Crystal structure of 4-chloro-2-{(E)-[(3,4-di­methyl­phen­yl)imino]­meth­yl}phenol

Abstract

In the title compound, C₁₅H₁₄ClNO, which is isostructural with its bromo analogue [Tahir et al. (2012 ▸). Acta Cryst., E68, o2730], the dihedral angle between the planes of the aromatic rings is 2.71 (7)° and an intra­molecular O—H⋯N hydrogen bond closes an S(6) ring. In the crystal, extremely weak C—H⋯π inter­actions link the mol­ecules into a three-dimensional network.

Related literature  

For related structures, see: Demircioğlu et al. (2014 ▸); Jin et al. (2012 ▸); Sun et al. (2013 ▸); Tahir et al. (2012 ▸).

Experimental  

Crystal data  

• C₁₅H₁₄ClNO

• M _r = 259.72

• Monoclinic,

• a = 12.1875 (10) Å

• b = 7.4438 (5) Å

• c = 14.3141 (12) Å

• β = 101.549 (4)°

• V = 1272.30 (17) ų

• Z = 4

• Mo Kα radiation

• μ = 0.29 mm⁻¹

• T = 296 K

• 0.25 × 0.20 × 0.14 mm

Data collection  

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T _min = 0.933, T _max = 0.968

• 10293 measured reflections

• 2785 independent reflections

• 1871 reflections with I > 2σ(I)

• R _int = 0.024

Refinement  

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.116

• S = 1.04

• 2785 reflections

• 166 parameters

• H-atom parameters constrained

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Supplementary Material

CCDC reference: 1401503

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg2 are the centroids of the C1C6 and C8C13 benzene rings, respectively.

DHA	DH	HA	D A	DHA
O1H1N1	0.82	1.87	2.5998(19)	149
C3H3Cg1i	0.93	2.98	3.732(2)	139
C6H6Cg2ii	0.93	2.93	3.576(2)	128
C14H14B Cg2iii	0.96	2.96	3.656(2)	131

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

S1. Comment

The title compound, (I, Fig. 1) has been synthesized in continuation of forming different derivatives of 3,4-dimethylaniline. (I) will also be utilized for synthesizing different metal complexes.

The crystal structures of 4-bromo-2-((E)-[(3,4-dimethylphenyl)imino]methyl)phenol (Tahir et al., 2012), 2-((3,4-dimethylphenyl)carbonoimidoyl)-3-methoxyphenol (Demircioğlu et al., 2014), N-[(E)-4-bromobenzylidene]-3,4-dimethylaniline (Sun et al., 2013) and N-[(E)-4-fluorobenzylidene]-3,4-dimethylaniline (Jin et al., 2012) have been published which are related to the title compound.

The title compound is isostructural to 4-bromo-2-((E)-[(3,4-dimethyl phenyl)imino]methyl)phenol (Tahir et al., 2012) and is almost planar with r. m. s. deviation of 0.0325 Å, with maximum deviation of 0.0803 (9) Å for Cl1 atom from the mean square plane. There exist intramolecular H-bonding of O—H···N type (Table 1, Fig. 1) with S(6) ring motif. There exist C—H···π interactions (Table 1).

S2. Experimental

Equimolar quantities of 5-chlorosalicylaldehyde and 3,4-dimethylaniline were refluxed in methanol for 3 h. The solution was kept at room temperature for crystallization which affoarded light yellow plates after 72 h.

S3. Refinement

The H atoms were positioned geometrically (C–H = 0.93–0.96 Å, O—H= 0.82 Å) and refined as riding with U_iso(H) = xU_eq(C, O), where x = 1.5 for methyl & hydroxy and x = 1.2 for other H-atoms.

Figures

Fig. 1.

View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line shows intramolecular H-bonding.

Fig. 2.

Packing diagram for the title compound.

Crystal data

C15H14ClNO	F(000) = 544
Mr = 259.72	Dx = 1.356 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.1875 (10) Å	Cell parameters from 1871 reflections
b = 7.4438 (5) Å	θ = 2.0–27.0°
c = 14.3141 (12) Å	µ = 0.29 mm−1
β = 101.549 (4)°	T = 296 K
V = 1272.30 (17) Å3	Plate, light yellow
Z = 4	0.25 × 0.20 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2785 independent reflections
Radiation source: fine-focus sealed tube	1871 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 7.80 pixels mm-1	θmax = 27.0°, θmin = 2.0°
ω scans	h = −15→12
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −8→9
Tmin = 0.933, Tmax = 0.968	l = −18→15
10293 measured reflections

Refinement

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0519P)2 + 0.2053P] where P = (Fo2 + 2Fc2)/3
2785 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.31558 (4)	0.47763 (8)	0.94032 (3)	0.0702 (2)
O1	0.45252 (11)	0.6419 (2)	0.58212 (9)	0.0684 (4)
H1	0.4036	0.6151	0.5361	0.103*
N1	0.26240 (12)	0.51118 (17)	0.49303 (10)	0.0442 (4)
C1	0.41674 (14)	0.6064 (2)	0.66249 (12)	0.0462 (4)
C2	0.31233 (14)	0.5273 (2)	0.66205 (11)	0.0400 (4)
C3	0.28167 (14)	0.4894 (2)	0.74847 (12)	0.0434 (4)
H3	0.2128	0.4363	0.7492	0.052*
C4	0.35292 (14)	0.5305 (2)	0.83271 (12)	0.0447 (4)
C5	0.45476 (15)	0.6104 (2)	0.83316 (12)	0.0499 (4)
H5	0.5022	0.6383	0.8907	0.060*
C6	0.48620 (15)	0.6486 (2)	0.74880 (13)	0.0524 (5)
H6	0.5549	0.7035	0.7493	0.063*
C7	0.23682 (15)	0.4821 (2)	0.57324 (12)	0.0432 (4)
H7	0.1679	0.4304	0.5753	0.052*
C8	0.18970 (13)	0.4694 (2)	0.40504 (11)	0.0394 (4)
C9	0.23021 (14)	0.5050 (2)	0.32363 (12)	0.0414 (4)
H9	0.3016	0.5534	0.3296	0.050*
C10	0.16807 (14)	0.4712 (2)	0.23319 (12)	0.0407 (4)
C11	0.06064 (14)	0.3993 (2)	0.22426 (12)	0.0429 (4)
C12	0.02122 (14)	0.3625 (2)	0.30650 (12)	0.0455 (4)
H12	−0.0499	0.3133	0.3010	0.055*
C13	0.08330 (14)	0.3962 (2)	0.39585 (12)	0.0456 (4)
H13	0.0544	0.3701	0.4497	0.055*
C14	0.21523 (18)	0.5150 (3)	0.14640 (13)	0.0576 (5)
H14A	0.2165	0.4083	0.1089	0.086*
H14B	0.2901	0.5603	0.1659	0.086*
H14C	0.1693	0.6042	0.1090	0.086*
C15	−0.01190 (16)	0.3653 (3)	0.12815 (13)	0.0599 (5)
H15A	0.0236	0.2788	0.0943	0.090*
H15B	−0.0225	0.4756	0.0927	0.090*
H15C	−0.0832	0.3200	0.1360	0.090*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0742 (4)	0.1002 (4)	0.0366 (3)	−0.0049 (3)	0.0120 (2)	0.0047 (2)
O1	0.0658 (9)	0.0930 (10)	0.0483 (8)	−0.0276 (8)	0.0159 (7)	0.0033 (7)
N1	0.0472 (8)	0.0498 (8)	0.0349 (8)	−0.0009 (6)	0.0069 (6)	−0.0023 (6)
C1	0.0493 (10)	0.0475 (10)	0.0428 (10)	−0.0042 (8)	0.0116 (8)	0.0025 (7)
C2	0.0427 (9)	0.0390 (9)	0.0376 (9)	0.0015 (7)	0.0061 (7)	−0.0012 (7)
C3	0.0430 (10)	0.0469 (10)	0.0407 (9)	0.0001 (7)	0.0093 (8)	−0.0005 (7)
C4	0.0493 (11)	0.0476 (10)	0.0364 (9)	0.0048 (8)	0.0065 (8)	0.0002 (7)
C5	0.0519 (11)	0.0500 (10)	0.0432 (10)	−0.0005 (8)	−0.0013 (8)	−0.0027 (8)
C6	0.0476 (11)	0.0523 (11)	0.0550 (12)	−0.0103 (8)	0.0048 (9)	−0.0008 (9)
C7	0.0440 (10)	0.0450 (9)	0.0404 (10)	−0.0016 (7)	0.0080 (8)	−0.0015 (7)
C8	0.0421 (10)	0.0383 (9)	0.0376 (9)	0.0011 (7)	0.0073 (7)	−0.0016 (7)
C9	0.0404 (9)	0.0421 (9)	0.0423 (10)	−0.0036 (7)	0.0102 (7)	−0.0015 (7)
C10	0.0480 (10)	0.0368 (9)	0.0389 (9)	0.0015 (7)	0.0125 (7)	0.0007 (7)
C11	0.0482 (10)	0.0368 (9)	0.0417 (10)	0.0013 (7)	0.0040 (7)	−0.0007 (7)
C12	0.0410 (9)	0.0474 (10)	0.0482 (10)	−0.0044 (8)	0.0091 (8)	0.0017 (8)
C13	0.0467 (10)	0.0520 (10)	0.0400 (10)	−0.0016 (8)	0.0132 (8)	0.0029 (8)
C14	0.0672 (13)	0.0661 (12)	0.0422 (10)	−0.0091 (9)	0.0171 (9)	0.0008 (8)
C15	0.0621 (12)	0.0674 (13)	0.0461 (11)	−0.0079 (10)	0.0008 (9)	−0.0017 (9)

Geometric parameters (Å, º)

Cl1—C4	1.7365 (17)	C8—C13	1.389 (2)
O1—C1	1.336 (2)	C9—C10	1.386 (2)
O1—H1	0.8200	C9—H9	0.9300
N1—C7	1.267 (2)	C10—C11	1.396 (2)
N1—C8	1.422 (2)	C10—C14	1.505 (2)
C1—C6	1.387 (2)	C11—C12	1.385 (2)
C1—C2	1.401 (2)	C11—C15	1.500 (2)
C2—C3	1.391 (2)	C12—C13	1.372 (2)
C2—C7	1.452 (2)	C12—H12	0.9300
C3—C4	1.372 (2)	C13—H13	0.9300
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.375 (2)	C14—H14B	0.9600
C5—C6	1.368 (2)	C14—H14C	0.9600
C5—H5	0.9300	C15—H15A	0.9600
C6—H6	0.9300	C15—H15B	0.9600
C7—H7	0.9300	C15—H15C	0.9600
C8—C9	1.379 (2)
C1—O1—H1	109.5	C8—C9—H9	118.9
C7—N1—C8	122.85 (15)	C10—C9—H9	118.9
O1—C1—C6	118.44 (15)	C9—C10—C11	118.83 (15)
O1—C1—C2	122.14 (15)	C9—C10—C14	120.27 (16)
C6—C1—C2	119.42 (15)	C11—C10—C14	120.89 (15)
C3—C2—C1	119.12 (15)	C12—C11—C10	118.45 (15)
C3—C2—C7	119.72 (15)	C12—C11—C15	120.34 (16)
C1—C2—C7	121.15 (15)	C10—C11—C15	121.20 (16)
C4—C3—C2	120.07 (16)	C13—C12—C11	122.41 (16)
C4—C3—H3	120.0	C13—C12—H12	118.8
C2—C3—H3	120.0	C11—C12—H12	118.8
C3—C4—C5	120.82 (16)	C12—C13—C8	119.34 (15)
C3—C4—Cl1	119.80 (14)	C12—C13—H13	120.3
C5—C4—Cl1	119.37 (13)	C8—C13—H13	120.3
C6—C5—C4	119.86 (16)	C10—C14—H14A	109.5
C6—C5—H5	120.1	C10—C14—H14B	109.5
C4—C5—H5	120.1	H14A—C14—H14B	109.5
C5—C6—C1	120.69 (16)	C10—C14—H14C	109.5
C5—C6—H6	119.7	H14A—C14—H14C	109.5
C1—C6—H6	119.7	H14B—C14—H14C	109.5
N1—C7—C2	121.73 (16)	C11—C15—H15A	109.5
N1—C7—H7	119.1	C11—C15—H15B	109.5
C2—C7—H7	119.1	H15A—C15—H15B	109.5
C9—C8—C13	118.75 (15)	C11—C15—H15C	109.5
C9—C8—N1	116.19 (14)	H15A—C15—H15C	109.5
C13—C8—N1	125.06 (14)	H15B—C15—H15C	109.5
C8—C9—C10	122.23 (15)
O1—C1—C2—C3	178.21 (15)	C7—N1—C8—C9	−178.57 (14)
C6—C1—C2—C3	−1.3 (2)	C7—N1—C8—C13	1.2 (3)
O1—C1—C2—C7	−0.9 (3)	C13—C8—C9—C10	0.4 (2)
C6—C1—C2—C7	179.60 (15)	N1—C8—C9—C10	−179.85 (13)
C1—C2—C3—C4	0.4 (2)	C8—C9—C10—C11	0.3 (2)
C7—C2—C3—C4	179.50 (14)	C8—C9—C10—C14	179.07 (14)
C2—C3—C4—C5	0.5 (3)	C9—C10—C11—C12	−0.8 (2)
C2—C3—C4—Cl1	−178.37 (12)	C14—C10—C11—C12	−179.62 (15)
C3—C4—C5—C6	−0.4 (3)	C9—C10—C11—C15	178.03 (15)
Cl1—C4—C5—C6	178.42 (13)	C14—C10—C11—C15	−0.7 (2)
C4—C5—C6—C1	−0.5 (3)	C10—C11—C12—C13	0.8 (3)
O1—C1—C6—C5	−178.16 (16)	C15—C11—C12—C13	−178.10 (15)
C2—C1—C6—C5	1.4 (3)	C11—C12—C13—C8	−0.1 (3)
C8—N1—C7—C2	−179.54 (13)	C9—C8—C13—C12	−0.5 (2)
C3—C2—C7—N1	−178.66 (14)	N1—C8—C13—C12	179.79 (15)
C1—C2—C7—N1	0.4 (3)

Hydrogen-bond geometry (Å, º)

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.5998 (19)	149
C3—H3···Cg1i	0.93	2.98	3.732 (2)	139
C6—H6···Cg2ii	0.93	2.93	3.576 (2)	128
C14—H14B···Cg2iii	0.96	2.96	3.656 (2)	131

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