N 4-(3-Bromo­phen­yl)quinazoline-4,6-diamine

De-Liang Li; Yang Wu; Qiang Wang; Gu He; Luo-Ting Yu

doi:10.1107/S1600536810002631

. 2010 Jan 27;66(Pt 2):o447. doi: 10.1107/S1600536810002631

N ⁴-(3-Bromophenyl)quinazoline-4,6-diamine

De-Liang Li ^a, Yang Wu ^a, Qiang Wang ^a, Gu He ^a,^*, Luo-Ting Yu ^a

PMCID: PMC2979868 PMID: 21579862

Abstract

In the title compound, C₁₄H₁₁BrN₄, the fused benzene and pyrimidine rings are nearly coplanar, making dihedral angles of 1.26 (14) and 3.53 (15)° in the two independent molecules. In the crystal structure, π–π stacking interactions [centroid–centroid distances = 3.4736 (19) and 3.5416 (19) Å] and weak N—H⋯N and N—H⋯Br interactions contribute to the stability of the structure.

Related literature

For general background to the biological activity of N ⁴-(3-bromophenyl)quinazoline derivatives, see: Fry et al. (2005 ▶).

Experimental

Crystal data

C₁₄H₁₁BrN₄
M _r = 315.18
Triclinic,
a = 7.5579 (15) Å
b = 11.743 (2) Å
c = 15.554 (3) Å
α = 110.24 (3)°
β = 96.79 (3)°
γ = 96.75 (3)°
V = 1267.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.23 mm⁻¹
T = 113 K
0.36 × 0.26 × 0.23 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan [SADABS (Sheldrick, 1996 ▶) using a modified Dwiggins (1975 ▶) procedure] T _min = 0.389, T _max = 0.523
10616 measured reflections
5931 independent reflections
3735 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.110
S = 1.02
5931 reflections
360 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.42 e Å⁻³
Δρ_min = −1.54 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 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: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002631/pb2020sup1.cif

e-66-0o447-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002631/pb2020Isup2.hkl

e-66-0o447-Isup2.hkl^{(290.3KB, 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
N1—H1N⋯N4ⁱ	0.93 (4)	2.28 (4)	3.069 (4)	142 (3)
N4—H4A⋯N3ⁱⁱ	0.88	2.33	3.137 (4)	153
N4—H4B⋯N8ⁱⁱⁱ	0.88	2.39	3.178 (4)	149
N8—H8N1⋯Br1^iv	0.89 (4)	2.88 (4)	3.739 (4)	163 (3)
N8—H8N2⋯N7ⁱⁱ	0.77 (4)	2.31 (4)	3.053 (4)	162 (4)

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

Acknowledgments

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

supplementary crystallographic information

Comment

N4-(3-bromophenyl)quinazoline derivatives are of great importance owing to their wide biological properties (Fry et al. 1994). The title compound is one of the key intermediates in our synthetic investigations of antitumor drugs. We report here its crystal structure. As shown in Fig. 1, the benzene and pyrimidine rings of the title compound (I) are nearly coplanar, with the dihedral angle between them are 1.2° and 3.1°, respectively. A combination of intermolecular π-π packing interaction, N—H···N and N—H···Br hydrogen bonds plays important part in the connection of adjacent molecules.

Experimental

A mixture of N4-(3-bromophenyl)quinazoline-4,6-diamine (3.45 g, 10 mmol), Sodium sulfide nonahydrate (6.00 g, 25 mmol), sodium hydroxide (2.00 g, 50 mmol), ethanol (40 ml) and water (80 ml) was heated for 5.0 h under reflux. The ethanol was removed under vacuum. The solid was filtered, washed with cold water, dried to yield the title compound as a brown solid (2.2 g, 71% yield). Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of ethyl acetate.