Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001326/ob6209sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001326/ob6209Isup2.hkl |
CCDC reference: 204717
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.
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).
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.
C13H10ClNO2 | F(000) = 512 |
Mr = 247.67 | Dx = 1.486 Mg m−3 |
Monoclinic, P21/n | Melting point = 398–400 K |
Hall symbol: -P 2yn | Cu Kα radiation, λ = 1.5418 Å |
a = 5.9476 (8) Å | Cell parameters from 2093 reflections |
b = 14.613 (8) Å | θ = 2–12° |
c = 12.850 (6) Å | µ = 2.96 mm−1 |
β = 97.436 (6)° | T = 293 K |
V = 1107.4 (8) Å3 | Needle, pale yellow |
Z = 4 | 0.1 × 0.05 × 0.05 mm |
Enraf-Nnius CAD-4 diffractometer | 1779 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 69.9°, θmin = 4.6° |
ω–2θ scans | h = 0→7 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→17 |
Tmin = 0.835, Tmax = 0.862 | l = −15→15 |
2300 measured reflections | 3 standard reflections every 100 reflections |
2093 independent reflections | intensity decay: none |
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)] = 0.034 | H 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 reflections | Δρmax = 0.22 e Å−3 |
162 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0081 (6) |
C13H10ClNO2 | V = 1107.4 (8) Å3 |
Mr = 247.67 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 5.9476 (8) Å | µ = 2.96 mm−1 |
b = 14.613 (8) Å | T = 293 K |
c = 12.850 (6) Å | 0.1 × 0.05 × 0.05 mm |
β = 97.436 (6)° |
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 = 0.862 | 3 standard reflections every 100 reflections |
2300 measured reflections | intensity decay: none |
2093 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.22 e Å−3 |
2093 reflections | Δρmin = −0.15 e Å−3 |
162 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | 0.10997 (8) | 0.87607 (4) | 0.06473 (3) | 0.0673 (2) | |
O1 | 0.17729 (18) | 0.84631 (9) | 0.46978 (9) | 0.0507 (3) | |
O2 | 0.1357 (2) | 0.96928 (10) | 0.60065 (10) | 0.0542 (4) | |
H1 | 0.124 (4) | 0.9255 (18) | 0.5458 (19) | 0.081* | |
N | 0.3918 (2) | 0.86041 (9) | 0.45613 (10) | 0.0365 (3) | |
C1 | 0.3185 (3) | 0.84911 (12) | 0.16810 (13) | 0.0432 (4) | |
C2 | 0.5202 (3) | 0.81116 (12) | 0.14679 (14) | 0.0479 (4) | |
H2 | 0.5458 | 0.8002 | 0.0780 | 0.057* | |
C3 | 0.6826 (3) | 0.78987 (12) | 0.22973 (15) | 0.0486 (4) | |
H3 | 0.8193 | 0.7644 | 0.2164 | 0.058* | |
C4 | 0.6464 (3) | 0.80565 (12) | 0.33237 (13) | 0.0438 (4) | |
H4 | 0.7566 | 0.7909 | 0.3879 | 0.053* | |
C5 | 0.4422 (3) | 0.84400 (11) | 0.35048 (12) | 0.0364 (3) | |
C6 | 0.2753 (3) | 0.86601 (11) | 0.26927 (12) | 0.0395 (4) | |
H6 | 0.1383 | 0.8914 | 0.2824 | 0.047* | |
C7 | 0.5452 (3) | 0.88661 (11) | 0.53128 (12) | 0.0372 (4) | |
H7 | 0.691 (3) | 0.8939 (11) | 0.5110 (14) | 0.040 (5)* | |
C8 | 0.5097 (2) | 0.90366 (11) | 0.63910 (12) | 0.0355 (3) | |
C9 | 0.6919 (3) | 0.88394 (12) | 0.71651 (14) | 0.0444 (4) | |
H9 | 0.8273 | 0.8626 | 0.6966 | 0.053* | |
C10 | 0.6738 (3) | 0.89563 (13) | 0.82114 (14) | 0.0536 (5) | |
H10 | 0.7938 | 0.8800 | 0.8717 | 0.064* | |
C11 | 0.4762 (3) | 0.93081 (13) | 0.85066 (14) | 0.0525 (5) | |
H11 | 0.4641 | 0.9390 | 0.9215 | 0.063* | |
C12 | 0.2970 (3) | 0.95383 (13) | 0.77668 (13) | 0.0480 (4) | |
H12 | 0.1657 | 0.9781 | 0.7978 | 0.058* | |
C13 | 0.3110 (3) | 0.94098 (11) | 0.67035 (12) | 0.0393 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0592 (3) | 0.1059 (5) | 0.0345 (3) | −0.0032 (3) | −0.00284 (19) | 0.0013 (2) |
O1 | 0.0319 (6) | 0.0774 (9) | 0.0433 (7) | −0.0128 (6) | 0.0072 (5) | −0.0037 (6) |
O2 | 0.0390 (6) | 0.0742 (9) | 0.0485 (7) | 0.0154 (6) | 0.0019 (5) | 0.0027 (6) |
N | 0.0303 (6) | 0.0447 (7) | 0.0346 (7) | −0.0015 (5) | 0.0046 (5) | 0.0027 (5) |
C1 | 0.0445 (9) | 0.0498 (10) | 0.0349 (8) | −0.0084 (7) | 0.0039 (7) | −0.0010 (7) |
C2 | 0.0542 (10) | 0.0507 (10) | 0.0412 (9) | −0.0091 (8) | 0.0159 (7) | −0.0087 (7) |
C3 | 0.0445 (9) | 0.0469 (10) | 0.0571 (11) | 0.0010 (7) | 0.0171 (8) | −0.0076 (8) |
C4 | 0.0387 (8) | 0.0447 (9) | 0.0477 (9) | 0.0030 (7) | 0.0046 (7) | −0.0013 (7) |
C5 | 0.0362 (8) | 0.0385 (8) | 0.0348 (8) | −0.0034 (6) | 0.0058 (6) | −0.0007 (6) |
C6 | 0.0352 (8) | 0.0462 (9) | 0.0370 (8) | −0.0021 (7) | 0.0044 (6) | −0.0010 (7) |
C7 | 0.0303 (8) | 0.0430 (9) | 0.0379 (8) | −0.0002 (6) | 0.0036 (6) | 0.0010 (6) |
C8 | 0.0335 (7) | 0.0375 (8) | 0.0347 (8) | −0.0027 (6) | 0.0014 (6) | 0.0013 (6) |
C9 | 0.0387 (9) | 0.0490 (10) | 0.0434 (9) | 0.0017 (7) | −0.0031 (7) | −0.0022 (7) |
C10 | 0.0563 (11) | 0.0597 (12) | 0.0402 (9) | 0.0001 (8) | −0.0113 (8) | −0.0001 (8) |
C11 | 0.0654 (11) | 0.0575 (11) | 0.0346 (8) | −0.0112 (9) | 0.0066 (8) | −0.0035 (8) |
C12 | 0.0488 (9) | 0.0529 (10) | 0.0446 (9) | −0.0035 (8) | 0.0146 (7) | −0.0039 (8) |
C13 | 0.0357 (8) | 0.0418 (9) | 0.0402 (8) | −0.0009 (6) | 0.0041 (6) | 0.0034 (7) |
Cl—C1 | 1.7412 (18) | C5—C6 | 1.382 (2) |
O1—N | 1.3260 (16) | C6—H6 | 0.9300 |
O2—C13 | 1.3488 (19) | C7—C8 | 1.450 (2) |
O2—H1 | 0.95 (3) | C7—H7 | 0.942 (18) |
N—C7 | 1.298 (2) | C8—C9 | 1.403 (2) |
N—C5 | 1.448 (2) | C8—C13 | 1.406 (2) |
C1—C6 | 1.380 (2) | C9—C10 | 1.373 (3) |
C1—C2 | 1.380 (2) | C9—H9 | 0.9300 |
C2—C3 | 1.378 (3) | C10—C11 | 1.380 (3) |
C2—H2 | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.383 (2) | C11—C12 | 1.375 (3) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.384 (2) | C12—C13 | 1.392 (2) |
C4—H4 | 0.9300 | C12—H12 | 0.9300 |
C13—O2—H1 | 105.3 (15) | N—C7—C8 | 125.91 (14) |
C7—N—O1 | 122.91 (13) | N—C7—H7 | 114.2 (11) |
C7—N—C5 | 122.38 (13) | C8—C7—H7 | 119.9 (11) |
O1—N—C5 | 114.70 (12) | C9—C8—C13 | 118.54 (15) |
C6—C1—C2 | 122.11 (16) | C9—C8—C7 | 116.60 (14) |
C6—C1—Cl | 118.48 (13) | C13—C8—C7 | 124.83 (14) |
C2—C1—Cl | 119.41 (13) | C10—C9—C8 | 121.16 (16) |
C3—C2—C1 | 118.51 (16) | C10—C9—H9 | 119.4 |
C3—C2—H2 | 120.7 | C8—C9—H9 | 119.4 |
C1—C2—H2 | 120.7 | C9—C10—C11 | 119.53 (17) |
C2—C3—C4 | 121.31 (16) | C9—C10—H10 | 120.2 |
C2—C3—H3 | 119.3 | C11—C10—H10 | 120.2 |
C4—C3—H3 | 119.3 | C12—C11—C10 | 120.83 (17) |
C3—C4—C5 | 118.44 (16) | C12—C11—H11 | 119.6 |
C3—C4—H4 | 120.8 | C10—C11—H11 | 119.6 |
C5—C4—H4 | 120.8 | C11—C12—C13 | 120.40 (16) |
C6—C5—C4 | 121.84 (15) | C11—C12—H12 | 119.8 |
C6—C5—N | 116.97 (14) | C13—C12—H12 | 119.8 |
C4—C5—N | 121.17 (14) | O2—C13—C12 | 118.09 (15) |
C1—C6—C5 | 117.79 (15) | O2—C13—C8 | 122.38 (15) |
C1—C6—H6 | 121.1 | C12—C13—C8 | 119.45 (15) |
C5—C6—H6 | 121.1 | ||
C6—C1—C2—C3 | −0.1 (3) | C5—N—C7—C8 | −179.37 (14) |
Cl—C1—C2—C3 | −179.66 (13) | N—C7—C8—C9 | 147.22 (16) |
C1—C2—C3—C4 | 0.1 (3) | N—C7—C8—C13 | −35.1 (3) |
C2—C3—C4—C5 | −0.3 (3) | C13—C8—C9—C10 | 3.7 (3) |
C3—C4—C5—C6 | 0.4 (2) | C7—C8—C9—C10 | −178.45 (16) |
C3—C4—C5—N | 178.64 (15) | C8—C9—C10—C11 | −2.6 (3) |
C7—N—C5—C6 | −145.15 (16) | C9—C10—C11—C12 | 0.3 (3) |
O1—N—C5—C6 | 35.03 (19) | C10—C11—C12—C13 | 0.8 (3) |
C7—N—C5—C4 | 36.6 (2) | C11—C12—C13—O2 | −176.43 (16) |
O1—N—C5—C4 | −143.26 (15) | C11—C12—C13—C8 | 0.4 (3) |
C2—C1—C6—C5 | 0.3 (3) | C9—C8—C13—O2 | 174.12 (15) |
Cl—C1—C6—C5 | 179.81 (12) | C7—C8—C13—O2 | −3.5 (3) |
C4—C5—C6—C1 | −0.4 (2) | C9—C8—C13—C12 | −2.6 (2) |
N—C5—C6—C1 | −178.71 (14) | C7—C8—C13—C12 | 179.78 (15) |
O1—N—C7—C8 | 0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1 | 0.95 (3) | 1.57 (3) | 2.495 (2) | 163 (2) |
O2—H1···N | 0.95 (3) | 2.29 (2) | 3.005 (2) | 131.7 (19) |
C3—H3···Cg2i | 0.93 | 2.87 | 3.549 (3) | 131 |
C9—H9···Cg1ii | 0.93 | 2.98 | 3.536 (3) | 120 |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H10ClNO2 |
Mr | 247.67 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 5.9476 (8), 14.613 (8), 12.850 (6) |
β (°) | 97.436 (6) |
V (Å3) | 1107.4 (8) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.96 |
Crystal size (mm) | 0.1 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nnius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.835, 0.862 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2300, 2093, 1779 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.097, 1.06 |
No. of reflections | 2093 |
No. of parameters | 162 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
Cl—C1 | 1.7412 (18) | N—C7 | 1.298 (2) |
O1—N | 1.3260 (16) | N—C5 | 1.448 (2) |
O2—C13 | 1.3488 (19) | C7—C8 | 1.450 (2) |
C7—N—O1 | 122.91 (13) | C2—C1—Cl | 119.41 (13) |
C7—N—C5 | 122.38 (13) | C9—C8—C7 | 116.60 (14) |
O1—N—C5 | 114.70 (12) | O2—C13—C12 | 118.09 (15) |
C6—C1—Cl | 118.48 (13) | O2—C13—C8 | 122.38 (15) |
Cl—C1—C2—C3 | −179.66 (13) | C5—N—C7—C8 | −179.37 (14) |
O1—N—C5—C6 | 35.03 (19) | N—C7—C8—C9 | 147.22 (16) |
O1—N—C5—C4 | −143.26 (15) | N—C7—C8—C13 | −35.1 (3) |
O1—N—C7—C8 | 0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1 | 0.95 (3) | 1.57 (3) | 2.495 (2) | 163 (2) |
C3—H3···Cg2i | 0.93 | 2.87 | 3.549 (3) | 131 |
C9—H9···Cg1ii | 0.93 | 2.98 | 3.536 (3) | 120 |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2. |
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 C═N as observed in many non-cyclic nitrones (Hamer et al., 1964). The multiplicity of the C═N 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 C═N 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 π–π 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 π–π 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).