Home The crystal structure of 25,27-(2,2′-[(2-thioxo-1,3-dithiole-4,5-diyl)disulfanediyl]diethanolate)-26,28-dihydroxycalix[4]arene — dichloromethane (1/1), C36H32Cl2O4S5
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The crystal structure of 25,27-(2,2′-[(2-thioxo-1,3-dithiole-4,5-diyl)disulfanediyl]diethanolate)-26,28-dihydroxycalix[4]arene — dichloromethane (1/1), C36H32Cl2O4S5

  • Lian-Wei Liu , Ji-Yan Zhong and Bang-Tun Zhao EMAIL logo
Published/Copyright: October 26, 2017

Abstract

C36H32Cl2O4S5, orthorhombic, Pccn (no. 56), a = 15.4426(11) Å, b = 17.4623(13) Å, c = 25.9153(19) Å, V = 6988.4(9) Å3, Z = 8, Rgt(F) = 0.0590, wRref(F2) = 0.1958, T = 291(2) K.

CCDC no.: 1549928

The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Yellow block
Size:0.38 × 0.27 × 0.13 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.52 mm−1
Diffractometer, scan mode:Bruker SMART, φ and ω-scans
2θmax, completeness:27.5°, >99%
N(hkl)measured, N(hkl)unique, Rint:42129, 8015, 0.032
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 4993
N(param)refined:426
Programs:Bruker programs [1, 2] , SHELX [3]
Table 2

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

AtomxyzUiso*/Ueq
Cl10.75994(12)0.63585(11)0.31194(7)0.1412(6)
Cl20.87877(9)0.67621(8)0.23222(7)0.1163(5)
S10.31810(6)1.09516(8)0.40616(4)0.0810(3)
S20.14302(7)1.16296(7)0.42987(4)0.0782(3)
S3−0.04293(7)1.15954(9)0.45992(5)0.1062(5)
S40.05758(6)1.01733(7)0.43961(4)0.0721(3)
S50.21069(6)0.92363(7)0.40802(4)0.0745(3)
O10.46017(14)1.07698(12)0.33079(9)0.0578(6)
O20.51328(14)0.99620(14)0.42124(10)0.0638(6)
H20.48560.95700.42670.096*
O30.40043(13)0.86555(12)0.41801(8)0.0499(5)
O40.39416(16)0.93281(12)0.32067(8)0.0574(6)
H40.40400.97820.31500.086*
C10.53234(19)1.06803(15)0.29898(12)0.0466(7)
C20.52000(19)1.04000(17)0.24921(12)0.0484(7)
C30.5928(2)1.03149(19)0.21806(13)0.0556(8)
H30.58641.01400.18440.067*
C40.6744(2)1.0487(2)0.23647(14)0.0577(8)
H4A0.72231.04430.21490.069*
C50.6852(2)1.07219(18)0.28651(14)0.0557(8)
H50.74071.08180.29890.067*
C60.6138(2)1.08206(17)0.31940(13)0.0493(7)
C70.6293(2)1.10263(19)0.37564(14)0.0622(9)
H7A0.67261.14270.37770.075*
H7B0.57611.12220.39050.075*
C80.6592(2)1.03458(19)0.40615(12)0.0529(7)
C90.7474(2)1.0196(2)0.41321(13)0.0632(9)
H90.78811.05380.40020.076*
C100.7752(2)0.9551(2)0.43918(14)0.0662(10)
H100.83410.94620.44370.079*
C110.7158(2)0.9041(2)0.45837(13)0.0620(9)
H110.73520.86070.47560.074*
C120.6268(2)0.9158(2)0.45272(12)0.0533(7)
C130.5995(2)0.98151(19)0.42665(12)0.0505(7)
C140.5622(2)0.8582(2)0.47303(13)0.0607(8)
H14A0.51110.88500.48530.073*
H14B0.58740.83100.50200.073*
C150.5360(2)0.80123(19)0.43190(13)0.0540(8)
C160.5915(2)0.7417(2)0.41828(15)0.0676(10)
H160.64280.73500.43650.081*
C170.5720(3)0.6928(2)0.37869(17)0.0736(11)
H170.60890.65220.37130.088*
C180.4983(2)0.70339(19)0.34972(15)0.0639(9)
H180.48710.67110.32200.077*
C190.43994(19)0.76204(17)0.36149(13)0.0511(7)
C200.45978(19)0.80813(16)0.40398(12)0.0464(7)
C210.3614(2)0.77487(19)0.32779(13)0.0570(8)
H21A0.33460.72580.32050.068*
H21B0.31970.80570.34660.068*
C220.38191(18)0.81403(18)0.27750(12)0.0506(7)
C230.3839(2)0.7740(2)0.23143(16)0.0686(10)
H230.37240.72170.23160.082*
C240.4025(2)0.8096(3)0.18558(15)0.0726(11)
H240.40410.78140.15510.087*
C250.4189(2)0.8879(2)0.18478(14)0.0645(9)
H250.43130.91190.15360.077*
C260.41713(18)0.93040(19)0.22966(12)0.0511(7)
C270.39856(17)0.89297(17)0.27589(12)0.0454(7)
C280.4314(2)1.01632(19)0.22848(14)0.0575(8)
H28A0.38681.04100.24890.069*
H28B0.42571.03430.19320.069*
C290.4127(2)1.14773(19)0.32570(16)0.0661(10)
H29A0.41481.16550.29020.079*
H29B0.43811.18680.34760.079*
C300.3208(2)1.1331(2)0.34143(16)0.0683(10)
H30A0.29451.09690.31780.082*
H30B0.28811.18040.34000.082*
C310.2064(2)1.0823(3)0.41640(14)0.0649(9)
C320.1661(2)1.0144(2)0.42095(13)0.0608(9)
C330.0468(2)1.1158(3)0.44374(14)0.0745(12)
C340.2769(2)0.9074(2)0.46489(13)0.0633(9)
H34A0.30940.95340.47290.076*
H34B0.24000.89570.49410.076*
C350.3385(2)0.8419(2)0.45553(14)0.0604(9)
H35A0.36750.82810.48740.072*
H35B0.30690.79750.44310.072*
C360.8656(3)0.6406(3)0.2943(2)0.0944(15)
H36A0.89090.58980.29620.113*
H36B0.89650.67320.31840.113*

Source of materials

A suspension of 25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene [4] (1.9 g, 3 mmol) and bis(tetraethylammonium) bis(1,3-dithiole-2-thione-4,5-dithiol)zincate [5] (1.5 g, 2.1 mmol) was refluxed for 20 h in acetonitrile (300 mL) under a nitrogen atmosphere. After the removal of the solvent, the residue was dissolved in methylene chloride (100 mL) and washed with water, and dried over anhydrous MgSO4. The crude product was purified by silica gel column chromatography with dichloromethane/petroleum ether (2:3) to give the title compound (49% yield) as a yellow powder [6]. Single crystals were obtained by slow evaporation from a dichloromethane and petroleum ether solution at room temperature.

Experimental details

In the crystal structure, all hydrogen atoms were positioned geometrically and refined using a riding model. Methyl C—H bonds were fixed at 0.97 Å with Uiso(H) = 1.5Ueq(C). Aromatic C—H distances were set to 0.93 Å and O—H set to 0.82 Å with Uiso(H) set to 1.2Ueq for the parent atoms.

Comment

Calixarene-tetrathiafulvalene derivatives have found a widespread use in molecular recognition, as molecular devices and electron transfer area [7]. As an intermediate of calixarene-tetrathiafulvalene, the synthesis of the title compound is important for us.

The title structure contains one 25,27-(2,2′-[(2-thioxo-1,3-dithiole-4,5-diyl)disulfanediyl]diethanolate)-26,28-dihydroxycalix[4]arene and one dichloromethane molecule. As shown in the figure, the calixarene skeleton adopts a cone conformation. The molecular conformation is stabilized by two intramolecular hydrogen bond (O2—H2⋯O3 (d(H2⋯O3) =2.08 Å) and O4—H4⋯O1 (d(H4⋯O1) = 1.97 Å).

All molecular geometric parameters are in the expected ranges [8].

Acknowledgement

This work was supported by the National Natural Science Foundation of China (Grant No. 20872058, 21172105).

References

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Received: 2017-6-4
Accepted: 2017-10-10
Published Online: 2017-10-26
Published in Print: 2018-1-26

©2018 Lian-Wei Liu et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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