(E)-3-[(2-Fluoro­phenyl­imino)meth­yl]­benzene-1,2-diol

The title compound, C₁₃H₁₀FNO₂, adopts the enol–imine tautomeric form. Intra­molecular O—H...O and O—H...N hydrogen bonds generate S(5) and S(6) ring motifs, respectively, whereas inter­molecular O—H...O hydrogen bonding links the mol­ecules into centrosymmetric R₂²(10) dimers. Inter­molecular C—H...π and π–π inter­actions link the mol­ecules into a three-dimensional network. The π–π interactions occur between the fluoro-substituted benzene rings and the centroid-to centroid distance is 3.7590 (12) Å.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.072
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         48 Perc.
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.72 mm
PLAT230_ALERT_2_C Hirshfeld Test Diff for    F1     -   C13     ..       6.07 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C7      ..       6.54 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C2      ..       5.94 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C7      ..       6.28 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

We have reported the crystal structures of Schiff base systems formed by organic amines and salicylaldehyde derivatives (Temel et al., 2006; Temel et al., 2007a, 2007b). The title compound, (I), is part of a structural study of these compounds.

Scheme (I)

The compound (I) adopts the enol-imine tautomeric form with an E configuration with respect to the C7═N1 double bond, with a C1—C7═ N1—C8 torsion angle of 177.58 (16)° and C7═N1—C8 angle of 120.70 (15)° (Fig. 1). The C2—O1 and C7═N1 bond lengths are 1.3545 (19)Å and 1.285 (2) Å, respectively (Table 1), and agree with the corresponding distances in 4-(2-hydroxyphenyliminomethylene)phenol [1.350 (2) Å and 1.285 (2) Å; Ersanlı et al., 2004]. The molecule of (I) is nonplanar, with a dihedral angle between the benzene rings of 52.12 (6)°.

Intra-molecular O—H···O and O—H···N hydrogen bonds generate S(5) and S(6) ring motifs, respectively (Bernstein et al., 1995) (Fig. 1). Molecules of (I) are linked by inter-molecular O—H···O hydrogen bonds, C6—H6···Cg1, C10—H10···Cg2 and Cg2···Cg2 intra-molecular interactions (Cg1 and Cg2 are the centroids of the C1—C6 and C8—C13 rings, respectively) (Fig. 2 and Table 2). The π···π interaction occurs between the C8—C13 ring and its symmetry-related counterpart at (1 - x, 1 - y, 1 - z), with a centroid-to centroid distance of 3.7590 (12) Å and a plane-to-plane separation of 3.467 Å.

Related literature

We have reported the crystal structures of Schiff base systems formed by organic amines and salicylaldehyde derivatives (Temel et al., 2006, 2007a,b). The title compound, (I), is part of a structural study of these compounds.

For related literature, see: Bernstein et al. (1995); Ersanlı, Albayrak, Büyükgüngör & Erdönmez (2004); Odabaşoğlu et al. (2005).

S2. Experimental

The title compound was prepared as described by Odabaşoğlu et al. (2005), using o-bromaniline and 2,3-dihydroxybenzaldehyde as starting materials (yield 75%; m.p. 410–411 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.

S3. Refinement

The hydroxyl H atoms were located in a difference Fourier synthesis and were refined freely. All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.93 Å (U_iso=1.2U_eq of the parent atom) for aromatic and d(C—H) = 0.96 Å (U_iso=1.5U_eq of the parent atom) for methyl C atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I), with the atom numbering scheme and the hydrogen bonds represented as a dashed lines. Thermal ellipsoids are drawn at the 40% probability level.
	Fig. 2. A packing diagram of (I), showing the intermolecular C—H···π, π-π interactions and O.H···O hydrogen-bonds (dashed lines). H atoms not participating in interaction have been omitted for clarity.

(E)-3-[(2-Fluorophenylimino)methyl]benzene-1,2-diol

Crystal data

C13H10FNO2	F(000) = 480
Mr = 231.22	Dx = 1.422 Mg m^−3
Monoclinic, P21/c	Melting point = 410–411 K
Hall symbol: -P 2 ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.6262 (14) Å	Cell parameters from 10732 reflections
b = 6.1497 (4) Å	θ = 2.8–27.8°
c = 14.5103 (14) Å	µ = 0.11 mm^−1
β = 117.307 (7)°	T = 296 K
V = 1080.42 (17) Å^3	Thin plate, brown
Z = 4	0.72 × 0.46 × 0.03 mm

Data collection

Stoe IPDS II diffractometer	2525 independent reflections
Radiation source: fine-focus sealed tube	1208 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.088
Detector resolution: 6.67 pixels mm^-1	θmax = 27.7°, θmin = 2.8°
ω scans	h = −17→17
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −8→8
Tmin = 0.940, Tmax = 0.997	l = −18→18
15801 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0274P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.80	(Δ/σ)max < 0.001
2525 reflections	Δρmax = 0.15 e Å^−3
163 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0054 (7)

Special details

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 > 2σ(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	0.05535 (13)	0.5384 (3)	0.39129 (13)	0.0344 (4)
C2	0.00883 (13)	0.3482 (3)	0.40674 (12)	0.0360 (4)
C3	−0.10529 (13)	0.3215 (3)	0.35703 (13)	0.0400 (4)
C4	−0.17155 (14)	0.4784 (3)	0.28977 (14)	0.0474 (5)
H4	−0.2477	0.4591	0.2557	0.057*
C5	−0.12565 (14)	0.6651 (3)	0.27237 (14)	0.0492 (5)
H5	−0.1711	0.7692	0.2259	0.059*
C6	−0.01373 (13)	0.6974 (3)	0.32318 (13)	0.0427 (5)
H6	0.0164	0.8247	0.3125	0.051*
C7	0.17369 (14)	0.5714 (3)	0.44446 (13)	0.0393 (4)
H7	0.2031	0.7031	0.4374	0.047*
C8	0.35361 (13)	0.4560 (3)	0.55637 (13)	0.0383 (4)
C9	0.40096 (14)	0.6385 (3)	0.61539 (13)	0.0458 (5)
H9	0.3564	0.7506	0.6178	0.055*
C10	0.51479 (15)	0.6550 (4)	0.67105 (15)	0.0577 (6)
H10	0.5463	0.7784	0.7108	0.069*
C11	0.58167 (15)	0.4898 (4)	0.66797 (16)	0.0588 (6)
H11	0.6580	0.5020	0.7057	0.071*
C12	0.53557 (15)	0.3066 (3)	0.60896 (16)	0.0569 (6)
H12	0.5799	0.1953	0.6054	0.068*
C13	0.42310 (15)	0.2932 (3)	0.55597 (14)	0.0463 (5)
F1	0.37648 (10)	0.11443 (17)	0.49716 (9)	0.0728 (4)
N1	0.23852 (11)	0.4208 (2)	0.50137 (10)	0.0384 (4)
O1	0.07060 (10)	0.18509 (19)	0.46908 (9)	0.0447 (3)
O2	−0.15320 (10)	0.1404 (2)	0.37397 (11)	0.0552 (4)
H1	0.1419 (18)	0.227 (3)	0.4930 (16)	0.081 (7)*
H2	−0.0978 (16)	0.057 (3)	0.4186 (15)	0.069 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0367 (10)	0.0367 (10)	0.0305 (10)	−0.0012 (8)	0.0160 (8)	−0.0015 (8)
C2	0.0352 (9)	0.0390 (10)	0.0308 (9)	0.0041 (8)	0.0124 (8)	−0.0017 (8)
C3	0.0407 (10)	0.0381 (10)	0.0404 (10)	−0.0025 (8)	0.0180 (8)	−0.0029 (9)
C4	0.0373 (10)	0.0543 (12)	0.0433 (11)	0.0045 (9)	0.0123 (9)	0.0003 (10)
C5	0.0478 (12)	0.0513 (12)	0.0435 (11)	0.0147 (9)	0.0168 (9)	0.0101 (9)
C6	0.0477 (11)	0.0403 (10)	0.0410 (10)	0.0044 (8)	0.0210 (9)	0.0066 (9)
C7	0.0464 (11)	0.0388 (10)	0.0370 (10)	−0.0044 (8)	0.0229 (9)	−0.0015 (9)
C8	0.0352 (10)	0.0433 (10)	0.0360 (11)	−0.0011 (8)	0.0160 (9)	0.0037 (9)
C9	0.0444 (11)	0.0478 (11)	0.0453 (11)	−0.0041 (9)	0.0208 (9)	−0.0044 (9)
C10	0.0515 (13)	0.0690 (14)	0.0483 (12)	−0.0165 (11)	0.0191 (10)	−0.0061 (11)
C11	0.0336 (11)	0.0848 (15)	0.0509 (13)	−0.0043 (11)	0.0132 (10)	0.0116 (12)
C12	0.0432 (12)	0.0665 (14)	0.0615 (13)	0.0139 (10)	0.0243 (10)	0.0144 (12)
C13	0.0482 (11)	0.0422 (11)	0.0467 (11)	−0.0012 (9)	0.0203 (9)	0.0022 (9)
F1	0.0696 (8)	0.0509 (7)	0.0902 (9)	0.0049 (6)	0.0299 (7)	−0.0128 (6)
N1	0.0353 (8)	0.0394 (8)	0.0379 (9)	−0.0011 (6)	0.0146 (7)	0.0022 (7)
O1	0.0363 (7)	0.0394 (7)	0.0511 (8)	−0.0001 (6)	0.0136 (6)	0.0091 (6)
O2	0.0340 (7)	0.0486 (8)	0.0703 (10)	−0.0029 (6)	0.0131 (7)	0.0095 (7)

Geometric parameters (Å, º)

C1—C2	1.397 (2)	C8—C9	1.379 (2)
C1—C6	1.402 (2)	C8—C13	1.380 (2)
C1—C7	1.447 (2)	C8—N1	1.412 (2)
C2—O1	1.3545 (19)	C9—C10	1.385 (2)
C2—C3	1.391 (2)	C9—H9	0.9300
C3—O2	1.369 (2)	C10—C11	1.379 (3)
C3—C4	1.375 (2)	C10—H10	0.9300
C4—C5	1.385 (2)	C11—C12	1.380 (3)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.370 (2)	C12—C13	1.366 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—F1	1.358 (2)
C7—N1	1.285 (2)	O1—H1	0.91 (2)
C7—H7	0.9300	O2—H2	0.90 (2)
C2—C1—C6	119.33 (15)	C9—C8—C13	117.82 (16)
C2—C1—C7	120.57 (15)	C9—C8—N1	123.87 (16)
C6—C1—C7	120.11 (16)	C13—C8—N1	118.21 (15)
O1—C2—C3	117.57 (15)	C8—C9—C10	120.09 (19)
O1—C2—C1	122.60 (14)	C8—C9—H9	120.0
C3—C2—C1	119.83 (15)	C10—C9—H9	120.0
O2—C3—C4	119.11 (16)	C11—C10—C9	120.46 (19)
O2—C3—C2	120.98 (15)	C11—C10—H10	119.8
C4—C3—C2	119.91 (17)	C9—C10—H10	119.8
C3—C4—C5	120.45 (17)	C10—C11—C12	120.14 (18)
C3—C4—H4	119.8	C10—C11—H11	119.9
C5—C4—H4	119.8	C12—C11—H11	119.9
C6—C5—C4	120.43 (17)	C13—C12—C11	118.19 (19)
C6—C5—H5	119.8	C13—C12—H12	120.9
C4—C5—H5	119.8	C11—C12—H12	120.9
C5—C6—C1	120.00 (18)	F1—C13—C12	118.91 (18)
C5—C6—H6	120.0	F1—C13—C8	117.78 (15)
C1—C6—H6	120.0	C12—C13—C8	123.28 (18)
N1—C7—C1	120.72 (16)	C7—N1—C8	120.70 (15)
N1—C7—H7	119.6	C2—O1—H1	105.9 (14)
C1—C7—H7	119.6	C3—O2—H2	106.4 (13)
C6—C1—C2—O1	178.10 (16)	C6—C1—C7—N1	−175.06 (16)
C7—C1—C2—O1	−1.6 (2)	C13—C8—C9—C10	0.6 (3)
C6—C1—C2—C3	−1.9 (2)	N1—C8—C9—C10	176.77 (17)
C7—C1—C2—C3	178.40 (16)	C8—C9—C10—C11	0.0 (3)
O1—C2—C3—O2	2.5 (2)	C9—C10—C11—C12	0.2 (3)
C1—C2—C3—O2	−177.45 (16)	C10—C11—C12—C13	−1.1 (3)
O1—C2—C3—C4	−177.49 (16)	C11—C12—C13—F1	179.68 (17)
C1—C2—C3—C4	2.5 (3)	C11—C12—C13—C8	1.8 (3)
O2—C3—C4—C5	178.92 (16)	C9—C8—C13—F1	−179.44 (16)
C2—C3—C4—C5	−1.1 (3)	N1—C8—C13—F1	4.1 (2)
C3—C4—C5—C6	−1.0 (3)	C9—C8—C13—C12	−1.5 (3)
C4—C5—C6—C1	1.6 (3)	N1—C8—C13—C12	−177.94 (17)
C2—C1—C6—C5	−0.2 (2)	C1—C7—N1—C8	−177.58 (16)
C7—C1—C6—C5	179.53 (17)	C9—C8—N1—C7	47.3 (2)
C2—C1—C7—N1	4.6 (2)	C13—C8—N1—C7	−136.53 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1^i	0.90 (2)	2.11 (2)	2.8474 (18)	138.8 (17)
O2—H2···O1	0.90 (2)	2.209 (19)	2.7237 (17)	116.0 (16)
O1—H1···N1	0.91 (2)	1.74 (2)	2.5637 (18)	150.1 (19)
C6—H6···Cg1^ii	0.93	2.77	3.519 (2)	138
C10—H10···Cg2^iii	0.93	2.92	3.615 (2)	133

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