Supramolecular Structures Based on Bis(2-hydroxy-5-chlorophenyl) Sulfide and Spirobicromane with Bipyridines Qingdao Zeng,* Dongxia Wu, Chen Wang,* Hongwei Ma, Jun Lu, Caiming Liu, Shandong Xu, Yan Li, and Chunli Bai*
CRYSTAL GROWTH & DESIGN 2005 VOL. 5, NO. 5 1889-1896
Center for Molecular Science, Institute of Chemistry, The Chinese Academy of Sciences, and National Center for Nanoscience and Nanotechnology, Beijing, 100080, People’s Republic of China Received April 24, 2005;
Revised Manuscript Received July 13, 2005
ABSTRACT: Six new supramolecular structures have been prepared by bis(2-hydroxy-5-chlorophenyl) sulfide (HCS) and/or spirobicromane (SBC) with bipyridine bases 4,4′-bipyridyl (bipy), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,2bis(4-pyridyl)ethane (bipy-eta), and 4,4′-dipyridyl N,N′-dioxide (dipy-dox). These molecular complexes are (HCS)‚ (bipy) 1, (HCS)‚(dipy-ete) 2, (HCS)‚(bipy-eta) 3, (HCS)‚(dipy-dox) 4, (SBC)‚(dipy-ete) 5, and (SBC)‚(dipy-dox)‚H2O 6, respectively. The crystal structures of 1-6 have been determined by single crystal X-ray diffraction. All of these molecular complexes exhibit supramolecular structures via O-H‚‚‚N or O-H‚‚‚O hydrogen bondings. Both 1 and 2 form interestingly [2 + 2] macrocyclic structures, whose sizes are ca. 12.495(6) Å × 5.087(6) Å and 14.774(6) Å × 5.300(6) Å, respectively. Compounds 3 and 5 form one-dimensional zigzag chain structures. Compounds 4 and 6 form two-dimensional double helices. These results demonstrate that by changing the guest molecule, we can obtain different hydrogen-bonded supramolecular structures through different interactions. Introduction Crystal engineering is of general interest in chemistry and materials science because of their potential applications, such as in magnetism, catalysis, molecular recognition, ion exchange, small molecule inclusion, nonlinear optics, molecular sensing, and, in general, the rational design of new materials.1-12 One of the major goals of crystal engineering is targeted at the predictable assembly of molecular species into extended architectures.12 During the past few decades, much effort has been given to explore self-assembled supramolecular complexes. A number of supramolecular architectures have been successfully designed and synthesized through self-assembly from different components by noncovalent, multiple intermolecular interaction.13-21 The binary or host-guest approach is a powerful strategy for supramolecular synthesis and crystal design.22,23 In the binary approach, the functionalities required for supramolecular structure and function are distributed over two molecules. Hydrogen bonding is the master key in crystal engineering, supramolecular chemistry, and biological recognition. The directional nature of hydrogen bonds is exploited in the organized self-assembly of molecules in solution and solid state and offers the unique opportunity for exploitation in noncovalent organic synthesis.24-26 Among many examples, the hydrogen bonding between hydroxy and pyridyl is a useful and powerful organizing force and has been utilized for the formation of supramolecules.27 To investigate the effect of conformation of guest molecule on an assembly, our design strategy was to create different supramolecular structures based on * To whom correspondence should be addressed. Tel: +86-1082614350. Fax: +86-10-82614350. E-mail:
[email protected], wangch@ iccas.ac.cn, and
[email protected].
host-guest interactions. This strategy leads us to use the change of flexibility, length, and symmetry of the guest molecule. As a result, we have used the rigid guest molecules viz. 4,4′-bipyridyl (bipy) and 1,2-di(4-pyridyl)ethylene (dipy-ete) and the flexible guest molecules viz. 1,2-bis(4-pyridyl)ethane (bipy-eta) and 4,4′-dipyridyl N,N′-dioxide (dipy-dox) to organize a class of materials containing diverse architectures and functions. Indeed, these different guest molecules act as a self-recognition motif forming host-guest interactions with another host molecule, and they are adequate to achieve directionally controlled aggregation in the solid state. Bipyridines can be used as precursors for helical assembly,28 chiral molecular recognition,29,30 luminescent devices,31,32 and other applications in photonics and optoelectronics33,34 and electrochemistry.35 Our laboratory reported recently a polymeric supramolecular structure by self-assembling of 4,4′-(9fluorenylidene)diphenol and 4,4′-cyclohexylidenebisphenol with bipyridines via O-H‚‚‚N or O-H‚‚‚O hydrogen bonding.36 These molecular complexes exhibit the double helices, infinite honeycomb-like architectures, brick supramolecular structures, the X-shaped supramolecular structures, and single-strand infinite helix. In continuation of this work, we wish to report here the syntheses and X-ray crystal structures of six new supramolecular complexes based on bis(2-hydroxy-5chlorophenyl) sulfide (HCS) and/or spirobicromane (SBC) with bipyridine bases bipy, dipy-ete, bipy-eta, and dipydox. This is an excellent opportunity to elucidate the difference in the formation of novel topologies in these six complexes. The structures of HCS and SBC are shown in Chart 1. To the best of our knowledge, the crystal structures of HCS and SBC have, so far, not been described.
10.1021/cg0501783 CCC: $30.25 © 2005 American Chemical Society Published on Web 08/11/2005
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Table 1. Crystallographic Data for 1-6 cocrystal
1
2
3
4
5
6
formula Mr crystal size (mm3) crystal system space group T (K) a (Å) b (Å) c (Å) R (°) β (°) γ (°) Z volume (Å3) Dcalcd (g cm-3) µ (mm-1) 2θ scan range (°) range h range k range l reflns collected unique reflns observed reflns goodness-of-fit R1, wR2 [I > 2σ(I)]
C22H16Cl2N2O2S 443.33 0.69 × 0.20 × 0.03 monoclinic P2(1)/c 293(2) 14.923(3) 14.369(3) 9.6105(19) 90 93.77(3) 90 4 2056.3(7) 1.432 0.439 2.74-54.96 -19 to 19 -18 to 16 -11 to 12 13907 4650 1613 0.973 0.0677, 0.1550
C24H18Cl2N2O2S 469.36 0.78 × 0.33 × 0.21 monoclinic P2(1)/c 293(2) 9.7293(19) 17.198(3) 13.894(3) 90 104.98(3) 90 4 2245.8(8) 1.388 0.406 3.84-54.96 -12 to 12 -22 to 22 -18 to 17 20668 5132 3270 1.028 0.0497, 0.1271
C24H20Cl2N2O2S 471.38 0.78 × 0.27 × 0.14 orthorhombic Pna2(1) 293(2) 23.188(5) 12.378(3) 7.9602(16) 90 90 90 4 2284.8(8) 1.370 0.399 3.52-54.96 0 to 30 -16 to 15 0 to 10 18524 2775 2087 1.018 0.0379, 0.1033
C22H16Cl2N2O4S 475.33 0.80 × 0.36 × 0.22 triclinic P1h 293(2) 7.6461(15) 9.5667(19) 14.891(3) 85.90(3) 89.07(3) 70.81(3) 2 1026.1(4) 1.539 0.452 2.74-54.96 -8 to 9 -11 to 12 -19 to 19 9617 4663 3987 0.966 0.0402, 0.1150
C33H34N2O4 522.62 0.66 × 0.48 × 0.43 monoclinic P2(1)/c 293(2) 10.536(2) 24.036(5) 11.377(2) 90 101.09(3) 90 4 2827.4(10) 1.228 0.081 3.38-54.88 -12 to 13 -30 to 31 -14 to 14 21188 5679 2946 1.028 0.0509,0.1083
C31H34N2O7 546.59 0.63 × 0.42 × 0.08 monoclinic P2(1)/c 293(2) 16.274(3) 10.564(2) 16.094(3 90 92.52(3) 90 4 2764.2(10) 1.309 0.093 2.50-54.96 -21 to 21 -13 to 14 -19 to 20 25052 6266 3115 0.984 0.0487,0.1052
Chart 1
Table 2. Hydrogen Bond Metrics cocrystal
D-H‚‚‚A
1
O(1)-H‚‚‚N(2)#1 O(2)-H‚‚‚N(1) O(1)-H‚‚‚N(2)#1 O(2)-H‚‚‚N(1)#2 O(1)-H‚‚‚N(1)#1 O(2)-H‚‚‚N(2)#2 O(1)-H‚‚‚O(4)#1 O(2)-H‚‚‚O(3)#2 O(4)-H‚‚‚N(1)#1 O(1)-H‚‚‚O(5)#1 O(4)-H‚‚‚O(6)#2
2 3 4 5 6
Experimental Section All materials (including HCS and SBC) were obtained from commercial suppliers (Acros Organics and Tokyo Kasei Kogyo Co., Ltd.) and used without further purification. General Synthesis of 1-6. An ethanolic solution of bipyridine base (0.1 mmol) was slowly added to a 20 mL ethanolic solution of HCS (28.7 mg, 0.1 mmol) and/or SBC (34.0 mg, 0.1 mmol) with stirring for 2 h at room temperature, and colorless crystals of 1-6 were obtained by slow evaporation of the solvent after a week. (HCS)‚(bipy) 1. Yield: 40.3 mg, 91%. Anal. calcd % (found %) for C22H16Cl2N2O2S: C, 59.60 (59.73); H, 3.64 (3.70); N, 6.32 (6.40). (HCS)‚(dipy-ete) 2. Yield: 42.2 mg, 90%. Anal. calcd % (found %) for C24H18Cl2N2O2S: C, 61.42 (61.33); H, 3.87 (3.95); N, 5.97 (5.91). (HCS)‚(bipy-eta) 3. Yield: 39.1 mg, 83%. Anal. calcd % (found %) for C24H20Cl2N2O2S: C, 61.15 (61.18); H, 4.28 (4.23); N, 5.94 (5.88). (HCS)‚(dipy-dox) 4. Yield: 40.4 mg, 85%. Anal. calcd % (found %) for C22H16Cl2N2O4S: C, 55.59 (55.51); H, 3.39 (3.43); N, 5.89 (5.83). (SBC)‚(dipy-ete) 5. Yield: 46.0 mg, 88%. Anal. calcd % (found %) for C33H34N2O4: C, 75.84 (75.79); H, 6.56 (6.58); N, 5.36 (5.41). (SBC)‚(dipy-dox)‚H2O 6. Yield: 48.7 mg, 89%. Anal. calcd % (found %) for C31H34N2O7: C, 68.12 (68.23); H, 6.27 (6.21); N, 5.13 (5.20).
d(D-H) d(H‚‚‚A) (Å) (Å) 0.82(2) 0.82(2) 0.82(2) 0.82(2) 0.82(2) 0.82(2) 0.82(2) 0.82(2) 0.82(2) 0.82(3) 0.82(3)
2.08(2) 2.00(2) 2.02(2) 2.01(2) 1.89(3) 1.92(3) 1.82(3) 1.76(3) 1.92(3) 1.84(3) 1.87(3)
d(D‚‚‚A) (Å)
