1(2,3),2(3,2),3(2,3),4(3,2)-Tetra­kis(1-benzothio­phena)cyclo­tetra­phane benzene sesquisolvate

Zhi-Hua Wang; Jian-Wu Shi; Sheng Zhu; Hua Wang

doi:10.1107/S1600536809026178

. 2009 Jul 11;65(Pt 8):o1841. doi: 10.1107/S1600536809026178

1(2,3),2(3,2),3(2,3),4(3,2)-Tetrakis(1-benzothiophena)cyclotetraphane benzene sesquisolvate

Zhi-Hua Wang ^a, Jian-Wu Shi ^a, Sheng Zhu ^a, Hua Wang ^a,^*

PMCID: PMC2977466 PMID: 21583541

Abstract

In the title compound, C₃₂H₁₆S₄·1.5C₆H₆, the substituted cyclooctatetraene (COT) ring compound has approximate local D ₂ point symmetry of the so-called ‘saddle’ form: the dihedral angles between neighboring benzo[b]thiophene units are 61.33 (4), 61.61 (4), 56.443 (14) and 58.32 (4)°. The short distance [3.545 (1) Å] between an S atom and the centroid of a benzene ring in a neighboring molecule may indicate S⋯π interactions in the crystal.

Related literature

For the synthesis, see: Kauffmann et al. (1978 ▶). For related structures, see: Krömer et al. (2000 ▶); Mak & Wong (1987 ▶); Rajca et al. (1997 ▶, 2000 ▶); Wang et al. (2007 ▶).

Experimental

Crystal data

C₃₂H₁₆S₄·1.5C₆H₆
M _r = 645.85
Triclinic,
a = 9.5167 (10) Å
b = 13.3035 (14) Å
c = 13.9186 (15) Å
α = 65.674 (1)°
β = 84.646 (1)°
γ = 81.955 (1)°
V = 1588.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 294 K
0.41 × 0.25 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.877, T _max = 0.952
11927 measured reflections
5873 independent reflections
4670 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.121
S = 1.04
5873 reflections
394 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026178/hb2996sup1.cif

e-65-o1841-sup1.cif^{(27.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026178/hb2996Isup2.hkl

e-65-o1841-Isup2.hkl^{(287.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank Dr Jiange Wang, Luoyang Normal University, for the crystal measurement and Mr Pengtao Ma for discussions. This research was supported by the NSFC (20572015, 20672028, 50803015), the Program for NCET-05–0610, the SRF for ROCS–SEM, the Program for Young Excellent Talents in Henan Universities and the Foundation of Henan University (07YB2R006).

supplementary crystallographic information

Comment

In current electronic and supramolecular chemistry, the rational design of macrocyclic compound represents one of the most exciting and rapidly developing fields, owing to their potential as functional materials (Krömer et al., 2000). Mostly, the compounds with central COT ring have the "saddle" form (Rajca et al., 1997, Mak & Wong, 1987, Rajca et al., 2000, Wang et al., 2007), such as tetra-o-phenylene, tetra-o-thiophene. In these "saddle" form molecules, the average dihedral angle of "saddle" form is different when the structural unit is different. Cycloocta[l,2-b:4,3-b':5,6-b":8,7-b"']tetrathionaphthene (I), with benza[b]thiophene as the structural unit was synthesized by Kauffmann et al. in 1978. In our ongoing studies of macrocyclic compounds, we find the structural unit plays an important role on the crystal structure and intermolecular interaction. In present paper, we report the crystal structure of I.

As shown in I (Fig. 1), three orthogonal C₂ axes of symmetry are compatible with the D₂ point group. One pair of the orthogonal chiral axes (e.g., R,R) corresponds to the two 1,1'-linkages and the other pair (e.g., S,S) corresponds to the two 2,2'-linkages of the benza[b]thiophene moieties. The four dihedral angles are 61.329 (35)° between C24—C25—C26—C27—C28—C29—C30—S4—C31 and C16—C17—C18—C23—C22—C21—C20—C19—S3, 61.610 (39)° between C8—C9—C10—C11—C12—C13—C14—S2—C15 and C1—C2—C3—C4—C5- C6—C7—C32—S1, 56.443 (14)° between C16—C17—C18—C23—C22—C21—C20—C19—S3 and C8—C9—C10—C11—C12—C13—C14—S2—C15, 58.315 (34)° between C24—C25—C26—C27—C28—C29—C30—S4—C31 and C1—C2—C3—C4—C5—C6—C7—C32—S1. The average value (59.4°) of the four dihedral angles is smaller than that in tetra-o-phenylene with 65° (Rajca et al., 1997) and larger than that in tetra-o-thiophene with 51.7° (Wang et al., 2007). The distance between S1 and the centroid of plane (C25, C26, C27, C28, C29, C30) is 3.378 Å, which indicating obvious S-π interaction between the neighboring molecules. Under the effect of S-π interaction, the molecular arranges with the reversal one in the crystal packing as shown in Fig. 2.

Experimental

The title compound was synthesized according to the method of Kauffmann (1978). The overall yield was improved from 11% to 42.4%. To a solution of 3,3'-bibenzo[b]thiophene (0.3850 g, 1.45 mmol) in anhyd Et₂O (50 ml), n-BuLi (2.28 M, 1.46 ml, 3.32 mmol, 2.3 eq) was added dropwise at -78 °C, then the reaction mixture was warmed slowly to 50 °C with refluxing for 2 h and then cooled to -78 °C. Dry CuCl₂ (0.9741 g, 7.22 mmol, 5.0 equiv) was added at -78 °C and warmed slowly to -55 °C for 1 h, and then slowly warmed to ambient temperature overnight. After normal work-up, the crude product was purified by column chromatography on silica gel with PE (60–90 °C) /CHCl₃ (3:1, v/v) as eluent to yield I (0.1621 g, 42.4%) as a white solid. mp>300 °C. ¹H NMR (400 MHz, DMSO-d₆): δ 8.12 (d, J = 8.0 Hz, 4H), 7.48 (t, J = 7.8 Hz, 4H), 7.37 (t, J = 7.4 Hz, 4H), 7.25 (d, J = 7.6 Hz, 4H). ¹³C NMR (100 MHz, CDCl₃): δ 140.8, 138.6, 134.8, 131.3, 125.1, 124.7, 124.4, 122.3. IR: 3056, 2922 (C—H), 1435.5 (C=C) cm^-1. HRMS (MAIDI-TOF MS EI⁺) m/z calcd for [C₃₂H₁₆S₄] 528.0135, found 528.0131. Yellow blocks of (I) were obtained by slow evaporation of benzene solution over a period of two weeks.