2-(1,3-Benzothia­zol-2-yl)guanidin-2-ium acetate

Horton, P.N.; Coles, S.J.; Mohamed, S.K.; El-Remaily, M.A.A.; Soliman, A.M.

doi:10.1107/S160053681104089X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2920

doi:10.1107/S160053681104089X

Open

access

2-(1,3-Benzothiazol-2-yl)guanidin-2-ium acetate

Peter N. Horton,^a ^* Simon J. Coles,^a Shaaban K. Mohamed,^b Mahmoud A. A. El-Remaily ^c and A. M. Soliman ^c

^aSchool of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, England, ^bChemistry and Environmental Division, Manchester Metropolitan University, England, and ^cDepartment of Chemistry, Faculty of Science, Sohag University, Egypt
^*Correspondence e-mail: pnh@soton.ac.uk

(Received 13 September 2011; accepted 4 October 2011; online 12 October 2011)

In the title compound, C₈H₉N₄S⁻·C₂H₃O₂⁻, the cation is essentially planar (r.m.s deviation = 0.037 Å) with the guanidine unit bent out of the plane of the fused-ring system by 4.6 (3)°. In the asymmetric unit, the cations and anions are linked into R₂²(8) motifs. In the crystal, further N—H⋯O and N—H⋯N hydrogen bonds link the components into a two-dimensional network.

Related literature

For the crystal structure of the neutral 2-(1,3-benzothiazol-2-yl)guanidine molecule, see: Mohamed et al. (2011 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₉N₄S⁺·C₂H₃O₂⁻
M_r = 252.30
Orthorhombic, P c a 2₁
a = 12.596 (2) Å
b = 11.276 (2) Å
c = 8.0936 (12) Å
V = 1149.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 120 K
0.14 × 0.10 × 0.02 mm

Data collection

Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.962, T_max = 0.995
7697 measured reflections
1991 independent reflections
1301 reflections with I > 2σ(I)
R_int = 0.116

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.154
S = 1.06
1991 reflections
155 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 897 Friedel pairs
Flack parameter: 0.3 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O12	0.88	1.82	2.671 (8)	162
N3—H3A⋯O11ⁱ	0.88	2.06	2.760 (8)	136
N3—H3B⋯N1	0.88	2.05	2.713 (9)	131
N4—H4A⋯O12ⁱⁱ	0.88	2.03	2.861 (7)	158
N4—H4B⋯O11	0.88	1.91	2.790 (8)	173
Symmetry codes: (i) $[-x+1, -y, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y, z]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681104089X/bx2373sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104089X/bx2373Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681104089X/bx2373Isup3.mol

Supporting information file. DOI: 10.1107/S160053681104089X/bx2373Isup4.cml

checkCIF report

Comment top

The title compound was synthesized and exists as the acetate salt of benzothiazolo-2-guanidinium. The benzothiazolo-2-guanidinium cation is almost planar with the guanidine unit bent out of the plane of the fused-ring system by just 4.6 (3)°. In the asymmetric unit, The cations and anions are linked into R²₂(8) motif (Bernstein, et al., 1995). The crystal packing is stabilized by intermolecular hydrogen bonds involving the cations and acetate counter-ions, Table 1, Fig.2.

Related literature top

For the crystal structure of the neutral 2-(1,3-benzothiazol-2-yl)guanidine molecule, see: Mohamed et al. (2011). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 1 mmol of 2-guanidyl benzothiazole with few drops of glacial acetic acid was heated in ethanol for 2 hours. The mixture was left at room temperature for two days to afford the shiny white crystals of benzothiazolo-2-guanidinium acetate in 94% yield. The single-crystal was obtained from a slow evaporation of the ethanolic solution of product over two days.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram for (I), showing the intermolecular and intramolecular hydrogen bonding (symmetry codes: (i) : -x+1, y,z+1/2; (ii) x+1/2,-y,z)

2-(1,3-Benzothiazol-2-yl)guanidin-2-ium acetate top

Crystal data top

C₈H₉N₄S⁺·C₂H₃O₂⁻	D_x = 1.458 Mg m⁻³
M_r = 252.30	Melting point = 463–465 K
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2099 reflections
a = 12.596 (2) Å	θ = 2.9–27.5°
b = 11.276 (2) Å	µ = 0.28 mm⁻¹
c = 8.0936 (12) Å	T = 120 K
V = 1149.6 (4) Å³	Plate, colourless
Z = 4	0.14 × 0.10 × 0.02 mm
F(000) = 528

Data collection top

Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer	1991 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1301 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.116
Detector resolution: 4096x4096pixels / 62x62mm pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −12→13
T_min = 0.962, T_max = 0.995	l = −9→9
7697 measured reflections

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)] = 0.078	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.P)² + 4.3921P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1991 reflections	Δρ_max = 0.42 e Å⁻³
155 parameters	Δρ_min = −0.36 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 897 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.3 (2)

Crystal data top

C₈H₉N₄S⁺·C₂H₃O₂⁻	V = 1149.6 (4) Å³
M_r = 252.30	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 12.596 (2) Å	µ = 0.28 mm⁻¹
b = 11.276 (2) Å	T = 120 K
c = 8.0936 (12) Å	0.14 × 0.10 × 0.02 mm

Data collection top

Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer	1991 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1301 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.995	R_int = 0.116
7697 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	H-atom parameters constrained
wR(F²) = 0.154	Δρ_max = 0.42 e Å⁻³
S = 1.06	Δρ_min = −0.36 e Å⁻³
1991 reflections	Absolute structure: Flack (1983), 897 Friedel pairs
155 parameters	Absolute structure parameter: 0.3 (2)
1 restraint

Special details top

Experimental. SADABS was used to perform the Absorption correction. Parameter refinement on 6249 reflections reduced R(int) from 0.1275 to 0.0768. Ratio of minimum to maximum apparent transmission: 0.627938. The given Tmin and Tmax were generated using the SHELX SIZE command

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.1251 (6)	0.3579 (8)	0.7101 (8)	0.0287 (19)
C2	0.2293 (5)	0.3958 (7)	0.7510 (9)	0.0232 (17)
C3	0.2434 (6)	0.4986 (7)	0.8427 (10)	0.037 (2)
H3	0.3127	0.5226	0.8751	0.045*
C4	0.1569 (6)	0.5650 (8)	0.8861 (9)	0.037 (2)
H4	0.1667	0.6362	0.9469	0.044*
C5	0.0545 (6)	0.5299 (8)	0.8424 (9)	0.037 (2)
H5	−0.0043	0.5775	0.8740	0.044*
C6	0.0372 (6)	0.4267 (8)	0.7537 (9)	0.034 (2)
H6	−0.0326	0.4034	0.7233	0.040*
C7	0.2709 (5)	0.2345 (7)	0.6117 (11)	0.0262 (18)
C8	0.4331 (5)	0.1292 (8)	0.5459 (9)	0.030 (2)
N1	0.3104 (5)	0.3205 (6)	0.6934 (7)	0.0294 (16)
N2	0.3265 (4)	0.1462 (6)	0.5312 (7)	0.0295 (16)
H2	0.2908	0.0978	0.4663	0.035*
N3	0.4938 (5)	0.2037 (6)	0.6268 (7)	0.0331 (17)
H3A	0.5628	0.1920	0.6311	0.040*
H3B	0.4655	0.2654	0.6768	0.040*
N4	0.4741 (5)	0.0366 (6)	0.4707 (8)	0.0347 (17)
H4A	0.5430	0.0241	0.4743	0.042*
H4B	0.4326	−0.0128	0.4168	0.042*
S1	0.13101 (12)	0.22884 (17)	0.5956 (3)	0.0316 (5)
C11	0.2365 (6)	−0.0922 (8)	0.3103 (10)	0.035 (2)
C12	0.1654 (6)	−0.1819 (8)	0.2300 (10)	0.039 (2)
H12A	0.1089	−0.1410	0.1695	0.058*
H12B	0.1340	−0.2329	0.3149	0.058*
H12C	0.2069	−0.2304	0.1531	0.058*
O11	0.3349 (4)	−0.1038 (6)	0.2875 (7)	0.0417 (15)
O12	0.1938 (4)	−0.0085 (5)	0.3904 (7)	0.0372 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.026 (4)	0.041 (6)	0.019 (4)	0.002 (4)	−0.003 (3)	0.003 (3)
C2	0.022 (4)	0.019 (4)	0.029 (4)	0.001 (3)	−0.004 (3)	0.000 (3)
C3	0.018 (3)	0.062 (6)	0.032 (4)	−0.006 (5)	0.002 (3)	0.004 (6)
C4	0.038 (5)	0.035 (6)	0.037 (5)	0.000 (4)	0.008 (4)	0.002 (4)
C5	0.026 (4)	0.045 (7)	0.040 (5)	0.002 (4)	0.007 (4)	−0.008 (4)
C6	0.016 (4)	0.049 (6)	0.035 (5)	0.007 (4)	0.003 (3)	0.010 (5)
C7	0.022 (3)	0.036 (5)	0.021 (4)	0.005 (3)	0.003 (4)	0.007 (4)
C8	0.022 (4)	0.037 (5)	0.031 (5)	−0.003 (4)	−0.001 (3)	0.010 (4)
N1	0.017 (3)	0.040 (5)	0.031 (4)	0.002 (3)	0.000 (3)	−0.003 (3)
N2	0.019 (3)	0.040 (5)	0.029 (4)	0.000 (3)	0.001 (3)	−0.002 (3)
N3	0.022 (3)	0.040 (5)	0.037 (4)	0.009 (3)	−0.006 (3)	−0.001 (4)
N4	0.015 (3)	0.037 (5)	0.052 (4)	0.003 (3)	0.001 (3)	0.001 (4)
S1	0.0167 (7)	0.0426 (13)	0.0355 (10)	−0.0010 (9)	−0.0014 (10)	−0.0046 (12)
C11	0.024 (5)	0.045 (6)	0.035 (5)	−0.002 (4)	−0.001 (4)	0.000 (4)
C12	0.029 (4)	0.041 (6)	0.046 (5)	−0.002 (4)	0.003 (4)	−0.006 (4)
O11	0.018 (3)	0.049 (4)	0.058 (4)	0.000 (3)	0.006 (2)	−0.015 (3)
O12	0.021 (3)	0.045 (4)	0.045 (3)	−0.003 (3)	0.002 (3)	−0.010 (3)

Geometric parameters (Å, º) top

C1—C6	1.398 (10)	C8—N3	1.311 (9)
C1—C2	1.420 (10)	C8—N4	1.314 (9)
C1—S1	1.727 (8)	C8—N2	1.361 (8)
C2—C3	1.388 (11)	N2—H2	0.8800
C2—N1	1.408 (9)	N3—H3A	0.8800
C3—C4	1.368 (10)	N3—H3B	0.8800
C3—H3	0.9500	N4—H4A	0.8800
C4—C5	1.395 (11)	N4—H4B	0.8800
C4—H4	0.9500	C11—O11	1.260 (9)
C5—C6	1.384 (11)	C11—O12	1.265 (10)
C5—H5	0.9500	C11—C12	1.499 (10)
C6—H6	0.9500	C12—H12A	0.9800
C7—N1	1.275 (10)	C12—H12B	0.9800
C7—N2	1.381 (10)	C12—H12C	0.9800
C7—S1	1.768 (6)

C6—C1—C2	120.4 (7)	N3—C8—N2	121.9 (8)
C6—C1—S1	129.6 (6)	N4—C8—N2	117.3 (7)
C2—C1—S1	109.8 (6)	C7—N1—C2	110.3 (6)
C3—C2—N1	126.0 (7)	C8—N2—C7	124.1 (7)
C3—C2—C1	119.7 (7)	C8—N2—H2	118.0
N1—C2—C1	114.3 (7)	C7—N2—H2	118.0
C4—C3—C2	119.5 (8)	C8—N3—H3A	120.0
C4—C3—H3	120.3	C8—N3—H3B	120.0
C2—C3—H3	120.3	H3A—N3—H3B	120.0
C3—C4—C5	121.1 (8)	C8—N4—H4A	120.0
C3—C4—H4	119.5	C8—N4—H4B	120.0
C5—C4—H4	119.5	H4A—N4—H4B	120.0
C6—C5—C4	121.1 (8)	C1—S1—C7	88.5 (4)
C6—C5—H5	119.5	O11—C11—O12	124.8 (8)
C4—C5—H5	119.5	O11—C11—C12	117.0 (8)
C5—C6—C1	118.2 (7)	O12—C11—C12	118.2 (7)
C5—C6—H6	120.9	C11—C12—H12A	109.5
C1—C6—H6	120.9	C11—C12—H12B	109.5
N1—C7—N2	126.5 (6)	H12A—C12—H12B	109.5
N1—C7—S1	117.0 (6)	C11—C12—H12C	109.5
N2—C7—S1	116.4 (6)	H12A—C12—H12C	109.5
N3—C8—N4	120.7 (7)	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O12	0.88	1.82	2.671 (8)	162
N3—H3A···O11ⁱ	0.88	2.06	2.760 (8)	136
N3—H3B···N1	0.88	2.05	2.713 (9)	131
N4—H4A···O12ⁱⁱ	0.88	2.03	2.861 (7)	158
N4—H4B···O11	0.88	1.91	2.790 (8)	173

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₄S⁺·C₂H₃O₂⁻
M_r	252.30
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	120
a, b, c (Å)	12.596 (2), 11.276 (2), 8.0936 (12)
V (Å³)	1149.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.14 × 0.10 × 0.02

Data collection
Diffractometer	Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.962, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	7697, 1991, 1301
R_int	0.116
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.154, 1.06
No. of reflections	1991
No. of parameters	155
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.36
Absolute structure	Flack (1983), 897 Friedel pairs
Absolute structure parameter	0.3 (2)

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O12	0.88	1.82	2.671 (8)	162.3
N3—H3A···O11ⁱ	0.88	2.06	2.760 (8)	135.6
N3—H3B···N1	0.88	2.05	2.713 (9)	130.9
N4—H4A···O12ⁱⁱ	0.88	2.03	2.861 (7)	158.2
N4—H4B···O11	0.88	1.91	2.790 (8)	173.1

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

Acknowledgements

The authors would like to thank Manchester Metropolitan University, Sohag University and the EPSRC for funding the crystallographic facilities.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). SADABS. Bruker AXS Inc., Madison, Wiscosin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Mohamed, S. K., El-Remaily, M. A. A., Soliman, A. M., Gurbanov, A. V. & Ng, S. W. (2011). Acta Cryst. E67, o786. Web of Science CSD CrossRef IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar