4'-tert-Butyl-5-chloro-3H-spiro-[1,3-benzothia-zole-2,1'-cyclo-hexa-ne].

In the title compound, C(16)H(22)ClNS, the nine-membered 2,3-dihydro-1,3-benzothia-zole ring system is essentially planar, with a maximum deviation of 0.025 (2) Å for the N atom. Its plane is almost perpendicular to the main plane of the substituted cyclo-hexane ring, which adopts a chair conformation. In the crystal, the molecules are linked by C-H⋯π inter-actions.

Related literature

For the pharmacological activity of benzothia­zole derivatives, see: Coudert et al. (1988 ▶); Karalı et al. (2010 ▶); Palmer et al. (1971 ▶). For the crystal structures of similar compounds, see, for example: Akkurt et al. (2010 ▶); Aryai et al. (1976 ▶); Karalı et al. (2010 ▶). For standard values of bond lengths, see: Allen et al. (1987 ▶). For details of ring-puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H22ClNS

M = 295.87

Monoclinic,

a = 15.2810 (18) Å

b = 8.9830 (8) Å

c = 11.8750 (13) Å

β = 109.580 (3)°

V = 1535.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.37 mm−1

T = 296 K

0.27 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.915, T max = 0.935

14074 measured reflections

3849 independent reflections

2330 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.128

S = 1.02

3849 reflections

179 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017539/su2411sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017539/su2411Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812017539/su2411Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H22ClNS	F(000) = 632
Mr = 295.87	Dx = 1.280 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 776 reflections
a = 15.2810 (18) Å	θ = 3.3–19.5°
b = 8.9830 (8) Å	µ = 0.37 mm−1
c = 11.8750 (13) Å	T = 296 K
β = 109.580 (3)°	Prism, colourless
V = 1535.8 (3) Å3	0.27 × 0.20 × 0.18 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3849 independent reflections
Radiation source: fine-focus sealed tube	2330 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 28.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −20→20
Tmin = 0.915, Tmax = 0.935	k = −11→10
14074 measured reflections	l = −15→15

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0473P)2 + 0.2285P] where P = (Fo2 + 2Fc2)/3
3849 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.25 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

Experimental. Spectroscopic data for the title compound: IR (KBr) ν = 3370 (N—H), 2962, 2912, 2862 (C—H), 1585, 1571, 1473, 1442 (C=C) cm-1; 1H-NMR (DMSO-d6, 500 MHz) d= 0.83–0.86 (9H, m, 4'-C(CH3)3-cyc.), 0.95–1.02 (1H, m, CH/CH2-cyc.), 1.09–1.36 (2H, m, CH/CH2-cyc.), 1.58–1.72 (4H, m, CH/CH2-cyc.), 2.15–2.22 (2H, m, CH/CH2-cyc.), 6.40, 6.47 (1H, 2 d, J=2.0 Hz, H4-bt.), 6.50 (1H, dd, J=8.1, 2.0 Hz, H6-bt.), 6.90 (1H, d, J=7.8 Hz, H7-bt.), 6.73, 6.97 (1H, 2 s, NH) p.p.m. (cyc.=cyclohexane, bt.=benzothiazole).

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.

	x	y	z	Uiso*/Ueq
Cl1	−0.35486 (5)	0.80459 (8)	0.13722 (7)	0.0761 (3)
S1	0.02827 (4)	0.69814 (6)	0.07426 (5)	0.0503 (2)
N1	−0.00626 (14)	0.8895 (2)	0.2213 (2)	0.0628 (8)
C1	−0.08493 (14)	0.7159 (2)	0.07911 (17)	0.0369 (7)
C2	−0.16334 (16)	0.6409 (2)	0.0125 (2)	0.0474 (8)
C3	−0.24750 (16)	0.6684 (2)	0.0286 (2)	0.0515 (8)
C4	−0.25028 (16)	0.7710 (2)	0.1132 (2)	0.0469 (8)
C5	−0.17272 (16)	0.8482 (2)	0.1807 (2)	0.0447 (7)
C6	−0.08920 (15)	0.8210 (2)	0.16337 (18)	0.0390 (7)
C7	0.07535 (15)	0.8422 (2)	0.1936 (2)	0.0442 (7)
C8	0.11774 (16)	0.9705 (2)	0.1463 (2)	0.0519 (8)
C9	0.20566 (15)	0.9285 (2)	0.1218 (2)	0.0500 (8)
C10	0.27931 (14)	0.8647 (2)	0.23261 (18)	0.0408 (7)
C11	0.23620 (15)	0.7316 (2)	0.27578 (19)	0.0438 (7)
C12	0.14820 (15)	0.7730 (2)	0.30136 (19)	0.0467 (8)
C13	0.37389 (16)	0.8291 (2)	0.2176 (2)	0.0509 (8)
C14	0.4048 (2)	0.9596 (3)	0.1572 (3)	0.0845 (14)
C15	0.44715 (18)	0.8047 (3)	0.3408 (2)	0.0800 (11)
C16	0.36933 (18)	0.6896 (3)	0.1415 (2)	0.0651 (10)
H1N	−0.0005 (17)	0.955 (2)	0.2742 (16)	0.070 (8)*
H2	−0.16000	0.57120	−0.04380	0.0570*
H3	−0.30100	0.61850	−0.01690	0.0620*
H5	−0.17650	0.91750	0.23700	0.0540*
H8A	0.07240	1.00700	0.07300	0.0620*
H8B	0.13160	1.05100	0.20410	0.0620*
H9A	0.23040	1.01600	0.09520	0.0600*
H9B	0.19090	0.85550	0.05810	0.0600*
H10	0.29130	0.94100	0.29500	0.0490*
H11A	0.22180	0.65430	0.21530	0.0520*
H11B	0.28120	0.69160	0.34790	0.0520*
H12A	0.12260	0.68450	0.32520	0.0560*
H12B	0.16360	0.84290	0.36740	0.0560*
H14A	0.46750	0.94360	0.15950	0.1270*
H14B	0.40160	1.05020	0.19850	0.1270*
H14C	0.36470	0.96690	0.07550	0.1270*
H15A	0.50660	0.78790	0.33200	0.1200*
H15B	0.43040	0.71970	0.37820	0.1200*
H15C	0.45040	0.89120	0.38960	0.1200*
H16A	0.31930	0.69930	0.06700	0.0980*
H16B	0.35900	0.60370	0.18350	0.0980*
H16C	0.42680	0.67840	0.12620	0.0980*

	U11	U22	U33	U12	U13	U23
Cl1	0.0543 (4)	0.0816 (5)	0.1046 (6)	0.0027 (3)	0.0428 (4)	−0.0018 (4)
S1	0.0456 (3)	0.0510 (4)	0.0568 (4)	−0.0017 (3)	0.0203 (3)	−0.0182 (3)
N1	0.0467 (12)	0.0636 (14)	0.0770 (15)	−0.0030 (10)	0.0191 (11)	−0.0390 (12)
C1	0.0441 (12)	0.0319 (11)	0.0363 (11)	0.0025 (9)	0.0158 (9)	0.0017 (8)
C2	0.0533 (14)	0.0404 (12)	0.0483 (13)	−0.0035 (10)	0.0168 (11)	−0.0086 (10)
C3	0.0460 (14)	0.0488 (14)	0.0571 (15)	−0.0096 (11)	0.0139 (12)	−0.0054 (11)
C4	0.0438 (13)	0.0414 (12)	0.0586 (15)	0.0046 (10)	0.0214 (11)	0.0072 (10)
C5	0.0531 (14)	0.0361 (11)	0.0492 (13)	0.0061 (10)	0.0229 (11)	−0.0011 (9)
C6	0.0455 (13)	0.0295 (10)	0.0412 (12)	0.0022 (9)	0.0133 (10)	−0.0016 (9)
C7	0.0402 (13)	0.0395 (12)	0.0517 (13)	−0.0018 (9)	0.0139 (11)	−0.0117 (10)
C8	0.0483 (14)	0.0382 (12)	0.0580 (15)	0.0040 (10)	0.0030 (11)	0.0069 (10)
C9	0.0518 (14)	0.0434 (12)	0.0515 (14)	−0.0031 (10)	0.0131 (11)	0.0118 (10)
C10	0.0424 (12)	0.0352 (11)	0.0411 (12)	−0.0016 (9)	0.0091 (10)	−0.0016 (9)
C11	0.0465 (13)	0.0404 (12)	0.0400 (12)	0.0039 (10)	0.0087 (10)	0.0094 (9)
C12	0.0554 (15)	0.0414 (12)	0.0440 (13)	−0.0032 (10)	0.0176 (11)	−0.0010 (9)
C13	0.0451 (14)	0.0488 (13)	0.0572 (15)	0.0010 (10)	0.0151 (11)	−0.0043 (11)
C14	0.070 (2)	0.0732 (19)	0.126 (3)	−0.0153 (15)	0.0536 (19)	0.0001 (18)
C15	0.0468 (16)	0.105 (2)	0.077 (2)	0.0111 (15)	0.0061 (15)	−0.0186 (16)
C16	0.0638 (17)	0.0669 (16)	0.0687 (17)	0.0053 (13)	0.0278 (14)	−0.0127 (13)

Cl1—C4	1.741 (3)	C2—H2	0.9300
S1—C1	1.757 (2)	C3—H3	0.9300
S1—C7	1.875 (2)	C5—H5	0.9300
N1—C6	1.369 (3)	C8—H8A	0.9700
N1—C7	1.456 (3)	C8—H8B	0.9700
N1—H1N	0.844 (18)	C9—H9A	0.9700
C1—C2	1.371 (3)	C9—H9B	0.9700
C1—C6	1.393 (3)	C10—H10	0.9800
C2—C3	1.384 (4)	C11—H11A	0.9700
C3—C4	1.375 (3)	C11—H11B	0.9700
C4—C5	1.375 (3)	C12—H12A	0.9700
C5—C6	1.381 (3)	C12—H12B	0.9700
C7—C12	1.519 (3)	C14—H14A	0.9600
C7—C8	1.519 (3)	C14—H14B	0.9600
C8—C9	1.515 (3)	C14—H14C	0.9600
C9—C10	1.528 (3)	C15—H15A	0.9600
C10—C13	1.548 (3)	C15—H15B	0.9600
C10—C11	1.534 (3)	C15—H15C	0.9600
C11—C12	1.521 (3)	C16—H16A	0.9600
C13—C15	1.531 (3)	C16—H16B	0.9600
C13—C16	1.533 (3)	C16—H16C	0.9600
C13—C14	1.529 (4)
C1—S1—C7	92.59 (10)	C7—C8—H8A	109.00
C6—N1—C7	118.31 (19)	C7—C8—H8B	109.00
C6—N1—H1N	122.4 (18)	C9—C8—H8A	109.00
C7—N1—H1N	119.2 (18)	C9—C8—H8B	109.00
C2—C1—C6	120.3 (2)	H8A—C8—H8B	108.00
S1—C1—C6	111.63 (16)	C8—C9—H9A	109.00
S1—C1—C2	128.03 (16)	C8—C9—H9B	109.00
C1—C2—C3	120.35 (19)	C10—C9—H9A	109.00
C2—C3—C4	118.6 (2)	C10—C9—H9B	109.00
Cl1—C4—C3	119.39 (19)	H9A—C9—H9B	108.00
Cl1—C4—C5	118.43 (17)	C9—C10—H10	107.00
C3—C4—C5	122.2 (2)	C11—C10—H10	107.00
C4—C5—C6	118.9 (2)	C13—C10—H10	107.00
C1—C6—C5	119.7 (2)	C10—C11—H11A	109.00
N1—C6—C1	114.0 (2)	C10—C11—H11B	109.00
N1—C6—C5	126.29 (19)	C12—C11—H11A	109.00
S1—C7—N1	103.38 (15)	C12—C11—H11B	109.00
N1—C7—C8	111.46 (17)	H11A—C11—H11B	108.00
S1—C7—C8	110.32 (15)	C7—C12—H12A	109.00
S1—C7—C12	109.96 (13)	C7—C12—H12B	109.00
C8—C7—C12	109.82 (19)	C11—C12—H12A	109.00
N1—C7—C12	111.75 (19)	C11—C12—H12B	109.00
C7—C8—C9	113.43 (16)	H12A—C12—H12B	108.00
C8—C9—C10	111.89 (18)	C13—C14—H14A	110.00
C9—C10—C11	107.78 (18)	C13—C14—H14B	109.00
C9—C10—C13	115.16 (18)	C13—C14—H14C	109.00
C11—C10—C13	113.56 (16)	H14A—C14—H14B	109.00
C10—C11—C12	112.56 (16)	H14A—C14—H14C	109.00
C7—C12—C11	112.28 (18)	H14B—C14—H14C	109.00
C10—C13—C15	109.36 (19)	C13—C15—H15A	110.00
C10—C13—C16	112.15 (19)	C13—C15—H15B	109.00
C14—C13—C16	108.1 (2)	C13—C15—H15C	110.00
C15—C13—C16	108.70 (18)	H15A—C15—H15B	110.00
C14—C13—C15	108.4 (2)	H15A—C15—H15C	109.00
C10—C13—C14	110.04 (18)	H15B—C15—H15C	109.00
C1—C2—H2	120.00	C13—C16—H16A	110.00
C3—C2—H2	120.00	C13—C16—H16B	109.00
C2—C3—H3	121.00	C13—C16—H16C	109.00
C4—C3—H3	121.00	H16A—C16—H16B	109.00
C4—C5—H5	121.00	H16A—C16—H16C	109.00
C6—C5—H5	121.00	H16B—C16—H16C	110.00
C7—S1—C1—C2	180.00 (19)	C4—C5—C6—N1	178.9 (2)
C7—S1—C1—C6	−0.14 (15)	C4—C5—C6—C1	−0.5 (3)
C1—S1—C7—N1	−1.11 (14)	S1—C7—C8—C9	−68.5 (2)
C1—S1—C7—C8	−120.40 (16)	N1—C7—C8—C9	177.21 (19)
C1—S1—C7—C12	118.33 (16)	C12—C7—C8—C9	52.8 (2)
C6—N1—C7—S1	2.3 (2)	S1—C7—C12—C11	69.25 (19)
C6—N1—C7—C8	120.8 (2)	N1—C7—C12—C11	−176.55 (16)
C6—N1—C7—C12	−115.9 (2)	C8—C7—C12—C11	−52.3 (2)
C7—N1—C6—C1	−2.6 (3)	C7—C8—C9—C10	−56.6 (2)
C7—N1—C6—C5	178.01 (19)	C8—C9—C10—C11	56.2 (2)
S1—C1—C2—C3	179.60 (16)	C8—C9—C10—C13	−175.93 (15)
C6—C1—C2—C3	−0.3 (3)	C9—C10—C11—C12	−56.7 (2)
S1—C1—C6—N1	1.5 (2)	C13—C10—C11—C12	174.45 (17)
S1—C1—C6—C5	−179.09 (15)	C9—C10—C13—C14	46.7 (2)
C2—C1—C6—N1	−178.61 (18)	C9—C10—C13—C15	165.71 (17)
C2—C1—C6—C5	0.8 (3)	C9—C10—C13—C16	−73.6 (2)
C1—C2—C3—C4	−0.6 (3)	C11—C10—C13—C14	171.7 (2)
C2—C3—C4—C5	0.9 (3)	C11—C10—C13—C15	−69.4 (2)
C2—C3—C4—Cl1	−178.66 (16)	C11—C10—C13—C16	51.3 (2)
Cl1—C4—C5—C6	179.20 (15)	C10—C11—C12—C7	56.6 (2)
C3—C4—C5—C6	−0.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg1i	0.97	2.84	3.796 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cg1i	0.97	2.84	3.796 (2)	169

Symmetry code: (i) .