(E)-4-Fluoro-2-[(phenyl­imino)­meth­yl]phenol

Swetha, G.; Ida Malarselvi, R.; Ramachandra Raja, C.; Thiruvalluvar, A.; Priscilla, J.

doi:10.1107/S2414314617016716

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171671

https://doi.org/10.1107/S2414314617016716

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(E)-4-Fluoro-2-[(phenylimino)methyl]phenol

G. Swetha,^a R. Ida Malarselvi,^b C. Ramachandra Raja,^a A. Thiruvalluvar ^c ^* and J. Priscilla ^d

^aPostgraduate Research Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 001, Tamilnadu, India, ^bPostgraduate Department of Physics, Dharmapuram Gnanambigai College for Women, Mayiladuthurai 609 001, Tamilnadu, India, ^cPrincipal, Kunthavai Naacchiyaar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India, and ^dPostgraduate Department of Physics, A.D.M. College for Women (Autonomous), Nagapattinam 611 001, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by P. C. Healy, Griffith University, Australia (Received 19 November 2017; accepted 20 November 2017; online 24 November 2017)

The title compound, C₁₃H₁₀FNO, is essentially planar (r.m.s. deviation = 0.022 Å) and the dihedral angle between the planes of the two aryl rings is 0.69 (15)°. An intramolecular O—H⋯N hydrogen bond generates an S(6) ring. The crystal structure features C—H⋯O hydrogen bonds.

Keywords: crystal structure; salicylaldehyde derivative; O—H⋯N hydrogen bonding; C—H⋯O hydrogen bonding.

CCDC reference: 1586558

Structure description

We report here, as part of our ongoing research (Ida Malarselvi et al., 2016 ), the synthesis and crystal structure (Fig. 1), of the title fluorinated Schiff base compound, synthesized from the condensation reaction of equimolar amounts of 5-fluorosalicylaldehyde and aniline in DMSO. In this structure, the benzene and phenyl rings subtend a dihedral angle of 0.69 (15)°. The molecule has an E conformation about the C=N bond, and the C1—C7=N1—C8 torsion angle is 180.0 (2)°. There is a strong intramolecular O1—H1⋯N1 hydrogen bond [H⋯N = 1.70 (5) Å], which generates an S(6) ring. The crystal structure features C7—H7⋯O1 hydrogen bonds (see Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.61	3.440 (3)	149
O1—H1⋯N1	0.99 (4)	1.70 (5)	2.595 (3)	148 (4)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
A view of the title compound, with displacement ellipsoids drawn at the 50% probability level. Dashed lines indicate the intramolecular hydrogen bond.

Figure 2
The crystal packing of the title compound, viewed down the crystallographic b axis. The hydrogen bonds (see Table 1

) are shown as dashed lines.

Yan et al., (2014 ) have reported the crystal structure of 4-bromo-2-[(phenylimino)methyl]phenol, in which the molecule is essentially planar (r.m.s. deviation = 0.026 Å), similar to our present study (r.m.s. deviation = 0.022 Å).

Synthesis and crystallization

0.35 g (0.0025 mol) of 5-fluorosalicylaldehyde were dissolved in 10 ml of DMSO. To this solution, 0.23 g (0.0025 mol) of aniline were added drop wise with constant stirring for 1 h. During this time, the solution turned deep yellow. On standing for two weeks with slow evaporation of the solvent, orange crystals of the title compound, suitable for X-ray study were obtained.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₀FNO
M_r	215.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	18.965 (2), 4.7214 (5), 12.2399 (13)
β (°)	107.881 (7)
V (Å³)	1043.0 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.83
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker Kappa APEX3CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.536, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	10586, 1997, 1069
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.173, 1.03
No. of reflections	1997
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16
Computer programs: APEX3, SAINT and XPREP (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1586558

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617016716/hg4032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617016716/hg4032Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617016716/hg4032Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617016716/hg4032Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 and SAINT (Bruker, 2016); data reduction: SAINT and XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(E)-4-Fluoro-2-[(phenylimino)methyl]phenol top

Crystal data top

C₁₃H₁₀FNO	F(000) = 448
M_r = 215.22	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 18.965 (2) Å	Cell parameters from 2681 reflections
b = 4.7214 (5) Å	θ = 4.9–70.9°
c = 12.2399 (13) Å	µ = 0.83 mm⁻¹
β = 107.881 (7)°	T = 296 K
V = 1043.0 (2) Å³	Plate, orange
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Bruker Kappa APEX3 CMOS diffractometer	1069 reflections with I > 2σ(I)
Radiation source: micro-focus sealed tube	R_int = 0.097
ω and φ scan	θ_max = 71.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −23→21
T_min = 0.536, T_max = 0.754	k = −4→5
10586 measured reflections	l = −14→15
1997 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.057	w = 1/[σ²(F_o²) + (0.0689P)² + 0.2085P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.173	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.16 e Å⁻³
1997 reflections	Δρ_min = −0.16 e Å⁻³
150 parameters	Extinction correction: SHELXL2017 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0042 (11)

Special details top

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. H atoms attached to C of (I) were placed in geometrically idealized positions with Csp²—H = 0.93 Å. The hydroxy H atom, H1, is located in a difference Fourier map and freely refined.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.31946 (14)	0.1990 (6)	0.8556 (2)	0.0569 (7)
C2	0.32137 (16)	0.1370 (6)	0.9681 (2)	0.0642 (8)
C3	0.37148 (17)	−0.0616 (7)	1.0310 (3)	0.0742 (9)
H3	0.373294	−0.100204	1.106307	0.089*
C4	0.41831 (17)	−0.2017 (7)	0.9837 (3)	0.0752 (9)
H4	0.451482	−0.336124	1.025813	0.090*
C5	0.41512 (16)	−0.1390 (7)	0.8726 (3)	0.0711 (8)
C6	0.36730 (16)	0.0553 (6)	0.8083 (2)	0.0664 (8)
H6	0.366494	0.092055	0.733234	0.080*
C7	0.26800 (16)	0.4054 (6)	0.7872 (2)	0.0612 (7)
H7	0.267062	0.436748	0.711738	0.073*
C8	0.17332 (15)	0.7488 (6)	0.7606 (2)	0.0592 (7)
C9	0.16766 (17)	0.8212 (7)	0.6485 (2)	0.0777 (9)
H9	0.198385	0.735704	0.611808	0.093*
C10	0.11625 (19)	1.0209 (7)	0.5914 (3)	0.0869 (10)
H10	0.112828	1.069505	0.516307	0.104*
C11	0.07008 (17)	1.1487 (7)	0.6439 (3)	0.0806 (9)
H11	0.035174	1.280954	0.604422	0.097*
C12	0.07608 (18)	1.0791 (7)	0.7551 (3)	0.0796 (9)
H12	0.045277	1.164804	0.791596	0.096*
C13	0.12772 (16)	0.8821 (7)	0.8129 (3)	0.0711 (8)
H13	0.131820	0.838381	0.888667	0.085*
N1	0.22382 (12)	0.5460 (5)	0.82746 (17)	0.0611 (6)
O1	0.27583 (12)	0.2678 (5)	1.01816 (17)	0.0817 (7)
F5	0.46145 (10)	−0.2803 (4)	0.82560 (15)	0.0977 (7)
H1	0.245 (2)	0.405 (9)	0.961 (4)	0.142 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0652 (16)	0.0505 (17)	0.0541 (14)	−0.0028 (13)	0.0168 (13)	−0.0012 (12)
C2	0.0727 (18)	0.0631 (19)	0.0565 (15)	0.0010 (15)	0.0195 (14)	0.0033 (14)
C3	0.083 (2)	0.076 (2)	0.0601 (17)	0.0034 (17)	0.0173 (16)	0.0073 (15)
C4	0.078 (2)	0.065 (2)	0.0738 (19)	0.0056 (16)	0.0101 (16)	0.0035 (16)
C5	0.0707 (19)	0.066 (2)	0.0771 (19)	0.0069 (16)	0.0242 (16)	−0.0088 (16)
C6	0.0742 (18)	0.065 (2)	0.0595 (15)	0.0016 (15)	0.0201 (14)	−0.0020 (14)
C7	0.0741 (18)	0.0568 (18)	0.0554 (15)	−0.0031 (14)	0.0238 (14)	0.0010 (13)
C8	0.0658 (16)	0.0495 (17)	0.0594 (15)	−0.0036 (13)	0.0151 (14)	0.0007 (13)
C9	0.090 (2)	0.080 (2)	0.0631 (17)	0.0172 (18)	0.0228 (16)	0.0054 (16)
C10	0.101 (3)	0.084 (3)	0.0687 (19)	0.016 (2)	0.0156 (18)	0.0096 (18)
C11	0.076 (2)	0.068 (2)	0.088 (2)	0.0054 (17)	0.0117 (18)	0.0079 (18)
C12	0.074 (2)	0.070 (2)	0.098 (2)	0.0075 (16)	0.0313 (18)	0.0044 (18)
C13	0.078 (2)	0.067 (2)	0.0732 (18)	0.0026 (16)	0.0313 (16)	0.0048 (15)
N1	0.0709 (15)	0.0551 (15)	0.0573 (13)	0.0004 (11)	0.0195 (11)	0.0024 (10)
O1	0.0998 (16)	0.0907 (17)	0.0631 (12)	0.0191 (13)	0.0374 (12)	0.0105 (11)
F5	0.0988 (13)	0.0962 (15)	0.0989 (13)	0.0253 (11)	0.0317 (11)	−0.0080 (11)

Geometric parameters (Å, º) top

C1—C6	1.394 (4)	C8—C13	1.376 (4)
C1—C2	1.397 (4)	C8—C9	1.386 (4)
C1—C7	1.450 (4)	C8—N1	1.422 (3)
C2—O1	1.352 (3)	C9—C10	1.382 (4)
C2—C3	1.388 (4)	C9—H9	0.9300
C3—C4	1.370 (4)	C10—C11	1.375 (4)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.375 (4)	C11—C12	1.371 (4)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.358 (4)	C12—C13	1.378 (4)
C5—F5	1.364 (3)	C12—H12	0.9300
C6—H6	0.9300	C13—H13	0.9300
C7—N1	1.280 (3)	O1—H1	0.99 (4)
C7—H7	0.9300

C6—C1—C2	119.0 (3)	C13—C8—C9	118.6 (3)
C6—C1—C7	119.7 (2)	C13—C8—N1	116.7 (2)
C2—C1—C7	121.3 (3)	C9—C8—N1	124.7 (3)
O1—C2—C3	118.8 (2)	C10—C9—C8	119.8 (3)
O1—C2—C1	121.6 (3)	C10—C9—H9	120.1
C3—C2—C1	119.6 (3)	C8—C9—H9	120.1
C4—C3—C2	121.0 (3)	C11—C10—C9	121.0 (3)
C4—C3—H3	119.5	C11—C10—H10	119.5
C2—C3—H3	119.5	C9—C10—H10	119.5
C3—C4—C5	118.4 (3)	C12—C11—C10	119.2 (3)
C3—C4—H4	120.8	C12—C11—H11	120.4
C5—C4—H4	120.8	C10—C11—H11	120.4
C6—C5—F5	119.2 (3)	C11—C12—C13	120.1 (3)
C6—C5—C4	122.5 (3)	C11—C12—H12	120.0
F5—C5—C4	118.3 (3)	C13—C12—H12	120.0
C5—C6—C1	119.4 (3)	C8—C13—C12	121.3 (3)
C5—C6—H6	120.3	C8—C13—H13	119.4
C1—C6—H6	120.3	C12—C13—H13	119.4
N1—C7—C1	122.0 (2)	C7—N1—C8	122.2 (2)
N1—C7—H7	119.0	C2—O1—H1	107 (2)
C1—C7—H7	119.0

C6—C1—C2—O1	−179.4 (3)	C6—C1—C7—N1	−178.9 (3)
C7—C1—C2—O1	−0.5 (4)	C2—C1—C7—N1	2.2 (4)
C6—C1—C2—C3	1.2 (4)	C13—C8—C9—C10	−0.8 (5)
C7—C1—C2—C3	−179.9 (3)	N1—C8—C9—C10	179.7 (3)
O1—C2—C3—C4	179.4 (3)	C8—C9—C10—C11	−0.3 (5)
C1—C2—C3—C4	−1.2 (4)	C9—C10—C11—C12	0.9 (5)
C2—C3—C4—C5	0.7 (5)	C10—C11—C12—C13	−0.3 (5)
C3—C4—C5—C6	−0.2 (5)	C9—C8—C13—C12	1.5 (4)
C3—C4—C5—F5	−179.5 (3)	N1—C8—C13—C12	−179.1 (3)
F5—C5—C6—C1	179.6 (2)	C11—C12—C13—C8	−0.9 (5)
C4—C5—C6—C1	0.2 (5)	C1—C7—N1—C8	180.0 (2)
C2—C1—C6—C5	−0.7 (4)	C13—C8—N1—C7	178.8 (3)
C7—C1—C6—C5	−179.7 (3)	C9—C8—N1—C7	−1.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.61	3.440 (3)	149
O1—H1···N1	0.99 (4)	1.70 (5)	2.595 (3)	148 (4)

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors are grateful to the Sophisticated Analytical Instrument Facility (SAIF), IITM, Chennai, Tamilnadu, India, for the single-crystal X-ray diffraction data.

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