2-Amino-5-chloro-pyridine-fumaric acid (1/2).

The asymmetric unit of the title compound, C(5)H(5)ClN(2)·0.5C(4)H(4)O(4), comprises a neutral 2-amino-5-chloro-pyridine mol-ecule and one half of a fumaric acid mol-ecule which lies on an inversion center. The dihedral angle between the pyridine ring and the plane formed by the fumaric acid mol-ecule is 3.22 (8)°. The 2-amino-5-chloro-pyridine mol-ecule is planar, with a maximum deviation of 0.004 (1) Å for the pyridine N atom. In the crystal, the 2-amino-5-chloro-pyridine mol-ecules inter-act with the carboxyl groups of fumaric acid mol-ecules through N-H⋯O and O-H⋯N hydrogen bonds, forming centrosymmetric R(2) (2)(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 = 186.60

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 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

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018192/sj5003sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018192/sj5003Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C5H5ClN2·0.5C4H4O4	F(000) = 384
Mr = 186.60	Dx = 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

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

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(Fo2) + (0.0898P)2 + 0.4122P] where P = (Fo2 + 2Fc2)/3
2771 reflections	(Δ/σ)max = 0.001
110 parameters	Δρmax = 0.70 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .