4-Amino­pyridinium 2-chloro-4-nitro­benzoate monohydrate

Kelsey L Savig; Andreas Lemmerer

doi:10.1107/S1600536812046077

. 2012 Nov 17;68(Pt 12):o3361. doi: 10.1107/S1600536812046077

4-Aminopyridinium 2-chloro-4-nitrobenzoate monohydrate

Kelsey L Savig ^a, Andreas Lemmerer ^a,^*

PMCID: PMC3588959 PMID: 23476195

Abstract

In the title hydrated molecular salt, C₅H₇N₂ ⁺·C₇H₃ClNO₄ ⁻·H₂O, the ions and water molecules assemble into ribbons of R ₆ ⁵(22) rings along the c axis via O(water)—H⋯O⁻, N⁺—H⋯O(water) and N—H⋯O⁻ hydrogen bonds. N—H⋯O⁻ hydrogen bonds connect adjacent ribbons along the c-axis direction via R ₄ ⁴(12) rings, forming hydrogen-bonded layers. The CO₂ and NO₂ groups make dihedral angles of 81.8 (2) and 1.4 (2)°, respectively, with the ring in the anion.

Related literature

For related structures, see: Lemmerer et al. (2010 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₅H₇N₂ ⁺·C₇H₃ClNO₄ ⁻·H₂O
M _r = 313.7
Monoclinic,
a = 14.4500 (5) Å
b = 14.3300 (5) Å
c = 6.9918 (2) Å
β = 97.804 (2)°
V = 1434.37 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.78 × 0.31 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: integration (XPREP; Bruker, 2004 ▶) T _min = 0.896, T _max = 0.977
14928 measured reflections
3456 independent reflections
2685 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.122
S = 1.04
3456 reflections
210 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.5 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(20.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812046077/fy2073sup1.cif

e-68-o3361-sup1.cif^{(20.4KB, cif)}

Click here for additional data file.^{(166.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046077/fy2073Isup2.hkl

e-68-o3361-Isup2.hkl^{(166.1KB, hkl)}

Click here for additional data file.^{(2.6KB, mol)}

Supplementary material file. DOI: 10.1107/S1600536812046077/fy2073Isup3.mol

Click here for additional data file.^{(5.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046077/fy2073Isup4.cml

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
N2—H2⋯O1W ⁱ	0.93 (3)	1.72 (3)	2.641 (2)	170 (2)
N3—H3A⋯O1	0.94 (2)	1.99 (2)	2.926 (2)	171.1 (19)
N3—H3B⋯O2ⁱⁱ	0.84 (2)	2.16 (3)	2.982 (2)	165 (2)
O1W—H1W⋯O1ⁱⁱⁱ	0.75 (3)	1.96 (3)	2.698 (2)	166 (3)
O1W—H2W⋯O2	0.78 (4)	1.99 (4)	2.729 (2)	158 (3)

Open in a new tab

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

Acknowledgments

This work was supported by the University of the Witwatersrand and the Molecular Sciences Institute, which are thanked for providing the infrastructure required to do this work, and the Friedel Sellshop grant for financial support.

supplementary crystallographic information

Comment

The title molecular salt is part of a larger research project looking at the factors that determine if a salt or a co-crystal forms between a specific carboxylic acid and various pyridine ring systems (Lemmerer et al., 2010).

In molecular salt (I) (Fig. 1), formed by dissolving 4-aminopyridine and 2-chloro-4-nitrobenzoic acid in methanol, two kinds of hydrogen-bonded rings are formed. The ring R⁵₆(22) (Bernstein et al., 1995) uses O1W—H···O^-, N⁺—H···O and N—H···O^- hydrogen bonds to connect all three species together into a 1-D ribbon (Fig. 2) along the c-axis. In addition, a R⁴₄(12) ring is formed between two amine groups and two carboxylate groups to connect two ribbons together to form layers (Fig. 3).

Experimental

Crystals were grown by slow evaporation of a methanol solution of 2-chloro-4-nitrobenzoic acid (0.100 g; 0.496 mmol) and 4-aminopyridine (0.047 g; 0.50 mmol) in 8 ml of methanol, and afforded colourless plates after three days of slow evaporation at ambient conditions.