5-Bromo-N-[(E)-(6-bromo-pyridin-2-yl)methyl-idene]pyridine-3,4-diamine.

The title compound, C(11)H(8)Br(2)N(4), is a Schiff base obtained from 6-bromo-picolinaldehyde and 5-bromo-pyridine-3,4-diamine. The mol-ecule has an E configuration about the C=N bond and the dihedral angle between the two pyridine rings is 14.02 (1)°. The observed conformation is stabilised by an intramolecular N-H⋯N hydrogen bond. In the crystal, mol-ecules are stacked along the b axis and are linked through N-H⋯N hydrogen bonds into chains along the c axis.

Related literature

For the use of Schiff bases in coordination, see: Burkhardt & Plass (2008 ▶); Keypour et al. (2011 ▶); Tarafder et al. (2002 ▶). For their properties, see: Kocyigit et al. (2010 ▶).

Experimental

Crystal data

C11H8Br2N4

M = 356.03

Monoclinic,

a = 24.941 (2) Å

b = 3.8306 (6) Å

c = 15.0868 (14) Å

β = 126.116 (14)°

V = 1164.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 6.94 mm−1

T = 113 K

0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn 724CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ▶) T min = 0.337, T max = 0.490

5047 measured reflections

2282 independent reflections

2070 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.055

S = 0.89

2282 reflections

118 parameters

38 restraints

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.63 e Å−3

Absolute structure: Flack (1983 ▶), 1093 Friedel pairs

Flack parameter: 0.002 (12)

Data collection: CrystalClear (Rigaku/MSC, 2002 ▶); 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: DIAMOND (Crystal Impact, 2009 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047702/ld2030sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047702/ld2030Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811047702/ld2030Isup3.cml

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

C11H8Br2N4	F(000) = 688
Mr = 356.03	Dx = 2.031 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 24.941 (2) Å	Cell parameters from 2086 reflections
b = 3.8306 (6) Å	θ = 1.7–27.9°
c = 15.0868 (14) Å	µ = 6.94 mm−1
β = 126.116 (14)°	T = 113 K
V = 1164.4 (2) Å3	Prism, colorless
Z = 4	0.20 × 0.18 × 0.12 mm

Rigaku Saturn 724CCD diffractometer	2282 independent reflections
Radiation source: rotating anode	2070 reflections with I > 2σ(I)
multilayer	Rint = 0.046
Detector resolution: 14.22 pixels mm-1	θmax = 26.4°, θmin = 2.0°
ω scans	h = −30→29
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	k = −4→4
Tmin = 0.337, Tmax = 0.490	l = −18→18
5047 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.055	(Δ/σ)max < 0.001
S = 0.89	Δρmax = 0.45 e Å−3
2282 reflections	Δρmin = −0.63 e Å−3
118 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
38 restraints	Extinction coefficient: 0.00177 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1093 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.002 (12)

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	−0.32411 (2)	−1.16292 (13)	−0.65216 (3)	0.01513 (13)
Br2	−0.60799 (2)	0.03838 (13)	−0.34064 (3)	0.01849 (14)
C6	−0.4590 (3)	−0.6690 (12)	−0.5248 (4)	0.0102 (6)
H6	−0.4959	−0.7657	−0.5913	0.012*
C1	−0.3284 (3)	−0.9595 (12)	−0.5398 (4)	0.0102 (7)
C9	−0.5986 (3)	−0.1427 (11)	−0.4469 (4)	0.0102 (6)
N2	−0.4692 (2)	−0.4839 (10)	−0.4673 (3)	0.0102 (6)
C4	−0.3354 (3)	−0.6323 (13)	−0.3902 (4)	0.0117 (12)
H4	−0.3393	−0.5114	−0.3393	0.014*
C5	−0.3928 (3)	−0.7397 (13)	−0.4927 (4)	0.0102 (7)
C8	−0.5367 (3)	−0.2611 (13)	−0.4152 (4)	0.0102 (6)
N1	−0.3883 (2)	−0.9064 (10)	−0.5679 (3)	0.0102 (10)
N3	−0.6504 (2)	−0.2897 (11)	−0.6358 (3)	0.0160 (11)
C2	−0.2699 (3)	−0.8765 (12)	−0.4417 (4)	0.0102 (7)
H2	−0.2282	−0.9341	−0.4266	0.012*
C10	−0.6531 (3)	−0.1634 (12)	−0.5552 (4)	0.0102 (6)
H10	−0.6947	−0.0846	−0.5738	0.012*
N4	−0.4818 (2)	−0.2585 (10)	−0.3118 (3)	0.0156 (10)
H4A	−0.4834	−0.1785	−0.2587	0.019*
H4B	−0.4441	−0.3367	−0.2969	0.019*
C3	−0.2743 (3)	−0.7040 (13)	−0.3652 (4)	0.0136 (12)
H3	−0.2353	−0.6368	−0.2963	0.016*
C11	−0.5907 (3)	−0.3985 (12)	−0.6050 (4)	0.0127 (13)
H11	−0.5878	−0.4893	−0.6606	0.015*
C7	−0.5329 (3)	−0.3906 (12)	−0.4994 (4)	0.0102 (6)

	U11	U22	U33	U12	U13	U23
Br1	0.0168 (3)	0.0139 (3)	0.0191 (3)	0.0022 (2)	0.0129 (2)	−0.0024 (2)
Br2	0.0207 (3)	0.0179 (3)	0.0219 (3)	0.0026 (3)	0.0153 (3)	−0.0004 (3)
C6	0.0118 (15)	0.0111 (14)	0.0086 (13)	−0.0005 (15)	0.0064 (12)	0.0002 (13)
C1	0.0100 (17)	0.0077 (15)	0.0135 (17)	−0.0007 (12)	0.0073 (14)	0.0026 (12)
C9	0.0122 (15)	0.0052 (13)	0.0154 (14)	−0.0006 (10)	0.0094 (12)	0.0015 (10)
N2	0.0118 (15)	0.0111 (14)	0.0086 (13)	−0.0005 (15)	0.0064 (12)	0.0002 (13)
C4	0.018 (3)	0.010 (3)	0.010 (3)	0.001 (2)	0.010 (3)	0.002 (2)
C5	0.0100 (17)	0.0077 (15)	0.0135 (17)	−0.0007 (12)	0.0073 (14)	0.0026 (12)
C8	0.0122 (15)	0.0052 (13)	0.0154 (14)	−0.0006 (10)	0.0094 (12)	0.0015 (10)
N1	0.013 (3)	0.008 (2)	0.008 (2)	−0.0011 (18)	0.006 (2)	0.0017 (17)
N3	0.009 (3)	0.023 (3)	0.012 (2)	0.003 (2)	0.004 (2)	0.0014 (19)
C2	0.0100 (17)	0.0077 (15)	0.0135 (17)	−0.0007 (12)	0.0073 (14)	0.0026 (12)
C10	0.0122 (15)	0.0052 (13)	0.0154 (14)	−0.0006 (10)	0.0094 (12)	0.0015 (10)
N4	0.005 (2)	0.031 (3)	0.010 (2)	0.0035 (19)	0.004 (2)	−0.0036 (18)
C3	0.008 (3)	0.017 (3)	0.008 (3)	−0.003 (2)	0.000 (2)	0.004 (2)
C11	0.016 (3)	0.011 (3)	0.012 (3)	0.002 (2)	0.009 (3)	0.000 (2)
C7	0.0122 (15)	0.0052 (13)	0.0154 (14)	−0.0006 (10)	0.0094 (12)	0.0015 (10)

Br1—C1	1.925 (5)	C5—N1	1.363 (6)
Br2—C9	1.884 (5)	C8—N4	1.337 (6)
C6—N2	1.256 (5)	C8—C7	1.418 (7)
C6—C5	1.447 (7)	N3—C11	1.339 (6)
C6—H6	0.9500	N3—C10	1.347 (5)
C1—N1	1.305 (7)	C2—C3	1.389 (7)
C1—C2	1.370 (7)	C2—H2	0.9500
C9—C10	1.380 (6)	C10—H10	0.9500
C9—C8	1.397 (7)	N4—H4A	0.8800
N2—C7	1.407 (7)	N4—H4B	0.8800
C4—C3	1.363 (7)	C3—H3	0.9500
C4—C5	1.414 (7)	C11—C7	1.382 (7)
C4—H4	0.9500	C11—H11	0.9500
N2—C6—C5	122.0 (4)	C11—N3—C10	115.9 (5)
N2—C6—H6	119.0	C1—C2—C3	116.9 (5)
C5—C6—H6	119.0	C1—C2—H2	121.6
N1—C1—C2	127.0 (5)	C3—C2—H2	121.6
N1—C1—Br1	115.1 (4)	N3—C10—C9	123.4 (5)
C2—C1—Br1	117.9 (4)	N3—C10—H10	118.3
C10—C9—C8	120.4 (5)	C9—C10—H10	118.3
C10—C9—Br2	119.9 (4)	C8—N4—H4A	120.0
C8—C9—Br2	119.6 (4)	C8—N4—H4B	120.0
C6—N2—C7	123.5 (4)	H4A—N4—H4B	120.0
C3—C4—C5	119.4 (5)	C4—C3—C2	119.2 (5)
C3—C4—H4	120.3	C4—C3—H3	120.4
C5—C4—H4	120.3	C2—C3—H3	120.4
N1—C5—C4	121.3 (5)	N3—C11—C7	125.8 (5)
N1—C5—C6	116.6 (5)	N3—C11—H11	117.1
C4—C5—C6	122.1 (5)	C7—C11—H11	117.1
N4—C8—C9	124.2 (5)	C11—C7—N2	126.2 (5)
N4—C8—C7	119.0 (5)	C11—C7—C8	117.7 (5)
C9—C8—C7	116.8 (5)	N2—C7—C8	116.0 (5)
C1—N1—C5	116.2 (4)
C5—C6—N2—C7	175.6 (5)	C11—N3—C10—C9	0.3 (7)
C3—C4—C5—N1	−1.5 (7)	C8—C9—C10—N3	−1.1 (7)
C3—C4—C5—C6	−179.4 (4)	Br2—C9—C10—N3	−180.0 (4)
N2—C6—C5—N1	−172.0 (4)	C5—C4—C3—C2	1.0 (7)
N2—C6—C5—C4	6.0 (7)	C1—C2—C3—C4	1.0 (7)
C10—C9—C8—N4	−178.3 (4)	C10—N3—C11—C7	−0.2 (8)
Br2—C9—C8—N4	0.6 (7)	N3—C11—C7—N2	−175.7 (5)
C10—C9—C8—C7	1.8 (7)	N3—C11—C7—C8	1.0 (8)
Br2—C9—C8—C7	−179.3 (3)	C6—N2—C7—C11	−19.0 (8)
C2—C1—N1—C5	2.4 (7)	C6—N2—C7—C8	164.2 (4)
Br1—C1—N1—C5	−175.4 (3)	N4—C8—C7—C11	178.4 (4)
C4—C5—N1—C1	−0.1 (7)	C9—C8—C7—C11	−1.7 (7)
C6—C5—N1—C1	177.9 (4)	N4—C8—C7—N2	−4.5 (7)
N1—C1—C2—C3	−2.9 (7)	C9—C8—C7—N2	175.4 (4)
Br1—C1—C2—C3	174.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N2	0.88	2.33	2.686 (6)	104.
N4—H4A···N1i	0.88	2.44	3.043 (5)	126.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯N2	0.88	2.33	2.686 (6)	104
N4—H4A⋯N1i	0.88	2.44	3.043 (5)	126

Symmetry code: (i) .