N-[2-(Benzyl­idene­amino)­phen­yl]-N′-phenyl­urea

Atioğlu, Z.; Buran, S.; Doğan, D.; Kökbudak, Z.; Aygün, M.; Akkurt, M.

doi:10.1107/S241431461701519X

organic compounds

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ISSN: 2414-3146

Volume 2| Part 10| October 2017| x171519

https://doi.org/10.1107/S241431461701519X

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N-[2-(Benzylideneamino)phenyl]-N′-phenylurea

Zeliha Atioğlu,^a ^* Sümeyye Buran,^b,^c Dilem Doğan,^c Zülbiye Kökbudak,^b Muhittin Aygün ^d and Mehmet Akkurt ^e

^aİlke Education and Health Foundation, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Chemistry, Faculty of Science, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Erciyes University, 38039 Kayseri, Turkey, ^dDepartment of Physics, Faculty of Arts and Sciences, Dokuz Eylül University, Buca 35160 İzmir, Turkey, and ^eDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey
^*Correspondence e-mail: zeliha.atioglu@kapadokya.edu.tr

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 6 October 2017; accepted 18 October 2017; online 24 October 2017)

In the title compound, C₂₀H₁₇N₃O [systematic name: 1-phenyl-3-{2-[(E)- (phenylmethylidene)amino]phenyl}urea], the middle benzene ring forms dihedral angles of 17.65 (17) and 29.48 (14)°, respectively, with the N- and C-bound phenyl rings, while the dihedral angle between the terminal rings is 46.53 (18)°. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming helical supramolecular chains running parallel to the c axis via an R₁²(6) ring motif. The structure was refined as a two-component twin with a 0.966 (3):0.034 (3) domain ratio.

Keywords: crystal structure; twin; non-merohedry; urea.

CCDC reference: 1580619

Structure description

Schiff bases, also known as imines or azomethines, are nitrogen analogues of aldehydes or ketones in which the carbonyl group has been replaced by an imine or azomethine group (Ghose, 1983 ). The classical synthesis reported by Schiff involves the condensation of a carbonyl compound with an amine. Various Schiff base-containing compounds are widely used owing to their antifungal, antibacterial, antimalarial, antiproliferative, anti-inflammatory, antiviral and antipyretic properties. In addition to the aforementioned activities, Schiff bases are used as pigments and dyes, catalysts, intermediates in organic synthesis and as polymer stabilizers (da Silva et al., 2011 ). In this study, starting from o-phenylenediamine, we synthesized a new hybrid molecule containing imine and urea functionalities in the same molecule.

Referring to Fig. 1, the middle benzene ring (C8–C13) make dihedral angles of 17.65 (17) and 29.48 (14)°, respectively, with the terminal phenyl rings (C1–C6 and C15–C20). The dihedral angle between the latter is 46.53 (18)°. All bond lengths and angles are within normal ranges and are in agreement with those reported for 1-(2-aminophenyl)-3- phenylurea (Mague et al., 2015 ).

Figure 1
View of the title compound with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

In the crystal, N—H⋯O hydrogen bonds link molecules into chains running parallel to the c axis with an $[R_{1}^{2}]$ (6) ring motif, Fig. 2 and Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.08	2.921 (3)	166
N2—H2⋯O1ⁱ	0.86	2.36	3.144 (3)	152
Symmetry code: (i) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ .

Figure 2
A view of the N—H⋯O hydrogen bonding (dashed lines) along the a axis in the crystal of the title compound.

Synthesis and crystallization

To a solution of [N-(2-aminophenyl)-N′-phenylurea] (0.01 mol, 2.27 g) in absolute ethanol (50 mL) stirred at room temperature was added benzaldehyde (0.01 mol, 1.1 g). The mixture was stirred at reflux conditions, until complete, and then cooled to room temperature. The precipitate was filtered off and washed with cold ethanol. The resulting residue was purified by crystallization from EtOH to afford the title compound (2.1 g, 67% yield) as a light-orange solid (m.p. 473–475 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal investigated was refined as a two-component twin by non-merohedry. The twin ratio refined to a value of 0.966 (3):0.034 (3). The N-bound ring displayed high displacement parameters and was refined with several constraints.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₇N₃O
M_r	315.36
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	297
a, b, c (Å)	10.3381 (6), 17.6843 (13), 9.0562 (5)
V (Å³)	1655.67 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.42 × 0.23 × 0.20

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur, Eos
Absorption correction	Analytical (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan.]$ )
T_min, T_max	0.980, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5335, 2499, 1574
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.066, 0.85
No. of reflections	2499
No. of parameters	217
No. of restraints	29
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.12
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1580619

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S241431461701519X/tk4039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461701519X/tk4039Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461701519X/tk4039Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

N-[2-(Benzylideneamino)phenyl]-N'-phenylurea top

Crystal data top

C₂₀H₁₇N₃O	D_x = 1.265 Mg m⁻³
M_r = 315.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 1544 reflections
a = 10.3381 (6) Å	θ = 4.5–25.2°
b = 17.6843 (13) Å	µ = 0.08 mm⁻¹
c = 9.0562 (5) Å	T = 297 K
V = 1655.67 (18) Å³	Prism, light-orange
Z = 4	0.42 × 0.23 × 0.20 mm
F(000) = 664

Data collection top

Rigaku Oxford Diffraction Xcalibur, Eos diffractometer	2499 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1574 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 8.0667 pixels mm^-1	θ_max = 26.4°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: analytical (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −22→16
T_min = 0.980, T_max = 0.988	l = −8→11
5335 measured reflections

Refinement top

Refinement on F²	29 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0306P)²] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max < 0.001
2499 reflections	Δρ_max = 0.12 e Å⁻³
217 parameters	Δρ_min = −0.12 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 H atoms attached to C and N atoms were placed in calculated positions (C—H = 0.93 Å and N—H = 0.86 Å) and treated as riding with U_iso(H) = 1.2 or 1.5U_eq(N,C).

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

	x	y	z	U_iso*/U_eq
O1	0.17464 (16)	0.71846 (10)	0.29408 (19)	0.0609 (5)
N1	0.21897 (19)	0.66269 (12)	0.5158 (2)	0.0554 (6)
H1	0.2541	0.6711	0.6004	0.066*
N2	0.28671 (18)	0.78190 (12)	0.4728 (2)	0.0524 (6)
H2	0.3177	0.7775	0.5605	0.063*
N3	0.51212 (19)	0.84938 (10)	0.5281 (2)	0.0500 (5)
C1	0.1652 (3)	0.59015 (18)	0.4960 (3)	0.0578 (7)
C2	0.2172 (3)	0.5321 (2)	0.5740 (4)	0.0964 (12)
H2A	0.2877	0.5412	0.6352	0.116*
C3	0.1681 (4)	0.4604 (2)	0.5645 (6)	0.1319 (17)
H3	0.2041	0.4216	0.6204	0.158*
C4	0.0664 (5)	0.4460 (3)	0.4733 (5)	0.136 (2)
H4	0.0337	0.3973	0.4646	0.163*
C5	0.0134 (5)	0.5036 (3)	0.3950 (5)	0.151 (2)
H5	−0.0563	0.4943	0.3327	0.181*
C6	0.0625 (4)	0.5765 (2)	0.4074 (4)	0.1091 (13)
H6	0.0248	0.6159	0.3546	0.131*
C7	0.2223 (2)	0.72075 (16)	0.4189 (3)	0.0472 (6)
C8	0.3085 (2)	0.85135 (15)	0.4020 (3)	0.0473 (6)
C9	0.2214 (3)	0.88489 (17)	0.3065 (3)	0.0578 (7)
H9	0.1442	0.8605	0.2837	0.069*
C10	0.2486 (4)	0.95423 (17)	0.2450 (3)	0.0657 (8)
H10	0.1906	0.9759	0.1789	0.079*
C11	0.3603 (3)	0.99154 (17)	0.2803 (3)	0.0683 (8)
H11	0.3770	1.0389	0.2401	0.082*
C12	0.4482 (3)	0.95884 (16)	0.3756 (3)	0.0575 (7)
H12	0.5234	0.9847	0.4007	0.069*
C13	0.4250 (2)	0.88802 (15)	0.4337 (3)	0.0479 (7)
C14	0.6317 (3)	0.85566 (15)	0.5046 (3)	0.0545 (7)
H14	0.6585	0.8878	0.4293	0.065*
C15	0.7306 (3)	0.81545 (15)	0.5886 (3)	0.0539 (7)
C16	0.8592 (3)	0.83093 (18)	0.5624 (3)	0.0684 (8)
H16	0.8811	0.8696	0.4974	0.082*
C17	0.9554 (3)	0.7904 (2)	0.6301 (4)	0.0802 (10)
H17	1.0418	0.8013	0.6114	0.096*
C18	0.9223 (4)	0.7340 (2)	0.7255 (4)	0.0858 (11)
H18	0.9870	0.7056	0.7705	0.103*
C19	0.7937 (4)	0.71814 (17)	0.7563 (4)	0.0839 (10)
H19	0.7726	0.6802	0.8232	0.101*
C20	0.6977 (3)	0.75878 (17)	0.6877 (3)	0.0621 (8)
H20	0.6112	0.7484	0.7075	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0729 (12)	0.0698 (13)	0.0400 (10)	−0.0055 (10)	−0.0054 (9)	−0.0038 (10)
N1	0.0683 (15)	0.0557 (13)	0.0421 (11)	−0.0115 (13)	−0.0086 (11)	0.0021 (13)
N2	0.0584 (13)	0.0574 (14)	0.0413 (12)	−0.0126 (12)	−0.0069 (11)	0.0018 (12)
N3	0.0507 (12)	0.0504 (14)	0.0488 (12)	−0.0037 (12)	−0.0036 (11)	−0.0010 (13)
C1	0.0637 (17)	0.062 (2)	0.0476 (16)	−0.0081 (17)	0.0150 (16)	−0.0039 (17)
C2	0.093 (3)	0.064 (2)	0.132 (3)	−0.007 (2)	−0.003 (2)	0.013 (2)
C3	0.146 (4)	0.058 (3)	0.191 (5)	−0.008 (3)	0.027 (3)	0.012 (3)
C4	0.193 (5)	0.089 (3)	0.124 (4)	−0.064 (4)	0.073 (4)	−0.043 (3)
C5	0.187 (5)	0.163 (5)	0.103 (3)	−0.126 (5)	−0.007 (3)	−0.001 (4)
C6	0.119 (3)	0.118 (3)	0.090 (2)	−0.059 (3)	−0.026 (2)	0.024 (2)
C7	0.0437 (14)	0.0593 (19)	0.0386 (15)	0.0012 (14)	0.0055 (13)	−0.0026 (15)
C8	0.0549 (17)	0.0470 (16)	0.0401 (14)	0.0026 (14)	0.0039 (13)	−0.0019 (14)
C9	0.0563 (17)	0.0654 (19)	0.0516 (18)	0.0116 (16)	−0.0051 (14)	−0.0084 (16)
C10	0.081 (2)	0.064 (2)	0.0522 (18)	0.021 (2)	−0.0107 (15)	0.0018 (18)
C11	0.091 (2)	0.0533 (18)	0.0605 (17)	0.0100 (19)	0.001 (2)	0.0124 (17)
C12	0.0656 (19)	0.0483 (17)	0.0587 (18)	−0.0056 (15)	0.0060 (15)	0.0033 (16)
C13	0.0531 (15)	0.0501 (17)	0.0405 (15)	0.0014 (14)	0.0028 (13)	0.0000 (14)
C14	0.0575 (17)	0.0549 (17)	0.0512 (15)	−0.0035 (14)	0.0005 (15)	−0.0004 (15)
C15	0.0533 (17)	0.0558 (18)	0.0526 (16)	−0.0012 (15)	−0.0053 (15)	−0.0110 (15)
C16	0.0549 (17)	0.084 (2)	0.0657 (18)	0.0032 (18)	−0.0014 (16)	−0.0070 (18)
C17	0.061 (2)	0.104 (3)	0.075 (2)	0.012 (2)	−0.0023 (19)	−0.023 (2)
C18	0.079 (3)	0.094 (3)	0.085 (3)	0.026 (2)	−0.030 (2)	−0.017 (2)
C19	0.102 (3)	0.065 (2)	0.084 (2)	0.006 (2)	−0.025 (2)	0.004 (2)
C20	0.0677 (19)	0.0566 (19)	0.0622 (17)	−0.0030 (17)	−0.0063 (16)	−0.0011 (16)

Geometric parameters (Å, º) top

O1—C7	1.234 (3)	C9—C10	1.376 (3)
N1—C7	1.351 (3)	C9—H9	0.9300
N1—C1	1.409 (3)	C10—C11	1.368 (4)
N1—H1	0.8600	C10—H10	0.9300
N2—C7	1.361 (3)	C11—C12	1.381 (3)
N2—C8	1.404 (3)	C11—H11	0.9300
N2—H2	0.8600	C12—C13	1.380 (3)
N3—C14	1.259 (3)	C12—H12	0.9300
N3—C13	1.417 (3)	C14—C15	1.460 (4)
C1—C6	1.353 (4)	C14—H14	0.9300
C1—C2	1.357 (4)	C15—C16	1.377 (4)
C2—C3	1.368 (5)	C15—C20	1.388 (4)
C2—H2A	0.9300	C16—C17	1.371 (4)
C3—C4	1.361 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.364 (4)
C4—C5	1.356 (6)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.386 (4)
C5—C6	1.389 (5)	C18—H18	0.9300
C5—H5	0.9300	C19—C20	1.375 (4)
C6—H6	0.9300	C19—H19	0.9300
C8—C9	1.382 (3)	C20—H20	0.9300
C8—C13	1.398 (3)

C7—N1—C1	128.2 (2)	C11—C10—C9	120.5 (3)
C7—N1—H1	115.9	C11—C10—H10	119.7
C1—N1—H1	115.9	C9—C10—H10	119.7
C7—N2—C8	127.6 (2)	C10—C11—C12	120.0 (3)
C7—N2—H2	116.2	C10—C11—H11	120.0
C8—N2—H2	116.2	C12—C11—H11	120.0
C14—N3—C13	118.6 (2)	C13—C12—C11	120.3 (3)
C6—C1—C2	119.0 (3)	C13—C12—H12	119.9
C6—C1—N1	123.2 (3)	C11—C12—H12	119.9
C2—C1—N1	117.8 (3)	C12—C13—C8	119.5 (2)
C1—C2—C3	121.4 (4)	C12—C13—N3	123.9 (2)
C1—C2—H2A	119.3	C8—C13—N3	116.6 (2)
C3—C2—H2A	119.3	N3—C14—C15	123.8 (3)
C4—C3—C2	119.9 (4)	N3—C14—H14	118.1
C4—C3—H3	120.1	C15—C14—H14	118.1
C2—C3—H3	120.1	C16—C15—C20	119.5 (3)
C5—C4—C3	119.3 (5)	C16—C15—C14	119.3 (3)
C5—C4—H4	120.4	C20—C15—C14	121.1 (2)
C3—C4—H4	120.4	C17—C16—C15	121.3 (3)
C4—C5—C6	120.4 (5)	C17—C16—H16	119.4
C4—C5—H5	119.8	C15—C16—H16	119.4
C6—C5—H5	119.8	C18—C17—C16	118.9 (3)
C1—C6—C5	120.0 (4)	C18—C17—H17	120.5
C1—C6—H6	120.0	C16—C17—H17	120.5
C5—C6—H6	120.0	C17—C18—C19	121.0 (3)
O1—C7—N1	124.1 (3)	C17—C18—H18	119.5
O1—C7—N2	123.4 (3)	C19—C18—H18	119.5
N1—C7—N2	112.5 (2)	C20—C19—C18	119.7 (3)
C9—C8—C13	119.4 (2)	C20—C19—H19	120.1
C9—C8—N2	123.8 (2)	C18—C19—H19	120.1
C13—C8—N2	116.7 (2)	C19—C20—C15	119.5 (3)
C10—C9—C8	120.2 (3)	C19—C20—H20	120.2
C10—C9—H9	119.9	C15—C20—H20	120.2
C8—C9—H9	119.9

C7—N1—C1—C6	−30.1 (5)	C10—C11—C12—C13	1.0 (4)
C7—N1—C1—C2	152.2 (3)	C11—C12—C13—C8	−3.5 (3)
C6—C1—C2—C3	0.1 (5)	C11—C12—C13—N3	177.8 (2)
N1—C1—C2—C3	177.9 (3)	C9—C8—C13—C12	3.5 (3)
C1—C2—C3—C4	1.2 (7)	N2—C8—C13—C12	−175.6 (2)
C2—C3—C4—C5	−1.4 (7)	C9—C8—C13—N3	−177.7 (2)
C3—C4—C5—C6	0.3 (8)	N2—C8—C13—N3	3.2 (3)
C2—C1—C6—C5	−1.2 (6)	C14—N3—C13—C12	−37.0 (3)
N1—C1—C6—C5	−178.9 (3)	C14—N3—C13—C8	144.3 (2)
C4—C5—C6—C1	1.0 (7)	C13—N3—C14—C15	−176.5 (2)
C1—N1—C7—O1	1.1 (4)	N3—C14—C15—C16	−174.6 (3)
C1—N1—C7—N2	−177.5 (2)	N3—C14—C15—C20	9.3 (4)
C8—N2—C7—O1	1.3 (4)	C20—C15—C16—C17	1.3 (4)
C8—N2—C7—N1	179.9 (2)	C14—C15—C16—C17	−174.8 (3)
C7—N2—C8—C9	34.6 (3)	C15—C16—C17—C18	−0.2 (4)
C7—N2—C8—C13	−146.4 (2)	C16—C17—C18—C19	−1.2 (5)
C13—C8—C9—C10	−0.9 (3)	C17—C18—C19—C20	1.4 (5)
N2—C8—C9—C10	178.1 (2)	C18—C19—C20—C15	−0.3 (4)
C8—C9—C10—C11	−1.6 (4)	C16—C15—C20—C19	−1.1 (4)
C9—C10—C11—C12	1.6 (4)	C14—C15—C20—C19	175.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.08	2.921 (3)	166
N2—H2···O1ⁱ	0.86	2.36	3.144 (3)	152

Symmetry code: (i) −x+1/2, y, z+1/2.

References

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