2,25-Dioxo-27,28-diphenyl-30-oxa-29-thia-3,10,17,24-tetra­aza­penta­cyclo­[24.2.1.112,15.04,9.018,23]triaconta-5,7,9(4),10,12,14,16,18,20,22,26,28-dodeca­ene chloro­form disolvate

Rizvan K Askerov; Vladimir V Roznyatovsky; Evgeny A Katayev; Abel M Maharramov; Victor N Khrustalev

doi:10.1107/S1600536810006173

. 2010 Feb 20;66(Pt 3):o660–o661. doi: 10.1107/S1600536810006173

2,25-Dioxo-27,28-diphenyl-30-oxa-29-thia-3,10,17,24-tetraazapentacyclo[24.2.1.1^12,15.0^4,9.0^18,23]triaconta-5,7,9(4),10,12,14,16,18,20,22,26,28-dodecaene chloroform disolvate

Rizvan K Askerov ^a,^*, Vladimir V Roznyatovsky ^b, Evgeny A Katayev ^c, Abel M Maharramov ^a, Victor N Khrustalev ^c

PMCID: PMC2983673 PMID: 21580409

Abstract

The macrocycle of the title compound, C₃₆H₂₄N₄O₃S·2CHCl₃, contains a rigid framework with the nitrogen and oxygen heteroatoms pointing in towards the center of the macrocyclic cavity. The macrocycle is essentially planar (r.m.s. deviation = 0.027 Å) except for the thiophene ring. The dihedral angle between the thiophene ring plane and the mean plane of the central macrocyclic core including all atoms except sulfur is 21.6 (1)°. Four intramolecular hydrogen bonds occur: two are between the amide hydrogen atoms and the Schiff base nitrogen atoms, while the others are between the amide hydrogen atoms and the sulfur atom of the thiophene. The two solvate chloroform molecules are bound to the carbonyl oxygen atoms of the ligand by weak C—H⋯O hydrogen bonding. In addition, the structure reveals intermolecular Cl⋯Cl close contacts [3.308 (2), 3.404 (2) and 3.280 (2) Å] between the chloroform solvate molecules. In the crystal, the macrocycles form layers parallel to (101), with an interlayer distance of 3.362 (3) Å. This short distance is determined by the stacking interactions between the amide carbonyl and imine fragments of neighboring ligands.

Related literature

For general background to biological anion–receptor interactions, see: Caltagirone & Gale (2009 ▶). For the synthesis of synthetic anion receptors, see: Aydogan et al. (2008 ▶). For related compounds, see: Sessler et al. (2005a ▶,b ▶).

Experimental

Crystal data

C₃₆H₂₄N₄O₃S·2CHCl₃
M _r = 831.40
Monoclinic,
a = 13.0957 (15) Å
b = 31.854 (3) Å
c = 8.7368 (9) Å
β = 98.857 (3)°
V = 3601.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 120 K
0.30 × 0.24 × 0.21 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.845, T _max = 0.888
29858 measured reflections
7802 independent reflections
4582 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.108
S = 1.01
7802 reflections
469 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); 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/S1600536810006173/rk2192sup1.cif

e-66-0o660-sup1.cif^{(29KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006173/rk2192Isup2.hkl

e-66-0o660-Isup2.hkl^{(381.7KB, 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
N1—H1N⋯N2	0.90	2.13	2.622 (3)	114
N1—H1N⋯S1	0.90	2.48	2.970 (3)	115
N4—H4N⋯N3	0.90	2.13	2.620 (3)	114
N4—H4N⋯S1	0.90	2.53	2.986 (3)	112
C32—H32⋯Cl6ⁱ	0.95	2.69	3.461 (3)	139
C37—H37⋯O1	1.00	2.34	3.149 (3)	137
C38—H38⋯O3	1.00	2.46	3.205 (3)	131

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

The ubiquity of anions in nature makes an understanding of biological anion–receptor interactions a topic of considerable current interest (Caltagirone & Gale, 2009). It is also inspiring the synthesis of synthetic anion receptors, systems whose potential utility could span the full spectrum of applications from separations and waste remediation to biomedical analysis and therapy (Aydogan et al., 2008). We are particularly interested in the design of rigid macrocyclic hosts for anions and use for this purpose aromatics linked by amide or imine bonds. These bonds and pyrrole rings serve as efficient coordination site for anions functioning by means of hydrogen bonds. In our previous works, it has been shown that rigid scaffold of a receptor results in a higher selectivity that the one with flexible skeleton (Sessler et al., 2005a,b). In this work, we present the new receptor bearing furan and thiophen-2,5-dicarboxamide units in one macrocycle.

The target receptor was synthesized according to the method of template synthesis using chloride anion as a template. The dialdehyde (2,5–diformylfuran) and diamine (N,N'-bis(2-aminophenyl)-3,4-diphenylthiophen-2,5-dicarboxamide) were condensed in the presence of hydrochloric acid affording hydrochloric acid salt of the macrocyclic receptor I. The HCl that was subsequently neutralized by triethylamine to give free base ligand I (Fig. 1). The single crystals of I suitable for X–ray diffraction analysis were obtained by slow crystallization from chloroform–methanol mixture.

The title compound I crystallizes as a solvate with two chloroform molecules, i. e., C₃₆H₂₄N₄O₃S^.2CHCl₃. The macrocycle I contains a rigid framework with the N1, N2, O2, N3 and N4 heteroatoms pointing in toward the center of the macrocyclic cavity (Fig. 2). It is practically planar excepting for the thiophene ring. By the intermolecular C—H···O hydrogen bond (Table 1), the phenyl group at the C3 carbon atom of the thiophene forces this ring to deviate from the plane of the central macrocyclic core passed through the C1/C4/C5/N1/C6/C7/N2/C12/C13/O2/C16/C17/N3/C18/C19/N4/C24 atoms (the dihedral angle is 21.6 (1)°. There are four internal hydrogen bonds in I. Two are between the amide NH protons and the Schiff base nitrogen atoms, while the other are between the amide NH protons and the sulfur atom of the thiophene (Table 1). The two solvate chloroform molecules are bound to the carbonyl oxygen atoms of the ligand by weak C—H···O hydrogen bonding (Table 1). In addition to these effects, the structure reveals the intermolecular Cl···Cl attractive interactions between the chloroform solvate molecules (Cl1···Cl3ⁱⁱ, Cl1···Cl4ⁱⁱⁱ and Cl2···Cl5^iv distances are 3.308 (2)Å, 3.404 (2)Å and 3.280 (2)Å, respectively). In the crystal, the macrocycles I form the layers parallel to (101), with the interlayer distance of 3.362 (3)Å (Fig. 3). This short distance is determined by the stacking interactions between amide carbonyl and imine fragments of neighboring ligands. Symmetry codes: (ii) x, -y+1/2, z-1/2; (iii) x-1, y, z; (iv) x-1, y, z+1.

Experimental

Concentrated hydrochloric acid (21.5 µl, 0.18 mmol) was added to a mixture of 2,5-diformylfuran (13 mg, 0.1 mmol) and N,N'-bis(2-aminophenyl)-3,4-diphenylthiophen-2,5-dicarboxamide (51 mg, 0.1 mmol) in 20 ml dry MeOH. The colourless clear solution was stirred for overnight at 296 K. The precipitate formed was filtrated off and suspended in 1.5 ml dry dichloromethane. Then triethylamine (25.3 µl, 0.18 mmol) was added to the suspension affording yellow clear solution, which was passed through a plug of silica gel. Evaporation of the solvent yielded 44 mg (73%) of product I. M.p. > 623 K (decomp.). Found (%): C, 72.87; H, 4.08; N, 9.43. Calcd. for C₃₆H₂₄N₄O₃S (%): C, 72.96; H, 4.08; N, 9.45. ¹H NMR (CDCl₃, 293 K): \d = 7.05–7.24 (m, 16H), 7.36 (d, 2H), 8.50 (d, 2H), 8.52 (s, 2H), 10.38 (s, 2H). ¹³C NMR (CDCl₃, 293 K): \d = 114.67, 119.41, 120.56, 123.68, 127.37, 127.54, 129.43, 130.12, 132.25, 134.41, 135.43, 135.82, 142.66, 148.52, 154.21, 157.99. Mass spectrum (MALDI–TOF), m/z (I_r, %): 593.10 [M+H]⁺.