2-Amino-1,3-benzothia-zol-3-ium dihydrogen phosphate.

The cation of the title compound, C(7)H(7)N(2)S(+)·H(2)PO(4) (-), is almost planar (r.m.s deviation = 0.017 Å for all non-H atoms). In the crystal structure, the cations and anions are connected by N-H⋯O and O-H⋯O hydrogen bonds, with π-π stacking inter-actions between neighbouring 1,3-thia-zole and benzene rings [centroid-centroid distance = 3.5711 (11) Å], forming a three-dimensional network.

Related literature

For the structural parameters of some organic dihydrogeno­monophosphates, see: Gholivand et al. (2007 ▶); Mrad et al. (2009 ▶). For the biological and pharmacological properties of heterocyclic compounds, see: Malik et al. (2010 ▶); Sinha & Tiwari (1986 ▶). For the synthesis, see: Thomas et al. (2003 ▶).

Experimental

Crystal data

C7H7N2S+·H2PO4 −

M = 248.20

Monoclinic,

a = 12.3915 (4) Å

b = 10.1572 (3) Å

c = 8.3159 (2) Å

β = 103.775 (1)°

V = 1016.56 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.47 mm−1

T = 296 K

0.25 × 0.09 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

9333 measured reflections

2490 independent reflections

1938 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.096

S = 1.03

2490 reflections

151 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025547/bt5282sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025547/bt5282Isup2.hkl

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

C7H7N2S+·H2PO4−	F(000) = 512
Mr = 248.20	Dx = 1.622 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2983 reflections
a = 12.3915 (4) Å	θ = 2.6–27.1°
b = 10.1572 (3) Å	µ = 0.47 mm−1
c = 8.3159 (2) Å	T = 296 K
β = 103.775 (1)°	Rod, off-white
V = 1016.56 (5) Å3	0.25 × 0.09 × 0.07 mm
Z = 4

Bruker APEXII CCD diffractometer	1938 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.033
graphite	θmax = 28.3°, θmin = 3.2°
φ and ω scans	h = −13→16
9333 measured reflections	k = −8→13
2490 independent reflections	l = −11→8

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0508P)2 + 0.1064P] where P = (Fo2 + 2Fc2)/3
2490 reflections	(Δ/σ)max = 0.001
151 parameters	Δρmax = 0.31 e Å−3
5 restraints	Δρmin = −0.25 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.35481 (4)	0.35955 (5)	1.06135 (6)	0.0400 (2)
N1	0.28028 (14)	0.13298 (14)	0.95775 (19)	0.0362 (5)
N2	0.43880 (16)	0.12254 (17)	1.1731 (2)	0.0460 (6)
C1	0.23286 (16)	0.35055 (18)	0.9039 (2)	0.0363 (6)
C2	0.16650 (19)	0.4518 (2)	0.8240 (3)	0.0494 (7)
C3	0.07398 (19)	0.4193 (2)	0.7023 (3)	0.0555 (8)
C4	0.04759 (19)	0.2898 (2)	0.6589 (3)	0.0525 (7)
C5	0.11376 (17)	0.1882 (2)	0.7386 (2)	0.0436 (6)
C6	0.20561 (15)	0.22026 (17)	0.8625 (2)	0.0340 (6)
C7	0.36161 (16)	0.18903 (19)	1.0689 (2)	0.0350 (5)
P1	0.31052 (4)	0.78446 (4)	0.06814 (5)	0.0321 (2)
O1	0.21014 (12)	0.72357 (14)	0.12333 (17)	0.0448 (5)
O2	0.26558 (12)	0.87196 (11)	−0.07803 (14)	0.0396 (4)
O3	0.38850 (12)	0.84982 (13)	0.21213 (15)	0.0441 (4)
O4	0.37402 (14)	0.66563 (15)	0.01419 (16)	0.0497 (5)
H1	0.271 (2)	0.0479 (16)	0.948 (3)	0.0600*
H2	0.18390	0.53930	0.85170	0.0590*
H3	0.02810	0.48600	0.64790	0.0670*
H4	−0.01510	0.27070	0.57560	0.0630*
H5	0.09680	0.10090	0.70950	0.0520*
H6	0.4904 (18)	0.164 (2)	1.242 (3)	0.0600*
H7	0.430 (2)	0.0391 (17)	1.184 (3)	0.0600*
H8	0.228 (2)	0.690 (3)	0.214 (2)	0.0750*
H9	0.379 (2)	0.663 (3)	−0.080 (2)	0.0750*

	U11	U22	U33	U12	U13	U23
S1	0.0424 (3)	0.0331 (3)	0.0412 (3)	−0.0075 (2)	0.0035 (2)	−0.0034 (2)
N1	0.0421 (9)	0.0296 (8)	0.0326 (8)	−0.0059 (7)	0.0007 (7)	0.0004 (6)
N2	0.0446 (10)	0.0425 (9)	0.0417 (10)	−0.0074 (8)	−0.0079 (8)	0.0031 (8)
C1	0.0357 (10)	0.0384 (10)	0.0352 (9)	−0.0013 (8)	0.0092 (8)	−0.0010 (8)
C2	0.0530 (13)	0.0418 (11)	0.0525 (12)	0.0090 (10)	0.0110 (10)	0.0023 (10)
C3	0.0512 (13)	0.0605 (14)	0.0515 (13)	0.0172 (11)	0.0055 (10)	0.0062 (11)
C4	0.0370 (11)	0.0749 (16)	0.0409 (11)	0.0027 (11)	0.0000 (9)	0.0000 (10)
C5	0.0400 (11)	0.0500 (11)	0.0383 (10)	−0.0081 (9)	0.0043 (8)	−0.0034 (9)
C6	0.0347 (10)	0.0382 (10)	0.0290 (9)	−0.0026 (8)	0.0074 (7)	0.0013 (7)
C7	0.0371 (10)	0.0350 (9)	0.0321 (9)	−0.0055 (8)	0.0068 (8)	0.0006 (7)
P1	0.0371 (3)	0.0314 (3)	0.0236 (2)	0.0020 (2)	−0.0009 (2)	0.0029 (2)
O1	0.0399 (8)	0.0585 (9)	0.0308 (7)	−0.0073 (7)	−0.0021 (6)	0.0036 (6)
O2	0.0562 (9)	0.0307 (6)	0.0256 (6)	0.0059 (6)	−0.0027 (6)	0.0010 (5)
O3	0.0462 (8)	0.0503 (8)	0.0292 (7)	−0.0127 (6)	−0.0038 (6)	0.0042 (6)
O4	0.0685 (10)	0.0476 (8)	0.0334 (7)	0.0263 (7)	0.0128 (7)	0.0122 (7)

S1—C1	1.7504 (19)	N2—H7	0.862 (18)
S1—C7	1.735 (2)	N2—H6	0.86 (2)
P1—O3	1.5024 (14)	C1—C6	1.389 (3)
P1—O1	1.5531 (16)	C1—C2	1.384 (3)
P1—O2	1.5017 (12)	C2—C3	1.377 (3)
P1—O4	1.5638 (17)	C3—C4	1.382 (3)
O1—H8	0.809 (19)	C4—C5	1.385 (3)
O4—H9	0.801 (17)	C5—C6	1.380 (3)
N1—C6	1.386 (2)	C2—H2	0.9300
N1—C7	1.323 (2)	C3—H3	0.9300
N2—C7	1.314 (3)	C4—H4	0.9300
N1—H1	0.873 (16)	C5—H5	0.9300
S1···O4i	3.1497 (16)	C1···C7xi	3.547 (3)
S1···N1	2.5519 (16)	C1···C5iii	3.469 (3)
S1···O3ii	3.2897 (15)	C4···C6xi	3.496 (3)
S1···C5iii	3.664 (2)	C5···S1xi	3.664 (2)
S1···C6iii	3.5429 (18)	C5···C1xi	3.469 (3)
P1···O2iv	3.5032 (13)	C6···C4iii	3.496 (3)
P1···H6v	2.87 (2)	C6···C7xi	3.577 (3)
P1···H8vi	2.890 (16)	C6···S1xi	3.5429 (18)
P1···H9iv	2.896 (17)	C7···C6iii	3.577 (3)
P1···H1vii	2.857 (17)	C7···C1iii	3.547 (3)
P1···H7vii	3.02 (2)	C3···H3xii	3.0400
O1···O2iv	2.6017 (18)	C3···H5xiii	3.0300
O2···N1vii	2.6693 (18)	C5···H3xiv	3.0000
O2···P1vi	3.5032 (13)	H1···P1x	2.857 (17)
O2···O1vi	2.6017 (18)	H1···O2x	1.800 (16)
O3···N2vii	2.875 (2)	H1···H7	2.43 (3)
O3···S1v	3.2897 (15)	H2···O4i	2.7400
O3···N2v	3.138 (2)	H2···O1i	2.8900
O3···O4iv	2.5654 (18)	H3···C5xiii	3.0000
O4···S1viii	3.1497 (16)	H3···H3xii	2.4100
O4···O3vi	2.5654 (18)	H3···H5xiii	2.4600
O4···N2v	3.076 (2)	H3···C3xii	3.0400
O1···H4ix	2.6300	H4···O1xv	2.6300
O1···H2viii	2.8900	H5···H3xiv	2.4600
O2···H8vi	1.795 (18)	H5···C3xiv	3.0300
O2···H1vii	1.799 (16)	H6···O4ii	2.31 (2)
O3···H7vii	2.018 (18)	H6···O3ii	2.39 (2)
O3···H9iv	1.765 (17)	H6···P1ii	2.87 (2)
O3···H6v	2.39 (2)	H7···O3x	2.018 (18)
O4···H6v	2.31 (2)	H7···H1	2.43 (3)
O4···H2viii	2.7400	H7···P1x	3.02 (2)
N1···O2x	2.6693 (18)	H8···P1iv	2.890 (16)
N1···S1	2.5519 (16)	H8···O2iv	1.795 (19)
N2···O3ii	3.138 (2)	H9···P1vi	2.896 (17)
N2···O4ii	3.076 (2)	H9···O3vi	1.765 (17)
N2···O3x	2.875 (2)
C1—S1—C7	90.04 (9)	C1—C2—C3	118.06 (19)
O2—P1—O4	109.85 (7)	C2—C3—C4	121.6 (2)
O3—P1—O4	107.32 (8)	C3—C4—C5	120.5 (2)
O1—P1—O2	107.83 (8)	C4—C5—C6	118.07 (19)
O1—P1—O3	110.41 (8)	C1—C6—C5	121.24 (17)
O1—P1—O4	105.70 (8)	N1—C6—C1	112.22 (15)
O2—P1—O3	115.33 (7)	N1—C6—C5	126.55 (17)
P1—O1—H8	112.5 (18)	N1—C7—N2	123.59 (18)
P1—O4—H9	118 (2)	S1—C7—N1	112.46 (13)
C6—N1—C7	114.70 (15)	S1—C7—N2	123.95 (15)
C7—N1—H1	123.5 (16)	C3—C2—H2	121.00
C6—N1—H1	121.7 (16)	C1—C2—H2	121.00
H6—N2—H7	120 (2)	C4—C3—H3	119.00
C7—N2—H6	119.8 (14)	C2—C3—H3	119.00
C7—N2—H7	119.0 (17)	C3—C4—H4	120.00
C2—C1—C6	120.50 (18)	C5—C4—H4	120.00
S1—C1—C6	110.54 (13)	C4—C5—H5	121.00
S1—C1—C2	128.96 (15)	C6—C5—H5	121.00
C7—S1—C1—C2	178.1 (2)	S1—C1—C2—C3	179.72 (17)
C7—S1—C1—C6	−1.63 (15)	C6—C1—C2—C3	−0.5 (3)
C1—S1—C7—N2	−178.14 (18)	C2—C1—C6—N1	−178.75 (18)
C1—S1—C7—N1	1.89 (15)	C2—C1—C6—C5	1.6 (3)
C6—N1—C7—N2	178.35 (18)	C1—C2—C3—C4	−0.5 (4)
C7—N1—C6—C5	−179.97 (19)	C2—C3—C4—C5	0.6 (4)
C7—N1—C6—C1	0.4 (2)	C3—C4—C5—C6	0.5 (3)
C6—N1—C7—S1	−1.7 (2)	C4—C5—C6—C1	−1.5 (3)
S1—C1—C6—N1	1.0 (2)	C4—C5—C6—N1	178.86 (19)
S1—C1—C6—C5	−178.61 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2x	0.873 (16)	1.800 (16)	2.6693 (18)	174 (3)
N2—H6···O3ii	0.86 (2)	2.39 (2)	3.138 (2)	147 (2)
N2—H6···O4ii	0.86 (2)	2.31 (2)	3.076 (2)	149.3 (19)
N2—H7···O3x	0.862 (18)	2.018 (18)	2.875 (2)	172 (2)
O1—H8···O2iv	0.809 (19)	1.795 (19)	2.6017 (18)	175 (3)
O4—H9···O3vi	0.801 (17)	1.765 (17)	2.5654 (18)	178 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.873 (16)	1.800 (16)	2.6693 (18)	174 (3)
N2—H6⋯O3ii	0.86 (2)	2.39 (2)	3.138 (2)	147 (2)
N2—H6⋯O4ii	0.86 (2)	2.31 (2)	3.076 (2)	149.3 (19)
N2—H7⋯O3i	0.862 (18)	2.018 (18)	2.875 (2)	172 (2)
O1—H8⋯O2iii	0.809 (19)	1.795 (19)	2.6017 (18)	175 (3)
O4—H9⋯O3iv	0.801 (17)	1.765 (17)	2.5654 (18)	178 (3)

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