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The identity of the title complex, C13H10ClNO·C7H6O2, is confirmed to be a hydrogen-bonded adduct of benzoic acid and N-(3-chloro­phenyl)-[alpha]-phenyl­nitro­ne. The two aromatic rings in the nitro­ne are trans about the C=N bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011379/vj1113sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011379/vj1113Isup2.hkl
Contains datablock I

CCDC reference: 156152

Comment top

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 CN 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 –N8C11 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 CN 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)°].

Experimental top

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.

Refinement top

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.

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: 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.

Figures top
[Figure 1] 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.
N-(benzylidene)(3-chlorophenyl)N-oxide top
Crystal data top
C13H10ClNO·C7H6O2F(000) = 368
Mr = 353.79Dx = 1.350 Mg m3
Triclinic, P1Melting point: 112 K
a = 7.609 (3) ÅCu Kα radiation, λ = 1.54180 Å
b = 9.630 (2) ÅCell parameters from 25 reflections
c = 12.858 (2) Åθ = 5–30°
α = 110.14 (1)°µ = 2.10 mm1
β = 94.80 (2)°T = 293 K
γ = 96.83 (2)°Needle, light yellow
V = 870.5 (4) Å30.20 × 0.20 × 0.10 mm
Z = 2
Data collection top
Enraf Nonius CAD-4
diffractometer
2515 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.010
Graphite monochromatorθmax = 67.9°, θmin = 3.7°
ω–2θ scansh = 09
Absorption correction: ψ-scans
(North et al., 1968)
k = 1111
Tmin = 0.594, Tmax = 0.811l = 1515
3424 measured reflections2 standard reflections every 100 reflections
3163 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)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146Calculated w = 1/[σ2(Fo2) + (0.077P)2 + 0.2612P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3163 reflectionsΔρmax = 0.27 e Å3
227 parametersΔρmin = 0.27 e Å3
0 restraintsExtinction correction: SHELXL93 (Sheldrick, 1993), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0045 (9)
Crystal data top
C13H10ClNO·C7H6O2γ = 96.83 (2)°
Mr = 353.79V = 870.5 (4) Å3
Triclinic, P1Z = 2
a = 7.609 (3) ÅCu Kα radiation
b = 9.630 (2) ŵ = 2.10 mm1
c = 12.858 (2) ÅT = 293 K
α = 110.14 (1)°0.20 × 0.20 × 0.10 mm
β = 94.80 (2)°
Data collection top
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 = 0.8112 standard reflections every 100 reflections
3424 measured reflections intensity decay: none
3163 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.27 e Å3
3163 reflectionsΔρmin = 0.27 e Å3
227 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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.28501 (12)0.83929 (9)0.86866 (6)0.0874 (3)
C20.2404 (3)0.8297 (3)0.7310 (2)0.0555 (6)
C30.2356 (3)0.6936 (2)0.6463 (2)0.0500 (5)
C40.1973 (3)0.6860 (2)0.5369 (2)0.0439 (5)
C50.1630 (3)0.8119 (3)0.5142 (2)0.0556 (6)
C60.1677 (4)0.9452 (3)0.6016 (2)0.0683 (7)
C70.2076 (4)0.9563 (3)0.7113 (2)0.0633 (7)
N80.1907 (2)0.5471 (2)0.44268 (14)0.0433 (4)
O90.1157 (2)0.5455 (2)0.34595 (12)0.0513 (4)
O100.5424 (3)0.5716 (3)0.3216 (2)0.0782 (6)
C110.2562 (3)0.4333 (2)0.4541 (2)0.0484 (5)
C120.2563 (3)0.2880 (2)0.3697 (2)0.0488 (5)
C130.3261 (4)0.1836 (3)0.4092 (2)0.0627 (6)
C140.3325 (4)0.0413 (3)0.3374 (3)0.0739 (8)
C150.2705 (4)0.0012 (3)0.2253 (3)0.0788 (9)
C160.2029 (4)0.0993 (3)0.1849 (2)0.0734 (8)
C170.1949 (4)0.2436 (3)0.2558 (2)0.0590 (6)
O180.3283 (2)0.6305 (2)0.22562 (14)0.0617 (5)
C190.4938 (3)0.6108 (2)0.2455 (2)0.0481 (5)
C200.6142 (3)0.6410 (2)0.1684 (2)0.0452 (5)
C210.5518 (3)0.6805 (2)0.0790 (2)0.0499 (5)
C220.6679 (4)0.7053 (3)0.0079 (2)0.0592 (6)
C230.8447 (4)0.6900 (3)0.0237 (2)0.0662 (7)
C240.9080 (4)0.6500 (3)0.1121 (3)0.0684 (7)
C250.7930 (3)0.6262 (3)0.1843 (2)0.0587 (6)
H30.26040.60420.66000.055*
H50.12530.80160.44000.047*
H60.14071.03460.58000.087*
H70.21211.05760.78000.068*
H110.30790.45000.54000.055*
H130.37580.22540.50000.068*
H140.39290.02580.38000.078*
H150.25980.11340.16000.079*
H160.15110.05830.10000.092*
H170.14860.31790.22000.069*
H180.24580.60590.28000.084*
H210.41250.68400.06000.068*
H220.61420.73180.06000.068*
H230.92320.70010.04000.068*
H241.03950.63160.12000.063*
H250.83320.58470.24000.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1078 (7)0.1008 (6)0.0506 (4)0.0302 (5)0.0066 (4)0.0199 (4)
C20.0495 (13)0.0632 (14)0.0541 (13)0.0091 (11)0.0092 (10)0.0208 (11)
C30.0526 (13)0.0519 (12)0.0523 (12)0.0144 (10)0.0106 (10)0.0244 (10)
C40.0404 (11)0.0446 (11)0.0517 (11)0.0087 (9)0.0096 (9)0.0221 (9)
C50.0612 (15)0.0524 (13)0.0613 (14)0.0150 (11)0.0070 (11)0.0290 (11)
C60.080 (2)0.0510 (14)0.081 (2)0.0176 (13)0.0115 (14)0.0293 (13)
C70.064 (2)0.0501 (13)0.070 (2)0.0088 (11)0.0121 (12)0.0136 (11)
N80.0407 (9)0.0503 (10)0.0466 (9)0.0100 (7)0.0090 (7)0.0251 (8)
O90.0530 (9)0.0608 (9)0.0475 (8)0.0147 (7)0.0028 (7)0.0278 (7)
O100.0694 (12)0.119 (2)0.0741 (12)0.0254 (11)0.0068 (9)0.0670 (12)
C110.0514 (13)0.0505 (12)0.0508 (12)0.0150 (10)0.0096 (10)0.0244 (10)
C120.0450 (12)0.0479 (11)0.0607 (13)0.0113 (9)0.0160 (10)0.0252 (10)
C130.061 (2)0.0567 (14)0.081 (2)0.0181 (12)0.0134 (13)0.0341 (13)
C140.069 (2)0.0566 (15)0.107 (2)0.0227 (13)0.027 (2)0.036 (2)
C150.077 (2)0.0502 (14)0.108 (2)0.0150 (13)0.039 (2)0.0192 (15)
C160.084 (2)0.059 (2)0.070 (2)0.0097 (14)0.0227 (15)0.0127 (13)
C170.066 (2)0.0536 (13)0.0592 (14)0.0112 (11)0.0168 (12)0.0194 (11)
O180.0560 (10)0.0874 (12)0.0614 (10)0.0250 (9)0.0134 (8)0.0453 (9)
C190.0559 (14)0.0453 (11)0.0448 (11)0.0132 (10)0.0001 (10)0.0183 (9)
C200.0520 (13)0.0379 (10)0.0447 (11)0.0094 (9)0.0021 (9)0.0140 (8)
C210.0553 (14)0.0520 (12)0.0437 (11)0.0129 (10)0.0026 (9)0.0184 (9)
C220.064 (2)0.0672 (15)0.0511 (12)0.0136 (12)0.0075 (11)0.0262 (11)
C230.064 (2)0.076 (2)0.0634 (15)0.0121 (13)0.0157 (12)0.0281 (13)
C240.0502 (15)0.079 (2)0.083 (2)0.0169 (13)0.0084 (13)0.0346 (15)
C250.0569 (15)0.0612 (14)0.0639 (14)0.0144 (11)0.0006 (11)0.0302 (12)
Geometric parameters (Å, º) top
Cl1—C21.743 (2)C14—C151.379 (5)
C2—C71.374 (4)C14—H141.10
C2—C31.380 (3)C15—C161.375 (4)
C3—C41.386 (3)C15—H151.11
C3—H30.97C16—C171.387 (3)
C4—C51.390 (3)C16—H161.05
C4—N81.455 (3)C17—H171.05
C5—C61.379 (4)O18—C191.313 (3)
C5—H50.94O18—H181.05
C6—C71.382 (4)C19—C201.482 (3)
C6—H61.03C20—C251.390 (3)
C7—H71.06C20—C211.395 (3)
N8—C111.304 (3)C21—C221.381 (3)
N8—O91.318 (2)C21—H211.08
O10—C191.209 (3)C22—C231.377 (4)
C11—C121.446 (3)C22—H221.06
C11—H111.09C23—C241.388 (4)
C12—C171.397 (3)C23—H231.08
C12—C131.409 (3)C24—C251.384 (4)
C13—C141.373 (4)C24—H241.04
C13—H131.11C25—H250.98
C7—C2—C3122.8 (2)C15—C14—H14128
C7—C2—Cl1118.9 (2)C16—C15—C14120.1 (3)
C3—C2—Cl1118.3 (2)C16—C15—H15112
C2—C3—C4118.1 (2)C14—C15—H15128
C2—C3—H3123C15—C16—C17120.7 (3)
C4—C3—H3119C15—C16—H16116
C3—C4—C5120.6 (2)C17—C16—H16123
C3—C4—N8121.6 (2)C16—C17—C12119.9 (2)
C5—C4—N8117.9 (2)C16—C17—H17118
C6—C5—C4119.3 (2)C12—C17—H17122
C6—C5—H5121C19—O18—H18113
C4—C5—H5119O10—C19—O18121.9 (2)
C5—C6—C7121.3 (2)O10—C19—C20123.3 (2)
C5—C6—H6116O18—C19—C20114.8 (2)
C7—C6—H6123C25—C20—C21119.3 (2)
C2—C7—C6118.0 (2)C25—C20—C19119.0 (2)
C2—C7—H7119C21—C20—C19121.7 (2)
C6—C7—H7123C22—C21—C20119.9 (2)
C11—N8—O9122.9 (2)C22—C21—H21119
C11—N8—C4121.7 (2)C20—C21—H21121
O9—N8—C4115.4 (2)C23—C22—C21120.6 (2)
N8—C11—C12128.2 (2)C23—C22—H22122
N8—C11—H11114C21—C22—H22117
C12—C11—H11118C22—C23—C24120.0 (2)
C17—C12—C13118.4 (2)C22—C23—H23116
C17—C12—C11126.5 (2)C24—C23—H23124
C13—C12—C11115.0 (2)C25—C24—C23119.8 (2)
C14—C13—C12120.7 (3)C25—C24—H24121
C14—C13—H13124C23—C24—H24119
C12—C13—H13116C24—C25—C20120.4 (2)
C13—C14—C15120.2 (3)C24—C25—H25120
C13—C14—H14112C20—C25—H25119
C7—C2—C3—C40.5 (4)C11—C12—C13—C14179.6 (2)
Cl1—C2—C3—C4179.0 (2)C12—C13—C14—C150.0 (4)
C2—C3—C4—C50.6 (3)C13—C14—C15—C160.4 (5)
C2—C3—C4—N8179.6 (2)C14—C15—C16—C170.5 (5)
C3—C4—C5—C60.1 (4)C15—C16—C17—C120.1 (4)
N8—C4—C5—C6179.8 (2)C13—C12—C17—C160.3 (4)
C4—C5—C6—C70.6 (4)C11—C12—C17—C16179.6 (2)
C3—C2—C7—C60.3 (4)O10—C19—C20—C251.0 (3)
Cl1—C2—C7—C6178.3 (2)O18—C19—C20—C25178.7 (2)
C5—C6—C7—C20.8 (4)O10—C19—C20—C21177.5 (2)
C3—C4—N8—C1114.7 (3)O18—C19—C20—C212.8 (3)
C5—C4—N8—C11165.5 (2)C25—C20—C21—C220.4 (3)
C3—C4—N8—O9165.8 (2)C19—C20—C21—C22178.9 (2)
C5—C4—N8—O914.0 (3)C20—C21—C22—C230.6 (4)
O9—N8—C11—C122.0 (4)C21—C22—C23—C240.3 (4)
C4—N8—C11—C12178.6 (2)C22—C23—C24—C250.2 (4)
N8—C11—C12—C174.3 (4)C23—C24—C25—C200.4 (4)
N8—C11—C12—C13175.6 (2)C21—C20—C25—C240.1 (4)
C17—C12—C13—C140.3 (4)C19—C20—C25—C24178.4 (2)

Experimental details

Crystal data
Chemical formulaC13H10ClNO·C7H6O2
Mr353.79
Crystal system, space groupTriclinic, 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)
V3)870.5 (4)
Z2
Radiation typeCu Kα
µ (mm1)2.10
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerEnraf Nonius CAD-4
diffractometer
Absorption correctionψ-scans
(North et al., 1968)
Tmin, Tmax0.594, 0.811
No. of measured, independent and
observed [I > 2σ(I)] reflections
3424, 3163, 2515
Rint0.010
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.146, 1.05
No. of reflections3163
No. of parameters227
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Cl1—C21.743 (2)O10—C191.209 (3)
C4—N81.455 (3)C11—C121.446 (3)
N8—C111.304 (3)O18—C191.313 (3)
N8—O91.318 (2)O18—H181.05
C7—C2—Cl1118.9 (2)C19—O18—H18113
C3—C2—Cl1118.3 (2)O10—C19—O18121.9 (2)
C11—N8—O9122.9 (2)O10—C19—C20123.3 (2)
C11—N8—C4121.7 (2)O18—C19—C20114.8 (2)
O9—N8—C4115.4 (2)
C4—N8—C11—C12178.6 (2)
 

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