2-Amino-5-chloro-pyridinium 4-carb-oxy-butano-ate.

In the title salt, C(5)H(6)ClN(2) (+)·C(5)H(7)O(4) (-), the 2-amino-5-chloro-pyridinium cation is essentially planar, with a maximum deviation of 0.010 (3) Å. In the crystal structure, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are further connected via O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, forming a layer parallel to the bc plane. In the layer, the hydrogen glutarate anions self-assemble via O-H⋯O hydrogen bonds, forming a supra-molecular chain along the c axis. Furthermore, the cations and anions are stacked down along the a axis, forming a three-dimensional network.

Related literature

For background to the chemistry of substituted pyridines, see: Katritzky et al. (1996 ▶); Pozharski et al. (1997 ▶). For related structures, see: Hemamalini & Fun (2010a ▶,b ▶). For the conformation of glutaric acid, see: Saraswathi et al. (2001 ▶). 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

C5H6ClN2 +·C5H7O4 −

M = 260.67

Orthorhombic,

a = 5.1970 (14) Å

b = 14.509 (4) Å

c = 15.970 (5) Å

V = 1204.2 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 296 K

0.31 × 0.13 × 0.07 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.908, T max = 0.979

8054 measured reflections

3346 independent reflections

2007 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.111

S = 1.01

3346 reflections

162 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 1288 Friedel pairs

Flack parameter: 0.00 (9)

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/S1600536810027091/is2574sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027091/is2574Isup2.hkl

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

C5H6ClN2+·C5H7O4−	F(000) = 544
Mr = 260.67	Dx = 1.438 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1567 reflections
a = 5.1970 (14) Å	θ = 2.8–25.9°
b = 14.509 (4) Å	µ = 0.32 mm−1
c = 15.970 (5) Å	T = 296 K
V = 1204.2 (6) Å3	Plate, brown
Z = 4	0.31 × 0.13 × 0.07 mm

Bruker APEXII DUO CCD area-detector diffractometer	3346 independent reflections
Radiation source: fine-focus sealed tube	2007 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 30.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.908, Tmax = 0.979	k = −20→17
8054 measured reflections	l = −22→22

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
3346 reflections	Δρmax = 0.15 e Å−3
162 parameters	Δρmin = −0.20 e Å−3
0 restraints	Absolute structure: Flack (1983), 1288 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (9)

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	0.34184 (19)	0.28909 (5)	0.39845 (5)	0.0846 (3)
N1	−0.1438 (4)	0.22907 (12)	0.21798 (11)	0.0464 (5)
H1	−0.2637	0.1890	0.2106	0.056*
N2	−0.2316 (5)	0.28468 (18)	0.08678 (14)	0.0633 (6)
C1	−0.0138 (5)	0.22829 (16)	0.29108 (14)	0.0493 (6)
H1A	−0.0532	0.1844	0.3315	0.059*
C2	0.1721 (5)	0.29045 (15)	0.30579 (15)	0.0533 (6)
C3	0.2266 (6)	0.35662 (17)	0.24403 (18)	0.0628 (7)
H3A	0.3520	0.4011	0.2536	0.075*
C4	0.0971 (5)	0.35565 (17)	0.17106 (17)	0.0590 (7)
H4A	0.1352	0.3992	0.1302	0.071*
C5	−0.0947 (5)	0.28969 (15)	0.15589 (14)	0.0480 (6)
O1	0.5116 (3)	0.09526 (11)	0.19901 (9)	0.0523 (4)
O2	0.4048 (4)	0.14235 (12)	0.07274 (9)	0.0606 (5)
O3	0.1889 (4)	−0.04241 (12)	−0.15991 (10)	0.0631 (5)
H1O3	0.1253	−0.0541	−0.2050	0.095*
O4	−0.1908 (4)	−0.06355 (14)	−0.10194 (11)	0.0672 (5)
C6	0.3720 (4)	0.09123 (14)	0.13352 (12)	0.0401 (5)
C7	0.1567 (5)	0.02110 (16)	0.13408 (13)	0.0465 (5)
H7A	0.0346	0.0381	0.1773	0.056*
H7B	0.2281	−0.0384	0.1491	0.056*
C8	0.0127 (5)	0.01093 (16)	0.05204 (13)	0.0476 (6)
H8A	−0.1445	−0.0236	0.0617	0.057*
H8B	−0.0348	0.0715	0.0315	0.057*
C9	0.1709 (5)	−0.03760 (16)	−0.01336 (13)	0.0501 (6)
H9A	0.3275	−0.0027	−0.0229	0.060*
H9B	0.2198	−0.0978	0.0078	0.060*
C10	0.0341 (5)	−0.04956 (14)	−0.09493 (14)	0.0442 (5)
H1N2	−0.187 (7)	0.3179 (19)	0.0435 (19)	0.076 (9)*
H2N2	−0.353 (7)	0.242 (2)	0.0786 (17)	0.082 (10)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0957 (6)	0.0674 (4)	0.0908 (5)	−0.0065 (5)	−0.0402 (5)	−0.0032 (4)
N1	0.0463 (11)	0.0449 (9)	0.0481 (10)	−0.0088 (10)	0.0025 (9)	0.0045 (8)
N2	0.0720 (16)	0.0697 (15)	0.0482 (13)	−0.0195 (14)	0.0022 (11)	0.0144 (13)
C1	0.0560 (15)	0.0430 (12)	0.0488 (13)	−0.0006 (12)	−0.0008 (12)	0.0034 (11)
C2	0.0518 (14)	0.0437 (12)	0.0642 (14)	0.0028 (13)	−0.0088 (13)	−0.0028 (11)
C3	0.0545 (17)	0.0447 (14)	0.089 (2)	−0.0090 (13)	−0.0021 (15)	0.0035 (14)
C4	0.0580 (17)	0.0483 (13)	0.0706 (17)	−0.0088 (13)	0.0105 (14)	0.0126 (13)
C5	0.0526 (15)	0.0433 (12)	0.0481 (13)	−0.0006 (12)	0.0097 (11)	0.0044 (11)
O1	0.0570 (10)	0.0671 (10)	0.0327 (7)	−0.0186 (9)	−0.0060 (7)	0.0075 (7)
O2	0.0792 (13)	0.0617 (10)	0.0409 (8)	−0.0187 (10)	−0.0131 (8)	0.0155 (8)
O3	0.0598 (11)	0.0885 (12)	0.0409 (9)	−0.0110 (11)	−0.0013 (9)	−0.0122 (8)
O4	0.0462 (10)	0.1013 (14)	0.0540 (10)	−0.0025 (11)	−0.0084 (9)	−0.0141 (10)
C6	0.0429 (13)	0.0446 (11)	0.0328 (10)	0.0016 (11)	0.0009 (10)	−0.0014 (9)
C7	0.0513 (13)	0.0518 (12)	0.0364 (10)	−0.0062 (12)	0.0032 (10)	−0.0012 (9)
C8	0.0453 (13)	0.0537 (13)	0.0438 (12)	−0.0013 (12)	−0.0018 (10)	−0.0068 (10)
C9	0.0490 (13)	0.0598 (15)	0.0417 (12)	0.0065 (13)	−0.0080 (11)	−0.0099 (10)
C10	0.0479 (15)	0.0412 (11)	0.0437 (12)	0.0040 (10)	−0.0075 (11)	−0.0037 (10)

Cl1—C2	1.723 (3)	O2—C6	1.233 (2)
N1—C1	1.349 (3)	O3—C10	1.317 (3)
N1—C5	1.350 (3)	O3—H1O3	0.8102
N1—H1	0.8600	O4—C10	1.192 (3)
N2—C5	1.315 (3)	C6—C7	1.513 (3)
N2—H1N2	0.87 (3)	C7—C8	1.516 (3)
N2—H2N2	0.89 (3)	C7—H7A	0.9700
C1—C2	1.342 (3)	C7—H7B	0.9700
C1—H1A	0.9300	C8—C9	1.504 (3)
C2—C3	1.405 (4)	C8—H8A	0.9700
C3—C4	1.346 (4)	C8—H8B	0.9700
C3—H3A	0.9300	C9—C10	1.494 (3)
C4—C5	1.403 (3)	C9—H9A	0.9700
C4—H4A	0.9300	C9—H9B	0.9700
O1—C6	1.274 (2)
C1—N1—C5	123.1 (2)	O2—C6—C7	120.75 (19)
C1—N1—H1	118.4	O1—C6—C7	116.57 (18)
C5—N1—H1	118.4	C6—C7—C8	115.19 (18)
C5—N2—H1N2	119 (2)	C6—C7—H7A	108.5
C5—N2—H2N2	123.0 (19)	C8—C7—H7A	108.5
H1N2—N2—H2N2	117 (3)	C6—C7—H7B	108.5
C2—C1—N1	120.4 (2)	C8—C7—H7B	108.5
C2—C1—H1A	119.8	H7A—C7—H7B	107.5
N1—C1—H1A	119.8	C9—C8—C7	112.1 (2)
C1—C2—C3	118.8 (2)	C9—C8—H8A	109.2
C1—C2—Cl1	120.74 (19)	C7—C8—H8A	109.2
C3—C2—Cl1	120.5 (2)	C9—C8—H8B	109.2
C4—C3—C2	120.0 (2)	C7—C8—H8B	109.2
C4—C3—H3A	120.0	H8A—C8—H8B	107.9
C2—C3—H3A	120.0	C10—C9—C8	113.5 (2)
C3—C4—C5	120.8 (2)	C10—C9—H9A	108.9
C3—C4—H4A	119.6	C8—C9—H9A	108.9
C5—C4—H4A	119.6	C10—C9—H9B	108.9
N2—C5—N1	118.6 (2)	C8—C9—H9B	108.9
N2—C5—C4	124.5 (2)	H9A—C9—H9B	107.7
N1—C5—C4	116.9 (2)	O4—C10—O3	122.6 (2)
C10—O3—H1O3	115.7	O4—C10—C9	124.6 (2)
O2—C6—O1	122.7 (2)	O3—C10—C9	112.8 (2)
C5—N1—C1—C2	1.1 (4)	C3—C4—C5—N2	179.2 (3)
N1—C1—C2—C3	0.6 (4)	C3—C4—C5—N1	0.9 (4)
N1—C1—C2—Cl1	−179.20 (18)	O2—C6—C7—C8	7.5 (3)
C1—C2—C3—C4	−1.4 (4)	O1—C6—C7—C8	−173.7 (2)
Cl1—C2—C3—C4	178.4 (2)	C6—C7—C8—C9	72.4 (3)
C2—C3—C4—C5	0.7 (4)	C7—C8—C9—C10	179.51 (19)
C1—N1—C5—N2	179.8 (2)	C8—C9—C10—O4	−34.9 (3)
C1—N1—C5—C4	−1.8 (3)	C8—C9—C10—O3	144.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	1.80	2.659 (3)	173
O3—H1O3···O1ii	0.81	1.79	2.598 (2)	173
N2—H1N2···O2iii	0.87 (3)	2.00 (3)	2.848 (3)	163 (3)
N2—H2N2···O2i	0.89 (3)	1.92 (3)	2.808 (3)	173 (2)
C1—H1A···O4iv	0.93	2.44	3.315 (3)	156
C4—H4A···O4v	0.93	2.59	3.396 (3)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	1.80	2.659 (3)	173
O3—H1O3⋯O1ii	0.81	1.79	2.598 (2)	173
N2—H1N2⋯O2iii	0.87 (3)	2.00 (3)	2.848 (3)	163 (3)
N2—H2N2⋯O2i	0.89 (3)	1.92 (3)	2.808 (3)	173 (2)
C1—H1A⋯O4iv	0.93	2.44	3.315 (3)	156
C4—H4A⋯O4v	0.93	2.59	3.396 (3)	145

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .