4-[(2,4-Dihydroxy-benzyl-idene)ammonio]benzene-sulfonate trihydrate.

The title Schiff base compound, C(13)H(11)NO(5)S·3H(2)O, formed from sulfanilic acid and 2,4-dihydroxy-benzaldehyde, crystallized out as a zwitterion with the N atom protonated. The asymmetric unit consists of one 4-[(2,4-dihydroxy-benzyl-idene)ammonio]benzene-sulfonate and three water mol-ecules. The zwitterion exists in an E configuration with respect to the central C=N double bond. The two benzene rings of the mol-ecule are oriented at a dihedral angle of 27.33 (8)°. An intra-molecular N-H⋯O hydrogen bond stabilizes the mol-ecular structure. In the crystal, the zwitterions are linked into chains along [101] by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds. The three water mol-ecules link these chains into a three-dimensional framework by additional inter-molecular O-H⋯O hydrogen bonds. A π⋯π inter-action [3.5485 (9) Å] further stabilizes the crystal structure.

Related literature

For Schiff bases and their applications, see: Singh et al. (1975 ▶); Elmali et al. (1999 ▶); Patel et al. (1999 ▶). For details of sulfanilic acid, see: Rae & Maslen (1962 ▶); Banu & Golzar Hossain (2006 ▶); Hempel et al. (1999 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C13H11NO5S·3H2O

M = 347.34

Triclinic,

a = 7.7855 (1) Å

b = 9.0820 (1) Å

c = 11.8526 (2) Å

α = 70.022 (1)°

β = 79.271 (1)°

γ = 76.141 (1)°

V = 759.70 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 100 K

0.36 × 0.16 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.914, T max = 0.980

19799 measured reflections

5420 independent reflections

4177 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.147

S = 1.05

5420 reflections

220 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.61 e Å−3

Δρmin = −0.60 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004526/sj2719sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004526/sj2719Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H11NO5S·3H2O	Z = 2
Mr = 347.34	F(000) = 364
Triclinic, P1	Dx = 1.518 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7855 (1) Å	Cell parameters from 7701 reflections
b = 9.0820 (1) Å	θ = 2.6–32.1°
c = 11.8526 (2) Å	µ = 0.26 mm−1
α = 70.022 (1)°	T = 100 K
β = 79.271 (1)°	Block, yellow
γ = 76.141 (1)°	0.36 × 0.16 × 0.08 mm
V = 759.70 (2) Å3

Bruker SMART APEXII CCD area-detector diffractometer	5420 independent reflections
Radiation source: fine-focus sealed tube	4177 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 32.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.914, Tmax = 0.980	k = −13→13
19799 measured reflections	l = −17→17

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.070P)2 + 0.4045P] where P = (Fo2 + 2Fc2)/3
5420 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
S1	0.71640 (6)	0.60676 (5)	1.18660 (4)	0.02504 (12)
O1	0.33982 (17)	0.77778 (14)	0.52286 (11)	0.0226 (2)
O2	0.00861 (17)	1.21132 (17)	0.24684 (11)	0.0256 (3)
O3	0.89905 (19)	0.52191 (18)	1.16735 (13)	0.0371 (3)
O4	0.7119 (3)	0.75067 (16)	1.21434 (16)	0.0530 (5)
O5	0.60457 (18)	0.50241 (15)	1.27306 (10)	0.0267 (3)
N1	0.41704 (17)	0.82152 (16)	0.71713 (11)	0.0170 (2)
C1	0.2641 (2)	0.93133 (18)	0.48282 (13)	0.0170 (3)
C2	0.1775 (2)	0.99664 (19)	0.37933 (13)	0.0190 (3)
H2A	0.1728	0.9331	0.3333	0.023*
C3	0.0980 (2)	1.15723 (19)	0.34488 (13)	0.0195 (3)
C4	0.1103 (2)	1.25788 (19)	0.40959 (14)	0.0207 (3)
H4A	0.0593	1.3658	0.3843	0.025*
C5	0.1987 (2)	1.19458 (18)	0.51051 (14)	0.0188 (3)
H5A	0.2090	1.2609	0.5528	0.023*
C6	0.2748 (2)	1.02971 (17)	0.55143 (13)	0.0162 (3)
C7	0.3521 (2)	0.97063 (18)	0.66134 (13)	0.0171 (3)
H7A	0.3572	1.0454	0.6975	0.021*
C8	0.4854 (2)	0.76888 (17)	0.83072 (13)	0.0169 (3)
C9	0.4177 (2)	0.85045 (19)	0.91434 (14)	0.0212 (3)
H9A	0.3246	0.9379	0.8979	0.025*
C10	0.4905 (2)	0.79988 (19)	1.02271 (14)	0.0219 (3)
H10A	0.4466	0.8537	1.0793	0.026*
C11	0.6291 (2)	0.66864 (18)	1.04650 (14)	0.0197 (3)
C12	0.6933 (2)	0.58417 (18)	0.96441 (14)	0.0203 (3)
H12A	0.7847	0.4954	0.9817	0.024*
C13	0.6196 (2)	0.63345 (18)	0.85627 (14)	0.0188 (3)
H13A	0.6595	0.5765	0.8014	0.023*
O1W	0.1128 (3)	0.7226 (3)	0.22066 (18)	0.0639 (6)
H1W1	0.0299	0.6832	0.2044	0.096*
H2W1	0.0754	0.8189	0.1836	0.096*
O2W	0.0858 (3)	1.0446 (3)	0.0769 (2)	0.0815 (7)
H1W2	0.1929	0.9994	0.0628	0.122*
H2W2	0.0424	1.1170	0.1224	0.122*
O3W	0.3001 (2)	0.59375 (18)	0.41308 (14)	0.0368 (3)
H1W3	0.4180	0.5558	0.3796	0.055*
H2W3	0.2254	0.6348	0.3604	0.055*
H1N1	0.415 (3)	0.747 (3)	0.689 (2)	0.041 (7)*
H1O1	0.327 (4)	0.719 (4)	0.478 (3)	0.057 (8)*
H1O2	−0.027 (3)	1.305 (3)	0.236 (2)	0.036 (7)*

	U11	U22	U33	U12	U13	U23
S1	0.0369 (2)	0.01588 (18)	0.0241 (2)	−0.00608 (15)	−0.01801 (17)	−0.00021 (14)
O1	0.0310 (6)	0.0164 (5)	0.0212 (5)	−0.0008 (4)	−0.0084 (5)	−0.0063 (4)
O2	0.0257 (6)	0.0297 (7)	0.0188 (5)	−0.0058 (5)	−0.0101 (5)	−0.0001 (5)
O3	0.0291 (7)	0.0386 (8)	0.0338 (7)	−0.0045 (6)	−0.0170 (6)	0.0066 (6)
O4	0.0943 (14)	0.0183 (6)	0.0590 (10)	−0.0066 (7)	−0.0542 (10)	−0.0072 (6)
O5	0.0367 (7)	0.0239 (6)	0.0173 (5)	−0.0029 (5)	−0.0064 (5)	−0.0037 (4)
N1	0.0192 (6)	0.0167 (6)	0.0146 (5)	−0.0028 (5)	−0.0048 (4)	−0.0031 (5)
C1	0.0172 (6)	0.0175 (6)	0.0165 (6)	−0.0047 (5)	−0.0019 (5)	−0.0047 (5)
C2	0.0198 (7)	0.0228 (7)	0.0158 (6)	−0.0070 (5)	−0.0033 (5)	−0.0051 (5)
C3	0.0176 (7)	0.0241 (7)	0.0145 (6)	−0.0066 (5)	−0.0037 (5)	−0.0004 (5)
C4	0.0208 (7)	0.0186 (7)	0.0195 (7)	−0.0035 (5)	−0.0043 (6)	−0.0008 (5)
C5	0.0219 (7)	0.0161 (6)	0.0175 (6)	−0.0034 (5)	−0.0042 (5)	−0.0033 (5)
C6	0.0177 (6)	0.0159 (6)	0.0145 (6)	−0.0032 (5)	−0.0035 (5)	−0.0031 (5)
C7	0.0193 (7)	0.0165 (6)	0.0152 (6)	−0.0035 (5)	−0.0047 (5)	−0.0031 (5)
C8	0.0174 (6)	0.0165 (6)	0.0150 (6)	−0.0039 (5)	−0.0044 (5)	−0.0012 (5)
C9	0.0247 (7)	0.0184 (7)	0.0182 (7)	0.0005 (6)	−0.0065 (6)	−0.0039 (5)
C10	0.0288 (8)	0.0176 (7)	0.0183 (7)	−0.0018 (6)	−0.0067 (6)	−0.0038 (5)
C11	0.0234 (7)	0.0158 (6)	0.0194 (7)	−0.0068 (5)	−0.0082 (6)	0.0004 (5)
C12	0.0192 (7)	0.0170 (7)	0.0211 (7)	−0.0025 (5)	−0.0063 (5)	−0.0002 (5)
C13	0.0195 (7)	0.0176 (6)	0.0178 (6)	−0.0031 (5)	−0.0025 (5)	−0.0038 (5)
O1W	0.0496 (11)	0.1022 (17)	0.0610 (12)	−0.0363 (11)	−0.0095 (9)	−0.0358 (12)
O2W	0.0746 (15)	0.120 (2)	0.0831 (16)	−0.0358 (15)	0.0051 (12)	−0.0697 (16)
O3W	0.0402 (8)	0.0364 (7)	0.0420 (8)	−0.0097 (6)	0.0007 (6)	−0.0238 (6)

S1—O4	1.4441 (14)	C5—H5A	0.9300
S1—O5	1.4512 (14)	C6—C7	1.417 (2)
S1—O3	1.4636 (15)	C7—H7A	0.9300
S1—C11	1.7706 (16)	C8—C9	1.389 (2)
O1—C1	1.3325 (18)	C8—C13	1.394 (2)
O1—H1O1	0.90 (3)	C9—C10	1.388 (2)
O2—C3	1.3500 (18)	C9—H9A	0.9300
O2—H1O2	0.80 (3)	C10—C11	1.390 (2)
N1—C7	1.3083 (19)	C10—H10A	0.9300
N1—C8	1.4247 (19)	C11—C12	1.389 (2)
N1—H1N1	0.85 (3)	C12—C13	1.390 (2)
C1—C2	1.389 (2)	C12—H12A	0.9300
C1—C6	1.422 (2)	C13—H13A	0.9300
C2—C3	1.390 (2)	O1W—H1W1	0.8863
C2—H2A	0.9300	O1W—H2W1	0.8403
C3—C4	1.408 (2)	O2W—H1W2	0.8500
C4—C5	1.372 (2)	O2W—H2W2	0.9519
C4—H4A	0.9300	O3W—H1W3	0.9617
C5—C6	1.419 (2)	O3W—H2W3	0.8594
O4—S1—O5	113.78 (10)	C7—C6—C1	123.35 (13)
O4—S1—O3	111.65 (11)	C5—C6—C1	118.67 (13)
O5—S1—O3	111.87 (8)	N1—C7—C6	126.60 (14)
O4—S1—C11	106.23 (8)	N1—C7—H7A	116.7
O5—S1—C11	106.54 (8)	C6—C7—H7A	116.7
O3—S1—C11	106.16 (8)	C9—C8—C13	121.03 (14)
C1—O1—H1O1	114.3 (19)	C9—C8—N1	120.33 (13)
C3—O2—H1O2	106.3 (18)	C13—C8—N1	118.64 (13)
C7—N1—C8	123.83 (13)	C10—C9—C8	119.21 (14)
C7—N1—H1N1	121.2 (17)	C10—C9—H9A	120.4
C8—N1—H1N1	114.9 (17)	C8—C9—H9A	120.4
O1—C1—C2	123.11 (14)	C9—C10—C11	119.89 (15)
O1—C1—C6	116.94 (13)	C9—C10—H10A	120.1
C2—C1—C6	119.94 (14)	C11—C10—H10A	120.1
C1—C2—C3	119.77 (14)	C12—C11—C10	120.89 (14)
C1—C2—H2A	120.1	C12—C11—S1	120.66 (12)
C3—C2—H2A	120.1	C10—C11—S1	118.41 (12)
O2—C3—C2	116.77 (15)	C11—C12—C13	119.41 (14)
O2—C3—C4	121.90 (15)	C11—C12—H12A	120.3
C2—C3—C4	121.33 (14)	C13—C12—H12A	120.3
C5—C4—C3	119.07 (14)	C12—C13—C8	119.48 (14)
C5—C4—H4A	120.5	C12—C13—H13A	120.3
C3—C4—H4A	120.5	C8—C13—H13A	120.3
C4—C5—C6	121.14 (14)	H1W1—O1W—H2W1	97.0
C4—C5—H5A	119.4	H1W2—O2W—H2W2	127.8
C6—C5—H5A	119.4	H1W3—O3W—H2W3	113.2
C7—C6—C5	117.94 (13)
O1—C1—C2—C3	178.43 (14)	C7—N1—C8—C13	−150.63 (15)
C6—C1—C2—C3	−1.5 (2)	C13—C8—C9—C10	2.8 (2)
C1—C2—C3—O2	−176.86 (14)	N1—C8—C9—C10	−177.92 (15)
C1—C2—C3—C4	3.1 (2)	C8—C9—C10—C11	−0.2 (2)
O2—C3—C4—C5	178.14 (14)	C9—C10—C11—C12	−1.7 (3)
C2—C3—C4—C5	−1.8 (2)	C9—C10—C11—S1	−179.29 (13)
C3—C4—C5—C6	−1.1 (2)	O4—S1—C11—C12	146.08 (15)
C4—C5—C6—C7	−175.27 (15)	O5—S1—C11—C12	−92.28 (15)
C4—C5—C6—C1	2.5 (2)	O3—S1—C11—C12	27.10 (16)
O1—C1—C6—C7	−3.5 (2)	O4—S1—C11—C10	−36.33 (17)
C2—C1—C6—C7	176.45 (14)	O5—S1—C11—C10	85.31 (14)
O1—C1—C6—C5	178.82 (14)	O3—S1—C11—C10	−155.30 (14)
C2—C1—C6—C5	−1.2 (2)	C10—C11—C12—C13	1.1 (2)
C8—N1—C7—C6	−176.86 (14)	S1—C11—C12—C13	178.61 (12)
C5—C6—C7—N1	174.98 (15)	C11—C12—C13—C8	1.5 (2)
C1—C6—C7—N1	−2.7 (3)	C9—C8—C13—C12	−3.4 (2)
C7—N1—C8—C9	30.1 (2)	N1—C8—C13—C12	177.29 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3i	0.89	2.17	3.020 (3)	161
O1W—H1W1···O4i	0.89	2.39	3.083 (3)	135
O1W—H2W1···O2W	0.84	2.02	2.817 (4)	158
O2W—H2W2···O2	0.95	1.89	2.812 (3)	161
O3W—H1W3···O5ii	0.96	1.83	2.756 (2)	161
O3W—H2W3···O1W	0.86	1.86	2.701 (3)	166
N1—H1N1···O1	0.86 (3)	2.07 (2)	2.6601 (18)	126 (2)
N1—H1N1···O5iii	0.86 (3)	2.19 (3)	2.948 (2)	148 (2)
O1—H1O1···O3W	0.90 (3)	1.64 (4)	2.543 (2)	173 (4)
O2—H1O2···O3iv	0.80 (3)	1.85 (3)	2.627 (2)	164 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O3i	0.89	2.17	3.020 (3)	161
O1W—H1W1⋯O4i	0.89	2.39	3.083 (3)	135
O1W—H2W1⋯O2W	0.84	2.02	2.817 (4)	158
O2W—H2W2⋯O2	0.95	1.89	2.812 (3)	161
O3W—H1W3⋯O5ii	0.96	1.83	2.756 (2)	161
O3W—H2W3⋯O1W	0.86	1.86	2.701 (3)	166
N1—H1N1⋯O1	0.86 (3)	2.07 (2)	2.6601 (18)	126 (2)
N1—H1N1⋯O5iii	0.86 (3)	2.19 (3)	2.948 (2)	148 (2)
O1—H1O1⋯O3W	0.90 (3)	1.64 (4)	2.543 (2)	173 (4)
O2—H1O2⋯O3iv	0.80 (3)	1.85 (3)	2.627 (2)	164 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .