organic compounds
2-[(4-Chlorophenyl)iminomethyl]hydroquinone
aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayís University, TR-55139 Kurupelit–Samsun, Turkey, and bDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayís University, TR-55139 Kurupelit–Samsun, Turkey
*Correspondence e-mail: orhanb@omu.edu.tr
The title compound, C13H10ClNO2, exists in the phenol–imine form in the crystal, and the aromatic rings are oriented at a dihedral angle of 2.82 (9)°. An intramolecular O—H⋯N hydrogen bond results in the formation of a planar six-membered ring. In the intermolecular O—H⋯O hydrogen bonds link the molecules into chains.
Related literature
For general background to o-hydroxy see: Calligaris et al. (1972); Hadjoudis et al. (1987); Hökelek et al. (2004); Maslen & Waters (1975); Moustakali-Mavridis et al. (1980); Xu et al. (1994). For related structures, see: Filarowski et al. (2003); Karadayı et al. (2003); Yıldız et al. (1998).
Experimental
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2002); cell X-RED32 (Stoe & Cie, 2002); data reduction: X-RED32; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536809015396/hk2670sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809015396/hk2670Isup2.hkl
The title compound was prepared by refluxing a mixture of a solution containing 2,5-dihydroxybenzaldehyde (0.034 g 0.246 mmol) in ethanol (20 ml) and a solution containing 4-chloroaniline (0.031 g 0.246 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. Crystals suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield; 69%; m.p. 439-441 K).
H atoms were positioned geometrically, with O-H = 0.82 Å (for OH) and C-H = 0.93 Å for aromatic H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.5 for OH H and x = 1.2 for aromatic H atoms.
Data collection: X-AREA (Stoe & Cie, 2002); cell
X-RED32 (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).C13H10ClNO2 | F(000) = 512 |
Mr = 247.67 | Dx = 1.481 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 13223 reflections |
a = 20.3347 (14) Å | θ = 1.7–27.2° |
b = 4.5848 (2) Å | µ = 0.33 mm−1 |
c = 12.0383 (9) Å | T = 296 K |
β = 98.231 (6)° | Plate, brown |
V = 1110.78 (12) Å3 | 0.80 × 0.40 × 0.06 mm |
Z = 4 |
Stoe IPDS-II diffractometer | 2185 independent reflections |
Radiation source: fine-focus sealed tube | 1575 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.0° |
ω scans | h = −25→25 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −5→5 |
Tmin = 0.819, Tmax = 0.978 | l = −14→14 |
15373 measured reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0571P)2] where P = (Fo2 + 2Fc2)/3 |
2185 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C13H10ClNO2 | V = 1110.78 (12) Å3 |
Mr = 247.67 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.3347 (14) Å | µ = 0.33 mm−1 |
b = 4.5848 (2) Å | T = 296 K |
c = 12.0383 (9) Å | 0.80 × 0.40 × 0.06 mm |
β = 98.231 (6)° |
Stoe IPDS-II diffractometer | 2185 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 1575 reflections with I > 2σ(I) |
Tmin = 0.819, Tmax = 0.978 | Rint = 0.069 |
15373 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.13 e Å−3 |
2185 reflections | Δρmin = −0.25 e Å−3 |
154 parameters |
Experimental. 370 frames, detector distance = 120 mm |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.46483 (2) | 1.40871 (10) | 0.33464 (4) | 0.06076 (18) | |
O1 | 0.21937 (7) | 0.2322 (3) | 0.60021 (10) | 0.0600 (4) | |
H1 | 0.2441 | 0.3500 | 0.5759 | 0.090* | |
O2 | 0.03814 (6) | −0.1943 (3) | 0.25297 (11) | 0.0554 (3) | |
H2 | 0.0127 | −0.3115 | 0.2757 | 0.083* | |
N1 | 0.26643 (6) | 0.5541 (3) | 0.44912 (11) | 0.0404 (3) | |
C1 | 0.31206 (7) | 0.7617 (3) | 0.41651 (14) | 0.0390 (3) | |
C2 | 0.35972 (8) | 0.8701 (4) | 0.50029 (14) | 0.0469 (4) | |
H2A | 0.3599 | 0.8079 | 0.5739 | 0.056* | |
C3 | 0.40681 (8) | 1.0686 (4) | 0.47659 (15) | 0.0491 (4) | |
H3 | 0.4388 | 1.1380 | 0.5334 | 0.059* | |
C4 | 0.40585 (8) | 1.1623 (3) | 0.36807 (15) | 0.0445 (4) | |
C5 | 0.35838 (9) | 1.0629 (4) | 0.28379 (15) | 0.0499 (4) | |
H5 | 0.3578 | 1.1304 | 0.2108 | 0.060* | |
C6 | 0.31162 (8) | 0.8628 (4) | 0.30758 (14) | 0.0480 (4) | |
H6 | 0.2796 | 0.7954 | 0.2504 | 0.058* | |
C7 | 0.22399 (8) | 0.4302 (3) | 0.37519 (13) | 0.0409 (4) | |
H7 | 0.2238 | 0.4777 | 0.3000 | 0.049* | |
C8 | 0.17625 (7) | 0.2186 (3) | 0.40433 (13) | 0.0384 (3) | |
C9 | 0.13019 (8) | 0.1001 (3) | 0.31857 (14) | 0.0421 (4) | |
H9 | 0.1312 | 0.1561 | 0.2446 | 0.051* | |
C10 | 0.08364 (8) | −0.0975 (3) | 0.34244 (14) | 0.0427 (4) | |
C11 | 0.08231 (9) | −0.1840 (4) | 0.45228 (16) | 0.0510 (4) | |
H11 | 0.0504 | −0.3164 | 0.4686 | 0.061* | |
C12 | 0.12807 (9) | −0.0745 (4) | 0.53729 (15) | 0.0530 (4) | |
H12 | 0.1274 | −0.1360 | 0.6107 | 0.064* | |
C13 | 0.17529 (8) | 0.1273 (4) | 0.51433 (13) | 0.0436 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0545 (3) | 0.0499 (3) | 0.0821 (4) | −0.0131 (2) | 0.0244 (2) | −0.0049 (2) |
O1 | 0.0675 (8) | 0.0733 (8) | 0.0374 (7) | −0.0226 (7) | 0.0010 (6) | 0.0007 (6) |
O2 | 0.0450 (7) | 0.0519 (7) | 0.0651 (8) | −0.0090 (5) | −0.0062 (6) | −0.0033 (6) |
N1 | 0.0395 (7) | 0.0397 (7) | 0.0417 (7) | −0.0030 (6) | 0.0047 (6) | −0.0009 (6) |
C1 | 0.0380 (8) | 0.0355 (7) | 0.0436 (9) | −0.0002 (6) | 0.0065 (7) | −0.0012 (7) |
C2 | 0.0499 (9) | 0.0477 (9) | 0.0426 (9) | −0.0046 (7) | 0.0049 (7) | −0.0003 (7) |
C3 | 0.0448 (9) | 0.0481 (9) | 0.0527 (11) | −0.0080 (8) | 0.0012 (7) | −0.0062 (8) |
C4 | 0.0402 (9) | 0.0367 (8) | 0.0590 (11) | −0.0017 (6) | 0.0148 (8) | −0.0036 (7) |
C5 | 0.0546 (10) | 0.0507 (9) | 0.0457 (10) | −0.0048 (8) | 0.0115 (8) | 0.0037 (8) |
C6 | 0.0469 (9) | 0.0514 (10) | 0.0446 (10) | −0.0094 (7) | 0.0025 (7) | 0.0003 (8) |
C7 | 0.0436 (8) | 0.0408 (8) | 0.0383 (9) | −0.0014 (7) | 0.0062 (7) | 0.0019 (7) |
C8 | 0.0380 (8) | 0.0371 (8) | 0.0400 (9) | 0.0013 (6) | 0.0050 (7) | −0.0007 (6) |
C9 | 0.0445 (9) | 0.0414 (8) | 0.0398 (9) | 0.0004 (7) | 0.0036 (7) | 0.0026 (7) |
C10 | 0.0360 (8) | 0.0390 (8) | 0.0514 (10) | 0.0006 (7) | 0.0008 (7) | −0.0037 (7) |
C11 | 0.0454 (10) | 0.0472 (9) | 0.0622 (12) | −0.0074 (7) | 0.0141 (8) | 0.0023 (8) |
C12 | 0.0591 (11) | 0.0559 (10) | 0.0458 (10) | −0.0076 (9) | 0.0138 (8) | 0.0056 (8) |
C13 | 0.0444 (9) | 0.0474 (9) | 0.0391 (9) | −0.0027 (7) | 0.0060 (7) | −0.0019 (7) |
O1—H1 | 0.8200 | C7—N1 | 1.280 (2) |
O2—H2 | 0.8200 | C7—C8 | 1.451 (2) |
C1—C2 | 1.387 (2) | C7—H7 | 0.9300 |
C1—C6 | 1.390 (2) | C8—C13 | 1.392 (2) |
C1—N1 | 1.4229 (19) | C8—C9 | 1.401 (2) |
C2—C3 | 1.380 (2) | C9—C10 | 1.370 (2) |
C2—H2A | 0.9300 | C9—H9 | 0.9300 |
C3—C4 | 1.373 (3) | C10—C11 | 1.384 (2) |
C3—H3 | 0.9300 | C10—O2 | 1.3883 (19) |
C4—C5 | 1.374 (2) | C11—C12 | 1.376 (3) |
C4—Cl1 | 1.7365 (16) | C11—H11 | 0.9300 |
C5—C6 | 1.381 (2) | C12—C13 | 1.389 (2) |
C5—H5 | 0.9300 | C12—H12 | 0.9300 |
C6—H6 | 0.9300 | C13—O1 | 1.3557 (19) |
C13—O1—H1 | 109.5 | N1—C7—C8 | 122.44 (14) |
C10—O2—H2 | 109.5 | N1—C7—H7 | 118.8 |
C7—N1—C1 | 120.41 (14) | C8—C7—H7 | 118.8 |
C2—C1—C6 | 118.42 (15) | C13—C8—C9 | 119.06 (15) |
C2—C1—N1 | 117.03 (14) | C13—C8—C7 | 122.16 (14) |
C6—C1—N1 | 124.55 (14) | C9—C8—C7 | 118.78 (14) |
C3—C2—C1 | 121.29 (16) | C10—C9—C8 | 120.75 (15) |
C3—C2—H2A | 119.4 | C10—C9—H9 | 119.6 |
C1—C2—H2A | 119.4 | C8—C9—H9 | 119.6 |
C4—C3—C2 | 119.16 (16) | C9—C10—C11 | 119.88 (15) |
C4—C3—H3 | 120.4 | C9—C10—O2 | 116.90 (15) |
C2—C3—H3 | 120.4 | C11—C10—O2 | 123.20 (15) |
C3—C4—C5 | 120.78 (15) | C12—C11—C10 | 120.16 (16) |
C3—C4—Cl1 | 120.53 (13) | C12—C11—H11 | 119.9 |
C5—C4—Cl1 | 118.69 (14) | C10—C11—H11 | 119.9 |
C4—C5—C6 | 119.93 (16) | C11—C12—C13 | 120.54 (16) |
C4—C5—H5 | 120.0 | C11—C12—H12 | 119.7 |
C6—C5—H5 | 120.0 | C13—C12—H12 | 119.7 |
C5—C6—C1 | 120.39 (15) | O1—C13—C12 | 118.99 (15) |
C5—C6—H6 | 119.8 | O1—C13—C8 | 121.41 (14) |
C1—C6—H6 | 119.8 | C12—C13—C8 | 119.59 (15) |
C8—C7—N1—C1 | −179.65 (13) | N1—C7—C8—C9 | 178.06 (15) |
C2—C1—N1—C7 | −175.30 (14) | C13—C8—C9—C10 | 1.7 (2) |
C6—C1—N1—C7 | 5.2 (2) | C7—C8—C9—C10 | −179.12 (14) |
C6—C1—C2—C3 | −1.5 (2) | C8—C9—C10—C11 | −0.7 (2) |
N1—C1—C2—C3 | 178.92 (14) | C8—C9—C10—O2 | 177.31 (14) |
C1—C2—C3—C4 | 0.7 (3) | C9—C10—C11—C12 | −0.7 (3) |
C2—C3—C4—C5 | 0.6 (3) | O2—C10—C11—C12 | −178.57 (15) |
C2—C3—C4—Cl1 | −179.27 (12) | C10—C11—C12—C13 | 1.1 (3) |
C3—C4—C5—C6 | −1.1 (3) | C11—C12—C13—O1 | 179.57 (16) |
Cl1—C4—C5—C6 | 178.81 (13) | C11—C12—C13—C8 | −0.1 (3) |
C4—C5—C6—C1 | 0.2 (3) | C9—C8—C13—O1 | 179.08 (14) |
C2—C1—C6—C5 | 1.1 (2) | C7—C8—C13—O1 | −0.1 (2) |
N1—C1—C6—C5 | −179.43 (15) | C9—C8—C13—C12 | −1.3 (2) |
N1—C7—C8—C13 | −2.7 (2) | C7—C8—C13—C12 | 179.54 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.90 | 2.6270 (18) | 147 |
O2—H2···O2i | 0.82 | 2.04 | 2.7631 (13) | 147 |
Symmetry code: (i) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H10ClNO2 |
Mr | 247.67 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 20.3347 (14), 4.5848 (2), 12.0383 (9) |
β (°) | 98.231 (6) |
V (Å3) | 1110.78 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.80 × 0.40 × 0.06 |
Data collection | |
Diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.819, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15373, 2185, 1575 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.091, 0.95 |
No. of reflections | 2185 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.25 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.90 | 2.6270 (18) | 147.2 |
O2—H2···O2i | 0.82 | 2.04 | 2.7631 (13) | 146.7 |
Symmetry code: (i) −x, y−1/2, −z+1/2. |
Acknowledgements
The authors wish to acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant No. F279 of the University Research Fund).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
o-Hydroxy Schiff bases derived from the reactions of o-hydroxyaldehydes with aniline have been examined extensively (Calligaris et al., 1972; Maslen & Waters, 1975). In general, o-hydroxy Schiff bases exhibit two possible tautomeric forms, namely, phenol-imine and keto-amine. Naphthaldimine and salicylaldimine can also exist in the phenol-imine and keto-amine forms, respectively depending on the stereochemistry of the molecule and the type of nitrogen substituents in naphthaldimine and salicylaldimine Schiff bases (Hökelek et al., 2004). Schiff base compounds display interesting photochromic and thermochromic features and can be classified in terms of these ( Moustakali-Mavridis et al., 1980; Hadjoudis et al., 1987). Photo- and thermochromism arise via H atom transfer from the hydroxy O atom to the N atom (Hadjoudis et al., 1987; Xu et al., 1994).
In the title compound (Fig. 1), the phenol-imine form is favored over the keto-amine form, as indicated by C13-O1 [1.356 (2) Å] and C7-N1 [1.280 (2) Å] bonds, which are in accordance with the corresponding values in a similar compound [C-O = 1.352 (3) and C-N = 1.280 (4) Å; Karadayı et al., 2003]. As a common feature of o-hydroxysalicylidene systems, the title compound displays a strong hydrogen bond between atoms N1 and O1 (Filarowski et al., 2003; Yıldız et al., 1998).
It is known that Schiff bases may exhibit thermochromism or photochromism, depending on the planarity or non-planarity of the molecule, respectively. Therefore, one can expect thermochromic properties in the title compound caused by planarity of the molecule; the dihedral angle between rings A (C1-C6) and B (C8-C13) is 2.82 (9)°. Intramolecular O-H···N hydrogen bond (Table 1) results in the formation of a planar six-membered ring C (O1/N1/C7/C8/C13/H1), which is oriented with respect to rings A and B at dihedral angles of A/C = 2.97 (8) and B/C = 1.35 (8) °. So, they are nearly coplanar.
In the crystal structure, intermolecular O-H···O hydrogen bonds (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure.