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An almost planar conformation exhibited by the title mol­ecule, C14H12ClNO2, is stabilized by an intramolecular O—H...N hydrogen bond, which forms a ring of graph-set motif S(6). In the crystal structure, π–π and C—H...π interactions involving both the aromatic rings form two-dimensional networks.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013606/ci6231sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013606/ci6231Isup2.hkl
Contains datablock I

CCDC reference: 217613

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.050
  • wR factor = 0.144
  • Data-to-parameter ratio = 7.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
ABSTM_02 Alert A The ratio of Tmax/Tmin expected RT(exp) is > 1.30 An absorption correction should be applied. Tmin and Tmax expected: 0.267 0.586 RT(exp) = 2.200 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 69.91 From the CIF: _reflns_number_total 1220 Count of symmetry unique reflns 1231 Completeness (_total/calc) 99.11% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

The title compound, (I), was obtained by condensing o-vanillin with o-chloroaniline. Vanillin occurs naturally in vanilla, in potato parings, in siam benzoin, etc. Vanillin is used as a flavoring agent in confectionary, beverages,foods, etc. and as a reagent in analytical chemistry. Vanillin is of current interest due to its non-linear optical properties (Singh et al., 1991). The crystal structures of vanillin-I (Velavan et al., 1995), the polymorphic forms of isovanillin (Iwasaki, 1973), o-vanillin (Iwasaki et al., 1976) and the vanillin derivatives (Usman et al., 2002; Li et al., 1999) have been reported. A study on the condensation of aniline and its derivatives with salicylaldehyde has been reported (Khera et al., 1983). The Schiff base ligands of o-vanillin derivatives with aniline and o-, m- and p-toluidine have also been reported (Viswanathamuthy et al., 2000). In order to gain more structural information on these systems, compound (I) was investigated.

The title molecule (Fig. 1) is slightly distorted from a planar arrangement. The dihedral angle between the two aromatic rings is 7.8 (2)° and the torsion angle C6—N1—C7—C8 is −179.1 (3)°. The almost planar conformation exhibited by the molecule is stabilized by an intramolecular O2—H2···N1 hydrogen bond, which forms a ring of graph-set motif S(6). The methoxy group is coplanar with the attached benzene ring. The bond distances observed in the molecule (Table 1) are comparable with those reported for related structures (Usman et al., 2002; Sethuraman & Muthiah, 2002). In the crystal, the molecules translated by one unit along the a axis are arranged such that the two phenyl rings are stacked with a centroid-to-centroid distance of 3.724 (3) Å, indicating weak ππ interactions. The adjacent symmetry-related stackings are linked by C—H···π interactions (Desiraju, 2002), involving the two phenyl rings (Table 2), to form two-dimensional networks (Fig. 2).

Experimental top

Methanol solutions of o-vanillin (152 mg, Merck) and o-chloroaniline (127 mg, Merck) were mixed in 1:1 molar ratio and refluxed for 1 h, yielding the title compound. Recrystallization from methanol gave orange plate-like crystals suitable for X-ray study.

Refinement top

H atoms were treated as riding atoms, with C—H distances in the range 0.93–0.96 Å and O—H distance of 0.82 Å. As the intensities of Friedel opposites were not measured, the absolute configuration could not be established. Since the crystal belongs to a non-centrosymmetric space group and intensities for Friedel opposites were not measured, the r/p ratio (7.48) is poor. The ratio of Tmax/Tmin expected is 2.2. But we were unable to apply absorption correction, as the ψ scan data were not collected.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the intramolecular hydrogen bond.
[Figure 2] Fig. 2. The molecular packing in the unit cell, viewed down the b axis.
3-methoxysalicylidene-2-chloroaniline top
Crystal data top
C14H12ClNO2Dx = 1.399 Mg m3
Mr = 261.70Melting point: 108 K
Orthorhombic, Pn21aCu Kα radiation, λ = 1.54180 Å
Hall symbol: P -2ac -2nCell parameters from 25 reflections
a = 6.409 (1) Åθ = 4.5–69.9°
b = 13.062 (1) ŵ = 2.67 mm1
c = 14.842 (1) ÅT = 293 K
V = 1242.5 (2) Å3Plate, orange
Z = 40.6 × 0.6 × 0.2 mm
F(000) = 544
Data collection top
Enraf-Nonius CAD-4 four-circle
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 69.9°, θmin = 4.5°
Graphite monochromatorh = 07
ω–2θ scansk = 015
1220 measured reflectionsl = 018
1220 independent reflections1 standard reflections every 100 reflections
1136 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.1185P)2 + 0.0697P]
where P = (Fo2 + 2Fc2)/3
1220 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.64 e Å3
1 restraintΔρmin = 0.32 e Å3
0 constraints
Crystal data top
C14H12ClNO2V = 1242.5 (2) Å3
Mr = 261.70Z = 4
Orthorhombic, Pn21aCu Kα radiation
a = 6.409 (1) ŵ = 2.67 mm1
b = 13.062 (1) ÅT = 293 K
c = 14.842 (1) Å0.6 × 0.6 × 0.2 mm
Data collection top
Enraf-Nonius CAD-4 four-circle
diffractometer
Rint = 0.000
1220 measured reflections1 standard reflections every 100 reflections
1220 independent reflections intensity decay: none
1136 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0501 restraint
wR(F2) = 0.144H-atom parameters constrained
S = 1.06Δρmax = 0.64 e Å3
1220 reflectionsΔρmin = 0.32 e Å3
163 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl11.0284 (2)0.01223 (10)0.11971 (7)0.0696 (4)
O10.2849 (5)0.0199 (3)0.1305 (2)0.0642 (10)
O20.6194 (4)0.0583 (2)0.0390 (2)0.0598 (9)
N10.8944 (4)0.1886 (3)0.01662 (19)0.0464 (8)
C11.1601 (6)0.1279 (3)0.1171 (3)0.0507 (11)
C21.3403 (7)0.1381 (4)0.1665 (3)0.0613 (12)
C31.4420 (7)0.2319 (4)0.1664 (3)0.0643 (14)
C41.3658 (7)0.3113 (4)0.1168 (3)0.0563 (11)
C51.1858 (6)0.3002 (3)0.0670 (3)0.0539 (11)
C61.0773 (5)0.2076 (3)0.0667 (2)0.0443 (9)
C70.7918 (6)0.2599 (3)0.0219 (3)0.0508 (11)
C80.6053 (6)0.2372 (3)0.0741 (2)0.0502 (11)
C90.5288 (6)0.1382 (3)0.0795 (3)0.0473 (10)
C100.3454 (6)0.1186 (3)0.1296 (3)0.0512 (10)
C110.2485 (6)0.1996 (4)0.1735 (3)0.0566 (11)
C120.3271 (7)0.2987 (4)0.1680 (3)0.0640 (14)
C130.5035 (6)0.3190 (4)0.1185 (3)0.0583 (14)
C140.1065 (7)0.0049 (5)0.1839 (3)0.0747 (18)
H20.723370.077680.011720.0897*
H31.562800.240560.200240.0770*
H41.435890.373680.116660.0677*
H51.136160.355060.033200.0648*
H70.836830.327280.016510.0610*
H110.128840.187280.207240.0682*
H120.259600.351700.198010.0769*
H130.555070.385420.114250.0698*
H14A0.078780.076970.179710.1120*
H14B0.012190.032640.162350.1120*
H14C0.132880.013030.245640.1120*
H201.392900.083240.199350.0736*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0814 (7)0.0484 (5)0.0790 (7)0.0009 (6)0.0116 (5)0.0022 (5)
O10.0519 (15)0.0662 (19)0.0745 (16)0.0049 (16)0.0134 (12)0.0017 (14)
O20.0510 (15)0.0507 (15)0.0777 (16)0.0006 (13)0.0191 (14)0.0009 (14)
N10.0373 (12)0.0506 (15)0.0514 (14)0.0041 (13)0.0013 (11)0.0023 (13)
C10.0490 (19)0.049 (2)0.054 (2)0.0037 (17)0.0002 (14)0.0020 (15)
C20.060 (2)0.064 (2)0.060 (2)0.012 (2)0.0118 (18)0.0014 (19)
C30.047 (2)0.082 (3)0.064 (2)0.001 (2)0.0078 (17)0.005 (2)
C40.0460 (19)0.060 (2)0.063 (2)0.0080 (18)0.0012 (15)0.0073 (17)
C50.0476 (19)0.056 (2)0.058 (2)0.0028 (16)0.0008 (15)0.0001 (17)
C60.0370 (14)0.0514 (19)0.0445 (15)0.0060 (15)0.0033 (13)0.0070 (14)
C70.0485 (18)0.0465 (19)0.0574 (19)0.0006 (16)0.0011 (15)0.0014 (16)
C80.0433 (18)0.055 (2)0.0522 (18)0.0084 (15)0.0012 (15)0.0020 (16)
C90.0419 (16)0.053 (2)0.0471 (17)0.0077 (16)0.0047 (14)0.0051 (15)
C100.0387 (16)0.062 (2)0.0528 (18)0.0033 (17)0.0019 (13)0.0039 (15)
C110.0447 (18)0.072 (2)0.053 (2)0.0089 (19)0.0074 (15)0.001 (2)
C120.057 (2)0.070 (3)0.065 (2)0.022 (2)0.0065 (17)0.005 (2)
C130.053 (2)0.055 (2)0.067 (3)0.0053 (18)0.0019 (16)0.0039 (18)
C140.045 (2)0.095 (4)0.084 (3)0.018 (2)0.014 (2)0.004 (3)
Geometric parameters (Å, º) top
Cl1—C11.731 (4)C9—C101.414 (6)
O1—C101.346 (6)C10—C111.389 (6)
O1—C141.428 (6)C11—C121.391 (7)
O2—C91.337 (5)C12—C131.374 (6)
O2—H20.82C2—H200.93
N1—C71.275 (5)C3—H30.93
N1—C61.410 (4)C4—H40.93
C1—C61.387 (5)C5—H50.93
C1—C21.374 (6)C7—H70.93
C2—C31.388 (7)C11—H110.93
C3—C41.362 (7)C12—H120.93
C4—C51.378 (6)C13—H130.93
C5—C61.395 (5)C14—H14A0.96
C7—C81.455 (5)C14—H14B0.96
C8—C131.415 (6)C14—H14C0.96
C8—C91.385 (6)
Cl1···N12.896 (4)C11···H11iv3.0168
Cl1···H22.8910C11···H14C2.7630
Cl1···H7i2.9880C12···H11iv3.0474
Cl1···H12ii3.0256C14···H112.5381
Cl1···H13i3.1427H2···Cl12.8910
Cl1···H20iii2.9709H2···N11.8648
O1···O22.587 (4)H2···C63.0627
O2···N12.585 (4)H2···C72.4249
O2···O12.587 (4)H3···C2viii2.9776
O1···H14Civ2.8916H4···O1ix2.6253
O1···H4i2.6253H4···O2ix2.6962
O2···H4i2.6962H5···C72.6617
N1···Cl12.896 (4)H5···H72.0872
N1···O22.585 (4)H7···C52.5814
N1···H21.8648H7···H52.0872
C4···C7v3.485 (6)H7···H132.4376
C4···C8v3.365 (6)H7···Cl1ix2.9880
C5···C8v3.506 (5)H11···C142.5381
C5···C13v3.433 (6)H11···H14B2.3110
C6···C10v3.577 (5)H11···H14C2.3465
C7···C4vi3.485 (6)H11···C11x3.0168
C8···C4vi3.365 (6)H11···C12x3.0474
C8···C5vi3.506 (5)H12···Cl1vii3.0256
C10···C6vi3.577 (5)H13···H72.4376
C13···C5vi3.433 (6)H13···Cl1ix3.1427
C2···H3iii2.9776H14A···C5ii2.8719
C5···H14Avii2.8719H14B···C112.7522
C5···H72.5814H14B···H112.3110
C6···H23.0627H14C···C112.7630
C7···H22.4249H14C···H112.3465
C7···H52.6617H14C···O1x2.8916
C10···H14Civ2.9538H14C···C10x2.9538
C11···H14B2.7522H20···Cl1viii2.9709
C10—O1—C14116.9 (4)C11—C12—C13120.6 (4)
C9—O2—H2109.51C8—C13—C12118.9 (4)
C6—N1—C7122.4 (4)C1—C2—H20120.64
Cl1—C1—C2118.8 (3)C3—C2—H20120.70
C2—C1—C6122.4 (4)C2—C3—H3119.86
Cl1—C1—C6118.7 (3)C4—C3—H3119.85
C1—C2—C3118.7 (4)C3—C4—H4119.66
C2—C3—C4120.3 (4)C5—C4—H4119.68
C3—C4—C5120.7 (4)C4—C5—H5119.63
C4—C5—C6120.7 (4)C6—C5—H5119.69
N1—C6—C1118.0 (3)N1—C7—H7119.52
C1—C6—C5117.3 (3)C8—C7—H7119.59
N1—C6—C5124.7 (3)C10—C11—H11119.31
N1—C7—C8120.9 (4)C12—C11—H11119.42
C7—C8—C9120.8 (3)C11—C12—H12119.74
C7—C8—C13118.2 (4)C13—C12—H12119.68
C9—C8—C13121.0 (4)C8—C13—H13120.58
O2—C9—C8123.3 (4)C12—C13—H13120.56
O2—C9—C10117.1 (3)O1—C14—H14A109.55
C8—C9—C10119.6 (4)O1—C14—H14B109.49
O1—C10—C11126.6 (4)O1—C14—H14C109.45
C9—C10—C11118.7 (4)H14A—C14—H14B109.43
O1—C10—C9114.7 (4)H14A—C14—H14C109.47
C10—C11—C12121.3 (4)H14B—C14—H14C109.43
C14—O1—C10—C9176.9 (4)N1—C7—C8—C93.2 (6)
C14—O1—C10—C111.9 (6)N1—C7—C8—C13177.3 (4)
C7—N1—C6—C1170.5 (4)C9—C8—C13—C120.5 (6)
C6—N1—C7—C8179.1 (3)C7—C8—C13—C12180.0 (4)
C7—N1—C6—C511.8 (5)C7—C8—C9—O20.7 (6)
Cl1—C1—C2—C3178.1 (3)C7—C8—C9—C10179.0 (4)
Cl1—C1—C6—C5179.2 (3)C13—C8—C9—O2179.8 (4)
C2—C1—C6—N1178.5 (4)C13—C8—C9—C100.4 (6)
C2—C1—C6—C50.6 (6)O2—C9—C10—O10.3 (6)
C6—C1—C2—C30.5 (7)C8—C9—C10—C111.1 (6)
Cl1—C1—C6—N12.9 (5)O2—C9—C10—C11179.2 (4)
C1—C2—C3—C41.2 (7)C8—C9—C10—O1179.9 (4)
C2—C3—C4—C50.8 (7)C9—C10—C11—C120.8 (6)
C3—C4—C5—C60.3 (7)O1—C10—C11—C12179.5 (4)
C4—C5—C6—C11.0 (6)C10—C11—C12—C130.1 (7)
C4—C5—C6—N1178.8 (4)C11—C12—C13—C80.8 (6)
Symmetry codes: (i) x+2, y1/2, z; (ii) x+1, y1/2, z; (iii) x1/2, y, z1/2; (iv) x+1/2, y, z+1/2; (v) x+1, y, z; (vi) x1, y, z; (vii) x+1, y+1/2, z; (viii) x+1/2, y, z1/2; (ix) x+2, y+1/2, z; (x) x1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.862.585 (4)146
C3—H3···Cg1viii0.933.013.819 (5)146
C11—H11···Cg2x0.932.853.656 (5)145
Symmetry codes: (viii) x+1/2, y, z1/2; (x) x1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H12ClNO2
Mr261.70
Crystal system, space groupOrthorhombic, Pn21a
Temperature (K)293
a, b, c (Å)6.409 (1), 13.062 (1), 14.842 (1)
V3)1242.5 (2)
Z4
Radiation typeCu Kα
µ (mm1)2.67
Crystal size (mm)0.6 × 0.6 × 0.2
Data collection
DiffractometerEnraf-Nonius CAD-4 four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1220, 1220, 1136
Rint0.000
(sin θ/λ)max1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.144, 1.06
No. of reflections1220
No. of parameters163
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.64, 0.32

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

Selected geometric parameters (Å, º) top
Cl1—C11.731 (4)O2—C91.337 (5)
O1—C101.346 (6)N1—C71.275 (5)
O1—C141.428 (6)N1—C61.410 (4)
C10—O1—C14116.9 (4)N1—C7—C8120.9 (4)
C6—N1—C7122.4 (4)O2—C9—C8123.3 (4)
Cl1—C1—C2118.8 (3)O2—C9—C10117.1 (3)
Cl1—C1—C6118.7 (3)O1—C10—C11126.6 (4)
N1—C6—C1118.0 (3)O1—C10—C9114.7 (4)
N1—C6—C5124.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.862.585 (4)146
C3—H3···Cg1i0.933.013.819 (5)146
C11—H11···Cg2ii0.932.853.656 (5)145
Symmetry codes: (i) x+1/2, y, z1/2; (ii) x1/2, y, z+1/2.
 

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