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The crystal structures of the title 4-chloro­phenyl, (I), and 2-chloro­phenyl, (II), compounds, both C14H12ClNO2, have been determined using X-ray diffraction techniques and the mol­ecular structures have also been optimized at the B3LYP/6-31 G(d,p) level using density functional theory (DFT). The X-ray study shows that the title compounds both have strong intra­molecular O-H...N hydrogen bonds and that the crystal networks are primarily determined by weak C-H...[pi] and van der Waals inter­actions. The strong intra­molecular O-H...N hydrogen bond is evidence of the preference for the phenol-imine tautomeric form in the solid state. The IR spectra of the compounds were recorded experimentally and also calculated for comparison. The results from both the experiment and theoretical calculations are compared in this study.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109034350/sf3113sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109034350/sf3113Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109034350/sf3113IIsup3.hkl
Contains datablock II

CCDC references: 642259; 653503

Comment top

Schiff bases are widely used as ligands in the field of coordination chemistry and are formed by reaction of a primary amine and an aldehyde (March, 1992). Schiff bases, especially ortho-hydroxy Schiff base derivatives, are one of the most commonly investigated classes of compound, and have attracted the interest of chemists and physicists because they show photochromism and thermochromism in the solid state. These photo- and thermochromic features are caused by proton transfer to the N atom from the O atom with light or temperature, respectively. It has been claimed that the molecules showing thermochromism are planar and that those showing photochromism are non-planar (Moustakali-Mavridis et al., 1980; Hadjoudis et al., 1987).

o-Hydroxy Schiff bases exist either as phenol–imine (benzenoid) or keto–amine (quinoid) tautomers. Quinoid tautomers can also be found in zwitterionic form and zwitterionics can differ from keto–amines with [respect to] their N+—H bond distances and the aromaticity of the rings. Depending on these tautomers, three different types of intramolecular hydrogen bonding are possible in o-hydroxy Schiff bases: O—H···N in phenol–imine, N—H···O in keto–amine and ionic N+—H···O- in zwitterionic forms [labelled (a), (b) and (c), respectively, in the scheme].

These forms [types of bonding] have been previously observed and investigated in the phenol–imine (Ünver et al., 2002; Karadayı et al., 2003), keto–amine (Pavlović & Sosa, 2000; Koşar et al., 2004) and zwitterionic (Nazır et al., 2000; Karabıyık et al., 2008) forms. Related to this phenomenon, we present here the crystallographic and molecular structures of the title compounds, (I) and (II).

In computational procedures, the geometry optimization of the molecules leading to energy minima was achieved by using the B3LYP hybrid exchange-correlation functional with the 6-31 G(d,p) basis set (Lee et al., 1988; Becke, 1993). The calculations were started from the crystallographically achieved geometries of the molecules. All calculations in this work were carried out using the GAUSSIAN03W package (Frisch et al., 2004). The optimized molecular geometries, total molecular energies, dipole moments, Mulliken charges and theoretical IR spectra were obtained from the computational process.

ORTEP-3 plots (Farrugia, 1997) with the atom-numbering schemes of the title compounds are shown in Fig. 1. It is seen that the structures reported here adopt phenol–imine tautomeric forms with their C7N1 double bonds and C9—O1 single bonds. These bond distances [1.282 (2), 1.346 (2) Å for (I) and 1.280 (2), 1.345 (2) Å for (II)] are in good agreement with each other and with those observed for (E)-4-methoxy-2-[(4-nitrophenyl)iminomethyl]phenol [1.277 (2), 1.351 (2) Å] (Ko˛sar et al., 2005) and N-(2-methyl-5-chlorophenyl)salicylaldimine [1.281 (3), 1.354 (3) Å] (Dey et al., 2001) which are also phenol–imine tautomers. On the other hand, in keto–amine tautomers of o-hydroxy Schiff bases, these distances show differences due to proton transfer. The same bond distances can be compared with the corresponding distances in 2-{[tris(hydroxymethyl) methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one [1.3025 (16), 1.2952 (18) Å] which is a keto–amine tautomer (Odabas˛ogˇlu et al., 2003).

In the phenol–imine tautomeric form, both rings of the compound must be aromatic [see (a) in the scheme]. In order to provide further verification of the phenol–imine form in the solid state and investigate the aromaticity of the rings, HOMA (Harmonic Oscillator Model of Aromaticity) indices were calculated for compounds (I) and (II) (Krygowski, 1993). The HOMA index is equal to 1 for aromatic systems (like aromatic benzene) and 0 for non-aromatics. While the calculated indices of the chloro-attached ring and the methoxy-attached ring are 0.950 and 0.951 for (I), those of (II) are 0.967 and 0.939, respectively. These values also indicate that the compounds show phenol–imine tautomerism. In both molecules, the aromatic rings adopt an E configuration around the CN double bonds and the dihedral angle between the two aromatic rings of the molecules is 15.39 (2)° for (I) and 24.49 (8)° for (II). Against this background, we can say that the compounds are non-planar and display photochromic features. On the whole, there is harmony between the X-ray crystallographic results of both title compounds.

The title compounds display strong intramolecular hydrogen bonds between the atoms O1 and N1, which is a common feature of o-hydroxysalicylidene systems (Yıldız et al., 1998; Filarowski et al., 2003). The crystal structures are stabilized by weak van der Waals and C—H···π interactions in three dimensions. Figs. 2 and 3 illustrate these C—H···π interactions. The geometric parameters of the intramolecular hydrogen bonds and the intermolecular C—H···π interactions are listed in Tables 1 and 2.

In DFT/B3LYP calculations, the total energy of the optimized geometry and the dipole moment of the molecules are obtained as -1206.12 a.u. and 2.9778 debye for (I) and -1206.12 a.u. and 23162 debye for (I). It is not surprising that the molecules have the same total energy because their only difference is the position of the chloro atom according to DFT/B3LYP calculations. Mulliken charges were calculated by determining the electron population of each atom as defined by the basis sets. According to the calculated results for Mulliken atomic charge analysis, atoms N1, O1 and O2 have larger negative charges relative to other atoms for both molecules, as expected. The charges are calculated as -0.609, -0.569, -0.512 e for (I) and -0.605, -0.566, -0.513 e for (II), respectively. The Mulliken atomic charges for the other non-H atoms and H1 are listed in Table 4.

Comparative results obtained from the X-ray crystallographic and computational studies of selected bond distances, angles and torsion angles are presented in Table 3 for (I) and (II). As can be seen from the Table, it is possible to say that there are no considerable differences between results from the X-ray experimental study and results from the DFT/B3LYP calculations for geometric parameters of the molecules, except for the torsion angles. For example, the main deviance from X-ray results is about 0.024 Å for bond lengths, about 0.43 ° for bond angles and about 14.22 ° for torsion angles. It is well known that DFT and similar calculations underestimate interactions such as inter- and intramolecular hydrogen bonds and handle molecules in the gaseous phase (in vacuo).

The experimental and computational IR spectra of compounds (I) and (II) are compared in Table 5. The DFT-based IR results show significant differences from experimental values for CN, O—H and C—O stretching due to intramolecular hydrogen bonds between N and O for both molecules. In experimental-based IR results, while CN stretching is shifted to lower frequency, O—H stretching is widened to the 2000–3000 cm-1 range.

Related literature top

For related literature, see: Becke (1993); Dey et al. (2001); Farrugia (1997); Filarowski et al. (2003); Frisch et al. (2004); Hadjoudis et al. (1987); Karabıyık, Ocak-İskeleli, Petek, Albayrak & Ağar (2008); Karadayı, Gözüyeşil, Güzel, Kazak & Büyükgüngör (2003); Koşar et al. (2004); Ko˛sar et al. (2005); Krygowski (1993); Lee et al. (1988); March (1992); Moustakali-Mavridis, Hadjoudis & Mavridis (1980); Odabas˛ogˇlu et al. (2003); Pavlović & Sosa (2000); Yıldız, Kılıç & Hökelek (1998); Ünver et al. (2002).

Experimental top

(I) was prepared by reflux of a mixture of a solution containing 4-methoxysalicylaldehyde (0.5 g 3.3 mmol) in 20 ml ethanol and a solution containing 4-chloroaniline (0.42 g 3.3 mmol) in 20 ml ethanol. The reaction mixture was stirred for 1 h under reflux. Crystals of (I) suitable for X-ray analysis were obtained from ethanol by slow evaporation (yield 80%; m.p. 396–397 K). (II) was prepared by reflux of a mixture of a solution containing 4-methoxysalicylaldehyde (0.5 g 3.3 mmol) in 20 ml ethanol and a solution containing 2-chloroaniline (0.42 g 3.3 mmol) in 20 ml ethanol. The reaction mixture was stirred for 1 h under reflux. Crystals of (II) suitable for X-ray analysis were obtained from ethanol by slow evaporation (yield 73%; m.p. 386–387 K). The IR spectra of the title compounds were recorded on a KBr disc with a Bruker 2000 FT infrared spectrometer.

Refinement top

All non-H-atom parameters were refined anisotropically for both compounds. All H atoms except for H1 in (I) were refined using riding models, with C—H distances of 0.96 Å for methyl groups and 0.93 Å for aromatic groups. The displacement parameters of these H atoms were fixed at 1.2Ueq of their parent C atom for aromatic groups and 1.5Ueq of their parent atoms for methyl groups. All H atoms in (II) were located in a difference Fourier map at the end of the refinement procedure and were refined freely.

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid views of the asymmetric units with the atom-numbering scheme for (I) (top) and (II) (bottom). Displacement ellipsoids are drawn at the 30% probability level and dashed lines indicate the intramolecular hydrogen bonds.
[Figure 2] Fig. 2. Part of the crystal structure of compound (I), showing the C—H···π bonds. For clarity, H atoms not included in intermolecular bonding have been omitted. For the symmetry codes, see Table 1.
[Figure 3] Fig. 3. Part of the crystal structure of compound (II), showing the C—H···π bonds. For the symmetry codes, see Table 2.
(I) (E)-2-[(4-Chlorophenyl)iminomethyl]-5-methoxyphenol top
Crystal data top
C14H12ClNO2F(000) = 544
Mr = 261.70Dx = 1.374 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 5.5859 (6) ÅCell parameters from 1034 reflections
b = 8.9617 (6) Åθ = 1.6–26.1°
c = 25.333 (3) ŵ = 0.29 mm1
β = 93.880 (9)°T = 293 K
V = 1265.2 (2) Å3Prism, yellow
Z = 40.52 × 0.31 × 0.12 mm
Data collection top
Stoe IPDS 2
diffractometer
2440 independent reflections
Radiation source: fine-focus sealed tube1505 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 6.67 pixels mm-1θmax = 26.0°, θmin = 1.6°
ω scanh = 66
Absorption correction: integration
(X-RED; Stoe & Cie, 2002)
k = 1111
Tmin = 0.864, Tmax = 0.968l = 3031
10988 measured reflections
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0528P)2]
where P = (Fo2 + 2Fc2)/3
2440 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.11 e Å3
1 restraintΔρmin = 0.17 e Å3
Crystal data top
C14H12ClNO2V = 1265.2 (2) Å3
Mr = 261.70Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.5859 (6) ŵ = 0.29 mm1
b = 8.9617 (6) ÅT = 293 K
c = 25.333 (3) Å0.52 × 0.31 × 0.12 mm
β = 93.880 (9)°
Data collection top
Stoe IPDS 2
diffractometer
2440 independent reflections
Absorption correction: integration
(X-RED; Stoe & Cie, 2002)
1505 reflections with I > 2σ(I)
Tmin = 0.864, Tmax = 0.968Rint = 0.036
10988 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0381 restraint
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.11 e Å3
2440 reflectionsΔρmin = 0.17 e Å3
167 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8979 (3)0.5450 (2)0.19344 (7)0.0630 (5)
C21.1110 (4)0.4659 (2)0.19480 (8)0.0736 (5)
H21.17080.42260.22640.088*
C31.2356 (4)0.4505 (2)0.14998 (8)0.0756 (5)
H31.37850.39690.15130.091*
C41.1475 (4)0.5146 (2)0.10348 (8)0.0696 (5)
C50.9382 (4)0.5941 (2)0.10109 (8)0.0782 (5)
H50.87850.63660.06940.094*
C60.8172 (3)0.6103 (2)0.14625 (8)0.0746 (5)
H60.67730.66690.14490.090*
C70.7795 (3)0.4844 (2)0.27826 (8)0.0680 (5)
H70.89510.40960.28000.082*
C80.6311 (3)0.50368 (18)0.32191 (7)0.0619 (4)
C90.4484 (3)0.61090 (19)0.32117 (6)0.0618 (4)
C100.3072 (3)0.6283 (2)0.36363 (7)0.0671 (5)
H100.18640.69990.36250.081*
C110.3473 (4)0.5386 (2)0.40754 (7)0.0678 (5)
C120.5264 (4)0.4304 (2)0.40925 (8)0.0799 (6)
H120.55250.36970.43880.096*
C130.6627 (4)0.4147 (2)0.36714 (8)0.0774 (5)
H130.78150.34180.36850.093*
C140.0517 (4)0.6660 (2)0.45455 (8)0.0924 (7)
H14A0.06620.66030.42520.111*
H14B0.13460.75970.45360.111*
H14C0.02610.65820.48710.111*
N10.7574 (3)0.56732 (17)0.23696 (6)0.0663 (4)
O10.4055 (3)0.70146 (15)0.27921 (5)0.0807 (4)
H10.507 (4)0.675 (3)0.2574 (8)0.115 (9)*
O20.2195 (3)0.54679 (16)0.45124 (5)0.0881 (4)
Cl11.30643 (11)0.49517 (7)0.04711 (2)0.0971 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0589 (11)0.0669 (10)0.0631 (11)0.0078 (8)0.0045 (9)0.0090 (8)
C20.0720 (12)0.0836 (13)0.0651 (11)0.0051 (10)0.0044 (10)0.0010 (9)
C30.0686 (12)0.0803 (13)0.0791 (14)0.0026 (10)0.0131 (10)0.0041 (10)
C40.0660 (11)0.0780 (12)0.0655 (11)0.0188 (10)0.0089 (9)0.0078 (9)
C50.0672 (12)0.1012 (15)0.0660 (12)0.0121 (11)0.0018 (10)0.0083 (10)
C60.0627 (11)0.0848 (13)0.0762 (13)0.0007 (10)0.0035 (10)0.0070 (11)
C70.0670 (11)0.0651 (11)0.0723 (12)0.0006 (9)0.0069 (9)0.0086 (9)
C80.0672 (10)0.0539 (10)0.0641 (10)0.0006 (8)0.0012 (9)0.0011 (8)
C90.0708 (11)0.0568 (10)0.0575 (10)0.0004 (9)0.0021 (9)0.0021 (8)
C100.0727 (12)0.0623 (11)0.0667 (11)0.0049 (9)0.0078 (9)0.0013 (9)
C110.0773 (12)0.0639 (11)0.0630 (11)0.0053 (9)0.0117 (10)0.0001 (9)
C120.0938 (15)0.0713 (12)0.0750 (13)0.0067 (11)0.0080 (11)0.0162 (10)
C130.0848 (13)0.0678 (11)0.0805 (13)0.0133 (10)0.0123 (11)0.0084 (10)
C140.1133 (18)0.0852 (14)0.0825 (14)0.0049 (13)0.0359 (13)0.0010 (11)
N10.0694 (10)0.0680 (9)0.0619 (9)0.0043 (7)0.0070 (7)0.0045 (7)
O10.0942 (10)0.0851 (9)0.0640 (8)0.0227 (7)0.0126 (7)0.0135 (7)
O20.1078 (11)0.0845 (9)0.0753 (9)0.0089 (8)0.0303 (8)0.0120 (7)
Cl10.0862 (4)0.1320 (5)0.0755 (4)0.0201 (3)0.0247 (3)0.0077 (3)
Geometric parameters (Å, º) top
C1—C61.379 (3)C8—C91.401 (2)
C1—C21.384 (3)C9—O11.346 (2)
C1—N11.410 (2)C9—C101.385 (2)
C2—C31.379 (2)C10—C111.379 (2)
C2—H20.9300C10—H100.9300
C3—C41.372 (3)C11—O21.359 (2)
C3—H30.9300C11—C121.392 (3)
C4—C51.367 (3)C12—C131.359 (3)
C4—Cl11.7404 (19)C12—H120.9300
C5—C61.375 (3)C13—H130.9300
C5—H50.9300C14—O21.428 (2)
C6—H60.9300C14—H14A0.9600
C7—N11.282 (2)C14—H14B0.9600
C7—C81.436 (2)C14—H14C0.9600
C7—H70.9300O1—H10.851 (16)
C8—C131.398 (3)
C6—C1—C2117.99 (17)O1—C9—C10117.73 (16)
C6—C1—N1116.80 (17)O1—C9—C8120.97 (15)
C2—C1—N1125.19 (18)C10—C9—C8121.30 (16)
C3—C2—C1120.82 (19)C11—C10—C9119.41 (17)
C3—C2—H2119.6C11—C10—H10120.3
C1—C2—H2119.6C9—C10—H10120.3
C4—C3—C2119.57 (19)O2—C11—C10124.09 (17)
C4—C3—H3120.2O2—C11—C12115.35 (17)
C2—C3—H3120.2C10—C11—C12120.57 (17)
C5—C4—C3120.82 (18)C13—C12—C11119.18 (18)
C5—C4—Cl1119.88 (16)C13—C12—H12120.4
C3—C4—Cl1119.30 (16)C11—C12—H12120.4
C4—C5—C6119.05 (19)C12—C13—C8122.53 (18)
C4—C5—H5120.5C12—C13—H13118.7
C6—C5—H5120.5C8—C13—H13118.7
C5—C6—C1121.71 (18)O2—C14—H14A109.5
C5—C6—H6119.1O2—C14—H14B109.5
C1—C6—H6119.1H14A—C14—H14B109.5
N1—C7—C8122.02 (18)O2—C14—H14C109.5
N1—C7—H7119.0H14A—C14—H14C109.5
C8—C7—H7119.0H14B—C14—H14C109.5
C13—C8—C9116.99 (16)C7—N1—C1121.88 (17)
C13—C8—C7121.01 (17)C9—O1—H1104.9 (17)
C9—C8—C7122.00 (16)C11—O2—C14118.11 (15)
C6—C1—C2—C31.3 (3)C7—C8—C9—C10179.83 (17)
N1—C1—C2—C3179.94 (18)O1—C9—C10—C11179.37 (17)
C1—C2—C3—C40.1 (3)C8—C9—C10—C110.1 (3)
C2—C3—C4—C50.2 (3)C9—C10—C11—O2179.88 (18)
C2—C3—C4—Cl1179.78 (15)C9—C10—C11—C120.6 (3)
C3—C4—C5—C60.6 (3)O2—C11—C12—C13179.97 (19)
Cl1—C4—C5—C6178.92 (15)C10—C11—C12—C130.4 (3)
C4—C5—C6—C11.9 (3)C11—C12—C13—C80.3 (3)
C2—C1—C6—C52.2 (3)C9—C8—C13—C120.7 (3)
N1—C1—C6—C5179.05 (17)C7—C8—C13—C12179.63 (19)
N1—C7—C8—C13178.25 (18)C8—C7—N1—C1177.86 (16)
N1—C7—C8—C92.1 (3)C6—C1—N1—C7162.47 (17)
C13—C8—C9—O1179.97 (17)C2—C1—N1—C718.9 (3)
C7—C8—C9—O10.4 (3)C10—C11—O2—C147.3 (3)
C13—C8—C9—C100.5 (3)C12—C11—O2—C14173.10 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.85 (2)1.81 (2)2.596 (2)154 (2)
C13—H13···Cg1i0.933.043.896 (2)154
C14—H14a···Cg2ii0.963.103.975 (2)153
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x1, y, z.
(II) (E)-2-[(2-chlorophenyl)iminomethyl]-5-methoxyphenol top
Crystal data top
C14H12ClNO2F(000) = 1088
Mr = 261.70Dx = 1.397 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1405 reflections
a = 22.446 (3) Åθ = 2.0–27.9°
b = 7.2259 (7) ŵ = 0.30 mm1
c = 16.727 (2) ÅT = 293 K
β = 113.428 (9)°Prism, yellow
V = 2489.3 (5) Å30.50 × 0.47 × 0.21 mm
Z = 8
Data collection top
Stoe IPDS 2
diffractometer
2885 independent reflections
Radiation source: fine-focus sealed tube1854 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 6.67 pixels mm-1θmax = 27.8°, θmin = 2.0°
ω scanh = 2929
Absorption correction: integration
(X-RED; Stoe & Cie, 2002)
k = 99
Tmin = 0.838, Tmax = 0.939l = 2120
10001 measured reflections
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102All H-atom parameters refined
S = 0.91 w = 1/[σ2(Fo2) + (0.0624P)2]
where P = (Fo2 + 2Fc2)/3
2885 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C14H12ClNO2V = 2489.3 (5) Å3
Mr = 261.70Z = 8
Monoclinic, C2/cMo Kα radiation
a = 22.446 (3) ŵ = 0.30 mm1
b = 7.2259 (7) ÅT = 293 K
c = 16.727 (2) Å0.50 × 0.47 × 0.21 mm
β = 113.428 (9)°
Data collection top
Stoe IPDS 2
diffractometer
2885 independent reflections
Absorption correction: integration
(X-RED; Stoe & Cie, 2002)
1854 reflections with I > 2σ(I)
Tmin = 0.838, Tmax = 0.939Rint = 0.039
10001 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.102All H-atom parameters refined
S = 0.91Δρmax = 0.14 e Å3
2885 reflectionsΔρmin = 0.24 e Å3
211 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.42395 (8)0.2233 (2)0.11846 (11)0.0527 (4)
C20.44456 (10)0.4022 (2)0.14697 (13)0.0648 (5)
C30.40265 (11)0.5267 (3)0.16034 (14)0.0750 (6)
C40.33993 (12)0.4775 (3)0.14362 (14)0.0759 (6)
C50.31725 (10)0.3051 (3)0.11152 (13)0.0665 (5)
C60.35919 (8)0.1802 (2)0.09859 (12)0.0565 (4)
C70.52583 (9)0.0879 (2)0.15313 (12)0.0562 (4)
C80.56799 (7)0.0562 (2)0.14682 (10)0.0502 (4)
C90.54375 (7)0.2107 (2)0.09273 (10)0.0486 (4)
C100.58516 (7)0.3512 (2)0.08971 (11)0.0501 (4)
C110.65098 (7)0.3360 (2)0.13993 (11)0.0508 (4)
C120.67613 (8)0.1835 (2)0.19309 (12)0.0579 (4)
C130.63524 (8)0.0480 (2)0.19656 (12)0.0581 (4)
C140.67348 (10)0.6226 (3)0.08690 (16)0.0701 (5)
Cl10.33013 (2)0.03715 (7)0.05831 (4)0.0800 (2)
N10.46449 (6)0.08415 (17)0.10849 (9)0.0550 (3)
O10.48004 (5)0.22914 (17)0.04290 (9)0.0624 (3)
O20.69536 (5)0.46541 (16)0.14193 (8)0.0657 (3)
H10.4612 (12)0.132 (3)0.0508 (16)0.098 (8)*
H20.4878 (9)0.440 (2)0.1559 (12)0.065 (5)*
H30.4211 (10)0.645 (3)0.1778 (14)0.083 (6)*
H40.3104 (10)0.555 (3)0.1530 (14)0.084 (6)*
H50.2739 (9)0.264 (2)0.0993 (12)0.065 (5)*
H70.5468 (9)0.180 (3)0.1964 (14)0.075 (6)*
H100.5676 (8)0.450 (2)0.0544 (12)0.060 (5)*
H120.7217 (9)0.176 (2)0.2244 (12)0.066 (5)*
H130.6525 (8)0.058 (2)0.2338 (12)0.066 (5)*
H14A0.7106 (10)0.694 (3)0.0989 (13)0.078 (6)*
H14B0.6502 (10)0.585 (3)0.0235 (16)0.082 (6)*
H14C0.6424 (11)0.686 (3)0.1015 (14)0.085 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0635 (10)0.0500 (8)0.0462 (9)0.0111 (7)0.0233 (7)0.0058 (7)
C20.0715 (12)0.0538 (9)0.0623 (12)0.0075 (8)0.0194 (9)0.0069 (8)
C30.0920 (15)0.0504 (10)0.0703 (14)0.0146 (10)0.0191 (11)0.0016 (9)
C40.0932 (15)0.0633 (11)0.0717 (14)0.0312 (11)0.0333 (11)0.0035 (9)
C50.0677 (11)0.0647 (10)0.0711 (13)0.0180 (9)0.0317 (9)0.0085 (9)
C60.0652 (10)0.0522 (8)0.0538 (10)0.0116 (7)0.0256 (8)0.0074 (7)
C70.0606 (10)0.0578 (9)0.0497 (10)0.0024 (7)0.0215 (8)0.0025 (7)
C80.0509 (8)0.0542 (8)0.0452 (9)0.0014 (6)0.0187 (7)0.0013 (7)
C90.0422 (8)0.0561 (8)0.0460 (9)0.0015 (6)0.0158 (6)0.0003 (7)
C100.0457 (8)0.0534 (8)0.0479 (10)0.0020 (6)0.0150 (7)0.0058 (7)
C110.0444 (8)0.0590 (9)0.0465 (9)0.0043 (6)0.0157 (6)0.0015 (7)
C120.0419 (8)0.0698 (10)0.0524 (10)0.0020 (7)0.0086 (7)0.0071 (8)
C130.0560 (9)0.0622 (9)0.0489 (10)0.0044 (8)0.0132 (7)0.0116 (8)
C140.0580 (11)0.0659 (11)0.0780 (15)0.0100 (9)0.0182 (10)0.0109 (10)
Cl10.0656 (3)0.0608 (3)0.1120 (5)0.0026 (2)0.0337 (3)0.0128 (3)
N10.0571 (8)0.0540 (7)0.0565 (9)0.0076 (5)0.0254 (7)0.0023 (6)
O10.0412 (6)0.0636 (7)0.0726 (8)0.0017 (5)0.0121 (5)0.0117 (6)
O20.0467 (6)0.0705 (7)0.0684 (8)0.0102 (5)0.0107 (5)0.0121 (6)
Geometric parameters (Å, º) top
C1—C61.391 (2)C8—C131.405 (2)
C1—C21.392 (2)C9—O11.3451 (18)
C1—N11.4097 (19)C9—C101.391 (2)
C2—C31.383 (3)C10—C111.383 (2)
C2—H20.961 (18)C10—H100.908 (18)
C3—C41.369 (3)C11—O21.3567 (18)
C3—H30.94 (2)C11—C121.388 (2)
C4—C51.372 (3)C12—C131.359 (2)
C4—H40.92 (2)C12—H120.947 (18)
C5—C61.382 (2)C13—H130.966 (18)
C5—H50.959 (17)C14—O21.421 (2)
C6—Cl11.7309 (18)C14—H14A0.93 (2)
C7—N11.279 (2)C14—H14B1.01 (2)
C7—C81.439 (2)C14—H14C0.94 (2)
C7—H70.96 (2)O1—H10.85 (2)
C8—C91.403 (2)
C6—C1—C2117.60 (15)O1—C9—C10117.80 (14)
C6—C1—N1118.31 (14)O1—C9—C8121.50 (13)
C2—C1—N1124.10 (16)C10—C9—C8120.70 (14)
C3—C2—C1120.3 (2)C11—C10—C9119.21 (15)
C3—C2—H2120.1 (11)C11—C10—H10122.7 (11)
C1—C2—H2119.5 (11)C9—C10—H10118.1 (11)
C4—C3—C2120.6 (2)O2—C11—C10123.83 (14)
C4—C3—H3126.0 (12)O2—C11—C12115.09 (13)
C2—C3—H3113.3 (12)C10—C11—C12121.08 (14)
C3—C4—C5120.47 (18)C13—C12—C11119.35 (15)
C3—C4—H4123.9 (13)C13—C12—H12122.4 (11)
C5—C4—H4115.7 (13)C11—C12—H12118.2 (11)
C4—C5—C6118.99 (19)C12—C13—C8121.94 (16)
C4—C5—H5123.5 (10)C12—C13—H13119.6 (10)
C6—C5—H5117.4 (11)C8—C13—H13118.4 (10)
C5—C6—C1121.89 (17)O2—C14—H14A104.8 (12)
C5—C6—Cl1118.61 (14)O2—C14—H14B111.6 (11)
C1—C6—Cl1119.49 (12)H14A—C14—H14B114.5 (17)
N1—C7—C8121.89 (16)O2—C14—H14C108.7 (13)
N1—C7—H7123.1 (11)H14A—C14—H14C111.4 (17)
C8—C7—H7114.8 (11)H14B—C14—H14C105.8 (17)
C9—C8—C13117.72 (14)C7—N1—C1120.76 (15)
C9—C8—C7121.69 (14)C9—O1—H1107.0 (16)
C13—C8—C7120.58 (15)C11—O2—C14118.26 (13)
C6—C1—C2—C34.3 (3)C7—C8—C9—C10177.98 (15)
N1—C1—C2—C3175.78 (17)O1—C9—C10—C11179.74 (15)
C1—C2—C3—C41.7 (3)C8—C9—C10—C110.9 (2)
C2—C3—C4—C51.4 (3)C9—C10—C11—O2179.74 (15)
C3—C4—C5—C61.8 (3)C9—C10—C11—C120.1 (2)
C4—C5—C6—C11.0 (3)O2—C11—C12—C13178.88 (16)
C4—C5—C6—Cl1179.85 (16)C10—C11—C12—C130.8 (3)
C2—C1—C6—C54.0 (3)C11—C12—C13—C80.9 (3)
N1—C1—C6—C5176.07 (17)C9—C8—C13—C120.2 (3)
C2—C1—C6—Cl1177.18 (14)C7—C8—C13—C12178.91 (17)
N1—C1—C6—Cl12.7 (2)C8—C7—N1—C1177.44 (15)
N1—C7—C8—C91.4 (3)C6—C1—N1—C7154.24 (16)
N1—C7—C8—C13179.85 (17)C2—C1—N1—C725.8 (2)
C13—C8—C9—O1179.88 (16)C10—C11—O2—C142.4 (3)
C7—C8—C9—O11.4 (2)C12—C11—O2—C14177.88 (18)
C13—C8—C9—C100.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.85 (2)1.82 (2)2.5991 (18)150 (2)
C7—H7···Cg(1)i0.96 (2)2.98 (2)3.893 (2)160.2 (17)
C14—H14b···Cg(1)ii1.01 (2)2.91 (2)3.864 (3)157 (2)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+3/2, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H12ClNO2C14H12ClNO2
Mr261.70261.70
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/c
Temperature (K)293293
a, b, c (Å)5.5859 (6), 8.9617 (6), 25.333 (3)22.446 (3), 7.2259 (7), 16.727 (2)
β (°) 93.880 (9) 113.428 (9)
V3)1265.2 (2)2489.3 (5)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.290.30
Crystal size (mm)0.52 × 0.31 × 0.120.50 × 0.47 × 0.21
Data collection
DiffractometerStoe IPDS 2
diffractometer
Stoe IPDS 2
diffractometer
Absorption correctionIntegration
(X-RED; Stoe & Cie, 2002)
Integration
(X-RED; Stoe & Cie, 2002)
Tmin, Tmax0.864, 0.9680.838, 0.939
No. of measured, independent and
observed [I > 2σ(I)] reflections
10988, 2440, 1505 10001, 2885, 1854
Rint0.0360.039
(sin θ/λ)max1)0.6170.655
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.098, 0.98 0.038, 0.102, 0.91
No. of reflections24402885
No. of parameters167211
No. of restraints10
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.11, 0.170.14, 0.24

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.851 (16)1.806 (18)2.596 (2)154 (2)
C13—H13···Cg1i0.9303.043.896 (2)154.32
C14—H14a···Cg2ii0.9603.103.975 (2)152.80
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.85 (2)1.82 (2)2.5991 (18)150 (2)
C7—H7···Cg(1)i0.96 (2)2.98 (2)3.893 (2)160.2 (17)
C14—H14b···Cg(1)ii1.01 (2)2.91 (2)3.864 (3)156.9 (17)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+3/2, y+1/2, z.
Comparison of the optimized and experimental geometric parameters of (I) and (II) (Å, °). top
For (I)For (II)
X-rayDFT/B3LYPX-rayDFT/B3LYP
Cl1-C41.7404 (19)1.758Cl1-C61.7309 (18)1.755
C1-N11.410 (2)1.404C1-N11.4097 (19)1.398
N1=C71.282 (2)1.297N1=C71.279 (2)1.296
C7-C81.436 (2)1.440C7-C81.439 (2)1.439
C9-O11.346 (2)1.337C9-O11.3451 (18)1.336
C11-O21.359 (2)1.357C11-O21.3567 (18)1.357
C1-N1=C7121.88 (2)121.34C1-N1=C7120.76 (2)121.17
N1=C7-C8122.02 (2)122.38N1=C7-C8121.89 (2)122.24
C6-C1-N1=C7162.47 (17)148.23C6-C1-N1=C7154.24 (2)145.48
C1-N1=C7-C8-177.86 (16)-177.15C1-N1=C7-C8-177.44 (2)-176.61
N1=C7-C8-C13-178.25 (18)-179.26N1=C7-C8-C13-179.85 (2)-179.85
Mulliken atomic charges for (I) and (II) (e). top
AtomFor (I)For (II)
Cl1-0.024-0.005
N1-0.609-0.605
O1-0.569-0.566
O2-0.512-0.513
C10.2660.292
C2-0.095-0.093
C3-0.085-0.099
C4-0.093-0.079
C5-0.079-0.082
C6-0.092-0.128
C70.1700.171
C80.0400.039
C90.3050.307
C10-0.164-0.164
C110.3610.361
C12-0.126-0.126
C13-0.137-0.136
C14-0.0830.083
H10.3540.366
Comparison of the observed and calculated vibrational spectra of (I) and (II). top
For (I)For (II)
Experimental (cm-1)DFT/B3LYP (cm-1)Experimental (cm-1)DFT/B3LYP (cm-1)
ν(C-Cl)*10891108ν(C-Cl)*11121060
ν(N=C)*16111673ν(N=C)*16121674
N=C-H**13971393N=C-H**13941392
ν(C-C)*15641561ν(C-C)*15621560
ν(C-C)*14421447ν(C-C)*14711477
ν(O-H)*2000-30003121ν(O-H)*2000-30003157
* stretching, ** bending
 

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