Crystal structure of ethyl 2-(2-{(1E)-[(E)-2-(2-hy­droxy­benzyl­idene)hydrazin-1-yl­idene]meth­yl}phen­oxy)acetate

Akkurt, M.; Mague, J.T.; Mohamed, S.K.; Ahmed, E.A.; Albayati, M.R.

doi:10.1107/S2056989014027273

Crystal structure of ethyl 2-(2-{(1E)-[(E)-2-(2-hydroxybenzylidene)hydrazin-1-ylidene]methyl}phenoxy)acetate

M. Akkurt, J. T. Mague, S. K. Mohamed, E. A. Ahmed and M. R. Albayati

In the title compound, C₁₈H₁₈N₂O₄, the planes of the benzene rings are twisted with respect to each other at 27.25 (7)°. The molecule displays an extended conformation with an intramolecular O—H

N hydrogen bond. In the crystal, weak C—H

O interactions link the molecules, forming supramolecular chains running along the b-axis direction.

Keywords: crystal structure; Schiff base ligand; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989014027273/xu5832sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989014027273/xu5832Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989014027273/xu5832Isup3.cml Supplementary material

CCDC reference: 1039095

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.002 Å
R factor = 0.038
wR factor = 0.109
Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         37 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Schiff bases of salicylaldehyde have gained importance from physiological and pharmacological activities point of view (Adsule et al., 2006; Karthikeyan et al., 2006). They also may exhibit thermochromism or photochromism depending on the planarity or nonplanarity, respectively, of the molecule (Amimoto & Kawato, 2005; Cohen & Schmidt, 1964). As part of our research efforts in the area of schiff base ligands we report in this study the synthesis and crystal structure determination of the title compound.

The title molecule is in an extended conformation with the phenyl rings C1–C6 and C9–C14, respectively, making dihedral angles of 7.4 (1)° and 19.8 (1)° with the mean plane of the central C7, N1, N2, C8 unit. The bond lengths and bond angles of the title molecule are normal and are comparable to those reported for a similar structure (Mague et al., 2015).

The former angle is smaller as a result of the intramolecular O1—H1a···N1 hydrogen bond (Table 1). The packing consists of chains of molecules formed by weak C15—H15B···O3 interactions running parallel to the b axis with adjacent pairs of chains associated via C15—H15a···O4 interactions across centers of symmetry (Fig. 2 and Table 1).

Related literature top

For a similar structure, see: Mague et al. (2015). For background to related Schiff base ligands and their biological activity, see: Adsule et al. (2006); Karthikeyan et al. (2006); Amimoto & Kawato (2005); Cohen & Schmidt (1964).

Experimental top

A mixture of 0.01 mol of 2-hydroxybenzohydrazide and 0.01 mol of ethyl 2-(2-formylphenoxy)acetate in 20 ml of ethanol was heated under reflux for 2 h. The solid product which precipitated from the hot solution was collected by filtration and dried under vacuum. Colourless crystals sufficient for X-ray diffraction were obtained by recrystallization from an ethanol solution. m.p. 428 K, yield 92%.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of the title molecule with 50% probability ellipsoids and showing the atom labeling scheme and the intramolecular O—H···N hydrogen bond.
	Fig. 2. Packing viewed down the b axis showing C—H···O interactions as black dotted lines.

Ethyl 2-(2-{(1E)-[(E)-2-(2-hydroxybenzylidene)hydrazin-1-ylidene]methyl}phenoxy)acetate top

Crystal data top

C₁₈H₁₈N₂O₄	F(000) = 688
M_r = 326.34	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 17.6846 (4) Å	Cell parameters from 6837 reflections
b = 4.8645 (1) Å	θ = 4.1–72.5°
c = 19.2235 (4) Å	µ = 0.81 mm⁻¹
β = 107.357 (1)°	T = 150 K
V = 1578.43 (6) Å³	Column, colourless
Z = 4	0.20 × 0.09 × 0.06 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3063 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2538 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.031
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.5°, θ_min = 3.0°
ω scans	h = −18→21
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −5→6
T_min = 0.90, T_max = 0.95	l = −23→23
11331 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0535P)² + 0.5415P] where P = (F_o² + 2F_c²)/3
3063 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₈H₁₈N₂O₄	V = 1578.43 (6) Å³
M_r = 326.34	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 17.6846 (4) Å	µ = 0.81 mm⁻¹
b = 4.8645 (1) Å	T = 150 K
c = 19.2235 (4) Å	0.20 × 0.09 × 0.06 mm
β = 107.357 (1)°

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3063 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	2538 reflections with I > 2σ(I)
T_min = 0.90, T_max = 0.95	R_int = 0.031
11331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
3063 reflections	Δρ_min = −0.21 e Å⁻³
218 parameters

Special details top

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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while that attached to oxygen was placed in a location derived from a difference map and its parameters adjusted to give O—H = 0.84 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

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

	x	y	z	U_iso*/U_eq
O1	0.26107 (6)	0.1064 (3)	0.62511 (6)	0.0392 (3)
H1A	0.2450	0.2256	0.5924	0.047*
O2	0.33072 (6)	1.1408 (2)	0.46429 (6)	0.0318 (3)
O3	0.42576 (7)	0.9110 (2)	0.38921 (7)	0.0394 (3)
O4	0.49863 (7)	1.2963 (2)	0.40435 (6)	0.0365 (3)
N1	0.17349 (7)	0.4391 (3)	0.52416 (6)	0.0274 (3)
N2	0.15351 (7)	0.6296 (3)	0.46651 (7)	0.0286 (3)
C1	0.11819 (9)	0.1146 (3)	0.58929 (8)	0.0259 (3)
C2	0.19168 (9)	0.0129 (3)	0.63240 (8)	0.0277 (3)
C3	0.19421 (10)	−0.1914 (3)	0.68369 (8)	0.0322 (3)
H3	0.2438	−0.2593	0.7130	0.039*
C4	0.12504 (10)	−0.2958 (3)	0.69212 (8)	0.0333 (4)
H4	0.1274	−0.4362	0.7271	0.040*
C5	0.05185 (10)	−0.1982 (4)	0.65017 (9)	0.0355 (4)
H5	0.0044	−0.2718	0.6561	0.043*
C6	0.04881 (9)	0.0071 (3)	0.59976 (9)	0.0326 (4)
H6	−0.0012	0.0767	0.5717	0.039*
C7	0.11221 (9)	0.3247 (3)	0.53449 (8)	0.0273 (3)
H7	0.0611	0.3800	0.5051	0.033*
C8	0.21343 (9)	0.7639 (3)	0.46080 (8)	0.0259 (3)
H8	0.2637	0.7370	0.4958	0.031*
C9	0.20573 (8)	0.9589 (3)	0.40100 (8)	0.0248 (3)
C10	0.13833 (9)	0.9571 (3)	0.33998 (8)	0.0298 (3)
H10	0.0963	0.8334	0.3385	0.036*
C11	0.13200 (9)	1.1324 (3)	0.28202 (8)	0.0323 (4)
H11	0.0860	1.1286	0.2409	0.039*
C12	0.19294 (9)	1.3133 (3)	0.28420 (8)	0.0314 (3)
H12	0.1885	1.4344	0.2444	0.038*
C13	0.26054 (9)	1.3203 (3)	0.34376 (8)	0.0291 (3)
H13	0.3022	1.4450	0.3447	0.035*
C14	0.26682 (8)	1.1433 (3)	0.40201 (8)	0.0251 (3)
C15	0.39957 (9)	1.2843 (3)	0.46170 (8)	0.0312 (3)
H15A	0.4364	1.3016	0.5117	0.037*
H15B	0.3846	1.4718	0.4425	0.037*
C16	0.44124 (9)	1.1381 (3)	0.41393 (8)	0.0290 (3)
C17	0.54618 (11)	1.1827 (4)	0.36101 (11)	0.0423 (4)
H17A	0.5114	1.1105	0.3142	0.051*
H17B	0.5796	1.0304	0.3876	0.051*
C18	0.59662 (11)	1.4085 (4)	0.34751 (11)	0.0444 (4)
H18A	0.5629	1.5554	0.3199	0.067*
H18B	0.6306	1.3375	0.3196	0.067*
H18C	0.6297	1.4814	0.3942	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0279 (6)	0.0439 (7)	0.0432 (7)	−0.0035 (5)	0.0066 (5)	0.0125 (5)
O2	0.0294 (5)	0.0372 (6)	0.0291 (5)	−0.0080 (5)	0.0091 (4)	0.0026 (5)
O3	0.0414 (7)	0.0279 (6)	0.0506 (7)	−0.0041 (5)	0.0164 (5)	−0.0039 (5)
O4	0.0364 (6)	0.0330 (6)	0.0461 (7)	−0.0077 (5)	0.0212 (5)	−0.0072 (5)
N1	0.0294 (6)	0.0258 (7)	0.0276 (6)	−0.0011 (5)	0.0092 (5)	0.0035 (5)
N2	0.0296 (6)	0.0270 (7)	0.0299 (6)	0.0001 (5)	0.0101 (5)	0.0053 (5)
C1	0.0290 (7)	0.0236 (7)	0.0256 (7)	−0.0023 (6)	0.0091 (6)	−0.0019 (6)
C2	0.0291 (7)	0.0262 (8)	0.0270 (7)	−0.0039 (6)	0.0073 (6)	−0.0035 (6)
C3	0.0351 (8)	0.0310 (8)	0.0280 (7)	0.0007 (7)	0.0058 (6)	0.0022 (7)
C4	0.0459 (9)	0.0284 (8)	0.0286 (7)	0.0006 (7)	0.0157 (7)	0.0035 (6)
C5	0.0360 (8)	0.0355 (9)	0.0405 (9)	−0.0024 (7)	0.0197 (7)	0.0038 (7)
C6	0.0288 (8)	0.0336 (9)	0.0367 (8)	0.0000 (7)	0.0119 (6)	0.0036 (7)
C7	0.0259 (7)	0.0260 (8)	0.0301 (7)	0.0004 (6)	0.0084 (6)	0.0008 (6)
C8	0.0269 (7)	0.0243 (8)	0.0278 (7)	0.0006 (6)	0.0102 (6)	0.0002 (6)
C9	0.0266 (7)	0.0222 (7)	0.0280 (7)	0.0029 (6)	0.0121 (6)	0.0006 (6)
C10	0.0265 (7)	0.0300 (8)	0.0340 (8)	−0.0003 (6)	0.0108 (6)	0.0013 (7)
C11	0.0292 (8)	0.0357 (9)	0.0308 (8)	0.0051 (7)	0.0069 (6)	0.0045 (7)
C12	0.0372 (8)	0.0286 (8)	0.0314 (8)	0.0082 (7)	0.0147 (6)	0.0080 (7)
C13	0.0333 (8)	0.0251 (8)	0.0335 (8)	−0.0007 (6)	0.0170 (6)	0.0015 (6)
C14	0.0261 (7)	0.0244 (7)	0.0272 (7)	0.0025 (6)	0.0115 (6)	−0.0007 (6)
C15	0.0295 (8)	0.0331 (9)	0.0309 (8)	−0.0079 (7)	0.0090 (6)	−0.0026 (7)
C16	0.0275 (7)	0.0271 (8)	0.0302 (7)	−0.0022 (6)	0.0053 (6)	0.0018 (6)
C17	0.0435 (10)	0.0358 (10)	0.0562 (11)	0.0005 (8)	0.0280 (8)	−0.0050 (8)
C18	0.0440 (10)	0.0438 (11)	0.0537 (11)	0.0029 (8)	0.0273 (8)	0.0046 (9)

Geometric parameters (Å, º) top

O1—C2	1.3548 (18)	C8—C9	1.465 (2)
O1—H1A	0.8403	C8—H8	0.9500
O2—C14	1.3797 (17)	C9—C14	1.400 (2)
O2—C15	1.4172 (17)	C9—C10	1.401 (2)
O3—C16	1.2016 (19)	C10—C11	1.381 (2)
O4—C16	1.3295 (18)	C10—H10	0.9500
O4—C17	1.4577 (19)	C11—C12	1.382 (2)
N1—C7	1.2854 (19)	C11—H11	0.9500
N1—N2	1.4064 (17)	C12—C13	1.387 (2)
N2—C8	1.2772 (19)	C12—H12	0.9500
C1—C6	1.402 (2)	C13—C14	1.390 (2)
C1—C2	1.406 (2)	C13—H13	0.9500
C1—C7	1.449 (2)	C15—C16	1.515 (2)
C2—C3	1.391 (2)	C15—H15A	0.9900
C3—C4	1.378 (2)	C15—H15B	0.9900
C3—H3	0.9500	C17—C18	1.486 (3)
C4—C5	1.389 (2)	C17—H17A	0.9900
C4—H4	0.9500	C17—H17B	0.9900
C5—C6	1.381 (2)	C18—H18A	0.9800
C5—H5	0.9500	C18—H18B	0.9800
C6—H6	0.9500	C18—H18C	0.9800
C7—H7	0.9500

C2—O1—H1A	101.2	C9—C10—H10	119.5
C14—O2—C15	117.06 (11)	C10—C11—C12	119.60 (14)
C16—O4—C17	117.01 (13)	C10—C11—H11	120.2
C7—N1—N2	112.44 (12)	C12—C11—H11	120.2
C8—N2—N1	112.64 (12)	C11—C12—C13	120.84 (14)
C6—C1—C2	118.59 (14)	C11—C12—H12	119.6
C6—C1—C7	119.35 (14)	C13—C12—H12	119.6
C2—C1—C7	122.06 (13)	C12—C13—C14	119.45 (14)
O1—C2—C3	118.34 (14)	C12—C13—H13	120.3
O1—C2—C1	121.82 (14)	C14—C13—H13	120.3
C3—C2—C1	119.84 (14)	O2—C14—C13	123.53 (13)
C4—C3—C2	120.30 (15)	O2—C14—C9	115.80 (12)
C4—C3—H3	119.9	C13—C14—C9	120.65 (14)
C2—C3—H3	119.9	O2—C15—C16	111.61 (13)
C3—C4—C5	120.80 (15)	O2—C15—H15A	109.3
C3—C4—H4	119.6	C16—C15—H15A	109.3
C5—C4—H4	119.6	O2—C15—H15B	109.3
C6—C5—C4	119.29 (15)	C16—C15—H15B	109.3
C6—C5—H5	120.4	H15A—C15—H15B	108.0
C4—C5—H5	120.4	O3—C16—O4	124.80 (15)
C5—C6—C1	121.17 (15)	O3—C16—C15	125.22 (14)
C5—C6—H6	119.4	O4—C16—C15	109.98 (13)
C1—C6—H6	119.4	O4—C17—C18	107.37 (14)
N1—C7—C1	122.39 (14)	O4—C17—H17A	110.2
N1—C7—H7	118.8	C18—C17—H17A	110.2
C1—C7—H7	118.8	O4—C17—H17B	110.2
N2—C8—C9	120.88 (13)	C18—C17—H17B	110.2
N2—C8—H8	119.6	H17A—C17—H17B	108.5
C9—C8—H8	119.6	C17—C18—H18A	109.5
C14—C9—C10	118.41 (13)	C17—C18—H18B	109.5
C14—C9—C8	120.88 (13)	H18A—C18—H18B	109.5
C10—C9—C8	120.65 (13)	C17—C18—H18C	109.5
C11—C10—C9	121.06 (14)	H18A—C18—H18C	109.5
C11—C10—H10	119.5	H18B—C18—H18C	109.5

C7—N1—N2—C8	173.32 (13)	C8—C9—C10—C11	−177.30 (14)
C6—C1—C2—O1	179.77 (14)	C9—C10—C11—C12	−0.2 (2)
C7—C1—C2—O1	0.1 (2)	C10—C11—C12—C13	0.3 (2)
C6—C1—C2—C3	0.4 (2)	C11—C12—C13—C14	−0.2 (2)
C7—C1—C2—C3	−179.22 (14)	C15—O2—C14—C13	−13.6 (2)
O1—C2—C3—C4	−178.94 (14)	C15—O2—C14—C9	168.16 (13)
C1—C2—C3—C4	0.4 (2)	C12—C13—C14—O2	−178.18 (13)
C2—C3—C4—C5	−0.5 (2)	C12—C13—C14—C9	0.0 (2)
C3—C4—C5—C6	−0.4 (3)	C10—C9—C14—O2	178.35 (13)
C4—C5—C6—C1	1.2 (3)	C8—C9—C14—O2	−4.28 (19)
C2—C1—C6—C5	−1.3 (2)	C10—C9—C14—C13	0.0 (2)
C7—C1—C6—C5	178.39 (15)	C8—C9—C14—C13	177.39 (13)
N2—N1—C7—C1	177.86 (13)	C14—O2—C15—C16	−71.06 (17)
C6—C1—C7—N1	177.23 (14)	C17—O4—C16—O3	−0.4 (2)
C2—C1—C7—N1	−3.1 (2)	C17—O4—C16—C15	178.44 (14)
N1—N2—C8—C9	175.83 (12)	O2—C15—C16—O3	−9.9 (2)
N2—C8—C9—C14	167.75 (14)	O2—C15—C16—O4	171.21 (12)
N2—C8—C9—C10	−14.9 (2)	C16—O4—C17—C18	170.82 (14)
C14—C9—C10—C11	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84	1.85	2.6441 (17)	158
C15—H15A···O4ⁱ	0.99	2.58	3.3568 (19)	136
C15—H15B···O3ⁱⁱ	0.99	2.57	3.440 (2)	147

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