5-Chloro-N-(4,5-dihydro-1H-imidazol-2-yl)-2,1,3-benzothia­diazol-4-amine (tizanidine)

John, P.; Khan, I.U.; Akkurt, M.; Ramzan, M.S.; Sharif, S.

doi:10.1107/S1600536811008348

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o838-o839

doi:10.1107/S1600536811008348

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5-Chloro-N-(4,5-dihydro-1H-imidazol-2-yl)-2,1,3-benzothiadiazol-4-amine (tizanidine)

Peter John,^a Islam Ullah Khan,^a Mehmet Akkurt,^b ^* Muhammad Shahid Ramzan ^a and Shahzad Sharif ^a

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr, iukhan@gcu.edu.pk

(Received 17 February 2011; accepted 4 March 2011; online 12 March 2011)

There are two independent molecules (A and B) with similar conformations in the asymmetric unit of the title compound, C₉H₈ClN₅S. The benzothiadiazole ring systems of both molecules are essentially planar [maximum deviation = 0.021 (2) Å in molecule A and 0.022 (1) Å in molecule B] and make dihedral angles of 68.78 (9) and 54.39 (8)°, respectively, with the mean planes of their 4,5-dihydro-1H-imidazole rings. An intramolecular N—H⋯Cl hydrogen bond occurs in molecule B. In the crystal, both molecules form centrosymmetric dimers through π-stacking of their benzothiadiazole rings, with interplanar distances of 3.3174 (7) and 3.2943 (6) Å. These dimers are further linked via pairs of N—H⋯N hydrogen bonds with the dihydroimidazole rings as the hydrogen-bonding donors and one of the benzothiadiazole N atoms as the acceptors, generating R₂²(16) ring motifs. The A₂ and B₂ dimers in turn form additional N—H⋯N hydrogen bonds with the secondary amine as the H-atom donor and the dihydroimidazole N atom as the acceptor. These R₂²(8)-type interactions connect the A₂ and B₂ dimers with each other, forming infinite chains along [1 $[\overline{1}]$ 1].

Related literature

For the medicinal importance of tizanidine, see: Koch et al. (1989 ); Shellenberger et al. (1999 ); Tse et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₈ClN₅S
M_r = 253.72
Triclinic, $[P \overline 1]$
a = 7.6927 (3) Å
b = 10.8558 (4) Å
c = 12.9969 (5) Å
α = 95.790 (1)°
β = 101.126 (1)°
γ = 92.192 (1)°
V = 1057.69 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 296 K
0.29 × 0.18 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
17897 measured reflections
5104 independent reflections
4449 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.120
S = 1.03
5104 reflections
302 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3A—HN3A⋯N5B	0.92 (2)	2.10 (2)	3.003 (2)	168 (3)
N4A—HN4A⋯N1Aⁱ	0.86 (3)	2.38 (3)	3.205 (3)	160 (2)
N3B—HN3B⋯N5A	0.88 (2)	1.98 (2)	2.864 (2)	177 (2)
N4B—HN4B⋯Cl1B	0.84 (2)	2.75 (2)	3.1927 (15)	114 (2)
N4B—HN4B⋯N1Bⁱⁱ	0.84 (2)	2.48 (2)	3.227 (2)	150 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+3, -y, -z+2.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008348/zl2351sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008348/zl2351Isup2.hkl

checkCIF report

Comment top

Tizanidine {or (5-chloro-N-(4,5-dihydro-1H-imidazol-2-yl)-2,1,3-benzothiadiazol-4-amine)} is an adrenergic agonist and proved to be an active myotonolytic skeletal muscle relaxant with a chemical structure different from other muscle relaxants (Koch et al., 1989; Tse et al., 1987). It also reduces increased muscle tone associated with spasticity in patients with multiple sclerosis or spinal cord injury (Shellenberger et al., 1999). Herein, we report the crystal structure of Tizanidine.

The title compound crystallized with two unique molecules A and B in the asymmetric unit (Fig. 1). The benzothiadiazole ring systems (S1A/N1A/N2A/C1A–C6A and S1B/N1B/N2B/C1B) of both molecules A and B are essentially planar [max. deviations = 0.021 (2) Å for C5A in molecule A and 0.022 (1) Å for C6B in molecule B] and they form dihedral angles of 68.78 (9) and 54.39 (8)°, respectively, with the mean planes of their 4,5-dihydro-1H-imidazole rings (N4A/N5A/C7A–C9A and N4B/N5B/C7B–C9B). The conformations of molecules A and B are similar (Fig. 2).

Molecular conformations in the crystal structure are stabilized by intramolecular N—H···N and N—H···Cl interactions (Table 1). Both molecules A and B are forming centrosymmetric dimers through π-stacking of their benzothiadiazole rings with interplanar distances of 3.3174 (7) and 3.2943 (6) Å [Cg1···Cg2ⁱⁱ = 3.6026 (10) Å and Cg3···Cg4^iv = 3.5096 (9) Å; symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 3-x, -y, 2-z; Cg1, Cg2, Cg3 and Cg4 are the centroids of the S1A/N1A/N2A/C4A/C5A, C1A–C6A, S1B/N1B/N2B/C4B/C5B and C1B–C6B rings, respectively]. These dimers are further tied together via pairs of N—H···N hydrogen-bonds with the dihydroimidazole rings as the hydrogen bonding donor (Table 1 and Fig. 3) and one of the benzothiadiazole N atoms as the acceptor, generating rings of graph set motifs of the type R²₂(16) (Bernstein et al., 1995). The A₂ and B₂ dimers do in turn form additional N—H···N hydrogen-bonds, with the secondary amine as the H donor and the dihydroimidazole N atom as the acceptor. These R²₂(8) type interactions connect the A₂ and B₂ dimers with each other to form infinite chains that stretch along the (1 -1 1) direction of the unit cell (Fig. 3).

Related literature top

For the medicinal importance of tizanidine, see: Koch et al. (1989); Shellenberger et al. (1999); Tse et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

To 0.3 g of tizanidine in 10 ml methanol were added several drops of sodium hydroxide solution (3%) to adjust the pH to 8. The resulting solution was left for slow evaporation. Orange crystals were obtained after three days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	Fig. 1. View of the two crystallographically independent molecules, A and B, with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. An overlay of the two molecules A (black line) and B (red line).
	Fig. 3. A view of the π-π stacking interactions and the hydrogen bonding of the title compound. The H atoms not involved in the hydrogen bonds forming the complete motif were omitted. (Symmetry codes: (e) 1-x, 1-y, 1-z; (f) 3-x, -y, 2-z).

5-Chloro-N-(4,5-dihydro-1H-imidazol-2-yl)-2,1,3-benzothiadiazol- 4-amine top

Crystal data top

C₉H₈ClN₅S	Z = 4
M_r = 253.72	F(000) = 520
Triclinic, P1	D_x = 1.593 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6927 (3) Å	Cell parameters from 9959 reflections
b = 10.8558 (4) Å	θ = 2.9–28.3°
c = 12.9969 (5) Å	µ = 0.54 mm⁻¹
α = 95.790 (1)°	T = 296 K
β = 101.126 (1)°	Block, orange
γ = 92.192 (1)°	0.29 × 0.18 × 0.08 mm
V = 1057.69 (7) Å³

Data collection top

Bruker APEXII CCD diffractometer	4449 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.3°, θ_min = 3.2°
ϕ and ω scans	h = −10→10
17897 measured reflections	k = −14→14
5104 independent reflections	l = −17→17

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0635P)² + 0.4931P] where P = (F_o² + 2F_c²)/3
5104 reflections	(Δ/σ)_max = 0.001
302 parameters	Δρ_max = 0.65 e Å⁻³
5 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₉H₈ClN₅S	γ = 92.192 (1)°
M_r = 253.72	V = 1057.69 (7) Å³
Triclinic, P1	Z = 4
a = 7.6927 (3) Å	Mo Kα radiation
b = 10.8558 (4) Å	µ = 0.54 mm⁻¹
c = 12.9969 (5) Å	T = 296 K
α = 95.790 (1)°	0.29 × 0.18 × 0.08 mm
β = 101.126 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4449 reflections with I > 2σ(I)
17897 measured reflections	R_int = 0.024
5104 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	5 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.65 e Å⁻³
5104 reflections	Δρ_min = −0.43 e Å⁻³
302 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cl1A	0.40681 (8)	0.26166 (5)	0.72358 (5)	0.0597 (2)
S1A	0.85136 (8)	0.69598 (5)	0.58255 (5)	0.0609 (2)
N1A	0.6430 (3)	0.71482 (15)	0.57232 (14)	0.0518 (5)
N2A	0.8692 (2)	0.56543 (15)	0.63157 (15)	0.0504 (5)
N3A	0.7911 (2)	0.33724 (14)	0.71346 (12)	0.0441 (5)
N4A	0.6996 (2)	0.18129 (15)	0.56630 (12)	0.0426 (4)
N5A	0.9113 (2)	0.14570 (13)	0.69909 (11)	0.0393 (4)
C1A	0.4819 (3)	0.39656 (17)	0.68103 (13)	0.0410 (5)
C2A	0.3519 (3)	0.48262 (19)	0.65002 (14)	0.0449 (6)
C3A	0.3954 (3)	0.58968 (17)	0.61257 (15)	0.0452 (5)
C4A	0.5753 (3)	0.61502 (15)	0.60785 (13)	0.0407 (5)
C5A	0.7058 (2)	0.52907 (15)	0.64166 (13)	0.0378 (5)
C6A	0.6584 (2)	0.41428 (15)	0.67789 (13)	0.0375 (5)
C7A	0.7965 (2)	0.22922 (15)	0.66323 (12)	0.0333 (4)
C8A	0.7270 (3)	0.0496 (2)	0.55046 (19)	0.0588 (7)
C9A	0.9066 (3)	0.0408 (2)	0.62174 (16)	0.0526 (6)
Cl1B	1.12566 (6)	0.18138 (5)	1.13956 (4)	0.0505 (1)
S1B	1.35483 (8)	−0.13008 (5)	0.75206 (4)	0.0509 (2)
N1B	1.3845 (2)	−0.19353 (14)	0.86079 (14)	0.0469 (5)
N2B	1.2747 (2)	−0.00089 (13)	0.78769 (11)	0.0380 (4)
N3B	1.13963 (18)	0.19625 (12)	0.90223 (11)	0.0321 (3)
N4B	1.32552 (18)	0.36020 (13)	1.01366 (12)	0.0352 (4)
N5B	1.09790 (19)	0.40512 (13)	0.89434 (12)	0.0388 (4)
C1B	1.2069 (2)	0.07385 (17)	1.05470 (13)	0.0359 (5)
C2B	1.2668 (2)	−0.03721 (19)	1.09644 (15)	0.0452 (6)
C3B	1.3290 (2)	−0.12898 (18)	1.03814 (16)	0.0454 (5)
C4B	1.3311 (2)	−0.11275 (15)	0.93194 (14)	0.0367 (4)
C5B	1.26880 (19)	−0.00179 (14)	0.88987 (12)	0.0306 (4)
C6B	1.20705 (18)	0.09766 (14)	0.95246 (12)	0.0288 (4)
C7B	1.18549 (19)	0.31124 (14)	0.93720 (12)	0.0297 (4)
C8B	1.3016 (2)	0.49159 (16)	1.03987 (15)	0.0406 (5)
C9B	1.1930 (2)	0.52377 (16)	0.93606 (16)	0.0424 (5)
H8AA	0.73030	0.02310	0.47730	0.0710*
H8BA	0.63520	0.00040	0.57190	0.0710*
H2A	0.23490	0.46520	0.65550	0.0540*
H9AA	0.91290	−0.03620	0.65370	0.0630*
H3A	0.30950	0.64460	0.59070	0.0540*
H9BA	1.00250	0.04780	0.58350	0.0630*
HN3A	0.887 (3)	0.368 (3)	0.7644 (17)	0.0720*
HN4A	0.597 (3)	0.209 (3)	0.544 (2)	0.0720*
H2B	1.26270	−0.04660	1.16630	0.0540*
H3B	1.36890	−0.20030	1.06680	0.0550*
H8AB	1.41440	0.53940	1.05880	0.0490*
H8BB	1.23730	0.50460	1.09690	0.0490*
H9AB	1.11220	0.58780	0.94760	0.0510*
H9BB	1.26870	0.55020	0.88970	0.0510*
HN3B	1.072 (3)	0.179 (2)	0.8391 (15)	0.0610*
HN4B	1.370 (3)	0.317 (2)	1.0608 (18)	0.0610*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0697 (3)	0.0577 (3)	0.0579 (3)	0.0072 (2)	0.0179 (3)	0.0245 (2)
S1A	0.0653 (3)	0.0384 (3)	0.0738 (4)	−0.0043 (2)	0.0007 (3)	0.0089 (2)
N1A	0.0690 (11)	0.0306 (7)	0.0500 (9)	0.0073 (7)	−0.0036 (8)	0.0047 (7)
N2A	0.0487 (9)	0.0364 (8)	0.0591 (10)	0.0036 (6)	−0.0049 (7)	0.0019 (7)
N3A	0.0512 (9)	0.0320 (7)	0.0401 (8)	0.0131 (6)	−0.0144 (6)	0.0016 (6)
N4A	0.0459 (8)	0.0443 (8)	0.0320 (7)	0.0146 (6)	−0.0074 (6)	0.0016 (6)
N5A	0.0450 (8)	0.0329 (7)	0.0348 (7)	0.0129 (6)	−0.0057 (6)	0.0016 (6)
C1A	0.0548 (10)	0.0375 (9)	0.0300 (8)	0.0107 (7)	0.0041 (7)	0.0054 (6)
C2A	0.0492 (10)	0.0483 (10)	0.0367 (9)	0.0146 (8)	0.0070 (7)	0.0002 (7)
C3A	0.0545 (10)	0.0386 (9)	0.0392 (9)	0.0227 (8)	−0.0003 (8)	−0.0008 (7)
C4A	0.0570 (10)	0.0274 (7)	0.0320 (8)	0.0130 (7)	−0.0048 (7)	−0.0017 (6)
C5A	0.0466 (9)	0.0286 (7)	0.0324 (8)	0.0089 (6)	−0.0053 (6)	−0.0021 (6)
C6A	0.0496 (9)	0.0305 (8)	0.0275 (7)	0.0119 (7)	−0.0054 (6)	0.0008 (6)
C7A	0.0368 (7)	0.0328 (7)	0.0286 (7)	0.0056 (6)	−0.0007 (6)	0.0082 (6)
C8A	0.0549 (12)	0.0512 (11)	0.0555 (12)	0.0199 (9)	−0.0183 (9)	−0.0148 (9)
C9A	0.0517 (11)	0.0503 (11)	0.0456 (10)	0.0224 (9)	−0.0109 (8)	−0.0116 (8)
Cl1B	0.0461 (2)	0.0679 (3)	0.0390 (2)	−0.0006 (2)	0.0148 (2)	0.0023 (2)
S1B	0.0633 (3)	0.0406 (3)	0.0434 (3)	0.0166 (2)	−0.0008 (2)	−0.0036 (2)
N1B	0.0479 (9)	0.0308 (7)	0.0561 (10)	0.0076 (6)	−0.0055 (7)	0.0050 (7)
N2B	0.0453 (8)	0.0328 (7)	0.0325 (7)	0.0074 (6)	−0.0015 (6)	0.0034 (5)
N3B	0.0340 (6)	0.0299 (6)	0.0288 (6)	0.0031 (5)	−0.0030 (5)	0.0034 (5)
N4B	0.0299 (6)	0.0325 (7)	0.0393 (7)	0.0007 (5)	−0.0014 (5)	0.0014 (5)
N5B	0.0375 (7)	0.0281 (6)	0.0467 (8)	0.0076 (5)	−0.0014 (6)	0.0007 (6)
C1B	0.0292 (7)	0.0442 (9)	0.0332 (8)	−0.0048 (6)	0.0033 (6)	0.0074 (7)
C2B	0.0396 (9)	0.0578 (11)	0.0386 (9)	−0.0080 (8)	0.0012 (7)	0.0236 (8)
C3B	0.0422 (9)	0.0414 (9)	0.0514 (10)	−0.0022 (7)	−0.0029 (8)	0.0246 (8)
C4B	0.0309 (7)	0.0293 (7)	0.0456 (9)	−0.0014 (6)	−0.0057 (6)	0.0100 (6)
C5B	0.0280 (7)	0.0273 (7)	0.0330 (7)	−0.0019 (5)	−0.0034 (5)	0.0065 (6)
C6B	0.0243 (6)	0.0293 (7)	0.0304 (7)	−0.0020 (5)	−0.0012 (5)	0.0056 (5)
C7B	0.0265 (6)	0.0311 (7)	0.0312 (7)	0.0037 (5)	0.0052 (5)	0.0016 (6)
C8B	0.0336 (8)	0.0370 (8)	0.0477 (10)	−0.0001 (6)	0.0066 (7)	−0.0087 (7)
C9B	0.0403 (9)	0.0292 (8)	0.0560 (11)	0.0053 (6)	0.0071 (7)	0.0007 (7)

Geometric parameters (Å, º) top

Cl1A—C1A	1.734 (2)	C1A—C2A	1.424 (3)
Cl1B—C1B	1.7412 (18)	C1A—C6A	1.373 (3)
S1A—N2A	1.6114 (18)	C2A—C3A	1.359 (3)
S1A—N1A	1.605 (2)	C3A—C4A	1.415 (3)
S1B—N2B	1.6145 (16)	C4A—C5A	1.434 (3)
S1B—N1B	1.6148 (18)	C5A—C6A	1.434 (2)
N1A—C4A	1.345 (3)	C8A—C9A	1.520 (3)
N2A—C5A	1.338 (2)	C2A—H2A	0.9300
N3A—C7A	1.290 (2)	C3A—H3A	0.9300
N3A—C6A	1.384 (2)	C8A—H8AA	0.9700
N4A—C7A	1.375 (2)	C8A—H8BA	0.9700
N4A—C8A	1.453 (3)	C9A—H9BA	0.9700
N5A—C7A	1.344 (2)	C9A—H9AA	0.9700
N5A—C9A	1.436 (3)	C1B—C6B	1.379 (2)
N3A—HN3A	0.92 (2)	C1B—C2B	1.428 (3)
N4A—HN4A	0.86 (3)	C2B—C3B	1.349 (3)
N1B—C4B	1.343 (2)	C3B—C4B	1.412 (3)
N2B—C5B	1.339 (2)	C4B—C5B	1.434 (2)
N3B—C7B	1.296 (2)	C5B—C6B	1.437 (2)
N3B—C6B	1.376 (2)	C8B—C9B	1.524 (3)
N4B—C8B	1.460 (2)	C2B—H2B	0.9300
N4B—C7B	1.366 (2)	C3B—H3B	0.9300
N5B—C9B	1.457 (2)	C8B—H8AB	0.9700
N5B—C7B	1.351 (2)	C8B—H8BB	0.9700
N3B—HN3B	0.88 (2)	C9B—H9AB	0.9700
N4B—HN4B	0.84 (2)	C9B—H9BB	0.9700

N1A—S1A—N2A	101.46 (9)	N4A—C8A—H8BA	111.00
N1B—S1B—N2B	101.08 (8)	C9A—C8A—H8AA	111.00
S1A—N1A—C4A	105.99 (15)	C9A—C8A—H8BA	111.00
S1A—N2A—C5A	106.15 (13)	N4A—C8A—H8AA	111.00
C6A—N3A—C7A	120.01 (15)	H8AA—C8A—H8BA	109.00
C7A—N4A—C8A	108.65 (16)	H9AA—C9A—H9BA	109.00
C7A—N5A—C9A	111.44 (15)	C8A—C9A—H9BA	111.00
C6A—N3A—HN3A	120.0 (19)	C8A—C9A—H9AA	111.00
C7A—N3A—HN3A	118.9 (18)	N5A—C9A—H9AA	111.00
C8A—N4A—HN4A	121 (2)	N5A—C9A—H9BA	111.00
C7A—N4A—HN4A	119.2 (19)	Cl1B—C1B—C6B	119.74 (13)
S1B—N1B—C4B	106.09 (12)	C2B—C1B—C6B	123.76 (16)
S1B—N2B—C5B	106.29 (11)	Cl1B—C1B—C2B	116.49 (13)
C6B—N3B—C7B	123.72 (14)	C1B—C2B—C3B	122.33 (17)
C7B—N4B—C8B	108.92 (13)	C2B—C3B—C4B	117.52 (17)
C7B—N5B—C9B	110.47 (14)	C3B—C4B—C5B	120.03 (15)
C6B—N3B—HN3B	117.1 (14)	N1B—C4B—C3B	126.69 (16)
C7B—N3B—HN3B	118.8 (14)	N1B—C4B—C5B	113.27 (15)
C7B—N4B—HN4B	119.4 (15)	N2B—C5B—C6B	124.10 (14)
C8B—N4B—HN4B	120.4 (15)	C4B—C5B—C6B	122.63 (14)
C2A—C1A—C6A	124.01 (18)	N2B—C5B—C4B	113.27 (14)
Cl1A—C1A—C6A	119.56 (15)	N3B—C6B—C1B	128.30 (15)
Cl1A—C1A—C2A	116.43 (17)	N3B—C6B—C5B	117.62 (14)
C1A—C2A—C3A	121.3 (2)	C1B—C6B—C5B	113.69 (14)
C2A—C3A—C4A	117.99 (19)	N3B—C7B—N4B	129.45 (15)
N1A—C4A—C3A	126.55 (19)	N4B—C7B—N5B	108.75 (14)
N1A—C4A—C5A	113.2 (2)	N3B—C7B—N5B	121.71 (14)
C3A—C4A—C5A	120.22 (16)	N4B—C8B—C9B	101.13 (14)
C4A—C5A—C6A	121.60 (15)	N5B—C9B—C8B	101.10 (14)
N2A—C5A—C6A	125.17 (15)	C1B—C2B—H2B	119.00
N2A—C5A—C4A	113.17 (16)	C3B—C2B—H2B	119.00
N3A—C6A—C1A	125.98 (16)	C2B—C3B—H3B	121.00
N3A—C6A—C5A	118.99 (14)	C4B—C3B—H3B	121.00
C1A—C6A—C5A	114.83 (15)	N4B—C8B—H8AB	112.00
N3A—C7A—N5A	122.83 (15)	N4B—C8B—H8BB	112.00
N3A—C7A—N4A	128.44 (16)	C9B—C8B—H8AB	112.00
N4A—C7A—N5A	108.66 (14)	C9B—C8B—H8BB	112.00
N4A—C8A—C9A	102.08 (17)	H8AB—C8B—H8BB	109.00
N5A—C9A—C8A	101.67 (17)	N5B—C9B—H9AB	112.00
C1A—C2A—H2A	119.00	N5B—C9B—H9BB	112.00
C3A—C2A—H2A	119.00	C8B—C9B—H9AB	112.00
C2A—C3A—H3A	121.00	C8B—C9B—H9BB	112.00
C4A—C3A—H3A	121.00	H9AB—C9B—H9BB	109.00

N2A—S1A—N1A—C4A	−0.35 (15)	C2A—C1A—C6A—C5A	0.8 (2)
N1A—S1A—N2A—C5A	0.49 (16)	Cl1A—C1A—C2A—C3A	−178.11 (15)
N2B—S1B—N1B—C4B	−0.13 (13)	C6A—C1A—C2A—C3A	1.2 (3)
N1B—S1B—N2B—C5B	0.42 (13)	Cl1A—C1A—C6A—C5A	−179.89 (12)
S1A—N1A—C4A—C5A	0.10 (18)	C1A—C2A—C3A—C4A	−1.7 (3)
S1A—N1A—C4A—C3A	−179.03 (15)	C2A—C3A—C4A—C5A	0.2 (3)
S1A—N2A—C5A—C6A	176.96 (14)	C2A—C3A—C4A—N1A	179.23 (18)
S1A—N2A—C5A—C4A	−0.48 (19)	C3A—C4A—C5A—N2A	179.45 (17)
C6A—N3A—C7A—N4A	10.0 (3)	C3A—C4A—C5A—C6A	1.9 (3)
C7A—N3A—C6A—C5A	−115.36 (18)	N1A—C4A—C5A—N2A	0.3 (2)
C7A—N3A—C6A—C1A	70.1 (2)	N1A—C4A—C5A—C6A	−177.28 (16)
C6A—N3A—C7A—N5A	−173.51 (15)	C4A—C5A—C6A—N3A	−177.48 (15)
C8A—N4A—C7A—N3A	−169.83 (18)	N2A—C5A—C6A—C1A	−179.54 (17)
C7A—N4A—C8A—C9A	−24.8 (2)	C4A—C5A—C6A—C1A	−2.3 (2)
C8A—N4A—C7A—N5A	13.3 (2)	N2A—C5A—C6A—N3A	5.3 (3)
C7A—N5A—C9A—C8A	−20.2 (2)	N4A—C8A—C9A—N5A	26.1 (2)
C9A—N5A—C7A—N3A	−171.84 (17)	Cl1B—C1B—C6B—N3B	−4.3 (2)
C9A—N5A—C7A—N4A	5.3 (2)	C2B—C1B—C6B—C5B	1.7 (2)
S1B—N1B—C4B—C5B	−0.18 (17)	C6B—C1B—C2B—C3B	−0.1 (3)
S1B—N1B—C4B—C3B	178.69 (15)	Cl1B—C1B—C6B—C5B	−176.84 (11)
S1B—N2B—C5B—C6B	179.30 (13)	C2B—C1B—C6B—N3B	174.28 (16)
S1B—N2B—C5B—C4B	−0.57 (17)	Cl1B—C1B—C2B—C3B	178.50 (14)
C7B—N3B—C6B—C1B	55.9 (2)	C1B—C2B—C3B—C4B	−0.9 (3)
C7B—N3B—C6B—C5B	−131.72 (16)	C2B—C3B—C4B—N1B	−178.73 (17)
C6B—N3B—C7B—N5B	−170.11 (15)	C2B—C3B—C4B—C5B	0.1 (2)
C6B—N3B—C7B—N4B	13.9 (3)	N1B—C4B—C5B—N2B	0.5 (2)
C8B—N4B—C7B—N5B	14.92 (18)	N1B—C4B—C5B—C6B	−179.36 (14)
C7B—N4B—C8B—C9B	−28.11 (16)	C3B—C4B—C5B—N2B	−178.44 (15)
C8B—N4B—C7B—N3B	−168.70 (16)	C3B—C4B—C5B—C6B	1.7 (2)
C7B—N5B—C9B—C8B	−22.90 (17)	C4B—C5B—C6B—C1B	−2.5 (2)
C9B—N5B—C7B—N3B	−170.68 (15)	N2B—C5B—C6B—C1B	177.67 (15)
C9B—N5B—C7B—N4B	6.04 (19)	C4B—C5B—C6B—N3B	−175.91 (14)
Cl1A—C1A—C6A—N3A	−5.1 (2)	N2B—C5B—C6B—N3B	4.2 (2)
C2A—C1A—C6A—N3A	175.59 (17)	N4B—C8B—C9B—N5B	29.36 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—HN3A···N5B	0.92 (2)	2.10 (2)	3.003 (2)	168 (3)
N4A—HN4A···N1Aⁱ	0.86 (3)	2.38 (3)	3.205 (3)	160 (2)
N3B—HN3B···N5A	0.88 (2)	1.98 (2)	2.864 (2)	177 (2)
N4B—HN4B···Cl1B	0.84 (2)	2.75 (2)	3.1927 (15)	114 (2)
N4B—HN4B···N1Bⁱⁱ	0.84 (2)	2.48 (2)	3.227 (2)	150 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₉H₈ClN₅S
M_r	253.72
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.6927 (3), 10.8558 (4), 12.9969 (5)
α, β, γ (°)	95.790 (1), 101.126 (1), 92.192 (1)
V (Å³)	1057.69 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.29 × 0.18 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	17897, 5104, 4449
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.120, 1.03
No. of reflections	5104
No. of parameters	302
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)	0.65, −0.43

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—HN3A···N5B	0.92 (2)	2.10 (2)	3.003 (2)	168 (3)
N4A—HN4A···N1Aⁱ	0.86 (3)	2.38 (3)	3.205 (3)	160 (2)
N3B—HN3B···N5A	0.88 (2)	1.98 (2)	2.864 (2)	177.2 (19)
N4B—HN4B···Cl1B	0.84 (2)	2.75 (2)	3.1927 (15)	114.4 (19)
N4B—HN4B···N1Bⁱⁱ	0.84 (2)	2.48 (2)	3.227 (2)	150 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3, −y, −z+2.

Acknowledgements

The authors are grateful to the Higher Education Commission (HEC), Pakistan, for providing funds for the single-crystal XRD facilities at GC University, Lahore.

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 (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, 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
Koch, P., Hirst, D. R. & Wartburg Von, B. R. (1989). Xenobiotica, 19, 1255–1260. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shellenberger, M. K., Groves, L., Shah, J. & Novak, G. D. (1999). Drug Metab. Dispos. 27, 201–205. Web of Science CAS PubMed Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tse, F. L. S., Jaffe, J. M. & Bhuta, S. (1987). Fundam. Clin. Pharmacol. 1, 479–485. CrossRef CAS PubMed Web of Science Google Scholar

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Volume 67| Part 4| April 2011| Pages o838-o839

doi:10.1107/S1600536811008348

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5-Chloro-N-(4,5-di­hydro-1H-imidazol-2-yl)-2,1,3-benzo­thia­diazol-4-amine (tizanidine)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5-Chloro-N-(4,5-dihydro-1H-imidazol-2-yl)-2,1,3-benzothiadiazol-4-amine (tizanidine)