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Acta Cryst. (2009). E65, o1304    [ doi:10.1107/S1600536809017462 ]

3-Ammonio-4-hydroxybenzoate monohydrate

S. Ullah, M. N. Tahir, D. Shahwar, Z.-D. Khan and M. A. Khan

Abstract top

The title compound, C7H7NO3·H2O, which crystallized as a hydrate, was obtained from an extraction of the plant species Saussurea atkinsonii of the asteraceae family collected from the hilly area (Ayubia) of Pakistan during the flowering season. The dihedral angle between the benzene ring and the carboxylate group is 25.64 (5)°. In the crystal, the packing is consolidated by N-H...O and O-H...O hydrogen bonds, as well as weak aromatic [pi]-[pi] stacking [centroid-centroid separation = 3.9365 (9) Å] and C=O...[pi] interactions.

Comment top

The medicinal plants are available all over the world. Locally available plant specie Saussurea atkinsonii of asteraceae family was collected from hilly area (Ayubia) of Pakistan during the flowering season. The plant was dried inside room for 20–25 days. The title compound (I), (Fig. 1), is an extract of it in chloroform and methanol. The study of its bio-activity is in progress.

The crystal structure of (II) (4-vinylphenyl 3-amino-4-hydroxybenzoate or bagremycin A (Bertasso et al., 2001), has been reported which contains the aromatic ring along with heavy atoms of the substituants of (I). In the title compound, the bond distances and bond angles are within normal ranges (Allen et al., 1987). The benzene ring A (C1–C6) is planar and is oriented at a dihedral angle of 25.64 (5)° with the CO2 group. The N-atom of ammonium is in plane of the ring A, whereas the O-atom of hydroxy group is at a distance of -0.0580 (21) Å from the same.

There exist intensive intermolecular H-bonding (Table 1), resulting in three-dimensional polymeric network. There also exist CgA···CgAi [symmetry code i = 1 - x, 1 - y, -z] interaction at a distance of 3.9365 (9) Å, where CgA is the centroid of aromatic ring. The molecules may also be stabilized due to C==O···π interaction (Table 1).

Related literature top

For a related structure, see: Bertasso et al. (2001). For reference structural data, see: Allen et al. (1987).

Experimental top

The Specie Saussurea atkinsonii of asteraceae family was dried inside room for 20–25 days as a whole and grinded. The extract was obtained using soxhlet apparatus in 50% chloroform and 50% methanol and it was subjected to isolation by performing column chromatography and thin layer chromatography. The extract obtained was recrystallized from methanol and light brown rods of (I) were obtained. The water found in the structure was presumably incorporated from the atomsphere.

Refinement top

The coordinates of H-atoms of hydroxy, ammonium moiety and water molecule were refined. The other H-atoms were positioned geometrically, with C-H = 0.93 Å for aromatic type and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N, O).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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
[Figure 1] Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radius.
[Figure 2] Fig. 2. The partial packing of (I), showing that molecules form three-dimensional polymeric network.
3-Ammonio-4-hydroxybenzoate monohydrate top
Crystal data top
C7H7NO3·H2OF000 = 720
Mr = 171.15Dx = 1.576 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1725 reflections
a = 8.7711 (3) Åθ = 3.2–28.3º
b = 12.7193 (7) ŵ = 0.13 mm−1
c = 12.9289 (6) ÅT = 296 K
V = 1442.38 (11) Å3Rod, light brown
Z = 80.26 × 0.20 × 0.20 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		1752 independent reflections
Radiation source: fine-focus sealed tube1277 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
Detector resolution: 7.40 pixels mm-1θmax = 28.3º
T = 296 Kθmin = 3.2º
ω scansh = −11→11
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		k = −15→16
Tmin = 0.971, Tmax = 0.976l = −11→17
8827 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.118  w = 1/[σ2(Fo2) + (0.0684P)2 + 0.0409P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1725 reflectionsΔρmax = 0.31 e Å−3
127 parametersΔρmin = −0.24 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
C7H7NO3·H2OV = 1442.38 (11) Å3
Mr = 171.15Z = 8
Orthorhombic, PbcaMo Kα
a = 8.7711 (3) ŵ = 0.13 mm−1
b = 12.7193 (7) ÅT = 296 K
c = 12.9289 (6) Å0.26 × 0.20 × 0.20 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		1752 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		1277 reflections with I > 2σ(I)
Tmin = 0.971, Tmax = 0.976Rint = 0.033
8827 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042127 parameters
wR(F2) = 0.118H atoms treated by a mixture of
independent and constrained refinement
S = 1.06Δρmax = 0.31 e Å−3
1725 reflectionsΔρmin = −0.24 e Å−3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
xyzUiso*/Ueq
O10.69598 (12)0.67023 (9)0.16442 (9)0.0284 (4)
O20.83764 (11)0.53206 (10)0.12269 (9)0.0302 (4)
O30.20823 (11)0.29862 (10)0.11448 (10)0.0319 (4)
N10.48231 (14)0.21872 (11)0.16388 (11)0.0232 (4)
C10.57236 (15)0.50443 (12)0.14203 (11)0.0205 (5)
C20.58869 (15)0.39732 (13)0.15731 (11)0.0203 (4)
C30.46511 (14)0.33137 (12)0.14912 (11)0.0193 (4)
C40.32078 (15)0.37051 (12)0.12444 (12)0.0212 (4)
C50.30300 (15)0.47766 (13)0.11230 (12)0.0241 (5)
C60.42742 (15)0.54444 (13)0.12153 (12)0.0232 (4)
C70.71208 (15)0.57284 (13)0.14299 (11)0.0216 (5)
O40.43081 (12)0.34489 (11)0.45169 (10)0.0308 (4)
H1A0.587 (2)0.2008 (14)0.1721 (12)0.0278*
H1B0.4519 (19)0.1828 (14)0.1034 (15)0.0278*
H1C0.4229 (18)0.1948 (14)0.2189 (14)0.0278*
H20.684030.369740.173250.0243*
H30.119 (2)0.3252 (16)0.0913 (15)0.0383*
H50.207140.505240.097850.0289*
H60.414020.616560.113980.0279*
H410.3898 (19)0.4057 (16)0.4289 (15)0.0369*
H420.381 (2)0.2927 (16)0.4217 (15)0.0369*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0316 (5)0.0154 (7)0.0383 (7)−0.0051 (4)0.0053 (4)−0.0044 (5)
O20.0231 (5)0.0245 (7)0.0430 (7)−0.0032 (5)0.0043 (4)−0.0063 (5)
O30.0193 (5)0.0217 (7)0.0548 (8)−0.0032 (4)−0.0059 (5)0.0000 (6)
N10.0214 (6)0.0150 (8)0.0331 (8)0.0010 (5)0.0027 (5)0.0015 (6)
C10.0236 (7)0.0164 (9)0.0216 (8)−0.0029 (5)0.0013 (5)−0.0026 (6)
C20.0183 (6)0.0190 (9)0.0235 (8)0.0006 (5)0.0011 (5)−0.0006 (6)
C30.0209 (6)0.0142 (9)0.0228 (8)0.0003 (5)0.0018 (5)0.0013 (6)
C40.0195 (6)0.0188 (9)0.0254 (8)−0.0024 (5)−0.0004 (5)−0.0019 (6)
C50.0205 (6)0.0218 (9)0.0300 (9)0.0041 (6)−0.0024 (6)0.0003 (7)
C60.0290 (7)0.0137 (8)0.0270 (8)0.0014 (6)0.0000 (5)0.0005 (7)
C70.0265 (7)0.0169 (9)0.0214 (8)−0.0044 (6)0.0013 (5)−0.0002 (6)
O40.0257 (5)0.0255 (8)0.0412 (7)0.0017 (5)−0.0044 (4)0.0023 (6)
Geometric parameters (Å, °) top
O1—C71.277 (2)C1—C71.503 (2)
O2—C71.2453 (17)C1—C61.3948 (19)
O3—C41.3518 (18)C1—C21.384 (2)
O3—H30.904 (18)C2—C31.375 (2)
O4—H410.90 (2)C3—C41.3972 (19)
O4—H420.884 (19)C4—C51.381 (2)
N1—C31.453 (2)C5—C61.388 (2)
N1—H1C0.933 (17)C2—H20.9300
N1—H1A0.952 (18)C5—H50.9300
N1—H1B0.944 (19)C6—H60.9300
C4—O3—H3114.3 (13)O3—C4—C5125.06 (12)
H41—O4—H42107.7 (17)C3—C4—C5118.69 (13)
C3—N1—H1A110.5 (11)O3—C4—C3116.26 (13)
C3—N1—H1B109.8 (11)C4—C5—C6120.36 (13)
H1A—N1—H1B104.4 (14)C1—C6—C5120.64 (15)
H1A—N1—H1C112.1 (14)O1—C7—O2123.20 (14)
C3—N1—H1C111.3 (11)O2—C7—C1118.57 (14)
H1B—N1—H1C108.4 (15)O1—C7—C1118.24 (12)
C2—C1—C6118.72 (13)C3—C2—H2120.00
C2—C1—C7118.97 (12)C1—C2—H2120.00
C6—C1—C7122.24 (14)C4—C5—H5120.00
C1—C2—C3120.53 (13)C6—C5—H5120.00
N1—C3—C2120.64 (12)C1—C6—H6120.00
C2—C3—C4120.97 (14)C5—C6—H6120.00
N1—C3—C4118.38 (12)
C6—C1—C2—C32.1 (2)C1—C2—C3—C40.5 (2)
C7—C1—C2—C3−175.02 (13)N1—C3—C4—O3−1.1 (2)
C2—C1—C6—C5−2.7 (2)N1—C3—C4—C5178.75 (14)
C7—C1—C6—C5174.30 (14)C2—C3—C4—O3177.60 (14)
C2—C1—C7—O1−156.35 (14)C2—C3—C4—C5−2.5 (2)
C2—C1—C7—O223.8 (2)O3—C4—C5—C6−178.25 (15)
C6—C1—C7—O126.7 (2)C3—C4—C5—C61.9 (2)
C6—C1—C7—O2−153.17 (15)C4—C5—C6—C10.7 (2)
C1—C2—C3—N1179.24 (13)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.952 (18)1.945 (18)2.8884 (16)170.4 (14)
N1—H1A···O2i0.952 (18)2.335 (18)2.9008 (18)117.6 (13)
N1—H1B···O4ii0.944 (19)2.001 (19)2.8957 (19)157.4 (16)
N1—H1C···O1iii0.933 (17)1.860 (17)2.7846 (18)170.5 (16)
O3—H3···O4iv0.904 (18)1.760 (18)2.6456 (15)166.0 (19)
O4—H41···O2iv0.90 (2)1.80 (2)2.6945 (18)171.1 (17)
O4—H42···O1iii0.884 (19)2.03 (2)2.9027 (18)168.8 (17)
C6—H6···O3v0.932.553.446 (2)161
C7—O2···CgAvi1.2453 (17)3.4940 (13)3.9313 (16)101.24 (9)
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) −x+1/2, y+1/2, z; (vi) x+1/2, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.952 (18)1.945 (18)2.8884 (16)170.4 (14)
N1—H1A···O2i0.952 (18)2.335 (18)2.9008 (18)117.6 (13)
N1—H1B···O4ii0.944 (19)2.001 (19)2.8957 (19)157.4 (16)
N1—H1C···O1iii0.933 (17)1.860 (17)2.7846 (18)170.5 (16)
O3—H3···O4iv0.904 (18)1.760 (18)2.6456 (15)166.0 (19)
O4—H41···O2iv0.90 (2)1.80 (2)2.6945 (18)171.1 (17)
O4—H42···O1iii0.884 (19)2.03 (2)2.9027 (18)168.8 (17)
C6—H6···O3v0.932.553.446 (2)161
C7—O2···CgAvi1.2453 (17)3.4940 (13)3.9313 (16)101.24 (9)
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) −x+1/2, y+1/2, z; (vi) x+1/2, y, −z+1/2.
Acknowledgements top

SU greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing a Scholarship under the Indigenous PhD Program (PIN 042–121314-PS2–287).

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bertasso, M., Holzenkampfer, M., Zeeck, A., Dall'Antonia, F. & Fiedler, H.-P. (2001). J. Antibiot. 54, 730–737.

Bruker (2005). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.