1-(5-Amino-2,4-dinitro­phen­yl)pyridinium chloride monohydrate

Rajamanickam Babykala; Doraisamyraja Kalaivani

doi:10.1107/S1600536812038834

. 2012 Sep 15;68(Pt 10):o2941. doi: 10.1107/S1600536812038834

1-(5-Amino-2,4-dinitrophenyl)pyridinium chloride monohydrate

Rajamanickam Babykala ^a, Doraisamyraja Kalaivani ^a,^*

PMCID: PMC3470313 PMID: 23125726

Abstract

In the cation of the title hydrated salt, C₁₁H₉N₄O₄ ⁺·Cl⁻·H₂O, the six-membered rings are inclined to each other at 79.0 (1)° and an intramolecular N—H⋯O hydrogen bond occurs. In the crystal, N—H⋯Cl hydrogen bonds link two cations and two anions into centrosymmetric group, and O—H⋯Cl hydrogen bonds involving the water molecules further link these groups into chains in [101]. An O—H⋯O interaction is also present. The water molecule is disordered over two sets of sites in a 0.555 (13):0.445 (13) ratio

Related literature

For applications of N-substituted pyridinium salts, see: Sliwa (1996 ▶); Ali et al. (2005 ▶); Chelossi et al. (2006 ▶); Azzouz et al. (2008 ▶). For related structures, see: Shmidt et al. (2005 ▶); Wojtas et al. (2006 ▶); Manickkam & Kalaivani (2011 ▶); Chernyshev et al. (2011 ▶); Sridevi & Kalaivani (2012 ▶).

Experimental

Crystal data

C₁₁H₉N₄O₄ ⁺·Cl⁻·H₂O
M _r = 314.69
Monoclinic,
a = 5.4312 (4) Å
b = 21.493 (2) Å
c = 11.3892 (9) Å
β = 92.362 (3)°
V = 1328.33 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.871, T _max = 0.939
14754 measured reflections
3125 independent reflections
2288 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.112
S = 1.03
3125 reflections
224 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812038834/cv5319sup1.cif

e-68-o2941-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038834/cv5319Isup2.hkl

e-68-o2941-Isup2.hkl^{(153.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812038834/cv5319Isup3.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
N4—H4A⋯O4	0.86 (2)	2.09 (2)	2.671 (2)	124 (2)
N4—H4B⋯Cl1	0.87 (2)	2.35 (2)	3.2162 (19)	171 (2)
N4—H4A⋯Cl1ⁱ	0.86 (2)	2.56 (2)	3.2268 (16)	135 (2)
O5—H5B⋯Cl1	0.90 (2)	2.34 (3)	3.187 (3)	158 (5)
O5—H5A⋯Cl1ⁱⁱ	0.93 (2)	2.51 (2)	3.429 (9)	169 (5)
O5′—H5D⋯O5ⁱⁱⁱ	0.91 (2)	1.94 (3)	2.815 (16)	160 (5)

Open in a new tab

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

Acknowledgments

The authors are thankful to SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

Comment

N-Substitued pyridinium salts are widely used in organic synthesis (Azzouz et al., 2008), medicinal field (Chelossi et al., 2006), electrodeposition (Ali et al., 2005) and dye preparations (Sliwa, 1996). As a continuation of our studies of new substituted pyridinium barbiturates (Manickkam & Kalaivani, 2011; Sridevi & Kalaivani, 2012), we report the crystal structure of the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related compounds (Shmidt et al., 2005; Wojtas et al., 2006; Chernyshev et al., 2011). In the cation, the pyridine ring is twisted notably from the dinitrophenyl ring and the dihedral angle between their planes is 78.93 (5)°. The two nitro groups, O1—N2—O2 and O3—N3—O4, deviate from the benzene ring at 7.97 (10)° and 4.18 (17)°, respectively. Intermolecular N—H···Cl and O—H···Cl hydrogen bonds (Table 1) consolidate the crystal packing. The overall molecular packing forming a herring bone arrangement when view down c axis is shown in Fig. 2.

Experimental

Analytical grade 1,3-dichloro-4,6-dinitrobenzene (DCDNB) and barbituric acid were used as supplied by Aldrich company. Pyridine was distilled under reduced pressure and the fraction boiling over at its boiling point was used for the preparation of the title molecular salt.DCDNB (2.01 g, 0.01 mol) in 15 ml absolute ethanol was mixed with barbituric acid (1.28 g, 0.01 mol) in 30 ml of absolute ethanol. Pyridine (3.16 g, 0.04 mol)was added to the above mixture which was heated to 40°C and shaken well for 5–6 hrs. The solution was kept as such at room temperature for 48 hrs. On standing dark violet colour crystals separate out.After filtering out these violet crystals, the filterate was kept as such at room temperature (25°C).From the filtrate, one of the by-products of the reaction between DCDNB, barbituric acid and pyridine, separates as pale greenish yellow crystals after 3 months. These crystals were powdered well, and washed with copious amount of ethanol and dry ether, recrystallized from absolute alcohol and subjected to single-crystal X-ray analysis. Yield: 40–50%; m.p.: 508 K.