An ortho­rhom­bic polymorph of 2-(1,3-benzothia­zol-2-yl)-6-eth­oxy­phenol

Abstract

In the title mol­ecule, C₁₅H₁₃NO₂S, an intra­molecular O—H⋯N hydrogen bond forms an S(6) ring motif. The benzothia­zole ring system and the benzene ring form a dihedral angle of 8.9 (3) Å. In the crystal, mol­ecules are linked by weak C—H⋯O hydrogen bonds, forming chains along the b axis. In addition, π–π inter­actions [centroid–centroid distances = 3.772 (4) and 3.879 (4) Å] are observed.

Related literature  

For the monoclinic polymorph, see: Lakshmanan et al. (2011 ▶). For background to and examples of the structures of Schiff base ligands see: Kargar et al. (2011 ▶); Kia et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental  

Crystal data  

• C₁₅H₁₃NO₂S

• M _r = 271.32

• Orthorhombic,

• a = 4.8728 (10) Å

• b = 11.711 (3) Å

• c = 23.378 (6) Å

• V = 1334.1 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.24 mm⁻¹

• T = 296 K

• 0.33 × 0.23 × 0.21 mm

Data collection  

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.925, T _max = 0.952

• 4083 measured reflections

• 2239 independent reflections

• 1207 reflections with I > 2σ(I)

• R _int = 0.073

Refinement  

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 0.144

• S = 0.99

• 2239 reflections

• 173 parameters

• H-atom parameters constrained

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

• Absolute structure: Flack (1983 ▶), 874 Friedel pairs

• Flack parameter: −0.1 (2)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812033879/lh5505Isup3.cml

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
O1—H1⋯N1	0.88	1.76	2.592 (6)	158
C2—H2⋯O1i	0.93	2.55	3.372 (8)	148

Symmetry code: (i) .

supplementary crystallographic information

Comment

In continuation of our work on the crystal structures of Schiff base ligands from different substituted salicylaldehyde and amines (Kargar et al., 2011; Kia et al., 2010), we have determined the X-ray structure of the title compound. The crystal structure of a monoclinic polymorph of the title compound has already been published (Lakshmanan et al., 2011).

The molecular structure of the title compound is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. An intramolecular O—H···N hydrogen bond forms a S(6) ring motif (Bernstein et al., 1995). In the crystal, molecules are linked by weak intermolecular C—H···O hydrogen bonds forming one-dimensional chains along the b axis (Table 2, Fig. 2). In addition, weak intermolecular π–π interactions are observed [Cg1···Cg2ⁱⁱ = 3.772 (4) Å, (ii) -1 + x, y, z; Cg1···Cg3ⁱⁱⁱ = 3.879 (4), (iii) 1 + x, y, z, Cg1, Cg2 and Cg3 are centroid of S1/C1/C6/N1/C7, C1–C6, and C8–C13 rings].

Experimental

The title compound was synthesized by adding 3-ethoxysalicylaldehyde (2 mmol) to a solution of 2-aminothiophenol (2mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant solution was filtered. Light-yellow prismatic single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent at room temperature over several days.

Refinement

The O-bound H atom was located in a difference Fourier map and constrained to refine on the parent atom with U_iso(H) = 1.5U_eq(O). The other H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.93, 0.97 and 0.96 Å for CH, CH₂ and CH₃ H-atoms, respectively, with U_iso (H) = k × U_eq(C), k = 1.2 for CH, CH₂ and 1.5 for CH₃.

Figures

Fig. 1.

The molecular structure of the title compound, showing 40% probability displacement ellipsoids. The dashed line indicates an intramolecular hydrogen bond.

Fig. 2.

Part of the crystal structure with weak hydrogen bonds shown as dashed lines.

Crystal data

C15H13NO2S	F(000) = 568
Mr = 271.32	Dx = 1.351 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 864 reflections
a = 4.8728 (10) Å	θ = 2.5–28.8°
b = 11.711 (3) Å	µ = 0.24 mm−1
c = 23.378 (6) Å	T = 296 K
V = 1334.1 (6) Å3	Prism, light-yellow
Z = 4	0.33 × 0.23 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer	2239 independent reflections
Radiation source: fine-focus sealed tube	1207 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −3→5
Tmin = 0.925, Tmax = 0.952	k = −9→13
4083 measured reflections	l = −27→19

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068	H-atom parameters constrained
wR(F2) = 0.144	w = 1/[σ2(Fo2) + (0.0413P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max < 0.001
2239 reflections	Δρmax = 0.19 e Å−3
173 parameters	Δρmin = −0.30 e Å−3
0 restraints	Absolute structure: Flack (1983), 874 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.1 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	1.2770 (11)	0.2177 (4)	0.2096 (3)	0.0485 (16)
C2	1.4128 (13)	0.1882 (5)	0.1606 (3)	0.0647 (19)
H2	1.3725	0.1196	0.1423	0.078*
C3	1.6064 (14)	0.2590 (6)	0.1386 (3)	0.073 (2)
H3	1.6970	0.2397	0.1049	0.087*
C4	1.6692 (13)	0.3614 (6)	0.1667 (3)	0.0670 (18)
H4	1.8030	0.4093	0.1516	0.080*
C5	1.5378 (14)	0.3923 (5)	0.2160 (3)	0.0599 (17)
H5	1.5816	0.4606	0.2342	0.072*
C6	1.3392 (11)	0.3211 (5)	0.2386 (3)	0.0458 (15)
N1	1.1883 (9)	0.3431 (4)	0.2872 (2)	0.0468 (12)
C8	0.8322 (12)	0.2602 (5)	0.3462 (3)	0.0509 (16)
C9	0.8043 (12)	0.3576 (5)	0.3797 (3)	0.0530 (16)
C10	0.6091 (12)	0.3608 (6)	0.4232 (3)	0.0603 (17)
C11	0.4481 (14)	0.2664 (6)	0.4350 (3)	0.0664 (19)
H11	0.3218	0.2685	0.4648	0.080*
C12	0.4756 (15)	0.1698 (6)	0.4026 (3)	0.0686 (18)
H12	0.3661	0.1067	0.4105	0.082*
C13	0.6598 (12)	0.1642 (5)	0.3590 (3)	0.0568 (16)
H13	0.6740	0.0979	0.3373	0.068*
C14	0.3939 (15)	0.4754 (6)	0.4949 (3)	0.084 (2)
H14A	0.4162	0.4185	0.5246	0.101*
H14B	0.2133	0.4663	0.4780	0.101*
C15	0.4237 (18)	0.5927 (7)	0.5194 (3)	0.118 (3)
H15A	0.6144	0.6088	0.5257	0.176*
H15B	0.3265	0.5970	0.5551	0.176*
H15C	0.3492	0.6476	0.4932	0.176*
C7	1.0189 (12)	0.2585 (4)	0.2991 (2)	0.0472 (15)
O1	0.9557 (8)	0.4529 (3)	0.37058 (16)	0.0633 (12)
H1	1.0595	0.4317	0.3417	0.095*
O2	0.5994 (9)	0.4617 (4)	0.45248 (18)	0.0741 (13)
S1	1.0285 (3)	0.14638 (12)	0.24914 (8)	0.0574 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.039 (4)	0.049 (4)	0.057 (4)	0.007 (3)	−0.008 (3)	0.004 (3)
C2	0.064 (5)	0.063 (4)	0.067 (5)	0.008 (4)	−0.006 (4)	−0.003 (4)
C3	0.065 (5)	0.088 (6)	0.064 (5)	0.004 (4)	0.007 (4)	0.009 (5)
C4	0.064 (4)	0.063 (5)	0.074 (5)	−0.013 (4)	−0.008 (4)	0.019 (4)
C5	0.066 (5)	0.048 (4)	0.066 (4)	−0.001 (4)	−0.012 (4)	0.003 (4)
C6	0.038 (3)	0.036 (3)	0.063 (5)	0.005 (3)	−0.005 (3)	0.009 (3)
N1	0.040 (3)	0.036 (3)	0.064 (3)	−0.001 (3)	−0.010 (3)	0.001 (3)
C8	0.043 (4)	0.045 (4)	0.065 (4)	0.001 (3)	−0.010 (3)	0.008 (4)
C9	0.043 (4)	0.049 (4)	0.067 (5)	0.005 (3)	−0.006 (3)	0.018 (4)
C10	0.055 (4)	0.066 (4)	0.060 (4)	0.005 (4)	−0.006 (3)	−0.001 (4)
C11	0.055 (5)	0.076 (5)	0.068 (5)	−0.005 (4)	0.002 (4)	0.010 (4)
C12	0.063 (4)	0.065 (5)	0.078 (5)	−0.011 (4)	−0.004 (4)	0.019 (4)
C13	0.057 (4)	0.041 (4)	0.072 (5)	−0.006 (4)	−0.008 (4)	0.008 (4)
C14	0.083 (6)	0.105 (6)	0.063 (5)	0.004 (5)	0.014 (4)	−0.007 (5)
C15	0.142 (8)	0.116 (7)	0.095 (6)	0.016 (6)	0.027 (6)	−0.035 (5)
C7	0.046 (4)	0.038 (3)	0.057 (4)	0.008 (3)	−0.015 (3)	0.000 (3)
O1	0.066 (3)	0.045 (2)	0.078 (3)	0.000 (2)	0.011 (2)	−0.004 (2)
O2	0.073 (3)	0.077 (3)	0.072 (3)	−0.004 (3)	0.015 (3)	−0.007 (3)
S1	0.0528 (9)	0.0410 (7)	0.0784 (11)	−0.0014 (8)	−0.0047 (10)	−0.0030 (10)

Geometric parameters (Å, º)

C1—C2	1.368 (8)	C9—C10	1.393 (7)
C1—C6	1.421 (7)	C10—O2	1.366 (7)
C1—S1	1.737 (6)	C10—C11	1.384 (8)
C2—C3	1.358 (8)	C11—C12	1.368 (8)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.402 (8)	C12—C13	1.360 (8)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.368 (8)	C13—H13	0.9300
C4—H4	0.9300	C14—O2	1.418 (7)
C5—C6	1.382 (7)	C14—C15	1.496 (9)
C5—H5	0.9300	C14—H14A	0.9700
C6—N1	1.377 (7)	C14—H14B	0.9700
N1—C7	1.318 (6)	C15—H15A	0.9600
C8—C9	1.391 (8)	C15—H15B	0.9600
C8—C7	1.428 (7)	C15—H15C	0.9600
C8—C13	1.435 (8)	C7—S1	1.758 (5)
C9—O1	1.355 (6)	O1—H1	0.8797
C2—C1—C6	120.8 (6)	C12—C11—C10	119.7 (6)
C2—C1—S1	131.4 (5)	C12—C11—H11	120.2
C6—C1—S1	107.7 (4)	C10—C11—H11	120.2
C3—C2—C1	120.0 (6)	C13—C12—C11	121.3 (6)
C3—C2—H2	120.0	C13—C12—H12	119.3
C1—C2—H2	120.0	C11—C12—H12	119.3
C2—C3—C4	119.7 (6)	C12—C13—C8	120.3 (6)
C2—C3—H3	120.1	C12—C13—H13	119.8
C4—C3—H3	120.1	C8—C13—H13	119.8
C5—C4—C3	121.4 (6)	O2—C14—C15	107.7 (6)
C5—C4—H4	119.3	O2—C14—H14A	110.2
C3—C4—H4	119.3	C15—C14—H14A	110.2
C4—C5—C6	119.4 (6)	O2—C14—H14B	110.2
C4—C5—H5	120.3	C15—C14—H14B	110.2
C6—C5—H5	120.3	H14A—C14—H14B	108.5
N1—C6—C5	125.2 (6)	C14—C15—H15A	109.5
N1—C6—C1	116.0 (5)	C14—C15—H15B	109.5
C5—C6—C1	118.7 (5)	H15A—C15—H15B	109.5
C7—N1—C6	111.6 (5)	C14—C15—H15C	109.5
C9—C8—C7	120.5 (5)	H15A—C15—H15C	109.5
C9—C8—C13	117.9 (6)	H15B—C15—H15C	109.5
C7—C8—C13	121.5 (6)	N1—C7—C8	123.4 (5)
O1—C9—C8	122.2 (5)	N1—C7—S1	113.9 (4)
O1—C9—C10	117.7 (6)	C8—C7—S1	122.6 (5)
C8—C9—C10	120.0 (6)	C9—O1—H1	101.7
O2—C10—C11	124.9 (6)	C10—O2—C14	118.2 (5)
O2—C10—C9	114.3 (6)	C1—S1—C7	90.7 (3)
C11—C10—C9	120.7 (6)
C6—C1—C2—C3	−1.2 (8)	C8—C9—C10—C11	2.3 (9)
S1—C1—C2—C3	−178.3 (5)	O2—C10—C11—C12	179.8 (6)
C1—C2—C3—C4	1.0 (9)	C9—C10—C11—C12	−1.8 (9)
C2—C3—C4—C5	−0.5 (10)	C10—C11—C12—C13	0.4 (10)
C3—C4—C5—C6	0.1 (9)	C11—C12—C13—C8	0.5 (10)
C4—C5—C6—N1	−178.7 (5)	C9—C8—C13—C12	0.1 (9)
C4—C5—C6—C1	−0.3 (8)	C7—C8—C13—C12	−177.2 (6)
C2—C1—C6—N1	179.4 (5)	C6—N1—C7—C8	−178.1 (5)
S1—C1—C6—N1	−2.9 (6)	C6—N1—C7—S1	−1.6 (6)
C2—C1—C6—C5	0.8 (8)	C9—C8—C7—N1	5.5 (8)
S1—C1—C6—C5	178.6 (4)	C13—C8—C7—N1	−177.3 (5)
C5—C6—N1—C7	−178.6 (5)	C9—C8—C7—S1	−170.7 (4)
C1—C6—N1—C7	3.0 (6)	C13—C8—C7—S1	6.6 (8)
C7—C8—C9—O1	−1.9 (8)	C11—C10—O2—C14	−5.8 (9)
C13—C8—C9—O1	−179.3 (5)	C9—C10—O2—C14	175.7 (5)
C7—C8—C9—C10	175.9 (5)	C15—C14—O2—C10	−178.9 (6)
C13—C8—C9—C10	−1.5 (8)	C2—C1—S1—C7	179.0 (6)
O1—C9—C10—O2	−1.2 (8)	C6—C1—S1—C7	1.5 (4)
C8—C9—C10—O2	−179.1 (5)	N1—C7—S1—C1	0.0 (4)
O1—C9—C10—C11	−179.8 (5)	C8—C7—S1—C1	176.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.88	1.76	2.592 (6)	158
C2—H2···O1i	0.93	2.55	3.372 (8)	148

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