Tris(2-amino-1,3-thia-zolium) hydrogen sulfate sulfate monohydrate.

The centrosymmetric crystal structure of the novel semi-organic compound, 3C(3)H(5)N(2)S(+)·HSO(4) (-)·SO(4) (2-)·H(2)O, is based on chains of alternating anions and water mol-ecules (formed by O-H⋯O hydrogen bonds). The chains are inter-connected with the 2-amino-1,3-thia-zolium cations via strong N-H⋯O and weak C-H⋯O hydrogen-bonding inter-actions into a three-dimensional network.

Related literature

For the use of 2-amino­thia­zole as organo-functionalized films of TiO2 or SiO2 particles for decontamination of aqueous media or ethanol fuel, see: Cristante et al. (2007 ▶); Takeuchi et al. (2007 ▶) and for the use of 2-amino­thia­zole and its derivatives as anti­corrosive films, see: Ciftci et al. (2011 ▶). For use of 2-amino­thia­zole and its derivatives in medicine, see: De et al. (2008 ▶); Aridoss et al. (2009 ▶); Franklin et al. (2008 ▶); Li et al. (2009 ▶); Alexandru et al. (2010 ▶). For the non-linear optical properties of similar amino­triazole compounds, see: Yesilel et al. (2008 ▶); Matulková et al. (2007 ▶, 2008 ▶).

Experimental

Crystal data

3C3H5N2S+·HSO4 −·SO4 2−·H2O

M = 514.59

Monoclinic,

a = 11.6418 (1) Å

b = 9.8549 (1) Å

c = 17.4291 (1) Å

β = 90.3853 (7)°

V = 1999.57 (3) Å3

Z = 4

Cu Kα radiation

μ = 5.89 mm−1

T = 120 K

0.52 × 0.15 × 0.10 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.136, T max = 1.000

25544 measured reflections

3558 independent reflections

3455 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.075

S = 1.05

3558 reflections

280 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.68 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046010/vm2128sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046010/vm2128Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811046010/vm2128Isup3.cml

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

3C3H5N2S+·HSO4−·SO42−·H2O	F(000) = 1064
Mr = 514.59	Dx = 1.709 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 19931 reflections
a = 11.6418 (1) Å	θ = 3.8–66.9°
b = 9.8549 (1) Å	µ = 5.89 mm−1
c = 17.4291 (1) Å	T = 120 K
β = 90.3853 (7)°	Plate, colourless
V = 1999.57 (3) Å3	0.52 × 0.15 × 0.10 mm
Z = 4

Agilent Xcalibur Atlas Gemini ultra diffractometer	3558 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	3455 reflections with I > 2σ(I)
mirror	Rint = 0.040
Detector resolution: 10.3784 pixels mm-1	θmax = 67.0°, θmin = 4.6°
Rotation method data acquisition using ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→11
Tmin = 0.136, Tmax = 1.000	l = −18→20
25544 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0412P)2 + 1.5439P] where P = (Fo2 + 2Fc2)/3
3558 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.68 e Å−3

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. The hydrogen atoms were localized from the difference Fourier map. Despite of that,all hydrogen atoms connected to C were constrained to ideal positions. The N—H and O—H distances were left unrestrained. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*Ueq of the parent atom.

	x	y	z	Uiso*/Ueq
C1	0.29359 (14)	0.74559 (18)	0.51444 (9)	0.0168 (3)
C2	0.16124 (15)	0.69841 (19)	0.60694 (10)	0.0203 (4)
H2	0.1057	0.7191	0.6432	0.024*
C3	0.19494 (15)	0.57200 (18)	0.59119 (10)	0.0207 (4)
H3	0.1662	0.4948	0.6150	0.025*
O1	−0.10315 (11)	0.07767 (13)	0.22736 (8)	0.0248 (3)
O2	0.03550 (11)	0.11665 (13)	0.12781 (7)	0.0231 (3)
O3	−0.10426 (12)	0.29105 (13)	0.15778 (8)	0.0261 (3)
H1O3	−0.153 (2)	0.265 (2)	0.1193 (14)	0.031*
O4	0.04573 (11)	0.24617 (13)	0.24574 (7)	0.0264 (3)
O5	0.11893 (12)	0.41726 (14)	0.36173 (8)	0.0243 (3)
H2O5	0.127 (2)	0.354 (3)	0.3937 (14)	0.029*
H1O5	0.091 (2)	0.380 (3)	0.3292 (15)	0.029*
O6	0.16351 (11)	0.06136 (12)	0.56939 (7)	0.0232 (3)
O7	0.29107 (11)	0.10060 (13)	0.46267 (8)	0.0259 (3)
O8	0.10714 (11)	0.21584 (13)	0.46956 (7)	0.0239 (3)
O9	0.25934 (12)	0.27724 (13)	0.55539 (8)	0.0308 (3)
S1	−0.02774 (3)	0.17660 (4)	0.19126 (2)	0.01635 (10)
S2	0.20561 (3)	0.16181 (4)	0.51308 (2)	0.01708 (10)
S3	0.29952 (4)	0.57034 (4)	0.52038 (2)	0.01888 (10)
N1	0.35685 (14)	0.82017 (17)	0.46841 (9)	0.0221 (3)
H1N1	0.399 (2)	0.780 (2)	0.4378 (14)	0.026*
H2N1	0.344 (2)	0.903 (3)	0.4650 (13)	0.026*
N2	0.21729 (13)	0.79555 (16)	0.56378 (8)	0.0178 (3)
H1N2	0.2031 (19)	0.875 (3)	0.5679 (12)	0.021*
C7	0.08543 (14)	0.75482 (19)	0.37523 (10)	0.0180 (3)
C8	0.12455 (15)	0.96823 (19)	0.33003 (10)	0.0223 (4)
H8	0.1162	1.0619	0.3267	0.027*
C9	0.19866 (16)	0.89764 (19)	0.28789 (11)	0.0243 (4)
H9	0.2476	0.9356	0.2518	0.029*
S5	0.19216 (4)	0.72483 (5)	0.30915 (2)	0.02143 (10)
N5	0.03629 (14)	0.65995 (17)	0.41708 (9)	0.0223 (3)
H1N5	−0.012 (2)	0.683 (2)	0.4538 (14)	0.027*
H2N5	0.055 (2)	0.580 (3)	0.4078 (13)	0.027*
N6	0.06105 (13)	0.88732 (16)	0.37947 (8)	0.0200 (3)
H1N6	0.003 (2)	0.915 (2)	0.4024 (13)	0.024*
S4	−0.01139 (4)	0.57716 (4)	0.14954 (2)	0.020
C4	0.00150 (14)	0.75220 (18)	0.15074 (10)	0.017
C5	−0.13895 (15)	0.71377 (19)	0.23921 (10)	0.022
H5	−0.1933	0.7379	0.2757	0.026*
C6	−0.11839 (16)	0.58563 (19)	0.21834 (10)	0.0230 (4)
H6	−0.1565	0.5106	0.2381	0.028*
N3	−0.07096 (12)	0.80736 (16)	0.20091 (8)	0.0176 (3)
H1N3	−0.0797 (19)	0.889 (3)	0.2095 (12)	0.021*
N4	0.07243 (14)	0.82190 (17)	0.10758 (10)	0.0238 (3)
H1N4	0.116 (2)	0.782 (3)	0.0809 (14)	0.029*
H2N4	0.073 (2)	0.906 (3)	0.1111 (13)	0.029*

	U11	U22	U33	U12	U13	U23
C1	0.0194 (8)	0.0133 (8)	0.0176 (8)	0.0016 (6)	−0.0015 (6)	−0.0017 (6)
C2	0.0194 (8)	0.0210 (9)	0.0206 (8)	−0.0009 (7)	0.0042 (7)	−0.0008 (7)
C3	0.0222 (8)	0.0190 (9)	0.0208 (8)	−0.0029 (7)	0.0025 (7)	0.0020 (7)
O1	0.0255 (6)	0.0157 (6)	0.0333 (7)	−0.0002 (5)	0.0138 (5)	0.0015 (5)
O2	0.0280 (7)	0.0184 (6)	0.0231 (6)	−0.0021 (5)	0.0101 (5)	−0.0029 (5)
O3	0.0332 (7)	0.0145 (6)	0.0305 (7)	0.0028 (5)	−0.0066 (6)	−0.0013 (5)
O4	0.0310 (7)	0.0227 (7)	0.0255 (7)	−0.0009 (6)	−0.0037 (5)	−0.0041 (5)
O5	0.0306 (7)	0.0198 (7)	0.0225 (7)	−0.0021 (5)	0.0012 (6)	−0.0019 (6)
O6	0.0280 (6)	0.0156 (6)	0.0260 (6)	0.0041 (5)	0.0109 (5)	0.0048 (5)
O7	0.0255 (7)	0.0224 (7)	0.0298 (7)	0.0039 (5)	0.0122 (5)	0.0043 (6)
O8	0.0229 (6)	0.0261 (7)	0.0228 (6)	0.0032 (5)	0.0004 (5)	0.0026 (5)
O9	0.0349 (7)	0.0148 (7)	0.0425 (8)	0.0003 (5)	−0.0122 (6)	−0.0016 (6)
S1	0.0188 (2)	0.0124 (2)	0.0179 (2)	−0.00083 (15)	0.00330 (16)	−0.00037 (15)
S2	0.0185 (2)	0.0126 (2)	0.0201 (2)	0.00032 (15)	0.00292 (16)	0.00103 (15)
S3	0.0230 (2)	0.0126 (2)	0.0210 (2)	0.00234 (15)	0.00299 (16)	−0.00110 (15)
N1	0.0297 (8)	0.0143 (8)	0.0223 (8)	0.0016 (6)	0.0099 (6)	0.0001 (6)
N2	0.0203 (7)	0.0123 (7)	0.0208 (7)	0.0027 (6)	0.0033 (6)	−0.0020 (6)
C7	0.0157 (8)	0.0204 (9)	0.0178 (8)	0.0019 (7)	−0.0013 (6)	−0.0020 (7)
C8	0.0240 (9)	0.0175 (9)	0.0253 (9)	−0.0007 (7)	−0.0001 (7)	0.0022 (7)
C9	0.0233 (9)	0.0227 (10)	0.0269 (9)	−0.0025 (7)	0.0038 (7)	0.0029 (8)
S5	0.0196 (2)	0.0205 (2)	0.0243 (2)	0.00299 (16)	0.00520 (17)	−0.00179 (17)
N5	0.0250 (8)	0.0178 (8)	0.0243 (8)	0.0031 (6)	0.0056 (6)	0.0015 (6)
N6	0.0188 (7)	0.0208 (8)	0.0204 (7)	0.0041 (6)	0.0044 (6)	−0.0007 (6)
S4	0.025	0.013	0.024	0.000	0.004	0.002
C4	0.018	0.013	0.021	0.000	0.000	0.001
C5	0.022	0.022	0.021	0.001	0.006	−0.001
C6	0.0271 (9)	0.0211 (9)	0.0210 (9)	−0.0051 (7)	0.0040 (7)	0.0028 (7)
N3	0.0189 (7)	0.0120 (7)	0.0220 (7)	0.0011 (6)	0.0032 (6)	−0.0014 (6)
N4	0.0251 (8)	0.0148 (8)	0.0317 (9)	−0.0014 (6)	0.0128 (7)	−0.0032 (7)

C1—N1	1.317 (2)	C7—N5	1.319 (2)
C1—N2	1.335 (2)	C7—N6	1.338 (2)
C1—S3	1.7315 (18)	C7—S5	1.7254 (17)
C2—C3	1.335 (3)	C8—C9	1.333 (3)
C2—N2	1.384 (2)	C8—N6	1.390 (2)
C2—H2	0.9300	C8—H8	0.9300
C3—S3	1.7395 (18)	C9—S5	1.7446 (19)
C3—H3	0.9300	C9—H9	0.9300
O1—S1	1.4576 (13)	N5—H1N5	0.88 (2)
O2—S1	1.4577 (12)	N5—H2N5	0.83 (3)
O3—S1	1.5490 (13)	N6—H1N6	0.83 (2)
O3—H1O3	0.91 (3)	S4—C4	1.7316 (18)
O4—S1	1.4465 (13)	S4—C6	1.7369 (18)
O5—H2O5	0.84 (3)	C4—N4	1.314 (2)
O5—H1O5	0.75 (3)	C4—N3	1.335 (2)
O6—S2	1.4797 (13)	C5—C6	1.336 (3)
O7—S2	1.4620 (13)	C5—N3	1.389 (2)
O8—S2	1.4701 (13)	C5—H5	0.9300
O9—S2	1.4908 (14)	C6—H6	0.9300
N1—H1N1	0.83 (3)	N3—H1N3	0.83 (2)
N1—H2N1	0.83 (3)	N4—H1N4	0.80 (3)
N2—H1N2	0.81 (2)	N4—H2N4	0.83 (3)
N1—C1—N2	124.34 (17)	N5—C7—S5	124.39 (14)
N1—C1—S3	124.81 (14)	N6—C7—S5	110.97 (13)
N2—C1—S3	110.84 (13)	C9—C8—N6	113.02 (17)
C3—C2—N2	113.17 (16)	C9—C8—H8	123.5
C3—C2—H2	123.4	N6—C8—H8	123.5
N2—C2—H2	123.4	C8—C9—S5	111.31 (14)
C2—C3—S3	111.26 (13)	C8—C9—H9	124.3
C2—C3—H3	124.4	S5—C9—H9	124.3
S3—C3—H3	124.4	C7—S5—C9	90.40 (9)
S1—O3—H1O3	115.0 (15)	C7—N5—H1N5	119.7 (15)
H2O5—O5—H1O5	101 (3)	C7—N5—H2N5	116.7 (16)
O4—S1—O1	112.89 (8)	H1N5—N5—H2N5	124 (2)
O4—S1—O2	113.00 (8)	C7—N6—C8	114.30 (15)
O1—S1—O2	111.42 (7)	C7—N6—H1N6	121.2 (16)
O4—S1—O3	103.77 (8)	C8—N6—H1N6	123.1 (15)
O1—S1—O3	107.65 (8)	C4—S4—C6	90.36 (9)
O2—S1—O3	107.55 (8)	N4—C4—N3	124.35 (17)
O7—S2—O8	111.76 (8)	N4—C4—S4	124.64 (14)
O7—S2—O6	110.62 (7)	N3—C4—S4	111.01 (13)
O8—S2—O6	108.90 (8)	C6—C5—N3	113.14 (16)
O7—S2—O9	109.09 (8)	C6—C5—H5	123.4
O8—S2—O9	107.58 (8)	N3—C5—H5	123.4
O6—S2—O9	108.80 (8)	C5—C6—S4	111.34 (14)
C1—S3—C3	90.30 (8)	C5—C6—H6	124.3
C1—N1—H1N1	117.7 (16)	S4—C6—H6	124.3
C1—N1—H2N1	119.3 (16)	C4—N3—C5	114.15 (15)
H1N1—N1—H2N1	122 (2)	C4—N3—H1N3	126.5 (15)
C1—N2—C2	114.42 (15)	C5—N3—H1N3	119.3 (15)
C1—N2—H1N2	123.7 (16)	C4—N4—H1N4	118.6 (18)
C2—N2—H1N2	121.9 (15)	C4—N4—H2N4	118.9 (16)
N5—C7—N6	124.62 (16)	H1N4—N4—H2N4	122 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O9i	0.91 (2)	1.56 (2)	2.474 (2)	178 (2)
O5—H2O5···O8	0.84 (3)	1.91 (3)	2.7376 (19)	166 (2)
O5—H1O5···O4	0.75 (3)	2.03 (3)	2.7628 (19)	166 (3)
N1—H1N1···O2ii	0.83 (2)	2.12 (2)	2.904 (2)	158 (2)
N1—H2N1···O7iii	0.83 (3)	2.04 (3)	2.869 (2)	172 (2)
N2—H1N2···O6iii	0.80 (3)	1.89 (3)	2.695 (2)	175 (2)
N3—H1N3···O1iii	0.83 (3)	1.91 (3)	2.730 (2)	179 (3)
N4—H1N4···O7ii	0.80 (3)	2.23 (3)	2.968 (2)	156 (3)
N4—H2N4···O2iii	0.83 (3)	2.14 (3)	2.958 (2)	167 (2)
N5—H1N5···O8iv	0.88 (2)	2.01 (2)	2.870 (2)	165.0 (19)
N5—H2N5···O5	0.83 (3)	1.94 (3)	2.755 (2)	164 (2)
N6—H1N6···O6iv	0.83 (2)	2.02 (2)	2.814 (2)	160 (2)
C8—H8···O4iii	0.93	2.44	3.238 (2)	144
C9—H9···O5ii	0.93	2.53	3.380 (2)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O9i	0.91 (2)	1.56 (2)	2.474 (2)	178 (2)
O5—H2O5⋯O8	0.84 (3)	1.91 (3)	2.7376 (19)	166 (2)
O5—H1O5⋯O4	0.75 (3)	2.03 (3)	2.7628 (19)	166 (3)
N1—H1N1⋯O2ii	0.83 (2)	2.12 (2)	2.904 (2)	158 (2)
N1—H2N1⋯O7iii	0.83 (3)	2.04 (3)	2.869 (2)	172 (2)
N2—H1N2⋯O6iii	0.80 (3)	1.89 (3)	2.695 (2)	175 (2)
N3—H1N3⋯O1iii	0.83 (3)	1.91 (3)	2.730 (2)	179 (3)
N4—H1N4⋯O7ii	0.80 (3)	2.23 (3)	2.968 (2)	156 (3)
N4—H2N4⋯O2iii	0.83 (3)	2.14 (3)	2.958 (2)	167 (2)
N5—H1N5⋯O8iv	0.88 (2)	2.01 (2)	2.870 (2)	165.0 (19)
N5—H2N5⋯O5	0.83 (3)	1.94 (3)	2.755 (2)	164 (2)
N6—H1N6⋯O6iv	0.83 (2)	2.02 (2)	2.814 (2)	160 (2)
C8—H8⋯O4iii	0.93	2.44	3.238 (2)	144
C9—H9⋯O5ii	0.93	2.53	3.380 (2)	152

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