1-(2,4-Difluoro­phen­yl)-2-(1H-1,2,4-triazol-1-yl)ethanol

Liu, D.; Li, C.; Tian, X.; Li, S.; Xiao, T.

doi:10.1107/S1600536812001110

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o431

doi:10.1107/S1600536812001110

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1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanol

Dong-liang Liu,^a Chen Li,^a Xin Tian,^a Song Li ^a and Tao Xiao ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: taoxiao@njut.edu.cn

(Received 4 January 2012; accepted 10 January 2012; online 18 January 2012)

In the title compound, C₁₀H₉F₂N₃O, the dihedral angle between the rings is 22.90 (4)°. In the crystal, C—H⋯F and O—H⋯N hydrogen bonds link the molecules into chains along [010].

Related literature

For related compounds containing a 2-(1H-1,2,4-triazol-1-yl)-1-phenylethanol fragment, see: Bu et al. (2000 ). For related structures, see: Tao et al. (2007 ); Liu et al. (2011 ); Yu et al. (2011 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₉F₂N₃O
M_r = 225.20
Monoclinic, C 2/c
a = 14.261 (3) Å
b = 5.6150 (11) Å
c = 25.823 (5) Å
β = 94.84 (3)°
V = 2060.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.964, T_max = 0.988
1969 measured reflections
1886 independent reflections
1059 reflections with I > 2σ(I)
R_int = 0.035
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.143
S = 1.01
1886 reflections
148 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O—H0A⋯N3ⁱ	0.83 (3)	1.98 (3)	2.794 (3)	169 (3)
C8—H8B⋯F2ⁱⁱ	0.97	2.46	3.388 (4)	159
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001110/zq2149sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001110/zq2149Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812001110/zq2149Isup3.cml

checkCIF report

Comment top

The title compound, C₁₀H₉O₁N₃F₂, is the key intermediate in the synthesis of a new kind of antifungal drug (Bu et al., 2000). We previously reported the crystal structures of similar compounds (Tao et al., 2007; Liu et al., 2011; Yu et al., 2011). The X-ray diffraction study has been carried out in order to elucidate the molecular conformation.We report here its crystal structure (Fig. 1). The bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the ring A (N1/N2/C9—C11) and B (C1—C6) is 22.90 (4)°. In the crystal, intermolecular C—H···F and O—H···N hydrogen bonds link the molecules into one-dimensional [010] chains (Fig. 2).

Related literature top

For related compounds containing a 2-(1H-1,2,4-triazol-1-yl)-1-phenylethanol fragment, see: Bu et al. (2000). For related structures, see: Tao et al. (2007); Liu et al. (2011); Yu et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

A mixture of 1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone (2.25 g, 10 mol), sodium borohydride (0.756 g, 20 mmol) and 30 ml dry ethanol was refluxed for 3 h. After solvent evaporation, the mixture was neutralized with dilute hydrochloric acid and then refluxed for 30 min. After the mixture was cooled, the solution was alkalinized with sodium hydroxide, the precipitate collected and recrystallized with ethanol, and a yellow deposit was obtain (m.p. 395–396 K). Crystals suitable for X-ray analysis were obtained by dissolving the crude product (1.0 g) in ethanol (30 ml) and then allowing the solution to evaporate slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanol top

Crystal data top

C₁₀H₉F₂N₃O	F(000) = 928
M_r = 225.20	D_x = 1.452 Mg m⁻³
Monoclinic, C2/c	Melting point: 395 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 14.261 (3) Å	Cell parameters from 25 reflections
b = 5.6150 (11) Å	θ = 9–13°
c = 25.823 (5) Å	µ = 0.12 mm⁻¹
β = 94.84 (3)°	T = 293 K
V = 2060.4 (7) Å³	Prism, colourless
Z = 8	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1059 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 25.4°, θ_min = 1.6°
ω/2θ scans	h = 0→17
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.964, T_max = 0.988	l = −31→30
1969 measured reflections	3 standard reflections every 200 reflections
1886 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.070P)²] where P = (F_o² + 2F_c²)/3
1886 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.17 e Å⁻³
3 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₀H₉F₂N₃O	V = 2060.4 (7) Å³
M_r = 225.20	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.261 (3) Å	µ = 0.12 mm⁻¹
b = 5.6150 (11) Å	T = 293 K
c = 25.823 (5) Å	0.30 × 0.10 × 0.10 mm
β = 94.84 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1059 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.035
T_min = 0.964, T_max = 0.988	3 standard reflections every 200 reflections
1969 measured reflections	intensity decay: 1%
1886 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	3 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.17 e Å⁻³
1886 reflections	Δρ_min = −0.15 e Å⁻³
148 parameters

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
O	0.06636 (12)	0.1378 (4)	0.69742 (7)	0.0730 (6)
H0A	0.080 (2)	0.037 (5)	0.7204 (11)	0.088*
N1	0.25384 (13)	0.1969 (4)	0.66832 (7)	0.0604 (6)
F1	−0.20749 (13)	−0.0256 (4)	0.49804 (8)	0.1263 (8)
C1	−0.05951 (18)	0.1696 (6)	0.60844 (11)	0.0895 (10)
H1A	−0.0572	0.2907	0.6331	0.107*
F2	0.07930 (15)	−0.3219 (4)	0.57292 (8)	0.1337 (9)
N2	0.30591 (16)	0.0018 (5)	0.68043 (10)	0.0848 (8)
C2	−0.13473 (19)	0.1639 (7)	0.57217 (12)	0.0971 (11)
H2B	−0.1831	0.2752	0.5718	0.117*
N3	0.36133 (15)	0.3146 (5)	0.72719 (8)	0.0787 (7)
C3	−0.1347 (2)	−0.0224 (7)	0.53496 (12)	0.0873 (10)
C4	−0.0688 (2)	−0.1827 (6)	0.53470 (12)	0.1006 (11)
H4A	−0.0714	−0.3041	0.5101	0.121*
C5	0.0087 (2)	−0.1631 (5)	0.57445 (11)	0.0821 (9)
C6	0.01250 (17)	0.0092 (5)	0.61091 (9)	0.0617 (7)
C7	0.09468 (17)	0.0301 (5)	0.65216 (9)	0.0604 (7)
H7A	0.1195	−0.1292	0.6607	0.072*
C8	0.17176 (16)	0.1809 (5)	0.63143 (9)	0.0686 (7)
H8A	0.1898	0.1118	0.5993	0.082*
H8B	0.1477	0.3397	0.6238	0.082*
C9	0.36890 (19)	0.0821 (6)	0.71531 (12)	0.0851 (9)
H9A	0.4161	−0.0143	0.7311	0.102*
C10	0.2871 (2)	0.3760 (5)	0.69662 (11)	0.0760 (8)
H10A	0.2613	0.5282	0.6952	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0753 (11)	0.0893 (15)	0.0522 (10)	0.0145 (11)	−0.0081 (8)	0.0017 (10)
N1	0.0569 (11)	0.0675 (13)	0.0548 (12)	0.0103 (11)	−0.0083 (9)	−0.0079 (11)
F1	0.1093 (14)	0.1456 (18)	0.1112 (15)	−0.0102 (13)	−0.0652 (12)	0.0063 (13)
C1	0.0722 (17)	0.121 (3)	0.0707 (18)	0.0322 (19)	−0.0212 (14)	−0.0251 (19)
F2	0.1684 (18)	0.0919 (14)	0.1278 (16)	0.0621 (14)	−0.0645 (14)	−0.0378 (12)
N2	0.0710 (14)	0.0808 (16)	0.0969 (18)	0.0165 (13)	−0.0257 (13)	−0.0199 (14)
C2	0.0697 (17)	0.141 (3)	0.0767 (19)	0.039 (2)	−0.0157 (15)	−0.005 (2)
N3	0.0761 (15)	0.095 (2)	0.0616 (13)	−0.0125 (14)	−0.0126 (11)	−0.0080 (13)
C3	0.0747 (19)	0.104 (2)	0.078 (2)	−0.0099 (19)	−0.0289 (16)	0.0163 (19)
C4	0.127 (3)	0.073 (2)	0.091 (2)	−0.002 (2)	−0.051 (2)	−0.0071 (18)
C5	0.101 (2)	0.0584 (17)	0.0804 (19)	0.0165 (17)	−0.0334 (16)	−0.0083 (15)
C6	0.0612 (14)	0.0680 (16)	0.0533 (14)	0.0083 (14)	−0.0098 (11)	0.0007 (13)
C7	0.0643 (14)	0.0636 (16)	0.0506 (13)	0.0115 (12)	−0.0114 (11)	−0.0024 (12)
C8	0.0683 (15)	0.0824 (18)	0.0519 (13)	0.0105 (14)	−0.0147 (11)	0.0038 (14)
C9	0.0644 (17)	0.102 (3)	0.084 (2)	0.0084 (17)	−0.0214 (15)	−0.0041 (19)
C10	0.0809 (18)	0.0693 (18)	0.0763 (19)	−0.0009 (15)	−0.0025 (15)	−0.0094 (16)

Geometric parameters (Å, º) top

O—C7	1.405 (3)	N3—C10	1.312 (3)
O—H0A	0.83 (3)	N3—C9	1.347 (4)
N1—C10	1.308 (3)	C3—C4	1.302 (4)
N1—N2	1.345 (3)	C4—C5	1.448 (3)
N1—C8	1.448 (3)	C4—H4A	0.9300
F1—C3	1.349 (3)	C5—C6	1.348 (3)
C1—C6	1.363 (3)	C6—C7	1.520 (3)
C1—C2	1.364 (3)	C7—C8	1.520 (4)
C1—H1A	0.9300	C7—H7A	0.9800
F2—C5	1.348 (3)	C8—H8A	0.9700
N2—C9	1.298 (3)	C8—H8B	0.9700
C2—C3	1.420 (4)	C9—H9A	0.9300
C2—H2B	0.9300	C10—H10A	0.9300

C7—O—H0A	104 (2)	C5—C6—C1	117.1 (2)
C10—N1—N2	109.2 (2)	C5—C6—C7	121.9 (2)
C10—N1—C8	130.5 (2)	C1—C6—C7	121.0 (2)
N2—N1—C8	120.1 (2)	O—C7—C8	108.7 (2)
C6—C1—C2	124.2 (3)	O—C7—C6	110.93 (19)
C6—C1—H1A	117.9	C8—C7—C6	109.5 (2)
C2—C1—H1A	117.9	O—C7—H7A	109.2
C9—N2—N1	102.4 (2)	C8—C7—H7A	109.2
C1—C2—C3	115.9 (3)	C6—C7—H7A	109.2
C1—C2—H2B	122.0	N1—C8—C7	111.78 (19)
C3—C2—H2B	122.0	N1—C8—H8A	109.3
C10—N3—C9	101.2 (2)	C7—C8—H8A	109.3
C4—C3—F1	120.0 (3)	N1—C8—H8B	109.3
C4—C3—C2	123.6 (3)	C7—C8—H8B	109.3
F1—C3—C2	116.4 (3)	H8A—C8—H8B	107.9
C3—C4—C5	116.9 (3)	N2—C9—N3	115.5 (3)
C3—C4—H4A	121.6	N2—C9—H9A	122.2
C5—C4—H4A	121.6	N3—C9—H9A	122.2
F2—C5—C6	120.6 (2)	N1—C10—N3	111.7 (3)
F2—C5—C4	117.2 (2)	N1—C10—H10A	124.1
C6—C5—C4	122.2 (3)	N3—C10—H10A	124.1

C10—N1—N2—C9	−1.0 (3)	C2—C1—C6—C7	179.1 (3)
C8—N1—N2—C9	−177.4 (2)	C5—C6—C7—O	−152.5 (3)
C6—C1—C2—C3	−0.7 (5)	C1—C6—C7—O	29.4 (4)
C1—C2—C3—C4	0.9 (5)	C5—C6—C7—C8	87.5 (3)
C1—C2—C3—F1	−178.2 (3)	C1—C6—C7—C8	−90.6 (3)
F1—C3—C4—C5	177.9 (3)	C10—N1—C8—C7	−108.9 (3)
C2—C3—C4—C5	−1.1 (5)	N2—N1—C8—C7	66.5 (3)
C3—C4—C5—F2	−177.0 (3)	O—C7—C8—N1	61.5 (3)
C3—C4—C5—C6	1.3 (5)	C6—C7—C8—N1	−177.2 (2)
F2—C5—C6—C1	177.0 (3)	N1—N2—C9—N3	0.5 (4)
C4—C5—C6—C1	−1.2 (5)	C10—N3—C9—N2	0.2 (4)
F2—C5—C6—C7	−1.1 (4)	N2—N1—C10—N3	1.3 (3)
C4—C5—C6—C7	−179.3 (3)	C8—N1—C10—N3	177.1 (2)
C2—C1—C6—C5	0.9 (5)	C9—N3—C10—N1	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H0A···N3ⁱ	0.83 (3)	1.98 (3)	2.794 (3)	169 (3)
C8—H8B···F2ⁱⁱ	0.97	2.46	3.388 (4)	159

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₉F₂N₃O
M_r	225.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.261 (3), 5.6150 (11), 25.823 (5)
β (°)	94.84 (3)
V (Å³)	2060.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.964, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	1969, 1886, 1059
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.143, 1.01
No. of reflections	1886
No. of parameters	148
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H0A···N3ⁱ	0.83 (3)	1.98 (3)	2.794 (3)	169 (3)
C8—H8B···F2ⁱⁱ	0.9700	2.4600	3.388 (4)	159.00

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x, y+1, z.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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