(E)-4-Fluoro-2-[(4-hy­droxy­pheneth­yl)imino­meth­yl]phenol

Fang, R.-Q.; Song, T.; Li, Y.-X.

doi:10.1107/S1600536811055875

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o332

doi:10.1107/S1600536811055875

Open

access

(E)-4-Fluoro-2-[(4-hydroxyphenethyl)iminomethyl]phenol

Rui-Qin Fang,^a,^b ^* Tao Song ^a and Yu-Xiang Li ^a

^aSchool of Life Science and Technology, University of Electronic Science and Technology of China, Chengdu 610054, People's Republic of China, and ^bState Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: fangrq@uestc.edu.cn

(Received 26 December 2011; accepted 27 December 2011; online 11 January 2012)

The title compound, C₁₅H₁₄FNO₂, has an E conformation about the C=N bond, which facilitates the formation of an intramolecular O—H⋯N hydrogen bond. The F atom is disordered over two adjacent sites in a 0.65 (7):0.35 (7) ratio. The dihedral angle between the benzene ring planes is 14.2 (2)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming C(14) [010] chains.

Related literature

For a related structure, see: Li et al. (2006 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₄FNO₂
M_r = 259.27
Monoclinic, C 2/c
a = 15.979 (3) Å
b = 12.941 (3) Å
c = 15.040 (3) Å
β = 121.72 (3)°
V = 2645.5 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.963, T_max = 0.972
2692 measured reflections
2599 independent reflections
1431 reflections with I > 2σ(I)
R_int = 0.052
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.179
S = 1.03
2599 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.82	2.565 (3)	150
O2—H2⋯O1ⁱ	0.82	1.89	2.707 (3)	173
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811055875/hb6581sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055875/hb6581Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811055875/hb6581Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811055875/hb6581Isup4.cml

checkCIF report

Comment top

The cystal structure of (E)-2-((4-hydroxyphenethylimino)methyl)phenol, synthesized by salicylaldehyde and tyramine, has been reported before (Li et al., 2006). There are no fluoro subsitituent on the 5-position of benzene, as compared with the title compound. The molecular structure of title compound (I), Fig. 1, possesses an E configuration about C7=N1 double bond, and the bond length 1.283 (3) Å is in the normal range (Allen et al., 1987). Disorder is observed concerning fluoro atom in a ratio of 0.35 (7): 0.65 (7). The torsion angle of C9—C8—N1—C7 and N1—C8—C9—C10 are 123.3 (3) ° and 177.8 (2) °, respectively. The dihedral angles between two benzene ring planes is 14.18 (20) °. In the crystal, intramolecular O1—H1···N1 hydrogen bonds occur, and the intermolecular O2—H2···O1 hydrogen bonds lead to chains of molecules along the b axis.(Fig. 2).

Related literature top

For a related structure, see: Li et al. (2006). For reference bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was prepared by stirring a mixture of 5-fluoro-salicylaldehyde (122 mg, 1 mmol) and tyramine (137 mg, 1 mmol) in methanol (15 ml) for 2 h at room temperature. After keeping the solution in air for 3 d, brown block-shaped crystals of (I) were formed. The crystals were isolated, washed three times with methanol and dried in a vacuum desiccator containing anhydrous CaCl₂.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound (I) showing 35% probability displacement ellipsoids.
	Fig. 2. The crystal packing of (I), viewed along the b axis. Hydrogen bonds are shown as dashed lines.

(E)-4-Fluoro-2-[(4-hydroxyphenethyl)iminomethyl]phenol top

Crystal data top

C₁₅H₁₄FNO₂	F(000) = 1088
M_r = 259.27	D_x = 1.302 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1056 reflections
a = 15.979 (3) Å	θ = 3.2–23.5°
b = 12.941 (3) Å	µ = 0.10 mm⁻¹
c = 15.040 (3) Å	T = 293 K
β = 121.72 (3)°	Block, brown
V = 2645.5 (9) Å³	0.40 × 0.30 × 0.30 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1431 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 26.0°, θ_min = 2.2°
ω/2θ scan	h = 0→19
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.963, T_max = 0.972	l = −18→15
2692 measured reflections	3 standard reflections every 200 reflections
2599 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.064	H-atom parameters constrained
wR(F²) = 0.179	w = 1/[σ²(F_o²) + (0.0762P)² + 1.0201P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2599 reflections	Δρ_max = 0.31 e Å⁻³
185 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0055 (9)

Crystal data top

C₁₅H₁₄FNO₂	V = 2645.5 (9) Å³
M_r = 259.27	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.979 (3) Å	µ = 0.10 mm⁻¹
b = 12.941 (3) Å	T = 293 K
c = 15.040 (3) Å	0.40 × 0.30 × 0.30 mm
β = 121.72 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1431 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.052
T_min = 0.963, T_max = 0.972	3 standard reflections every 200 reflections
2692 measured reflections	intensity decay: 1%
2599 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.03	Δρ_max = 0.31 e Å⁻³
2599 reflections	Δρ_min = −0.21 e Å⁻³
185 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	Occ. (<1)
C1	0.42192 (19)	0.8367 (2)	0.0160 (2)	0.0580 (7)
C2	0.46488 (18)	0.7365 (2)	0.0453 (2)	0.0534 (7)
C3	0.5012 (2)	0.6926 (2)	−0.0131 (2)	0.0610 (7)
H3	0.5303	0.6276	0.0050	0.073*
C4	0.4948 (2)	0.7430 (3)	−0.0953 (3)	0.0810 (10)
H4	0.5193	0.7128	−0.1333	0.097*
C5	0.4516 (3)	0.8397 (3)	−0.1224 (3)	0.1024 (13)
C6	0.4166 (3)	0.8873 (3)	−0.0690 (3)	0.0888 (11)
H6	0.3893	0.9530	−0.0884	0.107*
C7	0.38330 (19)	0.8852 (2)	0.0720 (2)	0.0642 (8)
H7	0.3559	0.9508	0.0515	0.077*
C8	0.3470 (2)	0.8918 (2)	0.2089 (2)	0.0725 (9)
H8A	0.3195	0.9586	0.1782	0.087*
H8B	0.4007	0.9030	0.2802	0.087*
C9	0.2695 (2)	0.8273 (2)	0.2094 (3)	0.0762 (9)
H9A	0.2963	0.7595	0.2375	0.091*
H9B	0.2147	0.8184	0.1382	0.091*
C10	0.23315 (19)	0.8764 (2)	0.2740 (2)	0.0637 (8)
C11	0.1726 (2)	0.9632 (2)	0.2386 (2)	0.0662 (8)
H11	0.1546	0.9911	0.1739	0.079*
C12	0.13856 (19)	1.0090 (2)	0.2964 (2)	0.0604 (7)
H12	0.0985	1.0671	0.2709	0.072*
C13	0.1641 (2)	0.9681 (2)	0.3921 (2)	0.0581 (7)
C14	0.2249 (2)	0.8830 (2)	0.4294 (2)	0.0709 (8)
H14	0.2434	0.8556	0.4944	0.085*
C15	0.2583 (2)	0.8387 (2)	0.3706 (2)	0.0709 (8)
H15	0.2993	0.7813	0.3969	0.085*
F	0.419 (2)	0.865 (3)	−0.230 (2)	0.109 (7)	0.35 (7)
F'	0.462 (4)	0.900 (3)	−0.191 (4)	0.155 (10)	0.65 (7)
N1	0.38481 (16)	0.84202 (18)	0.14957 (18)	0.0634 (7)
O1	0.46969 (16)	0.68714 (14)	0.12319 (15)	0.0701 (6)
H1	0.4446	0.7223	0.1484	0.105*
O2	0.13257 (18)	1.00897 (15)	0.45299 (17)	0.0813 (7)
H2	0.1042	1.0638	0.4277	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0563 (16)	0.0548 (16)	0.0674 (17)	0.0037 (13)	0.0356 (14)	0.0071 (13)
C2	0.0498 (15)	0.0504 (16)	0.0570 (16)	−0.0013 (12)	0.0261 (13)	0.0013 (12)
C3	0.0576 (16)	0.0568 (17)	0.0675 (18)	0.0049 (13)	0.0320 (15)	−0.0015 (14)
C4	0.084 (2)	0.091 (2)	0.093 (2)	0.0150 (19)	0.064 (2)	0.008 (2)
C5	0.135 (3)	0.101 (3)	0.119 (3)	0.036 (2)	0.099 (3)	0.048 (2)
C6	0.112 (3)	0.071 (2)	0.117 (3)	0.0284 (19)	0.083 (2)	0.033 (2)
C7	0.0601 (17)	0.0536 (16)	0.080 (2)	0.0072 (13)	0.0379 (16)	0.0005 (14)
C8	0.0685 (19)	0.073 (2)	0.081 (2)	0.0003 (15)	0.0427 (17)	−0.0167 (16)
C9	0.0679 (19)	0.074 (2)	0.092 (2)	0.0005 (16)	0.0456 (18)	−0.0165 (17)
C10	0.0554 (16)	0.0629 (18)	0.076 (2)	0.0038 (14)	0.0367 (15)	−0.0064 (15)
C11	0.0640 (17)	0.0708 (19)	0.0629 (18)	0.0087 (15)	0.0328 (15)	0.0015 (14)
C12	0.0542 (16)	0.0575 (17)	0.0662 (18)	0.0104 (12)	0.0294 (14)	0.0029 (14)
C13	0.0636 (16)	0.0485 (15)	0.0713 (18)	−0.0033 (13)	0.0418 (15)	−0.0040 (13)
C14	0.084 (2)	0.0572 (17)	0.077 (2)	0.0102 (16)	0.0461 (18)	0.0121 (15)
C15	0.0696 (19)	0.0562 (18)	0.086 (2)	0.0164 (14)	0.0405 (17)	0.0111 (16)
F	0.158 (13)	0.103 (10)	0.095 (11)	0.016 (9)	0.088 (12)	0.038 (6)
F'	0.25 (2)	0.134 (10)	0.186 (16)	0.067 (13)	0.182 (17)	0.072 (12)
N1	0.0639 (14)	0.0665 (15)	0.0672 (15)	0.0008 (11)	0.0394 (13)	−0.0078 (12)
O1	0.0915 (15)	0.0562 (12)	0.0742 (13)	0.0158 (10)	0.0515 (12)	0.0103 (10)
O2	0.1126 (18)	0.0673 (14)	0.0924 (15)	0.0134 (12)	0.0734 (15)	0.0073 (11)

Geometric parameters (Å, º) top

C1—C6	1.399 (4)	C8—H8B	0.9700
C1—C7	1.425 (4)	C9—C10	1.511 (4)
C1—C2	1.425 (4)	C9—H9A	0.9700
C2—O1	1.300 (3)	C9—H9B	0.9700
C2—C3	1.403 (3)	C10—C15	1.376 (4)
C3—C4	1.353 (4)	C10—C11	1.392 (4)
C3—H3	0.9300	C11—C12	1.379 (4)
C4—C5	1.383 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.378 (4)
C5—C6	1.345 (4)	C12—H12	0.9300
C5—F'	1.373 (11)	C13—O2	1.363 (3)
C5—F	1.456 (18)	C13—C14	1.378 (4)
C6—H6	0.9300	C14—C15	1.376 (4)
C7—N1	1.283 (3)	C14—H14	0.9300
C7—H7	0.9300	C15—H15	0.9300
C8—N1	1.464 (3)	O1—H1	0.8200
C8—C9	1.496 (4)	O2—H2	0.8200
C8—H8A	0.9700

C6—C1—C7	119.8 (3)	H8A—C8—H8B	108.0
C6—C1—C2	119.8 (3)	C8—C9—C10	111.6 (2)
C7—C1—C2	120.4 (2)	C8—C9—H9A	109.3
O1—C2—C3	121.2 (2)	C10—C9—H9A	109.3
O1—C2—C1	121.1 (2)	C8—C9—H9B	109.3
C3—C2—C1	117.7 (2)	C10—C9—H9B	109.3
C4—C3—C2	121.4 (3)	H9A—C9—H9B	108.0
C4—C3—H3	119.3	C15—C10—C11	116.7 (3)
C2—C3—H3	119.3	C15—C10—C9	122.2 (3)
C3—C4—C5	119.4 (3)	C11—C10—C9	121.2 (3)
C3—C4—H4	120.3	C12—C11—C10	122.0 (3)
C5—C4—H4	120.3	C12—C11—H11	119.0
C6—C5—F'	115.9 (10)	C10—C11—H11	119.0
C6—C5—C4	122.6 (3)	C13—C12—C11	119.7 (3)
F'—C5—C4	119.9 (5)	C13—C12—H12	120.1
C6—C5—F	123.0 (9)	C11—C12—H12	120.1
F'—C5—F	32.0 (12)	O2—C13—C14	117.8 (3)
C4—C5—F	111.2 (12)	O2—C13—C12	122.8 (2)
C5—C6—C1	119.1 (3)	C14—C13—C12	119.3 (3)
C5—C6—H6	120.4	C15—C14—C13	120.0 (3)
C1—C6—H6	120.4	C15—C14—H14	120.0
N1—C7—C1	122.6 (3)	C13—C14—H14	120.0
N1—C7—H7	118.7	C14—C15—C10	122.2 (3)
C1—C7—H7	118.7	C14—C15—H15	118.9
N1—C8—C9	111.4 (2)	C10—C15—H15	118.9
N1—C8—H8A	109.3	C7—N1—C8	123.1 (2)
C9—C8—H8A	109.3	C2—O1—H1	109.5
N1—C8—H8B	109.3	C13—O2—H2	109.5
C9—C8—H8B	109.3

C6—C1—C2—O1	−179.2 (3)	C2—C1—C7—N1	−0.3 (4)
C7—C1—C2—O1	0.1 (4)	N1—C8—C9—C10	177.8 (2)
C6—C1—C2—C3	0.5 (4)	C8—C9—C10—C15	−106.5 (3)
C7—C1—C2—C3	179.7 (2)	C8—C9—C10—C11	73.0 (3)
O1—C2—C3—C4	178.8 (3)	C15—C10—C11—C12	−0.5 (4)
C1—C2—C3—C4	−0.8 (4)	C9—C10—C11—C12	179.9 (3)
C2—C3—C4—C5	0.0 (5)	C10—C11—C12—C13	−0.4 (4)
C3—C4—C5—C6	1.2 (6)	C11—C12—C13—O2	−179.5 (2)
C3—C4—C5—F'	167 (3)	C11—C12—C13—C14	1.2 (4)
C3—C4—C5—F	−159.1 (16)	O2—C13—C14—C15	179.7 (3)
F'—C5—C6—C1	−167 (3)	C12—C13—C14—C15	−1.0 (4)
C4—C5—C6—C1	−1.5 (6)	C13—C14—C15—C10	0.1 (5)
F—C5—C6—C1	156 (2)	C11—C10—C15—C14	0.7 (4)
C7—C1—C6—C5	−178.6 (3)	C9—C10—C15—C14	−179.7 (3)
C2—C1—C6—C5	0.6 (5)	C1—C7—N1—C8	178.9 (2)
C6—C1—C7—N1	179.0 (3)	C9—C8—N1—C7	123.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.82	2.565 (3)	150
O2—H2···O1ⁱ	0.82	1.89	2.707 (3)	173

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄FNO₂
M_r	259.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.979 (3), 12.941 (3), 15.040 (3)
β (°)	121.72 (3)
V (Å³)	2645.5 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.963, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	2692, 2599, 1431
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.179, 1.03
No. of reflections	2599
No. of parameters	185
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.82	2.565 (3)	150
O2—H2···O1ⁱ	0.82	1.89	2.707 (3)	173

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

Acknowledgements

We are grateful to the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20110185120016) and the Fundamental Research Funds for the Central Universities (ZYGX2009J085) for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Li, Y.-G., Zhu, H.-L., Huang, W.-Q. & Ai, L. (2006). Acta Cryst. E62, o689–o690. Web of Science CSD CrossRef IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar