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The title compound, C13H10ClNO2, is identified to be a nitro­ne which is stabilized by an intramolecular O—H...O hydrogen bond. In the crystal structure, the mol­ecules are packed in layers. The closest distance between the centroids of chloro­phenyl and hydroxy­phenyl rings in adjacent layers is 3.178 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001326/ob6209sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001326/ob6209Isup2.hkl
Contains datablock I

CCDC reference: 204717

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.034
  • wR factor = 0.097
  • Data-to-parameter ratio = 12.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The reaction of salicylaldehyde with 1-chloro-3-nitrobenzene yielded a solid. Its 1H NMR spectrum revealed the presence of phenyl groups. This investigation was undertaken to assign the structure and the configuration of the title compound, (I).

The ellipsoid plot (Fig. 1) and the C5—N—-C7–C8 torsion angle show that the two rings are oriented trans around the CN as observed in many non-cyclic nitrones (Hamer et al., 1964). The multiplicity of the CN indicates that the (I) exists as a nitrone and not as the isomeric oxaziridine. The molecule is non planar as revealed by plane calculations. The chlorophenyl and the hydroxyphenyl rings are planar, the r.m.s. deviation from the planarity for the two rings being 0.0012 and 0.0109 Å, respectively. The dihedral angles between by the above two planes and the C7/N/O1 plane are 35.77 (7) and 33.93 (7)°, respectively. The two aromatic rings are nearly parallel with a dihedral angle of 1.85 (8)°. The CN and N—O bond lengths are unexceptional and are very similar to the corresponding lengths observed in similar nitrones (Chandrasekar et al., 2000; Bedford et al., 1991; Pritchard et al., 1991).

The OH group is intramolecularly hydrogen bonded to the O atom of the nitrone moiety, leading to a R11(7) (Bernstein et al., 1995) arrangement (Fig. 2 and Table 2). In the crystal, the molecules are stacked in layers in which they are held together by ππ interactions, with a distance of 3.718 (2) Å between the centroids of the adjacent chlorophenyl and hydroxyphenyl rings (symmetry code: 1 − x, 2 − y, 1 − z). These rings are nearly parallel, with a dihedral angle of 1.85 (8)°. The two molecules are also held together by C—H···π interactions between the H atoms on C3 and C9 and the hydroxyphenyl and chlorophenyl rings, respectively (Table 2). These ππ and C—H···π interactions compare well with the corresponding distances of 3.563 (2) and 3.543 (3) Å observed in 3-methyl-1,4-diphenyl-1H-pyrazolo[3,4-b]pyridine (Low et al., 2002). The centroids of the chlorophenyl and hydroxyphenyl rings in the opposite direction (symmetry code: −1/2 + x, 3/2 − y, −1/2 + z) are separated by 4.612 (3) Å, leading to a segregated stacked arrangement (Desiraju, 1989).

Experimental top

The title compound was prepared by the reductive coupling of 1-chloro-3-nitrobenzene with salicylaldehyde using anhydrous tin(II) chloride in tetrahydrofuran as solvent. The product was extracted with diethyl ether and obtained as diffraction quality crystals.

Refinement top

Atoms H1 and H7 were located from a difference Fourier maps and their positional parameters were refined. The displacement parameter of H1 was fixed as 1.5Ueq(carrier atom), while that of atom H7 was refined. The O2—H1 and C7—H7 distances are 0.95 (3) and 0.94 (2) Å, respectively. The H atoms of the aromatic rings were included in the refinement at calculated positions, with Uiso = 1.2Ueq(carrier atom).

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-labelling scheme.
[Figure 2] Fig. 2. Diagram showing the packing and intramolecular hydrogen-bonding interaction.
N-(3-chlorophenyl)-α-(2-hydroxyphenyl)nitrone top
Crystal data top
C13H10ClNO2F(000) = 512
Mr = 247.67Dx = 1.486 Mg m3
Monoclinic, P21/nMelting point = 398–400 K
Hall symbol: -P 2ynCu Kα radiation, λ = 1.5418 Å
a = 5.9476 (8) ÅCell parameters from 2093 reflections
b = 14.613 (8) Åθ = 2–12°
c = 12.850 (6) ŵ = 2.96 mm1
β = 97.436 (6)°T = 293 K
V = 1107.4 (8) Å3Needle, pale yellow
Z = 40.1 × 0.05 × 0.05 mm
Data collection top
Enraf-Nnius CAD-4
diffractometer
1779 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.044
Graphite monochromatorθmax = 69.9°, θmin = 4.6°
ω–2θ scansh = 07
Absorption correction: ψ scan
(North et al., 1968)
k = 017
Tmin = 0.835, Tmax = 0.862l = 1515
2300 measured reflections3 standard reflections every 100 reflections
2093 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0449P)2 + 0.3447P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2093 reflectionsΔρmax = 0.22 e Å3
162 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0081 (6)
Crystal data top
C13H10ClNO2V = 1107.4 (8) Å3
Mr = 247.67Z = 4
Monoclinic, P21/nCu Kα radiation
a = 5.9476 (8) ŵ = 2.96 mm1
b = 14.613 (8) ÅT = 293 K
c = 12.850 (6) Å0.1 × 0.05 × 0.05 mm
β = 97.436 (6)°
Data collection top
Enraf-Nnius CAD-4
diffractometer
1779 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.044
Tmin = 0.835, Tmax = 0.8623 standard reflections every 100 reflections
2300 measured reflections intensity decay: none
2093 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.22 e Å3
2093 reflectionsΔρmin = 0.15 e Å3
162 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. The non hydrogen atoms are refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.10997 (8)0.87607 (4)0.06473 (3)0.0673 (2)
O10.17729 (18)0.84631 (9)0.46978 (9)0.0507 (3)
O20.1357 (2)0.96928 (10)0.60065 (10)0.0542 (4)
H10.124 (4)0.9255 (18)0.5458 (19)0.081*
N0.3918 (2)0.86041 (9)0.45613 (10)0.0365 (3)
C10.3185 (3)0.84911 (12)0.16810 (13)0.0432 (4)
C20.5202 (3)0.81116 (12)0.14679 (14)0.0479 (4)
H20.54580.80020.07800.057*
C30.6826 (3)0.78987 (12)0.22973 (15)0.0486 (4)
H30.81930.76440.21640.058*
C40.6464 (3)0.80565 (12)0.33237 (13)0.0438 (4)
H40.75660.79090.38790.053*
C50.4422 (3)0.84400 (11)0.35048 (12)0.0364 (3)
C60.2753 (3)0.86601 (11)0.26927 (12)0.0395 (4)
H60.13830.89140.28240.047*
C70.5452 (3)0.88661 (11)0.53128 (12)0.0372 (4)
H70.691 (3)0.8939 (11)0.5110 (14)0.040 (5)*
C80.5097 (2)0.90366 (11)0.63910 (12)0.0355 (3)
C90.6919 (3)0.88394 (12)0.71651 (14)0.0444 (4)
H90.82730.86260.69660.053*
C100.6738 (3)0.89563 (13)0.82114 (14)0.0536 (5)
H100.79380.88000.87170.064*
C110.4762 (3)0.93081 (13)0.85066 (14)0.0525 (5)
H110.46410.93900.92150.063*
C120.2970 (3)0.95383 (13)0.77668 (13)0.0480 (4)
H120.16570.97810.79780.058*
C130.3110 (3)0.94098 (11)0.67035 (12)0.0393 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0592 (3)0.1059 (5)0.0345 (3)0.0032 (3)0.00284 (19)0.0013 (2)
O10.0319 (6)0.0774 (9)0.0433 (7)0.0128 (6)0.0072 (5)0.0037 (6)
O20.0390 (6)0.0742 (9)0.0485 (7)0.0154 (6)0.0019 (5)0.0027 (6)
N0.0303 (6)0.0447 (7)0.0346 (7)0.0015 (5)0.0046 (5)0.0027 (5)
C10.0445 (9)0.0498 (10)0.0349 (8)0.0084 (7)0.0039 (7)0.0010 (7)
C20.0542 (10)0.0507 (10)0.0412 (9)0.0091 (8)0.0159 (7)0.0087 (7)
C30.0445 (9)0.0469 (10)0.0571 (11)0.0010 (7)0.0171 (8)0.0076 (8)
C40.0387 (8)0.0447 (9)0.0477 (9)0.0030 (7)0.0046 (7)0.0013 (7)
C50.0362 (8)0.0385 (8)0.0348 (8)0.0034 (6)0.0058 (6)0.0007 (6)
C60.0352 (8)0.0462 (9)0.0370 (8)0.0021 (7)0.0044 (6)0.0010 (7)
C70.0303 (8)0.0430 (9)0.0379 (8)0.0002 (6)0.0036 (6)0.0010 (6)
C80.0335 (7)0.0375 (8)0.0347 (8)0.0027 (6)0.0014 (6)0.0013 (6)
C90.0387 (9)0.0490 (10)0.0434 (9)0.0017 (7)0.0031 (7)0.0022 (7)
C100.0563 (11)0.0597 (12)0.0402 (9)0.0001 (8)0.0113 (8)0.0001 (8)
C110.0654 (11)0.0575 (11)0.0346 (8)0.0112 (9)0.0066 (8)0.0035 (8)
C120.0488 (9)0.0529 (10)0.0446 (9)0.0035 (8)0.0146 (7)0.0039 (8)
C130.0357 (8)0.0418 (9)0.0402 (8)0.0009 (6)0.0041 (6)0.0034 (7)
Geometric parameters (Å, º) top
Cl—C11.7412 (18)C5—C61.382 (2)
O1—N1.3260 (16)C6—H60.9300
O2—C131.3488 (19)C7—C81.450 (2)
O2—H10.95 (3)C7—H70.942 (18)
N—C71.298 (2)C8—C91.403 (2)
N—C51.448 (2)C8—C131.406 (2)
C1—C61.380 (2)C9—C101.373 (3)
C1—C21.380 (2)C9—H90.9300
C2—C31.378 (3)C10—C111.380 (3)
C2—H20.9300C10—H100.9300
C3—C41.383 (2)C11—C121.375 (3)
C3—H30.9300C11—H110.9300
C4—C51.384 (2)C12—C131.392 (2)
C4—H40.9300C12—H120.9300
C13—O2—H1105.3 (15)N—C7—C8125.91 (14)
C7—N—O1122.91 (13)N—C7—H7114.2 (11)
C7—N—C5122.38 (13)C8—C7—H7119.9 (11)
O1—N—C5114.70 (12)C9—C8—C13118.54 (15)
C6—C1—C2122.11 (16)C9—C8—C7116.60 (14)
C6—C1—Cl118.48 (13)C13—C8—C7124.83 (14)
C2—C1—Cl119.41 (13)C10—C9—C8121.16 (16)
C3—C2—C1118.51 (16)C10—C9—H9119.4
C3—C2—H2120.7C8—C9—H9119.4
C1—C2—H2120.7C9—C10—C11119.53 (17)
C2—C3—C4121.31 (16)C9—C10—H10120.2
C2—C3—H3119.3C11—C10—H10120.2
C4—C3—H3119.3C12—C11—C10120.83 (17)
C3—C4—C5118.44 (16)C12—C11—H11119.6
C3—C4—H4120.8C10—C11—H11119.6
C5—C4—H4120.8C11—C12—C13120.40 (16)
C6—C5—C4121.84 (15)C11—C12—H12119.8
C6—C5—N116.97 (14)C13—C12—H12119.8
C4—C5—N121.17 (14)O2—C13—C12118.09 (15)
C1—C6—C5117.79 (15)O2—C13—C8122.38 (15)
C1—C6—H6121.1C12—C13—C8119.45 (15)
C5—C6—H6121.1
C6—C1—C2—C30.1 (3)C5—N—C7—C8179.37 (14)
Cl—C1—C2—C3179.66 (13)N—C7—C8—C9147.22 (16)
C1—C2—C3—C40.1 (3)N—C7—C8—C1335.1 (3)
C2—C3—C4—C50.3 (3)C13—C8—C9—C103.7 (3)
C3—C4—C5—C60.4 (2)C7—C8—C9—C10178.45 (16)
C3—C4—C5—N178.64 (15)C8—C9—C10—C112.6 (3)
C7—N—C5—C6145.15 (16)C9—C10—C11—C120.3 (3)
O1—N—C5—C635.03 (19)C10—C11—C12—C130.8 (3)
C7—N—C5—C436.6 (2)C11—C12—C13—O2176.43 (16)
O1—N—C5—C4143.26 (15)C11—C12—C13—C80.4 (3)
C2—C1—C6—C50.3 (3)C9—C8—C13—O2174.12 (15)
Cl—C1—C6—C5179.81 (12)C7—C8—C13—O23.5 (3)
C4—C5—C6—C10.4 (2)C9—C8—C13—C122.6 (2)
N—C5—C6—C1178.71 (14)C7—C8—C13—C12179.78 (15)
O1—N—C7—C80.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1···O10.95 (3)1.57 (3)2.495 (2)163 (2)
O2—H1···N0.95 (3)2.29 (2)3.005 (2)131.7 (19)
C3—H3···Cg2i0.932.873.549 (3)131
C9—H9···Cg1ii0.932.983.536 (3)120
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x+1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC13H10ClNO2
Mr247.67
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)5.9476 (8), 14.613 (8), 12.850 (6)
β (°) 97.436 (6)
V3)1107.4 (8)
Z4
Radiation typeCu Kα
µ (mm1)2.96
Crystal size (mm)0.1 × 0.05 × 0.05
Data collection
DiffractometerEnraf-Nnius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.835, 0.862
No. of measured, independent and
observed [I > 2σ(I)] reflections
2300, 2093, 1779
Rint0.044
(sin θ/λ)max1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.097, 1.06
No. of reflections2093
No. of parameters162
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.15

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 1998), SHELXL97.

Selected geometric parameters (Å, º) top
Cl—C11.7412 (18)N—C71.298 (2)
O1—N1.3260 (16)N—C51.448 (2)
O2—C131.3488 (19)C7—C81.450 (2)
C7—N—O1122.91 (13)C2—C1—Cl119.41 (13)
C7—N—C5122.38 (13)C9—C8—C7116.60 (14)
O1—N—C5114.70 (12)O2—C13—C12118.09 (15)
C6—C1—Cl118.48 (13)O2—C13—C8122.38 (15)
Cl—C1—C2—C3179.66 (13)C5—N—C7—C8179.37 (14)
O1—N—C5—C635.03 (19)N—C7—C8—C9147.22 (16)
O1—N—C5—C4143.26 (15)N—C7—C8—C1335.1 (3)
O1—N—C7—C80.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1···O10.95 (3)1.57 (3)2.495 (2)163 (2)
C3—H3···Cg2i0.932.873.549 (3)131
C9—H9···Cg1ii0.932.983.536 (3)120
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x+1/2, y+3/2, z+1/2.
 

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