3,4-Bis(4-bromo­phen­yl)-N-phenyl­maleimide

Yong Liu; Shuai Zheng; Jing Zhou; Dongmei Gao; Zhen-Ting Du

doi:10.1107/S1600536811014152

. 2011 Apr 22;67(Pt 5):o1198. doi: 10.1107/S1600536811014152

3,4-Bis(4-bromophenyl)-N-phenylmaleimide

Yong Liu ^a, Shuai Zheng ^b, Jing Zhou ^b, Dongmei Gao ^b, Zhen-Ting Du ^b,^*

PMCID: PMC3089159 PMID: 21754500

Abstract

In the title molecule, C₂₂H₁₃Br₂NO₂, the three benzene rings are arranged in a propeller-like fashion around the central malemide ring, making dihedral angles of 48.2 (4), 30.2 (4) and 34.8 (4)° with the malemide ring. The C—C single-bond lengths connecting benzene groups and maleimide are significantly shorter [C—C = 1.468 (9) and 1.478 (9) Å] than a typical Csp ³—Csp ³ single bond, indicating partial conjugation between the benzene and the maleimide. A weak nonclassical C—H⋯O hydrogen bond helps to stabilize the crystal structure.

Related literature

For general background to 3,4-diaryl-substituted maleimide derivatives, see: Fujii et al. (2001 ▶); Onimura et al. (2010 ▶); Shorunov et al. (2006 ▶).

Experimental

Crystal data

C₂₂H₁₃Br₂NO₂
M _r = 483.13
Monoclinic,
a = 10.844 (5) Å
b = 18.594 (9) Å
c = 9.602 (5) Å
β = 102.760 (6)°
V = 1888.3 (16) Å³
Z = 4
Mo Kα radiation
μ = 4.31 mm⁻¹
T = 296 K
0.32 × 0.30 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.339, T _max = 0.424
8594 measured reflections
3382 independent reflections
1427 reflections with I > 2σ(I)
R _int = 0.117

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.133
S = 0.94
3382 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); 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 global, I. DOI: 10.1107/S1600536811014152/rk2272sup1.cif

e-67-o1198-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014152/rk2272Isup2.hkl

e-67-o1198-Isup2.hkl^{(165.9KB, 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
C21—H21⋯O1ⁱ	0.93	2.41	3.267 (9)	153

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Fundamental Research Funds for the Central Universities in NWSUAF (QN2009048) and the Excellent Young Funds 211020712 is greatly appreciated.

supplementary crystallographic information

Comment

3,4-Diaryl-substituted maleimide is a conjugated unit which has interesting optical and electronic properties. A number of 3,4-diaryl-substituted maleimide derivatives have been designed and synthesized to be used as monomer of some electro–optic polymers (Shorunov et al., 2006; Onimura et al., 2010). In the course of exploring new electro–optic compounds, we obtained a intermediate compound 3,4-bis(4-bromophenyl)-N-phenylmaleimide I. Here we report the structure and synthesis of title compound.

The molecule holds four rings. The maleimide ring locates the core position, and the other three benzene rings are arranged in a propeller–like fashion around the central malemide 5–membering ring with the dihedral angeles being 48.2 (4)° (C1–C6), 30.2 (4)° (C9–C14) and 34.8 (4)° (C17–C22). The C—C single bond lengths conecting benzene groups and maleimide unit are respectively 1.468 (9)Å (C4—C7) and 1.478 (9)Å (C17—C18), which are obviously shorter than typical Csp³—Csp³ single bond. This means that the bonding between the benzenes and the maleimide is quite conjugated.

The molecules of I are crystalized in P2₁/c space group which is different from that of N–3,4–triphenylmaleimide (Pbca, Fujii et al., 2001). There are no classic hydrogen bonds in this crystal structure. However, the weak intermolecular interaction C21—H21···O1ⁱ is helpful to the stabilization of the packing (Fig. 2). This intermolecular non–classical H–bond is characterized by the parameters: bond lengths of 0.93Å (C21—H21), 2.41Å (H21···O1ⁱ), 3.267 (9)Å (C21···O1ⁱ) and angle 153° (C21—H21···O1ⁱ). Symmetry code: (i) 1-x, -1/2+y, 1/2-z.

Experimental

3,4–Bis(4–bromophenyl)maleic anhydride (0.60 g, 1.47 mmol), 4–methylbenzenesulfonic acid (0.30 g, 3.26 mmol) and H₂SO₄ (2 ml) were dissolved in N,N–dimethylformamide (DMF, 1.0 ml) and toluene (20 ml) mixed solvent. After heating the mixture to refluxing, a toluene solution of anilin (0.20 g, 2.17 mmol) was slowly added. After stirring for 2 h, the mixture was cooled to 333 K and poured into 8% Na₂CO₃ solution and further stirred for 10 min. The solution was extracted with toluene and dried over Na₂SO₄. After removing the solvent, the crude product was purified by recrystallization from ethanol, affording the title compound, I, (0.51 g, 72%). Then the compound I was dissolved in THF, and yellow crystals were formed on slow evaporation at room temperature over one week.