2-Amino­benzothia­zolium 2,4-dicarboxy­benzoate monohydrate

Zhang, N.; Liu, K.-S.; Zhao, X.-J.

doi:10.1107/S160053680901890X

organic compounds

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Volume 65| Part 6| June 2009| Page o1398

doi:10.1107/S160053680901890X

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2-Aminobenzothiazolium 2,4-dicarboxybenzoate monohydrate

Na Zhang,^a Kai-Sheng Liu ^a and Xiao-Jun Zhao ^a ^*

^aCollege of Chemistry and Life Science, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: xiaojun_zhao15@yahoo.com.cn

(Received 15 May 2009; accepted 19 May 2009; online 23 May 2009)

Cocrystallization of 2-aminobenzothiazole with benzene-1,2,4-tricarboxylic acid in a mixed solvent affords the title ternary cocrystal, C₇H₇N₂S⁺·C₉H₅O₆⁻·H₂O, in which one of the carboxyl groups of the benzenetricarboxylic acid is deprotonated and the heterocyclic N atom of the 2-aminobenzothiazole is protonated. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen-bonding interactions stabilize the packing.

Related literature

For the properties of benzothiazole and its derivative and their uses in crystal engineering, see: Batista et al. (2007 ); Leng et al. (2001 ); Chen et al. (2008 ); Kovalska et al. (2006 ); Marconato et al. (1998 ). For 2-aminobenzothiazole (Abt) metal complexes, see: Batı et al. (2005 ); Sieroń & Bukowska-Strzyzewska (1999 ); Usman et al. (2003 ). For Abt-based cocrystals, see: Lynch et al. (1998 , 1999 ).

Experimental

Crystal data

C₇H₇N₂S⁺·C₉H₅O₆⁻·H₂O
M_r = 378.35
Orthorhombic, P n a 2₁
a = 6.8510 (4) Å
b = 24.3789 (15) Å
c = 9.7043 (6) Å
V = 1620.81 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.953, T_max = 0.960
7728 measured reflections
2632 independent reflections
2446 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.070
S = 1.04
2632 reflections
237 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 1116 Friedel pairs
Flack parameter: 0.10 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O7ⁱ	0.82	1.86	2.674 (2)	171
O6—H6⋯O2ⁱⁱ	0.82	1.82	2.635 (2)	171
N1—H1⋯O1ⁱⁱⁱ	0.86	1.85	2.698 (2)	170
N2—H2A⋯O3ⁱⁱⁱ	0.86	2.03	2.838 (3)	156
N2—H2B⋯O5	0.86	1.95	2.776 (3)	160
O7—H7A⋯O1^iv	0.85	2.00	2.851 (2)	177
O7—H7B⋯O2ⁱⁱ	0.85	2.05	2.891 (2)	170
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+1]$ ; (ii) x, y, z-1; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-1]$ ; (iv) x-1, y, z-1.

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901890X/bt2963sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901890X/bt2963Isup2.hkl

checkCIF report

Comment top

Benzothiazole and its derivatives are extensively used in the field of crystal engineering owing to their beautiful structure and potential applications as electroluminescent devices (Batista et al., 2007; Leng et al., 2001, Chen et al., 2008), fluorescent probes for DNA (Kovalska et al., 2006), and corrosion inhibitors (Marconato et al., 1998).

As one of the typical benzothiazole derivatives, 2-aminobenzothiazole (Abt) has been becoming a promising candidate for both the metal complexes and organic cocrystals, because they have rigid heterocyclic backbone and functional amino group. Consequently, various Abt–based metal complexes with diverse coligands have been considerably investigated (Batı et al., 2005; Sieroń et al., 1999; Usman et al., 2003). In contrast, the Abt-based cocrystals are limited documented (Lynch et al., 1998; Lynch et al., 1999). Thus, as a continuation of acid–base crystalline adducts, in the present paper, we choose Abt and aromatic 1, 2, 4-benzenetricarboxylic acid (H₃btc) as building blocks to cocrystallize. As a result, an intermolecular proton–transfer adduct, (I), was obtained, which exhibits a two–dimensional hydrogen–bonded network.

As shown in Fig. 1, the asymmetric unit of (I) comprises one HAbt cation, a monodeprontonated H₂btc anion and one water molecule. The exocyclic amino group of HAbt is roughly coplanar with the benzothiazole ring. In contrast, the deprotonated carboxy group of H₂btc makes dihedral angle of 86.103 (1)°, and the other carboxylic groups form dihedral angles of 8.231 (1) and 1.962 (2)° with the benzene ring of H₂btc, respectively. The benzothiazole and the benzene rings of H₂btc exhibits a dihedral angle of 7.083 (2)°. In the asymmetric unit, an intermolecular N2–H2B ···O5 hydrogen–bonding interaction (Table 1) was observed to stabilize the adduct.

Two H₂btc anions from the adjacent units are held together by intermolecular O6–H6···O2 interactions (Table 1) to form an infinite one–dimensional ribbon along the crystallographic c–axis (Fig. 2), in which lattice water molecules was entrapped by O4–H4···O7 hydrogen–bonding interaction between the carboxylic group of H₂btc and water molecule..

Furthermore, the neighboring 1–D ribbons are head–to–tail connected together by four fold O4–H4···O7, N1–H1···O1, N2–H2A···O3, O7–H7A···O1 and O7–H7B···O2 hydrogen-bonding to form a separate two-dimensional supramolecular sheet without any weak π···πinteractions between neighboring sheets (Fig. 3). Thus, it can be concluded that the extensive hydrogen–bonding interactions play essentially roles for the extension of (I).

Related literature top

For the properties of benzothiazole and its derivative and their uses in crystal engineering, see: Batista et al. (2007); Leng et al. (2001); Chen et al. (2008); Kovalska et al. (2006); Marconato et al. (1998). For 2-aminobenzothiazole (Abt) metal complexes, see: Batı et al. (2005); Sieroń et al. (1999); Usman et al. (2003). For Abt-based cocrystals, see: Lynch et al. (1998, 1999).

Experimental top

2–Aminobenzothiazole (0.1 mmol, 15.0 mg) and 1, 2, 4–benzenetricarboxylic acid (0.1 mmol, 21.0 mg) were mixed in a CH₃OH/H₂O solution (v: v = 1:1, 10 ml) and stirred constantly for about 30 min. The resulting mixture was filtered. Colorless block crystals suitable for X–ray diffraction were collected by slow evaporation of the filtrate within one week. Yield: 56%. Anal. Calcd for C₁₆H₁₄N₂O₇S: C, 50.79; H, 3.73; N, 7.40%. Found: C, 50.66; H, 3.52; N, 7.28%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids.
	Fig. 2. A perspective view of the one-dimensional hydrogen–bonded ribbon of (I). Hydrogen bonds are indicated by dashed lines.
	Fig. 3. The separate two-dimensional supramolecular sheet of (I).

2-Aminobenzothiazolium 2,4-dicarboxybenzoate monohydrate top

Crystal data top

C₇H₇N₂S⁺·C₉H₅O₆⁻·H₂O	D_x = 1.551 Mg m⁻³
M_r = 378.35	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 4384 reflections
a = 6.8510 (4) Å	θ = 3.1–27.9°
b = 24.3789 (15) Å	µ = 0.25 mm⁻¹
c = 9.7043 (6) Å	T = 296 K
V = 1620.81 (17) Å³	Block, colourless
Z = 4	0.20 × 0.18 × 0.17 mm
F(000) = 784

Data collection top

Bruker APEXII CCD area-detector diffractometer	2632 independent reflections
Radiation source: fine-focus sealed tube	2446 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.953, T_max = 0.960	k = −29→19
7728 measured reflections	l = −11→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0386P)² + 0.1846P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2632 reflections	Δρ_max = 0.15 e Å⁻³
237 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1116 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.10 (8)

Crystal data top

C₇H₇N₂S⁺·C₉H₅O₆⁻·H₂O	V = 1620.81 (17) Å³
M_r = 378.35	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 6.8510 (4) Å	µ = 0.25 mm⁻¹
b = 24.3789 (15) Å	T = 296 K
c = 9.7043 (6) Å	0.20 × 0.18 × 0.17 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2632 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2446 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.960	R_int = 0.023
7728 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.15 e Å⁻³
S = 1.04	Δρ_min = −0.18 e Å⁻³
2632 reflections	Absolute structure: Flack (1983), 1116 Friedel pairs
237 parameters	Absolute structure parameter: 0.10 (8)
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.41587 (9)	0.29601 (2)	0.74515 (7)	0.04137 (16)
O1	0.6936 (2)	0.09280 (7)	1.31365 (15)	0.0397 (4)
O2	0.3712 (2)	0.10037 (7)	1.34480 (16)	0.0415 (4)
O3	0.5680 (3)	0.20862 (7)	1.2595 (2)	0.0566 (5)
O4	0.4844 (3)	0.25690 (7)	1.07597 (17)	0.0464 (4)
H4	0.5055	0.2826	1.1284	0.070*
O5	0.3884 (3)	0.17106 (7)	0.63412 (16)	0.0484 (5)
O6	0.3848 (3)	0.08050 (6)	0.61157 (14)	0.0382 (4)
H6	0.3681	0.0882	0.5302	0.057*
N1	0.3226 (3)	0.35998 (8)	0.54800 (19)	0.0397 (5)
H1	0.2880	0.3717	0.4681	0.048*
N2	0.3039 (3)	0.26695 (9)	0.4919 (2)	0.0515 (6)
H2A	0.2647	0.2740	0.4096	0.062*
H2B	0.3190	0.2335	0.5180	0.062*
C1	0.3639 (3)	0.39498 (10)	0.6569 (3)	0.0369 (5)
C2	0.4157 (3)	0.36673 (10)	0.7762 (3)	0.0376 (6)
C3	0.4535 (4)	0.39391 (12)	0.8975 (3)	0.0497 (7)
H3	0.4875	0.3751	0.9773	0.060*
C4	0.4387 (4)	0.45033 (13)	0.8957 (4)	0.0601 (8)
H4A	0.4624	0.4699	0.9763	0.072*
C5	0.3892 (4)	0.47875 (11)	0.7767 (4)	0.0625 (9)
H5	0.3814	0.5168	0.7790	0.075*
C6	0.3515 (4)	0.45135 (10)	0.6548 (3)	0.0508 (7)
H6A	0.3191	0.4702	0.5747	0.061*
C7	0.3406 (3)	0.30693 (10)	0.5769 (2)	0.0393 (6)
C8	0.4935 (3)	0.10831 (9)	1.1180 (2)	0.0288 (5)
C9	0.4830 (3)	0.16013 (9)	1.0568 (2)	0.0287 (5)
C10	0.4490 (3)	0.16392 (9)	0.9160 (2)	0.0303 (5)
H10	0.4394	0.1983	0.8753	0.036*
C11	0.4293 (3)	0.11747 (10)	0.8351 (2)	0.0281 (5)
C12	0.4424 (3)	0.06607 (10)	0.8962 (2)	0.0308 (5)
H12	0.4298	0.0345	0.8431	0.037*
C13	0.4741 (3)	0.06218 (9)	1.0367 (2)	0.0325 (5)
H13	0.4826	0.0277	1.0773	0.039*
C14	0.5236 (3)	0.10060 (9)	1.2723 (2)	0.0307 (5)
C15	0.5155 (3)	0.21044 (9)	1.1409 (2)	0.0324 (5)
C16	0.3977 (3)	0.12557 (10)	0.6837 (2)	0.0314 (5)
O7	0.0300 (2)	0.15288 (7)	0.2293 (2)	0.0530 (5)
H7A	−0.0728	0.1356	0.2522	0.080*
H7B	0.1377	0.1409	0.2607	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0528 (3)	0.0398 (3)	0.0315 (3)	0.0040 (3)	−0.0078 (3)	0.0088 (3)
O1	0.0446 (9)	0.0454 (10)	0.0289 (9)	0.0028 (8)	−0.0099 (7)	−0.0020 (7)
O2	0.0454 (9)	0.0585 (11)	0.0205 (7)	−0.0054 (8)	0.0019 (7)	0.0018 (7)
O3	0.0987 (14)	0.0412 (9)	0.0299 (11)	−0.0003 (10)	−0.0185 (11)	−0.0048 (9)
O4	0.0738 (12)	0.0311 (9)	0.0343 (9)	0.0022 (9)	−0.0091 (9)	−0.0041 (8)
O5	0.0828 (14)	0.0361 (10)	0.0264 (9)	0.0095 (9)	−0.0025 (9)	0.0046 (8)
O6	0.0583 (10)	0.0387 (10)	0.0177 (8)	−0.0019 (8)	−0.0019 (7)	−0.0019 (7)
N1	0.0446 (12)	0.0445 (12)	0.0300 (11)	0.0067 (9)	−0.0005 (9)	0.0139 (9)
N2	0.0771 (16)	0.0469 (13)	0.0305 (11)	0.0143 (11)	−0.0101 (11)	0.0037 (10)
C1	0.0276 (12)	0.0414 (13)	0.0415 (14)	−0.0011 (11)	0.0045 (10)	0.0082 (11)
C2	0.0299 (11)	0.0423 (13)	0.0406 (16)	−0.0003 (10)	−0.0001 (9)	0.0062 (11)
C3	0.0397 (14)	0.0623 (18)	0.0470 (16)	−0.0023 (12)	−0.0069 (12)	−0.0050 (14)
C4	0.0449 (16)	0.0600 (19)	0.075 (2)	−0.0081 (14)	−0.0057 (14)	−0.0189 (17)
C5	0.0496 (15)	0.0393 (14)	0.099 (3)	−0.0044 (13)	0.0061 (16)	−0.0028 (17)
C6	0.0430 (15)	0.0393 (14)	0.0701 (19)	−0.0007 (12)	0.0043 (13)	0.0131 (14)
C7	0.0399 (13)	0.0484 (14)	0.0295 (13)	0.0094 (11)	0.0009 (10)	0.0085 (11)
C8	0.0320 (12)	0.0339 (12)	0.0204 (11)	−0.0010 (9)	−0.0001 (9)	−0.0003 (9)
C9	0.0322 (11)	0.0314 (12)	0.0225 (10)	0.0011 (9)	−0.0002 (9)	0.0000 (9)
C10	0.0361 (12)	0.0298 (12)	0.0249 (11)	0.0009 (9)	0.0010 (9)	0.0029 (9)
C11	0.0305 (11)	0.0348 (14)	0.0191 (10)	−0.0002 (9)	0.0009 (8)	−0.0004 (9)
C12	0.0351 (12)	0.0324 (12)	0.0248 (11)	−0.0016 (9)	−0.0019 (9)	−0.0033 (9)
C13	0.0403 (12)	0.0296 (12)	0.0278 (12)	−0.0013 (10)	−0.0011 (10)	0.0050 (9)
C14	0.0431 (13)	0.0283 (11)	0.0207 (12)	−0.0029 (9)	−0.0024 (10)	−0.0006 (9)
C15	0.0383 (13)	0.0329 (12)	0.0261 (12)	0.0022 (9)	0.0007 (10)	−0.0019 (9)
C16	0.0319 (13)	0.0364 (13)	0.0259 (12)	0.0012 (10)	0.0006 (9)	−0.0007 (10)
O7	0.0487 (10)	0.0494 (10)	0.0609 (13)	0.0003 (8)	0.0007 (10)	0.0200 (10)

Geometric parameters (Å, º) top

S1—C7	1.733 (2)	C3—H3	0.9300
S1—C2	1.750 (2)	C4—C5	1.389 (5)
O1—C14	1.246 (3)	C4—H4A	0.9300
O2—C14	1.259 (3)	C5—C6	1.382 (4)
O3—C15	1.207 (3)	C5—H5	0.9300
O4—C15	1.313 (3)	C6—H6A	0.9300
O4—H4	0.8200	C8—C13	1.380 (3)
O5—C16	1.211 (3)	C8—C9	1.398 (3)
O6—C16	1.306 (3)	C8—C14	1.523 (3)
O6—H6	0.8200	C9—C10	1.389 (3)
N1—C7	1.329 (3)	C9—C15	1.490 (3)
N1—C1	1.388 (3)	C10—C11	1.385 (3)
N1—H1	0.8600	C10—H10	0.9300
N2—C7	1.301 (3)	C11—C12	1.389 (3)
N2—H2A	0.8600	C11—C16	1.498 (3)
N2—H2B	0.8600	C12—C13	1.384 (3)
C1—C6	1.377 (3)	C12—H12	0.9300
C1—C2	1.393 (3)	C13—H13	0.9300
C2—C3	1.376 (4)	O7—H7A	0.8502
C3—C4	1.379 (4)	O7—H7B	0.8498

C7—S1—C2	90.61 (12)	N1—C7—S1	112.06 (18)
C15—O4—H4	109.5	C13—C8—C9	119.23 (19)
C16—O6—H6	109.5	C13—C8—C14	118.3 (2)
C7—N1—C1	114.8 (2)	C9—C8—C14	122.44 (19)
C7—N1—H1	122.6	C10—C9—C8	119.1 (2)
C1—N1—H1	122.6	C10—C9—C15	120.6 (2)
C7—N2—H2A	120.0	C8—C9—C15	120.23 (19)
C7—N2—H2B	120.0	C11—C10—C9	121.3 (2)
H2A—N2—H2B	120.0	C11—C10—H10	119.3
C6—C1—N1	126.2 (2)	C9—C10—H10	119.3
C6—C1—C2	121.4 (2)	C10—C11—C12	119.3 (2)
N1—C1—C2	112.4 (2)	C10—C11—C16	117.6 (2)
C3—C2—C1	121.4 (2)	C12—C11—C16	123.2 (2)
C3—C2—S1	128.4 (2)	C13—C12—C11	119.5 (2)
C1—C2—S1	110.14 (19)	C13—C12—H12	120.2
C2—C3—C4	117.1 (3)	C11—C12—H12	120.2
C2—C3—H3	121.5	C8—C13—C12	121.5 (2)
C4—C3—H3	121.5	C8—C13—H13	119.3
C3—C4—C5	121.7 (3)	C12—C13—H13	119.3
C3—C4—H4A	119.1	O1—C14—O2	126.5 (2)
C5—C4—H4A	119.1	O1—C14—C8	117.49 (18)
C6—C5—C4	121.1 (3)	O2—C14—C8	115.9 (2)
C6—C5—H5	119.5	O3—C15—O4	122.5 (2)
C4—C5—H5	119.5	O3—C15—C9	122.5 (2)
C1—C6—C5	117.3 (3)	O4—C15—C9	115.03 (19)
C1—C6—H6A	121.4	O5—C16—O6	123.6 (2)
C5—C6—H6A	121.4	O5—C16—C11	121.2 (2)
N2—C7—N1	125.3 (2)	O6—C16—C11	115.1 (2)
N2—C7—S1	122.65 (19)	H7A—O7—H7B	117.1

C7—N1—C1—C6	−178.2 (2)	C14—C8—C9—C15	4.4 (3)
C7—N1—C1—C2	−0.3 (3)	C8—C9—C10—C11	−1.3 (3)
C6—C1—C2—C3	1.1 (4)	C15—C9—C10—C11	176.37 (19)
N1—C1—C2—C3	−177.0 (2)	C9—C10—C11—C12	0.5 (3)
C6—C1—C2—S1	179.4 (2)	C9—C10—C11—C16	−178.6 (2)
N1—C1—C2—S1	1.4 (2)	C10—C11—C12—C13	0.2 (3)
C7—S1—C2—C3	176.6 (2)	C16—C11—C12—C13	179.2 (2)
C7—S1—C2—C1	−1.59 (18)	C9—C8—C13—C12	−0.7 (3)
C1—C2—C3—C4	−0.3 (4)	C14—C8—C13—C12	178.6 (2)
S1—C2—C3—C4	−178.29 (19)	C11—C12—C13—C8	−0.1 (3)
C2—C3—C4—C5	−0.4 (4)	C13—C8—C14—O1	84.9 (3)
C3—C4—C5—C6	0.4 (4)	C9—C8—C14—O1	−95.7 (3)
N1—C1—C6—C5	176.7 (2)	C13—C8—C14—O2	−92.1 (2)
C2—C1—C6—C5	−1.1 (4)	C9—C8—C14—O2	87.3 (3)
C4—C5—C6—C1	0.4 (4)	C10—C9—C15—O3	−171.0 (2)
C1—N1—C7—N2	178.0 (2)	C8—C9—C15—O3	6.6 (3)
C1—N1—C7—S1	−1.0 (3)	C10—C9—C15—O4	8.4 (3)
C2—S1—C7—N2	−177.5 (2)	C8—C9—C15—O4	−173.95 (19)
C2—S1—C7—N1	1.47 (18)	C10—C11—C16—O5	−0.5 (3)
C13—C8—C9—C10	1.4 (3)	C12—C11—C16—O5	−179.5 (2)
C14—C8—C9—C10	−178.0 (2)	C10—C11—C16—O6	178.40 (19)
C13—C8—C9—C15	−176.3 (2)	C12—C11—C16—O6	−0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O7ⁱ	0.82	1.86	2.674 (2)	171
O6—H6···O2ⁱⁱ	0.82	1.82	2.635 (2)	171
N1—H1···O1ⁱⁱⁱ	0.86	1.85	2.698 (2)	170
N2—H2A···O3ⁱⁱⁱ	0.86	2.03	2.838 (3)	156
N2—H2B···O5	0.86	1.95	2.776 (3)	160
O7—H7A···O1^iv	0.85	2.00	2.851 (2)	177
O7—H7B···O2ⁱⁱ	0.85	2.05	2.891 (2)	170

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂S⁺·C₉H₅O₆⁻·H₂O
M_r	378.35
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	6.8510 (4), 24.3789 (15), 9.7043 (6)
V (Å³)	1620.81 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.20 × 0.18 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.953, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	7728, 2632, 2446
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.070, 1.04
No. of reflections	2632
No. of parameters	237
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18
Absolute structure	Flack (1983), 1116 Friedel pairs
Absolute structure parameter	0.10 (8)

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O7ⁱ	0.82	1.86	2.674 (2)	171.4
O6—H6···O2ⁱⁱ	0.82	1.82	2.635 (2)	170.5
N1—H1···O1ⁱⁱⁱ	0.86	1.85	2.698 (2)	169.7
N2—H2A···O3ⁱⁱⁱ	0.86	2.03	2.838 (3)	156.3
N2—H2B···O5	0.86	1.95	2.776 (3)	159.8
O7—H7A···O1^iv	0.85	2.00	2.851 (2)	176.9
O7—H7B···O2ⁱⁱ	0.85	2.05	2.891 (2)	170.4

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

Acknowledgements

The authors gratefully acknowledge financial support from the Tianjin Education Committee (2006ZD07).

References

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