2-Amino-5-chloro­pyridine–fumaric acid (1/2)

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

doi:10.1107/S1600536810018192

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages o1416-o1417

https://doi.org/10.1107/S1600536810018192

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2-Amino-5-chloropyridine–fumaric acid (1/2)

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 13 May 2010; accepted 17 May 2010; online 22 May 2010)

The asymmetric unit of the title compound, C₅H₅ClN₂·0.5C₄H₄O₄, comprises a neutral 2-amino-5-chloropyridine molecule and one half of a fumaric acid molecule which lies on an inversion center. The dihedral angle between the pyridine ring and the plane formed by the fumaric acid molecule is 3.22 (8)°. The 2-amino-5-chloropyridine molecule is planar, with a maximum deviation of 0.004 (1) Å for the pyridine N atom. In the crystal, the 2-amino-5-chloropyridine molecules interact with the carboxyl groups of fumaric acid molecules through N—H⋯O and O—H⋯N hydrogen bonds, forming centrosymmetric R₂²(8) ring motifs and another N—H⋯O hydrogen bond links these motifs into a two-dimensional network parallel to (100).

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ); Katritzky et al. (1996 ). For the details of fumaric acid, see: Batchelor et al. (2000 ). 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

C₅H₅ClN₂·0.5C₄H₄O₄
M_r = 186.60
Monoclinic, P 2₁ /c
a = 13.678 (4) Å
b = 5.0586 (15) Å
c = 11.531 (3) Å
β = 103.442 (7)°
V = 776.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 100 K
0.57 × 0.25 × 0.08 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.784, T_max = 0.967
8439 measured reflections
2771 independent reflections
2420 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.143
S = 1.06
2771 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.82	2.5852 (17)	154
N2—H2A⋯O1	0.86	2.00	2.856 (2)	171
N2—H2B⋯O2ⁱ	0.86	2.26	3.0718 (18)	158
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536810018192/sj5003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018192/sj5003Isup2.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). Fumaric acid is among the organic compounds widely found in nature, and is key intermediate in the biosynthesis of organic acids. Fumaric acid is of interest since it is known to form supramolecular assemblies with N–aromatic complexes (Batchelor et al., 2000). In order to study some interesting hydrogen bonding interactions, the synthesis and structure of the title compound, (I), is presented here.

The asymmetric unit of the title compond consists of a 2-amino-5- chloropyridine molecule and a half of the fumaric acid molecule (Fig. 1). The planar fumaric acid molecule is centrosymmetric with the mid-point of the C═C double bond located at an inversion center. The C6–O1 bond distance of 1.2375 (17) Å is much shorter than the C6–O2 bond distance of 13061 (16) Å, suggesting that the carboxyl group is not deprotonated in the crystal structure. The 2-amino- 5-chloropyridine molecule is planar, with a maximum deviation of 0.004 (1) Å for atom N1. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the 2-amino-5-chloropyridine molecules interact with the carboxyl groups (O1 & O2) of fumaric acid molecules through N2—H2A···O1 and O2—H2···N1 hydrogen bonds (Table 1), forming cyclic hydrogen-bonded motifs R₂²(8) (Bernstein et al., 1995) and the N2—H2B···O2 hydrogen bond links these motifs into a two-dimensional network parallel to (100) plane.

Related literature top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For the details of fumaric acid, see: Batchelor et al. (2000). 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-chloropyridine (64 mg, Aldrich) and fumaric acid (58 mg, Merck) was mixed and warmed over a a magnetic stirrer hotplate 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.

Structure description top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For the details of fumaric acid, see: Batchelor et al. (2000). 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).

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. H atoms not involved in hydrogen bond interactions are omitted for clarity.

2-Amino-5-chloropyridine–(E)-butenedioic acid (1/2) top

Crystal data top

C₅H₅ClN₂·0.5C₄H₄O₄	F(000) = 384
M_r = 186.60	D_x = 1.597 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3958 reflections
a = 13.678 (4) Å	θ = 3.6–36.5°
b = 5.0586 (15) Å	µ = 0.45 mm⁻¹
c = 11.531 (3) Å	T = 100 K
β = 103.442 (7)°	Plate, colourless
V = 776.0 (4) Å³	0.57 × 0.25 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	2771 independent reflections
Radiation source: fine-focus sealed tube	2420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 32.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −20→16
T_min = 0.784, T_max = 0.967	k = −7→7
8439 measured reflections	l = −17→17

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0898P)² + 0.4122P] where P = (F_o² + 2F_c²)/3
2771 reflections	(Δ/σ)_max = 0.001
110 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₅H₅ClN₂·0.5C₄H₄O₄	V = 776.0 (4) Å³
M_r = 186.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.678 (4) Å	µ = 0.45 mm⁻¹
b = 5.0586 (15) Å	T = 100 K
c = 11.531 (3) Å	0.57 × 0.25 × 0.08 mm
β = 103.442 (7)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	2771 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2420 reflections with I > 2σ(I)
T_min = 0.784, T_max = 0.967	R_int = 0.036
8439 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.06	Δρ_max = 0.70 e Å⁻³
2771 reflections	Δρ_min = −0.59 e Å⁻³
110 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
Cl1	0.03621 (3)	−0.27603 (7)	0.40770 (3)	0.01778 (13)
N1	0.25244 (9)	0.1952 (2)	0.34964 (11)	0.0130 (2)
N2	0.34626 (11)	0.2094 (3)	0.20667 (12)	0.0182 (3)
H2A	0.3772	0.3457	0.2420	0.022*
H2B	0.3615	0.1481	0.1436	0.022*
C1	0.17992 (10)	0.0834 (3)	0.39610 (12)	0.0133 (2)
H1A	0.1661	0.1550	0.4648	0.016*
C2	0.12664 (10)	−0.1319 (3)	0.34452 (12)	0.0133 (2)
C3	0.14697 (11)	−0.2407 (3)	0.24014 (13)	0.0149 (3)
H3A	0.1109	−0.3861	0.2037	0.018*
C4	0.22039 (11)	−0.1301 (3)	0.19295 (12)	0.0153 (3)
H4A	0.2349	−0.2000	0.1242	0.018*
C5	0.27436 (10)	0.0926 (3)	0.24997 (12)	0.0133 (2)
O1	0.44882 (8)	0.6317 (2)	0.34908 (10)	0.0177 (2)
O2	0.34481 (8)	0.5851 (2)	0.47334 (9)	0.0143 (2)
H2	0.3331	0.4402	0.4412	0.022*
C6	0.41907 (10)	0.6973 (3)	0.43840 (12)	0.0127 (2)
C7	0.46749 (10)	0.9183 (3)	0.51670 (12)	0.0138 (2)
H7A	0.4520	0.9427	0.5904	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01527 (19)	0.01894 (19)	0.0195 (2)	−0.00319 (10)	0.00484 (13)	0.00275 (11)
N1	0.0146 (5)	0.0132 (5)	0.0113 (5)	−0.0018 (4)	0.0033 (4)	−0.0012 (4)
N2	0.0230 (6)	0.0172 (6)	0.0176 (6)	−0.0049 (4)	0.0111 (5)	−0.0033 (4)
C1	0.0145 (6)	0.0146 (5)	0.0112 (5)	−0.0013 (4)	0.0036 (4)	−0.0002 (4)
C2	0.0125 (5)	0.0142 (6)	0.0127 (5)	−0.0013 (4)	0.0021 (4)	0.0015 (4)
C3	0.0157 (6)	0.0144 (5)	0.0133 (6)	−0.0021 (4)	0.0008 (5)	−0.0012 (4)
C4	0.0189 (6)	0.0148 (6)	0.0121 (5)	−0.0006 (4)	0.0035 (4)	−0.0020 (4)
C5	0.0157 (6)	0.0131 (5)	0.0109 (5)	0.0001 (4)	0.0029 (4)	−0.0004 (4)
O1	0.0197 (5)	0.0184 (5)	0.0175 (5)	−0.0051 (4)	0.0089 (4)	−0.0060 (4)
O2	0.0155 (5)	0.0153 (4)	0.0130 (4)	−0.0039 (3)	0.0049 (4)	−0.0023 (3)
C6	0.0120 (5)	0.0124 (5)	0.0133 (6)	−0.0001 (4)	0.0021 (4)	−0.0007 (4)
C7	0.0144 (6)	0.0135 (5)	0.0133 (6)	−0.0011 (4)	0.0030 (4)	−0.0028 (4)

Geometric parameters (Å, º) top

Cl1—C2	1.7352 (14)	C3—H3A	0.9300
N1—C1	1.3555 (17)	C4—C5	1.422 (2)
N1—C5	1.3565 (17)	C4—H4A	0.9300
N2—C5	1.3393 (18)	O1—C6	1.2375 (17)
N2—H2A	0.8600	O2—C6	1.3061 (16)
N2—H2B	0.8600	O2—H2	0.8200
C1—C2	1.3675 (19)	C6—C7	1.4920 (19)
C1—H1A	0.9300	C7—C7ⁱ	1.335 (3)
C2—C3	1.409 (2)	C7—H7A	0.9300
C3—C4	1.368 (2)

C1—N1—C5	120.10 (12)	C3—C4—C5	119.37 (13)
C5—N2—H2A	120.0	C3—C4—H4A	120.3
C5—N2—H2B	120.0	C5—C4—H4A	120.3
H2A—N2—H2B	120.0	N2—C5—N1	118.25 (13)
N1—C1—C2	121.69 (12)	N2—C5—C4	121.64 (13)
N1—C1—H1A	119.2	N1—C5—C4	120.10 (12)
C2—C1—H1A	119.2	C6—O2—H2	109.5
C1—C2—C3	119.45 (12)	O1—C6—O2	124.75 (13)
C1—C2—Cl1	120.79 (11)	O1—C6—C7	121.27 (12)
C3—C2—Cl1	119.76 (11)	O2—C6—C7	113.98 (12)
C4—C3—C2	119.29 (13)	C7ⁱ—C7—C6	121.41 (16)
C4—C3—H3A	120.4	C7ⁱ—C7—H7A	119.3
C2—C3—H3A	120.4	C6—C7—H7A	119.3

C5—N1—C1—C2	−0.5 (2)	C1—N1—C5—N2	179.77 (13)
N1—C1—C2—C3	−0.3 (2)	C1—N1—C5—C4	0.9 (2)
N1—C1—C2—Cl1	178.49 (11)	C3—C4—C5—N2	−179.38 (14)
C1—C2—C3—C4	0.6 (2)	C3—C4—C5—N1	−0.5 (2)
Cl1—C2—C3—C4	−178.16 (11)	O1—C6—C7—C7ⁱ	11.5 (3)
C2—C3—C4—C5	−0.2 (2)	O2—C6—C7—C7ⁱ	−168.52 (17)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.82	2.5852 (17)	154
N2—H2A···O1	0.86	2.00	2.856 (2)	171
N2—H2B···O2ⁱⁱ	0.86	2.26	3.0718 (18)	158

Symmetry code: (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₅H₅ClN₂·0.5C₄H₄O₄
M_r	186.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.678 (4), 5.0586 (15), 11.531 (3)
β (°)	103.442 (7)
V (Å³)	776.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.57 × 0.25 × 0.08

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.784, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	8439, 2771, 2420
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.143, 1.06
No. of reflections	2771
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.59

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
O2—H2···N1	0.8200	1.8200	2.5852 (17)	154.00
N2—H2A···O1	0.8600	2.0000	2.856 (2)	171.00
N2—H2B···O2ⁱ	0.86	2.26	3.0718 (18)	158.3

Symmetry code: (i) 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 also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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