2-(1,3-Benzothia­zol-2-yl)guanidinium chloride

Mohamed, S.K.; Horton, P.N.; El-Remaily, M.A.A.; Ng, S.W.

doi:10.1107/S1600536811044643

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3132

doi:10.1107/S1600536811044643

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2-(1,3-Benzothiazol-2-yl)guanidinium chloride

Shaaban K. Mohamed,^a Peter N. Horton,^b Mahmoud A.A. El-Remaily ^c and Seik Weng Ng ^d,^e ^*

^aChemistry and Environmental Division, Manchester Metropolitan University, Manchester M15 6BH, England, ^bSchool of Chemistry, University of Southampton, Southampton SO17 1BJ, England, ^cDepartment of Chemistry, Faculty of Science, Sohag University, Egypt, ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^eChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 17 October 2011; accepted 25 October 2011; online 29 October 2011)

The non-H atoms of the cation of the title salt, C₈H₉N₄S⁺·Cl⁻, are approximately co-planar (r.m.s. deviation = 0.037 Å), with one amino group forming an intramolecular hydrogen bond to the tertiary N atom of the benzothiazole fused-ring system. The cations and anions are linked by cyclic R₂¹(6) N—H⋯Cl hydrogen-bonding associations, generating helical chains running along the b-axis direction.

Related literature

For the synthesis, see: Takahashi & Niino (1943 ). For the structure of 2-(1,3-benzothiazol-2-yl)guanidine, see: Mohamed et al. (2011 ). For graph-set analysis, see: Etter et al. (1990 ).

Experimental

Crystal data

C₈H₉N₄S⁺·Cl⁻
M_r = 228.71
Orthorhombic, P 2₁ 2₁ 2₁
a = 3.8857 (5) Å
b = 11.0349 (17) Å
c = 22.186 (3) Å
V = 951.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 120 K
0.12 × 0.03 × 0.01 mm

Data collection

Rigaku Saturn 724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2011 ) T_min = 0.933, T_max = 0.994
14016 measured reflections
2146 independent reflections
2117 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.076
S = 1.07
2146 reflections
147 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 839 Friedel pairs
Flack parameter: −0.01 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯Cl1ⁱ	0.88 (1)	2.21 (1)	3.074 (2)	165 (2)
N3—H2⋯Cl1	0.88 (1)	2.62 (2)	3.380 (2)	146 (2)
N4—H3⋯Cl1	0.88 (1)	2.31 (1)	3.157 (2)	160 (2)
N4—H4⋯N1	0.88 (1)	2.06 (2)	2.713 (2)	131 (2)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2011); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811044643/zs2157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044643/zs2157Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044643/zs2157Isup3.cml

checkCIF report

Comment top

A recent study (Mohamed et al., 2011) describes the crystal structure of 2-(1,3-benzothiazol-2-yl)guanidine, which was synthesized by the reaction of 2-aminothiophenol and cyanoguanidine in 10% sulfuric acid medium. The product of the reaction is probably a sulfate or bisulfate salt that is then converted to the neutral compound upon treatment with sodium hydroxide. In the present study, 2-(1,3-benzothioazol-2-yl)guanidine is converted to the hydrochloride salt by treatment with hydrochloric acid. The non-H atoms of the cation of the title salt, C₈H₉N₄S⁺ Cl^- (Scheme I), lie on a plane (r.m.s. deviation 0.037 Å), with one amino group forming an intramolecular hydrogen bond to the tertiary N atom of the benzothiazole fused-ring (Fig. 1). The cations and anions are linked by cyclic N—H···Cl hydrogen-bonding associations [graph set R¹₂(6) (Etter et al., 1990)] (Table 1), to generate helical chains running along the b-axis of the orthorhombic unit cell. This salt was first reported in 1943 (Takahashi & Niino, 1943).

Related literature top

For the synthesis, see: Takahashi & Niino (1943). For the structure of 2-(1,3-benzothiazol-2-yl)guanidine, see: Mohamed et al. (2011). For graph-set analysis, see: Etter et al. (1990).

Experimental top

2-(1,3-Benzothiazol-2-yl)guanidine (0.05 mol) was heated in ethanol (50 ml) in the presence of a few drops of hydrochloric acid for 3 h. The mixture was cooled and the product was collected and recrystallized from ethanol to give the title compound (m.p. 523 K) in 95% yield; .

Computing details top

Data collection: CrystalClear (Rigaku, 2011); cell refinement: CrystalClear (Rigaku, 2011); data reduction: CrystalClear (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF(Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₈H₉N₄S⁺ Cl^- at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

2-(1,3-Benzothiazol-2-yl)guanidinium chloride top

Crystal data top

C₈H₉N₄S⁺·Cl⁻	D_x = 1.597 Mg m⁻³
M_r = 228.71	Melting point: 523 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3321 reflections
a = 3.8857 (5) Å	θ = 2.1–31.0°
b = 11.0349 (17) Å	µ = 0.58 mm⁻¹
c = 22.186 (3) Å	T = 120 K
V = 951.3 (2) Å³	Lath, colorless
Z = 4	0.12 × 0.03 × 0.01 mm
F(000) = 472

Data collection top

Rigaku Saturn 724+ diffractometer	2146 independent reflections
Radiation source: rotating anode	2117 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.034
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 2.1°
ω scans	h = −4→4
Absorption correction: multi-scan (CrystalClear; Rigaku, 2011)	k = −14→14
T_min = 0.933, T_max = 0.994	l = −28→28
14016 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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0454P)² + 0.3169P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2146 reflections	Δρ_max = 0.26 e Å⁻³
147 parameters	Δρ_min = −0.27 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 839 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (7)

Crystal data top

C₈H₉N₄S⁺·Cl⁻	V = 951.3 (2) Å³
M_r = 228.71	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 3.8857 (5) Å	µ = 0.58 mm⁻¹
b = 11.0349 (17) Å	T = 120 K
c = 22.186 (3) Å	0.12 × 0.03 × 0.01 mm

Data collection top

Rigaku Saturn 724+ diffractometer	2146 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2011)	2117 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.994	R_int = 0.034
14016 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	Δρ_max = 0.26 e Å⁻³
S = 1.07	Δρ_min = −0.27 e Å⁻³
2146 reflections	Absolute structure: Flack (1983), 839 Friedel pairs
147 parameters	Absolute structure parameter: −0.01 (7)
5 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.94400 (14)	0.19472 (4)	0.72036 (2)	0.02120 (13)
S1	0.32449 (13)	0.63436 (4)	0.96176 (2)	0.01619 (12)
N1	0.6155 (4)	0.42234 (14)	0.95141 (7)	0.0168 (4)
N2	0.4500 (5)	0.51363 (15)	0.85919 (7)	0.0175 (4)
H1	0.344 (7)	0.5752 (17)	0.8420 (12)	0.032 (7)*
N3	0.4832 (5)	0.43982 (16)	0.76315 (7)	0.0209 (4)
H2	0.539 (7)	0.3806 (17)	0.7388 (10)	0.027 (7)*
H5	0.390 (8)	0.5097 (17)	0.7530 (14)	0.053 (10)*
N4	0.7193 (5)	0.32801 (15)	0.83996 (8)	0.0211 (4)
H3	0.792 (7)	0.2752 (18)	0.8130 (9)	0.029 (7)*
H4	0.766 (7)	0.320 (2)	0.8786 (5)	0.023 (6)*
C1	0.4490 (5)	0.55994 (17)	1.02742 (9)	0.0168 (4)
C2	0.4162 (5)	0.59888 (18)	1.08674 (9)	0.0179 (4)
H2A	0.3142	0.6748	1.0962	0.021*
C3	0.5382 (5)	0.52252 (18)	1.13174 (9)	0.0195 (4)
H3A	0.5207	0.5467	1.1727	0.023*
C4	0.6856 (6)	0.41107 (18)	1.11753 (9)	0.0188 (4)
H4A	0.7657	0.3602	1.1491	0.023*
C5	0.7178 (6)	0.37284 (18)	1.05846 (9)	0.0186 (4)
H5A	0.8187	0.2967	1.0492	0.022*
C6	0.5993 (5)	0.44847 (17)	1.01311 (9)	0.0160 (4)
C7	0.4809 (5)	0.51068 (17)	0.92100 (9)	0.0158 (4)
C8	0.5560 (6)	0.42508 (17)	0.82086 (8)	0.0162 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0242 (3)	0.0190 (2)	0.0205 (2)	−0.0008 (2)	−0.00028 (19)	−0.00403 (19)
S1	0.0198 (2)	0.0132 (2)	0.0156 (2)	0.00165 (17)	−0.0007 (2)	0.00035 (18)
N1	0.0209 (9)	0.0139 (7)	0.0155 (8)	−0.0013 (6)	−0.0004 (7)	−0.0005 (6)
N2	0.0254 (9)	0.0127 (7)	0.0144 (8)	0.0006 (7)	−0.0006 (7)	0.0001 (6)
N3	0.0310 (10)	0.0157 (8)	0.0159 (8)	−0.0017 (8)	−0.0003 (8)	−0.0036 (7)
N4	0.0290 (10)	0.0167 (8)	0.0174 (8)	0.0022 (8)	0.0016 (8)	−0.0009 (7)
C1	0.0172 (9)	0.0141 (8)	0.0191 (9)	−0.0010 (8)	−0.0012 (8)	0.0029 (7)
C2	0.0183 (10)	0.0164 (9)	0.0189 (9)	−0.0014 (8)	0.0021 (8)	−0.0008 (7)
C3	0.0190 (10)	0.0228 (10)	0.0167 (9)	−0.0059 (9)	0.0013 (8)	0.0004 (8)
C4	0.0181 (9)	0.0204 (9)	0.0178 (9)	−0.0017 (9)	−0.0013 (8)	0.0053 (7)
C5	0.0205 (10)	0.0155 (9)	0.0199 (9)	0.0007 (8)	0.0004 (8)	0.0007 (7)
C6	0.0158 (10)	0.0154 (9)	0.0169 (9)	−0.0022 (7)	0.0009 (7)	0.0000 (7)
C7	0.0161 (10)	0.0134 (8)	0.0179 (9)	−0.0015 (7)	0.0011 (8)	0.0006 (7)
C8	0.0191 (9)	0.0142 (8)	0.0154 (9)	−0.0024 (8)	0.0033 (8)	0.0008 (7)

Geometric parameters (Å, º) top

S1—C1	1.7409 (19)	N4—H4	0.882 (10)
S1—C7	1.746 (2)	C1—C2	1.390 (3)
N1—C7	1.296 (2)	C1—C6	1.398 (3)
N1—C6	1.400 (2)	C2—C3	1.390 (3)
N2—C8	1.359 (2)	C2—H2A	0.9500
N2—C7	1.377 (2)	C3—C4	1.393 (3)
N2—H1	0.882 (10)	C3—H3A	0.9500
N3—C8	1.321 (3)	C4—C5	1.382 (3)
N3—H2	0.876 (10)	C4—H4A	0.9500
N3—H5	0.880 (10)	C5—C6	1.386 (3)
N4—C8	1.315 (3)	C5—H5A	0.9500
N4—H3	0.883 (10)

C1—S1—C7	88.16 (9)	C2—C3—H3A	119.6
C7—N1—C6	109.63 (17)	C4—C3—H3A	119.6
C8—N2—C7	125.43 (17)	C5—C4—C3	121.41 (19)
C8—N2—H1	115.2 (19)	C5—C4—H4A	119.3
C7—N2—H1	119.3 (19)	C3—C4—H4A	119.3
C8—N3—H2	116.9 (18)	C4—C5—C6	118.31 (19)
C8—N3—H5	116 (2)	C4—C5—H5A	120.8
H2—N3—H5	127 (3)	C6—C5—H5A	120.8
C8—N4—H3	118.3 (16)	C5—C6—C1	120.25 (18)
C8—N4—H4	119.6 (16)	C5—C6—N1	124.80 (18)
H3—N4—H4	122 (2)	C1—C6—N1	114.95 (17)
C2—C1—C6	121.68 (18)	N1—C7—N2	124.85 (18)
C2—C1—S1	128.38 (15)	N1—C7—S1	117.31 (15)
C6—C1—S1	109.95 (14)	N2—C7—S1	117.84 (14)
C3—C2—C1	117.47 (18)	N4—C8—N3	121.06 (18)
C3—C2—H2A	121.3	N4—C8—N2	122.02 (18)
C1—C2—H2A	121.3	N3—C8—N2	116.92 (18)
C2—C3—C4	120.87 (19)

C7—S1—C1—C2	179.9 (2)	S1—C1—C6—N1	−0.1 (2)
C7—S1—C1—C6	0.28 (16)	C7—N1—C6—C5	179.4 (2)
C6—C1—C2—C3	−0.1 (3)	C7—N1—C6—C1	−0.3 (2)
S1—C1—C2—C3	−179.68 (17)	C6—N1—C7—N2	−178.94 (19)
C1—C2—C3—C4	−0.3 (3)	C6—N1—C7—S1	0.5 (2)
C2—C3—C4—C5	0.4 (3)	C8—N2—C7—N1	−0.2 (3)
C3—C4—C5—C6	0.0 (3)	C8—N2—C7—S1	−179.64 (17)
C4—C5—C6—C1	−0.5 (3)	C1—S1—C7—N1	−0.50 (16)
C4—C5—C6—N1	179.77 (19)	C1—S1—C7—N2	179.02 (17)
C2—C1—C6—C5	0.6 (3)	C7—N2—C8—N4	−3.7 (3)
S1—C1—C6—C5	−179.81 (16)	C7—N2—C8—N3	175.3 (2)
C2—C1—C6—N1	−179.68 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···Cl1ⁱ	0.88 (1)	2.21 (1)	3.074 (2)	165 (2)
N3—H2···Cl1	0.88 (1)	2.62 (2)	3.380 (2)	146 (2)
N4—H3···Cl1	0.88 (1)	2.31 (1)	3.157 (2)	160 (2)
N4—H4···N1	0.88 (1)	2.06 (2)	2.713 (2)	131 (2)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₉N₄S⁺·Cl⁻
M_r	228.71
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	3.8857 (5), 11.0349 (17), 22.186 (3)
V (Å³)	951.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.12 × 0.03 × 0.01

Data collection
Diffractometer	Rigaku Saturn 724+ diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2011)
T_min, T_max	0.933, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	14016, 2146, 2117
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.076, 1.07
No. of reflections	2146
No. of parameters	147
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27
Absolute structure	Flack (1983), 839 Friedel pairs
Absolute structure parameter	−0.01 (7)

Computer programs: CrystalClear (Rigaku, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF(Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···Cl1ⁱ	0.88 (1)	2.21 (1)	3.074 (2)	165 (2)
N3—H2···Cl1	0.88 (1)	2.62 (2)	3.380 (2)	146 (2)
N4—H3···Cl1	0.88 (1)	2.31 (1)	3.157 (2)	160 (2)
N4—H4···N1	0.88 (1)	2.06 (2)	2.713 (2)	131 (2)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

The use of the EPSRC X-ray crystallographic facilities at the University of Southampton, England, is gratefully acknowledged. We thank Manchester Metropolitan University, Sohag University and the University of Malaya for supporting this study.

References

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