X-ray crystal and computational structural study of (E)-2-[(2-chloro-phenyl)-iminometh-yl]-4-methoxy-phenol.

In the mol-ecule of the title compound, C(14)H(12)ClNO, the two aromatic rings are oriented at a dihedral angle of 12.28 (7)°. An intra-molecular 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 inter-molecular C-H⋯O hydrogen bonds link the mol-ecules into chains along the c axis. There is a C-H⋯π contact between the methyl group and the chloro-phenyl 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 = 261.70

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.089

S = 1.05

2441 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.13 e Å−3

Δρmin = −0.21 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H12ClNO2	F000 = 544
Mr = 261.70	Dx = 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 = 2.0–28.0º
b = 8.4701 (4) Å	µ = 0.30 mm−1
c = 12.0115 (8) Å	T = 296 K
β = 112.846 (5)º	Prismatic plate, red
V = 1240.86 (13) Å3	0.56 × 0.40 × 0.11 mm
Z = 4

Stoe IPDSII diffractometer	2441 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
Monochromator: plane graphite	Rint = 0.042
Detector resolution: 6.67 pixels mm-1	θmax = 26.0º
T = 296 K	θmin = 2.9º
ω scans	h = −16→16
Absorption correction: integration(X-RED32; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.851, Tmax = 0.966	l = −14→14
15517 measured reflections

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089	w = 1/[σ2(Fo2) + (0.0523P)2 + 0.0594P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
2441 reflections	Δρmax = 0.13 e Å−3
167 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

Parameters	X-ray	AM1	PM3	HFa	DFT/B3LYPa
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

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) ; (ii) .

Table 2

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

Parameters	X-ray	AM1	PM3	HFa	DFT/B3LYPa
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).