2-[((E)-{2-[(E)-(2-Hy­droxy­benzyl­idene)amino]­benz­yl}imino)­meth­yl]phenol

Raghuvarman, B.; Gayathri, J.; Selvan, K.S.; Aravindhan, S.; Ponnuswamy, M.N.

doi:10.1107/S2414314617012093

organic compounds

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ISSN: 2414-3146

Volume 2| Part 9| September 2017| x171209

https://doi.org/10.1107/S2414314617012093

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2-[((E)-{2-[(E)-(2-Hydroxybenzylidene)amino]benzyl}imino)methyl]phenol

B. Raghuvarman,^a Jayagopi Gayathri,^b Kumar Sangeetha Selvan,^b S. Aravindhan ^a and M. N. Ponnuswamy ^c ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^bDepartment of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 8 August 2017; accepted 22 August 2017; online 8 September 2017)

In the title hydroxyphenyl-substituted salophene compound, C₂₁H₁₈N₂O₂, there are two intramolecular O—H⋯N hydrogen bonds forming S(6) ring motifs. The phenol rings are inclined to one another by 65.9 (3)°, and by 0.0 (2) and 65.9 (2)°, respectively, to the central benzene ring. In the crystal, molecules are linked by a weak C—H⋯O contact forming chains along [010].

Keywords: crystal structure; salophene; Schiff base; intramolecular O—H⋯N hydrogen bonds.

CCDC reference: 1570194

Structure description

The title hydroxyphenyl-substituted salophene compound was synthesized using Schiff base reactions, which play an important role in coordination chemistry (Ben Guzzi & El Alagi, 2013 ).

The molecular structure of the title compound is shown in Fig. 1. In the molecule, there are two intramolecular O—H⋯N hydrogen bonds forming S(6) ring motifs (Table 1 and Fig. 1). The phenol rings (C1–C6 and C16–C21) are inclined to one another by 65.9 (3)°. The C1–C6 phenol ring lies in the plane of the central benzene ring (C8–C13), with a dihedral angle of 0.0 (2)°, while the C16–C21 phenol ring is inclined to the central benzene ring (C8–C13) by 65.9 (2)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.96 (6)	1.75 (6)	2.581 (5)	142 (5)
O2—H2⋯N2	0.92 (5)	1.77 (5)	2.589 (5)	147 (5)
C7—H7⋯O2ⁱ	0.93	2.63	3.526 (6)	161
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at the 30% probability level. The intramolecular O—H⋯N hydrogen bonds are shown as dashed lines (see Table 1

In the crystal, molecules are linked by weak C—H⋯O contacts forming chains propagating along the b-axis direction (Table 1 and Fig. 2).

Figure 2
The crystal packing of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

Synthesis and crystallization

2-Aminobenzylamine (2 mmol) in methanol (50 ml) was added dropwise, with continuous stirring, to a warm methanolic solution of the appropriate salicylaldehyde (4 mmol), and the mixture was refluxed for 3 h. The yellow solid obtained was filtered off, washed with cold Et₂O (10 ml) and dried in a vacuum. After a few minutes, yellow block-like crystals appeared, which were isolated via filtration and used without further purification.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₁₈N₂O₂
M_r	330.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	4.8654 (14), 17.652 (6), 19.927 (6)
β (°)	91.727 (8)
V (Å³)	1710.6 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.971, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	17523, 2177, 1427
R_int	0.069
θ_max (°)	22.3
(sin θ/λ)_max (Å⁻¹)	0.535

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.150, 1.16
No. of reflections	2177
No. of parameters	234
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS2016 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1570194

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617012093/su4163sup1.cif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2016 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

2-[((E)-{2-[(E)-(2-Hydroxybenzylidene)amino]benzyl}imino)methyl]phenol top

Crystal data top

C₂₁H₁₈N₂O₂	F(000) = 696
M_r = 330.37	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.8654 (14) Å	Cell parameters from 1427 reflections
b = 17.652 (6) Å	θ = 1.5–22.3°
c = 19.927 (6) Å	µ = 0.08 mm⁻¹
β = 91.727 (8)°	T = 296 K
V = 1710.6 (9) Å³	Block, yellow
Z = 4	0.35 × 0.15 × 0.10 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	2177 independent reflections
Radiation source: fine-focus sealed tube	1427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ω and φ scans	θ_max = 22.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −5→5
T_min = 0.971, T_max = 0.992	k = −18→18
17523 measured reflections	l = −21→21

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)] = 0.066	Hydrogen site location: mixed
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0136P)² + 3.0321P] where P = (F_o² + 2F_c²)/3
2177 reflections	(Δ/σ)_max < 0.001
234 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 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.

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

	x	y	z	U_iso*/U_eq
O1	−0.0311 (9)	0.4754 (2)	0.09631 (18)	0.0762 (11)
H1	0.112 (12)	0.455 (3)	0.126 (3)	0.11 (2)*
O2	0.7654 (10)	0.1330 (2)	0.12620 (19)	0.0856 (13)
H2	0.656 (11)	0.175 (3)	0.131 (3)	0.09 (2)*
N1	0.2561 (7)	0.4637 (2)	0.20684 (17)	0.0440 (9)
N2	0.6237 (8)	0.2743 (2)	0.12028 (18)	0.0491 (10)
C1	−0.0757 (9)	0.5601 (2)	0.1879 (2)	0.0489 (12)
C2	−0.1524 (10)	0.5363 (3)	0.1230 (3)	0.0572 (13)
C3	−0.3537 (11)	0.5745 (3)	0.0867 (3)	0.0766 (16)
H3	−0.402875	0.558447	0.043505	0.092*
C4	−0.4815 (12)	0.6357 (4)	0.1136 (4)	0.088 (2)
H4	−0.618823	0.660737	0.088810	0.105*
C5	−0.4099 (13)	0.6606 (3)	0.1764 (4)	0.090 (2)
H5	−0.495865	0.702795	0.194215	0.108*
C6	−0.2102 (11)	0.6230 (3)	0.2133 (3)	0.0696 (15)
H6	−0.163483	0.640004	0.256330	0.084*
C7	0.1301 (9)	0.5220 (3)	0.2282 (2)	0.0476 (12)
H7	0.173152	0.540229	0.270990	0.057*
C8	0.4603 (8)	0.4252 (2)	0.2448 (2)	0.0398 (11)
C9	0.5489 (10)	0.4456 (3)	0.3096 (2)	0.0551 (13)
H9	0.471246	0.487282	0.330369	0.066*
C10	0.7494 (10)	0.4046 (3)	0.3429 (2)	0.0575 (13)
H10	0.804140	0.418456	0.386321	0.069*
C11	0.8712 (9)	0.3433 (3)	0.3133 (2)	0.0544 (13)
H11	1.008338	0.315912	0.335980	0.065*
C12	0.7847 (9)	0.3234 (3)	0.2490 (2)	0.0503 (12)
H12	0.866455	0.282191	0.228447	0.060*
C13	0.5812 (8)	0.3627 (2)	0.2145 (2)	0.0392 (11)
C14	0.4834 (9)	0.3410 (3)	0.1441 (2)	0.0529 (13)
H14	0.287088	0.331458	0.143787	0.063*
H13	0.515840	0.382958	0.113827	0.063*
C15	0.7827 (9)	0.2816 (2)	0.0713 (2)	0.0468 (12)
H15	0.798118	0.328849	0.050982	0.056*
C16	0.9399 (9)	0.2192 (2)	0.0461 (2)	0.0425 (11)
C17	1.1157 (10)	0.2311 (3)	−0.0068 (2)	0.0569 (13)
H17	1.125123	0.278977	−0.026086	0.068*
C18	1.2748 (11)	0.1740 (4)	−0.0312 (3)	0.0718 (16)
H18	1.390668	0.182823	−0.066642	0.086*
C19	1.2609 (13)	0.1040 (4)	−0.0028 (3)	0.0872 (19)
H19	1.368830	0.065028	−0.019071	0.105*
C20	1.0912 (14)	0.0900 (3)	0.0493 (3)	0.0870 (19)
H20	1.084064	0.041860	0.068086	0.104*
C21	0.9311 (11)	0.1473 (3)	0.0738 (2)	0.0612 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.100 (3)	0.074 (3)	0.053 (2)	0.018 (2)	−0.012 (2)	−0.005 (2)
O2	0.133 (4)	0.061 (3)	0.064 (3)	0.012 (3)	0.013 (3)	0.016 (2)
N1	0.050 (2)	0.043 (2)	0.039 (2)	0.0002 (19)	0.0056 (18)	−0.0015 (18)
N2	0.061 (3)	0.049 (2)	0.037 (2)	0.004 (2)	−0.001 (2)	−0.0075 (18)
C1	0.044 (3)	0.044 (3)	0.059 (3)	0.000 (2)	0.010 (2)	0.005 (2)
C2	0.059 (3)	0.052 (3)	0.061 (4)	−0.002 (3)	0.000 (3)	0.013 (3)
C3	0.079 (4)	0.076 (4)	0.074 (4)	−0.004 (3)	−0.010 (3)	0.022 (3)
C4	0.067 (4)	0.078 (5)	0.119 (6)	0.010 (4)	0.003 (4)	0.044 (4)
C5	0.079 (5)	0.064 (4)	0.127 (6)	0.019 (3)	0.023 (4)	0.007 (4)
C6	0.068 (4)	0.062 (4)	0.079 (4)	0.009 (3)	0.009 (3)	0.000 (3)
C7	0.053 (3)	0.049 (3)	0.041 (3)	−0.006 (2)	0.005 (2)	−0.004 (2)
C8	0.043 (3)	0.044 (3)	0.032 (3)	−0.006 (2)	0.003 (2)	0.001 (2)
C9	0.067 (3)	0.055 (3)	0.044 (3)	0.001 (3)	0.001 (3)	−0.004 (2)
C10	0.074 (4)	0.066 (3)	0.032 (3)	−0.020 (3)	−0.003 (3)	−0.002 (3)
C11	0.056 (3)	0.064 (3)	0.042 (3)	−0.004 (3)	−0.013 (2)	0.013 (3)
C12	0.053 (3)	0.051 (3)	0.047 (3)	0.001 (2)	−0.002 (2)	−0.001 (2)
C13	0.041 (3)	0.043 (3)	0.034 (2)	−0.005 (2)	0.002 (2)	0.002 (2)
C14	0.053 (3)	0.063 (3)	0.042 (3)	0.004 (2)	−0.004 (2)	−0.010 (2)
C15	0.056 (3)	0.046 (3)	0.037 (3)	0.002 (2)	−0.012 (2)	0.001 (2)
C16	0.051 (3)	0.045 (3)	0.030 (3)	0.002 (2)	−0.009 (2)	−0.008 (2)
C17	0.060 (3)	0.064 (3)	0.046 (3)	0.005 (3)	−0.003 (3)	−0.005 (3)
C18	0.069 (4)	0.099 (5)	0.047 (3)	0.017 (4)	−0.002 (3)	−0.011 (3)
C19	0.098 (5)	0.094 (5)	0.069 (4)	0.040 (4)	−0.009 (4)	−0.025 (4)
C20	0.131 (6)	0.058 (4)	0.071 (4)	0.038 (4)	−0.012 (4)	0.005 (3)
C21	0.085 (4)	0.055 (3)	0.043 (3)	0.010 (3)	−0.008 (3)	0.001 (3)

Geometric parameters (Å, º) top

O1—C2	1.344 (6)	C9—H9	0.9300
O1—H1	0.96 (6)	C10—C11	1.375 (6)
O2—C21	1.362 (6)	C10—H10	0.9300
O2—H2	0.92 (5)	C11—C12	1.382 (6)
N1—C7	1.278 (5)	C11—H11	0.9300
N1—C8	1.405 (5)	C12—C13	1.376 (6)
N2—C15	1.271 (5)	C12—H12	0.9300
N2—C14	1.448 (5)	C13—C14	1.518 (5)
C1—C6	1.393 (6)	C14—H14	0.9700
C1—C2	1.398 (6)	C14—H13	0.9700
C1—C7	1.432 (6)	C15—C16	1.440 (6)
C2—C3	1.377 (7)	C15—H15	0.9300
C3—C4	1.365 (8)	C16—C21	1.385 (6)
C3—H3	0.9300	C16—C17	1.394 (6)
C4—C5	1.362 (8)	C17—C18	1.369 (7)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.371 (8)	C18—C19	1.361 (8)
C5—H5	0.9300	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.368 (8)
C7—H7	0.9300	C19—H19	0.9300
C8—C13	1.397 (6)	C20—C21	1.375 (7)
C8—C9	1.397 (6)	C20—H20	0.9300
C9—C10	1.370 (6)

C2—O1—H1	112 (3)	C10—C11—H11	120.8
C21—O2—H2	107 (3)	C12—C11—H11	120.8
C7—N1—C8	123.3 (4)	C13—C12—C11	122.0 (4)
C15—N2—C14	118.2 (4)	C13—C12—H12	119.0
C6—C1—C2	117.4 (5)	C11—C12—H12	119.0
C6—C1—C7	119.9 (5)	C12—C13—C8	119.3 (4)
C2—C1—C7	122.7 (4)	C12—C13—C14	122.4 (4)
O1—C2—C3	119.8 (5)	C8—C13—C14	118.3 (4)
O1—C2—C1	119.9 (4)	N2—C14—C13	111.7 (4)
C3—C2—C1	120.3 (5)	N2—C14—H14	109.3
C4—C3—C2	120.4 (6)	C13—C14—H14	109.3
C4—C3—H3	119.8	N2—C14—H13	109.3
C2—C3—H3	119.8	C13—C14—H13	109.3
C5—C4—C3	120.6 (6)	H14—C14—H13	107.9
C5—C4—H4	119.7	N2—C15—C16	122.1 (4)
C3—C4—H4	119.7	N2—C15—H15	118.9
C4—C5—C6	119.6 (6)	C16—C15—H15	118.9
C4—C5—H5	120.2	C21—C16—C17	117.8 (4)
C6—C5—H5	120.2	C21—C16—C15	122.7 (4)
C5—C6—C1	121.6 (6)	C17—C16—C15	119.5 (4)
C5—C6—H6	119.2	C18—C17—C16	121.6 (5)
C1—C6—H6	119.2	C18—C17—H17	119.2
N1—C7—C1	121.7 (4)	C16—C17—H17	119.2
N1—C7—H7	119.1	C19—C18—C17	119.0 (5)
C1—C7—H7	119.1	C19—C18—H18	120.5
C13—C8—C9	118.7 (4)	C17—C18—H18	120.5
C13—C8—N1	116.7 (4)	C18—C19—C20	121.2 (5)
C9—C8—N1	124.6 (4)	C18—C19—H19	119.4
C10—C9—C8	120.5 (4)	C20—C19—H19	119.4
C10—C9—H9	119.7	C19—C20—C21	119.8 (5)
C8—C9—H9	119.7	C19—C20—H20	120.1
C9—C10—C11	121.2 (4)	C21—C20—H20	120.1
C9—C10—H10	119.4	O2—C21—C20	119.4 (5)
C11—C10—H10	119.4	O2—C21—C16	120.1 (4)
C10—C11—C12	118.3 (4)	C20—C21—C16	120.5 (5)

C6—C1—C2—O1	−179.3 (4)	C11—C12—C13—C14	−179.6 (4)
C7—C1—C2—O1	0.0 (7)	C9—C8—C13—C12	−0.5 (6)
C6—C1—C2—C3	0.0 (7)	N1—C8—C13—C12	179.2 (4)
C7—C1—C2—C3	179.3 (4)	C9—C8—C13—C14	180.0 (4)
O1—C2—C3—C4	179.0 (5)	N1—C8—C13—C14	−0.3 (5)
C1—C2—C3—C4	−0.3 (8)	C15—N2—C14—C13	−113.7 (4)
C2—C3—C4—C5	0.8 (9)	C12—C13—C14—N2	1.7 (6)
C3—C4—C5—C6	−0.9 (9)	C8—C13—C14—N2	−178.7 (4)
C4—C5—C6—C1	0.6 (9)	C14—N2—C15—C16	177.3 (4)
C2—C1—C6—C5	−0.1 (7)	N2—C15—C16—C21	−0.7 (7)
C7—C1—C6—C5	−179.5 (5)	N2—C15—C16—C17	−178.6 (4)
C8—N1—C7—C1	179.6 (4)	C21—C16—C17—C18	0.2 (7)
C6—C1—C7—N1	179.3 (4)	C15—C16—C17—C18	178.2 (4)
C2—C1—C7—N1	0.0 (7)	C16—C17—C18—C19	−0.2 (8)
C7—N1—C8—C13	−179.5 (4)	C17—C18—C19—C20	0.1 (9)
C7—N1—C8—C9	0.2 (6)	C18—C19—C20—C21	−0.1 (9)
C13—C8—C9—C10	−0.4 (6)	C19—C20—C21—O2	−179.2 (5)
N1—C8—C9—C10	179.9 (4)	C19—C20—C21—C16	0.1 (8)
C8—C9—C10—C11	0.9 (7)	C17—C16—C21—O2	179.1 (4)
C9—C10—C11—C12	−0.6 (7)	C15—C16—C21—O2	1.2 (7)
C10—C11—C12—C13	−0.4 (7)	C17—C16—C21—C20	−0.1 (7)
C11—C12—C13—C8	0.9 (6)	C15—C16—C21—C20	−178.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.96 (6)	1.75 (6)	2.581 (5)	142 (5)
O2—H2···N2	0.92 (5)	1.77 (5)	2.589 (5)	147 (5)
C7—H7···O2ⁱ	0.93	2.63	3.526 (6)	161

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

The authors thank TBI consultancy, University of Madras, India, for the data collection.

References

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