3,5-Di­bromo-6-methyl­pyridin-2-amine

Krishna Murthy, P.; Sreenivasa Rao, R.; Suneetha, V.; Giri, L.; Suchetan, P.A.

doi:10.1107/S2414314617007283

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170728

https://doi.org/10.1107/S2414314617007283

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3,5-Dibromo-6-methylpyridin-2-amine

P. Krishna Murthy,^a ‡ R. Sreenivasa Rao,^b V. Suneetha,^b L. Giri ^c and P. A. Suchetan ^d ^*

^aDepartment of Chemistry, Bapatla Engineering College (Autonomous), Acharaya Nagarjuna University Postgraduate Research Centre, Bapatla 522 101, A.P., India, ^bDepartment of Chemistry, Bapatla College of Arts and Sciences, Bapatla 522 101, A.P., India, ^cSolid State and Supramolecular Structural Chemistry Laboratory, School of Basic Sciences, IIT Bhubaneswar, Bhubaneswar 751 008, India, and ^dDepartment of Chemistry, University College of Science, Tumkur University, Tumkur 572103, India
^*Correspondence e-mail: pasuchetan@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 May 2017; accepted 17 May 2017; online 19 May 2017)

The title molecule, C₆H₆Br₂N₂, is almost planar (r.m.s. deviation for the non-H atoms = 0.012 Å). In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R₂²(8) loops.

Keywords: crystal structure; halogenated compounds; N—H⋯N hydrogen bonds; $[R_{2}^{2}]$ (8) dimers.

CCDC reference: 1532242

Structure description

Halogenated organic compounds are known to exhibit diverse biological activities showing anticancer (Nussbaumer et al., 2011 ), antiviral (De Clercq, 2013 ), anti-tuberculosis (Beena & Rawat, 2013 ), anti-malarial (Biamonte et al., 2013 ), antifungal and anti-diabetic (Hector, 2005 ) properties. As part of our studies in this area, the crystal structure of the commercially available title compound was determined.

The molecule is almost planar (Fig. 1) with the r.m.s. deviation for the non-H atoms being 0.012 Å. An intramolecular N—H⋯Br interaction occurs. In the crystal, inversion dimers linked by pairs of N2—H2⋯N1 hydrogen bonds generate $[R_{2}^{2}]$ (8) loops (Fig. 2, Table 1). The crystal structure does not feature any other interactions, and thus, the supramolecular architecture displayed is zero dimensional.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯Br1	0.87 (5)	2.68 (5)	3.128 (4)	114 (4)
N2—H2⋯N1ⁱ	0.88 (4)	2.19 (4)	3.070 (6)	173 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Figure 1
A view of the molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Figure 2
Crystal packing of the title compound, displaying N—H⋯N hydrogen-bonded $[R_{2}^{2}]$ (8) loops.

Synthesis and crystallization

The title compound was purchased from Avra Synthesis Pvt. Ltd, India, and was used as such. Colourless blocks were grown by recrystallization from methanol solution at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₆Br₂N₂
M_r	265.95
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	13.1047 (16), 4.0310 (4), 15.7631 (18)
β (°)	105.720 (4)
V (Å³)	801.54 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	10.04
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.085, 0.134
No. of measured, independent and observed [I > 2σ(I)] reflections	10577, 1670, 1461
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.09
No. of reflections	1670
No. of parameters	101
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.03, −0.86
Computer programs: APEX2, SAINT-Plus and XPREP (Bruker, 2009), SHELXT2016 (Sheldrick, 2015 a), SHELXL2016 (Sheldrick, 2015b) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1532242

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617007283/hb4147sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617007283/hb4147Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617007283/hb4147Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus and XPREP (Bruker, 2009); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

3,5-Dibromo-6-methylpyridin-2-amine top

Crystal data top

C₆H₆Br₂N₂	F(000) = 504
M_r = 265.95	Prism
Monoclinic, P2₁/n	D_x = 2.204 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 13.1047 (16) Å	Cell parameters from 133 reflections
b = 4.0310 (4) Å	θ = 2.4–26.7°
c = 15.7631 (18) Å	µ = 10.04 mm⁻¹
β = 105.720 (4)°	T = 296 K
V = 801.54 (16) Å³	Block, colourless
Z = 4	0.26 × 0.22 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	1670 independent reflections
Radiation source: fine-focus sealed tube	1461 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
phi and φ scans	θ_max = 26.7°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→16
T_min = 0.085, T_max = 0.134	k = −5→4
10577 measured reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0701P)² + 0.463P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.108	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 1.03 e Å⁻³
1670 reflections	Δρ_min = −0.86 e Å⁻³
101 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.064 (4)

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3237 (3)	0.5000 (10)	0.4445 (2)	0.0352 (8)
C2	0.2125 (3)	0.5194 (10)	0.4153 (2)	0.0343 (8)
C3	0.1522 (3)	0.3994 (10)	0.4668 (2)	0.0360 (8)
H3	0.078637	0.410750	0.448303	0.043*
C4	0.2038 (3)	0.2597 (9)	0.5477 (3)	0.0366 (9)
C5	0.3126 (3)	0.2404 (10)	0.5746 (3)	0.0377 (9)
C6	0.3748 (4)	0.0910 (15)	0.6593 (3)	0.0566 (12)
H6A	0.417884	−0.086130	0.647437	0.085*
H6B	0.327119	0.005584	0.690749	0.085*
H6C	0.419361	0.257416	0.694366	0.085*
N1	0.3710 (3)	0.3633 (9)	0.5226 (2)	0.0385 (8)
N2	0.3883 (3)	0.6093 (13)	0.3955 (3)	0.0517 (10)
BR1	0.14692 (3)	0.70991 (12)	0.30385 (3)	0.0436 (2)
BR2	0.11914 (4)	0.10117 (13)	0.61976 (3)	0.0544 (3)
H1	0.359 (4)	0.736 (12)	0.351 (3)	0.056 (16)*
H2	0.458 (3)	0.609 (15)	0.415 (3)	0.063 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.026 (2)	0.046 (2)	0.0313 (18)	−0.0019 (16)	0.0032 (15)	−0.0038 (16)
C2	0.029 (2)	0.040 (2)	0.0304 (18)	0.0003 (16)	0.0019 (15)	−0.0044 (15)
C3	0.0243 (19)	0.044 (2)	0.038 (2)	−0.0019 (15)	0.0046 (16)	−0.0047 (17)
C4	0.037 (2)	0.040 (2)	0.035 (2)	−0.0040 (16)	0.0123 (17)	−0.0031 (15)
C5	0.036 (2)	0.045 (2)	0.0288 (19)	0.0000 (16)	0.0029 (16)	−0.0006 (15)
C6	0.052 (3)	0.074 (3)	0.040 (2)	−0.001 (2)	0.004 (2)	0.011 (2)
N1	0.0260 (17)	0.056 (2)	0.0308 (16)	−0.0020 (15)	0.0031 (13)	0.0018 (15)
N2	0.032 (2)	0.085 (3)	0.037 (2)	−0.0064 (19)	0.0073 (17)	0.0091 (19)
BR1	0.0351 (3)	0.0561 (3)	0.0337 (3)	0.00406 (17)	−0.00072 (19)	0.00301 (17)
BR2	0.0524 (4)	0.0647 (4)	0.0525 (3)	−0.0082 (2)	0.0248 (2)	0.0056 (2)

Geometric parameters (Å, º) top

C1—N1	1.338 (5)	C4—BR2	1.900 (4)
C1—N2	1.364 (5)	C5—N1	1.358 (5)
C1—C2	1.407 (5)	C5—C6	1.491 (6)
C2—C3	1.366 (6)	C6—H6A	0.9600
C2—BR1	1.896 (4)	C6—H6B	0.9600
C3—C4	1.390 (6)	C6—H6C	0.9600
C3—H3	0.9300	N2—H1	0.87 (3)
C4—C5	1.375 (6)	N2—H2	0.88 (3)

N1—C1—N2	116.7 (4)	N1—C5—C6	115.3 (4)
N1—C1—C2	120.3 (3)	C4—C5—C6	124.6 (4)
N2—C1—C2	123.0 (4)	C5—C6—H6A	109.5
C3—C2—C1	120.1 (3)	C5—C6—H6B	109.5
C3—C2—BR1	120.3 (3)	H6A—C6—H6B	109.5
C1—C2—BR1	119.7 (3)	C5—C6—H6C	109.5
C2—C3—C4	118.2 (4)	H6A—C6—H6C	109.5
C2—C3—H3	120.9	H6B—C6—H6C	109.5
C4—C3—H3	120.9	C1—N1—C5	120.6 (3)
C5—C4—C3	120.7 (4)	C1—N2—H1	117 (4)
C5—C4—BR2	121.5 (3)	C1—N2—H2	123 (4)
C3—C4—BR2	117.8 (3)	H1—N2—H2	118 (5)
N1—C5—C4	120.1 (4)

N1—C1—C2—C3	0.2 (6)	C3—C4—C5—N1	1.1 (6)
N2—C1—C2—C3	178.7 (4)	BR2—C4—C5—N1	−178.4 (3)
N1—C1—C2—BR1	−179.4 (3)	C3—C4—C5—C6	−179.1 (4)
N2—C1—C2—BR1	−0.8 (6)	BR2—C4—C5—C6	1.4 (6)
C1—C2—C3—C4	0.0 (6)	N2—C1—N1—C5	−178.3 (4)
BR1—C2—C3—C4	179.5 (3)	C2—C1—N1—C5	0.3 (6)
C2—C3—C4—C5	−0.6 (6)	C4—C5—N1—C1	−0.9 (6)
C2—C3—C4—BR2	178.9 (3)	C6—C5—N1—C1	179.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···Br1	0.87 (5)	2.68 (5)	3.128 (4)	114 (4)
N2—H2···N1ⁱ	0.88 (4)	2.19 (4)	3.070 (6)	173 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Footnotes

‡These authors contributed equally.

Acknowledgements

The authors acknowledge Professor V. R. Pedireddi, Solid State & Supramolecular Structural Chemistry Laboratory, School of Basic Sciences, IIT Bhubaneswar, for the data collection.

Funding information

Funding for this research was provided by: University Grants Commission (award No. UGC-MRP: 2015–16).

References

Beena & Rawat, D. S. (2013). Med. Res. Rev. 33, 693–764. Google Scholar
Biamonte, M. A., Wanner, J. & Le Roch, K. G. (2013). Bioorg. Med. Chem. Lett. 23, 2829–2843. Web of Science CrossRef CAS PubMed Google Scholar
Bruker (2009). APEX2, SADABS, SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
De Clercq, E. (2013). Biochem. Pharmacol. 85, 727–744. CrossRef CAS PubMed Google Scholar
Hector, R. F. (2005). Clin. Tech. Small Anim. Pract. 20, 240–249. CrossRef PubMed Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nussbaumer, S., Bonnabry, P., Veuthey, J. L. & Fleury-Souverain, S. (2011). Talanta, 85, 2265–2289. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar