The 2:1 charge-transfer complex of 4,6-di­methyl­dibenzo­thio­phene and 7,7,8,8-tetra­cyano-2,3,5,6-tetra­fluoro­quinodi­methane

Fujii, T.; Yamakado, H.

doi:10.1107/S2414314618000779

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180077

https://doi.org/10.1107/S2414314618000779

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The 2:1 charge-transfer complex of 4,6-dimethyldibenzothiophene and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane

Takuya Fujii ^a and Hideo Yamakado ^a ^*

^aFaculty of Systems Engineering, Wakayama University, Sakaedani 930, Wakayama 640-8510, Japan
^*Correspondence e-mail: yamakado@sys.wakayama-u.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 15 December 2017; accepted 12 January 2018; online 19 January 2018)

The title compound, 2C₁₄H₁₂S·C₁₂N₄F₄, was obtained by using 4,6-dimethyldibenzothiophene (DMDBT) as an electron donor and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (F₄TCNQ) as an electron acceptor. The asymmetric unit consists of one DMDBT molecule and one half of an F₄TCNQ molecule, which lies on an inversion centre. In the crystal, the DMDBT and F₄TCNQ molecules form a 2:1 unit via a charge-transfer interaction, with a centroid–centroid distance of 3.3681 (15) Å between the five-membered ring of DMDBT and the six-membered ring of F₄TCNQ. An F⋯F contact [2.911 (1) Å] is also observed.

Keywords: crystal structure; charge-transfer complex; 4,6-dimethyldibenzothiophene; 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane.

CCDC reference: 1816551

Structure description

4,6-Dimethyldibenzothiophene (DMDBT) is one of the sulfur compounds contained in light oil. Hydrodesulfurization is used to remove the sulfur compounds in light oil. However, DMDBT is difficult to desulfurize because the two methyl groups interfere with the reaction of hydrodesulfurization. Although Milenkovic et al. (1999 ) succeeded in desulfurizing from light oil by the formation of charge-transfer complexes using 2,4,5,7-tetranitro-9-fluorene (TNF) as an electron acceptor, the crystal structure of DMDBT–TNF was not determined. The crystal structures of DMDBT and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (F₄TCNQ) have been determined by Meille et al. (1996 ) and Krupskaya et al. (2015 ), respectively. In this study, we obtained a novel complex using DMDBT as a donor and F₄TCNQ as an acceptor, and determined the crystal structure.

The asymmetric unit consists of one DMDBT molecule and one half of an F₄TCNQ molecule, which lies on an inversion centre (Fig. 1). A donor–acceptor–donor 2:1 unit is formed via a charge-transfer interaction (Fig. 2); the centroid–centroid distance between the five-membered ring of DMDBT and the six-membered ring of F₄TCNQ is 3.3681 (15) Å. The units are stacked in a column along [110]. An F⋯F contact [2.911 (1) Å] is also observed (Fig. 3).

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level and H atoms are shown as small spheres. [Symmetry code: (i) −x + 2, −y + 1, −z.]

Figure 2
A packing diagram of the title compound, showing the 2:1 electron donor and acceptor unit.

Figure 3
A packing diagram of the title compound, showing the F⋯F contacts as blue dashed lines.

Synthesis and crystallization

The title complex was obtained by mixing an acetonitrile solution (3 ml) of DMDBT (2.2 mg) with an acetonitrile solution (2.5 ml) of F₄TCNQ (2.7 mg), and then concentrating the solution for one day. The obtained black complex showed new charge-transfer bands around 600 nm in the UV–vis absorption spectrum, which were not observed for the raw materials.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	2C₁₄H₁₂S·C₁₂F₄N₄
M_r	700.77
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	93
a, b, c (Å)	7.570 (2), 10.206 (3), 11.549 (4)
α, β, γ (°)	113.400 (2), 90.010 (3), 108.607 (3)
V (Å³)	767.8 (4)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.42 × 0.10 × 0.02

Data collection
Diffractometer	Rigaku Saturn724
Absorption correction	Multi-scan (REQAB; Rigaku, 1998 )
T_min, T_max	0.854, 0.995
No. of measured, independent and observed [F² > 2σ(F²)] reflections	6222, 3311, 2887
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.091, 1.03
No. of reflections	3311
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.25
Computer programs: CrystalClear (Rigaku, 2008 ), SIR2014 (Burla et al., 2012 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), CrystalStructure (Rigaku, 2016 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1816551

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618000779/is4022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000779/is4022Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000779/is4022Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR2014 (Burla et al., 2012); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2016) and publCIF (Westrip, 2010).

Bis[6,10-dimethyl-8-thiatricyclo[7.4.0.0^2,7]trideca-1(9),2,4,6,10,12-hexaene] 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile top

Crystal data top

2C₁₄H₁₂S·C₁₂F₄N₄	Z = 1
M_r = 700.77	F(000) = 360.00
Triclinic, P1	D_x = 1.516 Mg m⁻³
a = 7.570 (2) Å	Mo Kα radiation, λ = 0.71075 Å
b = 10.206 (3) Å	Cell parameters from 2475 reflections
c = 11.549 (4) Å	θ = 3.7–27.5°
α = 113.400 (2)°	µ = 0.24 mm⁻¹
β = 90.010 (3)°	T = 93 K
γ = 108.607 (3)°	Prism, black
V = 767.8 (4) Å³	0.42 × 0.10 × 0.02 mm

Data collection top

Rigaku Saturn724 diffractometer	2887 reflections with F² > 2σ(F²)
Detector resolution: 28.445 pixels mm^-1	R_int = 0.021
ω scans	θ_max = 27.3°, θ_min = 3.7°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −8→9
T_min = 0.854, T_max = 0.995	k = −13→13
6222 measured reflections	l = −14→12
3311 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.047P)² + 0.4352P] where P = (F_o² + 2F_c²)/3
3311 reflections	(Δ/σ)_max < 0.001
228 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³
Primary atom site location: structure-invariant direct methods

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. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
S1	0.50372 (5)	0.19776 (4)	0.00985 (3)	0.01267 (11)
F1	0.66794 (11)	0.46548 (10)	−0.11943 (8)	0.01555 (19)
F2	0.73704 (12)	0.60156 (10)	0.13100 (8)	0.0156 (2)
N1	1.37660 (19)	0.69718 (16)	0.40939 (13)	0.0196 (3)
N2	0.8594 (2)	0.75756 (17)	0.42387 (13)	0.0234 (3)
C1	1.0005 (2)	0.24541 (16)	0.16420 (14)	0.0134 (3)
H1	1.106198	0.219533	0.132407	0.016*
C2	1.0013 (2)	0.31783 (17)	0.29404 (14)	0.0144 (3)
H2	1.107384	0.340458	0.351784	0.017*
C3	0.8466 (2)	0.35811 (16)	0.34113 (14)	0.0149 (3)
H3	0.850956	0.408757	0.430689	0.018*
C4	0.6867 (2)	0.32626 (16)	0.26081 (14)	0.0135 (3)
C5	0.6874 (2)	0.25106 (16)	0.12964 (14)	0.0123 (3)
C6	0.6322 (2)	0.12100 (16)	−0.10872 (14)	0.0120 (3)
C7	0.5684 (2)	0.05155 (16)	−0.24017 (14)	0.0134 (3)
C8	0.6910 (2)	−0.00336 (16)	−0.31948 (14)	0.0150 (3)
H8	0.652923	−0.051750	−0.409160	0.018*
C9	0.8694 (2)	0.01070 (17)	−0.27078 (14)	0.0151 (3)
H9	0.949518	−0.027864	−0.327803	0.018*
C10	0.9300 (2)	0.08007 (16)	−0.14069 (14)	0.0134 (3)
H10	1.050959	0.089629	−0.108152	0.016*
C11	0.8102 (2)	0.13592 (16)	−0.05784 (14)	0.0119 (3)
C12	0.8422 (2)	0.21067 (15)	0.08018 (13)	0.0116 (3)
C13	0.5213 (2)	0.36983 (18)	0.31136 (15)	0.0174 (3)
H13A	0.514343	0.452297	0.290378	0.026*
H13B	0.536587	0.404189	0.404152	0.026*
H13C	0.405198	0.281435	0.272533	0.026*
C14	0.3773 (2)	0.03761 (17)	−0.29078 (15)	0.0167 (3)
H14A	0.371282	0.139434	−0.266854	0.025*
H14B	0.280501	−0.018362	−0.254580	0.025*
H14C	0.355357	−0.017344	−0.383911	0.025*
C15	0.83036 (19)	0.48166 (16)	−0.06107 (14)	0.0114 (3)
C16	0.86612 (19)	0.55144 (16)	0.06696 (14)	0.0117 (3)
C17	1.03840 (19)	0.57591 (15)	0.13883 (13)	0.0113 (3)
C18	1.0752 (2)	0.64812 (16)	0.26997 (14)	0.0131 (3)
C19	1.2464 (2)	0.67300 (16)	0.34279 (14)	0.0146 (3)
C20	0.9484 (2)	0.70676 (17)	0.35044 (14)	0.0156 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01041 (17)	0.01487 (18)	0.01270 (18)	0.00466 (13)	0.00217 (13)	0.00553 (13)
F1	0.0113 (4)	0.0217 (5)	0.0136 (4)	0.0073 (3)	−0.0004 (3)	0.0062 (4)
F2	0.0127 (4)	0.0201 (4)	0.0142 (4)	0.0091 (3)	0.0050 (3)	0.0048 (3)
N1	0.0190 (7)	0.0225 (7)	0.0150 (6)	0.0063 (5)	0.0002 (5)	0.0064 (5)
N2	0.0234 (7)	0.0268 (7)	0.0163 (7)	0.0101 (6)	0.0058 (6)	0.0045 (6)
C1	0.0128 (7)	0.0123 (7)	0.0163 (7)	0.0044 (5)	0.0037 (6)	0.0072 (6)
C2	0.0128 (7)	0.0155 (7)	0.0158 (7)	0.0039 (5)	0.0001 (5)	0.0081 (6)
C3	0.0173 (7)	0.0144 (7)	0.0123 (7)	0.0041 (6)	0.0026 (6)	0.0059 (6)
C4	0.0136 (7)	0.0123 (7)	0.0150 (7)	0.0039 (5)	0.0040 (5)	0.0067 (5)
C5	0.0113 (6)	0.0114 (6)	0.0145 (7)	0.0023 (5)	0.0014 (5)	0.0070 (5)
C6	0.0116 (6)	0.0093 (6)	0.0147 (7)	0.0024 (5)	0.0026 (5)	0.0057 (5)
C7	0.0132 (7)	0.0107 (7)	0.0153 (7)	0.0020 (5)	0.0012 (5)	0.0063 (5)
C8	0.0172 (7)	0.0127 (7)	0.0126 (7)	0.0036 (6)	0.0011 (6)	0.0040 (5)
C9	0.0154 (7)	0.0129 (7)	0.0163 (7)	0.0060 (6)	0.0046 (6)	0.0047 (6)
C10	0.0125 (7)	0.0119 (7)	0.0166 (7)	0.0045 (5)	0.0026 (5)	0.0065 (5)
C11	0.0123 (7)	0.0087 (6)	0.0139 (7)	0.0017 (5)	0.0014 (5)	0.0054 (5)
C12	0.0134 (7)	0.0093 (6)	0.0131 (7)	0.0034 (5)	0.0030 (5)	0.0061 (5)
C13	0.0156 (7)	0.0225 (8)	0.0156 (7)	0.0089 (6)	0.0051 (6)	0.0076 (6)
C14	0.0146 (7)	0.0174 (7)	0.0156 (7)	0.0042 (6)	−0.0007 (6)	0.0055 (6)
C15	0.0089 (6)	0.0115 (6)	0.0140 (7)	0.0032 (5)	0.0012 (5)	0.0059 (5)
C16	0.0101 (6)	0.0114 (6)	0.0148 (7)	0.0045 (5)	0.0049 (5)	0.0060 (5)
C17	0.0119 (7)	0.0096 (6)	0.0128 (7)	0.0028 (5)	0.0026 (5)	0.0056 (5)
C18	0.0138 (7)	0.0118 (7)	0.0122 (7)	0.0032 (5)	0.0024 (5)	0.0047 (5)
C19	0.0183 (7)	0.0134 (7)	0.0100 (7)	0.0040 (6)	0.0040 (6)	0.0040 (5)
C20	0.0166 (7)	0.0149 (7)	0.0119 (7)	0.0032 (6)	−0.0007 (6)	0.0041 (6)

Geometric parameters (Å, º) top

S1—C5	1.7500 (15)	C8—C9	1.405 (2)
S1—C6	1.7520 (15)	C8—H8	0.9500
F1—C15	1.3322 (17)	C9—C10	1.384 (2)
F2—C16	1.3350 (15)	C9—H9	0.9500
N1—C19	1.148 (2)	C10—C11	1.4003 (19)
N2—C20	1.147 (2)	C10—H10	0.9500
C1—C2	1.383 (2)	C11—C12	1.448 (2)
C1—C12	1.400 (2)	C13—H13A	0.9800
C1—H1	0.9500	C13—H13B	0.9800
C2—C3	1.402 (2)	C13—H13C	0.9800
C2—H2	0.9500	C14—H14A	0.9800
C3—C4	1.393 (2)	C14—H14B	0.9800
C3—H3	0.9500	C14—H14C	0.9800
C4—C5	1.401 (2)	C15—C16	1.344 (2)
C4—C13	1.5015 (19)	C15—C17ⁱ	1.4466 (19)
C5—C12	1.4105 (19)	C16—C17	1.442 (2)
C6—C7	1.402 (2)	C17—C18	1.377 (2)
C6—C11	1.408 (2)	C18—C20	1.438 (2)
C7—C8	1.393 (2)	C18—C19	1.439 (2)
C7—C14	1.502 (2)

C5—S1—C6	91.18 (7)	C10—C11—C12	128.65 (13)
C2—C1—C12	119.20 (13)	C6—C11—C12	112.03 (12)
C2—C1—H1	120.4	C1—C12—C5	119.36 (13)
C12—C1—H1	120.4	C1—C12—C11	128.77 (13)
C1—C2—C3	120.50 (14)	C5—C12—C11	111.87 (13)
C1—C2—H2	119.7	C4—C13—H13A	109.5
C3—C2—H2	119.7	C4—C13—H13B	109.5
C4—C3—C2	122.11 (14)	H13A—C13—H13B	109.5
C4—C3—H3	118.9	C4—C13—H13C	109.5
C2—C3—H3	118.9	H13A—C13—H13C	109.5
C3—C4—C5	116.59 (13)	H13B—C13—H13C	109.5
C3—C4—C13	122.05 (13)	C7—C14—H14A	109.5
C5—C4—C13	121.35 (13)	C7—C14—H14B	109.5
C4—C5—C12	122.23 (13)	H14A—C14—H14B	109.5
C4—C5—S1	125.29 (11)	C7—C14—H14C	109.5
C12—C5—S1	112.48 (11)	H14A—C14—H14C	109.5
C7—C6—C11	122.66 (13)	H14B—C14—H14C	109.5
C7—C6—S1	124.90 (11)	F1—C15—C16	118.90 (12)
C11—C6—S1	112.45 (11)	F1—C15—C17ⁱ	118.30 (12)
C8—C7—C6	116.35 (13)	C16—C15—C17ⁱ	122.80 (13)
C8—C7—C14	122.58 (14)	F2—C16—C15	118.70 (13)
C6—C7—C14	121.07 (13)	F2—C16—C17	118.20 (12)
C7—C8—C9	121.94 (14)	C15—C16—C17	123.10 (13)
C7—C8—H8	119.0	C18—C17—C16	123.02 (13)
C9—C8—H8	119.0	C18—C17—C15ⁱ	122.88 (13)
C10—C9—C8	120.80 (13)	C16—C17—C15ⁱ	114.10 (13)
C10—C9—H9	119.6	C17—C18—C20	124.50 (13)
C8—C9—H9	119.6	C17—C18—C19	123.55 (13)
C9—C10—C11	118.93 (13)	C20—C18—C19	111.96 (13)
C9—C10—H10	120.5	N1—C19—C18	174.55 (15)
C11—C10—H10	120.5	N2—C20—C18	173.74 (16)
C10—C11—C6	119.32 (13)

C12—C1—C2—C3	−0.9 (2)	C7—C6—C11—C12	−179.64 (12)
C1—C2—C3—C4	0.7 (2)	S1—C6—C11—C12	0.22 (15)
C2—C3—C4—C5	0.2 (2)	C2—C1—C12—C5	0.4 (2)
C2—C3—C4—C13	−179.84 (13)	C2—C1—C12—C11	−179.92 (13)
C3—C4—C5—C12	−0.7 (2)	C4—C5—C12—C1	0.5 (2)
C13—C4—C5—C12	179.28 (13)	S1—C5—C12—C1	−179.87 (11)
C3—C4—C5—S1	179.65 (11)	C4—C5—C12—C11	−179.28 (13)
C13—C4—C5—S1	−0.3 (2)	S1—C5—C12—C11	0.39 (15)
C6—S1—C5—C4	179.43 (13)	C10—C11—C12—C1	0.1 (2)
C6—S1—C5—C12	−0.22 (11)	C6—C11—C12—C1	179.90 (14)
C5—S1—C6—C7	179.85 (13)	C10—C11—C12—C5	179.81 (14)
C5—S1—C6—C11	0.00 (11)	C6—C11—C12—C5	−0.39 (17)
C11—C6—C7—C8	0.2 (2)	F1—C15—C16—F2	0.2 (2)
S1—C6—C7—C8	−179.66 (11)	C17ⁱ—C15—C16—F2	179.72 (12)
C11—C6—C7—C14	179.91 (13)	F1—C15—C16—C17	−179.32 (12)
S1—C6—C7—C14	0.1 (2)	C17ⁱ—C15—C16—C17	0.2 (2)
C6—C7—C8—C9	−0.4 (2)	F2—C16—C17—C18	0.1 (2)
C14—C7—C8—C9	179.90 (14)	C15—C16—C17—C18	179.65 (13)
C7—C8—C9—C10	0.2 (2)	F2—C16—C17—C15ⁱ	−179.71 (11)
C8—C9—C10—C11	0.2 (2)	C15—C16—C17—C15ⁱ	−0.2 (2)
C9—C10—C11—C6	−0.4 (2)	C16—C17—C18—C20	0.2 (2)
C9—C10—C11—C12	179.42 (14)	C15ⁱ—C17—C18—C20	−179.97 (13)
C7—C6—C11—C10	0.2 (2)	C16—C17—C18—C19	179.89 (13)
S1—C6—C11—C10	−179.95 (11)	C15ⁱ—C17—C18—C19	−0.3 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Funding information

This work was supported by JSPS KAKENHI grant No. JP17KT0100.

References

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