(±)-4,12,15,18,26-Penta­hydroxy-13,17-dioxahepta­cyclo­[14.10.0.03,14.04,12.06,11.018,26.019,24]hexa­cosa-1,3(14),6(11),7,9,15,19,21,23-nona­ene-5,25-dione methanol disolvate

Maayan Gil; Joseph Almog; Faina Dubnikova; Benny Bogoslavski; Shmuel Cohen

doi:10.1107/S1600536814006643

. 2014 Apr 2;70(Pt 5):o506. doi: 10.1107/S1600536814006643

(±)-4,12,15,18,26-Pentahydroxy-13,17-dioxaheptacyclo[14.10.0.0^3,14.0^4,12.0^6,11.0^18,26.0^19,24]hexacosa-1,3(14),6(11),7,9,15,19,21,23-nonaene-5,25-dione methanol disolvate

Maayan Gil ^a, Joseph Almog ^a,^*, Faina Dubnikova ^a, Benny Bogoslavski ^a, Shmuel Cohen ^a

PMCID: PMC4011206 PMID: 24860323

Abstract

The title compound, C₂₄H₁₄O₉·2CH₃OH, displays a chair-shaped form. The two dihydroindenone ring systems are located above and below the central fused-ring system, the dihedral angles between the mean planes of dihydroindenone ring systems and the mean plane of central fused-ring system are 67.91 (5) and 73.52 (4)°, respectively. In the crystal, extensive O—H⋯O hydrogen bonds, weak C—H⋯O hydrogen bonds and C—H⋯π interactions link the molecules into a three-dimensional supramolecular architecture.

Related literature

For an isomer of the title compound possessing a cup-shaped form, see: Mahmood et al. (2011 ▶). For a related structure, see: Almog et al. (2009 ▶). graphic file with name e-70-0o506-scheme1.jpg

Experimental

Crystal data

C₂₄H₁₄O₉·2CH₄O
M _r = 510.44
Triclinic,
a = 8.8243 (13) Å
b = 10.3974 (16) Å
c = 14.348 (2) Å
α = 72.936 (3)°
β = 74.639 (2)°
γ = 75.792 (3)°
V = 1193.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.20 × 0.13 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
13982 measured reflections
5549 independent reflections
3395 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.153
S = 1.01
5549 reflections
345 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814006643/xu5780sup1.cif

e-70-0o506-sup1.cif^{(28.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006643/xu5780Isup2.hkl

e-70-0o506-Isup2.hkl^{(271.7KB, hkl)}

Click here for additional data file.^{(8.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814006643/xu5780Isup3.cml

CCDC reference: 993652

Additional supporting information: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 3

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

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O8ⁱ	0.82	1.92	2.702 (2)	160
O3—H3O⋯O5ⁱⁱ	0.82	1.91	2.725 (2)	171
O5—H5O⋯O10	0.82	1.80	2.610 (3)	171
O7—H7O⋯O1ⁱⁱⁱ	0.82	2.14	2.916 (2)	158
O9—H9O⋯O4^iv	0.82	1.95	2.751 (2)	166
O10—H10O⋯O11^iv	0.82 (1)	1.85 (2)	2.650 (4)	163 (5)
O11—H11O⋯O7	0.83 (1)	2.31 (3)	3.010 (3)	142 (4)
O11—H11O⋯O9	0.83 (1)	2.15 (3)	2.873 (3)	145 (4)
C18—H18⋯O6ⁱⁱⁱ	0.93	2.56	3.370 (3)	146
C21—H21⋯O1^v	0.93	2.57	3.231 (3)	129
C11—H11⋯Cg ^vi	0.93	2.63	3.501 (3)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

This project was supported financially by a joint grant from The Israel Atomic Energy Commission and The Israel Council of Higher Education.

supplementary crystallographic information

1. Introduction

Kim's synthesis of a novel cavitand by a one pot reaction between phloroglucinol and ninhydrin has been extended creating a new class of bowl-shaped compounds, which we have named Vasarenes (Almog et al., 2009). An isomeric form of the vasarene above, possessing a cup-shaped form has been reported in the past (Mahmood et al., 2011). Under our synthetic conditions only a chair-shaped form could be obtained. Quantum chemical DFT calculations show a small energy difference (less than 0.5 kcal/mol) between these two isomers.

2. Results and discussion

The content of the unit cell is actually the basic feature which extended itself in 3D space. It includes the two RRRR/SSSS enantiomers of I, and four methanol molecules. These two enantiomers link each other by two O(9)—H···O(4) hydrogen bonds , forming a 18-member ring centered at (0.5, 0.5, 0.5). Two methanol molecules bind each other through O(10)—H···O(11) and stabilize the dimer by two extra hydrogen bonds : O(5)—H···O(10) and O(11)—H···O(9). The same applies at the opposite side of the dimer with the other two methanol molecules. A pair of O(3)—H···O(5) hydrogen bonds, centered at (0.5, 1.0, 0.5), extend the structure in the y-direction, while a pair of O(7)—H···O(1) hydrogen bonds centered at (0.5, 0.5, 1.0) extend - in the z-direction. And finally these yz layers link themselves in the x-direction by O(1)—H···O(8) hydrogen bonds, thus completing the 3D structure. Fig. 2 describes it well.

2.1. Synthesis and crystallization

A mixture of ninhydrin (2.00 g, 11.23 mmol) and pyrogallol (0.70 g, 5.5 mmol) in acetic acid (40 ml), was stirred at 80°C for 24h. During the reaction the mixture turned brown, and a white solid precipitated. After cooling to room temperature, the solid was filtered and washed with cold acetic acid and ether. Crystallization from methanol produced colorless crystals suitable for single crystal X-ray crystallography. Yield: 1.27g, 51%, m.p. 218°C.

2.2. Refinement

Hydroxyl H atoms of methanol molecules were located in a different Fourier map and refined in riding mode with distance constraint of O—H = 0.82 (1) Å, U_iso(H) = 1.2U_eq(O). Other H atoms were placed in calculated positions with O—H = 0.82, C—H = 0.93 (aromatic) and 0.96 Å (methyl), and refined in riding mode with U_iso(H) = 1.2U_eq(C) for aromatic H atoms and 1.5U_eq(C,O) for the methyl h and other hydroxyl H atoms.