4-(2-Sulfanyl­idene-1,3-benzothia­zol-3-yl)butan-2-one

Abstract

In the title compound, C₁₁H₁₁NOS₂, the benzine ring is coplanar with the thia­zole ring, making a dihedral angle of 0.81 (1)°. In the crystal, adjacent mol­ecules are connected into a helical chain along the b axis by S⋯S contacts [3.4345 (18) Å]. These helical chains are further assembled into a three-dimensional supermolecular network by inter­molecular C—H⋯O hydrogen bond between aromatic ring H atoms and carbonyl groups.

Related literature

For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For a related structure, see: Zhu et al. (2009 ▶). For S⋯S contacts, see: Dai et al. (1997 ▶).

Experimental

Crystal data

• C₁₁H₁₁NOS₂

• M _r = 237.33

• Orthorhombic,

• a = 4.9457 (19) Å

• b = 11.586 (4) Å

• c = 19.830 (7) Å

• V = 1136.3 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.44 mm⁻¹

• T = 296 K

• 0.23 × 0.19 × 0.15 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.905, T _max = 0.936

• 12565 measured reflections

• 1476 independent reflections

• 1176 reflections with I > 2σ(I)

• R _int = 0.036

Refinement

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.117

• S = 1.07

• 1476 reflections

• 120 parameters

• 2 restraints

• H-atom parameters constrained

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯O1i	0.96	2.60	3.541 (5)	167

Symmetry code: (i) .

supplementary crystallographic information

Experimental

A solution of benzothiazole-2-thiol (167.2 mg, 1.00 mmol) and in acetone (15 ml) was slowly added to a solution of CH₂Cl₂ (170.0 mg, 2.00 mmol) in acetone (15 ml). The resultant solution was stirred and refluxed for 16 h and then filtered. Colorless crystals suitable for X-ray diffraction were obtained in about two weeks by slow diffusion of diethyl ether into a dilute solution of the title compound in methanol. yield: ca 35.8% (based on benzothiazole-2-thiol).

Refinement

The structure was solved using direct methods followed by Fourier synthesis. Non-H atoms were refined anisotropically. All of H atoms were placed in idealized positions (C—H = 0.93, 0.96 or 0.97 Å), forced to ride on the atom to which they are bonded, and were included in the refinement in the riding-model approximation. U_iso values were set equal to 1.5U_eq(parent atom) for methylic H atom and to 1.2U_eq(parent atom)for all other H atoms. Friedel opposites were merged as the data could not resolve the absolute structure and consequently, the Flack paarameter was not reported.

Figures

Fig. 1.

The structure of the title compound with 50% probability displacement ellipsoids.

Fig. 2.

View of right-handle helical chain connected by S···S contacts along b axis.

Fig. 3.

View of three-dimensional supermolecular network connected by S···S contacts and C—H···O hydrogen bonds along the c direction.

Crystal data

C11H11NOS2	F(000) = 496
Mr = 237.33	Dx = 1.387 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2911 reflections
a = 4.9457 (19) Å	θ = 2.7–22.7°
b = 11.586 (4) Å	µ = 0.44 mm−1
c = 19.830 (7) Å	T = 296 K
V = 1136.3 (7) Å3	Block, colorless
Z = 4	0.23 × 0.19 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer	1476 independent reflections
Radiation source: fine-focus sealed tube	1176 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −6→6
Tmin = 0.905, Tmax = 0.936	k = −14→14
12565 measured reflections	l = −25→25

Refinement

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0535P)2 + 0.413P] where P = (Fo2 + 2Fc2)/3
1476 reflections	(Δ/σ)max < 0.001
120 parameters	Δρmax = 0.27 e Å−3
2 restraints	Δρmin = −0.31 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C2	0.4190 (4)	−0.16020 (16)	0.16706 (8)	0.0559 (8)
C3	0.5987 (5)	−0.25022 (15)	0.15525 (10)	0.0688 (10)
H3	0.6161	−0.3094	0.1866	0.083*
C4	0.7524 (5)	−0.25173 (19)	0.09657 (12)	0.0762 (11)
H4	0.8726	−0.3120	0.0887	0.091*
C5	0.7264 (5)	−0.1632 (2)	0.04970 (10)	0.0727 (10)
H5	0.8293	−0.1642	0.0104	0.087*
C6	0.5468 (5)	−0.07320 (17)	0.06150 (9)	0.0635 (9)
H6	0.5294	−0.0140	0.0301	0.076*
C7	0.3931 (4)	−0.07169 (15)	0.12018 (10)	0.0517 (8)
S1	0.2105 (2)	−0.13581 (7)	0.23522 (4)	0.0652 (2)
S2	−0.1380 (2)	0.07257 (8)	0.23950 (6)	0.0796 (3)
O1	0.0395 (7)	0.3256 (2)	0.04435 (16)	0.0938 (9)
N1	0.2077 (6)	0.0109 (2)	0.13995 (13)	0.0527 (6)
C1	0.0920 (7)	−0.0080 (3)	0.20141 (17)	0.0563 (8)
C8	0.1402 (8)	0.1127 (2)	0.09994 (17)	0.0595 (9)
H8A	−0.0493	0.1312	0.1064	0.071*
H8B	0.1670	0.0953	0.0526	0.071*
C9	0.3097 (8)	0.2163 (3)	0.11870 (18)	0.0604 (9)
H9A	0.2941	0.2295	0.1668	0.072*
H9B	0.4978	0.1995	0.1089	0.072*
C10	0.2300 (5)	0.3236 (2)	0.08225 (17)	0.0677 (7)
C11	0.3976 (7)	0.4283 (2)	0.09581 (18)	0.0677 (7)
H11A	0.3297	0.4919	0.0699	0.102*
H11B	0.5818	0.4132	0.0833	0.102*
H11C	0.3892	0.4469	0.1429	0.102*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C2	0.0587 (19)	0.0440 (15)	0.0651 (18)	−0.0037 (15)	−0.0112 (17)	−0.0018 (14)
C3	0.071 (2)	0.0540 (17)	0.081 (2)	0.0062 (19)	−0.015 (2)	0.0014 (18)
C4	0.066 (2)	0.0627 (19)	0.100 (3)	0.010 (2)	−0.004 (2)	−0.011 (2)
C5	0.068 (2)	0.069 (2)	0.081 (2)	−0.005 (2)	0.008 (2)	−0.0089 (19)
C6	0.064 (2)	0.0609 (18)	0.066 (2)	−0.0031 (19)	−0.0016 (18)	0.0002 (17)
C7	0.0539 (19)	0.0446 (14)	0.0566 (16)	−0.0047 (15)	−0.0070 (16)	−0.0022 (13)
S1	0.0826 (6)	0.0508 (4)	0.0623 (4)	−0.0036 (5)	−0.0010 (5)	0.0044 (4)
S2	0.0827 (7)	0.0613 (5)	0.0950 (6)	−0.0010 (5)	0.0162 (6)	−0.0161 (5)
O1	0.0917 (17)	0.0742 (15)	0.115 (2)	0.0104 (17)	−0.0352 (14)	0.0259 (16)
N1	0.0536 (15)	0.0448 (12)	0.0598 (14)	−0.0007 (13)	−0.0075 (14)	0.0015 (11)
C1	0.0573 (19)	0.0456 (15)	0.0659 (18)	−0.0085 (16)	−0.0055 (18)	−0.0084 (14)
C8	0.058 (2)	0.0501 (15)	0.0710 (19)	0.0005 (16)	−0.0130 (17)	0.0067 (15)
C9	0.055 (2)	0.0501 (16)	0.076 (2)	0.0044 (17)	−0.0083 (19)	0.0091 (15)
C10	0.0791 (17)	0.0570 (12)	0.0671 (14)	0.0039 (15)	−0.0077 (12)	0.0097 (12)
C11	0.0791 (17)	0.0570 (12)	0.0671 (14)	0.0039 (15)	−0.0077 (12)	0.0097 (12)

Geometric parameters (Å, °)

C2—C3	1.3900	O1—C10	1.206 (4)
C2—C7	1.3900	N1—C1	1.364 (4)
C2—S1	1.724 (2)	N1—C8	1.460 (4)
C3—C4	1.3900	C8—C9	1.511 (4)
C3—H3	0.9300	C8—H8A	0.9700
C4—C5	1.3900	C8—H8B	0.9700
C4—H4	0.9300	C9—C10	1.491 (4)
C5—C6	1.3900	C9—H9A	0.9700
C5—H5	0.9300	C9—H9B	0.9700
C6—C7	1.3900	C10—C11	1.494 (4)
C6—H6	0.9300	C11—H11A	0.9600
C7—N1	1.382 (3)	C11—H11B	0.9600
S1—C1	1.728 (3)	C11—H11C	0.9600
S2—C1	1.654 (4)
C3—C2—C7	120.0	N1—C1—S1	110.0 (2)
C3—C2—S1	129.62 (11)	S2—C1—S1	122.7 (2)
C7—C2—S1	110.38 (11)	N1—C8—C9	112.4 (3)
C4—C3—C2	120.0	N1—C8—H8A	109.1
C4—C3—H3	120.0	C9—C8—H8A	109.1
C2—C3—H3	120.0	N1—C8—H8B	109.1
C3—C4—C5	120.0	C9—C8—H8B	109.1
C3—C4—H4	120.0	H8A—C8—H8B	107.9
C5—C4—H4	120.0	C10—C9—C8	113.4 (3)
C4—C5—C6	120.0	C10—C9—H9A	108.9
C4—C5—H5	120.0	C8—C9—H9A	108.9
C6—C5—H5	120.0	C10—C9—H9B	108.9
C7—C6—C5	120.0	C8—C9—H9B	108.9
C7—C6—H6	120.0	H9A—C9—H9B	107.7
C5—C6—H6	120.0	O1—C10—C9	121.6 (2)
N1—C7—C6	127.51 (16)	O1—C10—C11	122.1 (3)
N1—C7—C2	112.49 (16)	C9—C10—C11	116.3 (3)
C6—C7—C2	120.0	C10—C11—H11A	109.5
C2—S1—C1	92.25 (14)	C10—C11—H11B	109.5
C1—N1—C7	114.8 (2)	H11A—C11—H11B	109.5
C1—N1—C8	121.3 (3)	C10—C11—H11C	109.5
C7—N1—C8	123.8 (3)	H11A—C11—H11C	109.5
N1—C1—S2	127.3 (3)	H11B—C11—H11C	109.5
C7—C2—C3—C4	0.0	C2—C7—N1—C1	1.5 (3)
S1—C2—C3—C4	−178.85 (17)	C6—C7—N1—C8	0.9 (4)
C2—C3—C4—C5	0.0	C2—C7—N1—C8	−179.6 (2)
C3—C4—C5—C6	0.0	C7—N1—C1—S2	−179.4 (2)
C4—C5—C6—C7	0.0	C8—N1—C1—S2	1.7 (5)
C5—C6—C7—N1	179.5 (2)	C7—N1—C1—S1	−1.8 (3)
C5—C6—C7—C2	0.0	C8—N1—C1—S1	179.3 (2)
C3—C2—C7—N1	−179.6 (2)	C2—S1—C1—N1	1.2 (2)
S1—C2—C7—N1	−0.53 (18)	C2—S1—C1—S2	178.9 (2)
C3—C2—C7—C6	0.0	C1—N1—C8—C9	85.9 (4)
S1—C2—C7—C6	179.05 (14)	C7—N1—C8—C9	−93.0 (3)
C3—C2—S1—C1	178.56 (17)	N1—C8—C9—C10	−175.5 (3)
C7—C2—S1—C1	−0.38 (15)	C8—C9—C10—O1	3.4 (5)
C6—C7—N1—C1	−178.0 (2)	C8—C9—C10—C11	−177.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O1i	0.96	2.60	3.541 (5)	167

Symmetry codes: (i) x+1, y, z.