2-Amino-benzothia-zolium 2,4-dicarboxy-benzoate monohydrate.

Cocrystallization of 2-amino-benzothia-zole with benzene-1,2,4-tricarboxylic acid in a mixed solvent affords the title ternary cocrystal, C(7)H(7)N(2)S(+)·C(9)H(5)O(6) (-)·H(2)O, in which one of the carboxyl groups of the benzene-tricarboxylic acid is deproton-ated and the heterocyclic N atom of the 2-amino-benzothia-zole is protonated. In the crystal, inter-molecular N-H⋯O and O-H⋯O hydrogen-bonding inter-actions 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 = 378.35

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.070

S = 1.04

2632 reflections

237 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), 1116 Friedel pairs

Flack parameter: 0.10 (8)

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.

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

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

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

C7H7N2S+·C9H5O6−·H2O	Dx = 1.551 Mg m−3
Mr = 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

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

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(Fo2) + (0.0386P)2 + 0.1846P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2632 reflections	Δρmax = 0.14 e Å−3
237 parameters	Δρmin = −0.18 e Å−3
1 restraint	Absolute structure: Flack (1983), 1116 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.10 (8)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O1iv	0.85	2.00	2.851 (2)	177
O7—H7B···O2ii	0.85	2.05	2.891 (2)	170

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⋯O1iv	0.85	2.00	2.851 (2)	177
O7—H7B⋯O2ii	0.85	2.05	2.891 (2)	170

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