Crystal structure of dimethyl 2,5-bis­[(di­phen­oxy­phosphor­yl)­oxy]cyclo­hexa-1,4-diene-1,4-di­carboxyl­ate

Lei Gao; Zongshan Ma; Hong Yan

doi:10.1107/S2056989015008658

. 2015 May 13;71(Pt 6):o401–o402. doi: 10.1107/S2056989015008658

Crystal structure of dimethyl 2,5-bis[(diphenoxyphosphoryl)oxy]cyclohexa-1,4-diene-1,4-dicarboxylate

Lei Gao ^a, Zongshan Ma ^a, Hong Yan ^a,^*

PMCID: PMC4459327 PMID: 26090189

Abstract

In the title compound, C₃₄H₃₀O₁₂P₂, which was synthesized via the esterification of dimethyl 2,5-dioxo-1,4-cyclohexanedicarboxylate with diphenyl chlorophosphate, the molecule has crystallographic inversion symmetry. The dihedral angles between the plane of the cyclohexa-1,4-diene ring and those of the two benzene rings of the substituent phosphate groups are 41.0 (1) and 89.5 (1)°, while that with the ester group is 3.1 (3)°. In the crystal, only weak intermolecular C—H⋯O hydrogen bonds are present.

Keywords: crystal structure; cyclohexa-1,4-diene; C—H⋯O hydrogen bonds

Related literature

For background information on cyclohexa-1,4-dienes, see: El-Rayyes & Al-Hajjar (1978 ▸). For the synthesis of the title compound, see: Chaignaud et al. (2008 ▸). graphic file with name e-71-0o401-scheme1.jpg

Experimental

Crystal data

C₃₄H₃₀O₁₂P₂
M _r = 692.52
Monoclinic,
a = 12.272 (10) Å
b = 10.629 (8) Å
c = 13.174 (10) Å
β = 113.644 (10)°
V = 1574 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▸) T _min = 0.960, T _max = 0.976
15948 measured reflections
3758 independent reflections
2264 reflections with I > 2σ(I)
R _int = 0.100

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.099
S = 1.00
3758 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▸); cell refinement: CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku, 2005 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015008658/zs2331sup1.cif

e-71-0o401-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008658/zs2331Isup2.hkl

e-71-0o401-Isup2.hkl^{(184.3KB, hkl)}

Click here for additional data file.^{(11.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015008658/zs2331Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

x y z . DOI: 10.1107/S2056989015008658/zs2331fig1.tif

The molecular conformation and atom numbering scheme for the title compound, with probability ellipsoids drawn at the 50% level. For symmetry code (a): −x, −y + 1, −z.

Click here for additional data file.^{(911.6KB, tif)}

. DOI: 10.1107/S2056989015008658/zs2331fig2.tif

Synthetic route for the title compound.

CCDC reference: 1057648

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C6H6O3ⁱ	0.95	2.50	3.345(4)	148
C9H9O5ⁱⁱ	0.95	2.59	3.405(4)	144
C10H10O3ⁱⁱⁱ	0.95	2.46	3.381(4)	163
C15H15BO1^iv	0.99	2.56	3.409(4)	144

Open in a new tab

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

Acknowledgments

This work was supported financially by the Key Projects in the National Science and Technology Pillar Program (No. 2012ZX10001007-008-002) and the Doctoral Fund of Innovation of Beijing University of Technology.

supplementary crystallographic information

S1. Comment

1,4-Cyclohexadiene is a useful and fundamental structural motif found in a wide range of organic materials and biologically active molecules (El-Rayyes & Al-Hajjar, 1978). The synthetic routes for the preparation of derivatives of this parent compound have been reported (Chaignaud et al., 2008) but their crystal structures were not described.

The title compound, C₃₄H₃₀O₁₂P₂, was synthesized by the esterification of dimethyl 2,5-dioxo-1,4-cyclohexanedicarboxylate with diphenyl chlorophosphate using the reported procedure of Chaignaud et al. (2008) and the structure is reported herein.

The molecule of the title compound has crystallographic inversion symmetry (Fig. 1), with dihedral angles between the cyclohexa-1,4-diene ring and the two benzene rings of the substituent phosphate group of 41.0 (1) [C1–C6] and 89.5 (1)° [C7–C12]. The ester group is essentially coplanar with the cyclohexadiene group [dihedral angle = 3.1 (3)°]. In the crystal, only weak intermolecular C—H···O hydrogen bonds are present (Table 1).

S2. Experimental

The title compound was synthesized using the basic procedure of Chaignaud et al. (2008) (Fig. 2), as follows: A solution of LiHMDS (1 M in THF, 7.9 mL) in THF (20 mL) was cooled to -78 °C under nitrogen. Subsequently, a mixture of dimethyl 2,5-dioxo-1,4-cyclohexanedicarboxylate (3.19 mmol), diphenyl chlorophosphate (6.67 mmol) and HMPA (8.90 mmol) in anhydrous THF (5 mL) were added dropwise over 5 min. The mixture was stirred at -78 °C for 1h under nitrogen and after completion of the reaction, the mixture was diluted with water (30 mL) and extracted with ethyl acetate (3×15 mL), dried with anhydrous MgSO₄ and filtered. Subsequently, the product obtained by evaporation of the solvent was recrystallized from ethyl acetate giving a white solid in 10% yield (m.p. 118–120 °C).