
O1—C3—C2	124.63 (13)	C5—C8—H8B	109.5
O1—C3—C2ⁱⁱⁱ	124.63 (13)	C5—C8—H8A	109.5
C2ⁱⁱⁱ—C3—C2	110.7 (3)	C5—C8—H8C	109.5
C5—C4—N1	118.27 (10)	H8B—C8—H8A	109.5
C5ⁱⁱ—C4—N1	118.27 (10)	H8B—C8—H8C	109.5
C5—C4—C5ⁱⁱ	123.4 (2)	H8A—C8—H8C	109.5
N1—C1—S1	127.35 (13)	C7—C9—H9B	109.5
N1ⁱ—C1—S1	127.35 (13)	C7—C9—H9A	109.5
N1ⁱ—C1—N1	105.3 (3)	C7—C9—H9C	109.5
C4—C5—C6	117.05 (16)	H9B—C9—H9A	109.5
C4—C5—C8	121.05 (15)	H9B—C9—H9C	109.5
C6—C5—C8	121.90 (15)	H9A—C9—H9C	109.5

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

Acknowledgements

The authors would like to acknowledge support by funds from the Chemistry Department, Wright State University, College of Science and Mathematics. They also thank Dr Grossie, Wright State University for help with the low-temperature data collection.

Funding information

Funding for this research was provided by: National Institutes of Health, National Cancer Institute (grant No. CA232765 to KA); American Chemical Society Petroleum Research Fund (grant No. PRF-59893-UR7 to KA).

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