2-Amino-5-bromo­pyridinium hydrogen succinate

Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810006495

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages o689-o690

doi:10.1107/S1600536810006495

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2-Amino-5-bromopyridinium hydrogen succinate

Madhukar Hemamalini ^a and Hoong-Kun Fun ^a ^*‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 17 February 2010; accepted 19 February 2010; online 27 February 2010)

In the title compound, C₅H₆BrN₂⁺·C₄H₅O₄⁻, the pyridine N atom of the 2-amino-5-bromopyridine molecule is protonated. The protonated N atom and the amino group are linked via N—H⋯O hydrogen bonds to the carboxylate O atoms of the singly deprotonated succinate anion. The hydrogen succinate anions are linked via O—H⋯O hydrogen bonds. A weak intermolecular C—H⋯O hydrogen bond is also observed.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ); Katritzky et al. (1996 ). For related structures, see: Goubitz et al. (2001 ); Vaday & Foxman (1999 ). For applications of succinic acid, see: Sauer et al. (2008 ). For bond-length data, see: Allen et al. (1987 ). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ); Jeffrey (1997 ); Scheiner (1997 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₅H₆N₂Br⁺·C₄H₅O₄⁻
M_r = 291.11
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.3275 (2) Å
b = 13.6226 (5) Å
c = 15.1687 (5) Å
V = 1100.86 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.74 mm⁻¹
T = 296 K
0.80 × 0.15 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.155, T_max = 0.650
10042 measured reflections
2472 independent reflections
2138 reflections with I > 2s(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.057
S = 0.99
2472 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 995 Friedel pairs
Flack parameter: 0.013 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.85 (3)	1.88 (3)	2.720 (3)	171 (3)
N2—H2A⋯O1	0.86	1.92	2.782 (3)	178
N2—H2B⋯O1ⁱ	0.86	2.01	2.805 (3)	154
O4—H4⋯O2ⁱⁱ	0.82	1.85	2.609 (2)	154
C1—H1⋯O3ⁱⁱⁱ	0.93	2.43	3.280 (3)	152
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006495/is2526sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006495/is2526Isup2.hkl

checkCIF report

Comment top

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). They are often involved in hydrogen-bonding interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). Succinic acid derivatives are mostly used in chemicals, food and pharmaceuticals (Sauer et al., 2008). The crystal structures of 2-amino-5-bromopyridine (Goubitz et al., 2001) and 2-amino-5-bromopyridinium propynoate (Vaday & Foxman, 1999) have been reported. In this paper, we present the X-ray single-crystal structure of 2-amino-5-bromopyridinium hydrogen succinate (I).

The asymmetric unit of (I) (Fig. 1) contains a 2-amino-5-bromopyridinium cation and a hydrogen succinate anion, indicating that proton transfer has occurred during the co-crystallization experiment. In the 2-amino-5-bromopyridinium cation, a wider than normal angle [122.9 (2)°] is subtended at the protonated N1 atom. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the protonated N1 atom and the 2-amino group (N2) is hydrogen-bonded to the carboxylate oxygen atoms (O1 and O2) via a pair of N—H···O hydrogen bonds, forming a R₂²(8) ring motif (Bernstein et al., 1995). The hydrogen succinate anions self-assemble via O4—H4···O2 (Table 1) hydrogen bonds. Furthermore, the crystal structure is stabilized by weak C—H···O hydrogen bonds, forming a 3D-network.

Related literature top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For related structures, see: Goubitz et al. (2001); Vaday & Foxman (1999). For applications of succinic acid, see: Sauer et al. (2008). For bond-length data, see: Allen et al. (1987). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A hot methanol solution (10 ml) of 2-amino-5-bromopyridine (87 mg, Aldrich) and a hot aqueous solution (10 ml) of succinic acid (59 mg, Merck) were mixed and warmed over a water bath for 10 minutes. The resulting solution was allowed to cool slowly at room temperature. Single crystals of the title compound appeared from the mother liquor after a few days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, showing hydrogen-bonded (dashed lines) networks.

2-Amino-5-bromopyridinium hydrogen succinate top

Crystal data top

C₅H₆N₂Br⁺·C₄H₅O₄⁻	F(000) = 584
M_r = 291.11	D_x = 1.756 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4688 reflections
a = 5.3275 (2) Å	θ = 3.0–26.7°
b = 13.6226 (5) Å	µ = 3.74 mm⁻¹
c = 15.1687 (5) Å	T = 296 K
V = 1100.86 (7) Å³	Needle, yellow
Z = 4	0.80 × 0.15 × 0.13 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2472 independent reflections
Radiation source: fine-focus sealed tube	2138 reflections with I > 2s(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.155, T_max = 0.650	k = −17→16
10042 measured reflections	l = −19→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0248P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.002
2472 reflections	Δρ_max = 0.21 e Å⁻³
150 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 995 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (8)

Crystal data top

C₅H₆N₂Br⁺·C₄H₅O₄⁻	V = 1100.86 (7) Å³
M_r = 291.11	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.3275 (2) Å	µ = 3.74 mm⁻¹
b = 13.6226 (5) Å	T = 296 K
c = 15.1687 (5) Å	0.80 × 0.15 × 0.13 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2472 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2138 reflections with I > 2s(I)
T_min = 0.155, T_max = 0.650	R_int = 0.029
10042 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.057	Δρ_max = 0.21 e Å⁻³
S = 0.99	Δρ_min = −0.31 e Å⁻³
2472 reflections	Absolute structure: Flack (1983), 995 Friedel pairs
150 parameters	Absolute structure parameter: 0.013 (8)
0 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.0791 (3)	0.66915 (12)	0.38303 (10)	0.0490 (4)
O2	0.2588 (3)	0.53970 (10)	0.32236 (11)	0.0441 (4)
O3	0.0528 (4)	0.80559 (14)	0.20813 (14)	0.0633 (6)
O4	−0.3210 (4)	0.86482 (12)	0.24424 (12)	0.0561 (5)
H4	−0.2572	0.9169	0.2290	0.084*
C6	0.0954 (4)	0.60694 (15)	0.32351 (14)	0.0341 (5)
C7	−0.0907 (5)	0.61018 (17)	0.24855 (15)	0.0450 (6)
H7A	−0.1850	0.5493	0.2485	0.054*
H7B	0.0017	0.6134	0.1935	0.054*
C8	−0.2747 (5)	0.69486 (17)	0.25115 (16)	0.0437 (6)
H8A	−0.4068	0.6826	0.2085	0.052*
H8B	−0.3515	0.6971	0.3091	0.052*
C9	−0.1593 (5)	0.79274 (16)	0.23193 (13)	0.0377 (5)
Br1	1.17196 (5)	0.336238 (18)	0.513704 (18)	0.05230 (10)
N1	0.6002 (4)	0.52635 (13)	0.45518 (13)	0.0345 (4)
N2	0.4388 (4)	0.66737 (14)	0.51595 (13)	0.0459 (5)
H2A	0.3300	0.6690	0.4741	0.055*
H2B	0.4388	0.7123	0.5558	0.055*
C1	0.7639 (4)	0.45042 (15)	0.45213 (15)	0.0377 (5)
H1	0.7547	0.4047	0.4067	0.045*
C2	0.9404 (4)	0.44144 (16)	0.51537 (15)	0.0380 (5)
C3	0.9540 (5)	0.51139 (18)	0.58345 (16)	0.0414 (6)
H3	1.0756	0.5056	0.6271	0.050*
C4	0.7899 (5)	0.58693 (16)	0.58521 (14)	0.0405 (5)
H4A	0.7984	0.6332	0.6302	0.049*
C5	0.6060 (4)	0.59588 (15)	0.51909 (14)	0.0343 (5)
H1N1	0.482 (5)	0.5320 (17)	0.4180 (16)	0.047 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0616 (11)	0.0425 (9)	0.0428 (8)	0.0111 (9)	−0.0104 (8)	−0.0157 (8)
O2	0.0495 (10)	0.0309 (8)	0.0520 (9)	0.0067 (7)	−0.0090 (8)	−0.0090 (7)
O3	0.0470 (12)	0.0576 (12)	0.0852 (14)	−0.0024 (9)	0.0118 (11)	0.0229 (10)
O4	0.0603 (11)	0.0347 (9)	0.0733 (12)	0.0024 (10)	0.0199 (11)	0.0111 (8)
C6	0.0412 (13)	0.0265 (10)	0.0347 (11)	−0.0057 (9)	0.0013 (9)	−0.0001 (9)
C7	0.0572 (17)	0.0345 (12)	0.0432 (13)	−0.0017 (11)	−0.0075 (12)	−0.0049 (10)
C8	0.0426 (15)	0.0392 (12)	0.0493 (13)	−0.0033 (10)	−0.0088 (11)	0.0050 (10)
C9	0.0418 (13)	0.0385 (12)	0.0330 (10)	−0.0026 (12)	−0.0029 (12)	0.0039 (9)
Br1	0.04413 (14)	0.04024 (13)	0.07255 (17)	0.00556 (11)	−0.00191 (13)	0.00411 (12)
N1	0.0360 (11)	0.0308 (10)	0.0367 (10)	−0.0035 (8)	−0.0032 (9)	−0.0029 (8)
N2	0.0480 (11)	0.0377 (10)	0.0520 (10)	0.0049 (9)	−0.0099 (10)	−0.0151 (10)
C1	0.0415 (13)	0.0291 (11)	0.0426 (11)	−0.0051 (10)	0.0030 (10)	−0.0034 (9)
C2	0.0364 (12)	0.0334 (11)	0.0442 (11)	−0.0016 (9)	0.0024 (11)	0.0036 (10)
C3	0.0397 (13)	0.0436 (13)	0.0410 (12)	−0.0064 (12)	−0.0046 (11)	0.0035 (11)
C4	0.0443 (14)	0.0411 (12)	0.0362 (11)	−0.0048 (12)	−0.0015 (11)	−0.0057 (10)
C5	0.0355 (11)	0.0303 (10)	0.0370 (10)	−0.0069 (9)	0.0046 (10)	−0.0002 (9)

Geometric parameters (Å, º) top

O1—C6	1.241 (2)	N1—C1	1.354 (3)
O2—C6	1.264 (3)	N1—C5	1.356 (3)
O3—C9	1.199 (3)	N1—H1N1	0.85 (3)
O4—C9	1.319 (3)	N2—C5	1.321 (3)
O4—H4	0.8200	N2—H2A	0.8600
C6—C7	1.509 (3)	N2—H2B	0.8600
C7—C8	1.514 (3)	C1—C2	1.349 (3)
C7—H7A	0.9700	C1—H1	0.9300
C7—H7B	0.9700	C2—C3	1.407 (3)
C8—C9	1.497 (3)	C3—C4	1.351 (3)
C8—H8A	0.9700	C3—H3	0.9300
C8—H8B	0.9700	C4—C5	1.407 (3)
Br1—C2	1.891 (2)	C4—H4A	0.9300

C9—O4—H4	109.5	C1—N1—H1N1	121.6 (17)
O1—C6—O2	123.6 (2)	C5—N1—H1N1	115.4 (17)
O1—C6—C7	118.8 (2)	C5—N2—H2A	120.0
O2—C6—C7	117.60 (18)	C5—N2—H2B	120.0
C6—C7—C8	115.32 (18)	H2A—N2—H2B	120.0
C6—C7—H7A	108.4	C2—C1—N1	119.6 (2)
C8—C7—H7A	108.4	C2—C1—H1	120.2
C6—C7—H7B	108.4	N1—C1—H1	120.2
C8—C7—H7B	108.4	C1—C2—C3	119.8 (2)
H7A—C7—H7B	107.5	C1—C2—Br1	120.93 (17)
C9—C8—C7	114.1 (2)	C3—C2—Br1	119.31 (18)
C9—C8—H8A	108.7	C4—C3—C2	119.8 (2)
C7—C8—H8A	108.7	C4—C3—H3	120.1
C9—C8—H8B	108.7	C2—C3—H3	120.1
C7—C8—H8B	108.7	C3—C4—C5	120.2 (2)
H8A—C8—H8B	107.6	C3—C4—H4A	119.9
O3—C9—O4	123.3 (2)	C5—C4—H4A	119.9
O3—C9—C8	125.1 (2)	N2—C5—N1	118.3 (2)
O4—C9—C8	111.5 (2)	N2—C5—C4	123.99 (19)
C1—N1—C5	122.9 (2)	N1—C5—C4	117.7 (2)

O1—C6—C7—C8	3.3 (3)	C1—C2—C3—C4	0.2 (3)
O2—C6—C7—C8	−177.4 (2)	Br1—C2—C3—C4	179.88 (18)
C6—C7—C8—C9	70.8 (3)	C2—C3—C4—C5	−0.1 (3)
C7—C8—C9—O3	6.8 (3)	C1—N1—C5—N2	179.6 (2)
C7—C8—C9—O4	−173.26 (18)	C1—N1—C5—C4	−0.7 (3)
C5—N1—C1—C2	0.8 (3)	C3—C4—C5—N2	−180.0 (2)
N1—C1—C2—C3	−0.5 (3)	C3—C4—C5—N1	0.4 (3)
N1—C1—C2—Br1	179.82 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.85 (3)	1.88 (3)	2.720 (3)	171 (3)
N2—H2A···O1	0.86	1.92	2.782 (3)	178
N2—H2B···O1ⁱ	0.86	2.01	2.805 (3)	154
O4—H4···O2ⁱⁱ	0.82	1.85	2.609 (2)	154
C1—H1···O3ⁱⁱⁱ	0.93	2.43	3.280 (3)	152

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₆N₂Br⁺·C₄H₅O₄⁻
M_r	291.11
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	5.3275 (2), 13.6226 (5), 15.1687 (5)
V (Å³)	1100.86 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.74
Crystal size (mm)	0.80 × 0.15 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.155, 0.650
No. of measured, independent and observed [I > 2s(I)] reflections	10042, 2472, 2138
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.057, 0.99
No. of reflections	2472
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.31
Absolute structure	Flack (1983), 995 Friedel pairs
Absolute structure parameter	0.013 (8)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.85 (3)	1.88 (3)	2.720 (3)	171 (3)
N2—H2A···O1	0.8600	1.9200	2.782 (3)	178.00
N2—H2B···O1ⁱ	0.8600	2.0100	2.805 (3)	154.00
O4—H4···O2ⁱⁱ	0.8200	1.8500	2.609 (2)	154.00
C1—H1···O3ⁱⁱⁱ	0.9300	2.4300	3.280 (3)	152.00

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

MH and HKF thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. MH thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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