rac-1-(2-Amino­carbonyl-2-bromo­eth­yl)pyridinium bromide

Köppen, R.; Emmerling, F.; Koch, M.

doi:10.1107/S1600536812019721

organic compounds

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Volume 68| Part 6| June 2012| Page o1666

doi:10.1107/S1600536812019721

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rac-1-(2-Aminocarbonyl-2-bromoethyl)pyridinium bromide

Robert Köppen,^a ^* Franziska Emmerling ^a and Matthias Koch ^a

^aBAM Federal Institute for Materials Research and Testing, Department of Analytical Chemistry, Reference Materials, Richard-Willstätter-Strasse 11, D-12489 Berlin-Adlershof, Germany
^*Correspondence e-mail: robert.koeppen@bam.de

(Received 25 April 2012; accepted 2 May 2012; online 12 May 2012)

In the crystal structure of the title compound, C₈H₁₀BrN₂O⁺·Br⁻, intermolecular N—H⋯Br hydrogen bonds link the molecules into infinite chains along [001]. The inclined angle between the pyridine ring plane and the plane defined by the acid amide group is 63.97 (4)°.

Related literature

The title compound is an intermediate in the synthesis of 3-triphenylphosphoniumbromidopropionitrile and 1-triphenylphosphoniumbromido-2-pyridinium-bromidoethane, see: Khachikyan et al. (2009 ).

Experimental

Crystal data

C₈H₁₀BrN₂O⁺·Br⁻
M_r = 310.00
Monoclinic, P 2₁ /c
a = 8.6024 (9) Å
b = 16.1200 (19) Å
c = 9.5092 (12) Å
β = 121.501 (8)°
V = 1124.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 7.18 mm⁻¹
T = 296 K
0.14 × 0.11 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.85, T_max = 0.96
10331 measured reflections
2252 independent reflections
1442 reflections with I > 2σ(I)
R_int = 0.106

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.129
S = 1.00
2252 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Br2ⁱ	0.86	2.62	3.406 (7)	154
N2—H2B⋯Br2ⁱⁱ	0.86	2.57	3.428 (6)	173
Symmetry codes: (i) x-1, y, z; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812019721/fj2549sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019721/fj2549Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019721/fj2549Isup3.mol

Supporting information file. DOI: 10.1107/S1600536812019721/fj2549Isup4.cml

checkCIF report

Comment top

rac-1-(2-Aminocarbonyl-2-bromoethyl)pyridinium bromide is an intermediate in the synthesis of 3-triphenylphosphoniumbromidopropionitrile and 1-triphenylphosphoniumbromido-2-pyridinium-bromidoethane (Khachikyan et al., 2009). The compound crystallizes in the monoclinic space group P2₁/c. The molecular structure of the compound and the atom-labeling scheme are shown in Fig 1. The molecules are arranged in such a way that the pyridyl rings are stagged with respect to each other. However, the distance between the molecular planes (d_centroids=4.295 (4) Å) indicates only weak π-π interactions. Each molecule is connected to two adjacent bromine anions via intermolecular N—H···Br hydrogen bonds (see dashed orange bonds in Fig. 2). As a result infinite chains are formed along [001] direction.

Related literature top

The title compound is an intermediate in the synthesis of 3-triphenylphosphoniumbromidopropionitrile and 1-triphenylphosphoniumbromido-2-pyridinium-bromidoethane, see: Khachikyan et al. (2009).

Experimental top

In a 250 ml, one-necked, round-bottomed flask fitted with a reflux condenser and a magnetic stirrer a mixture of 1.85 g of rac-2,3-dibromopropionic acid amide (7.98 mmol) and 0.63 g of pyridine (7.98 mmol) was diluted in 100 ml of acetonitrile and refluxed for 25 h. After cooling the flask was capped with a rubber septum equipped with a needle outlet for slow evaporation and then left in the dark at room temperature for 3 days. The obtained colorless crystals were suitable for direct single-crystal X-ray crystallography.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : ORTEP representation of the title compound with atomic labeling shown with 30% probability displacement ellipsoids.
	Fig. 2. : View of the unit cell of the title compound along [100] (left) and [010] (right) showing the hydrogen-bonded chains along the [001] direction. Hydrogen bonds are drawn as dashed orange lines.

rac-1-(2-Aminocarbonyl-2-bromoethyl)pyridinium bromide top

Crystal data top

C₈H₁₀BrN₂O⁺·Br⁻	F(000) = 600
M_r = 310.00	D_x = 1.831 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 42 reflections
a = 8.6024 (9) Å	θ = 4–25°
b = 16.1200 (19) Å	µ = 7.18 mm⁻¹
c = 9.5092 (12) Å	T = 296 K
β = 121.501 (8)°	Block, colourless
V = 1124.3 (2) Å³	0.14 × 0.11 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2252 independent reflections
Radiation source: fine-focus sealed tube	1442 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.106
ω/2θ scans	θ_max = 26.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.85, T_max = 0.96	k = −19→18
10331 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0659P)²] where P = (F_o² + 2F_c²)/3
2252 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.96 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₈H₁₀BrN₂O⁺·Br⁻	V = 1124.3 (2) Å³
M_r = 310.00	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6024 (9) Å	µ = 7.18 mm⁻¹
b = 16.1200 (19) Å	T = 296 K
c = 9.5092 (12) Å	0.14 × 0.11 × 0.05 mm
β = 121.501 (8)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2252 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1442 reflections with I > 2σ(I)
T_min = 0.85, T_max = 0.96	R_int = 0.106
10331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.00	Δρ_max = 0.96 e Å⁻³
2252 reflections	Δρ_min = −0.56 e Å⁻³
118 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.23648 (10)	0.06295 (5)	0.72065 (9)	0.0538 (3)
O1	0.3105 (6)	0.2759 (3)	0.8640 (6)	0.0652 (15)
N1	0.6197 (6)	0.1137 (3)	0.7616 (6)	0.0384 (12)
N2	0.0498 (7)	0.2553 (4)	0.6168 (7)	0.0661 (18)
H2A	−0.0084	0.2935	0.6335	0.079*
H2B	−0.0038	0.2274	0.5263	0.079*
C1	0.3180 (8)	0.1706 (4)	0.6882 (7)	0.0357 (14)
H1	0.2813	0.1761	0.5722	0.043*
C2	0.2227 (9)	0.2392 (4)	0.7308 (8)	0.0460 (16)
C3	0.5231 (8)	0.1790 (4)	0.7954 (7)	0.0408 (15)
H3A	0.5591	0.2329	0.7764	0.049*
H3B	0.5590	0.1762	0.9104	0.049*
C4	0.6778 (10)	0.0453 (4)	0.8562 (8)	0.0487 (17)
H4	0.6589	0.0398	0.9435	0.058*
C5	0.7646 (11)	−0.0161 (5)	0.8247 (9)	0.061 (2)
H5	0.8030	−0.0639	0.8891	0.073*
C6	0.7945 (10)	−0.0071 (5)	0.6982 (10)	0.061 (2)
H6	0.8561	−0.0482	0.6778	0.073*
C7	0.7336 (10)	0.0633 (4)	0.6000 (9)	0.0541 (18)
H7	0.7516	0.0698	0.5123	0.065*
C8	0.6458 (8)	0.1229 (4)	0.6362 (8)	0.0432 (15)
H8	0.6038	0.1707	0.5720	0.052*
Br2	0.79943 (9)	0.35088 (4)	0.75292 (7)	0.0465 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0548 (5)	0.0502 (5)	0.0573 (5)	−0.0118 (3)	0.0299 (4)	−0.0013 (3)
O1	0.047 (3)	0.087 (4)	0.050 (3)	0.002 (3)	0.018 (3)	−0.035 (3)
N1	0.038 (3)	0.039 (3)	0.038 (3)	0.002 (2)	0.020 (3)	−0.003 (2)
N2	0.045 (4)	0.079 (4)	0.054 (4)	0.019 (3)	0.012 (3)	−0.027 (3)
C1	0.044 (4)	0.038 (3)	0.027 (3)	0.001 (3)	0.020 (3)	−0.001 (2)
C2	0.049 (5)	0.050 (4)	0.041 (4)	−0.002 (3)	0.025 (4)	−0.005 (3)
C3	0.040 (4)	0.040 (4)	0.044 (3)	−0.001 (3)	0.022 (3)	−0.003 (3)
C4	0.059 (5)	0.046 (4)	0.041 (4)	0.008 (3)	0.026 (4)	0.006 (3)
C5	0.068 (5)	0.051 (5)	0.057 (4)	0.018 (4)	0.028 (4)	0.010 (4)
C6	0.045 (4)	0.064 (5)	0.067 (5)	0.010 (4)	0.024 (4)	−0.016 (4)
C7	0.051 (5)	0.064 (5)	0.053 (4)	0.001 (4)	0.032 (4)	−0.001 (4)
C8	0.039 (4)	0.047 (4)	0.043 (4)	0.000 (3)	0.020 (3)	0.004 (3)
Br2	0.0511 (5)	0.0474 (4)	0.0384 (4)	0.0015 (3)	0.0216 (3)	−0.0004 (3)

Geometric parameters (Å, º) top

Br1—C1	1.956 (6)	C3—H3A	0.9700
O1—C2	1.235 (7)	C3—H3B	0.9700
N1—C8	1.333 (7)	C4—C5	1.364 (9)
N1—C4	1.343 (8)	C4—H4	0.9300
N1—C3	1.477 (7)	C5—C6	1.363 (10)
N2—C2	1.330 (8)	C5—H5	0.9300
N2—H2A	0.8599	C6—C7	1.386 (10)
N2—H2B	0.8601	C6—H6	0.9300
C1—C3	1.513 (8)	C7—C8	1.373 (9)
C1—C2	1.550 (9)	C7—H7	0.9300
C1—H1	0.9800	C8—H8	0.9300

C8—N1—C4	120.9 (5)	N1—C3—H3B	109.1
C8—N1—C3	119.4 (5)	C1—C3—H3B	109.1
C4—N1—C3	119.7 (5)	H3A—C3—H3B	107.9
C2—N2—H2A	120.0	N1—C4—C5	120.3 (6)
C2—N2—H2B	120.0	N1—C4—H4	119.9
H2A—N2—H2B	120.0	C5—C4—H4	119.9
C3—C1—C2	110.5 (5)	C4—C5—C6	119.5 (7)
C3—C1—Br1	111.2 (4)	C4—C5—H5	120.2
C2—C1—Br1	108.0 (4)	C6—C5—H5	120.2
C3—C1—H1	109.1	C5—C6—C7	120.2 (7)
C2—C1—H1	109.1	C5—C6—H6	119.9
Br1—C1—H1	109.1	C7—C6—H6	119.9
O1—C2—N2	124.5 (6)	C8—C7—C6	117.9 (6)
O1—C2—C1	119.0 (6)	C8—C7—H7	121.1
N2—C2—C1	116.4 (5)	C6—C7—H7	121.1
N1—C3—C1	112.3 (5)	N1—C8—C7	121.2 (6)
N1—C3—H3A	109.1	N1—C8—H8	119.4
C1—C3—H3A	109.1	C7—C8—H8	119.4

C3—C1—C2—O1	−18.5 (8)	C8—N1—C4—C5	−0.2 (10)
Br1—C1—C2—O1	103.3 (6)	C3—N1—C4—C5	178.9 (6)
C3—C1—C2—N2	160.2 (6)	N1—C4—C5—C6	1.1 (11)
Br1—C1—C2—N2	−78.1 (6)	C4—C5—C6—C7	−1.5 (12)
C8—N1—C3—C1	83.1 (7)	C5—C6—C7—C8	1.0 (11)
C4—N1—C3—C1	−96.1 (7)	C4—N1—C8—C7	−0.3 (9)
C2—C1—C3—N1	178.7 (5)	C3—N1—C8—C7	−179.4 (6)
Br1—C1—C3—N1	58.8 (6)	C6—C7—C8—N1	−0.1 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br2ⁱ	0.86	2.62	3.406 (7)	154
N2—H2B···Br2ⁱⁱ	0.86	2.57	3.428 (6)	173

Symmetry codes: (i) x−1, y, z; (ii) x−1, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₀BrN₂O⁺·Br⁻
M_r	310.00
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.6024 (9), 16.1200 (19), 9.5092 (12)
β (°)	121.501 (8)
V (Å³)	1124.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.18
Crystal size (mm)	0.14 × 0.11 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.85, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	10331, 2252, 1442
R_int	0.106
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.129, 1.00
No. of reflections	2252
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.56

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br2ⁱ	0.86	2.62	3.406 (7)	154
N2—H2B···Br2ⁱⁱ	0.86	2.57	3.428 (6)	173

Symmetry codes: (i) x−1, y, z; (ii) x−1, −y+1/2, z−1/2.

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Khachikyan, R. D., Tovmasyan, N. V. & Indzhikyan, M. G. (2009). Russ. J. Gen. Chem. 79, 759–761. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1666

doi:10.1107/S1600536812019721

Open

access