Int. J. Mol. Sci. 2007, 8(3), 241-258; doi:10.3390/i8030241

Articles
Crystal Engineering Based on Polymeric Hydrogen-Bonded Supramolecules by Self-Assembling of 9, 10-Bis(3,5-dihydroxyphenyl)anthracene and 2,2′,4,4′-Tetrahydroxybenzophenone with Bipyridines
Xiaokang Li 1, Lvyin Zhen 1, Yulan Fan 1, Xiaolin Fan 1,* and Qingdao Zeng 2,*
1
Key laboratory of organo-pharmaceutical chemistry jiangxi province, Gannan Normal University, Ganzhou, 341000, JiangXi, People’s Republic of China
2
Center for Molecular Science, Institute of Chemistry, The Chinese Academy of Sciences, Beijing, 100080, People’s Republic of China
*
Author to whom correspondence should be addressed. E-mail: fanxl2002@yahoo.com.cn and stmzqd@iccas.ac.cn
Received: 14 February 2007 / Accepted: 1 March 2007 / Published: 16 March 2007

Abstract

: 9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) are crystallized with bipyridine bases 4,4′-bipyridyl (bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4′-dipyridyl sulfide (dipy-sul), and 4,4′-dipyridyl disulfide (dipy-dis) to afford molecular complexes (BDHA)·(bipy)21, (BDHA) · (bipy-eta)22, (BDHA)0.5· (dipy-pra) ·CH3CH2OH 3, (BDHA)0.5· (dipy-sul) ·H2O 4, (BDHA)0.5· (dipy-dis) ·CH3CH2OH 5 and (THB) · (dipy-ete)2·H2O 6. The crystal structures of 16 have been determined by single-crystal X-ray diffraction. All these molecular complexes exhibit polymeric supramolecular structures via O–H· · ·N or O–H· · ·O hydrogen-bonding. 1 and 2 form infinitely rectangular macrocycles linked with one another, whose sizes are ca.12.477 å × 4.802 å and ca.14.575 å × 4.809 å, respectively. 3, 5 and 6 form the one-dimensional zigzag chain structure. 4 forms a ladder structure, and two dipy-sul molecules were included in a frame.
Keywords:
Crystal Engineering; crystal structures; polymeric supramolecular structurer; hydrogen-bonding

1. Introduction

Crystal engineering has attracted a great deal of interest 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 [111]. During past few decades, a number of supramolecular architectures have been successfully designed and synthesized through self-assembly from different components by noncovalent, multiple intermolecular interaction [1214]. 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 [1517]. Among many examples, hydrogen bonding between hydroxy and pyridyl is a useful and powerful organizing force and has been utilized for the formation of supramolecules [1828].

We have recently studied the supramolecular chemistry based on 4, 4′-(9-fluorenylidene)diphenol, 4, 4′-cyclohexylidenebisphenol, bis(2-hydroxy-5-chlorophenyl) sulfide, spirobicromane and adamantane derivatives with bipyridines via O–H· · ·N or O–H· · ·O hydrogen-bonding [2931]. We will report herein the preparation, and crystal structures of six related acid-base cocrystals based on 9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) with bipyridine bases 4,4′-bipyridyl (bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4′-dipyridyl sulfide (dipy-sul), and 4,4′-dipyridyl disulfide (dipy-dis). This provides an opportunity to elucidate the difference in the formation of novel topologies in these six cocrystals. The structures of 9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) are shown in Chart 1. BDHA is a host system, which has guest-removal, -addition, -exchange properties [3234], and THB is widely used as an ultraviolet protecting agent [35,36]. Each BDHA and THB molecule has four hydroxy groups, and one bipyridine molecule has two N atoms. Self-assembly via O–H· · ·N between BDHA or THB and bipyridine in EtOH was carried out. We anticipated that 1-D supramolecular hydrogen-bonded polymer would be formed. With this in mind, we prepared six polymeric hydrogen-bonded supramolecules by self-assembling of BDHA or THB with 4,4′-bipyridyl (bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4′-dipyridyl sulfide (dipy-sul), and 4,4′-dipyridyl disulfide (dipy-dis), respectively.

2. Results and Discussion

Synthesis

BDHA (1mmol) and/or THB (1mmol) can be reacted with bipyridines (2mmol) in ethanolic solution at room temperature. Colorless crystals were obtained by slow evaporation of the solvent after a week. The product was (BDHA) · (bipy)21, (BDHA) · (bipy-eta)22, (BDHA)0.5· (dipy-pra) ·CH3CH2OH 3, (BDHA)0.5· (dipy-sul) ·H2O 4, (BDHA)0.5· (dipy-dis) ·CH3CH2OH 5 and (THB) · (dipy-ete)2·H2O 6, respectively.

Crystal Structure of (BDHA) · (bipy)2 1

Single crystals of 1 (Figure 1) were obtained from ethanol solution after slow evaporation of the solvent at ambient conditions and examined using single-crystal X-ray diffraction method. It gave a triclinic crystal lattice with a P-1 space group. Selected crystal data and structural refinement parameters of 1 are given in Table 1 and hydrogen bond metrics are given in Table 2.

The crystal structure of 1 is shown in Figure 1a. The crystal consists of only chain frameworks without crystal solvent. The asymmetric unit of 1 consists of one molecules of BDHA and four equivalent halves of bipy formimg four different BDHA/bipy heterodimers. One BDHA molecule is alternatively linked with four bipy molecules through four intermolecular O–H· · ·N hydrogen-bondings, thus stacking in an alternating pattern of AB2AB2AB2. The four H atoms in OH groups of BDHA bond to N atoms of bipy molecules to form four intermolecular O–H· · ·N hydrogen-bondings. Figure 1b shows the crystal packing of 1 down the a axis and that 1-D supramolecular polymers are packed in a columnar manner to form infinitely rectangular macrocycles, where the neighboring two bipy molecules are nearly parallel to each other. These macrocycles are linked with one another and their sizes are ca.12.477 Å × 4.802 Å. In addition the neighboring macrocycles are also parallel to each other.

Crystal Structure of (BDHA) · (bipy-eta)2 2

Single crystals of 2 (Figure 2) were grown from ethanol solution by slow evaporation at room temperature and examined using single-crystal X-ray diffraction method. A triclinic crystal lattice with a P-1 space group is identified. Selected crystal data and structural refinement parameters of 2 are given in Table 1 and hydrogen bond metrics are given in Table 2.

The crystal structure of 2 is similar to that of 1 and they belong to the same space group (Table 1). Figure 2a shows the crystal structure of 2. The asymmetric unit of 2 also consists of one molecules of BDHA and four equivalent halves of bipy-eta formimg four different BDHA/bipy-eta heterodimers. One BDHA molecule is alternatively linked with four bipy-eta molecules through four intermolecular O–H· · ·N hydrogen-bondings, thus stacking in an alternating pattern of AB2AB2AB2. Figure 2a also shows the linear geometry with the chain frame bridged by bipy-eta. The four hydrogens in OH groups of BDHA bond to N atoms of bipy-eta molecules to form four intermolecular O–H· · ·N hydrogenbondings. Figure 2b shows the crystal packing of 2 down the a axis. Seen from the direction of the a axis, the crystal packing also seems to form infinitely rectangular macrocycles linked with one another, with sizes ca. 14.575 Å × 4.809 Å. The macrocyclic sizes of 2 are bigger than those of 1 because bipy-eta is longer than bipy. In each macrocycle, the neighboring two bipy-eta molecules are nearly parallel to each other. Additionally, the neighboring macrocycles have a parallel orientation.

Crystal Structure of (BDHA)0.5· (dipy-pra) ·CH3CH2OH 3

Single crystals of 3 (Figure 3) were obtained from ethanol solution after slow evaporation of the solvent at ambient conditions and examined using single-crystal X-ray diffraction method. It is associated with a triclinic crystal lattice with a P-1 space group. Selected crystal data and structural refinement parameters of 3 are given in Table 1 and hydrogen bond metrics are given in Table 2.

Figure 3a shows the geometry with the chain matrix bridged by dipy-pra and EtOH. One BDHA molecule is alternatively linked with two dipy-pra molecules and two EtOH molecules through O– H· · ·N and O–H· · ·O hydrogen-bondings, respectively. Figure 3b shows the crystal packing of 3 down the a axis. Three sorts of hydrogen-bondings form in the crystal packing of 3: Two H atoms in two OH groups of one BDHA molecule bond to two N atoms of two dipy-pra molecules to form two O–H· · ·N hydrogen-bondings; Two H atoms in the other two OH groups of the BDHA molecule bond to two O atoms of two EtOH molecules to form two O–H· · ·O hydrogen-bondings. The hydrogen in OH group of the EtOH molecule bonds to N of another dipy-pra molecule to form one O–H· · ·N hydrogen-bonding. This arrangement leads to one-dimensional zigzag chain structure.

Crystal Structure of (BDHA)0.5· (dipy-sul) ·H2O 4

Single crystals of 4 (Figure 4) were grown from ethanol solution after slow evaporation of the solvent at ambient conditions and examined using singlecrystal X-ray diffraction method. It is identified as a monoclinic crystal lattice with a C2/c space group. Selected crystal data and structural refinement parameters of 4 are given in Table 1 and hydrogen bond metrics are given in Table 2.

Figure 4a shows the geometry with the chain framework bridged by dipy-sul and H2O. One BDHA molecule is alternatively linked with two dipy-sul molecules and two H2O molecules through O–H· · ·N and O–H· · ·O hydrogen-bondings, respectively. Figure 4b shows the crystal packing of 4 down the c axis. Four sorts of hydrogen-bondings form in the crystal packing of 4: Two H atoms in two OH groups of one BDHA molecule bond to two N atoms of two dipy-sul molecules to form two O–H· · ·N hydrogen-bondings; Two H atoms in the other two OH groups of the BDHA molecule bond to two O atoms of two H2O molecules to form two O–H· · ·O hydrogen-bondings; One hydrogen of the H2O molecule bonds to one O atom in OH group of BDHA to form O–H· · ·O hydrogen-bonding; The another hydrogen of H2O bonds to N of dipy-sul molecule to form O–H· · ·N hydrogen-bonding. This arrangement leads to a ladder structure, and two dipy-sul molecules were included in a frame.

Crystal Structure of (BDHA)0.5· (dipy-dis) ·CH3CH2OH 5

Single crystals of 5 (Figure 5) were grown from ethanol solution after slow evaporation of the solvent at ambient conditions and examined using single-crystal X-ray diffraction method. A monoclinic crystal lattice with a P2(1)/c space group is identified. Selected crystal data and structural refinement parameters of 5 are given in Table 1 and hydrogen bond metrics are given in Table 2.

Figure 5a shows the geometry with the chain frame bridged by dipy-dis and EtOH. It is noteworthy that crystals 3 and 5 belong to two different space groups (Table 1). Nevertheless, they have very similar patterns of molecular packing. One BDHA molecule is alternatively linked with two dipy-dis molecules and two EtOH molecules through O–H· · ·N and O–H· · ·O hydrogen-bondings, respectively. Figure 5b shows the crystal packing of 5 down the a axis. Three sorts of hydrogen-bondings form in the crystal packing of 5: Two H atoms in two OH groups of one BDHA molecule bond to two N atoms of two dipy-dis molecules to form two O–H· · ·N hydrogen-bondings; Two H atoms in the other two OH groups of the BDHA molecule bond to two O atoms of two EtOH molecules to form two O–H· · ·O hydrogen-bondings; The hydrogen in OH group of the EtOH molecule bonds to N of another dipy-dis molecule to form one O–H· · ·N hydrogen-bonding. This arrangement leads to one-dimensional zigzag chain structure.

Crystal Structure of (THB) · (dipy-ete)2·H2O 6

Single crystals of 6 (Figure 6) were grown from ethanol solution after slow evaporation of the solvent at ambient conditions and examined using singlecrystal X-ray diffraction method. It belongs to a triclinic crystal lattice with a P-1 space group. Selected crystal data and structural refinement parameters of 6 are given in Table 1 and hydrogen bond metrics are given in Table 2.

The crystal structure of 6 is shown in Figure 6a. One THB molecule is alternatively linked with two dipy-ete molecules and one H2O molecule through O–H· · ·N and O–H· · ·O hydrogen-bondings, respectively. Figure 6b shows the crystal packing of 6 down the a axis. Four sorts of hydrogen-bondings form in the crystal packing of 6: Two H atoms in two OH groups of one THB molecule bond to two N atoms of two dipy-ete molecules to form two O–H· · ·N hydrogen-bondings; The H atom in the third OH group of the THB molecule bonds to the O atom of one H2O molecule to form one O–H· · ·O hydrogen-bonding; The H atom in the fourth OH group of the THB molecule bonds to the O atom in carbonyl group of the THB molecule to form the intramolecular hydrogen-bonding. The neighboring two dipy-ete molecules have a parallel orientation. This arrangement leads to one-dimensional zigzag chain structure, and there is one independent dipy-ete molecule along the zigzag chain. In addition the dihedral angle of two six membered aromatic rings in THB molecule is ca. 44º, which is in agreement with the published value [35,36].

The results of the X-ray structural studies involving host compound BDHA in 15 showed one common feature: the conformation was sustained by BDHA in all five structures where the planes of the anthracene backbone and the two phenolic units are twisted nearly perpendicular to each other, and the two phenolic units are nearly parallel to each other (Figures. 1 and 5) [[3234]].

For the BDHA molecule, by changing the guest molecule, we can obtain either structurally similar or different supramolecular hydrogen-bonded polymers through interactions of host-guest systems. The conformations of the bipyridines play an important role in the assembly processes. Both bipy and bipy-eta are linear molecules, 1 and 2 form infinitely rectangular macrocycles, whereas dipy-pra, dipy-sul and dipy-dis are V-shaped molecules [the N(1)C(25)N(2) in dipy-pra, N(1)S(1)N(2) in dipy-sul and N(1)S(1)N(2) angles in dipy-dis are 130º, 110º and 105º, respectively] and more flexible than bipy and bipy-eta, 3 and 5 easily form the one-dimensional zigzag chain structure, and 4 forms a ladder structure. For the THB molecule, although dipy-ete is also a linear molecule, it is unfavourable for 6 to form infinitely rectangular macrocycles, but rather a one-dimensional zigzag chain structure because of the intramolecular hydrogen-bonding that occurs in the THB molecule. Such studies are important to crystal engineering. It is possible to obtain novel topologies and extend the study to combinatorial libraries of intermolecular interactions for the exploration of formation of various types of host-guest systems, by changing the guest molecule. Some related experiments are in progress.

3. Conclusions

In this work, 9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) are used to construct supramolecular architecture based on crystal engineering. Either similar or different supramolecular hydrogen-bonded polymers would be formed through self-assembly via O–H· · ·N or O–H· · ·O hydrogen-bonding between BDHA and THB with bipyridines. Self-assembling of BDHA with bipy forms infinitely rectangular macrocycles linked with one another, whose sizes are 12.477 å × 4.802 å Self-assembling of BDHA with bipy-eta also forms infinitely rectangular macrocycles linked with one another, whose sizes are 14.575 å × 4.809 å Self-assembling of BDHA with dipy-pra forms the one-dimensional zigzag chain structure. Self-assembling of BDHA with dipy-sul forms a ladder structure. Self-assembling of BDHA with dipy-dis forms the one-dimensional zigzag chain structure. Self-assembling of THB with dipy-ete forms the one-dimensional zigzag chain structure.

4. Experimental Section

All materials (including BDHA and THB) were obtained from commercial suppliers (ACROS ORGANICS and TOKYO KASEI KOGYO CO., LTD) and used without further purification.

4.1. Syntheses of cocrystals 1–6

(BDHA) · (bipy)2 1

An ethanolic solution of 4,4′-bipyridine (31.2 mg, 0.2 mmol) was slowly added to a 20 ml ethanolic solution of 9, 10-bis(3,5-dihydroxyphenyl)anthracene (39.4 mg, 0.1mmol) with stirring for 2 hours at room temperature, colorless crystals were obtained by slow evaporation of the solvent after a week. Anal. calcd % (found %) for C46H34N4O4: C, 78.17 (78.41); H, 4.85 (4.72).

(BDHA) · (bipy-eta)2 2

An ethanolic solution of 1,2-bis(4-pyridyl)ethane (36.8 mg, 0.2 mmol) was slowly added to a 20 ml ethanolic solution of 9, 10-bis(3,5-dihydroxyphenyl)anthracene (39.4 mg, 0.1 mmol) with stirring for 2 hours at room temperature, colorless crystals were obtained by slow evaporation of the solvent after a week. Anal. calcd % (found %) for C50H42N4O4: C, 78.72 (78.94); H, 5.55 (5.71).

(BDHA)0.5· (dipy-pra) ·CH3CH2OH 3

An ethanolic solution of 1,3-di(4-pyridyl)propane (39.6 mg, 0.2 mmol) was slowly added to a 20 ml ethanolic solution of 9, 10-bis(3,5-dihydroxyphenyl)anthracene (39.4 mg, 0.1 mmol) with stirring for 2 hours at room temperature, colorless crystals were obtained by slow evaporation of the solvent after a week. Anal. calcd % (found %) for C28H29N2O3 : C, 76.17 (76.06); H, 6.62 (6.76).

(BDHA)0.5· (dipy-sul) ·H2O 4

An ethanolic solution of 4,4′-dipyridyl sulfide (37.6 mg, 0.2 mmol) was slowly added to a 20 ml ethanolic solution of 9, 10-bis(3,5-dihydroxyphenyl)anthracene (39.4 mg, 0.1 mmol) with stirring for 2 hours at room temperature, colorless crystals were obtained by slow evaporation of the solvent after a week. Anal. calcd % (found %) for C23H19N2O3S : C, 68.47 (68.60); H, 4.75 (4.65).

(BDHA)0.5· (dipy-dis) ·CH3CH2OH 5

An ethanolic solution of 4,4′-dipyridyl disulfide (44.0 mg, 0.2 mmol) was slowly added to a 20 ml ethanolic solution of 9, 10-bis(3,5-dihydroxyphenyl)anthracene (39.4 mg, 0.1 mmol) with stirring for 2 hours at room temperature, colorless crystals were obtained by slow evaporation of the solvent after a week. Anal. calcd % (found %) for C25H23N2O3S2 : C, 64.72 (64.56); H, 5.00 (4.95).

(THB) · (dipy-ete)2·H2O 6

An ethanolic solution of 1,2-di(4-pyridyl)ethylene (36.4 mg, 0.2 mmol) was slowly added to a 20 ml ethanolic solution of 2,2′,4,4′-tetrahydroxybenzophenone (24.6 mg, 0.1 mmol) with stirring for 2 hours at room temperature, colorless crystals were obtained by slow evaporation of the solvent after a week. Anal. calcd % (found %) for C37H32N4O6 : C, 70.63 (70.50); H, 5.13 (5.26).

4.2. X-ray Crystallographic Analyses

The diffraction data for 1–6 were collected on a Rigaku RAXISRAPID automated diffractometer at room temperature using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The structure was solved by direct methods and successive difference maps (SHELXS 97) [37] and refined by full-matrix least squares on F2 using all uniqe data (SHELXL 97) [38]. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms in these structures were placed in the ideal positions or located from the differiential Fourier map. Crystal data and experimental details for the crystals of 1–6 are given in Table 1. Hydrogen bond metrics are given in Table 2. All bond distances and angles of the molecule are normal [1828].

Ijms 08 00241f1 200
Figure 1. (a) The crystal structure of 1. Hydrogens were omitted for clarity. (b) The crystal-packing of 1 viewed down the a axis. Notice that 1 leads to infinitely rectangular macrocycles, whose sizes are ca. 12.477 Å × 4.802 Å.

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Figure 1. (a) The crystal structure of 1. Hydrogens were omitted for clarity. (b) The crystal-packing of 1 viewed down the a axis. Notice that 1 leads to infinitely rectangular macrocycles, whose sizes are ca. 12.477 Å × 4.802 Å.
Ijms 08 00241f1 1024
Ijms 08 00241f2 200
Figure 2. (a) The crystal structure of 2. Hydrogens were omitted for clarity. (b) The crystal-packing of 2 viewed down the a axis. Notice that 2 leads to infinitely rectangular macrocycles, with sizes ca. 14.575 Å × 4.809 Å.

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Figure 2. (a) The crystal structure of 2. Hydrogens were omitted for clarity. (b) The crystal-packing of 2 viewed down the a axis. Notice that 2 leads to infinitely rectangular macrocycles, with sizes ca. 14.575 Å × 4.809 Å.
Ijms 08 00241f2 1024
Ijms 08 00241f3 200
Figure 3. (a) The crystal structure of 3. Hydrogens were omitted for clarity. (b) The crystal-packing of 3 viewed down the a axis. Notice that 3 leads to a zigzag structure.

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Figure 3. (a) The crystal structure of 3. Hydrogens were omitted for clarity. (b) The crystal-packing of 3 viewed down the a axis. Notice that 3 leads to a zigzag structure.
Ijms 08 00241f3 1024
Ijms 08 00241f4 200
Figure 4. (a) The crystal structure of 4. Hydrogens were omitted for clarity. (b) The crystal-packing of 4 viewed down the c axis. Notice that 4 leads to a ladder structure, and two dipy-sul molecules were included in a frame.

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Figure 4. (a) The crystal structure of 4. Hydrogens were omitted for clarity. (b) The crystal-packing of 4 viewed down the c axis. Notice that 4 leads to a ladder structure, and two dipy-sul molecules were included in a frame.
Ijms 08 00241f4 1024
Ijms 08 00241f5 200
Figure 5. (a) The crystal structure of 5. Hydrogens were omitted for clarity. (b) The crystal-packing of 5 viewed down the a axis. Notice that 5 leads to a zigzag structure.

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Figure 5. (a) The crystal structure of 5. Hydrogens were omitted for clarity. (b) The crystal-packing of 5 viewed down the a axis. Notice that 5 leads to a zigzag structure.
Ijms 08 00241f5 1024
Ijms 08 00241f6 200
Figure 6. (a) The crystal structure of 6. Hydrogens were omitted for clarity. (b) The crystal-packing of 6 viewed down the a axis. Notice that 6 leads to a zigzag structure.

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Figure 6. (a) The crystal structure of 6. Hydrogens were omitted for clarity. (b) The crystal-packing of 6 viewed down the a axis. Notice that 6 leads to a zigzag structure.
Ijms 08 00241f6 1024
Chart 1.
Ijms 08 00241f7 1024
Table Table 1. Crystallographic Data for 1–6

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Table 1. Crystallographic Data for 1–6
cocrystal123456
formulaC46H34N4O4C50H42N4O4C28H29N2O3C23H19N2O3SC25H23N2O3S2C37H32N4O6
Mr706.77762.91441.53403.46463.57628.65
Crystal size (mm3)0.35 × 0.15 × 0.100.70 × 0.40 × 0.100.50 × 0.35 × 0.150.30 × 0.25 × 0.100.60 × 0.40 × 0.350.79 × 0.70 × 0.70
Crystal systemTriclinicTriclinicTriclinicMonoclinicMonoclinicTriclinic
space groupP-1P-1P-1C2/cP2(1)/cP-1
T (K)293(2)293(2)293(2)293(2)293(2)293(2)
a (Å)9.4497(19)9.1440(18)9.1264(18)12.801(3)9.776(2)12.233(2)
b (Å)10.065(2)9.5925(19)10.107(2)12.968(3)12.530(3)12.323(3)
c (Å)10.151(2)12.159(2)15.870(3)26.107(5)19.178(4)12.721(3)
α (º)93.60(3)92.53(3)107.16(3)909068.39(3)
β (º)103.94(3)98.09(3)93.50(3)100.68(3)92.57(3)84.53(3)
γ (º)108.30(3)109.22(3)113.27(3)909063.89(3)
Z112842
Volume (Å3)879.6(3)992.4(3)1258.3(4)4258.7(15)2346.8(8)1595.9(5)
Dcalc (g cm−3)1.3341.2801.1651.2591.3121.304
μ (mm−1)0.0860.0820.0760.1780.2560.090
2θ scan range (º)4.72 – 54.964.52 – 54.965.14 – 54.65.98 – 54.965.28 – 50.063.46 – 54.94
range h−12 to 11−11 to 11−11 to 10−16 to 16−11 to 110 to 15
range k−13 to 13−12 to 12−12 to 12−16 to 16−14 to 14−13 to 15
range l−13 to 13−15 to 15−20 to 19−33 to 33−22 to 22−16 to 16
reflns collected8015775710521154341508011133
unique reflns393242325407481941276601
observed reflns206120602492161922693722
Goodness-of-fit0.8211.1831.1200.8970.9971.043
R1, wR20.0406,0.0830.0545,0.1310.0551,0.1160.0475,0.0650.0458,0.1080.0808,0.237
[I>2σ(I)]927556
Table Table 2. Hydrogen Bond Metrics

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Table 2. Hydrogen Bond Metrics
cocrystalD-H· · ·Ad(D-H)/Åd(H· · ·A)/Åd(D· · ·A)/Å<(DHA)/Symmetry
1O(1)-H· · ·N(1)0.98(2)1.80(2)2.7445(18)159.4(18)
O(2)-H· · ·N(2)#20.946(18)1.872(19)2.8165(18)175.7(16)x + 2, −y + 2, −z + 1
2O(1)-H· · ·N(1)0.99(3)1.77(3)2.742(2)164(2)
O(2)-H· · ·N(2)#21.04(3)1.68(3)2.718(2)173(2)x + 2, −y −1, −z + 2
3O(1)-H· · ·N(2)0.99(3)1.79(3)2.764(3)167(2)
O(3)-H· · ·N(1)0.93(3)1.90(3)2.818(3)174(3)
O(2)-H· · ·O(3)#20.96(4)1.76(4)2.713(2)175(3)x − 1, y − 2, z − 1
4O(1)-H· · ·N(1)1.02(3)1.73(3)2.727(3)166(2)
O(2)-H· · ·O(3)0.96(3)1.67(3)2.628(2)176(2)
O(3)-H· · ·O(1)#20.9526(16)1.8539(17)2.790(2)166.95(16)x + 1/2, y −1/2, z
O(3)-H· · ·N(2)#31.1004(17)1.765(2)2.810(3)156.71(13)x + 1, −y, z + 1/2
5O(1)-H· · ·O(3)1.00(2)1.69(3)2.683(2)171.8(2)
O(2)-H· · ·N(1)1.09(3)1.71(3)2.759(3)159.4(3)
O(3)-H· · ·N(2)#21.12(3)1.69(3)2.801(2)170.2(2)x, −y + 1/2, z + 1/2
6O(2)-H· · ·N(1)#30.82(3)1.95(3)2.765(3)170.1(2)x + 1, y − 1, z
O(3)-H· · ·N(4)0.82(3)1.85(3)2.664(2)170.3(2)
O(4)-H· · ·O(1w)0.82(3)1.82(2)2.638(2)175.3(3)
O(5)-H· · ·O(1)0.82(3)1.80(2)2.528(3)147.7(3)

Acknowledgements

The authors thank the National Natural Science Foundation (Nos. 20103008 and 20573116) and the Foundation of the Chinese Academy of Sciences for financial support.

References and Notes

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