5-[(4-Bromo­benz­yl)­oxy]-4-(4-methyl­benzene­sulfon­yl)-1,3-thia­zole

Rajeev, N.; Chandra; Rajesh, B.M.; Bhuvaneswara Babu, T.; Sadashiva, M.P.

doi:10.1107/S2414314617015000

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 10| October 2017| x171500

https://doi.org/10.1107/S2414314617015000

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5-[(4-Bromobenzyl)oxy]-4-(4-methylbenzenesulfonyl)-1,3-thiazole

N. Rajeev,^a Chandra,^b B. M. Rajesh,^c T. Bhuvaneswara Babu ^c and M. P. Sadashiva ^a ^*

^aDepartment of Studies in Chemistry, Manasagangotri, University of Mysore, Mysore 570 006, India, ^bDepartment of Physics, The National Institutional of Engineering (NIE), Mysore 570 008, India, and ^cDepartment of Physics, RV College of Engineering, Bengaluru 560 059, India
^*Correspondence e-mail: mpsadashiva@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 September 2017; accepted 16 October 2017; online 31 October 2017)

In the title compound, C₁₇H₁₄BrNO₃S₂, the mean plane of the thiazole ring subtends dihedral angles of 3.6 (2) and 79.9 (2)° with the bromobenzyl and toluyl rings, respectively. In the crystal, short S⋯O contacts [3.012 (3) Å] and aromatic π–π stacking between the thiazole and toluyl rings [centroid–centroid separation = 3.687 (2) Å] are observed.

Keywords: crystal structure; thiazole derivative; hydrogen bonding; medicinal importance.

CCDC reference: 1543222

Structure description

Thiazoles have many applications in the field of medicinal chemistry, for instance as anti-microbial (Liaras et al., 2011 ), anti-cancer (Romagnoli et al., 2012 ) and anti-mycobacterium tuberculosis (Shiradkar et al., 2007 ) agents. As part of our studies of these compounds, we have synthesized the title compound to study its crystal structure.

In the molecular structure (Fig. 1), the mean plane of the thiazole moiety (C11/N12/C13/S14/C15), is approximately coplanar with the bromobenzyl ring [dihedral angle = 3.6 (2)°] and close to orthogonal to the toluyl ring [79.9 (2)°]. In the crystal, short S⋯O contacts [3.012 (3) Å] and aromatic π–π stacking between the thiazole and toluyl rings [centroid-centroid separation = 3.687 (2) Å] are observed. A packing diagram is shown in Fig. 2

Figure 1
The molecular structure with 50% probability displacement ellipsoids.

Figure 2
Packing diagram of the title compound viewed down [100].

Synthesis and crystallization

To a suspension of sodium hydride (60% suspension in paraffin; 4 mmol) in DMF (1.5 ml), a mixture of xanthate ester 2 (2 mmol), and active methylene isocyanide 3 (2 mmol) in DMF (1.5 ml) was added dropwise at 0°C. The mixture was allowed to stir at room temperature for 10–20 min (monitored by TLC). After completion of the reaction, the mixture was poured into a saturated solution of ammonium chloride (20 ml) and extracted with ethyl acetate (20 ml × 2). The combined ethyl acetate layer was washed with water (20 ml), brine (20 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure to get crude products, which were purified by column chromatography using ethyl acetate–hexane as eluent. Pale-yellow blocks of the title compound were recrystallized from ethyl acetate solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₇H₁₄BrNO₃S₂
M_r	424.31
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.6092 (4), 8.2768 (5), 13.8718 (8)
α, β, γ (°)	95.175 (5), 94.559 (5), 94.814 (5)
V (Å³)	863.67 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.64
Crystal size (mm)	0.28 × 0.25 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	7351, 3955, 2633
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.144, 1.04
No. of reflections	3955
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.67
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1543222

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617015000/hb4172sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617015000/hb4172Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

5-[(4-Bromobenzyl)oxy]-4-(4-methylbenzenesulfonyl)-1,3-thiazole top

Crystal data top

C₁₇H₁₄BrNO₃S₂	Z = 2
M_r = 424.31	F(000) = 428
Triclinic, P1	D_x = 1.632 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6092 (4) Å	Cell parameters from 3955 reflections
b = 8.2768 (5) Å	θ = 2.5–27.5°
c = 13.8718 (8) Å	µ = 2.64 mm⁻¹
α = 95.175 (5)°	T = 293 K
β = 94.559 (5)°	Block, pale yellow
γ = 94.814 (5)°	0.28 × 0.25 × 0.22 mm
V = 863.67 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.035
Detector resolution: 18.4 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω and φ scans	h = −9→9
7351 measured reflections	k = −10→8
3955 independent reflections	l = −16→18
2633 reflections with I > 2σ(I)

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.144	w = 1/[Σ²(FO²) + (0.0501P)² + 0.4404P] where P = (FO² + 2FC²)/3
S = 1.04	(Δ/σ)_max = 0.003
3955 reflections	Δρ_max = 0.35 e Å⁻³
218 parameters	Δρ_min = −0.67 e Å⁻³

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 esds 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 > 2sigma(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.

The H atoms were positioned geometrically and allowed to ride on their parent atom, with C–H distance in the range of 0.93 to 0.97 Å; U_iso(H) = 1.2–1.5U_eq (carrier atom) for all H atoms.

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

	x	y	z	U_iso*/U_eq
Br24	0.46321 (8)	0.97111 (7)	0.79555 (4)	0.0674 (2)
S8	0.12112 (14)	0.52364 (12)	1.29198 (8)	0.0382 (3)
S14	−0.39923 (15)	0.56970 (15)	1.16549 (9)	0.0508 (4)
O9	0.2178 (4)	0.5355 (4)	1.2075 (2)	0.0474 (10)
O10	0.1418 (4)	0.3884 (3)	1.3483 (2)	0.0516 (11)
O16	−0.0708 (5)	0.6623 (5)	1.1124 (3)	0.0779 (14)
N12	−0.2288 (5)	0.4619 (4)	1.3100 (3)	0.0450 (12)
C1	0.2819 (7)	1.1548 (6)	1.5513 (4)	0.0647 (19)
C2	0.2422 (6)	0.9961 (5)	1.4872 (3)	0.0458 (16)
C3	0.2264 (6)	0.9965 (5)	1.3866 (3)	0.0483 (16)
C4	0.1911 (6)	0.8518 (5)	1.3277 (3)	0.0445 (16)
C5	0.1718 (5)	0.7057 (5)	1.3686 (3)	0.0358 (12)
C6	0.1858 (6)	0.7040 (5)	1.4683 (3)	0.0458 (14)
C7	0.2221 (7)	0.8489 (6)	1.5267 (3)	0.0539 (16)
C11	−0.1060 (5)	0.5239 (5)	1.2538 (3)	0.0366 (12)
C13	−0.3864 (6)	0.4786 (6)	1.2722 (3)	0.0504 (17)
C15	−0.1693 (6)	0.5886 (5)	1.1725 (3)	0.0438 (14)
C17	−0.1435 (6)	0.7034 (6)	1.0217 (3)	0.0471 (16)
C18	0.0056 (6)	0.7718 (5)	0.9690 (3)	0.0393 (14)
C19	0.1812 (6)	0.7713 (5)	1.0047 (3)	0.0449 (14)
C20	0.3145 (6)	0.8305 (5)	0.9536 (3)	0.0490 (17)
C21	0.2766 (6)	0.8919 (5)	0.8658 (3)	0.0452 (14)
C22	0.1037 (7)	0.8947 (5)	0.8301 (3)	0.0496 (16)
C23	−0.0312 (6)	0.8358 (5)	0.8813 (3)	0.0473 (17)
H1A	0.20336	1.15773	1.60218	0.0970*
H1B	0.26522	1.24432	1.51311	0.0970*
H1C	0.40214	1.16313	1.57933	0.0970*
H3	0.23960	1.09451	1.35890	0.0580*
H4	0.18030	0.85259	1.26051	0.0540*
H6	0.17101	0.60604	1.49586	0.0550*
H7	0.23317	0.84745	1.59382	0.0650*
H13	−0.48714	0.44345	1.30113	0.0610*
H16A	−0.22813	0.78345	1.03150	0.0560*
H16B	−0.20413	0.60745	0.98417	0.0560*
H18	0.20832	0.73038	1.06380	0.0540*
H19	0.43168	0.82933	0.97807	0.0590*
H21	0.07767	0.93653	0.77112	0.0600*
H22	−0.14821	0.83882	0.85688	0.0570*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br24	0.0677 (4)	0.0740 (4)	0.0582 (4)	−0.0139 (3)	0.0067 (3)	0.0127 (3)
S8	0.0301 (5)	0.0405 (5)	0.0433 (6)	0.0046 (4)	−0.0011 (4)	0.0023 (5)
S14	0.0309 (6)	0.0608 (7)	0.0595 (8)	0.0038 (5)	−0.0024 (5)	0.0055 (6)
O9	0.0313 (17)	0.0651 (19)	0.0448 (17)	0.0062 (15)	0.0058 (13)	−0.0036 (15)
O10	0.051 (2)	0.0425 (16)	0.061 (2)	0.0102 (15)	−0.0057 (16)	0.0080 (15)
O16	0.038 (2)	0.134 (3)	0.065 (2)	−0.007 (2)	−0.0069 (17)	0.052 (2)
N12	0.037 (2)	0.051 (2)	0.047 (2)	0.0018 (17)	0.0046 (17)	0.0055 (17)
C1	0.068 (4)	0.058 (3)	0.064 (3)	0.011 (3)	−0.006 (3)	−0.011 (3)
C2	0.038 (3)	0.044 (2)	0.053 (3)	0.007 (2)	−0.002 (2)	−0.006 (2)
C3	0.058 (3)	0.038 (2)	0.049 (3)	0.001 (2)	0.003 (2)	0.009 (2)
C4	0.046 (3)	0.052 (3)	0.036 (2)	0.002 (2)	0.0059 (19)	0.008 (2)
C5	0.029 (2)	0.040 (2)	0.038 (2)	0.0019 (17)	−0.0013 (17)	0.0069 (18)
C6	0.049 (3)	0.048 (2)	0.040 (2)	0.000 (2)	0.000 (2)	0.010 (2)
C7	0.065 (3)	0.061 (3)	0.034 (2)	0.005 (3)	−0.005 (2)	0.004 (2)
C11	0.033 (2)	0.037 (2)	0.039 (2)	0.0032 (18)	0.0028 (18)	0.0004 (17)
C13	0.037 (3)	0.058 (3)	0.056 (3)	0.000 (2)	0.012 (2)	0.001 (2)
C15	0.034 (2)	0.048 (2)	0.048 (3)	−0.002 (2)	0.001 (2)	0.004 (2)
C17	0.040 (3)	0.059 (3)	0.041 (2)	0.007 (2)	−0.005 (2)	0.003 (2)
C18	0.044 (3)	0.038 (2)	0.035 (2)	0.0059 (19)	−0.0009 (18)	0.0012 (18)
C19	0.045 (3)	0.050 (2)	0.038 (2)	0.001 (2)	−0.004 (2)	0.005 (2)
C20	0.041 (3)	0.055 (3)	0.048 (3)	−0.001 (2)	−0.007 (2)	0.004 (2)
C21	0.048 (3)	0.044 (2)	0.041 (2)	0.000 (2)	0.000 (2)	−0.003 (2)
C22	0.059 (3)	0.050 (2)	0.039 (3)	0.005 (2)	−0.005 (2)	0.008 (2)
C23	0.042 (3)	0.054 (3)	0.045 (3)	0.009 (2)	−0.006 (2)	0.004 (2)

Geometric parameters (Å, º) top

Br24—C21	1.891 (4)	C18—C19	1.388 (6)
S8—O9	1.439 (3)	C18—C23	1.388 (6)
S8—O10	1.434 (3)	C19—C20	1.366 (6)
S8—C5	1.760 (4)	C20—C21	1.380 (6)
S8—C11	1.767 (4)	C21—C22	1.371 (7)
S14—C13	1.721 (5)	C22—C23	1.375 (7)
S14—C15	1.738 (5)	C1—H1A	0.9600
O16—C15	1.320 (6)	C1—H1B	0.9600
O16—C17	1.415 (6)	C1—H1C	0.9600
N12—C11	1.361 (6)	C3—H3	0.9300
N12—C13	1.294 (6)	C4—H4	0.9300
C1—C2	1.512 (7)	C6—H6	0.9300
C2—C3	1.391 (6)	C7—H7	0.9300
C2—C7	1.382 (6)	C13—H13	0.9300
C3—C4	1.382 (6)	C17—H16A	0.9700
C4—C5	1.383 (6)	C17—H16B	0.9700
C5—C6	1.380 (6)	C19—H18	0.9300
C6—C7	1.380 (6)	C20—H19	0.9300
C11—C15	1.363 (6)	C22—H21	0.9300
C17—C18	1.497 (6)	C23—H22	0.9300

O9—S8—O10	118.94 (19)	Br24—C21—C22	120.5 (3)
O9—S8—C5	108.10 (19)	C20—C21—C22	119.7 (4)
O9—S8—C11	107.43 (19)	C21—C22—C23	120.1 (4)
O10—S8—C5	108.85 (18)	C18—C23—C22	120.6 (4)
O10—S8—C11	108.17 (19)	C2—C1—H1A	109.00
C5—S8—C11	104.40 (19)	C2—C1—H1B	109.00
C13—S14—C15	88.4 (2)	C2—C1—H1C	110.00
C15—O16—C17	121.7 (4)	H1A—C1—H1B	109.00
C11—N12—C13	110.0 (4)	H1A—C1—H1C	109.00
C1—C2—C3	120.0 (4)	H1B—C1—H1C	109.00
C1—C2—C7	121.1 (4)	C2—C3—H3	120.00
C3—C2—C7	118.8 (4)	C4—C3—H3	120.00
C2—C3—C4	120.3 (4)	C3—C4—H4	120.00
C3—C4—C5	120.1 (4)	C5—C4—H4	120.00
S8—C5—C4	119.1 (3)	C5—C6—H6	120.00
S8—C5—C6	120.7 (3)	C7—C6—H6	120.00
C4—C5—C6	120.2 (4)	C2—C7—H7	119.00
C5—C6—C7	119.5 (4)	C6—C7—H7	119.00
C2—C7—C6	121.2 (4)	S14—C13—H13	122.00
S8—C11—N12	119.1 (3)	N12—C13—H13	122.00
S8—C11—C15	124.4 (3)	O16—C17—H16A	110.00
N12—C11—C15	116.5 (4)	O16—C17—H16B	110.00
S14—C13—N12	116.2 (3)	C18—C17—H16A	110.00
S14—C15—O16	125.8 (3)	C18—C17—H16B	110.00
S14—C15—C11	109.0 (3)	H16A—C17—H16B	108.00
O16—C15—C11	125.1 (4)	C18—C19—H18	120.00
O16—C17—C18	107.8 (4)	C20—C19—H18	120.00
C17—C18—C19	121.8 (4)	C19—C20—H19	120.00
C17—C18—C23	119.6 (4)	C21—C20—H19	120.00
C19—C18—C23	118.6 (4)	C21—C22—H21	120.00
C18—C19—C20	120.5 (4)	C23—C22—H21	120.00
C19—C20—C21	120.5 (4)	C18—C23—H22	120.00
Br24—C21—C20	119.8 (3)	C22—C23—H22	120.00

O9—S8—C5—C4	38.3 (4)	C3—C2—C7—C6	−0.4 (7)
O9—S8—C5—C6	−144.0 (3)	C2—C3—C4—C5	−0.2 (7)
O10—S8—C5—C4	168.8 (3)	C3—C4—C5—S8	178.3 (3)
O10—S8—C5—C6	−13.5 (4)	C3—C4—C5—C6	0.7 (7)
C11—S8—C5—C4	−75.8 (4)	S8—C5—C6—C7	−178.7 (4)
C11—S8—C5—C6	101.8 (4)	C4—C5—C6—C7	−1.1 (7)
O9—S8—C11—N12	158.7 (3)	C5—C6—C7—C2	1.0 (7)
O9—S8—C11—C15	−24.0 (4)	S8—C11—C15—S14	−177.6 (2)
O10—S8—C11—N12	29.2 (4)	S8—C11—C15—O16	−1.4 (7)
O10—S8—C11—C15	−153.6 (4)	N12—C11—C15—S14	−0.3 (5)
C5—S8—C11—N12	−86.7 (4)	N12—C11—C15—O16	176.0 (4)
C5—S8—C11—C15	90.6 (4)	O16—C17—C18—C19	6.7 (6)
C15—S14—C13—N12	−0.4 (4)	O16—C17—C18—C23	−174.2 (4)
C13—S14—C15—O16	−175.9 (4)	C17—C18—C19—C20	178.2 (4)
C13—S14—C15—C11	0.4 (3)	C23—C18—C19—C20	−1.0 (6)
C17—O16—C15—S14	−14.6 (6)	C17—C18—C23—C22	−178.0 (4)
C17—O16—C15—C11	169.8 (4)	C19—C18—C23—C22	1.2 (6)
C15—O16—C17—C18	−175.3 (4)	C18—C19—C20—C21	0.1 (6)
C13—N12—C11—S8	177.5 (3)	C19—C20—C21—Br24	−179.3 (3)
C13—N12—C11—C15	0.0 (5)	C19—C20—C21—C22	0.6 (6)
C11—N12—C13—S14	0.3 (5)	Br24—C21—C22—C23	179.5 (3)
C1—C2—C3—C4	179.7 (4)	C20—C21—C22—C23	−0.4 (6)
C7—C2—C3—C4	0.0 (7)	C21—C22—C23—C18	−0.5 (6)
C1—C2—C7—C6	180.0 (5)

Acknowledgements

NR thanks UGC for providing RGNF and grateful to IOE, University of Mysore for the spectroscopic characterization and MPS thanks UGC-SAP DRS III for financial support. The authors also thank The National Institute of Engineering (NIE), Mysuru, and RV College of Engineering, Bengaluru, for support.

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