1,4-Bis[3,11-di­thiatri­cyclo­[11.3.1.15,9]octa­deca-1(17),5,7,9(18),13,15-hexaen-7-yl]buta-1,3-diyne

Moriguchi, T.; Yakeya, D.; Jalli, V.; Tsuge, A.

doi:10.1107/S241431461601378X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161378

doi:10.1107/S241431461601378X

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1,4-Bis[3,11-dithiatricyclo[11.3.1.1^5,9]octadeca-1(17),5,7,9(18),13,15-hexaen-7-yl]buta-1,3-diyne

Tetsuji Moriguchi,^a ^* Daisuke Yakeya,^a Venkataprasad Jalli ^a and Akihiko Tsuge ^a

^aDepartment of Applied Chemistry, Graduate School of Engineering, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan
^*Correspondence e-mail: moriguch@che.kyutech.ac.jp

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 13 August 2016; accepted 29 August 2016; online 5 September 2016)

The complete molecule of the title compound, C₃₆H₃₀S₄ {common name: 1,4-[4-(9,17-dithia[3.3]metacyclophane)]-1,3-butadiyne}, is generated by a crystallographic inversion centre at the mid-point of the central C—C bond [1.367 (5) Å]. Both cyclophane units exist in cisoid pseudo-boat–chair chair–boat conformations. In the crystal, the packing is controlled by van der Waals interactions.

Keywords: crystal structure; cyclophane; butadiyne.

CCDC reference: 812220

Structure description

The synthesis and molecular structure analysis of bridged cyclophanes continue to attract interest in supramolecular chemistry. The understanding of preferred conformations in cyclophanes is of importance in the design of various supramolecular systems. Small-sized cyclophane molecules act as a model to explore the mobility of such cyclophanes due to the presence of a variety of conformational processes including ring-flipping, ring-tilting and syn–anti isomerization. Small-sized cyclophane units have been used as a platform to build cofacial bisporphyrins (Tsuge et al., 2012 ). The [3.3]dithiametacyclophane skeleton have also been used to provide an appropriate platform to arrange two oligomer chains side by side in stacked form because this kind of cyclophane assumes a syn structure (Tsuge et al., 2008 ). On the other hand, [3.3]dithiametacyclophanes consisting of oligothiophene units with extended π-conjugation have shown better fluorescence properties (Tsuge et al., 2008). Thus, the elucidation of the crystal structures of cyclophane derivatives has attracted much attention.

Here, we report the crystal structure of the title compound, possessing extended π-conjugation via a 1,3-butadiyne unit (Fig. 1). The complete molecule is generated by a crystallographic inversion centre at the mid-point of the central C—C bond. The C—C single- and triple-bond lengths match the reported values in the literature (Mo et al., 1996 ). Both cyclophane units exist in cisoid, pseudo boat-chair, chair-boat conformations with both substitutents positioned on the same side.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are generated by the symmetry operation (−x, −y + 2, −z + 1). H atoms have been omitted for clarity.

No directional interactions beyond normal van der Waals' contacts could be identified in the crystal. The crystal packing is shown in Fig. 2.

Figure 2
Crystal packing diagram of the title compound, viewed along the a axis, with H atoms omitted for clarity.

Synthesis and crystallization

The title compound was synthesized using Hay coupling as follows. The reaction scheme is shown in Fig. 3. A dichloromethane solution (10 ml) of 6-ethynyl-2,11-dithia[3.3]metacyclophane (40.2 mg, 0.125 mmol) was added dropwise to a solution of tetramethylethylenediamine (TMEDA) (0.80 ml, 5.7 mmol) and CuCl (0.28 g, 2.9 mmol) as a catalyst in dichloromethane (50 ml). The reaction mixture was stirred for 2 h. After the completion of reaction, the resulting mixture was poured into 10% HCl (aq.) and then, the organic layer was washed with water. The resulting organic layer was dried over MgSO₄ and the solvent was removed under reduced pressure. The resulting residue was purified by recrystallization and the title compound was obtained as white crystals (33.2 mg, 0.0562 mmol, 39% yield). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a dichloromethane–hexane solution at room temperature using the slow vapor diffusion technique.

Figure 3
The reaction scheme for the synthesis of the title compound.

¹H NMR (400 MHz, CDCl₃) 3.75 (s, 8 H, –CH₂–), 3.78 (s, 8 H, –CH₂–), 6.90 (d, 4 H, aryl C–H, J = 2.5 Hz), 6.97 (d, 4 H, aryl C–H, J = 2.5 Hz), 7.03 (m, 6 H, aryl C–H). EI–MS (75 eV): m/z 590 (M⁺). Elemental analysis: C 73.13% (73.18%, calculated), H 5.09% (5.12%, calculated).

Refinement

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

Table 1
Experimental details

Crystal data
Chemical formula	C₃₆H₃₀S₄
M_r	590.84
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	90
a, b, c (Å)	8.717 (3), 16.325 (5), 21.043 (7)
V (Å³)	2994.5 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.34
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.659, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	12443, 2641, 2172
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.130, 1.16
No. of reflections	2641
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014/7 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 812220

Crystal structure: contains datablocks global, I. DOI: 10.1107/S241431461601378X/hb4071sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461601378X/hb4071Isup2.hkl

checkcif. DOI: 10.1107/S241431461601378X/hb4071sup3.pdf

Supporting information file. DOI: 10.1107/S241431461601378X/hb4071Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014/7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

1,4-Bis[3,11-dithiatricyclo[11.3.1.1^5,9]octadeca-1(17),5,7,9(18),13,15-hexaen-7-yl]buta-1,3-diyne top

Crystal data top

C₃₆H₃₀S₄	D_x = 1.311 Mg m⁻³
M_r = 590.84	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 12443 reflections
a = 8.717 (3) Å	θ = 1.9–25.0°
b = 16.325 (5) Å	µ = 0.34 mm⁻¹
c = 21.043 (7) Å	T = 90 K
V = 2994.5 (17) Å³	Prism, yellow
Z = 4	0.35 × 0.25 × 0.20 mm
F(000) = 1240

Data collection top

Bruker APEXII CCD diffractometer	2641 independent reflections
Radiation source: fine focus sealed tube	2172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 8.333 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
ω scans	h = −10→6
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −19→19
T_min = 0.659, T_max = 0.934	l = −24→25
12443 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.064P)² + 2.2214P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.001
2641 reflections	Δρ_max = 0.37 e Å⁻³
181 parameters	Δρ_min = −0.22 e Å⁻³

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
C1	0.7566 (3)	0.93934 (17)	0.63894 (13)	0.0272 (6)
H1A	0.8431	0.9633	0.6167	0.033*
H1B	0.7974	0.9048	0.6724	0.033*
C2	0.6688 (3)	0.88566 (16)	0.59271 (12)	0.0232 (6)
C3	0.6204 (3)	0.91543 (16)	0.53423 (12)	0.0253 (6)
H3	0.6481	0.968	0.5216	0.03*
C4	0.5310 (3)	0.86717 (17)	0.49439 (13)	0.0291 (7)
H4	0.4995	0.8875	0.4552	0.035*
C5	0.4883 (4)	0.78859 (17)	0.51288 (13)	0.0315 (7)
H5	0.4252	0.7573	0.4868	0.038*
C6	0.5397 (4)	0.75665 (16)	0.57031 (12)	0.0297 (7)
C7	0.6325 (3)	0.80538 (16)	0.60904 (13)	0.0271 (6)
H7	0.6709	0.7836	0.6467	0.033*
C8	0.4951 (4)	0.66958 (17)	0.58834 (14)	0.0413 (8)
H8B	0.5769	0.6334	0.5746	0.05*
H8A	0.4043	0.6551	0.5642	0.05*
C9	0.2692 (3)	0.69461 (16)	0.68376 (13)	0.0285 (6)
H9A	0.1963	0.6704	0.6544	0.034*
H9B	0.2345	0.6827	0.7266	0.034*
C10	0.2712 (3)	0.78628 (15)	0.67415 (11)	0.0205 (6)
C11	0.1831 (3)	0.82242 (15)	0.62706 (11)	0.0194 (5)
H11	0.113	0.791	0.6044	0.023*
C12	0.1990 (3)	0.90631 (15)	0.61345 (11)	0.0169 (5)
C13	0.3051 (3)	0.95296 (15)	0.64694 (11)	0.0170 (5)
H13	0.3166	1.0083	0.6375	0.02*
C14	0.3943 (3)	0.91761 (14)	0.69438 (11)	0.0155 (5)
C15	0.3743 (3)	0.83492 (15)	0.70824 (11)	0.0189 (5)
H15	0.4309	0.8115	0.741	0.023*
C16	0.5167 (3)	0.96678 (16)	0.72801 (12)	0.0211 (6)
H16A	0.5767	0.93	0.7543	0.025*
H16B	0.4671	1.0059	0.756	0.025*
C17	0.1119 (3)	0.94410 (15)	0.56359 (12)	0.0190 (5)
C18	0.0414 (3)	0.97970 (15)	0.52266 (12)	0.0188 (5)
S1	0.64610 (8)	1.02199 (4)	0.67558 (3)	0.0240 (2)
S2	0.45632 (10)	0.64782 (4)	0.67156 (4)	0.0328 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0255 (14)	0.0334 (16)	0.0228 (14)	−0.0002 (12)	0.0054 (12)	0.0026 (12)
C2	0.0259 (14)	0.0251 (14)	0.0185 (13)	0.0024 (11)	0.0088 (11)	−0.0026 (11)
C3	0.0330 (15)	0.0248 (14)	0.0181 (14)	−0.0005 (12)	0.0082 (12)	0.0037 (11)
C4	0.0437 (17)	0.0301 (15)	0.0135 (13)	0.0048 (13)	0.0064 (12)	−0.0001 (11)
C5	0.0440 (17)	0.0298 (16)	0.0207 (14)	−0.0020 (13)	0.0086 (13)	−0.0119 (12)
C6	0.0493 (18)	0.0196 (14)	0.0204 (14)	0.0041 (13)	0.0115 (13)	−0.0041 (11)
C7	0.0377 (16)	0.0246 (14)	0.0191 (13)	0.0087 (12)	0.0079 (12)	0.0033 (11)
C8	0.072 (2)	0.0209 (15)	0.0308 (17)	0.0021 (15)	0.0123 (17)	−0.0049 (13)
C9	0.0409 (16)	0.0160 (14)	0.0287 (15)	−0.0041 (12)	−0.0035 (13)	0.0040 (11)
C10	0.0288 (14)	0.0144 (12)	0.0182 (13)	−0.0007 (11)	0.0017 (11)	−0.0011 (10)
C11	0.0252 (13)	0.0170 (12)	0.0161 (12)	−0.0032 (11)	−0.0015 (10)	−0.0047 (10)
C12	0.0200 (12)	0.0194 (12)	0.0113 (12)	0.0025 (10)	0.0010 (10)	0.0002 (10)
C13	0.0234 (13)	0.0129 (12)	0.0148 (12)	0.0019 (10)	0.0037 (11)	−0.0021 (9)
C14	0.0185 (12)	0.0157 (12)	0.0124 (12)	0.0021 (10)	0.0021 (10)	−0.0045 (9)
C15	0.0256 (13)	0.0186 (13)	0.0126 (12)	0.0044 (10)	−0.0004 (10)	0.0025 (10)
C16	0.0241 (13)	0.0239 (14)	0.0154 (13)	−0.0017 (11)	0.0006 (11)	−0.0035 (10)
C17	0.0223 (13)	0.0197 (13)	0.0151 (13)	−0.0014 (11)	0.0030 (11)	−0.0029 (10)
C18	0.0217 (13)	0.0190 (13)	0.0156 (12)	−0.0005 (10)	0.0006 (10)	−0.0026 (10)
S1	0.0276 (4)	0.0220 (4)	0.0224 (4)	−0.0074 (3)	0.0002 (3)	−0.0014 (3)
S2	0.0526 (5)	0.0131 (4)	0.0327 (4)	0.0065 (3)	0.0014 (4)	0.0054 (3)

Geometric parameters (Å, º) top

C1—C2	1.517 (4)	C9—S2	1.820 (3)
C1—S1	1.828 (3)	C9—H9A	0.97
C1—H1A	0.97	C9—H9B	0.97
C1—H1B	0.97	C10—C11	1.386 (4)
C2—C3	1.389 (4)	C10—C15	1.397 (4)
C2—C7	1.391 (4)	C11—C12	1.406 (3)
C3—C4	1.390 (4)	C11—H11	0.93
C3—H3	0.93	C12—C13	1.390 (3)
C4—C5	1.391 (4)	C12—C17	1.434 (3)
C4—H4	0.93	C13—C14	1.390 (4)
C5—C6	1.390 (4)	C13—H13	0.93
C5—H5	0.93	C14—C15	1.392 (3)
C6—C7	1.397 (4)	C14—C16	1.511 (3)
C6—C8	1.522 (4)	C15—H15	0.93
C7—H7	0.93	C16—S1	1.817 (3)
C8—S2	1.818 (3)	C16—H16A	0.97
C8—H8B	0.97	C16—H16B	0.97
C8—H8A	0.97	C17—C18	1.207 (4)
C9—C10	1.510 (3)	C18—C18ⁱ	1.367 (5)

C2—C1—S1	115.54 (19)	S2—C9—H9A	109.0
C2—C1—H1A	108.4	C10—C9—H9B	109.0
S1—C1—H1A	108.4	S2—C9—H9B	109.0
C2—C1—H1B	108.4	H9A—C9—H9B	107.8
S1—C1—H1B	108.4	C11—C10—C15	118.8 (2)
H1A—C1—H1B	107.5	C11—C10—C9	120.7 (2)
C3—C2—C7	118.7 (3)	C15—C10—C9	120.2 (2)
C3—C2—C1	121.3 (2)	C10—C11—C12	120.4 (2)
C7—C2—C1	120.0 (2)	C10—C11—H11	119.8
C2—C3—C4	120.4 (3)	C12—C11—H11	119.8
C2—C3—H3	119.8	C13—C12—C11	119.7 (2)
C4—C3—H3	119.8	C13—C12—C17	119.2 (2)
C3—C4—C5	120.3 (3)	C11—C12—C17	121.0 (2)
C3—C4—H4	119.9	C14—C13—C12	120.6 (2)
C5—C4—H4	119.9	C14—C13—H13	119.7
C6—C5—C4	120.2 (3)	C12—C13—H13	119.7
C6—C5—H5	119.9	C13—C14—C15	118.9 (2)
C4—C5—H5	119.9	C13—C14—C16	120.7 (2)
C5—C6—C7	118.7 (3)	C15—C14—C16	120.4 (2)
C5—C6—C8	119.0 (3)	C14—C15—C10	121.6 (2)
C7—C6—C8	122.3 (3)	C14—C15—H15	119.2
C2—C7—C6	121.6 (3)	C10—C15—H15	119.2
C2—C7—H7	119.2	C14—C16—S1	114.68 (17)
C6—C7—H7	119.2	C14—C16—H16A	108.6
C6—C8—S2	118.0 (2)	S1—C16—H16A	108.6
C6—C8—H8B	107.8	C14—C16—H16B	108.6
S2—C8—H8B	107.8	S1—C16—H16B	108.6
C6—C8—H8A	107.8	H16A—C16—H16B	107.6
S2—C8—H8A	107.8	C18—C17—C12	176.7 (3)
H8B—C8—H8A	107.1	C17—C18—C18ⁱ	178.6 (3)
C10—C9—S2	112.7 (2)	C16—S1—C1	102.53 (13)
C10—C9—H9A	109.0	C8—S2—C9	102.74 (15)

S1—C1—C2—C3	69.6 (3)	C9—C10—C11—C12	−172.5 (2)
S1—C1—C2—C7	−109.1 (3)	C10—C11—C12—C13	0.7 (4)
C7—C2—C3—C4	3.2 (4)	C10—C11—C12—C17	178.1 (2)
C1—C2—C3—C4	−175.5 (2)	C11—C12—C13—C14	−0.8 (4)
C2—C3—C4—C5	0.3 (4)	C17—C12—C13—C14	−178.3 (2)
C3—C4—C5—C6	−2.4 (4)	C12—C13—C14—C15	−0.7 (3)
C4—C5—C6—C7	0.9 (4)	C12—C13—C14—C16	176.1 (2)
C4—C5—C6—C8	−178.2 (3)	C13—C14—C15—C10	2.4 (4)
C3—C2—C7—C6	−4.8 (4)	C16—C14—C15—C10	−174.4 (2)
C1—C2—C7—C6	174.0 (2)	C11—C10—C15—C14	−2.5 (4)
C5—C6—C7—C2	2.7 (4)	C9—C10—C15—C14	171.0 (2)
C8—C6—C7—C2	−178.2 (3)	C13—C14—C16—S1	−49.5 (3)
C5—C6—C8—S2	−143.7 (3)	C15—C14—C16—S1	127.3 (2)
C7—C6—C8—S2	37.2 (4)	C14—C16—S1—C1	−69.7 (2)
S2—C9—C10—C11	118.5 (2)	C2—C1—S1—C16	69.8 (2)
S2—C9—C10—C15	−54.8 (3)	C6—C8—S2—C9	74.4 (3)
C15—C10—C11—C12	0.9 (4)	C10—C9—S2—C8	−62.9 (2)

Symmetry code: (i) −x, −y+2, −z+1.

Acknowledgements

We are grateful to the Center for Instrumental Analysis, Kyushu Institute of Technology (KITCIA), for the X-ray analysis.

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