3-Bromo­pyridine-2-carbo­nitrile

Sharif, M.; Razzaq, R.; Jackstell, R.; Spannenberg, A.

doi:10.1107/S2414314619013269

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 10| October 2019| x191326

https://doi.org/10.1107/S2414314619013269

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3-Bromopyridine-2-carbonitrile

Muhammad Sharif,^a ^* Rauf Razzaq,^b Ralf Jackstell ^b and Anke Spannenberg ^b

^aDepartment of Chemistry, King Fahd University of Petroleum and Minerals, 31261 Dhahran, Kingdom of Saudi Arabia, and ^bLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: msharif@kfupm.edu.sa

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 18 September 2019; accepted 27 September 2019; online 3 October 2019)

The title compound, C₆H₃BrN₂, also known as 3-bromopicolinonitrile, was synthesized by cyanation of 2,3-dibromopyridine. In the solid state, short intermolecular Br⋯N contacts are observed. Additionally, the crystal packing is consolidated by π–π stacking interactions with centroid–centroid distances of 3.7893 (9) Å.

Keywords: crystal structure; cyanation; 2,3-dibromopyridine; 3-bromopicolinonitrile.

CCDC reference: 1956264

Structure description

The new title compound is a pyridine derivative with a cyano group in the ortho and a bromine atom in the meta position. Its molecular structure is shown in Fig. 1. Non-H short intermolecular contacts along the b axis are observed [Br1⋯N2 = 3.1237 (17) Å, Fig. 2]. Additionally the crystal packing is stabilized by π–π stacking interactions between the pyridine rings along the c axis [centroid–centroid distance: 3.7893 (9) Å, dihedral angle between the planes of the pyridine rings: 4.01 (7)°, ring slippage 1.32 and 1.16 Å, respectively; Fig. 3].

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Figure 2
Partial packing diagram of the title compound showing the intermolecular Br⋯N contacts as dashed lines. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
Packing diagram of the title compound showing the π–π stacking interactions (dashed lines). Displacement ellipsoids are drawn at the 30% probability level.

Synthesis and crystallization

The title compound was obtained as the main product by synthesizing the mono- and dicyano derivatives of 2,3-dibromopyridine. The reaction was carried out in an Ace pressure tube. A mixture of 2,3-dibromopyridine (1.0 mmol, 237 mg), K₄[Fe(CN)₆]·3H₂O (0.4 mmol, 169 mg), Na₂CO₃ (1.2 mmol, 127 mg), CuI (0.1 mmol, 19 mg), 1-butyl-imidazole (2.0 mmol, 248 mg) and o-xylene (2 ml) was stirred at 160°C for 24 h. Afterwards the reaction mixture was quenched with water and diluted with dichloromethane. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 × 20 ml). The combined organic layers were dried on anhydrous Na₂SO₄. After filtering, the solvent was removed in vacuo, and the product was purified by column chromatography (silica gel, ethyl acetate/n-hexane 1:1 v/v; yield: 20%, 37 mg). Crystals suitable for X-ray analysis were obtained by recrystallization from an ethyl acetate/n-heptane (1:1 v/v) solution. ¹H NMR (300 MHz, CDCl₃): δ = 7.43 (dd, 1H, J = 744 Hz), 2.09 (s, 3H), 8.03 (dd, 1H, J = 8.03 Hz), 8.63 (dd, 1H, J = 744 Hz); ¹³C NMR (CDCl₃): δ = 115.7 (C), 124.6 (C), 127.8 (CH), 135.1 (C), 149.2 (CH), 149.2 (CH); GC–MS (EI, 70 eV): m/z = 184 (M⁺, 96), 181 (100), 103 (99), 76 (49), 75 (29), 51 (22), 50 (21).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. One outlier (100) was omitted in the last cycles of refinement.

Table 1
Experimental details

Crystal data
Chemical formula	C₆H₃BrN₂
M_r	183.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.8821 (2), 11.7480 (3), 7.4169 (2)
β (°)	113.906 (1)
V (Å³)	627.88 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.44
Crystal size (mm)	0.43 × 0.39 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII DUO
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.17, 0.34
No. of measured, independent and observed [I > 2σ(I)] reflections	18621, 1637, 1577
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.042, 1.16
No. of reflections	1637
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.37
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), XP in SHELXTL and SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ), publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1956264

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314619013269/rz4033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619013269/rz4033Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619013269/rz4033Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

3-Bromopyridine-2-carbonitrile top

Crystal data top

C₆H₃BrN₂	F(000) = 352
M_r = 183.01	D_x = 1.936 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8821 (2) Å	Cell parameters from 9981 reflections
b = 11.7480 (3) Å	θ = 2.8–28.8°
c = 7.4169 (2) Å	µ = 6.44 mm⁻¹
β = 113.906 (1)°	T = 150 K
V = 627.88 (3) Å³	Part of a needle, colourless
Z = 4	0.43 × 0.39 × 0.22 mm

Data collection top

Bruker Kappa APEXII DUO diffractometer	1637 independent reflections
Radiation source: fine-focus sealed tube	1577 reflections with I > 2σ(I)
Curved graphite monochromator	R_int = 0.020
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.8°, θ_min = 3.3°
ω and phi scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −15→15
T_min = 0.17, T_max = 0.34	l = −10→8
18621 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.0198P)² + 0.3045P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.001
1637 reflections	Δρ_max = 0.38 e Å⁻³
82 parameters	Δρ_min = −0.37 e Å⁻³

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.

Refinement. The H atoms were refined as riding, with C–H = 0.95 Å and U_iso(H) = -1.2U_eq(C).

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

	x	y	z	U_iso*/U_eq
Br1	0.30145 (2)	0.36783 (2)	0.19853 (2)	0.02306 (6)
C1	0.0879 (2)	0.16246 (12)	0.1697 (2)	0.0229 (3)
C2	0.08389 (19)	0.28060 (12)	0.1631 (2)	0.0219 (3)
C3	−0.0811 (2)	0.33623 (13)	0.1323 (2)	0.0272 (3)
H3	−0.0885	0.4170	0.1274	0.033*
C4	−0.2344 (2)	0.27070 (14)	0.1088 (2)	0.0286 (3)
H4	−0.3499	0.3058	0.0860	0.034*
C5	−0.2173 (2)	0.15295 (14)	0.1192 (3)	0.0287 (3)
H5	−0.3235	0.1090	0.1037	0.034*
C6	0.2574 (2)	0.10001 (14)	0.2049 (2)	0.0274 (3)
N1	−0.05951 (18)	0.09830 (12)	0.1497 (2)	0.0280 (3)
N2	0.3907 (2)	0.05012 (14)	0.2363 (2)	0.0384 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02029 (8)	0.02140 (8)	0.02829 (9)	−0.00458 (5)	0.01069 (6)	−0.00295 (5)
C1	0.0233 (6)	0.0217 (6)	0.0235 (7)	0.0023 (5)	0.0094 (5)	0.0002 (5)
C2	0.0219 (6)	0.0213 (6)	0.0222 (6)	−0.0009 (5)	0.0087 (5)	−0.0011 (5)
C3	0.0277 (7)	0.0211 (6)	0.0314 (8)	0.0040 (5)	0.0104 (6)	0.0003 (6)
C4	0.0226 (6)	0.0301 (8)	0.0330 (8)	0.0053 (6)	0.0110 (6)	0.0015 (6)
C5	0.0231 (7)	0.0278 (7)	0.0354 (8)	0.0006 (6)	0.0121 (6)	0.0022 (6)
C6	0.0273 (7)	0.0238 (7)	0.0320 (8)	0.0017 (6)	0.0129 (6)	−0.0017 (6)
N1	0.0255 (6)	0.0233 (6)	0.0362 (7)	0.0013 (5)	0.0136 (5)	0.0023 (5)
N2	0.0311 (7)	0.0354 (8)	0.0485 (9)	0.0077 (6)	0.0161 (7)	−0.0040 (7)

Geometric parameters (Å, º) top

Br1—C2	1.9220 (14)	C3—H3	0.9500
C1—N1	1.3418 (19)	C4—C5	1.389 (2)
C1—C2	1.389 (2)	C4—H4	0.9500
C1—C6	1.452 (2)	C5—N1	1.335 (2)
C2—C3	1.390 (2)	C5—H5	0.9500
C3—C4	1.382 (2)	C6—N2	1.141 (2)

N1—C1—C2	123.46 (14)	C3—C4—C5	119.18 (14)
N1—C1—C6	115.37 (13)	C3—C4—H4	120.4
C2—C1—C6	121.15 (14)	C5—C4—H4	120.4
C1—C2—C3	118.83 (13)	N1—C5—C4	123.44 (15)
C1—C2—Br1	121.45 (11)	N1—C5—H5	118.3
C3—C2—Br1	119.71 (11)	C4—C5—H5	118.3
C4—C3—C2	118.08 (14)	N2—C6—C1	178.55 (19)
C4—C3—H3	121.0	C5—N1—C1	117.00 (14)
C2—C3—H3	121.0

N1—C1—C2—C3	−0.6 (2)	C2—C3—C4—C5	0.7 (2)
C6—C1—C2—C3	−178.91 (14)	C3—C4—C5—N1	−0.4 (3)
N1—C1—C2—Br1	178.61 (11)	C4—C5—N1—C1	−0.5 (2)
C6—C1—C2—Br1	0.3 (2)	C2—C1—N1—C5	1.0 (2)
C1—C2—C3—C4	−0.3 (2)	C6—C1—N1—C5	179.35 (14)
Br1—C2—C3—C4	−179.52 (12)

Funding information

The authors acknowledge research funding from the Deanship of Scientific Research (DSR) at King Fahd University of Petroleum and Minerals (KFUPM) via project No. IN161012.

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