5-Carb­oxy-2,4-dihy­droxy­anilinium chloride dihydrate

Naz, S.S.; Islam, N.U.; Tahir, M.N.

doi:10.1107/S1600536811000559

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o299

doi:10.1107/S1600536811000559

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5-Carboxy-2,4-dihydroxyanilinium chloride dihydrate

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

^aInstitute of Chemical Sciences, University of Peshawar, Peshawar, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 4 January 2011; accepted 5 January 2011; online 8 January 2011)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.044
wR(F²) = 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

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
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y, -z+1; (iii) x-1, y, z+1; (iv) -x+1, -y+1, -z+1; (v) x+1, y, z; (vi) -x+1, -y, -z.

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii. The dotted line represents the intramolecular H-bonding.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form various ring motifs and molecules are interlinked through H-bondings to form three dimensional polymeric network.

5-Carboxy-2,4-dihydroxyanilinium chloride dihydrate top

Crystal data top

C₇H₈NO₄⁺·Cl⁻·2H₂O	Z = 2
M_r = 241.63	F(000) = 252
Triclinic, P1	D_x = 1.567 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0285 (8) Å	Cell parameters from 1853 reflections
b = 7.9597 (8) Å	θ = 1.9–28.4°
c = 10.9570 (13) Å	µ = 0.38 mm⁻¹
α = 100.135 (5)°	T = 296 K
β = 97.162 (4)°	Needle, brown
γ = 92.921 (5)°	0.28 × 0.15 × 0.10 mm
V = 512.10 (11) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	2548 independent reflections
Radiation source: fine-focus sealed tube	1853 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.4°, θ_min = 1.9°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→8
T_min = 0.935, T_max = 0.965	l = −14→14
8850 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0571P)² + 0.0225P] where P = (F_o² + 2F_c²)/3
2548 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₇H₈NO₄⁺·Cl⁻·2H₂O	γ = 92.921 (5)°
M_r = 241.63	V = 512.10 (11) Å³
Triclinic, P1	Z = 2
a = 6.0285 (8) Å	Mo Kα radiation
b = 7.9597 (8) Å	µ = 0.38 mm⁻¹
c = 10.9570 (13) Å	T = 296 K
α = 100.135 (5)°	0.28 × 0.15 × 0.10 mm
β = 97.162 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2548 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1853 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.965	R_int = 0.039
8850 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	Δρ_max = 0.40 e Å⁻³
2548 reflections	Δρ_min = −0.27 e Å⁻³
139 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.2807 (3)	0.0789 (2)	0.38672 (13)	0.0395 (4)
H1	0.3127	0.0453	0.3164	0.059*
O2	−0.0155 (3)	0.1663 (2)	0.27792 (13)	0.0454 (4)
O3	−0.2957 (3)	0.35281 (19)	0.40596 (13)	0.0401 (4)
H3	−0.2501	0.3044	0.3424	0.060*
O4	−0.1327 (3)	0.4424 (2)	0.84841 (13)	0.0415 (4)
H4A	−0.2380	0.5033	0.8442	0.062*
N1	0.2345 (3)	0.2711 (2)	0.84317 (14)	0.0306 (4)
H1A	0.3302	0.1906	0.8294	0.046*
H1B	0.1449	0.2439	0.8965	0.046*
H1C	0.3104	0.3712	0.8755	0.046*
C1	0.0937 (4)	0.1574 (2)	0.37826 (18)	0.0303 (5)
C2	0.0302 (3)	0.2322 (2)	0.50004 (17)	0.0268 (4)
C3	−0.1622 (4)	0.3252 (2)	0.50731 (18)	0.0284 (4)
C4	−0.2215 (3)	0.3963 (2)	0.62285 (18)	0.0303 (5)
H4	−0.3489	0.4570	0.6270	0.036*
C5	−0.0912 (3)	0.3766 (2)	0.73114 (18)	0.0286 (5)
C6	0.0990 (3)	0.2839 (2)	0.72445 (17)	0.0248 (4)
C7	0.1595 (3)	0.2145 (2)	0.61147 (17)	0.0259 (4)
H7	0.2879	0.1547	0.6086	0.031*
O5	0.9425 (3)	0.17641 (17)	0.00957 (13)	0.0372 (4)
H5A	0.9959	0.1488	0.0794	0.056*
H5B	0.8641	0.2602	0.0303	0.056*
O6	0.4319 (3)	−0.02049 (19)	0.16590 (14)	0.0427 (4)
H6A	0.4697	0.0818	0.1525	0.064*
H6B	0.3236	−0.0641	0.1078	0.064*
Cl1	0.53107 (9)	0.35035 (6)	0.11554 (5)	0.03442 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0407 (10)	0.0515 (9)	0.0269 (8)	0.0127 (7)	0.0097 (7)	0.0025 (7)
O2	0.0577 (11)	0.0566 (10)	0.0220 (8)	0.0189 (8)	0.0017 (7)	0.0056 (7)
O3	0.0422 (10)	0.0517 (9)	0.0257 (8)	0.0121 (7)	−0.0042 (7)	0.0093 (7)
O4	0.0478 (10)	0.0534 (10)	0.0251 (8)	0.0274 (8)	0.0074 (7)	0.0035 (7)
N1	0.0326 (10)	0.0357 (9)	0.0231 (9)	0.0089 (7)	0.0018 (7)	0.0043 (7)
C1	0.0377 (13)	0.0276 (10)	0.0255 (11)	0.0000 (9)	0.0033 (9)	0.0058 (8)
C2	0.0325 (12)	0.0258 (9)	0.0229 (10)	0.0025 (8)	0.0059 (9)	0.0050 (8)
C3	0.0319 (12)	0.0284 (10)	0.0246 (11)	0.0018 (8)	−0.0012 (9)	0.0081 (8)
C4	0.0282 (11)	0.0322 (10)	0.0323 (12)	0.0097 (8)	0.0035 (9)	0.0086 (9)
C5	0.0327 (12)	0.0271 (10)	0.0271 (11)	0.0052 (8)	0.0059 (9)	0.0062 (8)
C6	0.0289 (11)	0.0242 (9)	0.0205 (10)	0.0036 (8)	0.0000 (8)	0.0038 (8)
C7	0.0272 (11)	0.0251 (9)	0.0261 (11)	0.0037 (8)	0.0049 (8)	0.0047 (8)
O5	0.0415 (9)	0.0386 (8)	0.0343 (8)	0.0153 (7)	0.0085 (7)	0.0085 (7)
O6	0.0468 (10)	0.0400 (8)	0.0408 (9)	0.0073 (7)	0.0065 (8)	0.0045 (7)
Cl1	0.0335 (3)	0.0385 (3)	0.0323 (3)	0.0111 (2)	0.0022 (2)	0.0086 (2)

Geometric parameters (Å, º) top

O1—C1	1.317 (2)	C2—C7	1.397 (3)
O1—H1	0.8200	C2—C3	1.410 (3)
O2—C1	1.225 (2)	C3—C4	1.390 (3)
O3—C3	1.346 (2)	C4—C5	1.376 (3)
O3—H3	0.8199	C4—H4	0.9300
O4—C5	1.358 (2)	C5—C6	1.397 (3)
O4—H4A	0.8200	C6—C7	1.365 (3)
N1—C6	1.470 (2)	C7—H7	0.9300
N1—H1A	0.8900	O5—H5A	0.8616
N1—H1B	0.8900	O5—H5B	0.8517
N1—H1C	0.8900	O6—H6A	0.8764
C1—C2	1.467 (3)	O6—H6B	0.8647

C1—O1—H1	109.5	O3—C3—C2	123.24 (18)
C3—O3—H3	109.5	C4—C3—C2	120.50 (18)
C5—O4—H4A	109.5	C5—C4—C3	119.87 (18)
C6—N1—H1A	109.5	C5—C4—H4	120.1
C6—N1—H1B	109.5	C3—C4—H4	120.1
H1A—N1—H1B	109.5	O4—C5—C4	124.58 (17)
C6—N1—H1C	109.5	O4—C5—C6	115.57 (17)
H1A—N1—H1C	109.5	C4—C5—C6	119.85 (18)
H1B—N1—H1C	109.5	C7—C6—C5	120.75 (18)
O2—C1—O1	122.79 (18)	C7—C6—N1	121.88 (16)
O2—C1—C2	123.65 (19)	C5—C6—N1	117.31 (16)
O1—C1—C2	113.56 (17)	C6—C7—C2	120.62 (17)
C7—C2—C3	118.40 (17)	C6—C7—H7	119.7
C7—C2—C1	120.94 (18)	C2—C7—H7	119.7
C3—C2—C1	120.67 (18)	H5A—O5—H5B	104.7
O3—C3—C4	116.25 (17)	H6A—O6—H6B	106.8

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₇H₈NO₄⁺·Cl⁻·2H₂O
M_r	241.63
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.0285 (8), 7.9597 (8), 10.9570 (13)
α, β, γ (°)	100.135 (5), 97.162 (4), 92.921 (5)
V (Å³)	512.10 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.28 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.935, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	8850, 2548, 1853
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.115, 1.03
No. of reflections	2548
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.27

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) −x+1, −y, −z.

Acknowledgements

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.

References

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