6-Iodo-2-methyl-1,3-benzothia­zole

Đaković, M.; Čičak, H.

doi:10.1107/S1600536811004570

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o620

doi:10.1107/S1600536811004570

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6-Iodo-2-methyl-1,3-benzothiazole

Marijana Đaković ^a ^* and Helena Čičak ^a

^aDepartment of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
^*Correspondence e-mail: mdjakovic@chem.pmf.hr

(Received 21 January 2011; accepted 7 February 2011; online 12 February 2011)

The title compound, C₈H₆INS, is essentially planar, the largest deviation from the mean plane being for the I atom [0.075 (3) Å]. The crystal structure is mainly stabilized by intermolecular C—I⋯N halogen bonds, forming zigzag supramolecular chains in [10 $[\overline{1}]$ ]. Relatively short off-set π–π contacts [centroid–centroid distance = 3.758 (2) Å] between the thiazole rings of inversion-related molecules link neighbouring chains and provide the secondary interactions for building the crystal structure.

Related literature

For the application of benzothiazoles as biologically active compounds, see: Leong et al. (2004 ); Yildiz-Oren et al. (2004 ); Lockhart et al. (2005 ); Sheng et al. (2007 ). For the synthesis of the title compound, see: Racané et al. (2006 , 2011 ). For related 1,3-benzothiazole structures, see: Matković-Čalogović et al. (2003 ); Pavlović et al. (2009 ); Đaković et al. (2009 ); Čičak et al. (2010 ). For graph-set theory, see: Etter (1990 ); Bernstein et al. (1995 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₈H₆INS
M_r = 275.11
Monoclinic, P 2₁ /n
a = 8.3255 (3) Å
b = 7.6967 (3) Å
c = 13.8083 (5) Å
β = 90.686 (4)°
V = 884.76 (6) Å³
Z = 4
Mo Kα radiation
μ = 3.79 mm⁻¹
T = 296 K
0.47 × 0.38 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Saphire-3 CCD detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.253, T_max = 0.658
13190 measured reflections
1928 independent reflections
1729 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 1.06
1928 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Halogen-bond geometry (Å, °)

	C4—I1	I1⋯N1ⁱ	C4⋯N1ⁱ	C4—I1⋯N1ⁱ
C4—I1⋯N1ⁱ	2.103 (3)	3.158 (2)	5.257 (4)	175.99 (9)
Symmetry code: (i) $[{1\over 2}+x, {1\over 2}-y, -{1\over 2}+z]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004570/fj2389sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004570/fj2389Isup2.hkl

checkCIF report

Comment top

This work was a part of our preparative, structural, mechanistic and computational investigation of a series of substituted benzothiazoles (bta), which attract considerable interest due to their biological activities.

The molecule is almost ideally planar (r.m.s. deviation = 0.009 Å), with the largest deviation from the plane being that of atom I1 [0.075 (3) Å] (Fig.1). The geometry of the benzothiazole rings is consistent with other 1,3-benzothiazoles listed in the CSD base (Allen et al., 2002). The two S—C bonds of the thiazole ring [S1—C1 and S1—C2] differ with respect to each other, but both are within two bortherline cases, single S—C [1.82 Å] and double S=C [1.56 Å], while the endocyclic C—N bond is dominantly double in character. The differences in C—C bonds within benzene ring are common for such fused rings.

In the crystal structure halogen bonds are the principal specific interactions responsible for the crystal packing. There is only one short and directional C—I···N contact [C—I = 2.103 (3) Å] (see Table 1) that link the molecules into antiparallel zigzag C(7) chains (Etter, 1990; Bernstein et al., 1995) in [1 0 - 1] direction (Figs. 2 and 3).

Relatively short off-set π–π contacts [Cg···Cg = 3.758 (2) Å] between the thiazole rings, belonging to the molecules that are related by an inversion centre, link the neighboring supramolecular chains and provide the secondary interactions for building the crystal structure.

The structure of the title compound is one more example showing that halogen bonding is also as effective and reliable tool for assembling molecules into supramolecular architectures.

Related literature top

For the application of benzothiazoles as biologically active compounds, see: Leong et al. (2004); Yildiz-Oren et al. (2004); Lockhart et al. (2005); Sheng et al. (2007). For the synthesis of the title compound, see: Racané et al. (2006, 2011). For related 1,3-benzothiazole structures, see: Matković-Čalogović et al. (2003); Pavlović et al. (2009); Đaković et al. (2009); Čičak et al. (2010). For graph-set theory, see: Etter (1990); Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Colourless single crystals of the title compound were obtained by slow evaporation of a dichloromethane solution.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the title compound with the atom labeling scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound viewed down the b axis showing halogen bonds as dashed lines.
	Fig. 3. Spacefill representaton of a zigzag halogen bonding chain running in [1 0 - 1].

6-Iodo-2-methyl-1,3-benzothiazole top

Crystal data top

C₈H₆INS	F(000) = 520
M_r = 275.11	D_x = 2.065 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10010 reflections
a = 8.3255 (3) Å	θ = 4.4–32.6°
b = 7.6967 (3) Å	µ = 3.79 mm⁻¹
c = 13.8083 (5) Å	T = 296 K
β = 90.686 (4)°	Plate, colourless
V = 884.76 (6) Å³	0.47 × 0.38 × 0.14 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Saphire-3 CCD detector	1928 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1729 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.3426 pixels mm^-1	θ_max = 27.0°, θ_min = 4.6°
CCD scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −9→9
T_min = 0.253, T_max = 0.658	l = −17→17
13190 measured reflections

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0397P)² + 0.4162P] where P = (F_o² + 2F_c²)/3
1928 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

C₈H₆INS	V = 884.76 (6) Å³
M_r = 275.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3255 (3) Å	µ = 3.79 mm⁻¹
b = 7.6967 (3) Å	T = 296 K
c = 13.8083 (5) Å	0.47 × 0.38 × 0.14 mm
β = 90.686 (4)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Saphire-3 CCD detector	1928 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1729 reflections with I > 2σ(I)
T_min = 0.253, T_max = 0.658	R_int = 0.027
13190 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.06	Δρ_max = 0.84 e Å⁻³
1928 reflections	Δρ_min = −0.72 e Å⁻³
101 parameters

Special details top

Experimental. Solvent used: CH₂Cl₂ Crystal mount: glued on a glass fibre Mosaicity (°): 1.1 (1) Frames collected: 892 Seconds exposure per frame: 5 Degree rotation per frame: 1.0 Crystal-Detector distance (mm): 50.0.

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
I1	0.96733 (2)	0.14994 (3)	0.30624 (1)	0.0485 (1)
S1	0.66879 (11)	0.75187 (9)	0.49021 (6)	0.0518 (3)
N1	0.6453 (3)	0.5615 (3)	0.64355 (18)	0.0447 (8)
C1	0.6117 (4)	0.7135 (4)	0.6097 (2)	0.0457 (9)
C2	0.7440 (3)	0.5425 (3)	0.4842 (2)	0.0392 (8)
C3	0.8155 (3)	0.4585 (4)	0.40718 (19)	0.0430 (8)
C4	0.8633 (3)	0.2887 (4)	0.42068 (19)	0.0399 (8)
C5	0.8427 (4)	0.2058 (4)	0.5097 (2)	0.0452 (9)
C6	0.7728 (4)	0.2900 (4)	0.5857 (2)	0.0467 (9)
C7	0.7211 (3)	0.4614 (3)	0.5734 (2)	0.0386 (7)
C8	0.5343 (5)	0.8546 (4)	0.6669 (3)	0.0600 (11)
H3	0.83070	0.51470	0.34840	0.0520*
H5	0.87710	0.09160	0.51740	0.0540*
H6	0.75980	0.23380	0.64480	0.0560*
H8A	0.46780	0.80420	0.71580	0.0900*
H8B	0.46950	0.92540	0.62460	0.0900*
H8C	0.61580	0.92510	0.69710	0.0900*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0488 (1)	0.0567 (2)	0.0402 (1)	0.0012 (1)	0.0048 (1)	−0.0055 (1)
S1	0.0658 (5)	0.0376 (4)	0.0518 (4)	0.0063 (3)	−0.0035 (3)	0.0058 (3)
N1	0.0487 (13)	0.0419 (13)	0.0437 (13)	−0.0022 (10)	0.0082 (10)	−0.0014 (10)
C1	0.0416 (14)	0.0411 (14)	0.0543 (17)	−0.0019 (12)	−0.0027 (12)	−0.0054 (12)
C2	0.0424 (14)	0.0345 (12)	0.0407 (13)	−0.0029 (11)	−0.0035 (11)	0.0049 (11)
C3	0.0482 (15)	0.0457 (14)	0.0351 (13)	−0.0040 (12)	−0.0001 (11)	0.0075 (12)
C4	0.0393 (14)	0.0457 (14)	0.0347 (13)	−0.0025 (11)	0.0025 (11)	−0.0027 (11)
C5	0.0536 (16)	0.0347 (13)	0.0474 (16)	0.0044 (12)	0.0043 (13)	0.0030 (11)
C6	0.0593 (18)	0.0394 (13)	0.0415 (15)	−0.0005 (13)	0.0114 (13)	0.0073 (12)
C7	0.0396 (13)	0.0364 (12)	0.0399 (13)	−0.0035 (11)	0.0037 (10)	0.0013 (10)
C8	0.062 (2)	0.0511 (19)	0.067 (2)	0.0089 (15)	−0.0004 (17)	−0.0108 (15)

Geometric parameters (Å, º) top

I1—C4	2.103 (3)	C4—C5	1.397 (4)
S1—C1	1.748 (3)	C5—C6	1.369 (4)
S1—C2	1.731 (2)	C6—C7	1.397 (4)
N1—C1	1.289 (4)	C3—H3	0.9300
N1—C7	1.395 (4)	C5—H5	0.9300
C1—C8	1.494 (5)	C6—H6	0.9300
C2—C3	1.385 (4)	C8—H8A	0.9600
C2—C7	1.396 (4)	C8—H8B	0.9600
C3—C4	1.378 (4)	C8—H8C	0.9600

I1···C1ⁱ	3.826 (3)	H3···H8A^vii	2.5800
I1···N1ⁱⁱ	3.158 (2)	H5···S1^viii	3.1600
I1···H5ⁱⁱⁱ	3.3100	H5···I1ⁱⁱⁱ	3.3100
S1···H5^iv	3.1600	H5···H5ⁱⁱⁱ	2.5400
S1···H8B^v	3.1600	H8A···H3^ix	2.5800
N1···I1^vi	3.158 (2)	H8B···S1^v	3.1600
C1···I1ⁱ	3.826 (3)

C1—S1—C2	89.46 (14)	N1—C7—C6	125.3 (2)
C1—N1—C7	110.3 (2)	C2—C7—C6	119.0 (2)
S1—C1—N1	115.8 (2)	C2—C3—H3	121.00
S1—C1—C8	120.0 (2)	C4—C3—H3	121.00
N1—C1—C8	124.1 (3)	C4—C5—H5	119.00
S1—C2—C3	129.1 (2)	C6—C5—H5	120.00
S1—C2—C7	108.70 (19)	C5—C6—H6	120.00
C3—C2—C7	122.2 (2)	C7—C6—H6	120.00
C2—C3—C4	117.7 (2)	C1—C8—H8A	110.00
I1—C4—C3	120.06 (19)	C1—C8—H8B	110.00
I1—C4—C5	119.0 (2)	C1—C8—H8C	109.00
C3—C4—C5	120.9 (3)	H8A—C8—H8B	109.00
C4—C5—C6	121.1 (3)	H8A—C8—H8C	109.00
C5—C6—C7	119.1 (3)	H8B—C8—H8C	109.00
N1—C7—C2	115.7 (2)

C2—S1—C1—N1	0.5 (3)	S1—C2—C7—C6	180.0 (2)
C2—S1—C1—C8	178.5 (3)	C3—C2—C7—N1	−179.1 (2)
C1—S1—C2—C3	179.0 (3)	C3—C2—C7—C6	0.4 (4)
C1—S1—C2—C7	−0.6 (2)	C2—C3—C4—I1	178.41 (19)
C7—N1—C1—S1	−0.3 (3)	C2—C3—C4—C5	−1.1 (4)
C7—N1—C1—C8	−178.2 (3)	I1—C4—C5—C6	−178.8 (2)
C1—N1—C7—C2	−0.2 (3)	C3—C4—C5—C6	0.8 (5)
C1—N1—C7—C6	−179.6 (3)	C4—C5—C6—C7	0.2 (5)
S1—C2—C3—C4	−179.0 (2)	C5—C6—C7—N1	178.6 (3)
C7—C2—C3—C4	0.6 (4)	C5—C6—C7—C2	−0.8 (4)
S1—C2—C7—N1	0.5 (3)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x+2, −y, −z+1; (iv) x, y+1, z; (v) −x+1, −y+2, −z+1; (vi) x−1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+3/2, z−1/2; (viii) x, y−1, z; (ix) x−1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₆INS
M_r	275.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.3255 (3), 7.6967 (3), 13.8083 (5)
β (°)	90.686 (4)
V (Å³)	884.76 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.79
Crystal size (mm)	0.47 × 0.38 × 0.14

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Saphire-3 CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.253, 0.658
No. of measured, independent and observed [I > 2σ(I)] reflections	13190, 1928, 1729
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.064, 1.06
No. of reflections	1928
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.72

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Halogen-bond geometry (Å, °) top

	C4—I1	I1···N1ⁱ	C4···N1ⁱ	C4—I1···N1ⁱ
C4—I1···N1ⁱ	2.103 (3)	3.158 (2)	5.257 (4)	175.99 (9)

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

Acknowledgements

This research was supported by the Ministry of Science, Education and Sports of the Republic of Croatia, Zagreb (grant Nos. 119–1193079–1332 and 119–1191342–1339).

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