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organic compounds
2-(1,3-Benzothiazol-2-yl)guanidinium chloride
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
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
|
|
Data collection: CrystalClear (Rigaku, 2011); cell 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
10.1107/S1600536811044643/zs2157sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811044643/zs2157Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811044643/zs2157Isup3.cml
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; .
Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the
in the riding model approximation, with Uiso(H) set to 1.2Ueq(C). The amino H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N—H = 0.88±0.01 Å with their isotropic displacement parameters freely refining.Data collection: CrystalClear (Rigaku, 2011); cell
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). ![]() | Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C8H9N4S+ Cl- at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. |
C8H9N4S+·Cl− | Dx = 1.597 Mg m−3 |
Mr = 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 |
Rigaku Saturn 724+ diffractometer | 2146 independent reflections |
Radiation source: rotating anode | 2117 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.034 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −4→4 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2011) | k = −14→14 |
Tmin = 0.933, Tmax = 0.994 | l = −28→28 |
14016 measured reflections |
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(Fo2) + (0.0454P)2 + 0.3169P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2146 reflections | Δρmax = 0.26 e Å−3 |
147 parameters | Δρmin = −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) |
C8H9N4S+·Cl− | V = 951.3 (2) Å3 |
Mr = 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 |
Rigaku Saturn 724+ diffractometer | 2146 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2011) | 2117 reflections with I > 2σ(I) |
Tmin = 0.933, Tmax = 0.994 | Rint = 0.034 |
14016 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | Δρmax = 0.26 e Å−3 |
S = 1.07 | Δρmin = −0.27 e Å−3 |
2146 reflections | Absolute structure: Flack (1983), 839 Friedel pairs |
147 parameters | Absolute structure parameter: −0.01 (7) |
5 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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− |
Mr | 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) |
Tmin, Tmax | 0.933, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14016, 2146, 2117 |
Rint | 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 |
Δρmax, Δρmin (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).
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
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals 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
Rigaku (2011). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takahashi, T. & Niino, A. (1943). Yakugaku Zasshi, 63, 249–252. CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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).