2-Amino-5-bromo­pyridine–benzoic acid (1/1)

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

doi:10.1107/S1600536810005969

organic compounds

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Volume 66| Part 3| March 2010| Page o663

doi:10.1107/S1600536810005969

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2-Amino-5-bromopyridine–benzoic acid (1/1)

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 9 February 2010; accepted 14 February 2010; online 20 February 2010)

In the title adduct, C₅H₅BrN₂·C₇H₆O₂, the carboxyl group of the benzoic acid molecule is twisted away from the attached ring by 12.97 (11)°. The 2-amino-5-bromopyridine molecules interact with the carboxylic group of neighbouring benzoic acid molecules through N—H⋯O and O—H⋯N hydrogen bonds, forming cyclic R₂²(8) hydrogen-bonded motifs and linking the molecules into a two-dimensional network lying parallel to (100). The crystal structure is further stabilized by weak C—H⋯O hydrogen bonds.

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 details of hydrogen bonding, see: Jeffrey & Saenger (1991 ); Jeffrey (1997 ); Scheiner (1997 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ); For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₅H₅BrN₂·C₇H₆O₂
M_r = 295.14
Monoclinic, P 2₁ /c
a = 18.5614 (16) Å
b = 5.1769 (5) Å
c = 12.3613 (11) Å
β = 97.016 (2)°
V = 1178.91 (19) Å³
Z = 4
Mo Kα radiation
μ = 3.48 mm⁻¹
T = 100 K
0.61 × 0.21 × 0.07 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.228, T_max = 0.788
19825 measured reflections
5495 independent reflections
3709 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.01
5495 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 1.25 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.83	2.626 (2)	162
N2—H2A⋯O2ⁱⁱ	0.86	2.02	2.866 (3)	167
N2—H2B⋯O1ⁱⁱⁱ	0.86	2.25	3.105 (2)	171
C7—H7⋯O2^iv	0.93	2.51	3.064 (2)	118
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005969/rz2420sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005969/rz2420Isup2.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-bond interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). 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 the literature. In the present study, the hydrogen-bonding patterns in the 2-amino-5-bromopyridine benzoic acid (1/1) cocrystal are investigated.

The asymmetric unit (Fig 1), contains one 2-amino-5-bromopyridine molecule and one benzoic acid molecule. The 2-amino-5-bromopyridine molecule is planar, with a maximum deviation of 0.024 (2)Å for atom N2. The carboxyl group of the benzoic acid molecule is twisted away from the attached ring by 12.97 (11)° . The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the 2-amino-5-bromopyridine molecules interact with the carboxylic group of the respective benzoic acid molecules through N2—H2A···O2 and O1—H1···N1 hydrogen bonds, forming a cyclic hydrogen-bonded motif R₂²(8) (Bernstein et al., 1995), and linking the molecules into 2-dimensional networks parallel to the (100) plane. The crystal structure is further stabilized by strong N2—H2B···O1 and weak C7—H7···O2 (Table 1) hydrogen bonds.

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 details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995); For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

A hot methanol solution (20 ml) of 2-amino-5-bromopyridine (87 mg, Aldrich) and benzoic acid (61 mg, Merck) were mixed and warmed over a heating magnetic stirrer for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared 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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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-bromopyridine–benzoic acid (1/1) top

Crystal data top

C₅H₅BrN₂·C₇H₆O₂	F(000) = 592
M_r = 295.14	D_x = 1.663 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3648 reflections
a = 18.5614 (16) Å	θ = 3.8–32.0°
b = 5.1769 (5) Å	µ = 3.48 mm⁻¹
c = 12.3613 (11) Å	T = 100 K
β = 97.016 (2)°	Plate, colourless
V = 1178.91 (19) Å³	0.61 × 0.21 × 0.07 mm
Z = 4

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	5495 independent reflections
Radiation source: fine-focus sealed tube	3709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 35.9°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −30→30
T_min = 0.228, T_max = 0.788	k = −8→8
19825 measured reflections	l = −20→20

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.064P)²] where P = (F_o² + 2F_c²)/3
5495 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 1.25 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₅H₅BrN₂·C₇H₆O₂	V = 1178.91 (19) Å³
M_r = 295.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.5614 (16) Å	µ = 3.48 mm⁻¹
b = 5.1769 (5) Å	T = 100 K
c = 12.3613 (11) Å	0.61 × 0.21 × 0.07 mm
β = 97.016 (2)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	5495 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3709 reflections with I > 2σ(I)
T_min = 0.228, T_max = 0.788	R_int = 0.057
19825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.01	Δρ_max = 1.25 e Å⁻³
5495 reflections	Δρ_min = −0.50 e Å⁻³
155 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) k.

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
Br1	0.470134 (11)	0.30630 (5)	0.886018 (18)	0.02683 (8)
N1	0.31375 (10)	−0.1799 (3)	0.73265 (14)	0.0191 (3)
N2	0.25884 (11)	−0.2217 (4)	0.55605 (15)	0.0252 (4)
H2A	0.2364	−0.3558	0.5758	0.030*
H2B	0.2519	−0.1704	0.4894	0.030*
C1	0.30452 (10)	−0.0928 (4)	0.62906 (16)	0.0188 (3)
C2	0.34283 (11)	0.1260 (4)	0.59759 (17)	0.0214 (4)
H2	0.3351	0.1861	0.5262	0.026*
C3	0.39160 (12)	0.2490 (4)	0.67336 (19)	0.0231 (4)
H3	0.4172	0.3930	0.6543	0.028*
C4	0.40175 (11)	0.1516 (4)	0.78013 (17)	0.0210 (4)
C5	0.36211 (11)	−0.0591 (4)	0.80675 (16)	0.0206 (4)
H5	0.3688	−0.1204	0.8780	0.025*
O1	0.23842 (7)	0.4732 (3)	0.82571 (10)	0.0188 (3)
H1	0.2668	0.5550	0.7929	0.028*
O2	0.19345 (9)	0.3546 (3)	0.65709 (11)	0.0217 (3)
C7	0.13808 (11)	0.1436 (4)	0.91317 (15)	0.0186 (4)
H7	0.1616	0.2660	0.9600	0.022*
C8	0.09178 (11)	−0.0370 (4)	0.95201 (16)	0.0215 (4)
H8	0.0842	−0.0341	1.0250	0.026*
C9	0.05710 (11)	−0.2199 (4)	0.88304 (18)	0.0215 (4)
H9	0.0265	−0.3401	0.9097	0.026*
C10	0.06795 (12)	−0.2244 (4)	0.77347 (18)	0.0217 (4)
H10	0.0446	−0.3477	0.7269	0.026*
C11	0.11352 (10)	−0.0450 (4)	0.73404 (15)	0.0191 (3)
H11	0.1205	−0.0473	0.6608	0.023*
C12	0.14884 (10)	0.1389 (4)	0.80347 (15)	0.0163 (3)
C13	0.19580 (10)	0.3321 (4)	0.75609 (15)	0.0163 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02372 (11)	0.02522 (13)	0.03212 (12)	−0.00568 (8)	0.00565 (8)	−0.00818 (9)
N1	0.0222 (7)	0.0160 (8)	0.0196 (7)	−0.0029 (6)	0.0045 (6)	−0.0009 (6)
N2	0.0331 (9)	0.0235 (9)	0.0182 (7)	−0.0074 (8)	0.0000 (7)	0.0037 (7)
C1	0.0201 (8)	0.0154 (8)	0.0212 (8)	0.0012 (7)	0.0041 (7)	0.0016 (7)
C2	0.0221 (8)	0.0194 (9)	0.0239 (8)	0.0008 (7)	0.0076 (7)	0.0056 (8)
C3	0.0208 (8)	0.0181 (9)	0.0320 (10)	−0.0006 (7)	0.0097 (8)	0.0032 (8)
C4	0.0191 (8)	0.0176 (9)	0.0268 (9)	−0.0005 (7)	0.0053 (7)	−0.0045 (7)
C5	0.0220 (8)	0.0194 (9)	0.0208 (8)	−0.0005 (8)	0.0043 (7)	0.0011 (7)
O1	0.0209 (6)	0.0193 (7)	0.0159 (6)	−0.0052 (6)	0.0013 (5)	0.0003 (5)
O2	0.0310 (7)	0.0199 (7)	0.0145 (5)	−0.0032 (6)	0.0043 (5)	0.0000 (5)
C7	0.0219 (8)	0.0183 (9)	0.0153 (7)	−0.0007 (7)	0.0010 (6)	0.0010 (7)
C8	0.0225 (8)	0.0226 (10)	0.0199 (8)	−0.0018 (8)	0.0041 (7)	0.0052 (8)
C9	0.0207 (8)	0.0165 (9)	0.0277 (9)	−0.0007 (7)	0.0043 (7)	0.0054 (8)
C10	0.0218 (8)	0.0168 (9)	0.0266 (9)	−0.0009 (7)	0.0027 (7)	−0.0033 (8)
C11	0.0214 (8)	0.0171 (9)	0.0190 (8)	0.0013 (7)	0.0033 (6)	−0.0029 (7)
C12	0.0176 (7)	0.0141 (8)	0.0173 (7)	0.0018 (6)	0.0031 (6)	0.0008 (6)
C13	0.0191 (8)	0.0143 (8)	0.0158 (7)	0.0022 (7)	0.0028 (6)	0.0002 (6)

Geometric parameters (Å, º) top

Br1—C4	1.887 (2)	O1—H1	0.8200
N1—C1	1.349 (3)	O2—C13	1.225 (2)
N1—C5	1.355 (3)	C7—C8	1.394 (3)
N2—C1	1.339 (3)	C7—C12	1.395 (2)
N2—H2A	0.8600	C7—H7	0.9300
N2—H2B	0.8600	C8—C9	1.380 (3)
C1—C2	1.417 (3)	C8—H8	0.9300
C2—C3	1.377 (3)	C9—C10	1.394 (3)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.404 (3)	C10—C11	1.384 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.378 (3)	C11—C12	1.391 (3)
C5—H5	0.9300	C11—H11	0.9300
O1—C13	1.317 (2)	C12—C13	1.493 (3)

C1—N1—C5	118.98 (18)	C8—C7—H7	120.3
C1—N2—H2A	120.0	C12—C7—H7	120.3
C1—N2—H2B	120.0	C9—C8—C7	120.53 (18)
H2A—N2—H2B	120.0	C9—C8—H8	119.7
N2—C1—N1	118.04 (19)	C7—C8—H8	119.7
N2—C1—C2	120.74 (19)	C8—C9—C10	120.01 (19)
N1—C1—C2	121.21 (19)	C8—C9—H9	120.0
C3—C2—C1	119.56 (19)	C10—C9—H9	120.0
C3—C2—H2	120.2	C11—C10—C9	119.9 (2)
C1—C2—H2	120.2	C11—C10—H10	120.1
C2—C3—C4	118.38 (19)	C9—C10—H10	120.1
C2—C3—H3	120.8	C10—C11—C12	120.26 (18)
C4—C3—H3	120.8	C10—C11—H11	119.9
C5—C4—C3	119.6 (2)	C12—C11—H11	119.9
C5—C4—Br1	120.26 (16)	C11—C12—C7	119.95 (18)
C3—C4—Br1	120.10 (16)	C11—C12—C13	118.04 (16)
N1—C5—C4	122.22 (19)	C7—C12—C13	121.98 (18)
N1—C5—H5	118.9	O2—C13—O1	123.04 (18)
C4—C5—H5	118.9	O2—C13—C12	120.31 (18)
C13—O1—H1	109.5	O1—C13—C12	116.65 (16)
C8—C7—C12	119.37 (19)

C5—N1—C1—N2	177.14 (19)	C7—C8—C9—C10	−0.3 (3)
C5—N1—C1—C2	−1.8 (3)	C8—C9—C10—C11	−0.1 (3)
N2—C1—C2—C3	−177.5 (2)	C9—C10—C11—C12	0.4 (3)
N1—C1—C2—C3	1.4 (3)	C10—C11—C12—C7	−0.3 (3)
C1—C2—C3—C4	0.1 (3)	C10—C11—C12—C13	−178.42 (19)
C2—C3—C4—C5	−1.2 (3)	C8—C7—C12—C11	0.0 (3)
C2—C3—C4—Br1	178.02 (16)	C8—C7—C12—C13	177.99 (19)
C1—N1—C5—C4	0.6 (3)	C11—C12—C13—O2	12.0 (3)
C3—C4—C5—N1	0.9 (3)	C7—C12—C13—O2	−166.00 (19)
Br1—C4—C5—N1	−178.36 (15)	C11—C12—C13—O1	−168.26 (18)
C12—C7—C8—C9	0.3 (3)	C7—C12—C13—O1	13.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.83	2.626 (2)	162
N2—H2A···O2ⁱⁱ	0.86	2.02	2.866 (3)	167
N2—H2B···O1ⁱⁱⁱ	0.86	2.25	3.105 (2)	171
C7—H7···O2^iv	0.93	2.51	3.064 (2)	118

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

Experimental details

Crystal data
Chemical formula	C₅H₅BrN₂·C₇H₆O₂
M_r	295.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	18.5614 (16), 5.1769 (5), 12.3613 (11)
β (°)	97.016 (2)
V (Å³)	1178.91 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.48
Crystal size (mm)	0.61 × 0.21 × 0.07

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.228, 0.788
No. of measured, independent and observed [I > 2σ(I)] reflections	19825, 5495, 3709
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.825

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.01
No. of reflections	5495
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.25, −0.50

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
O1—H1···N1ⁱ	0.8200	1.8300	2.626 (2)	162.00
N2—H2A···O2ⁱⁱ	0.8600	2.0200	2.866 (3)	167.00
N2—H2B···O1ⁱⁱⁱ	0.8600	2.2500	3.105 (2)	171.00
C7—H7···O2^iv	0.9300	2.5100	3.064 (2)	118.00

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