Crystal structure of (S)-1-(1,3-benzo­thia­zol-2-yl)-2,2,2-tri­fluoro­ethanol

Shishkina, S.V.; Kucher, O.V.; Kolodiazhnaya, A.O.; Smolii, O.B.; Tolmachev, A.A.

doi:10.1107/S1600536814016547

organic compounds

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Crystal structure of (S)-1-(1,3-benzothiazol-2-yl)-2,2,2-trifluoroethanol

Svitlana V. Shishkina,^a ^* Olexandr V. Kucher,^b Anastasiya O. Kolodiazhnaya,^b Oleg B. Smolii ^b and Andrey A. Tolmachev ^c

^aSTC "Institute for Single Crystals", National Academy of Sciences of Ukraine, 60 Lenina ave., Kharkiv 61001, Ukraine, ^bInstitute of Bioorganic Chemistry and Petrochemistry, National Academy of Science of Ukraine, 1 Murmanska St, Kyiv 02904, Ukraine, and ^cChemBioCenter, Kyiv National Taras Shevchenko University, 61 Chervonotkatska St, Kyiv 02094, Ukraine
^*Correspondence e-mail: sveta@xray.isc.kharkov.com

Edited by A. J. Lough, University of Toronto, Canada (Received 26 June 2014; accepted 16 July 2014; online 1 August 2014)

In the title compound, C₉H₆F₃NOS, the 1,3-benzothiazole ring system is essentially planar, with an r.m.s. deviation of 0.006 Å. In the crystal, molecules are linked via O—H⋯N hydrogen bonds, forming zigzag chains along [010].

Keywords: crystal structure; 1,3-benzothiazole; 2,2,2-trifluoroethanol; hydrogen bonding.

CCDC reference: 1014380

1. Related literature

For the synthesis of 1-substituted 2,2,2-trifluoroethanols from ketones, see: Yamazaki et al. (1993 ). For the enzymatic kinetic resolution of 1-substituted 2,2,2-trifluoroethanols, see: Omote et al. (2001 ); Xu et al. (2009 ). For the utilization of cinchonidine as a chiral solvating reagent, see: Kolodyazhnyi et al. (2006 ).

2. Experimental

2.1. Crystal data

C₉H₆F₃NOS
M_r = 233.21
Monoclinic, P 2₁
a = 9.2116 (9) Å
b = 5.5052 (4) Å
c = 10.2279 (8) Å
β = 107.411 (9)°
V = 494.91 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.20 × 0.05 × 0.05 mm

2.2. Data collection

Agilent Xcalibur3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012 ) T_min = 0.935, T_max = 0.983
4650 measured reflections
2768 independent reflections
2293 reflections with I > 2σ(I)
R_int = 0.027

2.3. Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.108
S = 1.12
2768 reflections
160 parameters
4 restraints
All H-atom parameters refined
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1199 Friedel pairs
Absolute structure parameter: −0.03 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1ⁱ	0.84 (4)	1.96 (4)	2.781 (2)	166 (4)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+2]$ .

Data collection: CrysAlis CCD (Agilent, 2012); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Agilent, 2012); 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.

Supporting information

CCDC reference: 1014380

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814016547/lh5717sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016547/lh5717Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814016547/lh5717Isup3.cml

checkCIF report

Comment top

2,2,2-Trifluoro-1-substituted ethanols attract attention as building blocks for introducing a chiral CF₃-containing motif into biologically active molecules and mimicking carboxylic groups. Among them, 2,2,2-trifluoro-1-heteroaryl ethanols, promising synthetic targets, have been poorly explored because of a lack of suitable procedures for obtaining the enantipure compounds from racemates. We have recently proposed a convenient procedure for enzyme-catalyzed kinetic resolution of racemic 2,2,2-trifluoro-1-heteroaryl ethanols on a series of 14 compounds. Herein, we report the crystal structure of (S)-1-(benzo[d]thiazol-2-yl)-2,2,2-trifluoroethanol (I) (Fig. 1). The non-centrosymmetric space group clearly confirms the presence of one enantiomer in the crystal. The absolute configuration of the chiral center at atom C8 (S-configuration) is determined using the value of the Flack parameter (-0.03 (9)). The substituent on the bicyclic fragment is oriented in such way that the hydroxyl group has a conformation intermediate between sp- and -sc- relative to the N1—C7 endocyclic bond (the N1—C7—C8—O1 torsion angle is -30.8 (3) °). The trifluoromethyl group is oriented in such way that the C9—F2 bond is anti-periplanar to the C7—C8 bond (the N1—C7—C8—C9 and C7—C8—C9—F2 torsion angles are 88.5 (3) ° and 177.3 (2) °, respectively). In the crystal, molecules are linked via O—H···N hydrogen bonds (Fig. 2) forming zigzag chains along [0 1 0].

Related literature top

For the synthesis of 1-substituted 2,2,2-trifluoroethanols from ketones, see: Yamazaki et al. (1993). For the enzymatic kinetic resolution of 1-substituted 2,2,2-trifluoroethanols, see: Omote et al. (2001); Xu et al. (2009). For the utilization of cinchonidine as a chiral solvating reagent, see: Kolodyazhnyi et al. (2006).

Experimental top

Synthesis of rac-1-(benzo[d]thiazol-2-yl)-2,2,2-trifluoroethanol: To a solution of 1-(benzo[d]thiazol-2-yl)-2,2,2-trifluoroethanone (115.5 g, 0.5 mol) in methanol (500 ml) sodium borohydride (18.9 g, 0.5 mol) was added in small portions, maintaining the temperature of the reaction mixture below 303K. The mixture was stirred at room temperature until completion of the reaction (monitored by TLC). The solvent was removed under reduced pressure; to the crude was added 200 ml of water and the aqueous solution was extracted with dichloromethane (3 × 150 ml). The organic phase was dried over Na₂SO₄ and evaporated yield the desired product. Yield: 114.2 g, 98%; white solid; m.p.: 377 K; ¹H NMR (400 MHz, CDCl₃): δ_H = 5.19 (qd, 1H, ³J_F,H = 7 Hz, ³J_H,H = 7 Hz, CH), 6.98–7.08 (m, 2H, PhH), 7.48 (d, 1H, ³J_H,H = 7 Hz, OH), 7.56 (d, 1H, ³J_H,H = 7.6 Hz, PhH), 7.66 (d, 1H, ³J_H,H = 8 Hz, PhH); ¹³C NMR (125 MHz, APT, CDCl₃): δ_C = 69.4 (q, ²J_F,_C = 32 Hz, CH), 122.4 (PhH), 123.1 (PhH), 123.7 (q, ¹J_F,_C = 282 Hz, CF₃), 125.7 (PhH), 126.4 (PhH), 134.4 (C Ar), 152.7 (C Ar), 167.7 (C Ar); MS (APCI) m/z calculated for C₉H₇F₃NOS 234.0 [M+H]⁺, found 234.0.

Kinetic resolution of rac-1-(benzo[d]thiazol-2-yl)-2,2,2-trifluoroethanol with vinyl acetate and Burkholderia cepacia lipase: The racemic alcohol (11.4 g, 0.05 mol) and vinyl acetate (14.3 ml, 0.15 mol) were dissolved in TBME (250 ml) following by addition of Burkholderia cepacia lipase (6 g). The obtained mixture was incubated at 323 K, the progress of the reaction was monitored by the cinchonidine method (Kolodyazhnyi et al., 2006). Then, the enzyme was filtered off, washed with TBME and the combined TBME fractions were evaporated. The unacylated (S)-alcohol was separated from the (R)-ester by column chromatography (SiO₂, eluent: AcOEt/hexanes gradually changed from 1:20 to 1:1 (v/v)). The white needle-like crystals of the (S)-alcohol were formed after 1 week upon crystallization from chloroform.

Computing details top

Data collection: CrysAlis CCD (Agilent, 2012); cell refinement: CrysAlis CCD (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown by dashed lines. Only H atoms involved in H-bonds are shown.

(S)-1-(1,3-Benzothiazol-2-yl)-2,2,2-trifluoroethanol top

Crystal data top

C₉H₆F₃NOS	F(000) = 236
M_r = 233.21	D_x = 1.565 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1591 reflections
a = 9.2116 (9) Å	θ = 3.5–31.8°
b = 5.5052 (4) Å	µ = 0.34 mm⁻¹
c = 10.2279 (8) Å	T = 293 K
β = 107.411 (9)°	Needle, colourless
V = 494.91 (7) Å³	0.20 × 0.05 × 0.05 mm
Z = 2

Data collection top

Agilent Xcalibur3 diffractometer	2768 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2293 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.1827 pixels mm^-1	θ_max = 30.0°, θ_min = 3.6°
ω scans	h = −10→12
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	k = −7→7
T_min = 0.935, T_max = 0.983	l = −13→14
4650 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	All H-atom parameters refined
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0494P)²] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2768 reflections	Δρ_max = 0.21 e Å⁻³
160 parameters	Δρ_min = −0.20 e Å⁻³
4 restraints	Absolute structure: Flack (1983), 1199 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (9)

Crystal data top

C₉H₆F₃NOS	V = 494.91 (7) Å³
M_r = 233.21	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.2116 (9) Å	µ = 0.34 mm⁻¹
b = 5.5052 (4) Å	T = 293 K
c = 10.2279 (8) Å	0.20 × 0.05 × 0.05 mm
β = 107.411 (9)°

Data collection top

Agilent Xcalibur3 diffractometer	2768 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	2293 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.983	R_int = 0.027
4650 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	All H-atom parameters refined
wR(F²) = 0.108	Δρ_max = 0.21 e Å⁻³
S = 1.12	Δρ_min = −0.20 e Å⁻³
2768 reflections	Absolute structure: Flack (1983), 1199 Friedel pairs
160 parameters	Absolute structure parameter: −0.03 (9)
4 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.84725 (19)	0.5557 (5)	0.85264 (17)	0.0991 (7)
F2	0.89881 (19)	0.5084 (6)	1.06943 (16)	0.1122 (8)
F3	0.7640 (2)	0.2434 (2)	0.9323 (2)	0.0913 (6)
S1	0.51635 (7)	0.81353 (17)	0.68465 (5)	0.05600 (17)
N1	0.4284 (2)	0.4285 (3)	0.78357 (16)	0.0454 (4)
O1	0.5967 (2)	0.5338 (3)	1.05476 (15)	0.0604 (4)
H1O	0.582 (4)	0.637 (7)	1.110 (3)	0.088 (11)*
C1	0.3304 (2)	0.4556 (4)	0.65070 (19)	0.0434 (4)
C2	0.2101 (3)	0.3050 (6)	0.5878 (2)	0.0579 (5)
H2	0.189 (3)	0.176 (5)	0.643 (2)	0.046 (6)*
C3	0.1234 (3)	0.3593 (6)	0.4559 (3)	0.0651 (7)
H3	0.050 (4)	0.253 (7)	0.424 (3)	0.089 (11)*
C4	0.1525 (3)	0.5594 (6)	0.3878 (2)	0.0634 (7)
H4	0.093 (3)	0.582 (6)	0.293 (3)	0.067 (8)*
C5	0.2713 (3)	0.7138 (5)	0.4479 (2)	0.0569 (6)
H5	0.299 (3)	0.864 (7)	0.408 (3)	0.072 (9)*
C6	0.3606 (3)	0.6586 (4)	0.5814 (2)	0.0463 (5)
C7	0.5280 (3)	0.6011 (4)	0.81243 (18)	0.0440 (4)
C8	0.6483 (3)	0.6243 (5)	0.9503 (2)	0.0511 (5)
H8	0.689 (2)	0.799 (5)	0.976 (2)	0.044 (5)*
C9	0.7885 (2)	0.4822 (3)	0.95081 (14)	0.0689 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0638 (10)	0.153 (2)	0.0853 (11)	−0.0105 (12)	0.0298 (9)	−0.0049 (12)
F2	0.0743 (11)	0.165 (2)	0.0710 (10)	0.0026 (14)	−0.0187 (9)	−0.0216 (13)
F3	0.0854 (12)	0.0762 (13)	0.1038 (13)	0.0216 (10)	0.0154 (10)	−0.0137 (9)
S1	0.0703 (3)	0.0513 (3)	0.0463 (3)	−0.0111 (3)	0.0173 (2)	0.0057 (2)
N1	0.0535 (10)	0.0439 (9)	0.0372 (8)	−0.0022 (8)	0.0111 (7)	0.0016 (6)
O1	0.0912 (13)	0.0530 (10)	0.0380 (7)	−0.0013 (9)	0.0208 (7)	−0.0040 (7)
C1	0.0462 (10)	0.0442 (10)	0.0392 (9)	0.0031 (8)	0.0120 (7)	0.0018 (8)
C2	0.0510 (11)	0.0607 (13)	0.0571 (12)	−0.0075 (13)	0.0088 (9)	0.0033 (13)
C3	0.0495 (13)	0.078 (2)	0.0591 (13)	0.0007 (13)	0.0028 (10)	−0.0055 (13)
C4	0.0573 (13)	0.0851 (19)	0.0413 (11)	0.0148 (13)	0.0047 (9)	−0.0017 (11)
C5	0.0678 (15)	0.0633 (14)	0.0416 (11)	0.0140 (12)	0.0195 (10)	0.0101 (10)
C6	0.0545 (12)	0.0476 (11)	0.0392 (9)	0.0058 (9)	0.0177 (8)	0.0028 (8)
C7	0.0532 (11)	0.0427 (10)	0.0363 (9)	−0.0023 (9)	0.0137 (8)	−0.0020 (7)
C8	0.0655 (14)	0.0476 (12)	0.0369 (10)	−0.0071 (10)	0.0102 (9)	−0.0073 (8)
C9	0.0584 (15)	0.089 (2)	0.0496 (13)	−0.0059 (15)	0.0011 (10)	−0.0111 (13)

Geometric parameters (Å, º) top

F1—C9	1.3382 (10)	C2—C3	1.379 (3)
F2—C9	1.3372 (10)	C2—H2	0.96 (3)
F3—C9	1.3376 (10)	C3—C4	1.372 (4)
S1—C6	1.731 (2)	C3—H3	0.88 (4)
S1—C7	1.733 (2)	C4—C5	1.377 (4)
N1—C7	1.292 (3)	C4—H4	0.96 (3)
N1—C1	1.396 (2)	C5—C6	1.400 (3)
O1—C8	1.385 (3)	C5—H5	0.99 (4)
O1—H1O	0.84 (4)	C7—C8	1.516 (3)
C1—C2	1.379 (3)	C8—C9	1.509 (3)
C1—C6	1.395 (3)	C8—H8	1.04 (3)

C6—S1—C7	88.89 (10)	C1—C6—C5	121.4 (2)
C7—N1—C1	110.59 (17)	C1—C6—S1	109.85 (15)
C8—O1—H1O	116 (3)	C5—C6—S1	128.7 (2)
C2—C1—C6	119.94 (19)	N1—C7—C8	123.09 (18)
C2—C1—N1	125.8 (2)	N1—C7—S1	116.39 (14)
C6—C1—N1	114.27 (18)	C8—C7—S1	120.51 (17)
C1—C2—C3	118.3 (3)	O1—C8—C9	107.55 (18)
C1—C2—H2	116.4 (13)	O1—C8—C7	111.31 (19)
C3—C2—H2	125.0 (14)	C9—C8—C7	110.22 (16)
C4—C3—C2	121.8 (3)	O1—C8—H8	108.9 (11)
C4—C3—H3	126 (2)	C9—C8—H8	103.3 (13)
C2—C3—H3	112 (2)	C7—C8—H8	115.0 (12)
C3—C4—C5	121.3 (2)	F2—C9—F3	106.5 (2)
C3—C4—H4	118.2 (19)	F2—C9—F1	106.24 (18)
C5—C4—H4	120.3 (18)	F3—C9—F1	106.3 (2)
C4—C5—C6	117.2 (2)	F2—C9—C8	111.38 (19)
C4—C5—H5	127.0 (15)	F3—C9—C8	113.65 (17)
C6—C5—H5	115.7 (16)	F1—C9—C8	112.25 (18)

C7—N1—C1—C2	−179.2 (2)	C1—N1—C7—C8	178.7 (2)
C7—N1—C1—C6	−0.5 (3)	C1—N1—C7—S1	−0.2 (2)
C6—C1—C2—C3	0.8 (4)	C6—S1—C7—N1	0.62 (18)
N1—C1—C2—C3	179.4 (2)	C6—S1—C7—C8	−178.34 (19)
C1—C2—C3—C4	−1.1 (4)	N1—C7—C8—O1	−30.8 (3)
C2—C3—C4—C5	0.9 (4)	S1—C7—C8—O1	148.13 (17)
C3—C4—C5—C6	−0.3 (4)	N1—C7—C8—C9	88.5 (3)
C2—C1—C6—C5	−0.2 (3)	S1—C7—C8—C9	−92.6 (2)
N1—C1—C6—C5	−179.1 (2)	O1—C8—C9—F2	−61.2 (2)
C2—C1—C6—S1	179.74 (19)	C7—C8—C9—F2	177.3 (2)
N1—C1—C6—S1	0.9 (2)	O1—C8—C9—F3	59.1 (2)
C4—C5—C6—C1	0.0 (4)	C7—C8—C9—F3	−62.4 (2)
C4—C5—C6—S1	−180.0 (2)	O1—C8—C9—F1	179.82 (18)
C7—S1—C6—C1	−0.83 (16)	C7—C8—C9—F1	58.3 (2)
C7—S1—C6—C5	179.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1ⁱ	0.84 (4)	1.96 (4)	2.781 (2)	166 (4)

Symmetry code: (i) −x+1, y+1/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1ⁱ	0.84 (4)	1.96 (4)	2.781 (2)	166 (4)

Symmetry code: (i) −x+1, y+1/2, −z+2.

References

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