5-Carb­oxy-2,4-dihy­droxy­anilinium chloride dihydrate

Syeda Sohaila Naz; Nazar Ul Islam; M Nawaz Tahir

doi:10.1107/S1600536811000559

. 2011 Jan 8;67(Pt 2):o299. doi: 10.1107/S1600536811000559

5-Carboxy-2,4-dihydroxyanilinium chloride dihydrate

Syeda Sohaila Naz ^a, Nazar Ul Islam ^a, M Nawaz Tahir ^b,^*

PMCID: PMC3051567 PMID: 21522989

Abstract

In the title compound, C₇H₈NO₄ ⁺·Cl⁻·2H₂O, the organic molecule is almost planar with an r.m.s. deviation of 0.0164 Å for all non-H atoms. An S(6) ring motif is formed due to an intramolecular O—H⋯O hydrogen bond. In the crystal, the molecules are linked into a three-dimensional network by N—H⋯Cl, N—H⋯O, O—H⋯Cl and O—H⋯O hydrogen bonds.

Related literature

For a related structure, see: Naz et al. (2010 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₇H₈NO₄ ⁺·Cl⁻·2H₂O
M _r = 241.63
Triclinic,
a = 6.0285 (8) Å
b = 7.9597 (8) Å
c = 10.9570 (13) Å
α = 100.135 (5)°
β = 97.162 (4)°
γ = 92.921 (5)°
V = 512.10 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 296 K
0.28 × 0.15 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.935, T _max = 0.965
8850 measured reflections
2548 independent reflections
1853 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.115
S = 1.03
2548 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000559/dn2650sup1.cif

e-67-0o299-sup1.cif^{(14.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000559/dn2650Isup2.hkl

e-67-0o299-Isup2.hkl^{(122.6KB, 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
O1—H1⋯O6	0.82	1.88	2.6945 (19)	171
O3—H3⋯O2	0.82	1.96	2.672 (2)	145
O4—H4A⋯Cl1ⁱ	0.82	2.21	3.0097 (15)	164
N1—H1A⋯O6ⁱⁱ	0.89	2.02	2.903 (2)	169
N1—H1B⋯O5ⁱⁱⁱ	0.89	1.96	2.853 (2)	178
N1—H1C⋯Cl1^iv	0.89	2.35	3.1950 (18)	157
O5—H5A⋯O2^v	0.86	2.16	2.935 (2)	149
O5—H5B⋯Cl1	0.85	2.41	3.1494 (15)	146
O6—H6A⋯Cl1	0.88	2.27	3.1386 (16)	174
O6—H6B⋯O5^vi	0.86	1.99	2.850 (2)	173

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha. Pakistan.

supplementary crystallographic information

Comment

Recently we have reported the crystal structure of 5-carboxy-2,4-dihydroxyanilinium chloride (Naz et al., 2010). The title compound (I, Fig. 1) has been prepared in a slightly different way.

In (I), the organic group (C1—C7/O1—O4/N1) is planar with r. m. s. deviation of 0.0164 Å. In the organic part, there exist a strong intramolecular H-bond of O—H···O type (Table 1, Fig. 1) completing an S(6) ring motif (Bernstein et al., 1995). In the title compound, the Cl^- anion is penta coordinated due to H-bondings of N—H···Cl and O—H···Cl types (Table 1, Fig. 2). The NH₃⁺ ion makes H-bonding with the both water molecules and the Cl^- ion. Due to these strong H-bondings the molecules are stabilized in the form of three-dimensional polymeric network (Table 1, Fig. 2). There does not exist any π···π or C—H···π interaction.

Experimental

Concentrated nitric acid (2 mL, 67%) was added drop by drop to β-resorcylic acid (1 g, 97%, 6.3 mmol) in a round bottom flask. The mixture was protected from moisture by CaCl₂ (anhydrous) tube and was allowed to stand for 12 h at room temperature. Then reaction mixture was diluted with water. The crude material was filtered and recrystallized from water to affoard the 5-nitro-β-resorcylic acid.

Then a mixture of 5-nitro-β-resorcylic acid (1.5 g, 7.5 mmol), tin (3 g, 25 mmol) and absolute ethanol (5 ml) were taken in a 100 ml round bottom flask and passed HCl gas under reflux with stirring for 1 h. The completion of reaction was monitored by TLC. The reaction mixture was filtered to remove any unreacted tin. Filtrate was kept for seven days to afford light brown needles of (I).