3-(4-Hexyl-oxyphen-yl)-1,2,4-triazolo[3,4-b]benzo-thia-zole.

The title compound, C20H21N3OS, was prepared by Huisgen reaction of 5-(4-hexyl-oxyphen-yl)tetra-zole and chloro-benzo-thia-zole. The essentially planar benzo-thia-zolotriazole framework [maximum deviation from the mean plane of 0.077 (1) Å for the bridgehead N atom] and the phenyl ring form a dihedral angle of 53.34 (5)°. The hex-yloxy chain adopts a gauche-all-anti conformation. The intra-centroid separation of 3.7258 (8) Å between the triazole and benzene rings is the closest contact between individual mol-ecules in the crystal.

Related literature

For related benzo­thia­zolotriazoles, see: Butler et al. (1972 ▶); Reynolds & van Allan (1959 ▶). For triazolo-annulation via tetra­zoles, see: Christiano et al. (2008 ▶). For the Huisgen reaction, see: Huisgen et al. (1960 ▶,1961 ▶). For the structures of related triazolo-annulated heterocycles, see: Preis et al. (2011a ▶,b ▶); Herget et al. (2013 ▶); Puviarasnan et al. (1999 ▶).

Experimental

Crystal data

C20H21N3OS

M = 351.46

Orthorhombic,

a = 10.7369 (4) Å

b = 9.1770 (3) Å

c = 35.6567 (11) Å

V = 3513.3 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.20 mm−1

T = 193 K

0.50 × 0.20 × 0.20 mm

Data collection

Stoe IPDS 2T diffractometer

26869 measured reflections

4225 independent reflections

3441 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.119

S = 1.04

4225 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.23 e Å−3

Data collection: X-AREA (Stoe & Cie, 2011 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2011 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814002153/nc2323sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002153/nc2323Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002153/nc2323Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H21N3OS	Dx = 1.329 Mg m−3
Mr = 351.46	Melting point: 400 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 32877 reflections
a = 10.7369 (4) Å	θ = 2.2–33.7°
b = 9.1770 (3) Å	µ = 0.20 mm−1
c = 35.6567 (11) Å	T = 193 K
V = 3513.3 (2) Å3	Needle, colourless
Z = 8	0.50 × 0.20 × 0.20 mm
F(000) = 1488

Stoe IPDS 2T diffractometer	3441 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	Rint = 0.074
Graphite monochromator	θmax = 28.0°, θmin = 2.9°
Detector resolution: 6.67 pixels mm-1	h = −14→14
rotation method scans	k = −8→12
26869 measured reflections	l = −47→38
4225 independent reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0653P)2 + 0.9425P] where P = (Fo2 + 2Fc2)/3
4225 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Experimental. 1H-NMR (CDCl3): δ = 7.66 (m, 3 H); 7.51 (d, 1 H, J = 7.5 Hz), 7.35 ("t", 1 H), 7.29 ("t", 1H), 7.06 (d, 2 H, J = 8 Hz), 4.05, t, 2 H), 1.83 (qui, 2 H), 1.48 (qui, 2 H), 1.33 (m, 4 H), 0.90 ("t", 3H). 13C-NMR(CDCl3): δ = 156.0, 150.7, 154.3, 127.5, 125.5 (2c), 125.0, 121.2, 121.1, 119.7, 113.5, 109.9, 109.2, 63.2, 26.5, 24.1, 20.6, 17.5, 8.9. FD—MS:351.4 (M+H+). UV-Vis: dichloromethane: λmax = 260 nm (log ε = 4.11), λmax = 298 nm (log ε = 3.85); cyclohexane: λmax = 261 nm, λmax = 298 nm; λmax = 298 nm; ethanol: λmax = 258 nm, λmax = 295 nm; fluorescence: dichloromethane: λmax = 356 nm; cyclohexane: λmax = 333 nm; ethanol: λmax = 358 nm.

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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.

	x	y	z	Uiso*/Ueq
S1	0.41618 (4)	0.26300 (4)	0.696695 (10)	0.03581 (13)
C2	0.40821 (12)	0.43744 (15)	0.67607 (4)	0.0304 (3)
C3	0.41068 (14)	0.57003 (18)	0.69481 (4)	0.0364 (3)
H3	0.4124	0.5737	0.7214	0.044*
C4	0.41053 (13)	0.69677 (17)	0.67376 (5)	0.0374 (3)
H4	0.4115	0.7884	0.6861	0.045*
C5	0.40897 (13)	0.69200 (16)	0.63482 (5)	0.0340 (3)
H5	0.4109	0.7804	0.6210	0.041*
C6	0.40465 (12)	0.55988 (15)	0.61587 (4)	0.0299 (3)
H6	0.4030	0.5564	0.5892	0.036*
C7	0.40282 (11)	0.43353 (14)	0.63696 (4)	0.0260 (3)
N8	0.40149 (10)	0.28738 (12)	0.62443 (3)	0.0263 (2)
C9	0.40200 (12)	0.20746 (15)	0.59169 (4)	0.0280 (3)
N10	0.41399 (11)	0.06852 (13)	0.60013 (4)	0.0348 (3)
N11	0.42111 (12)	0.05377 (13)	0.63912 (4)	0.0361 (3)
C12	0.41293 (12)	0.18574 (15)	0.65223 (4)	0.0304 (3)
C13	0.38612 (12)	0.26957 (15)	0.55412 (4)	0.0280 (3)
C14	0.46740 (13)	0.23437 (15)	0.52481 (4)	0.0311 (3)
H14	0.5331	0.1670	0.5291	0.037*
C15	0.45328 (13)	0.29627 (16)	0.48985 (4)	0.0323 (3)
H15	0.5089	0.2710	0.4702	0.039*
C16	0.35734 (12)	0.39615 (15)	0.48326 (4)	0.0289 (3)
C17	0.27419 (12)	0.42904 (15)	0.51209 (4)	0.0307 (3)
H17	0.2073	0.4947	0.5077	0.037*
C18	0.28918 (12)	0.36596 (15)	0.54696 (4)	0.0304 (3)
H18	0.2321	0.3889	0.5664	0.036*
O19	0.35160 (9)	0.45394 (11)	0.44817 (3)	0.0345 (2)
C20	0.25760 (14)	0.56334 (16)	0.44224 (4)	0.0354 (3)
H20A	0.2658	0.6407	0.4614	0.043*
H20B	0.1739	0.5191	0.4448	0.043*
C21	0.27167 (14)	0.62833 (16)	0.40378 (4)	0.0367 (3)
H21A	0.3565	0.6698	0.4016	0.044*
H21B	0.2118	0.7098	0.4013	0.044*
C22	0.25134 (13)	0.52382 (17)	0.37123 (4)	0.0349 (3)
H22A	0.3231	0.4564	0.3695	0.042*
H22B	0.1757	0.4650	0.3760	0.042*
C23	0.23673 (14)	0.60407 (17)	0.33430 (4)	0.0368 (3)
H23A	0.1652	0.6716	0.3364	0.044*
H23B	0.3123	0.6635	0.3299	0.044*
C24	0.21655 (17)	0.50588 (19)	0.30070 (5)	0.0451 (4)
H24A	0.2927	0.4472	0.2965	0.054*
H24B	0.1475	0.4377	0.3063	0.054*
C25	0.1863 (2)	0.5888 (2)	0.26520 (5)	0.0612 (5)
H25A	0.1085	0.6430	0.2687	0.092*
H25B	0.1768	0.5200	0.2444	0.092*
H25C	0.2540	0.6570	0.2596	0.092*

	U11	U22	U33	U12	U13	U23
S1	0.0409 (2)	0.0353 (2)	0.0313 (2)	0.00007 (15)	−0.00034 (14)	0.00440 (14)
C2	0.0281 (6)	0.0311 (7)	0.0319 (7)	0.0002 (5)	−0.0004 (5)	−0.0004 (6)
C3	0.0350 (7)	0.0393 (8)	0.0350 (8)	−0.0002 (6)	−0.0015 (6)	−0.0103 (6)
C4	0.0349 (7)	0.0303 (7)	0.0471 (9)	0.0004 (6)	−0.0036 (6)	−0.0129 (7)
C5	0.0333 (7)	0.0239 (7)	0.0449 (8)	−0.0005 (5)	−0.0033 (6)	−0.0039 (6)
C6	0.0291 (6)	0.0258 (7)	0.0348 (7)	−0.0019 (5)	−0.0016 (5)	−0.0013 (6)
C7	0.0228 (6)	0.0231 (6)	0.0322 (7)	−0.0009 (5)	0.0001 (5)	−0.0043 (5)
N8	0.0271 (5)	0.0215 (5)	0.0302 (6)	−0.0011 (4)	0.0003 (4)	−0.0009 (4)
C9	0.0250 (6)	0.0237 (6)	0.0353 (7)	−0.0015 (5)	−0.0006 (5)	−0.0060 (5)
N10	0.0345 (6)	0.0243 (6)	0.0455 (7)	−0.0005 (5)	−0.0050 (5)	−0.0035 (5)
N11	0.0385 (6)	0.0255 (6)	0.0443 (7)	−0.0007 (5)	−0.0040 (5)	0.0030 (5)
C12	0.0283 (6)	0.0267 (7)	0.0360 (7)	−0.0010 (5)	−0.0005 (5)	0.0041 (6)
C13	0.0275 (6)	0.0249 (6)	0.0315 (7)	−0.0025 (5)	−0.0028 (5)	−0.0063 (5)
C14	0.0270 (6)	0.0281 (7)	0.0382 (7)	0.0043 (5)	−0.0008 (6)	−0.0067 (6)
C15	0.0304 (7)	0.0306 (7)	0.0358 (7)	0.0030 (5)	0.0038 (6)	−0.0060 (6)
C16	0.0286 (6)	0.0257 (6)	0.0324 (7)	−0.0016 (5)	−0.0025 (5)	−0.0061 (5)
C17	0.0267 (6)	0.0292 (7)	0.0361 (7)	0.0037 (5)	−0.0033 (5)	−0.0085 (6)
C18	0.0264 (6)	0.0314 (7)	0.0334 (7)	0.0008 (5)	0.0008 (5)	−0.0077 (6)
O19	0.0360 (5)	0.0331 (5)	0.0343 (5)	0.0066 (4)	0.0009 (4)	−0.0016 (4)
C20	0.0336 (7)	0.0292 (7)	0.0435 (8)	0.0034 (5)	0.0009 (6)	0.0006 (6)
C21	0.0346 (7)	0.0274 (7)	0.0482 (8)	−0.0013 (6)	0.0007 (6)	0.0057 (6)
C22	0.0319 (7)	0.0290 (7)	0.0437 (8)	−0.0024 (5)	−0.0040 (6)	0.0081 (6)
C23	0.0369 (7)	0.0303 (7)	0.0431 (8)	0.0024 (6)	0.0039 (6)	0.0081 (6)
C24	0.0515 (9)	0.0386 (9)	0.0452 (9)	−0.0031 (7)	0.0014 (7)	0.0053 (7)
C25	0.0812 (14)	0.0626 (12)	0.0398 (9)	0.0116 (11)	0.0092 (9)	0.0047 (9)

S1—C12	1.7370 (15)	C16—O19	1.3605 (17)
S1—C2	1.7638 (15)	C16—C17	1.395 (2)
C2—C3	1.388 (2)	C17—C18	1.381 (2)
C2—C7	1.396 (2)	C17—H17	0.9500
C3—C4	1.384 (2)	C18—H18	0.9500
C3—H3	0.9500	O19—C20	1.4392 (17)
C4—C5	1.389 (2)	C20—C21	1.503 (2)
C4—H4	0.9500	C20—H20A	0.9900
C5—C6	1.389 (2)	C20—H20B	0.9900
C5—H5	0.9500	C21—C22	1.521 (2)
C6—C7	1.382 (2)	C21—H21A	0.9900
C6—H6	0.9500	C21—H21B	0.9900
C7—N8	1.4137 (17)	C22—C23	1.517 (2)
N8—C12	1.3667 (18)	C22—H22A	0.9900
N8—C9	1.3787 (18)	C22—H22B	0.9900
C9—N10	1.3164 (18)	C23—C24	1.515 (2)
C9—C13	1.466 (2)	C23—H23A	0.9900
N10—N11	1.399 (2)	C23—H23B	0.9900
N11—C12	1.3012 (19)	C24—C25	1.512 (2)
C13—C18	1.3897 (19)	C24—H24A	0.9900
C13—C14	1.399 (2)	C24—H24B	0.9900
C14—C15	1.378 (2)	C25—H25A	0.9800
C14—H14	0.9500	C25—H25B	0.9800
C15—C16	1.399 (2)	C25—H25C	0.9800
C15—H15	0.9500
C12—S1—C2	89.37 (7)	C18—C17—H17	120.1
C3—C2—C7	120.26 (13)	C16—C17—H17	120.1
C3—C2—S1	126.43 (12)	C17—C18—C13	121.31 (13)
C7—C2—S1	113.28 (11)	C17—C18—H18	119.3
C4—C3—C2	118.38 (14)	C13—C18—H18	119.3
C4—C3—H3	120.8	C16—O19—C20	116.03 (11)
C2—C3—H3	120.8	O19—C20—C21	109.90 (12)
C3—C4—C5	121.03 (14)	O19—C20—H20A	109.7
C3—C4—H4	119.5	C21—C20—H20A	109.7
C5—C4—H4	119.5	O19—C20—H20B	109.7
C6—C5—C4	120.94 (14)	C21—C20—H20B	109.7
C6—C5—H5	119.5	H20A—C20—H20B	108.2
C4—C5—H5	119.5	C20—C21—C22	115.56 (12)
C7—C6—C5	117.91 (14)	C20—C21—H21A	108.4
C7—C6—H6	121.0	C22—C21—H21A	108.4
C5—C6—H6	121.0	C20—C21—H21B	108.4
C6—C7—C2	121.42 (13)	C22—C21—H21B	108.4
C6—C7—N8	128.61 (13)	H21A—C21—H21B	107.5
C2—C7—N8	109.90 (12)	C23—C22—C21	111.77 (13)
C12—N8—C9	104.52 (12)	C23—C22—H22A	109.3
C12—N8—C7	114.67 (12)	C21—C22—H22A	109.3
C9—N8—C7	140.56 (12)	C23—C22—H22B	109.3
N10—C9—N8	108.80 (13)	C21—C22—H22B	109.3
N10—C9—C13	126.64 (13)	H22A—C22—H22B	107.9
N8—C9—C13	124.51 (12)	C24—C23—C22	114.37 (13)
C9—N10—N11	109.03 (12)	C24—C23—H23A	108.7
C12—N11—N10	105.28 (12)	C22—C23—H23A	108.7
N11—C12—N8	112.37 (13)	C24—C23—H23B	108.7
N11—C12—S1	134.96 (12)	C22—C23—H23B	108.7
N8—C12—S1	112.65 (10)	H23A—C23—H23B	107.6
C18—C13—C14	118.47 (13)	C25—C24—C23	113.19 (15)
C18—C13—C9	120.17 (12)	C25—C24—H24A	108.9
C14—C13—C9	121.35 (12)	C23—C24—H24A	108.9
C15—C14—C13	120.78 (13)	C25—C24—H24B	108.9
C15—C14—H14	119.6	C23—C24—H24B	108.9
C13—C14—H14	119.6	H24A—C24—H24B	107.8
C14—C15—C16	120.21 (13)	C24—C25—H25A	109.5
C14—C15—H15	119.9	C24—C25—H25B	109.5
C16—C15—H15	119.9	H25A—C25—H25B	109.5
O19—C16—C17	124.37 (12)	C24—C25—H25C	109.5
O19—C16—C15	116.32 (12)	H25A—C25—H25C	109.5
C17—C16—C15	119.31 (13)	H25B—C25—H25C	109.5
C18—C17—C16	119.89 (12)
C12—S1—C2—C3	−177.71 (13)	C7—N8—C12—N11	−174.91 (11)
C12—S1—C2—C7	0.27 (10)	C9—N8—C12—S1	179.33 (9)
C7—C2—C3—C4	−1.4 (2)	C7—N8—C12—S1	3.92 (14)
S1—C2—C3—C4	176.40 (11)	C2—S1—C12—N11	176.13 (15)
C2—C3—C4—C5	−0.5 (2)	C2—S1—C12—N8	−2.34 (10)
C3—C4—C5—C6	1.5 (2)	N10—C9—C13—C18	128.50 (15)
C4—C5—C6—C7	−0.4 (2)	N8—C9—C13—C18	−48.64 (19)
C5—C6—C7—C2	−1.54 (19)	N10—C9—C13—C14	−51.7 (2)
C5—C6—C7—N8	−178.36 (12)	N8—C9—C13—C14	131.13 (14)
C3—C2—C7—C6	2.5 (2)	C18—C13—C14—C15	1.4 (2)
S1—C2—C7—C6	−175.59 (10)	C9—C13—C14—C15	−178.40 (13)
C3—C2—C7—N8	179.88 (12)	C13—C14—C15—C16	0.3 (2)
S1—C2—C7—N8	1.76 (13)	C14—C15—C16—O19	178.83 (13)
C6—C7—N8—C12	173.48 (13)	C14—C15—C16—C17	−1.9 (2)
C2—C7—N8—C12	−3.63 (15)	O19—C16—C17—C18	−179.06 (12)
C6—C7—N8—C9	0.5 (2)	C15—C16—C17—C18	1.7 (2)
C2—C7—N8—C9	−176.62 (14)	C16—C17—C18—C13	0.0 (2)
C12—N8—C9—N10	−0.47 (14)	C14—C13—C18—C17	−1.6 (2)
C7—N8—C9—N10	172.96 (14)	C9—C13—C18—C17	178.22 (12)
C12—N8—C9—C13	177.11 (12)	C17—C16—O19—C20	4.47 (19)
C7—N8—C9—C13	−9.5 (2)	C15—C16—O19—C20	−176.25 (12)
N8—C9—N10—N11	0.29 (15)	C16—O19—C20—C21	173.79 (12)
C13—C9—N10—N11	−177.22 (12)	O19—C20—C21—C22	63.84 (16)
C9—N10—N11—C12	0.02 (15)	C20—C21—C22—C23	166.39 (12)
N10—N11—C12—N8	−0.33 (15)	C21—C22—C23—C24	179.82 (13)
N10—N11—C12—S1	−178.80 (12)	C22—C23—C24—C25	172.79 (15)
C9—N8—C12—N11	0.50 (15)