N-(3-Bromo-phen-yl)quinazoline-4,6-diamine.

In the title compound, C(14)H(11)BrN(4), the fused benzene and pyrimidine rings are nearly coplanar, making dihedral angles of 1.26 (14) and 3.53 (15)° in the two independent mol-ecules. In the crystal structure, π-π stacking inter-actions [centroid-centroid distances = 3.4736 (19) and 3.5416 (19) Å] and weak N-H⋯N and N-H⋯Br inter-actions 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 = 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

Δρmax = 1.42 e Å−3

Δρmin = −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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H11BrN4	Z = 4
Mr = 315.18	F(000) = 632
Triclinic, P1	Dx = 1.652 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5579 (15) Å	Cell parameters from 3726 reflections
b = 11.743 (2) Å	θ = 1.9–27.9°
c = 15.554 (3) Å	µ = 3.23 mm−1
α = 110.24 (3)°	T = 113 K
β = 96.79 (3)°	Block, colourless
γ = 96.75 (3)°	0.36 × 0.26 × 0.23 mm
V = 1267.4 (4) Å3

Rigaku Saturn CCD area-detector diffractometer	5931 independent reflections
Radiation source: rotating anode	3735 reflections with I > 2σ(I)
confocal	Rint = 0.034
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 1.9°
ω and φ scans	h = −9→9
Absorption correction: multi-scan [SADABS (Sheldrick, 1996) using a modified Dwiggins (1975) procedure]	k = −9→15
Tmin = 0.389, Tmax = 0.523	l = −20→20
10616 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
5931 reflections	Δρmax = 1.42 e Å−3
360 parameters	Δρmin = −1.54 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0265 (14)

Experimental. Absorption correction: [interpolation using International Tables for Crystallography (Vol. C, 1992, p. 523, Table 6.3.3.3) for values of µR in the range 0–2.5, and International Tables for X-ray Crystallography (Vol. II, 1959, p. 302, Table 5.3.6B) for µR in the range 2.6–10.0; the interpolation procedure of Dwiggins (1975) was used with some modification]

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Br1	0.32081 (4)	0.54984 (3)	0.19450 (3)	0.02528 (13)
N1	0.7074 (3)	0.7482 (2)	0.01210 (19)	0.0175 (6)
H1N	0.622 (5)	0.800 (4)	0.026 (3)	0.036 (11)*
N2	0.9911 (3)	0.7443 (2)	−0.03199 (19)	0.0176 (6)
N3	1.0997 (3)	0.8702 (2)	−0.11423 (19)	0.0175 (6)
N4	0.4365 (3)	1.0316 (2)	−0.13941 (19)	0.0184 (6)
H4A	0.3481	1.0082	−0.1139	0.022*
H4B	0.4225	1.0832	−0.1684	0.022*
C1	0.5318 (4)	0.5673 (3)	0.1418 (2)	0.0179 (7)
C2	0.6659 (4)	0.4991 (3)	0.1522 (2)	0.0204 (7)
H2	0.6528	0.4433	0.1839	0.024*
C3	0.8198 (4)	0.5164 (3)	0.1143 (2)	0.0198 (7)
H3	0.9136	0.4711	0.1204	0.024*
C4	0.8412 (4)	0.5974 (3)	0.0679 (2)	0.0180 (7)
H4	0.9484	0.6074	0.0431	0.022*
C5	0.7044 (4)	0.6642 (3)	0.0580 (2)	0.0164 (7)
C6	0.5474 (4)	0.6477 (3)	0.0953 (2)	0.0167 (7)
H6	0.4524	0.6918	0.0885	0.020*
C7	0.8344 (4)	0.7850 (3)	−0.0327 (2)	0.0158 (7)
C8	1.1141 (4)	0.7914 (3)	−0.0728 (2)	0.0182 (7)
H8	1.2267	0.7632	−0.0710	0.022*
C9	0.9338 (4)	0.9078 (3)	−0.1195 (2)	0.0151 (6)
C10	0.7933 (4)	0.8659 (3)	−0.0804 (2)	0.0149 (6)
C11	0.6255 (4)	0.9061 (3)	−0.0889 (2)	0.0166 (7)
H11	0.5295	0.8771	−0.0633	0.020*
C12	0.5995 (4)	0.9869 (3)	−0.1338 (2)	0.0154 (7)
C13	0.7425 (4)	1.0290 (3)	−0.1721 (2)	0.0196 (7)
H13	0.7256	1.0854	−0.2026	0.024*
C14	0.9041 (4)	0.9895 (3)	−0.1658 (2)	0.0191 (7)
H14	0.9980	1.0175	−0.1929	0.023*
Br2	0.47743 (6)	0.69252 (4)	0.64544 (4)	0.05308 (17)
N5	0.0018 (4)	0.2805 (3)	0.5104 (2)	0.0236 (7)
H5N	−0.105 (6)	0.250 (4)	0.497 (3)	0.062 (16)*
N6	0.2839 (4)	0.2212 (3)	0.5094 (2)	0.0225 (6)
N7	0.3236 (3)	0.0159 (3)	0.4224 (2)	0.0220 (6)
N8	−0.4215 (4)	−0.1290 (3)	0.3066 (2)	0.0208 (6)
H8N1	−0.470 (5)	−0.207 (4)	0.292 (3)	0.031 (11)*
H8N2	−0.467 (5)	−0.080 (4)	0.339 (3)	0.029 (12)*
C15	0.2510 (5)	0.5963 (3)	0.6368 (3)	0.0297 (8)
C16	0.1242 (5)	0.6528 (4)	0.6842 (3)	0.0345 (9)
H16	0.1503	0.7376	0.7228	0.041*
C17	−0.0417 (5)	0.5833 (4)	0.6743 (3)	0.0353 (9)
H17	−0.1317	0.6202	0.7067	0.042*
C18	−0.0788 (5)	0.4601 (3)	0.6177 (3)	0.0294 (8)
H18	−0.1943	0.4132	0.6112	0.035*
C19	0.0523 (5)	0.4039 (3)	0.5700 (2)	0.0237 (8)
C20	0.2198 (5)	0.4734 (3)	0.5799 (3)	0.0270 (8)
H20	0.3112	0.4375	0.5483	0.032*
C21	0.1078 (4)	0.1919 (3)	0.4798 (2)	0.0200 (7)
C22	0.3821 (4)	0.1307 (3)	0.4780 (2)	0.0237 (8)
H22	0.5091	0.1530	0.4988	0.028*
C23	0.1403 (4)	−0.0162 (3)	0.3923 (2)	0.0176 (7)
C24	0.0232 (4)	0.0702 (3)	0.4192 (2)	0.0179 (7)
C25	−0.1655 (4)	0.0310 (3)	0.3887 (2)	0.0209 (7)
H25	−0.2446	0.0894	0.4047	0.025*
C26	−0.2359 (4)	−0.0901 (3)	0.3363 (2)	0.0200 (7)
C27	−0.1169 (4)	−0.1752 (3)	0.3086 (2)	0.0208 (7)
H27	−0.1645	−0.2585	0.2707	0.025*
C28	0.0670 (4)	−0.1386 (3)	0.3358 (2)	0.0209 (7)
H28	0.1452	−0.1968	0.3162	0.025*

	U11	U22	U33	U12	U13	U23
Br1	0.0237 (2)	0.0263 (2)	0.0295 (2)	0.00205 (15)	0.01249 (15)	0.01294 (17)
N1	0.0181 (13)	0.0173 (14)	0.0246 (17)	0.0096 (12)	0.0100 (12)	0.0127 (13)
N2	0.0158 (13)	0.0171 (14)	0.0222 (16)	0.0055 (11)	0.0069 (11)	0.0078 (13)
N3	0.0127 (12)	0.0170 (14)	0.0236 (16)	0.0032 (11)	0.0076 (11)	0.0068 (13)
N4	0.0159 (13)	0.0229 (15)	0.0244 (17)	0.0091 (12)	0.0096 (11)	0.0148 (14)
C1	0.0198 (16)	0.0165 (16)	0.0178 (18)	0.0030 (13)	0.0068 (13)	0.0058 (15)
C2	0.0245 (17)	0.0170 (17)	0.023 (2)	0.0053 (14)	0.0063 (14)	0.0095 (16)
C3	0.0224 (17)	0.0168 (17)	0.0229 (19)	0.0085 (14)	0.0046 (14)	0.0085 (15)
C4	0.0146 (15)	0.0190 (17)	0.0223 (19)	0.0058 (13)	0.0055 (13)	0.0082 (16)
C5	0.0207 (16)	0.0130 (15)	0.0144 (18)	0.0011 (13)	0.0053 (13)	0.0037 (14)
C6	0.0181 (16)	0.0149 (16)	0.0170 (18)	0.0061 (13)	0.0058 (13)	0.0036 (14)
C7	0.0145 (15)	0.0128 (15)	0.0182 (18)	0.0010 (13)	0.0063 (13)	0.0025 (14)
C8	0.0141 (15)	0.0147 (16)	0.027 (2)	0.0059 (13)	0.0073 (13)	0.0059 (15)
C9	0.0158 (15)	0.0131 (15)	0.0158 (17)	0.0030 (13)	0.0051 (12)	0.0036 (14)
C10	0.0150 (15)	0.0130 (15)	0.0163 (18)	0.0034 (13)	0.0058 (12)	0.0034 (14)
C11	0.0165 (15)	0.0152 (16)	0.0203 (19)	0.0038 (13)	0.0078 (13)	0.0075 (15)
C12	0.0137 (15)	0.0149 (16)	0.0163 (18)	0.0029 (13)	0.0025 (12)	0.0041 (14)
C13	0.0217 (17)	0.0207 (17)	0.0217 (19)	0.0057 (14)	0.0085 (14)	0.0120 (16)
C14	0.0164 (16)	0.0224 (18)	0.0209 (19)	0.0026 (14)	0.0082 (13)	0.0095 (16)
Br2	0.0563 (3)	0.0275 (2)	0.0698 (4)	−0.0053 (2)	0.0215 (3)	0.0114 (2)
N5	0.0242 (16)	0.0195 (16)	0.0269 (18)	0.0083 (14)	0.0065 (13)	0.0060 (14)
N6	0.0227 (15)	0.0241 (16)	0.0220 (17)	0.0070 (13)	0.0061 (12)	0.0084 (14)
N7	0.0180 (14)	0.0264 (16)	0.0234 (17)	0.0076 (13)	0.0052 (12)	0.0095 (14)
N8	0.0166 (14)	0.0225 (17)	0.0203 (18)	0.0056 (14)	0.0022 (12)	0.0037 (15)
C15	0.040 (2)	0.025 (2)	0.025 (2)	0.0030 (17)	0.0080 (17)	0.0102 (18)
C16	0.061 (3)	0.0206 (19)	0.024 (2)	0.0124 (19)	0.0130 (19)	0.0071 (18)
C17	0.047 (2)	0.035 (2)	0.030 (2)	0.015 (2)	0.0186 (19)	0.011 (2)
C18	0.038 (2)	0.026 (2)	0.028 (2)	0.0114 (17)	0.0147 (17)	0.0081 (18)
C19	0.0319 (19)	0.0238 (19)	0.019 (2)	0.0098 (16)	0.0056 (15)	0.0098 (17)
C20	0.036 (2)	0.0237 (19)	0.026 (2)	0.0098 (17)	0.0119 (16)	0.0119 (18)
C21	0.0244 (17)	0.0224 (18)	0.0176 (19)	0.0081 (15)	0.0091 (14)	0.0096 (16)
C22	0.0206 (17)	0.030 (2)	0.025 (2)	0.0069 (15)	0.0076 (14)	0.0129 (18)
C23	0.0187 (16)	0.0224 (18)	0.0144 (18)	0.0057 (14)	0.0046 (13)	0.0086 (15)
C24	0.0177 (16)	0.0239 (18)	0.0180 (18)	0.0092 (14)	0.0056 (13)	0.0121 (16)
C25	0.0221 (17)	0.0228 (18)	0.0201 (19)	0.0094 (15)	0.0079 (14)	0.0074 (16)
C26	0.0229 (17)	0.0239 (18)	0.0162 (19)	0.0067 (15)	0.0046 (13)	0.0094 (16)
C27	0.0242 (17)	0.0228 (18)	0.0160 (18)	0.0065 (15)	0.0050 (13)	0.0067 (15)
C28	0.0245 (17)	0.0270 (19)	0.0199 (19)	0.0160 (15)	0.0120 (14)	0.0128 (16)

Br1—C1	1.899 (3)	Br2—C15	1.900 (4)
N1—C7	1.365 (4)	N5—C21	1.376 (4)
N1—C5	1.403 (4)	N5—C19	1.401 (5)
N1—H1N	0.93 (4)	N5—H5N	0.82 (4)
N2—C7	1.328 (4)	N6—C21	1.319 (4)
N2—C8	1.354 (4)	N6—C22	1.353 (4)
N3—C8	1.305 (4)	N7—C22	1.313 (4)
N3—C9	1.380 (4)	N7—C23	1.372 (4)
N4—C12	1.400 (4)	N8—C26	1.392 (4)
N4—H4A	0.8800	N8—H8N1	0.89 (4)
N4—H4B	0.8800	N8—H8N2	0.77 (4)
C1—C6	1.377 (4)	C15—C16	1.372 (5)
C1—C2	1.391 (4)	C15—C20	1.381 (5)
C2—C3	1.390 (4)	C16—C17	1.374 (5)
C2—H2	0.9500	C16—H16	0.9500
C3—C4	1.384 (4)	C17—C18	1.383 (5)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.395 (4)	C18—C19	1.399 (5)
C4—H4	0.9500	C18—H18	0.9500
C5—C6	1.403 (4)	C19—C20	1.384 (5)
C6—H6	0.9500	C20—H20	0.9500
C7—C10	1.433 (4)	C21—C24	1.431 (5)
C8—H8	0.9500	C22—H22	0.9500
C9—C10	1.406 (4)	C23—C28	1.402 (5)
C9—C14	1.407 (4)	C23—C24	1.412 (4)
C10—C11	1.412 (4)	C24—C25	1.416 (4)
C11—C12	1.378 (4)	C25—C26	1.374 (5)
C11—H11	0.9500	C25—H25	0.9500
C12—C13	1.414 (4)	C26—C27	1.413 (4)
C13—C14	1.362 (4)	C27—C28	1.375 (4)
C13—H13	0.9500	C27—H27	0.9500
C14—H14	0.9500	C28—H28	0.9500
C7—N1—C5	131.2 (2)	C21—N5—C19	129.5 (3)
C7—N1—H1N	114 (2)	C21—N5—H5N	111 (3)
C5—N1—H1N	113 (2)	C19—N5—H5N	119 (3)
C7—N2—C8	115.9 (2)	C21—N6—C22	116.5 (3)
C8—N3—C9	115.2 (3)	C22—N7—C23	116.0 (3)
C12—N4—H4A	120.0	C26—N8—H8N1	121 (2)
C12—N4—H4B	120.0	C26—N8—H8N2	106 (3)
H4A—N4—H4B	120.0	H8N1—N8—H8N2	117 (4)
C6—C1—C2	122.4 (3)	C16—C15—C20	123.2 (4)
C6—C1—Br1	118.8 (2)	C16—C15—Br2	118.7 (3)
C2—C1—Br1	118.8 (2)	C20—C15—Br2	118.1 (3)
C1—C2—C3	117.0 (3)	C15—C16—C17	118.1 (4)
C1—C2—H2	121.5	C15—C16—H16	121.0
C3—C2—H2	121.5	C17—C16—H16	121.0
C4—C3—C2	122.3 (3)	C16—C17—C18	120.6 (4)
C4—C3—H3	118.9	C16—C17—H17	119.7
C2—C3—H3	118.9	C18—C17—H17	119.7
C3—C4—C5	119.5 (3)	C17—C18—C19	120.5 (4)
C3—C4—H4	120.2	C17—C18—H18	119.7
C5—C4—H4	120.2	C19—C18—H18	119.7
C4—C5—C6	119.1 (3)	C20—C19—C18	119.1 (3)
C4—C5—N1	125.6 (3)	C20—C19—N5	123.6 (3)
C6—C5—N1	115.3 (3)	C18—C19—N5	117.2 (3)
C1—C6—C5	119.6 (3)	C15—C20—C19	118.5 (3)
C1—C6—H6	120.2	C15—C20—H20	120.7
C5—C6—H6	120.2	C19—C20—H20	120.7
N2—C7—N1	119.6 (3)	N6—C21—N5	118.7 (3)
N2—C7—C10	121.8 (3)	N6—C21—C24	122.1 (3)
N1—C7—C10	118.6 (2)	N5—C21—C24	119.1 (3)
N3—C8—N2	129.1 (3)	N7—C22—N6	128.0 (3)
N3—C8—H8	115.4	N7—C22—H22	116.0
N2—C8—H8	115.4	N6—C22—H22	116.0
N3—C9—C10	121.7 (3)	N7—C23—C28	119.3 (3)
N3—C9—C14	119.1 (3)	N7—C23—C24	121.5 (3)
C10—C9—C14	119.1 (3)	C28—C23—C24	119.2 (3)
C9—C10—C11	119.4 (3)	C23—C24—C25	119.2 (3)
C9—C10—C7	116.1 (2)	C23—C24—C21	115.8 (3)
C11—C10—C7	124.6 (3)	C25—C24—C21	125.0 (3)
C12—C11—C10	120.6 (3)	C26—C25—C24	121.0 (3)
C12—C11—H11	119.7	C26—C25—H25	119.5
C10—C11—H11	119.7	C24—C25—H25	119.5
C11—C12—N4	121.3 (3)	C25—C26—N8	121.1 (3)
C11—C12—C13	119.4 (3)	C25—C26—C27	119.2 (3)
N4—C12—C13	119.2 (3)	N8—C26—C27	119.6 (3)
C14—C13—C12	120.7 (3)	C28—C27—C26	120.7 (3)
C14—C13—H13	119.7	C28—C27—H27	119.7
C12—C13—H13	119.7	C26—C27—H27	119.7
C13—C14—C9	120.8 (3)	C27—C28—C23	120.7 (3)
C13—C14—H14	119.6	C27—C28—H28	119.7
C9—C14—H14	119.6	C23—C28—H28	119.7

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···Br1iv	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)

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⋯Br1iv	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)

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