Ethane-1,2-diaminium 3,4,5,6-tetra­bromo-2-(methoxy­carbon­yl)benzoate methanol solvate

Zu-Pei Liang

doi:10.1107/S1600536808038166

. 2008 Nov 22;64(Pt 12):o2416. doi: 10.1107/S1600536808038166

Ethane-1,2-diaminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate methanol solvate

Zu-Pei Liang ^a,^*

PMCID: PMC2960063 PMID: 21581384

Abstract

In the title compound, C₂H₁₀N₂ ²⁺·2C₉H₃Br₄O₄ ⁻·CH₄O, the N atoms of the ethane-1,2-diamine molecule are protonated. The crystal structure is stabilized by N—H⋯O hydrogen bonds between the ethane-1,2-diaminium cations and 3,4,5,6-tetrabromo-2-(methoxycarbonyl)bromobenzoate anions, and by O—H⋯O and N—H⋯O hydrogen bonds between the methanol solvate and both the cation and the anion. In addition, the crystal structure exhibits a C—Br⋯O halogen bond [3.20 (3) Å] and a Br⋯Br interaction [3.560 (2) Å].

Related literature

For related structures, see: Liang et al. (2006 ▶, 2007 ▶); For a review of halogen bonding, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₂H₁₀N₂ ²⁺·2C₉H₃Br₄O₄ ⁻·CH₄O
M _r = 1083.67
Monoclinic,
a = 6.456 (2) Å
b = 19.036 (7) Å
c = 26.017 (9) Å
β = 96.002 (6)°
V = 3179.7 (19) Å³
Z = 4
Mo Kα radiation
μ = 10.14 mm⁻¹
T = 298 (2) K
0.41 × 0.25 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.062, T _max = 0.221
15827 measured reflections
5585 independent reflections
3448 reflections with I > 2σ(I)
R _int = 0.083

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.145
S = 0.98
5585 reflections
367 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 1.18 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038166/lx2065sup1.cif

e-64-o2416-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038166/lx2065Isup2.hkl

e-64-o2416-Isup2.hkl^{(273.5KB, 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—H1A⋯O2ⁱ	0.89	1.87	2.748 (8)	167
N1—H1B⋯O5ⁱⁱ	0.89	2.04	2.857 (8)	153
N1—H1C⋯O6	0.89	1.86	2.734 (8)	166
N2—H2A⋯O9ⁱⁱⁱ	0.89	1.97	2.801 (9)	154
N2—H2B⋯O2ⁱⁱⁱ	0.89	1.93	2.795 (9)	163
N2—H2B⋯O3ⁱⁱⁱ	0.89	2.57	3.000 (9)	110
N2—H2C⋯O5^iv	0.89	1.90	2.747 (9)	159
O9—H9⋯O1^v	0.82	1.89	2.695 (8)	168

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

Acknowledgments

This work was supported by the Natural Science Foundation of Shandong Province (grant No. Y2007B61).

supplementary crystallographic information

Comment

1,2-Bis(tetrabromophthalimido)ethane is an important flame retardant. 2-(Methoxycarbonyl)-3,4,5,6-tetrabromobenzoic acid is the intermediate of the flame retardant. In this paper, the structure of the title compound is reported.

The asymmetric unit of the title compound contains one ethane-1,2-diaminium, two 3,4,5,6-tetrabromo-2-(methoxycarbonyl)bromobenzoate and one methanol molecule (Fig. 1). The bond lengths and angles agree with those in those similar compounds 4-phthalimidobenzoic acid N,N-dimethylformamide solvate (Liang et al., 2006) and 4-(5-Bromo-1,3-dioxoisoindolin-2-yl)benzoic acid N,N-dimethylformamide solvate (Liang et al., 2007). The dihedral angle between two benzene rings is 74.6 (2)°.

The crystal structure is stabilized by various hydrogen bonds (Fig. 2 and Table 1; symmetry code as in Fig. 2); N—H···O hydrogen bonds between the ethane-1,2-diaminium and the 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate anions, O—H···O and N—H···O hydrogen bonds between the methanol and the 3,4,5,6-tetrabromo-2-(methoxycarbonyl)bromobenzoate anions and the ethane-1,2-diaminium. The further stability comes from a weak C—Br···O halogen bond (Fig. 2) (Politzer et al., 2007); between the bromine atom and the oxygen of a neighbouring methoxy group, i.e. C13—Br8···O4^v distance of 3.20 (3) Å and a C13—Br8···O4^v angle of 156.9 (3)°, and a Br2···Br6^vi interaction at 3.560 (2) Å (Fig. 2).

Experimental

A mixture of 4,5,6,7-tetrabromoisobenzofuran-1,3-dione (46.4 g, 0.1 mol) and methanol (150 ml) was refluxed for 0.5 h. And then ethane-1,2-diamine (3 g, 0.05 mol) was added to the above solution, being mixed round for 4 h at room temperature. After filtration and the filtrate was kept at room temperature for 3 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.