Bis(4-nitro­phen­yl) 1,3-phenyl­ene­dimethyl­ene dicarbonate

Syed Nawazish Ali; Sabira Begum; Mitchell A Winnik; Alan J Lough

doi:10.1107/S1600536808006132

. 2008 Mar 12;64(Pt 4):o692. doi: 10.1107/S1600536808006132

Bis(4-nitrophenyl) 1,3-phenylenedimethylene dicarbonate

Syed Nawazish Ali ^a,^b, Sabira Begum ^a, Mitchell A Winnik ^b, Alan J Lough ^b,^*

PMCID: PMC2960894 PMID: 21202084

Abstract

In the title molecule, C₂₂H₁₆N₂O₁₀, the dihedral angles between the benzene rings of the 4-nitrophenyl groups and the central benzene ring are 32.7 (1) and 34.7 (1)°, while the dihedral angle between the two benzene rings of the 4-nitrophenyl groups is 3.6 (2)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link molecules into centrosymmetric dimers.

Related literature

For related literature, see: Nawazish Ali et al. (2008 ▶).

Experimental

Crystal data

C₂₂H₁₆N₂O₁₀
M _r = 468.37
Triclinic,
a = 8.5956 (4) Å
b = 9.2367 (5) Å
c = 14.1550 (8) Å
α = 94.094 (2)°
β = 107.134 (3)°
γ = 105.674 (3)°
V = 1020.00 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 150 (1) K
0.34 × 0.20 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.808, T _max = 0.980
10107 measured reflections
4580 independent reflections
3182 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.166
S = 1.15
4580 reflections
308 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO–SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006132/cf2186sup1.cif

e-64-0o692-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006132/cf2186Isup2.hkl

e-64-0o692-Isup2.hkl^{(224.3KB, 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
C10—H10A⋯O10ⁱ	0.95	2.55	3.134 (4)	120
C15—H15B⋯O9ⁱ	0.99	2.58	3.504 (4)	155
C21—H21A⋯O7ⁱ	0.95	2.50	3.264 (3)	138

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Higher Education Commission (HEC) of Pakistan, Materials and Manufacturing Ontario (MMO), Canada, NSERC Canada and the University of Toronto for funding.

supplementary crystallographic information

Comment

For background information and relevant references see Ali et al. (2008). In the title molecule (Fig. 1) the dihedral angles between the benzene rings of the p-nitrophenyl groups and the central benzene ring are 32.7 (1) (for C9—C14) and 34.7 (1)° (for C17—C22), while the dihedral angle between the two benzene rings of the p-nitrophenyl groups is 3.6 (2)°. In the crystal structure, weak intermolecluar C—H···O hydrogen bonds link molecules into centrosymmetric dimers (Fig. 2).

Experimental

A solution of 4-nitrophenylchloroformate (14.1 g, 70 mmol) in dry dichloromethane (70 ml) was added dropwise via a 250 ml separatory funnel to a solution of 1,3-phenylenedimethanol (4.82 g, 35 mmol) in anhydrous pyridine (5.38 g, 5.5 ml, 68.0 mmol) and dry dichloromethane (20 ml) in a 250 ml round-bottom flask. A white suspension appeared which was stirred gently at room temperature for 10 h. After this time more dry dichloromethane (50 ml) was added, which dissolved the suspension and then the reaction mixture was stirred for another 6 h. It was then quenched by adding deionized water (50 ml). The reaction mixture was transferred to a separatory funnel (500 ml), and the lower organic phase was removed. The aqueous phase was washed with dichloromethane (30 ml x 3), and all the dichloromethane solutions were combined. These were then washed with deionized water (40 ml x 3), a 1.0% solution of acetic acid (50 ml x 4) and once more with deionized water (40 ml x 3), and then dried over anhydrous magnesium sulfate and filtered. After filtration, the solvent was removed by rotary evaporator. The product was dried in air overnight in a fume hood and then in a vacuum oven for 24 h at room temperature (< 1 Torr). The desired product was obtained in a moderate yield (11.4 g, 70.0%) as a white solid; the product was recrystallized by dissolving in a mixture of dichloromethane and ethanol (95%) (1:1). The reaction mixture was heated at 358 K, and filtered after 40 minutes. X-ray quality crystals were obtained after slow evaporation of the solvent at room temperature.