Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011379/vj1113sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011379/vj1113Isup2.hkl |
CCDC reference: 156152
To the equimolar mixture of 1-chloronitrobenzene and anhydrous tin(II) chloride in tetrahydrofuran, benzaldehyde was added. The mixture was stirred for 24 h and decomposed with dilute hydrochloric acid. The organic product was extracted with diethyl ether. Yellow crystals were obtained by the slow evaporation of solvent.
The structure was solved using SHELXS86(Sheldrick, 1985) and refined using SHELXL93(Sheldrick, 1993). The non-hydrogen atoms were refined anisotropically using their corresponding atomic scattering factors. All the hydrogen atoms were located from the difference map. Their positions were fixed in the subsequent cycles of refinement. Their thermal parameters were fixed as 1.1Ueq of the respective carrier atom save the hydrogen attached to O18 which was fixed as 1.5Ueq of the respective carrier atom. Geometrical calculations were performed using PARST96(Nardelli, 1983 & 1995) program and ZORTEP(Zsolnai, 1997) package was used to draw the thermal ellipsoidal plot.
Data collection: CAD-4 Software (Enraf Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL93.
Fig. 1. ZORTEP (Zsolnai, 1997) plot of the title compound. Displacement ellipsoids of 30% probability were used. The H atoms of the aromatic rings are omitted for clarity. |
C13H10ClNO·C7H6O2 | F(000) = 368 |
Mr = 353.79 | Dx = 1.350 Mg m−3 |
Triclinic, P1 | Melting point: 112 K |
a = 7.609 (3) Å | Cu Kα radiation, λ = 1.54180 Å |
b = 9.630 (2) Å | Cell parameters from 25 reflections |
c = 12.858 (2) Å | θ = 5–30° |
α = 110.14 (1)° | µ = 2.10 mm−1 |
β = 94.80 (2)° | T = 293 K |
γ = 96.83 (2)° | Needle, light yellow |
V = 870.5 (4) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 2 |
Enraf Nonius CAD-4 diffractometer | 2515 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.010 |
Graphite monochromator | θmax = 67.9°, θmin = 3.7° |
ω–2θ scans | h = 0→9 |
Absorption correction: ψ-scans (North et al., 1968) | k = −11→11 |
Tmin = 0.594, Tmax = 0.811 | l = −15→15 |
3424 measured reflections | 2 standard reflections every 100 reflections |
3163 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)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.146 | Calculated w = 1/[σ2(Fo2) + (0.077P)2 + 0.2612P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3163 reflections | Δρmax = 0.27 e Å−3 |
227 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Extinction correction: SHELXL93 (Sheldrick, 1993), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0045 (9) |
C13H10ClNO·C7H6O2 | γ = 96.83 (2)° |
Mr = 353.79 | V = 870.5 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.609 (3) Å | Cu Kα radiation |
b = 9.630 (2) Å | µ = 2.10 mm−1 |
c = 12.858 (2) Å | T = 293 K |
α = 110.14 (1)° | 0.20 × 0.20 × 0.10 mm |
β = 94.80 (2)° |
Enraf Nonius CAD-4 diffractometer | 2515 reflections with I > 2σ(I) |
Absorption correction: ψ-scans (North et al., 1968) | Rint = 0.010 |
Tmin = 0.594, Tmax = 0.811 | 2 standard reflections every 100 reflections |
3424 measured reflections | intensity decay: none |
3163 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.27 e Å−3 |
3163 reflections | Δρmin = −0.27 e Å−3 |
227 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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | 0.28501 (12) | 0.83929 (9) | 0.86866 (6) | 0.0874 (3) | |
C2 | 0.2404 (3) | 0.8297 (3) | 0.7310 (2) | 0.0555 (6) | |
C3 | 0.2356 (3) | 0.6936 (2) | 0.6463 (2) | 0.0500 (5) | |
C4 | 0.1973 (3) | 0.6860 (2) | 0.5369 (2) | 0.0439 (5) | |
C5 | 0.1630 (3) | 0.8119 (3) | 0.5142 (2) | 0.0556 (6) | |
C6 | 0.1677 (4) | 0.9452 (3) | 0.6016 (2) | 0.0683 (7) | |
C7 | 0.2076 (4) | 0.9563 (3) | 0.7113 (2) | 0.0633 (7) | |
N8 | 0.1907 (2) | 0.5471 (2) | 0.44268 (14) | 0.0433 (4) | |
O9 | 0.1157 (2) | 0.5455 (2) | 0.34595 (12) | 0.0513 (4) | |
O10 | 0.5424 (3) | 0.5716 (3) | 0.3216 (2) | 0.0782 (6) | |
C11 | 0.2562 (3) | 0.4333 (2) | 0.4541 (2) | 0.0484 (5) | |
C12 | 0.2563 (3) | 0.2880 (2) | 0.3697 (2) | 0.0488 (5) | |
C13 | 0.3261 (4) | 0.1836 (3) | 0.4092 (2) | 0.0627 (6) | |
C14 | 0.3325 (4) | 0.0413 (3) | 0.3374 (3) | 0.0739 (8) | |
C15 | 0.2705 (4) | −0.0012 (3) | 0.2253 (3) | 0.0788 (9) | |
C16 | 0.2029 (4) | 0.0993 (3) | 0.1849 (2) | 0.0734 (8) | |
C17 | 0.1949 (4) | 0.2436 (3) | 0.2558 (2) | 0.0590 (6) | |
O18 | 0.3283 (2) | 0.6305 (2) | 0.22562 (14) | 0.0617 (5) | |
C19 | 0.4938 (3) | 0.6108 (2) | 0.2455 (2) | 0.0481 (5) | |
C20 | 0.6142 (3) | 0.6410 (2) | 0.1684 (2) | 0.0452 (5) | |
C21 | 0.5518 (3) | 0.6805 (2) | 0.0790 (2) | 0.0499 (5) | |
C22 | 0.6679 (4) | 0.7053 (3) | 0.0079 (2) | 0.0592 (6) | |
C23 | 0.8447 (4) | 0.6900 (3) | 0.0237 (2) | 0.0662 (7) | |
C24 | 0.9080 (4) | 0.6500 (3) | 0.1121 (3) | 0.0684 (7) | |
C25 | 0.7930 (3) | 0.6262 (3) | 0.1843 (2) | 0.0587 (6) | |
H3 | 0.2604 | 0.6042 | 0.6600 | 0.055* | |
H5 | 0.1253 | 0.8016 | 0.4400 | 0.047* | |
H6 | 0.1407 | 1.0346 | 0.5800 | 0.087* | |
H7 | 0.2121 | 1.0576 | 0.7800 | 0.068* | |
H11 | 0.3079 | 0.4500 | 0.5400 | 0.055* | |
H13 | 0.3758 | 0.2254 | 0.5000 | 0.068* | |
H14 | 0.3929 | −0.0258 | 0.3800 | 0.078* | |
H15 | 0.2598 | −0.1134 | 0.1600 | 0.079* | |
H16 | 0.1511 | 0.0583 | 0.1000 | 0.092* | |
H17 | 0.1486 | 0.3179 | 0.2200 | 0.069* | |
H18 | 0.2458 | 0.6059 | 0.2800 | 0.084* | |
H21 | 0.4125 | 0.6840 | 0.0600 | 0.068* | |
H22 | 0.6142 | 0.7318 | −0.0600 | 0.068* | |
H23 | 0.9232 | 0.7001 | −0.0400 | 0.068* | |
H24 | 1.0395 | 0.6316 | 0.1200 | 0.063* | |
H25 | 0.8332 | 0.5847 | 0.2400 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1078 (7) | 0.1008 (6) | 0.0506 (4) | 0.0302 (5) | 0.0066 (4) | 0.0199 (4) |
C2 | 0.0495 (13) | 0.0632 (14) | 0.0541 (13) | 0.0091 (11) | 0.0092 (10) | 0.0208 (11) |
C3 | 0.0526 (13) | 0.0519 (12) | 0.0523 (12) | 0.0144 (10) | 0.0106 (10) | 0.0244 (10) |
C4 | 0.0404 (11) | 0.0446 (11) | 0.0517 (11) | 0.0087 (9) | 0.0096 (9) | 0.0221 (9) |
C5 | 0.0612 (15) | 0.0524 (13) | 0.0613 (14) | 0.0150 (11) | 0.0070 (11) | 0.0290 (11) |
C6 | 0.080 (2) | 0.0510 (14) | 0.081 (2) | 0.0176 (13) | 0.0115 (14) | 0.0293 (13) |
C7 | 0.064 (2) | 0.0501 (13) | 0.070 (2) | 0.0088 (11) | 0.0121 (12) | 0.0136 (11) |
N8 | 0.0407 (9) | 0.0503 (10) | 0.0466 (9) | 0.0100 (7) | 0.0090 (7) | 0.0251 (8) |
O9 | 0.0530 (9) | 0.0608 (9) | 0.0475 (8) | 0.0147 (7) | 0.0028 (7) | 0.0278 (7) |
O10 | 0.0694 (12) | 0.119 (2) | 0.0741 (12) | 0.0254 (11) | 0.0068 (9) | 0.0670 (12) |
C11 | 0.0514 (13) | 0.0505 (12) | 0.0508 (12) | 0.0150 (10) | 0.0096 (10) | 0.0244 (10) |
C12 | 0.0450 (12) | 0.0479 (11) | 0.0607 (13) | 0.0113 (9) | 0.0160 (10) | 0.0252 (10) |
C13 | 0.061 (2) | 0.0567 (14) | 0.081 (2) | 0.0181 (12) | 0.0134 (13) | 0.0341 (13) |
C14 | 0.069 (2) | 0.0566 (15) | 0.107 (2) | 0.0227 (13) | 0.027 (2) | 0.036 (2) |
C15 | 0.077 (2) | 0.0502 (14) | 0.108 (2) | 0.0150 (13) | 0.039 (2) | 0.0192 (15) |
C16 | 0.084 (2) | 0.059 (2) | 0.070 (2) | 0.0097 (14) | 0.0227 (15) | 0.0127 (13) |
C17 | 0.066 (2) | 0.0536 (13) | 0.0592 (14) | 0.0112 (11) | 0.0168 (12) | 0.0194 (11) |
O18 | 0.0560 (10) | 0.0874 (12) | 0.0614 (10) | 0.0250 (9) | 0.0134 (8) | 0.0453 (9) |
C19 | 0.0559 (14) | 0.0453 (11) | 0.0448 (11) | 0.0132 (10) | −0.0001 (10) | 0.0183 (9) |
C20 | 0.0520 (13) | 0.0379 (10) | 0.0447 (11) | 0.0094 (9) | 0.0021 (9) | 0.0140 (8) |
C21 | 0.0553 (14) | 0.0520 (12) | 0.0437 (11) | 0.0129 (10) | 0.0026 (9) | 0.0184 (9) |
C22 | 0.064 (2) | 0.0672 (15) | 0.0511 (12) | 0.0136 (12) | 0.0075 (11) | 0.0262 (11) |
C23 | 0.064 (2) | 0.076 (2) | 0.0634 (15) | 0.0121 (13) | 0.0157 (12) | 0.0281 (13) |
C24 | 0.0502 (15) | 0.079 (2) | 0.083 (2) | 0.0169 (13) | 0.0084 (13) | 0.0346 (15) |
C25 | 0.0569 (15) | 0.0612 (14) | 0.0639 (14) | 0.0144 (11) | −0.0006 (11) | 0.0302 (12) |
Cl1—C2 | 1.743 (2) | C14—C15 | 1.379 (5) |
C2—C7 | 1.374 (4) | C14—H14 | 1.10 |
C2—C3 | 1.380 (3) | C15—C16 | 1.375 (4) |
C3—C4 | 1.386 (3) | C15—H15 | 1.11 |
C3—H3 | 0.97 | C16—C17 | 1.387 (3) |
C4—C5 | 1.390 (3) | C16—H16 | 1.05 |
C4—N8 | 1.455 (3) | C17—H17 | 1.05 |
C5—C6 | 1.379 (4) | O18—C19 | 1.313 (3) |
C5—H5 | 0.94 | O18—H18 | 1.05 |
C6—C7 | 1.382 (4) | C19—C20 | 1.482 (3) |
C6—H6 | 1.03 | C20—C25 | 1.390 (3) |
C7—H7 | 1.06 | C20—C21 | 1.395 (3) |
N8—C11 | 1.304 (3) | C21—C22 | 1.381 (3) |
N8—O9 | 1.318 (2) | C21—H21 | 1.08 |
O10—C19 | 1.209 (3) | C22—C23 | 1.377 (4) |
C11—C12 | 1.446 (3) | C22—H22 | 1.06 |
C11—H11 | 1.09 | C23—C24 | 1.388 (4) |
C12—C17 | 1.397 (3) | C23—H23 | 1.08 |
C12—C13 | 1.409 (3) | C24—C25 | 1.384 (4) |
C13—C14 | 1.373 (4) | C24—H24 | 1.04 |
C13—H13 | 1.11 | C25—H25 | 0.98 |
C7—C2—C3 | 122.8 (2) | C15—C14—H14 | 128 |
C7—C2—Cl1 | 118.9 (2) | C16—C15—C14 | 120.1 (3) |
C3—C2—Cl1 | 118.3 (2) | C16—C15—H15 | 112 |
C2—C3—C4 | 118.1 (2) | C14—C15—H15 | 128 |
C2—C3—H3 | 123 | C15—C16—C17 | 120.7 (3) |
C4—C3—H3 | 119 | C15—C16—H16 | 116 |
C3—C4—C5 | 120.6 (2) | C17—C16—H16 | 123 |
C3—C4—N8 | 121.6 (2) | C16—C17—C12 | 119.9 (2) |
C5—C4—N8 | 117.9 (2) | C16—C17—H17 | 118 |
C6—C5—C4 | 119.3 (2) | C12—C17—H17 | 122 |
C6—C5—H5 | 121 | C19—O18—H18 | 113 |
C4—C5—H5 | 119 | O10—C19—O18 | 121.9 (2) |
C5—C6—C7 | 121.3 (2) | O10—C19—C20 | 123.3 (2) |
C5—C6—H6 | 116 | O18—C19—C20 | 114.8 (2) |
C7—C6—H6 | 123 | C25—C20—C21 | 119.3 (2) |
C2—C7—C6 | 118.0 (2) | C25—C20—C19 | 119.0 (2) |
C2—C7—H7 | 119 | C21—C20—C19 | 121.7 (2) |
C6—C7—H7 | 123 | C22—C21—C20 | 119.9 (2) |
C11—N8—O9 | 122.9 (2) | C22—C21—H21 | 119 |
C11—N8—C4 | 121.7 (2) | C20—C21—H21 | 121 |
O9—N8—C4 | 115.4 (2) | C23—C22—C21 | 120.6 (2) |
N8—C11—C12 | 128.2 (2) | C23—C22—H22 | 122 |
N8—C11—H11 | 114 | C21—C22—H22 | 117 |
C12—C11—H11 | 118 | C22—C23—C24 | 120.0 (2) |
C17—C12—C13 | 118.4 (2) | C22—C23—H23 | 116 |
C17—C12—C11 | 126.5 (2) | C24—C23—H23 | 124 |
C13—C12—C11 | 115.0 (2) | C25—C24—C23 | 119.8 (2) |
C14—C13—C12 | 120.7 (3) | C25—C24—H24 | 121 |
C14—C13—H13 | 124 | C23—C24—H24 | 119 |
C12—C13—H13 | 116 | C24—C25—C20 | 120.4 (2) |
C13—C14—C15 | 120.2 (3) | C24—C25—H25 | 120 |
C13—C14—H14 | 112 | C20—C25—H25 | 119 |
C7—C2—C3—C4 | 0.5 (4) | C11—C12—C13—C14 | 179.6 (2) |
Cl1—C2—C3—C4 | 179.0 (2) | C12—C13—C14—C15 | 0.0 (4) |
C2—C3—C4—C5 | −0.6 (3) | C13—C14—C15—C16 | 0.4 (5) |
C2—C3—C4—N8 | 179.6 (2) | C14—C15—C16—C17 | −0.5 (5) |
C3—C4—C5—C6 | 0.1 (4) | C15—C16—C17—C12 | 0.1 (4) |
N8—C4—C5—C6 | 179.8 (2) | C13—C12—C17—C16 | 0.3 (4) |
C4—C5—C6—C7 | 0.6 (4) | C11—C12—C17—C16 | −179.6 (2) |
C3—C2—C7—C6 | 0.3 (4) | O10—C19—C20—C25 | −1.0 (3) |
Cl1—C2—C7—C6 | −178.3 (2) | O18—C19—C20—C25 | 178.7 (2) |
C5—C6—C7—C2 | −0.8 (4) | O10—C19—C20—C21 | 177.5 (2) |
C3—C4—N8—C11 | −14.7 (3) | O18—C19—C20—C21 | −2.8 (3) |
C5—C4—N8—C11 | 165.5 (2) | C25—C20—C21—C22 | −0.4 (3) |
C3—C4—N8—O9 | 165.8 (2) | C19—C20—C21—C22 | −178.9 (2) |
C5—C4—N8—O9 | −14.0 (3) | C20—C21—C22—C23 | 0.6 (4) |
O9—N8—C11—C12 | −2.0 (4) | C21—C22—C23—C24 | −0.3 (4) |
C4—N8—C11—C12 | 178.6 (2) | C22—C23—C24—C25 | −0.2 (4) |
N8—C11—C12—C17 | 4.3 (4) | C23—C24—C25—C20 | 0.4 (4) |
N8—C11—C12—C13 | −175.6 (2) | C21—C20—C25—C24 | −0.1 (4) |
C17—C12—C13—C14 | −0.3 (4) | C19—C20—C25—C24 | 178.4 (2) |
Experimental details
Crystal data | |
Chemical formula | C13H10ClNO·C7H6O2 |
Mr | 353.79 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.609 (3), 9.630 (2), 12.858 (2) |
α, β, γ (°) | 110.14 (1), 94.80 (2), 96.83 (2) |
V (Å3) | 870.5 (4) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 2.10 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Enraf Nonius CAD-4 diffractometer |
Absorption correction | ψ-scans (North et al., 1968) |
Tmin, Tmax | 0.594, 0.811 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3424, 3163, 2515 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.146, 1.05 |
No. of reflections | 3163 |
No. of parameters | 227 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.27 |
Computer programs: CAD-4 Software (Enraf Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SHELXS86 (Sheldrick, 1985), SHELXL93 (Sheldrick, 1993), ZORTEP (Zsolnai, 1997), SHELXL93.
Cl1—C2 | 1.743 (2) | O10—C19 | 1.209 (3) |
C4—N8 | 1.455 (3) | C11—C12 | 1.446 (3) |
N8—C11 | 1.304 (3) | O18—C19 | 1.313 (3) |
N8—O9 | 1.318 (2) | O18—H18 | 1.05 |
C7—C2—Cl1 | 118.9 (2) | C19—O18—H18 | 113 |
C3—C2—Cl1 | 118.3 (2) | O10—C19—O18 | 121.9 (2) |
C11—N8—O9 | 122.9 (2) | O10—C19—C20 | 123.3 (2) |
C11—N8—C4 | 121.7 (2) | O18—C19—C20 | 114.8 (2) |
O9—N8—C4 | 115.4 (2) | ||
C4—N8—C11—C12 | 178.6 (2) |
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The title complex, (I), was isolated during our research on the organic functional group transformations mediated by anhydrous tin(II) chloride. Its IR and 1H NMR spectra indicated the presence of the nitrone as well as the carboxylic acid group. This investigation was undertaken to assign the stereochemistry of the nitrone and to precisely determine the nature of its bonding with the COOH group. \sch
As found by this investigation, the asymmetric unit is made up of one molecule each of benzoic acid and nitrone. In the latter, the 3-chlorophenyl and the phenyl groups are bonded to nitrogen and carbon, respectively. The ZORTEP (Zsolnai, 1997) plot (Fig. 1) and the C4—N8—C11—C12 torsion angle, 178.6 (2)°, show that the two rings are oriented trans around the C═N bond. That the non-acid part of the title complex, (I), exists as a nitrone and not as the isomeric oxaziridine is indicated by the multiplicity of the –N8═C11 bond. Further, the nitrone molecule is non-planar, the dihedral angle between the two aromatic rings being 11.1 (1)°. This precludes appreciable delocalization between them. As expected, the C4—N8—O9—C11—C12 part of the molecule is nearly planar, the deviations of the atoms from the least-squares plane being −0.005 (1), 0.000 (1), 0.002 (1), 0.012 (2) and −0.008 (1) Å, respectively. The C═N and N—O bond lengths are comparable to similar bond lengths in N-methyl(phenyl)nitrone and N-(4-fluorophenyl)diphenylnitrone (Bedford et al., 1991; Pritchard et al., 1991). The benzoic acid molecule is oriented away from the planes of the phenyl and the chlorophenyl groups with dihedral angles of 75.1 (2) and 76.1 (2)°, respectively. The two molecules are held together by a D18—H18···O9 hydrogen bond [O18···O9 = 2.580 (3) Å, O18—H18···O9 = 171.1 (3)°].