Propan-1-aminium 3,4,5,6-tetra­bromo-2-(meth­oxy­carbon­yl)benzoate N,N-dimethyl­formamide monosolvate

Jian Li

doi:10.1107/S1600536811016850

. 2011 May 7;67(Pt 6):o1356. doi: 10.1107/S1600536811016850

Propan-1-aminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate N,N-dimethylformamide monosolvate

Jian Li ^a,^*

PMCID: PMC3120559 PMID: 21754750

Abstract

In the anion of the title solvated molecular salt, C₃H₁₀N⁺·C₉H₃Br₄O₄ ⁻·C₃H₇NO, the dihedral angles formed by the aromatic ring and the mean planes of the carboxylate and methoxycarbonyl groups are 64.3 (3) and 75.2 (3)°, respectively. The C atoms of the propan-1-aminium cation are disordered over two sets of sites in a 0.65 (3):0.35 (3) ratio. The crystal structure is stabilized by N—H⋯O hydrogen bonds.

Related literature

For related structures, see: Li (2011a ▶,b ▶).

Experimental

Crystal data

C₃H₁₀N⁺·C₉H₃Br₄O₄ ⁻·C₃H₇NO
M _r = 627.97
Monoclinic,
a = 11.8964 (11) Å
b = 10.5198 (10) Å
c = 17.3743 (17) Å
β = 93.188 (1)°
V = 2171.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 7.44 mm⁻¹
T = 298 K
0.40 × 0.37 × 0.24 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.155, T _max = 0.268
10672 measured reflections
3821 independent reflections
1836 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.104
S = 1.03
3821 reflections
268 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.38 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 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016850/bt5538sup1.cif

e-67-o1356-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016850/bt5538Isup2.hkl

e-67-o1356-Isup2.hkl^{(187.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811016850/bt5538Isup3.cml

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⋯O3	0.89	1.87	2.757 (7)	175
N1—H1B⋯O4ⁱ	0.89	2.04	2.812 (8)	144
N1—H1C⋯O5ⁱⁱ	0.89	1.91	2.762 (8)	160

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

Acknowledgments

The author thanks Shandong Provincial Natural Science Foundation, China (ZR2010BM033) for support.

supplementary crystallographic information

Comment

4,5,6,7-Tetrabromo-2-ethylisoindoline-1,3-dione is an important flame retardant. 3,4,5,6-Tetrabromo-2-(methoxycarbonyl)benzoic acid is an intermediate in the synthesis of this flame retardant. The asymmetric unit of the title compound contains one propan-1-aminium cation, one 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate anion and one N,N-dimethylformamide solvent molecule (Fig. 1). In the anion of the title compound, the dihedral angles formed by the benzene ring and the mean planes of the carboxylate and methoxycarbonyl groups are 64.3 (3) and 75.2 (3) °, respectively. The carbon atoms of the propan-1-aminium cation are disordered. The bond lengths and angles are in agreement with those which are related in ethylammonium 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate methanol solvate (Li, 2011a) and in 2-Methylanilinium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate methanol monosolvate(Li, 2011b). The crystal structure is stabilized by N—H···O hydrogen bonds (see Fig. 2 and Table 1).

Experimental

A mixture of 4,5,6,7-tetrabromoisobenzofuran-1,3-dione (4.64 g, 0.01 mol) and methanol (15 ml) was refluxed for 0.5 h. Then propan-1-amine (0.59 g, 0.01 mol) was added to the above solution and mixed for 30 min at room temperature. After filtration, filter cake was disolved in N,N-dimethylformamide (10 ml), the solution was kept at room temperature for 15 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.