(E)-4-Methyl-2-(N-phenyl­carboximido­yl)phenol

Swetha, G.; Ida Malarselvi, R.; Ramachandra Raja, C.; Thiruvalluvar, A.; Priscilla, J.

doi:10.1107/S2414314618004649

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180464

https://doi.org/10.1107/S2414314618004649

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(E)-4-Methyl-2-(N-phenylcarboximidoyl)phenol

G. Swetha,^a R. Ida Malarselvi,^b C. Ramachandra Raja,^a A. Thiruvalluvar ^c ^* and J. Priscilla ^d

^aPostgraduate Research Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 001, Tamilnadu, India, ^bPostgraduate Department of Physics, Dharmapuram Gnanambigai Government Arts College (Women), Mayiladuthurai 609 001, Tamilnadu, India, ^cPrincipal, Kunthavai Naacchiyaar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India, and ^dPostgraduate Department of Physics, A.D.M. College for Women (Autonomous), Nagapattinam 611 001, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 19 March 2018; accepted 21 March 2018; online 27 March 2018)

The title compound, C₁₄H₁₃NO, is not planar with the dihedral angle between the planes of the two aryl rings being 6.22 (11)°. The configuration about the imine bond is E. An intramolecular O—H⋯N hydrogen bond generates an S(6) loop. In the crystal, molecules assemble into columns parallel to the a axis. The methyl group is disordered over two positions rotated from each other by 60°.

Keywords: crystal structure; salicylaldehyde; intramolecular O—H⋯N hydrogen bonding.

CCDC reference: 1831435

Structure description

We report here, as part of our on-going research (Ida Malarselvi et al., 2016 ; Swetha et al., 2017 ), the synthesis and the X-ray crystal structure of the title methylated Schiff base compound, Fig.1, synthesized from the condensation reaction of equimolar amounts of 5-methylsalicylaldehyde and aniline in a mixture of DMSO and CCl₄.

The benzene and phenyl rings deviate from co-planarity with the dihedral angle between the two rings being 6.22 (11)°. The molecule has an E configuration about the C=N bond; the C2—C7=N1—C8 torsion angle is −177.73 (17)°. There is an intramolecular O1—H1⋯N1 hydrogen bond with an H⋯N distance of 1.73 (3) Å generating an S(6) loop, see Table 1 and Fig. 1. In the crystal, molecules assemble into columns parallel to the a axis, Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.96 (3)	1.73 (3)	2.603 (2)	148 (3)

Figure 1
A view of the title compound with displacement ellipsoids drawn at the 30% probability level. The dashed lines indicate a hydrogen-bonding interaction. The methyl-H atoms are statistically disordered.

Figure 2
A perspective view of the molecular packing of the title compound, viewed down the a axis. The hydrogen bonds are shown as dashed lines (see Table 1

Swetha et al. (2017) have reported the crystal structure of (E)-4-fluoro-2-[(phenylimino)methyl]phenol, in which the molecule is essentially planar (r.m.s. deviation = 0.022 Å) and the dihedral angle between the planes of the two aryl rings is 0.69 (15)°.

Synthesis and crystallization

5-Methylsalicylaldehyde (0.64 g, 0.0047 mol) was dissolved in a mixture of DMSO (7.5 ml) and CCl₄ (7.5 ml). To this solution, aniline (0.42 g, 0.0045 mol) was added drop-wise with constant stirring for 1 h. During this time, the solution turned deep yellow. On standing for two weeks and with slow evaporation of the solvent, orange crystals of the title compound were deposited.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The methyl group was found to be disordered over two positions rotated from each other by 60°, and was refined as an idealized disordered methyl group.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO
M_r	211.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.6976 (4), 19.3656 (18), 12.3116 (12)
β (°)	95.831 (3)
V (Å³)	1114.21 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.15 × 0.10 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.699, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	20153, 2825, 1527
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.169, 1.05
No. of reflections	2825
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXT2014/5 (Sheldrick, 2015a ), ORTEP-3 for Windows (Farrugia, 2012 ), SHELXL2018/1 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1831435

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004649/tk4048sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004649/tk4048Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618004649/tk4048Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2018/1 (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(I) top

Crystal data top

C₁₄H₁₃NO	F(000) = 448
M_r = 211.25	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.6976 (4) Å	Cell parameters from 4170 reflections
b = 19.3656 (18) Å	θ = 2.7–25.3°
c = 12.3116 (12) Å	µ = 0.08 mm⁻¹
β = 95.831 (3)°	T = 296 K
V = 1114.21 (18) Å³	Needle, orange
Z = 4	0.15 × 0.10 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2825 independent reflections
Radiation source: fine-focus sealed tube	1527 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω and φ scan	θ_max = 28.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −5→6
T_min = 0.699, T_max = 0.746	k = −25→26
20153 measured reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.169	w = 1/[σ²(F_o²) + (0.0565P)² + 0.5019P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2825 reflections	Δρ_max = 0.21 e Å⁻³
149 parameters	Δρ_min = −0.18 e Å⁻³

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. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C)·The OH H atom was located in a difference Fourier map and refined freely.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.1821 (4)	0.78020 (11)	0.18545 (16)	0.0421 (5)
C2	0.2951 (4)	0.77295 (10)	0.29511 (15)	0.0373 (4)
C3	0.1864 (4)	0.81482 (11)	0.37342 (16)	0.0430 (5)
H3	0.259387	0.809976	0.446105	0.052*
C4	−0.0255 (4)	0.86316 (11)	0.34711 (18)	0.0464 (5)
C5	−0.1323 (5)	0.86888 (11)	0.23773 (18)	0.0502 (6)
H5	−0.274657	0.901142	0.217726	0.060*
C6	−0.0319 (5)	0.82791 (12)	0.15850 (17)	0.0505 (6)
H6	−0.109020	0.832407	0.086232	0.061*
C7	0.5179 (4)	0.72355 (10)	0.32756 (16)	0.0405 (5)
H7	0.589870	0.721013	0.400660	0.049*
C8	0.8311 (4)	0.63294 (10)	0.29122 (16)	0.0401 (5)
C9	0.9307 (5)	0.61802 (12)	0.39877 (19)	0.0533 (6)
H9	0.861945	0.642702	0.455421	0.064*
C10	1.1313 (5)	0.56665 (13)	0.4217 (2)	0.0625 (7)
H10	1.196216	0.556890	0.493922	0.075*
C11	1.2361 (5)	0.52984 (12)	0.3395 (2)	0.0653 (7)
H11	1.370708	0.495170	0.355807	0.078*
C12	1.1409 (5)	0.54455 (13)	0.2330 (2)	0.0663 (7)
H12	1.211556	0.519957	0.176631	0.080*
C13	0.9401 (5)	0.59586 (12)	0.20938 (19)	0.0531 (6)
H13	0.877201	0.605578	0.136922	0.064*
C14	−0.1393 (6)	0.90787 (13)	0.4329 (2)	0.0651 (7)
H14A	−0.284475	0.938039	0.399146	0.098*	0.5
H14B	−0.219813	0.879186	0.485566	0.098*	0.5
H14C	0.013807	0.934903	0.468760	0.098*	0.5
H14D	−0.042513	0.896713	0.503169	0.098*	0.5
H14E	−0.107174	0.955566	0.416749	0.098*	0.5
H14F	−0.340794	0.899849	0.433555	0.098*	0.5
N1	0.6195 (3)	0.68309 (9)	0.25867 (13)	0.0416 (4)
O1	0.2776 (4)	0.74103 (9)	0.10554 (12)	0.0595 (5)
H1	0.427 (7)	0.7120 (16)	0.140 (2)	0.097 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0427 (11)	0.0475 (12)	0.0359 (10)	−0.0030 (9)	0.0028 (8)	0.0041 (9)
C2	0.0344 (10)	0.0393 (10)	0.0378 (10)	−0.0050 (8)	0.0014 (8)	0.0039 (8)
C3	0.0439 (11)	0.0464 (12)	0.0380 (10)	−0.0040 (9)	0.0001 (9)	0.0013 (9)
C4	0.0466 (12)	0.0415 (11)	0.0514 (12)	−0.0039 (9)	0.0068 (10)	0.0010 (10)
C5	0.0463 (12)	0.0465 (12)	0.0571 (14)	0.0035 (10)	0.0021 (10)	0.0115 (10)
C6	0.0524 (13)	0.0573 (14)	0.0404 (11)	0.0031 (11)	−0.0018 (10)	0.0109 (10)
C7	0.0382 (11)	0.0460 (11)	0.0363 (10)	−0.0038 (9)	−0.0014 (8)	0.0024 (9)
C8	0.0343 (10)	0.0413 (11)	0.0444 (11)	−0.0045 (8)	0.0024 (8)	0.0006 (9)
C9	0.0559 (14)	0.0532 (13)	0.0497 (13)	0.0078 (11)	−0.0004 (10)	0.0013 (11)
C10	0.0654 (16)	0.0539 (14)	0.0649 (16)	0.0053 (12)	−0.0097 (12)	0.0062 (12)
C11	0.0550 (15)	0.0471 (14)	0.091 (2)	0.0068 (11)	−0.0067 (14)	−0.0006 (13)
C12	0.0588 (16)	0.0605 (16)	0.0800 (19)	0.0094 (12)	0.0097 (13)	−0.0170 (14)
C13	0.0510 (13)	0.0597 (14)	0.0481 (12)	0.0016 (11)	0.0029 (10)	−0.0057 (11)
C14	0.0708 (17)	0.0554 (15)	0.0692 (17)	0.0098 (12)	0.0074 (13)	−0.0064 (12)
N1	0.0392 (9)	0.0450 (10)	0.0400 (9)	−0.0004 (8)	0.0014 (7)	0.0012 (8)
O1	0.0679 (11)	0.0728 (11)	0.0370 (8)	0.0156 (9)	0.0008 (7)	−0.0007 (8)

Geometric parameters (Å, º) top

C1—O1	1.355 (2)	C9—C10	1.380 (3)
C1—C6	1.381 (3)	C9—H9	0.9300
C1—C2	1.407 (3)	C10—C11	1.369 (3)
C2—C3	1.396 (3)	C10—H10	0.9300
C2—C7	1.444 (3)	C11—C12	1.372 (4)
C3—C4	1.381 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.380 (3)
C4—C5	1.393 (3)	C12—H12	0.9300
C4—C14	1.505 (3)	C13—H13	0.9300
C5—C6	1.377 (3)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—N1	1.282 (2)	C14—H14D	0.9600
C7—H7	0.9300	C14—H14E	0.9600
C8—C13	1.377 (3)	C14—H14F	0.9600
C8—C9	1.389 (3)	O1—H1	0.96 (3)
C8—N1	1.418 (2)

O1—C1—C6	119.16 (18)	C10—C9—H9	119.9
O1—C1—C2	121.36 (18)	C8—C9—H9	119.9
C6—C1—C2	119.48 (19)	C11—C10—C9	120.9 (2)
C3—C2—C1	118.42 (18)	C11—C10—H10	119.5
C3—C2—C7	119.98 (17)	C9—C10—H10	119.5
C1—C2—C7	121.61 (18)	C10—C11—C12	119.4 (2)
C4—C3—C2	122.52 (19)	C10—C11—H11	120.3
C4—C3—H3	118.7	C12—C11—H11	120.3
C2—C3—H3	118.7	C11—C12—C13	120.0 (2)
C3—C4—C5	117.4 (2)	C11—C12—H12	120.0
C3—C4—C14	121.6 (2)	C13—C12—H12	120.0
C5—C4—C14	120.9 (2)	C8—C13—C12	121.2 (2)
C6—C5—C4	121.6 (2)	C8—C13—H13	119.4
C6—C5—H5	119.2	C12—C13—H13	119.4
C4—C5—H5	119.2	C4—C14—H14A	109.5
C5—C6—C1	120.6 (2)	C4—C14—H14B	109.5
C5—C6—H6	119.7	H14A—C14—H14B	109.5
C1—C6—H6	119.7	C4—C14—H14C	109.5
N1—C7—C2	122.01 (18)	H14A—C14—H14C	109.5
N1—C7—H7	119.0	H14B—C14—H14C	109.5
C2—C7—H7	119.0	H14D—C14—H14E	109.5
C13—C8—C9	118.3 (2)	H14D—C14—H14F	109.5
C13—C8—N1	116.88 (18)	H14E—C14—H14F	109.5
C9—C8—N1	124.77 (19)	C7—N1—C8	121.95 (17)
C10—C9—C8	120.1 (2)	C1—O1—H1	106.9 (18)

O1—C1—C2—C3	−179.81 (18)	C3—C2—C7—N1	178.48 (18)
C6—C1—C2—C3	−0.2 (3)	C1—C2—C7—N1	−1.4 (3)
O1—C1—C2—C7	0.0 (3)	C13—C8—C9—C10	−0.7 (3)
C6—C1—C2—C7	179.64 (19)	N1—C8—C9—C10	178.0 (2)
C1—C2—C3—C4	−0.5 (3)	C8—C9—C10—C11	0.2 (4)
C7—C2—C3—C4	179.67 (18)	C9—C10—C11—C12	0.3 (4)
C2—C3—C4—C5	0.5 (3)	C10—C11—C12—C13	−0.3 (4)
C2—C3—C4—C14	−179.9 (2)	C9—C8—C13—C12	0.7 (3)
C3—C4—C5—C6	0.2 (3)	N1—C8—C13—C12	−178.1 (2)
C14—C4—C5—C6	−179.4 (2)	C11—C12—C13—C8	−0.2 (4)
C4—C5—C6—C1	−0.9 (3)	C2—C7—N1—C8	−177.73 (17)
O1—C1—C6—C5	−179.5 (2)	C13—C8—N1—C7	−175.27 (19)
C2—C1—C6—C5	0.9 (3)	C9—C8—N1—C7	6.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.96 (3)	1.73 (3)	2.603 (2)	148 (3)

Acknowledgements

The authors are grateful to the Sophisticated Analytical Instrument Facility (SAIF), IITM, Chennai, Tamilnadu, India, for the single-crystal X-ray diffraction data.

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