2-Amino-5-chloro­pyridinium 2-carb­oxy­benzoate–benzene-1,2-dicarb­oxy­lic acid (3/1)

Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536810035853

. 2010 Sep 11;66(Pt 10):o2535. doi: 10.1107/S1600536810035853

2-Amino-5-chloropyridinium 2-carboxybenzoate–benzene-1,2-dicarboxylic acid (3/1)

Madhukar Hemamalini ^a, Hoong-Kun Fun ^a,^*,^‡

PMCID: PMC2983198 PMID: 21587526

Abstract

The asymmetric unit of the title compound, 3C₅H₆ClN₂ ⁺·3C₈H₅O₄ ⁻·C₈H₆O₄, contains three independent 2-amino-5-chloropyridinium cations, three independent hydrogen phthalate anions and one phthalic acid molecule. In the crystal structure, there are two kinds of supramolecular tapes. One is formed by two independent cations with two anions through N—H⋯O and C—H⋯O hydrogen bonds. Another one is formed by the other cation and anion, and the phthalic acid molecule via N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds. These two tapes are connected by an O—H⋯O hydrogen bond, forming a double-tape structure.

Related literature

For details of hydrogen bonding, see: Jeffery (1997 ▶). For details of structures incorporating phthalic acid, see: Dale et al. (2004 ▶); Ballabh et al. (2005 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

3C₅H₆ClN₂ ⁺·3C₈H₅O₄ ⁻·C₈H₆O₄
M _r = 1050.19
Triclinic,
a = 9.8522 (2) Å
b = 14.0242 (2) Å
c = 17.4312 (3) Å
α = 68.920 (1)°
β = 87.507 (1)°
γ = 83.906 (1)°
V = 2234.54 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.49 × 0.22 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.870, T _max = 0.940
63061 measured reflections
12966 independent reflections
11359 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.101
S = 1.03
12966 reflections
696 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.35 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 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035853/is2597sup1.cif

e-66-o2535-sup1.cif^{(36.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035853/is2597Isup2.hkl

e-66-o2535-Isup2.hkl^{(621.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2C—H2C⋯O3C	0.82	1.58	2.4004 (13)	177
O2A—H1OA⋯O3A	0.86	1.55	2.4123 (13)	177
O2B—H1OB⋯O3B	0.89	1.52	2.4126 (14)	178
O2X—H1OX⋯O4C	0.88 (2)	1.76 (2)	2.6091 (12)	163 (2)
O4X—H2OX⋯O1Aⁱ	0.83 (2)	1.86 (2)	2.6880 (13)	177 (2)
N2A—H2NA⋯O1Bⁱⁱ	0.895 (18)	2.018 (18)	2.9095 (14)	173.4 (19)
N1B—H1NB⋯O4Aⁱⁱⁱ	0.92 (2)	1.69 (2)	2.5938 (14)	169 (2)
N2B—H2NB⋯O3Aⁱⁱⁱ	0.87 (2)	2.12 (2)	2.9570 (14)	161.8 (17)
N1C—H1NC⋯O4B	0.94 (2)	1.69 (2)	2.6169 (16)	168 (2)
N2C—H3NC⋯O3B	0.83 (2)	2.11 (2)	2.9279 (15)	168.4 (19)
C4A—H4AA⋯O2Bⁱⁱ	0.93	2.26	3.1614 (14)	164

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

MH and HKF thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Hydrogen bonding is one of the key interactions for molecular assembly and molecular recognition (Jeffery, 1997). In nature, biopolymers such as nucleic acids and polypeptides form supramolecular structures through hydrogen bonding of which the dynamic nature of the interaction contributes to chemical and biological molecular processes. Phthalic acid forms hydrogen phthalate salts with various organic compounds. Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In this paper, the hydrogen-bonding patterns of tris(2-amino-5-chloropyridinium hydrogen phthalate) phthalic acid, (I), are discussed.

The asymmetric unit of the title compound consists of three crystallographically independent 2-amino-5-chloropyridinium cations (A, B & C), three hydrogen phthalate anions (A, B & C) and one phthalic acid molecule (Fig. 1). Each 2-amino-5-chloropyridinium cation is planar, with a maximum deviation of 0.008 (1) Å for atom C4A (molecule A), 0.019 (1) Å for atom Cl1B (molecule B) and 0.028 (1) Å for atom N2C (molecule C).

In the crystal structure, there are two kinds of supramolecular tapes. One is formed by the cations A and B with the anions B and C, through N—H···O and C—H···O hydrogen bonds (Fig. 2). The another one is formed by the cation B, the anion A and the phthalic acid molecule via N—H···O, O—H···O and C—H···O hydrogen bonds (Fig. 3). Furthermore, these two tapes are connected by an O—H···O hydrogen bond, forming a double tape structure (Fig. 4). There is an intramolecular O—H···O hydrogen bond in the hydrogen phthalate anions, which generates an S(6) (Bernstein et al., 1995) ring motif.

Experimental

A hot methanol solution (20 ml) of 2-amino-5-chloropyridine (65 mg, Aldrich) and phthalic acid (83 mg, Merck) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and yellow coloured crystals of the title compound appeared after a few days.