(E)-4-Nitro-2-[(phenyl­imino)­meth­yl]phenol

Ida Malarselvi, R.; Ramachandra Raja, C.; Thiruvalluvar, A.; Priscilla, J.; Panneer Selvam, K.

doi:10.1107/S2414314616015959

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161595

https://doi.org/10.1107/S2414314616015959

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(E)-4-Nitro-2-[(phenylimino)methyl]phenol

R. Ida Malarselvi,^a C. Ramachandra Raja,^a A. Thiruvalluvar,^b ^* J. Priscilla ^c and K. Panneer Selvam ^a

^aCentre for Advanced Material Research, Government Arts College (Autonomous), Kumbakonam 612 001, Tamilnadu, India, ^bPostgraduate Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, and ^cPG Department of Physics, A.D.M. College for Women (Autonomous), Nagapattinam 611 001, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by P. C. Healy, Griffith University, Australia (Received 3 October 2016; accepted 9 October 2016; online 14 October 2016)

In the title compound, C₁₃H₁₀N₂O₃, the dihedral angle between the planes of the two aryl rings is 7.42 (10)°. An intramolecular O—H⋯N hydrogen bond generates an S(6) ring. The crystal structure features C—H⋯O hydrogen bonds.

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

CCDC reference: 1508947

Structure description

We report here the synthesis and characterization of the title Schiff base derivative (Fig. 1)) prepared from the condensation reaction of an equimolar proportion of 5-nitrosalicylaldehyde and aniline in CCl₄. The diversified nature of salicylaldehyde derivatives containing Schiff bases as an integral part of the structure exhibit a variety of important biological properties, including anti-bacterial, anti-cancer and anti-tumor activities (Ida Malarselvi et al., 2016 ).

Figure 1
A view of the title molecule with displacement ellipsoids drawn at the 50% probability level. A dashed line indicates the hydrogen-bonding interaction.

The benzene and phenyl rings are inclined at 7.42 (10)° to one another. The molecule has an E conformation about the C=N bond, and the C5—C7=N2—C8 torsion angle is −177.03 (16)°. The 4-nitro group is slightly tilted away from the benzene ring to which it is attached [O1—N1—C1—C2 = −5.8 (3)° and O2—N1—C1—C6 = −2.7 (3)°]. The strong intramolecular O3—H3A⋯N2 hydrogen bond (N⋯H distance of 1.83 Å) generates an S(6) ring. The strong band in the IR at 1632 cm⁻¹ is assigned to the C7=N2 stretching frequency of the imine group of Schiff base with the C7=N2 bond distance of 1.276 (2) Å indicative of double-bond character. The crystal structure features C2—H2⋯O1 and C7—H7⋯O2 hydrogen bonds (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.60	3.278 (2)	130
C7—H7⋯O2ⁱⁱ	0.93	2.41	3.252 (2)	150
O3—H3A⋯N2	0.82	1.83	2.5637 (19)	149
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z.

Figure 2
The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1

). H atoms not involved in hydrogen bonding have been omitted for clarity.

Yan et al., (2014 ) have reported the crystal structure of 4-bromo-2-[(phenylimino)methyl]phenol, in which the molecule is essentially planar (r.m.s. deviation = 0.026 Å).

Synthesis and crystallization

0.2 g (0.001 mol) of 5-nitrosalicylaldehyde was dissolved in 5 ml of CCl₄. To this solution, 0.1 g (0.111 mol) of aniline was added dropwise with constant stirring for 1 h. During this time, the solution turned deep yellow. On standing for two weeks with slow evaporation of the solvent, yellow crystals of the title compound were obtained.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₀N₂O₃
M_r	242.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.0774 (10), 6.5801 (6), 21.668 (3)
β (°)	98.240 (5)
V (Å³)	1139.8 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.95, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	15249, 2857, 1645
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.135, 1.04
No. of reflections	2857
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.22
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993 ), ORTEP-3 for Windows (Farrugia, 2012 ), SHELXL2016 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1508947

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616015959/hg4016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616015959/hg4016Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015959/hg4016Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015959/hg4016Isup4.cml

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: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(E)-4-Nitro-2-[(phenylimino)methyl]phenol top

Crystal data top

C₁₃H₁₀N₂O₃	F(000) = 504
M_r = 242.23	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.0774 (10) Å	Cell parameters from 3323 reflections
b = 6.5801 (6) Å	θ = 4.0–24.5°
c = 21.668 (3) Å	µ = 0.10 mm⁻¹
β = 98.240 (5)°	T = 296 K
V = 1139.8 (2) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1645 reflections with I > 2σ(I)
Radiation source: Sealed tube	R_int = 0.029
ω and φ scan	θ_max = 28.4°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→9
T_min = 0.95, T_max = 0.96	k = −8→8
15249 measured reflections	l = −28→28
2857 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0473P)² + 0.3112P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2857 reflections	Δρ_max = 0.17 e Å⁻³
164 parameters	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
C1	0.2784 (2)	0.1044 (3)	−0.11963 (7)	0.0468 (4)
C2	0.1930 (3)	0.2130 (3)	−0.16876 (8)	0.0563 (5)
H2	0.179342	0.159614	−0.208907	0.068*
C3	0.1293 (3)	0.3986 (3)	−0.15790 (8)	0.0608 (5)
H3	0.072527	0.472297	−0.190992	0.073*
C4	0.1474 (2)	0.4797 (3)	−0.09835 (8)	0.0508 (5)
C5	0.2374 (2)	0.3697 (3)	−0.04848 (7)	0.0450 (4)
C6	0.3016 (2)	0.1809 (3)	−0.06025 (7)	0.0464 (4)
H6	0.360524	0.106126	−0.027877	0.056*
C7	0.2662 (2)	0.4542 (3)	0.01343 (8)	0.0506 (5)
H7	0.323271	0.377170	0.045658	0.061*
C8	0.2495 (2)	0.7204 (3)	0.08524 (8)	0.0464 (4)
C9	0.3526 (2)	0.6347 (3)	0.13497 (8)	0.0565 (5)
H9	0.403539	0.509943	0.130314	0.068*
C10	0.3796 (3)	0.7343 (3)	0.19118 (9)	0.0643 (6)
H10	0.449407	0.677035	0.224503	0.077*
C11	0.3043 (3)	0.9175 (4)	0.19849 (10)	0.0705 (6)
H11	0.322110	0.983561	0.236820	0.085*
C12	0.2030 (3)	1.0033 (3)	0.14949 (10)	0.0696 (6)
H12	0.151911	1.127794	0.154403	0.083*
C13	0.1768 (2)	0.9057 (3)	0.09319 (9)	0.0567 (5)
H13	0.108938	0.965574	0.059827	0.068*
N1	0.3522 (2)	−0.0902 (2)	−0.13139 (7)	0.0586 (4)
N2	0.21561 (19)	0.6317 (2)	0.02536 (6)	0.0486 (4)
O1	0.3253 (2)	−0.1609 (2)	−0.18406 (7)	0.0843 (5)
O2	0.4381 (2)	−0.1762 (2)	−0.08827 (7)	0.0723 (5)
O3	0.08189 (19)	0.6599 (2)	−0.08898 (6)	0.0665 (4)
H3A	0.106727	0.692303	−0.052274	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0517 (11)	0.0475 (10)	0.0416 (9)	−0.0074 (8)	0.0083 (8)	0.0025 (7)
C2	0.0634 (13)	0.0679 (13)	0.0357 (9)	−0.0131 (10)	0.0005 (8)	0.0027 (8)
C3	0.0643 (13)	0.0672 (13)	0.0456 (10)	−0.0038 (10)	−0.0102 (9)	0.0162 (9)
C4	0.0474 (11)	0.0519 (11)	0.0518 (10)	−0.0024 (9)	0.0028 (8)	0.0111 (8)
C5	0.0453 (10)	0.0492 (10)	0.0396 (9)	−0.0041 (8)	0.0027 (7)	0.0052 (7)
C6	0.0494 (11)	0.0506 (10)	0.0378 (9)	−0.0009 (8)	0.0009 (7)	0.0072 (7)
C7	0.0540 (12)	0.0545 (11)	0.0422 (9)	0.0021 (9)	0.0032 (8)	0.0063 (8)
C8	0.0416 (10)	0.0518 (10)	0.0465 (9)	−0.0046 (8)	0.0091 (8)	0.0000 (8)
C9	0.0554 (12)	0.0619 (12)	0.0525 (11)	0.0060 (9)	0.0087 (9)	−0.0016 (9)
C10	0.0556 (13)	0.0841 (15)	0.0515 (11)	0.0048 (11)	0.0018 (9)	−0.0030 (10)
C11	0.0585 (14)	0.0892 (16)	0.0627 (13)	−0.0009 (12)	0.0048 (10)	−0.0242 (11)
C12	0.0649 (15)	0.0666 (13)	0.0758 (14)	0.0072 (11)	0.0056 (11)	−0.0184 (11)
C13	0.0511 (12)	0.0586 (12)	0.0590 (11)	0.0041 (9)	0.0029 (9)	−0.0009 (9)
N1	0.0688 (12)	0.0590 (10)	0.0495 (9)	−0.0078 (9)	0.0134 (8)	−0.0047 (8)
N2	0.0477 (9)	0.0506 (9)	0.0483 (8)	−0.0002 (7)	0.0091 (7)	0.0006 (7)
O1	0.1271 (16)	0.0753 (10)	0.0519 (8)	−0.0080 (9)	0.0177 (9)	−0.0165 (7)
O2	0.0777 (11)	0.0665 (9)	0.0702 (10)	0.0142 (8)	0.0022 (8)	−0.0039 (7)
O3	0.0689 (10)	0.0614 (9)	0.0662 (9)	0.0136 (7)	−0.0008 (7)	0.0115 (7)

Geometric parameters (Å, º) top

C1—C6	1.369 (2)	C8—C9	1.384 (2)
C1—C2	1.382 (2)	C8—N2	1.413 (2)
C1—N1	1.450 (2)	C9—C10	1.373 (3)
C2—C3	1.359 (3)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.370 (3)
C3—C4	1.385 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.366 (3)
C4—O3	1.326 (2)	C11—H11	0.9300
C4—C5	1.412 (2)	C12—C13	1.368 (3)
C5—C6	1.384 (2)	C12—H12	0.9300
C5—C7	1.440 (2)	C13—H13	0.9300
C6—H6	0.9300	N1—O2	1.220 (2)
C7—N2	1.276 (2)	N1—O1	1.2228 (19)
C7—H7	0.9300	O3—H3A	0.8200
C8—C13	1.375 (3)

C6—C1—C2	121.32 (17)	C13—C8—N2	116.85 (16)
C6—C1—N1	119.04 (15)	C9—C8—N2	124.19 (16)
C2—C1—N1	119.58 (16)	C10—C9—C8	119.81 (19)
C3—C2—C1	119.42 (17)	C10—C9—H9	120.1
C3—C2—H2	120.3	C8—C9—H9	120.1
C1—C2—H2	120.3	C11—C10—C9	120.4 (2)
C2—C3—C4	121.04 (17)	C11—C10—H10	119.8
C2—C3—H3	119.5	C9—C10—H10	119.8
C4—C3—H3	119.5	C12—C11—C10	120.01 (19)
O3—C4—C3	119.74 (16)	C12—C11—H11	120.0
O3—C4—C5	120.94 (16)	C10—C11—H11	120.0
C3—C4—C5	119.31 (17)	C11—C12—C13	119.9 (2)
C6—C5—C4	118.98 (15)	C11—C12—H12	120.1
C6—C5—C7	120.24 (15)	C13—C12—H12	120.1
C4—C5—C7	120.76 (16)	C12—C13—C8	120.93 (19)
C1—C6—C5	119.92 (16)	C12—C13—H13	119.5
C1—C6—H6	120.0	C8—C13—H13	119.5
C5—C6—H6	120.0	O2—N1—O1	122.93 (18)
N2—C7—C5	121.91 (16)	O2—N1—C1	118.55 (15)
N2—C7—H7	119.0	O1—N1—C1	118.52 (17)
C5—C7—H7	119.0	C7—N2—C8	122.60 (15)
C13—C8—C9	118.95 (17)	C4—O3—H3A	109.5

C6—C1—C2—C3	−0.7 (3)	C13—C8—C9—C10	0.5 (3)
N1—C1—C2—C3	−177.65 (18)	N2—C8—C9—C10	179.08 (18)
C1—C2—C3—C4	−0.5 (3)	C8—C9—C10—C11	0.4 (3)
C2—C3—C4—O3	−179.07 (19)	C9—C10—C11—C12	−0.7 (3)
C2—C3—C4—C5	1.6 (3)	C10—C11—C12—C13	0.1 (3)
O3—C4—C5—C6	179.13 (17)	C11—C12—C13—C8	0.8 (3)
C3—C4—C5—C6	−1.6 (3)	C9—C8—C13—C12	−1.1 (3)
O3—C4—C5—C7	−2.6 (3)	N2—C8—C13—C12	−179.80 (18)
C3—C4—C5—C7	176.72 (17)	C6—C1—N1—O2	−2.7 (3)
C2—C1—C6—C5	0.7 (3)	C2—C1—N1—O2	174.36 (17)
N1—C1—C6—C5	177.68 (16)	C6—C1—N1—O1	177.16 (17)
C4—C5—C6—C1	0.4 (3)	C2—C1—N1—O1	−5.8 (3)
C7—C5—C6—C1	−177.87 (16)	C5—C7—N2—C8	−177.03 (16)
C6—C5—C7—N2	176.63 (17)	C13—C8—N2—C7	−174.99 (17)
C4—C5—C7—N2	−1.7 (3)	C9—C8—N2—C7	6.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.60	3.278 (2)	130
C7—H7···O2ⁱⁱ	0.93	2.41	3.252 (2)	150
O3—H3A···N2	0.82	1.83	2.5637 (19)	149

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

Acknowledgements

The authors would like to acknowledge the University Grants Commission (UGC), New Delhi, for providing funds under Minor Research Project Scheme No. FERP5150/14 (SERO/UGC). The authors are grateful to the Sophisticated Analytical Instrument Facility (SAIF), IITM, Chennai 600 036, Tamilnadu, India, for the single-crystal X-ray diffraction data.

References

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