5,17-Dibromo-26,28-dihy­droxy-25,27-diprop­oxy-2,8,14,20-tetra­thia­calix[4]arene

Ling-Ling Liu; Lu-Sheng Chen; Jian-Ping Ma; Dian-Shun Guo

doi:10.1107/S1600536811013043

. 2011 Apr 13;67(Pt 5):o1110–o1111. doi: 10.1107/S1600536811013043

5,17-Dibromo-26,28-dihydroxy-25,27-dipropoxy-2,8,14,20-tetrathiacalix[4]arene

Ling-Ling Liu ^a, Lu-Sheng Chen ^a, Jian-Ping Ma ^a, Dian-Shun Guo ^a,^*

PMCID: PMC3089239 PMID: 21754428

Abstract

In the title compound, C₃₀H₂₆Br₂O₄S₄, the thiacalix[4]arene unit adopts a pinched cone conformation, with one of the ether-substituted rings bent towards the calix cavity and the two phenolic rings bent outwards. The phenyl rings make dihedral angles of 27.12 (9), 36.71 (10), 75.04 (8), and 76.01 (7)° with the virtual plane defined by the four bridging S atoms. The two opposite ether-substituted rings are almost parallel to each other, with an interplanar anagle of 2.99 (12)°, while the two phenolic rings are nearly perpendicular to each other, making a dihedral angle of 74.52 (11)° and a Br⋯Br distance of 13.17 (2) Å. Two intramolecular O—H⋯O hydrogen bonds between the OH groups and the same ether O atom stabilize the cone conformation. In the crystal, two different chains of molecules, one with alternating and the other with tail-to-tail orientations, are formed by intermolecular offset-face-to-face π–π stacking interactions with distances of 3.606 (3) to 4.488 (4) Å between the centroids of the aromatic rings.

Related literature

For general background to the chemistry of thiacalix[4]arenes, see: Shokova & Kovalev (2003 ▶); Lhoták (2004 ▶); Morohashi et al. (2006 ▶); Kajiwara et al. (2007 ▶); Guo et al. (2007 ▶). For the synthesis and related structures, see: Lhoták et al. (2001 ▶); Kasyan et al. (2003 ▶); Desroches et al. (2004 ▶); Kasyan et al. (2006 ▶); Morohashi et al. (2006 ▶); Xu et al. (2008 ▶); Chen et al. (2010 ▶). For π–π stacking interactions, see: Tsuzuki et al. (2002 ▶).

Experimental

Crystal data

C₃₀H₂₆Br₂O₄S₄
M _r = 738.57
Triclinic,
a = 9.3788 (16) Å
b = 11.712 (2) Å
c = 14.768 (3) Å
α = 97.904 (2)°
β = 95.614 (1)°
γ = 107.738 (2)°
V = 1513.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 2.99 mm⁻¹
T = 298 K
0.29 × 0.21 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.478, T _max = 0.586
7993 measured reflections
5513 independent reflections
4162 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.108
S = 1.05
5513 reflections
365 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536811013043/im2275sup1.cif

e-67-o1110-sup1.cif^{(25.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013043/im2275Isup2.hkl

e-67-o1110-Isup2.hkl^{(269.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.82	2.20	2.926 (3)	148
O2—H2A⋯O3	0.82	2.12	2.849 (3)	148

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Acknowledgments

Financial support from the National Natural Science Foundation of China (grant No. 20572064) and the Natural Science Foundation of Shandong Province (grant No. ZR2010BM022) is gratefully acknowledged.

supplementary crystallographic information

Comment

Thiacalix[4]arenes are new versatile scaffolds for constructing highly organized receptors via appropriate chemical modifications at the upper or/and lower rim (Shokova & Kovalev, 2003; Lhoták, 2004; Morohashi et al., 2006; Kajiwara et al., 2007; Guo et al., 2007). Usually, it can be attained by electrophilic bromination at the upper rim to yield the corresponding bromosubstituted thiacalix[4]arene derivatives (Lhoták et al., 2001; Kasyan et al., 2003; Xu et al., 2008; Chen et al., 2010), which can be further used to create more elaborate molecules and novel supramolecular systems. Only a few cyrstal structures of such derivatives are known, however, most of which are tetrabromothiacalix[4]arenes. Recently, Lhoták et al. (2001) presented the synthesis of a dibromothiacalix[4]arene, namely 5,17-dibromo-25,27-dipropoxy-26,28-dihydroxy-2,8,14,20-tetrathiacalix[4]arene, by a selective bromination reaction. We now report the crystal structure of this compound.

In the crystal structure of the title compound, as illustrated in Fig. 1, the thiacalix[4]arene unit is found in a pinched cone conformation. Two opposite ether-substituted rings, one of which is bent towards the calix cavity, are almost parallel to each other, forming a dihedral anagle of 2.99 (12)°. On the other hand, both phenolic rings are bent outwards and nearly perpendicular to each other, with an interplanar angle of 74.52 (11)° and a Br···Br distance of 13.17 (2) Å. The dihedral angles between the virtual plane defined by the four bridging S atoms and C1–C6, C7–C12, C13–C18 and C19–C24 rings are 75.04 (8), 27.12 (9), 76.01 (7) and 36.71 (10) °, respectively. Two intramolecular O—H···O hydrogen bonds (Table 1) stabilizing the cone conformation, are formed in the crystal structure. Interestingly, both OH groups make the hydrogen bonds to the same ethereal O atom, O3 (Fig. 2). A similar arrangement of such hydrogen bonds was discussed by Kasyan et al. (2006), while a different pattern, in which one OH group forms the hydrogen bonds to its both adjacent ethereal O atoms, was reported by Desroches et al. (2004).

In the packing, two different chains of molecules are formed by aromatic-aromatic interactions (Tsuzuki et al., 2002). One chain, with alternating orientation, extends along the a axis (Fig. 3), and is established by intermolecular offset-face-to-face π-π stackings between the phenolic rings. Separations between the centroids of the phenolic rings C19–C24 and C19–C24 at (-x, -y, -z + 1), C7–C12 and C7–C12 at (-x + 1, -y + 1, -z + 2) are 3.606 (3) and 4.488 (4) Å, respectively, and the corresponding perpendicular distances are 3.454 (2) and 3.568 (2) Å. The other chain, with tail-to-tail orientation, is running along the b axis, with intermolecular offset-face-to-face π-π contacts between the ether-substituted rings. The distance between the centroids of the rings C1–C6 and C13–C18 at (x - 1, y, z) is 4.195 (2) Å, and the corresponding perpendicular distance is 3.611 (2) Å.

Experimental

The title compound was prepared by a published procedure (Lhoták et al., 2001). Single crystals of the title compound suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in CH₂Cl₂ and CH₃OH (v: v = 2: 1) at 273 K.