organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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[Pozharski, A. F., Soldatenkov, A. T. & Katritzky, A. R. (1997). Heterocycles in Life and Society. New York: Wiley.]); Katritzky et al. (1996[Katritzky, A. R., Rees, C. W. & Scriven, E. F. V. (1996). Comprehensive Heterocyclic Chemistry II. Oxford: Pergamon Press.]). For the details of fumaric acid, see: Batchelor et al. (2000[Batchelor, E., Klinowski, J. & Jones, W. (2000). J. Mater. Chem. 10, 839-848.]). For details of hydrogen bonding, see: Jeffrey & Saenger (1991[Jeffrey, G. A. & Saenger, W. (1991). Hydrogen Bonding in Biological Structures. Berlin: Springer.]); Jeffrey (1997[Jeffrey, G. A. (1997). An Introduction to Hydrogen Bonding. Oxford University Press.]); Scheiner (1997[Scheiner, S. (1997). Hydrogen Bonding. A Theoretical Perspective. Oxford University Press.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]).

[Scheme 1]

Experimental

Crystal data
  • C5H5ClN2·0.5C4H4O4

  • Mr = 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.784, Tmax = 0.967

  • 8439 measured reflections

  • 2771 independent reflections

  • 2420 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.143

  • S = 1.06

  • 2771 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 0.70 e Å−3

  • Δρmin = −0.59 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


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 CC 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.

Refinement top

All hydrogen atoms were positioned geometrically [C–H = 0.93 Å, N–H = 0.86 Å and O–H = 0.82 Å] and were refined using a riding model, with Uiso(H) = 1.2 Ueq(C, N) or 1.5 Ueq(O).

Structure description 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 CC 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.

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
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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
C5H5ClN2·0.5C4H4O4F(000) = 384
Mr = 186.60Dx = 1.597 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3958 reflections
a = 13.678 (4) Åθ = 3.6–36.5°
b = 5.0586 (15) ŵ = 0.45 mm1
c = 11.531 (3) ÅT = 100 K
β = 103.442 (7)°Plate, colourless
V = 776.0 (4) Å30.57 × 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 tube2420 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 32.5°, θmin = 3.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 2016
Tmin = 0.784, Tmax = 0.967k = 77
8439 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0898P)2 + 0.4122P]
where P = (Fo2 + 2Fc2)/3
2771 reflections(Δ/σ)max = 0.001
110 parametersΔρmax = 0.70 e Å3
0 restraintsΔρmin = 0.59 e Å3
Crystal data top
C5H5ClN2·0.5C4H4O4V = 776.0 (4) Å3
Mr = 186.60Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.678 (4) ŵ = 0.45 mm1
b = 5.0586 (15) ÅT = 100 K
c = 11.531 (3) Å0.57 × 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)
Tmin = 0.784, Tmax = 0.967Rint = 0.036
8439 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.06Δρmax = 0.70 e Å3
2771 reflectionsΔρmin = 0.59 e Å3
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
xyzUiso*/Ueq
Cl10.03621 (3)0.27603 (7)0.40770 (3)0.01778 (13)
N10.25244 (9)0.1952 (2)0.34964 (11)0.0130 (2)
N20.34626 (11)0.2094 (3)0.20667 (12)0.0182 (3)
H2A0.37720.34570.24200.022*
H2B0.36150.14810.14360.022*
C10.17992 (10)0.0834 (3)0.39610 (12)0.0133 (2)
H1A0.16610.15500.46480.016*
C20.12664 (10)0.1319 (3)0.34452 (12)0.0133 (2)
C30.14697 (11)0.2407 (3)0.24014 (13)0.0149 (3)
H3A0.11090.38610.20370.018*
C40.22039 (11)0.1301 (3)0.19295 (12)0.0153 (3)
H4A0.23490.20000.12420.018*
C50.27436 (10)0.0926 (3)0.24997 (12)0.0133 (2)
O10.44882 (8)0.6317 (2)0.34908 (10)0.0177 (2)
O20.34481 (8)0.5851 (2)0.47334 (9)0.0143 (2)
H20.33310.44020.44120.022*
C60.41907 (10)0.6973 (3)0.43840 (12)0.0127 (2)
C70.46749 (10)0.9183 (3)0.51670 (12)0.0138 (2)
H7A0.45200.94270.59040.017*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01527 (19)0.01894 (19)0.0195 (2)0.00319 (10)0.00484 (13)0.00275 (11)
N10.0146 (5)0.0132 (5)0.0113 (5)0.0018 (4)0.0033 (4)0.0012 (4)
N20.0230 (6)0.0172 (6)0.0176 (6)0.0049 (4)0.0111 (5)0.0033 (4)
C10.0145 (6)0.0146 (5)0.0112 (5)0.0013 (4)0.0036 (4)0.0002 (4)
C20.0125 (5)0.0142 (6)0.0127 (5)0.0013 (4)0.0021 (4)0.0015 (4)
C30.0157 (6)0.0144 (5)0.0133 (6)0.0021 (4)0.0008 (5)0.0012 (4)
C40.0189 (6)0.0148 (6)0.0121 (5)0.0006 (4)0.0035 (4)0.0020 (4)
C50.0157 (6)0.0131 (5)0.0109 (5)0.0001 (4)0.0029 (4)0.0004 (4)
O10.0197 (5)0.0184 (5)0.0175 (5)0.0051 (4)0.0089 (4)0.0060 (4)
O20.0155 (5)0.0153 (4)0.0130 (4)0.0039 (3)0.0049 (4)0.0023 (3)
C60.0120 (5)0.0124 (5)0.0133 (6)0.0001 (4)0.0021 (4)0.0007 (4)
C70.0144 (6)0.0135 (5)0.0133 (6)0.0011 (4)0.0030 (4)0.0028 (4)
Geometric parameters (Å, º) top
Cl1—C21.7352 (14)C3—H3A0.9300
N1—C11.3555 (17)C4—C51.422 (2)
N1—C51.3565 (17)C4—H4A0.9300
N2—C51.3393 (18)O1—C61.2375 (17)
N2—H2A0.8600O2—C61.3061 (16)
N2—H2B0.8600O2—H20.8200
C1—C21.3675 (19)C6—C71.4920 (19)
C1—H1A0.9300C7—C7i1.335 (3)
C2—C31.409 (2)C7—H7A0.9300
C3—C41.368 (2)
C1—N1—C5120.10 (12)C3—C4—C5119.37 (13)
C5—N2—H2A120.0C3—C4—H4A120.3
C5—N2—H2B120.0C5—C4—H4A120.3
H2A—N2—H2B120.0N2—C5—N1118.25 (13)
N1—C1—C2121.69 (12)N2—C5—C4121.64 (13)
N1—C1—H1A119.2N1—C5—C4120.10 (12)
C2—C1—H1A119.2C6—O2—H2109.5
C1—C2—C3119.45 (12)O1—C6—O2124.75 (13)
C1—C2—Cl1120.79 (11)O1—C6—C7121.27 (12)
C3—C2—Cl1119.76 (11)O2—C6—C7113.98 (12)
C4—C3—C2119.29 (13)C7i—C7—C6121.41 (16)
C4—C3—H3A120.4C7i—C7—H7A119.3
C2—C3—H3A120.4C6—C7—H7A119.3
C5—N1—C1—C20.5 (2)C1—N1—C5—N2179.77 (13)
N1—C1—C2—C30.3 (2)C1—N1—C5—C40.9 (2)
N1—C1—C2—Cl1178.49 (11)C3—C4—C5—N2179.38 (14)
C1—C2—C3—C40.6 (2)C3—C4—C5—N10.5 (2)
Cl1—C2—C3—C4178.16 (11)O1—C6—C7—C7i11.5 (3)
C2—C3—C4—C50.2 (2)O2—C6—C7—C7i168.52 (17)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.822.5852 (17)154
N2—H2A···O10.862.002.856 (2)171
N2—H2B···O2ii0.862.263.0718 (18)158
Symmetry code: (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC5H5ClN2·0.5C4H4O4
Mr186.60
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)13.678 (4), 5.0586 (15), 11.531 (3)
β (°) 103.442 (7)
V3)776.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.45
Crystal size (mm)0.57 × 0.25 × 0.08
Data collection
DiffractometerBruker APEXII DUO CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.784, 0.967
No. of measured, independent and
observed [I > 2σ(I)] reflections
8439, 2771, 2420
Rint0.036
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.143, 1.06
No. of reflections2771
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O2—H2···N10.82001.82002.5852 (17)154.00
N2—H2A···O10.86002.00002.856 (2)171.00
N2—H2B···O2i0.862.263.0718 (18)158.3
Symmetry code: (i) x, y+1/2, z1/2.
 

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.

References

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