Diethyl 6,13-dioxo-5,7,12,13b,13c,14-hexa­hydro-6H,13H-5a,6a,12a,13a-tetra­azabenz[5,6]azuleno[2,1,8-ija]benz[f]azulene-13b,13c-dicarboxyl­ate 1,2-dichloro­ethane solvate

Hong-Xia Liu; Zhi-Guo Wang

doi:10.1107/S1600536809041373

. 2009 Oct 17;65(Pt 11):o2746–o2747. doi: 10.1107/S1600536809041373

Diethyl 6,13-dioxo-5,7,12,13b,13c,14-hexahydro-6H,13H-5a,6a,12a,13a-tetraazabenz[5,6]azuleno[2,1,8-ija]benz[f]azulene-13b,13c-dicarboxylate 1,2-dichloroethane solvate

Hong-Xia Liu ^a, Zhi-Guo Wang ^b,^*

PMCID: PMC2970980 PMID: 21578341

Abstract

In the title inclusion compound, C₂₆H₂₆N₄O₆·C₂H₄Cl₂, the solvent molecule occupies a cavity inside the clip-type molecule which is based on the glycoluril skeleton with two ethyl acetate substituents on the convex face of the glycoluril system. The dihedral angle between the aromatic rings of the host is 43.59 (4)° and the centroid–centroid distance is 6.741 (5) Å. The 1,2-dichloroetane molecule adopts a gauche conformation enabling it to participate in C—H⋯π interactions with the host. The packing motif in the title compound differs from that observed in the crystal structures of the host and in the benzene solvate. The host molecules are linked into tapes by π–π stacking interactions (centroid–centroid distance = 3.733 Å) and are further assembled into layers via C—H⋯O interactions. One of the ethyl groups is disorded over two positions with site-occupancy factors of 0.702 (14) and 0.298 (14).

Related literature

For the related structures, see: Chen et al. (2007 ▶); Hof et al.,(2002 ▶); Hu et al. (2007 ▶); Isaacs & Fettinger (1999 ▶); Wang et al. (2006 ▶).

Experimental

Crystal data

C₂₆H₂₆N₄O₆·C₂H₄Cl₂
M _r = 589.46
Triclinic,
a = 8.9468 (10) Å
b = 11.1544 (13) Å
c = 15.6260 (18) Å
α = 69.257 (2)°
β = 82.688 (2)°
γ = 76.892 (2)°
V = 1418.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 292 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
10171 measured reflections
4947 independent reflections
4056 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.188
S = 1.04
4947 reflections
383 parameters
28 restraints
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536809041373/gk2232sup1.cif

e-65-o2746-sup1.cif^{(28.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041373/gk2232Isup2.hkl

e-65-o2746-Isup2.hkl^{(242.3KB, 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
C28—H28B⋯Cg2	0.97	2.55	3.476 (3)	160
C5—H5⋯O5ⁱ	0.93	2.59	3.393 (4)	145
C7—H7B⋯O5ⁱ	0.97	2.50	3.359 (3)	148
C14—H14A⋯O2ⁱⁱ	0.96	2.57	3.514 (9)	168
C14′—H14F⋯O2ⁱⁱ	0.96	2.47	3.351 (6)	153

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Symmetry codes: (i) Inline graphic ; (ii) . Cg2 is the centroid of the C21–C26 ring.

Acknowledgments

This study was financially supported by Huangshi Institute of Technology (B20083002).

supplementary crystallographic information

Comment

Molecular clips based on the glycoluril skeleton, which have a well defined geometry due to the rigidity of the fused rings, have been prepared for a wide variety of supramolecular applications, including molecular recognition (Hu et al., 2007), molecular assemblies (Hof et al., 2002), crystal engineering (Wang et al., 2006; Chen et al., 2007),

The title host compound is a kind of molecular receptor, possessing a well defined U-shaped cavity formed by the glycoluril framework with two aromatic side walls. The crystal structures of monoclinic apohost obtained from dichloroethane solution (C2/c, Z' = 1/2; Wang et al., 2006) and monoclinic benzene solvate, C₂₆H₂₆N₄O₆.0.25C₆H₆, (P2₁/c, Z' = 2; Isaacs et al., 1999) have been already reported. Here, we report the structure of a new solvate (P-1, Z' = 1), C₂₆H₂₆N₄O₆.C₂H₄Cl₂, crystallized from 1,2-dichoroethane/methanol (3:1 vol.) solution.

In the triclinic pseudopolymorph, the asymmetric unit contains one host molecule and one solvent molecule of 1,2-dichloroethane (Fig.1). There is a C-H···π interaction betweeen the host and the guest. The distance between atom H28B and Cg2 (the centroid of the C21—C26 ring) is 2.67 Å (Table 1).

As solvent molecule occupies the cavity, the title compound exhibits different packing motif than the previously known two monoclinic forms. In Isaacs structure, the molecule was kined into three-dimensional network structure by π-π stacking, C—H···π and C—H···O hydrogen-bonds. In our previously reported structure of the apohost, the ethyl group occupied the cavity with C—H···π interactions and the molecules were linked into layers to the ab plane by four pairs of C—H···O hydrogen-bonds parallel .

The title molecules are linked into tapes by π-π stacking interactions. The benzene rings Cg1 (C1—C6) in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel, with an interplanar spacing of 3.589 Å, a ring centroid separation of 3.733 Å and a centroid offset of 1.027 Å. In addition, intermolecular C—H···O (Table 1) hydrogen-bonds link molecules into two-dimensional layer structure.

Experimental

The host compound was synthesized as reported previously (Wang et al., 2006). Crystals of the title compound were obtained by slow evaporation at 293 K of 1,2-dichoroethane/methanol (vol. 3:1) solution .