X-ray crystal and computational structural study of (E)-2-[(2-chloro­phenyl)­iminometh­yl]-4-methoxy­phenol

Özek, A.; Büyükgüngör, O.; Albayrak, Ç.; Odabaşoğlu, M.

doi:10.1107/S1600536808021958

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages o1579-o1580

doi:10.1107/S1600536808021958

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X-ray crystal and computational structural study of (E)-2-[(2-chlorophenyl)iminomethyl]-4-methoxyphenol

Arzu Özek,^a ^* Orhan Büyükgüngör,^a Çiğdem Albayrak ^b and Mustafa Odabaşoğlu ^b

^aDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, and ^bDepartment of Chemistry, Ondokuz Mayıs University, TR-55139 Samsun, Turkey
^*Correspondence e-mail: arzuozek@omu.edu.tr

(Received 11 July 2008; accepted 14 July 2008; online 23 July 2008)

In the molecule of the title compound, C₁₄H₁₂ClNO, the two aromatic rings are oriented at a dihedral angle of 12.28 (7)°. An intramolecular O—H⋯N hydrogen bond results in the formation of a nearly planar six-membered ring, which is oriented with respect to the aromatic rings at dihedral angles of 0.18 (5) and 12.10 (6)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules into chains along the c axis. There is a C—H⋯π contact between the methyl group and the chlorophenyl ring and a π–π contact between the two benzene rings [centroid–centroid distance = 3.866 (1) Å].

Related literature

For related literature, see: Özek et al. (2007 ); Odabaşoğlu, Büyükgüngör et al. (2007 ); Odabaşoğlu, Arslan et al. (2007 ); Albayrak et al. (2005 ); Elerman et al. (1995 ); Frisch et al. (2004 ). For general background, see: Friesner (2005 ); Liu et al. (2004 ).

Experimental

Crystal data

C₁₄H₁₂ClNO₂
M_r = 261.70
Monoclinic, P 2₁ /c
a = 13.2348 (9) Å
b = 8.4701 (4) Å
c = 12.0115 (8) Å
β = 112.846 (5)°
V = 1240.86 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.56 × 0.40 × 0.11 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.851, T_max = 0.966
15517 measured reflections
2441 independent reflections
1977 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.05
2441 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.80 (2)	1.85 (2)	2.5896 (16)	152 (2)
C8—H8⋯O1ⁱ	0.93	2.58	3.4960 (19)	169
C7—H7b⋯Cg2ⁱⁱ	0.96	2.90	3.682	139
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Table 2
Selected geometric parameters (Å, °) calculated with X-ray, AM1, PM3, HF and DFT

Parameters	X-ray	AM1	PM3	HF^a	DFT/B3LYP^a
C8—N1	1.278 (17)	1.292	1.302	1.262	1.294
C2—O1	1.357 (17)	1.366	1.355	1.332	1.341
C1—C6	1.407 (18)	1.412	1.406	1.408	1.416
C1—C8	1.447 (19)	1.465	1.478	1.463	1.446
C1—C2	1.399 (19)	1.404	1.408	1.392	1.418
N1—C9	1.408 (17)	1.408	1.427	1.402	1.399
C9—C10	1.392 (18)	1.417	1.402	1.393	1.409
C10—Cl1	1.734 (14)	1.699	1.680	1.741	1.755
C5—O2	1.369 (17)	1.385	1.385	1.354	1.369

C9—C10—Cl1	120.02 (10)	120.869	120.554	120.163	119.783
C6—C5—O2	125.3 (15)	124.874	125.684	125.547	125.410
C6—C1—C8	119.24 (13)	116.155	117.987	117.891	119.224
C9—N1—C8	122.41 (12)	121.909	122.720	120.140	121.089
C14—C9—N1	124.73 (12)	123.114	123.424	122.078	122.787
N1—C8—C1	120.75 (13)	123.585	119.187	123.458	122.291
N1—C9—C10	117.64 (12)	118.844	116.913	119.874	119.562

C8—C1—C2—O1	0.6 (2)	−0.034	0.012	−0.194	−0.175
C6—C5—O2—C7	−1.7 (2)	0.543	−0.485	0.568	0.096
C10—C9—N1—C8	−165.93 (12)	−147.255	−179.982	−134.578	−144.790
N1—C8—C1—C6	176.91 (12)	176.946	−179.997	179.409	179.781
C1—C8—N1—C9	−178.32 (11)	−179.082	179.999	−178.064	−176.682
Note: (a) 6-31G(d,p).

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021958/hk2494sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021958/hk2494Isup2.hkl

checkCIF report

Comment top

The present work is part of a structural study of Schiff bases Özek et al., 2007; Odabaşoğlu, Büyükgüngör et al., 2007; Odabaşoğlu, Arslan et al., 2007). We report herein the crystal structure of the title compound, (I).

In general, O-hydroxy Schiff bases exhibit two possible tautomeric forms, the phenol-imine (or benzenoid) and keto-amine (or quinoid) forms. Depending on the tautomers, two types of intra-molecular hydrogen bonds are possible: O-H···N in benzenoid and N-H···O in quinoid tautomers. The H atom in (I) is located on atom O1, thus the phenol-imine tautomer is favored over the keto -amine form, as indicated by the C2-O1, C8-N1, C1-C8 and C1-C2 bonds (Fig. 1, Table 2). The O1-C2 bond has single-bond character, whereas the N1-C8 bond has a high degree of double-bond character as in 2-(3-methoxysalicylideneamino)-1H -benzimidazolemonohydrate, (II) [where the corresponding values are C-O = 1.357 (2) Å and C-N = 1.285 (2) Å] (Albayrak et al., 2005).

It is known that Schiff bases may exhibit thermochromism or photochromism, depending on the planarity or non-planarity of the molecule, respectively. Therefore, one can expect thermochromic properties in (I) caused by the planarity of the molecule; the dihedral angle between rings A (C1-C6) and B (C9-C14) is 12.28 (7)°. The intramolecular O-H···N hydrogen bond (Table 1) results in the formation of a nearly planar six-membered ring C (O1/H1/N1/C1/C2/C8), in which it is oriented with respect to rings A and B at dihedral angles of A/C = 0.18 (5)° and B/C = 12.10 (6)°. So, it is coplanar with the adjacent ring A. It generates an S(6) ring motif. The O1···N1 [2.589 (2) Å] distance is comparable to those observed for analogous ones in N-(2-hydroxyphenyl)salicylaldimine, (III) [2.675 (7) Å; Elerman et al., 1995] and in three(E)-2-[(bromophenyl)iminomethyl]-4-methoxyphenols, (IV) [2.603 (2), 2.638 (7) and 2.577 (4) Å;Özek et al., 2007].

In the crystal structure, weak intermolecular C-H···O hydrogen bonds (Table 1) results in the formation of C(5) chains along the c axis (Fig. 2), in which they may be effective in the stabilization of the structure. A C—H···π contact (Table 1) between the methyl group and ring B and a π—π contact (Fig. 3) between the symmetry related A rings Cg1···Cg1ⁱ [symmetry code: (i) 1 - x, 1 - y, - z, where Cg1 is the centroid of ring A] further stabilize the structure, with centroid-centroid distance of 3.866 (1) Å.

Ab-initio Hartree-Fock (HF), density-functional theory (DFT) and semi-empirical (AM1 and PM3) calculations and full-geometry optimizations were performed by means of GAUSSIAN 03 W package (Frisch et al., 2004). The selected bond lengths and angles together with the torsion angles are compared with the obtained ones from semi-empirical, ab-initio HF and DFT/B3LYP methods (Table 2). We observe an acceptable general agreement between them. Although the DFT molecular orbital theory was considered as the most accurate method for geometry optimization for free and complex ligands (Friesner, 2005; Liu et al., 2004), the HF method led to better results in regard to the bond lengths and angles.

Related literature top

For related literature, see: Özek et al. (2007); Odabaşoğlu, Büyükgüngör et al. (2007); Odabaşoğlu, Arslan et al. (2007); Albayrak et al. (2005); Elerman et al. (1995); Frisch et al. (2004). For general background, see: Friesner (2005); Liu et al. (2004).

Experimental top

The title compound was prepared by refluxing a mixture of a solution containing 5-methoxysalicylaldehyde (0.5 g 3.3 mmol) in ethanol (20 ml) and a solution containing 2-chloroaniline (0.420 g 3.3 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h, under reflux. The crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation (yield; 75%; m.p. 393-394 K).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram of (I), showing the formation of C(5) chains [symmetry code: (i) x, -y + 3/2, z + 1/2]. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. A partial packing diagram of (I), showing the formation of the C—H···π and π···π interactions [symmetry codes; (i) 1 - x, 1 - y, - z; (ii) 1 - x, 1 - y, 1 - z]. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

(E)-2-[(2-chlorophenyl)iminomethyl]-4-methoxyphenol top

Crystal data top

C₁₄H₁₂ClNO₂	F(000) = 544
M_r = 261.70	D_x = 1.401 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15517 reflections
a = 13.2348 (9) Å	θ = 2.0–28.0°
b = 8.4701 (4) Å	µ = 0.30 mm⁻¹
c = 12.0115 (8) Å	T = 296 K
β = 112.846 (5)°	Prismatic plate, red
V = 1240.86 (13) Å³	0.56 × 0.40 × 0.11 mm
Z = 4

Data collection top

Stoe IPDSII diffractometer	2441 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.042
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 2.9°
ω scans	h = −16→16
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→10
T_min = 0.851, T_max = 0.966	l = −14→14
15517 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0523P)² + 0.0594P] where P = (F_o² + 2F_c²)/3
2441 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₂ClNO₂	V = 1240.86 (13) Å³
M_r = 261.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2348 (9) Å	µ = 0.30 mm⁻¹
b = 8.4701 (4) Å	T = 296 K
c = 12.0115 (8) Å	0.56 × 0.40 × 0.11 mm
β = 112.846 (5)°

Data collection top

Stoe IPDSII diffractometer	2441 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1977 reflections with I > 2σ(I)
T_min = 0.851, T_max = 0.966	R_int = 0.042
15517 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.13 e Å⁻³
2441 reflections	Δρ_min = −0.21 e Å⁻³
167 parameters

Special details top

Experimental. 336 frames, detector distance = 80 mm

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 > 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

	x	y	z	U_iso*/U_eq
Cl1	0.11627 (3)	0.76700 (5)	0.55086 (4)	0.06604 (15)
O1	0.40106 (9)	0.86945 (14)	0.69518 (11)	0.0623 (3)
H1	0.3554 (17)	0.822 (2)	0.641 (2)	0.082 (6)*
O2	0.77703 (8)	0.90497 (15)	0.60329 (11)	0.0728 (3)
N1	0.31117 (9)	0.70603 (13)	0.49903 (10)	0.0454 (3)
C1	0.49336 (10)	0.80152 (15)	0.56335 (12)	0.0445 (3)
C2	0.49138 (11)	0.87192 (16)	0.66786 (13)	0.0494 (3)
C3	0.58388 (13)	0.95011 (19)	0.74523 (14)	0.0599 (4)
H3	0.5831	0.9978	0.8146	0.072*
C4	0.67628 (12)	0.95805 (19)	0.72077 (14)	0.0619 (4)
H4	0.7377	1.0109	0.7739	0.074*
C5	0.67990 (11)	0.88837 (17)	0.61772 (14)	0.0547 (3)
C6	0.58916 (11)	0.81123 (16)	0.53942 (13)	0.0501 (3)
H6	0.5909	0.7650	0.4700	0.060*
C7	0.78611 (14)	0.8339 (2)	0.50131 (18)	0.0726 (5)
H7A	0.7313	0.8768	0.4291	0.087*
H7B	0.7756	0.7220	0.5037	0.087*
H7C	0.8576	0.8544	0.5018	0.087*
C8	0.39782 (11)	0.72290 (15)	0.47745 (12)	0.0457 (3)
H8	0.3995	0.6842	0.4057	0.055*
C9	0.21762 (10)	0.62666 (15)	0.41915 (12)	0.0443 (3)
C10	0.12031 (11)	0.64486 (15)	0.43678 (13)	0.0479 (3)
C11	0.02522 (11)	0.56821 (18)	0.36454 (15)	0.0595 (4)
H11	−0.0391	0.5828	0.3773	0.071*
C12	0.02614 (12)	0.47049 (19)	0.27390 (15)	0.0637 (4)
H12	−0.0376	0.4188	0.2249	0.076*
C13	0.12142 (13)	0.4492 (2)	0.25577 (14)	0.0629 (4)
H13	0.1220	0.3819	0.1948	0.075*
C14	0.21635 (12)	0.52647 (17)	0.32687 (13)	0.0548 (3)
H14	0.2801	0.5114	0.3130	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0411 (7)	0.0489 (7)	0.0414 (7)	−0.0018 (5)	0.0136 (5)	0.0020 (5)
C2	0.0508 (7)	0.0523 (7)	0.0453 (7)	−0.0019 (6)	0.0190 (6)	0.0008 (6)
C3	0.0626 (9)	0.0646 (9)	0.0469 (8)	−0.0067 (7)	0.0153 (7)	−0.0092 (7)
C4	0.0500 (8)	0.0653 (9)	0.0580 (9)	−0.0116 (7)	0.0075 (7)	−0.0067 (7)
C5	0.0406 (7)	0.0569 (8)	0.0624 (9)	−0.0023 (6)	0.0154 (6)	0.0041 (7)
C6	0.0452 (7)	0.0553 (7)	0.0495 (8)	−0.0023 (6)	0.0180 (6)	−0.0003 (6)
C7	0.0531 (9)	0.0848 (11)	0.0877 (12)	−0.0008 (8)	0.0358 (9)	0.0109 (10)
C8	0.0453 (7)	0.0523 (7)	0.0395 (7)	−0.0034 (5)	0.0164 (5)	0.0004 (5)
C9	0.0422 (7)	0.0460 (6)	0.0422 (7)	−0.0028 (5)	0.0135 (5)	0.0062 (5)
C10	0.0451 (7)	0.0468 (7)	0.0511 (8)	−0.0005 (5)	0.0179 (6)	0.0037 (6)
C11	0.0410 (7)	0.0591 (8)	0.0747 (10)	−0.0029 (6)	0.0184 (7)	0.0021 (7)
C12	0.0500 (8)	0.0664 (9)	0.0622 (10)	−0.0138 (7)	0.0082 (7)	−0.0034 (7)
C13	0.0663 (10)	0.0682 (9)	0.0526 (9)	−0.0154 (7)	0.0214 (7)	−0.0101 (7)
C14	0.0533 (8)	0.0621 (8)	0.0525 (8)	−0.0088 (6)	0.0246 (6)	−0.0040 (7)
N1	0.0406 (6)	0.0517 (6)	0.0430 (6)	−0.0029 (4)	0.0153 (5)	0.0017 (5)
O1	0.0597 (7)	0.0781 (7)	0.0560 (6)	−0.0107 (5)	0.0301 (5)	−0.0142 (6)
O2	0.0437 (6)	0.0865 (8)	0.0880 (9)	−0.0134 (5)	0.0255 (6)	−0.0087 (7)
Cl1	0.0595 (2)	0.0677 (2)	0.0810 (3)	−0.00680 (17)	0.0382 (2)	−0.01591 (19)

Geometric parameters (Å, º) top

O1—H1	0.80 (2)	C7—H7C	0.9600
C1—C2	1.3992 (19)	C8—N1	1.2781 (17)
C1—C6	1.4071 (18)	C8—H8	0.9300
C1—C8	1.4470 (19)	C9—C14	1.3908 (19)
C2—O1	1.3572 (17)	C9—C10	1.3925 (18)
C2—C3	1.385 (2)	C9—N1	1.4082 (17)
C3—C4	1.366 (2)	C10—C11	1.3822 (19)
C3—H3	0.9300	C10—Cl1	1.7342 (14)
C4—C5	1.389 (2)	C11—C12	1.371 (2)
C4—H4	0.9300	C11—H11	0.9300
C5—O2	1.3694 (17)	C12—C13	1.372 (2)
C5—C6	1.370 (2)	C12—H12	0.9300
C6—H6	0.9300	C13—C14	1.379 (2)
C7—O2	1.411 (2)	C13—H13	0.9300
C7—H7A	0.9600	C14—H14	0.9300
C7—H7B	0.9600

C2—O1—H1	105.4 (15)	O2—C7—H7C	109.5
C5—O2—C7	117.81 (12)	H7A—C7—H7C	109.5
C8—N1—C9	122.41 (12)	H7B—C7—H7C	109.5
C2—C1—C6	119.38 (12)	N1—C8—C1	120.75 (13)
C2—C1—C8	121.36 (12)	N1—C8—H8	119.6
C6—C1—C8	119.24 (13)	C1—C8—H8	119.6
O1—C2—C3	118.51 (13)	C14—C9—C10	117.58 (12)
O1—C2—C1	122.37 (12)	C14—C9—N1	124.73 (12)
C3—C2—C1	119.10 (13)	C10—C9—N1	117.64 (12)
C4—C3—C2	120.75 (14)	C11—C10—C9	121.54 (13)
C4—C3—H3	119.6	C11—C10—Cl1	118.44 (11)
C2—C3—H3	119.6	C9—C10—Cl1	120.02 (10)
C3—C4—C5	120.96 (13)	C12—C11—C10	119.69 (14)
C3—C4—H4	119.5	C12—C11—H11	120.2
C5—C4—H4	119.5	C10—C11—H11	120.2
O2—C5—C6	125.30 (15)	C11—C12—C13	119.81 (13)
O2—C5—C4	115.35 (13)	C11—C12—H12	120.1
C6—C5—C4	119.35 (13)	C13—C12—H12	120.1
C5—C6—C1	120.45 (14)	C12—C13—C14	120.77 (15)
C5—C6—H6	119.8	C12—C13—H13	119.6
C1—C6—H6	119.8	C14—C13—H13	119.6
O2—C7—H7A	109.5	C13—C14—C9	120.61 (14)
O2—C7—H7B	109.5	C13—C14—H14	119.7
H7A—C7—H7B	109.5	C9—C14—H14	119.7

C6—C1—C2—O1	178.75 (13)	C4—C5—C6—C1	−0.4 (2)
C8—C1—C2—O1	0.6 (2)	C1—C8—N1—C9	−178.32 (11)
C6—C1—C2—C3	0.2 (2)	C14—C9—N1—C8	16.7 (2)
C8—C1—C2—C3	−177.93 (13)	C10—C9—N1—C8	−165.93 (12)
C2—C1—C6—C5	0.2 (2)	C14—C9—C10—C11	−0.9 (2)
C8—C1—C6—C5	178.38 (13)	N1—C9—C10—C11	−178.38 (12)
C2—C1—C8—N1	−4.9 (2)	C14—C9—C10—Cl1	179.58 (10)
C6—C1—C8—N1	176.91 (12)	N1—C9—C10—Cl1	2.05 (16)
O1—C2—C3—C4	−178.98 (14)	C10—C9—C14—C13	0.3 (2)
C1—C2—C3—C4	−0.4 (2)	N1—C9—C14—C13	177.61 (13)
C2—C3—C4—C5	0.1 (2)	C9—C10—C11—C12	0.6 (2)
C3—C4—C5—O2	179.83 (15)	Cl1—C10—C11—C12	−179.78 (12)
C3—C4—C5—C6	0.3 (2)	C10—C11—C12—C13	0.2 (2)
C6—C5—O2—C7	−1.7 (2)	C11—C12—C13—C14	−0.7 (2)
C4—C5—O2—C7	178.80 (14)	C12—C13—C14—C9	0.5 (2)
O2—C5—C6—C1	−179.95 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.80 (2)	1.85 (2)	2.5896 (16)	152 (2)
C8—H8···O1ⁱ	0.93	2.58	3.4960 (19)	169
C7—H7b···Cg2ⁱⁱ	0.96	2.90	3.682	139

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO₂
M_r	261.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.2348 (9), 8.4701 (4), 12.0115 (8)
β (°)	112.846 (5)
V (Å³)	1240.86 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.56 × 0.40 × 0.11

Data collection
Diffractometer	Stoe IPDSII diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.851, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	15517, 2441, 1977
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.05
No. of reflections	2441
No. of parameters	167
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.21

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.80 (2)	1.85 (2)	2.5896 (16)	152 (2)
C8—H8···O1ⁱ	0.93	2.58	3.4960 (19)	169
C7—H7b···Cg2ⁱⁱ	0.96	2.90	3.682	139.00

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+1.

Selected geometric parameters (Å, °) calculated with X-ray, AM1, PM3, HF and DFT for (I) top

Parameters	X-ray	AM1	PM3	HF^a	DFT/B3LYP^a
C8—N1	1.278 (17)	1.292	1.302	1.262	1.294
C2—O1	1357 (17)	1.366	1.355	1.332	1.341
C1—C6	1.407 (18)	1.412	1.406	1.408	1.416
C1—C8	1.447 (19)	1.465	1.478	1.463	1.446
C1—C2	1.399 (19)	1.404	1.408	1.392	1.418
N1—C9	1.408 (17)	1.408	1.427	1.402	1.399
C9—C10	1.392 (18)	1.417	1.402	1.393	1.409
C10—Cl1	1.734 (14)	1.699	1.680	1.741	1.755
C5—-O2	1.369 (17)	1.385	1.385	1.354	1.369

C9—C10—Cl1	120.02 (10)	120.869	120.554	120.163	119.783
C6—C5—O2	125.3 (15)	124.874	125.684	125.547	125.410
C6—C1—C8	119.24 (13)	116.155	117.987	117.891	119.224
C9—N1—C8	122.41 (12)	121.909	122.720	120.140	121.089
C14—C9—N1	124.73 (12)	123.114	123.424	122.078	122.787
N1—C8—C1	120.75 (13)	123.585	119.187	123.458	122.291
N1—C9—C10	117.64 (12)	118.844	116.913	119.874	119.562

C8—C1—C2—O1	0.6 (2)	-0.034	0.012	-0.194	-0.175
C6—C5—O2—C7	-1.7 (2)	0.543	-0.485	0.568	0.096
C10—C9—N1—C8	-165.93 (12)	-147.255	-179.982	-134.578	-144.790
N1—C8—C1—C6	176.91 (12)	176.946	-179.997	179.409	179.781
C1—C8—N1—C9	-178.32 (11)	-179.082	179.999	-178.064	-176.682

Notes: (a) 6-31G(d,p).

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant No. F.279 of the University Research Fund).

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