Ammonium 4-hydroxy­benzene­sulfonate

The title compound, NH₄⁺·C₆H₅SO₄⁻, consists of a 4-hydroxy­benzene­sulfonate anion and an ammonium cation which are linked together through O—H...O and N—H...O hydrogen bonds, resulting in the formation of an intricate three-dimensional hydrogen-bond network.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.085
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

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Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1C    ..  O3      ..       2.63 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Hydroxybenzene sulfonic acid is a useful intermediate in dye stuff and chemical synthesis(Yang et al., 2003). Many crystalline compounds of 4-hydroxybenzene sulfonic acid have been previously reported (Kosnic et al., 1992; Bu et al., 2000; Jin et al., 2004). Moreover, there are numerous examples of metal benzenesulfonate molecular complexes (Schreuer, 1999; Rombke et al., 2003).

The 4-hydroxybenzenesulfonate anion is linked to the ammonium cation by strong N—H···O hydrogen bond (Fig. 1, Table 1). The S—O distances are comparable to those previously reported for sulfonates (Gunderman et al., 1997; Chen et al., 2004; Sharma et al., 2005).

The packing arrangement in the crystal structure is governed by the occurrence of strong O—H···O and N—H···O hydrogen bonds between anions and cations resulting in the formation of an intricated three dimensionnal hydrogen bond network (Table 1, Fig. 2). Moreover, weak slipped π-π stacking exists between symmetry related rings (1 - x, -y, -z) with a centroid to centroid distances of 3.621 (1)Å and an interplanar distance of 3.40 Å resulting in an offset angle of 20.1°. This π-π stackings further stabilize the structure.

Related literature

For related literature, see: Bu et al. (2000); Chen et al. (2004); Gunderman et al. (1997); Jin et al. (2004); Kosnic et al. (1992); Francis et al. (2003); Rombke et al. (2003); Schreuer (1999); Sharma et al. (2005); Yang & Chen (2003).

S2. Experimental

4-hydroxybenzene sulfonic acid and famotidine in a 1:1 molar ratio were mixed and dissolved in sufficient acetone by heating to a temperature at which a clear solution resulted. Ammonium cations were split up from molecules of famotidine in the course. Thus crystals of (I) were formed by gradual evaporation of acetone over a period of three days at 298 K.

S3. Refinement

H atoms attaching to O and N atoms were deduced from difference Fourier maps, and incorporated in refinement freely. Others were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.94Å for aromatic group, with U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of (I) with atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bond is shown as dashed line.
	Fig. 2. Partial packing view showing the intricated hydrogen bonds network. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1/2 + y, 3/2 - z; (ii) 2 - x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 1 - z; (iv) x, 1 + y, z; (v) 2 - x, 1/2 + y, 3/2 - z].

Ammonium 4-hydroxybenzenesulfonate

Crystal data

NH4^+·C6H5O4S^−	F(000) = 400
Mr = 191.21	Dx = 1.541 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 3236 reflections
a = 10.227 (2) Å	θ = 3.4–25.3°
b = 7.1414 (13) Å	µ = 0.37 mm^−1
c = 11.461 (2) Å	T = 223 K
β = 100.163 (4)°	Block, colourless
V = 823.9 (3) Å^3	0.40 × 0.38 × 0.35 mm
Z = 4

Data collection

Rigaku Mercury diffractometer	1498 independent reflections
Radiation source: fine-focus sealed tube	1442 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 7.31 pixels mm^-1	θmax = 25.4°, θmin = 3.4°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −8→8
Tmin = 0.863, Tmax = 0.879	l = −13→13
7537 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 0.4222P] where P = (Fo^2 + 2Fc^2)/3
1498 reflections	(Δ/σ)max < 0.001
122 parameters	Δρmax = 0.27 e Å^−3
9 restraints	Δρmin = −0.37 e Å^−3

Special details

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

	x	y	z	Uiso*/Ueq
S1	0.81650 (4)	0.20307 (6)	0.62303 (3)	0.02096 (16)
O1	0.25361 (12)	0.3946 (2)	0.60586 (11)	0.0341 (3)
H1	0.2415	0.4491	0.6660	0.051*
O2	0.82941 (12)	0.1392 (2)	0.50524 (11)	0.0355 (3)
O3	0.83397 (12)	0.04653 (17)	0.70710 (11)	0.0305 (3)
O4	0.90302 (12)	0.35765 (19)	0.66613 (12)	0.0366 (3)
C1	0.38589 (16)	0.3607 (2)	0.61239 (14)	0.0224 (4)
C2	0.42366 (17)	0.2668 (2)	0.51755 (15)	0.0255 (4)
H2	0.3600	0.2316	0.4530	0.031*
C3	0.55608 (16)	0.2257 (2)	0.51934 (14)	0.0230 (4)
H3	0.5815	0.1626	0.4560	0.028*
C4	0.65111 (16)	0.2784 (2)	0.61549 (14)	0.0188 (3)
C5	0.61402 (17)	0.3763 (2)	0.70918 (14)	0.0224 (4)
H5	0.6780	0.4140	0.7729	0.027*
C6	0.48144 (17)	0.4175 (2)	0.70732 (14)	0.0231 (4)
H6	0.4563	0.4833	0.7698	0.028*
N1	0.95300 (15)	0.7327 (2)	0.59472 (14)	0.0264 (3)
H1A	1.0222 (13)	0.765 (3)	0.5683 (17)	0.040*
H1B	0.8939 (15)	0.717 (3)	0.5336 (12)	0.040*
H1C	0.959 (2)	0.6279 (17)	0.6300 (15)	0.040*
H1D	0.9321 (19)	0.817 (2)	0.6380 (14)	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0168 (2)	0.0235 (3)	0.0229 (3)	−0.00103 (15)	0.00433 (16)	0.00343 (15)
O1	0.0196 (6)	0.0514 (9)	0.0306 (7)	0.0073 (6)	0.0025 (5)	−0.0118 (6)
O2	0.0244 (7)	0.0572 (9)	0.0272 (7)	0.0025 (6)	0.0106 (5)	−0.0036 (6)
O3	0.0263 (7)	0.0293 (7)	0.0381 (7)	0.0082 (5)	0.0118 (5)	0.0131 (5)
O4	0.0242 (7)	0.0309 (7)	0.0511 (8)	−0.0080 (5)	−0.0033 (6)	0.0033 (6)
C1	0.0195 (8)	0.0240 (8)	0.0238 (8)	0.0034 (6)	0.0040 (6)	0.0015 (7)
C2	0.0207 (9)	0.0331 (9)	0.0215 (8)	−0.0006 (7)	0.0001 (7)	−0.0055 (7)
C3	0.0228 (9)	0.0269 (9)	0.0197 (8)	0.0004 (7)	0.0051 (7)	−0.0036 (7)
C4	0.0183 (8)	0.0185 (8)	0.0199 (8)	−0.0006 (6)	0.0041 (6)	0.0033 (6)
C5	0.0237 (8)	0.0240 (8)	0.0179 (8)	−0.0004 (7)	−0.0009 (6)	−0.0015 (6)
C6	0.0274 (9)	0.0239 (8)	0.0183 (8)	0.0039 (7)	0.0046 (6)	−0.0017 (6)
N1	0.0240 (8)	0.0280 (8)	0.0278 (8)	−0.0002 (6)	0.0064 (6)	0.0008 (6)

Geometric parameters (Å, º)

S1—O4	1.4461 (13)	C3—C4	1.387 (2)
S1—O2	1.4528 (13)	C3—H3	0.9300
S1—O3	1.4661 (12)	C4—C5	1.389 (2)
S1—C4	1.7624 (16)	C5—C6	1.384 (2)
O1—C1	1.363 (2)	C5—H5	0.9300
O1—H1	0.8200	C6—H6	0.9300
C1—C6	1.388 (2)	N1—H1A	0.849 (9)
C1—C2	1.389 (2)	N1—H1B	0.848 (9)
C2—C3	1.382 (2)	N1—H1C	0.848 (9)
C2—H2	0.9300	N1—H1D	0.834 (9)
O4—S1—O2	113.99 (8)	C3—C4—C5	120.15 (15)
O4—S1—O3	111.18 (8)	C3—C4—S1	119.22 (12)
O2—S1—O3	110.54 (8)	C5—C4—S1	120.42 (12)
O4—S1—C4	107.93 (8)	C6—C5—C4	119.70 (15)
O2—S1—C4	107.10 (7)	C6—C5—H5	120.1
O3—S1—C4	105.63 (7)	C4—C5—H5	120.1
C1—O1—H1	109.5	C5—C6—C1	120.15 (15)
O1—C1—C6	123.06 (15)	C5—C6—H6	119.9
O1—C1—C2	116.95 (15)	C1—C6—H6	119.9
C6—C1—C2	119.99 (15)	H1A—N1—H1B	105.1 (16)
C3—C2—C1	119.87 (15)	H1A—N1—H1C	115 (2)
C3—C2—H2	120.1	H1B—N1—H1C	104.9 (16)
C1—C2—H2	120.1	H1A—N1—H1D	109.4 (16)
C2—C3—C4	120.11 (15)	H1B—N1—H1D	111.5 (17)
C2—C3—H3	119.9	H1C—N1—H1D	111.2 (16)
C4—C3—H3	119.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.82	1.89	2.6930 (17)	164
N1—H1A···O2^ii	0.85 (1)	1.98 (1)	2.829 (2)	173 (2)
N1—H1B···O1^iii	0.85 (1)	2.15 (1)	2.977 (2)	166 (2)
N1—H1C···O4	0.85 (1)	2.08 (1)	2.873 (2)	157 (2)
N1—H1C···O3^iv	0.85 (1)	2.63 (2)	3.151 (2)	121 (2)
N1—H1D···O3^v	0.83 (1)	2.14 (1)	2.952 (2)	164 (2)
N1—H1D···O4^iv	0.83 (1)	2.58 (2)	3.009 (2)	114 (2)

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, y+1/2, −z+3/2; (v) x, y+1, z.