Crystal structure of 1-(2,4-di­methyl­phen­yl)urea

Jayalakshmi, L.; Ramalingan, C.; Sridhar, B.; Selvanayagam, S.

doi:10.1107/S2056989014027431

organic compounds

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ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages o60-o61

https://doi.org/10.1107/S2056989014027431

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Crystal structure of 1-(2,4-dimethylphenyl)urea

L. Jayalakshmi,^a C. Ramalingan,^a B. Sridhar ^b and S. Selvanayagam ^c ^*

^aDepartment of Chemistry, Kalasalingam University, Krishnankoil 626 126, India, ^bLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 067, India, and ^cDepartment of Physics & International Research Centre, Kalasalingam University, Krishnankoil 626 126, India
^*Correspondence e-mail: s_selvanayagam@rediffmail.com, ramalinganc@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 11 December 2014; accepted 16 December 2014; online 1 January 2015)

In the title urea derivative, C₉H₁₂N₂O, the dihedral angle between the benzene ring and the mean plane of the urea group, N—C(=O)—N, is 86.6 (1)°. In the crystal, the urea O atom is involved in three N—H⋯O hydrogen bonds. Molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R²₂(8) ring motif. The dimers are linked by further N—H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to (100).

Keywords: crystal structure; urea; urea derivatives; hydrogen bonding.

CCDC reference: 1039538

1. Related literature

For general background to urea derivatives and their biological applications and properties, see: Ramalingan & Kwak (2008 ); Ramalingan et al. (2010 ); Yang et al. (2013 ); Safari & Gandomi-Ravandi (2014 ); Suzuki et al. (2013 ); Boulahjar et al. (2012 ); Zhang et al. (2014 )

2. Experimental

2.1. Crystal data

C₉H₁₂N₂O
M_r = 164.21
Monoclinic, P 2₁ /c
a = 14.631 (4) Å
b = 7.0633 (19) Å
c = 8.786 (2) Å
β = 93.530 (4)°
V = 906.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 K
0.20 × 0.18 × 0.16 mm

2.2. Data collection

Bruker SMART APEX CCD area-detector diffractometer
8026 measured reflections
1556 independent reflections
1284 reflections with I > 2σ(I)
R_int = 0.028

2.3. Refinement

R[F² > 2σ(F²)] = 0.100
wR(F²) = 0.349
S = 1.59
1556 reflections
119 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.23	2.941 (3)	140
N2—H2A⋯O1ⁱ	0.86 (1)	2.24 (2)	2.985 (3)	145 (3)
N2—H2B⋯O1ⁱⁱ	0.86 (1)	2.12 (1)	2.977 (3)	173 (4)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL2013 and PLATON (Spek, 2009).

Supporting information

CCDC reference: 1039538

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989014027431/su5043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014027431/su5043Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989014027431/su5043Isup3.cml

checkCIF report

Comment top

Urea and its derivatives are important key starting materials for the construction of biologically important heterocycles (Ramalingan & Kwak, 2008; Ramalingan et al., 2010; Yang et al., 2013; Safari & Gandomi-Ravandi, 2014). They display various biological activities viz. antibacterial (Suzuki et al., 2013), antiproliferative and antitumor (Boulahjar et al., 2012), and HIV-1 integrase (Zhang et al., 2014). As a vital reactant and intermediate for the construction of heterocyclic chemical entities of biological importance, the title compound has been synthesized and single crystals were grown by slow evaporation in ethanol.

The single crystal X-ray analysis confirmed the molecular structure, as illustrated in Fig. 1. Methyl carbon atoms, C7 and C8, deviate by -0.000 (1) and -0.040 (1) Å, respectively, from the attached benzene ring. The dihedral angle between benzene ring and the mean plane through the urea atoms (N1/C9/O1/N2) is 86.6 (1)°.

In the crystal, three strong N—H···O hydrogen bonds stabilize the molecular packing (Fig. 2 and Table 1). Molecules are linked via pairs of N-H···O hydrogen bonds forming inversion dimers with an R²₂(8) ring motif. The dimers are linked by further N-H···O hydrogen bonds forming two-dimensional networks lying parallel to (100); see Table 1 and Fig. 2.

Related literature top

For general background to urea derivatives and their biological applications and properties, see: Ramalingan & Kwak (2008); Ramalingan et al. (2010); Yang et al. (2013); Safari & Gandomi-Ravandi (2014); Suzuki et al. (2013); Boulahjar et al. (2012); Zhang et al. (2014)

Experimental top

To a solution of 2,6-dimethylaniline (0.1 mol) in glacial acetic acid (30 ml), was added distilled water (70 ml). Sodium cyanate (0.1 mol) in medium-hot water (50 ml) was then added in a slow manner with constant stirring. The resulted solution was allowed to stand for 60 min. and then cooled in ice. It was then filtered using a Buchner funnel and the solid obtained was dried using high-vacuum. Single crystals of the title compound were obtained by slow evaporation of a solution in ethanol at room temperature.

Structure description top

For general background to urea derivatives and their biological applications and properties, see: Ramalingan & Kwak (2008); Ramalingan et al. (2010); Yang et al. (2013); Safari & Gandomi-Ravandi (2014); Suzuki et al. (2013); Boulahjar et al. (2012); Zhang et al. (2014)

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A projection of the crystal packing of the title compound, along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

1-(2,4-Dimethylphenyl)urea top

Crystal data top

C₉H₁₂N₂O	F(000) = 352
M_r = 164.21	D_x = 1.204 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.631 (4) Å	Cell parameters from 6568 reflections
b = 7.0633 (19) Å	θ = 2.8–24.6°
c = 8.786 (2) Å	µ = 0.08 mm⁻¹
β = 93.530 (4)°	T = 292 K
V = 906.2 (4) Å³	Block, colourless
Z = 4	0.20 × 0.18 × 0.16 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	R_int = 0.028
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.8°
ω scans	h = −17→17
8026 measured reflections	k = −8→8
1556 independent reflections	l = −10→10
1284 reflections with I > 2σ(I)

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.100	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.349	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
S = 1.59	(Δ/σ)_max = 0.001
1556 reflections	Δρ_max = 0.87 e Å⁻³
119 parameters	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₉H₁₂N₂O	V = 906.2 (4) Å³
M_r = 164.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.631 (4) Å	µ = 0.08 mm⁻¹
b = 7.0633 (19) Å	T = 292 K
c = 8.786 (2) Å	0.20 × 0.18 × 0.16 mm
β = 93.530 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1284 reflections with I > 2σ(I)
8026 measured reflections	R_int = 0.028
1556 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.100	2 restraints
wR(F²) = 0.349	H atoms treated by a mixture of independent and constrained refinement
S = 1.59	Δρ_max = 0.87 e Å⁻³
1556 reflections	Δρ_min = −0.32 e Å⁻³
119 parameters

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	0.40043 (14)	0.1453 (3)	0.55423 (18)	0.0634 (8)
N1	0.32526 (19)	0.2851 (4)	0.3520 (3)	0.0709 (10)
H1	0.3186	0.2927	0.2543	0.085*
N2	0.4476 (2)	0.0982 (4)	0.3174 (3)	0.0682 (9)
H2A	0.437 (2)	0.125 (4)	0.2228 (15)	0.060 (8)*
H2B	0.4934 (19)	0.036 (5)	0.360 (4)	0.089 (11)*
C1	0.1253 (4)	0.4077 (12)	0.5679 (5)	0.1144 (17)
H1A	0.0700	0.3530	0.5912	0.137*
C2	0.1467 (3)	0.5877 (12)	0.6154 (4)	0.122 (2)
C3	0.2259 (4)	0.6656 (8)	0.5753 (5)	0.1049 (17)
H3	0.2404	0.7876	0.6085	0.126*
C4	0.2873 (2)	0.5700 (6)	0.4854 (4)	0.0794 (11)
C5	0.2652 (2)	0.3904 (5)	0.4421 (3)	0.0666 (10)
C6	0.1852 (3)	0.3106 (8)	0.4870 (4)	0.0921 (13)
H6	0.1721	0.1855	0.4606	0.111*
C7	0.0822 (4)	0.7033 (13)	0.7118 (7)	0.178 (4)
H7A	0.0806	0.6477	0.8114	0.267*
H7B	0.0216	0.7030	0.6630	0.267*
H7C	0.1040	0.8312	0.7212	0.267*
C8	0.3708 (4)	0.6517 (7)	0.4485 (7)	0.1135 (16)
H8A	0.3942	0.5853	0.3638	0.170*
H8B	0.4142	0.6433	0.5348	0.170*
H8C	0.3612	0.7822	0.4217	0.170*
C9	0.39175 (19)	0.1749 (4)	0.4154 (3)	0.0519 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0806 (14)	0.0787 (15)	0.0316 (11)	0.0198 (9)	0.0094 (9)	0.0014 (7)
N1	0.0824 (18)	0.0971 (19)	0.0338 (12)	0.0270 (14)	0.0098 (11)	0.0074 (11)
N2	0.0857 (18)	0.0849 (18)	0.0353 (14)	0.0251 (13)	0.0137 (11)	0.0013 (10)
C1	0.090 (3)	0.193 (5)	0.063 (2)	0.031 (3)	0.025 (2)	0.007 (3)
C2	0.068 (2)	0.245 (7)	0.053 (2)	0.063 (3)	0.0003 (17)	−0.015 (3)
C3	0.104 (3)	0.123 (3)	0.084 (3)	0.036 (3)	−0.019 (3)	−0.036 (2)
C4	0.0685 (19)	0.105 (3)	0.064 (2)	0.0184 (17)	−0.0010 (15)	−0.0088 (16)
C5	0.0682 (19)	0.090 (2)	0.0417 (16)	0.0245 (15)	0.0069 (13)	0.0057 (13)
C6	0.086 (2)	0.128 (3)	0.064 (2)	0.018 (2)	0.0218 (17)	0.0214 (19)
C7	0.106 (4)	0.316 (9)	0.112 (4)	0.091 (5)	−0.002 (3)	−0.091 (5)
C8	0.112 (3)	0.101 (3)	0.129 (4)	−0.017 (3)	0.024 (3)	0.004 (3)
C9	0.0652 (16)	0.0572 (15)	0.0342 (14)	0.0069 (11)	0.0094 (11)	−0.0013 (9)

Geometric parameters (Å, º) top

O1—C9	1.236 (3)	C3—C4	1.406 (6)
N1—C9	1.340 (4)	C3—H3	0.9300
N1—C5	1.428 (4)	C4—C5	1.358 (6)
N1—H1	0.8600	C4—C8	1.407 (7)
N2—C9	1.337 (4)	C5—C6	1.377 (6)
N2—H2A	0.857 (10)	C6—H6	0.9300
N2—H2B	0.863 (10)	C7—H7A	0.9600
C1—C6	1.351 (7)	C7—H7B	0.9600
C1—C2	1.368 (10)	C7—H7C	0.9600
C1—H1A	0.9300	C8—H8A	0.9600
C2—C3	1.348 (9)	C8—H8B	0.9600
C2—C7	1.541 (6)	C8—H8C	0.9600

C9—N1—C5	121.9 (2)	C6—C5—N1	120.5 (4)
C9—N1—H1	119.1	C1—C6—C5	122.2 (6)
C5—N1—H1	119.1	C1—C6—H6	118.9
C9—N2—H2A	117 (2)	C5—C6—H6	118.9
C9—N2—H2B	115 (3)	C2—C7—H7A	109.5
H2A—N2—H2B	128 (4)	C2—C7—H7B	109.5
C6—C1—C2	119.2 (6)	H7A—C7—H7B	109.5
C6—C1—H1A	120.4	C2—C7—H7C	109.5
C2—C1—H1A	120.4	H7A—C7—H7C	109.5
C3—C2—C1	119.0 (4)	H7B—C7—H7C	109.5
C3—C2—C7	119.5 (7)	C4—C8—H8A	109.5
C1—C2—C7	121.5 (6)	C4—C8—H8B	109.5
C2—C3—C4	122.7 (5)	H8A—C8—H8B	109.5
C2—C3—H3	118.7	C4—C8—H8C	109.5
C4—C3—H3	118.7	H8A—C8—H8C	109.5
C5—C4—C3	117.1 (4)	H8B—C8—H8C	109.5
C5—C4—C8	121.0 (4)	O1—C9—N2	122.5 (2)
C3—C4—C8	121.8 (4)	O1—C9—N1	122.4 (2)
C4—C5—C6	119.7 (3)	N2—C9—N1	115.1 (2)
C4—C5—N1	119.8 (3)

C6—C1—C2—C3	2.3 (7)	C8—C4—C5—N1	−2.8 (5)
C6—C1—C2—C7	−178.3 (4)	C9—N1—C5—C4	90.7 (4)
C1—C2—C3—C4	0.5 (7)	C9—N1—C5—C6	−88.6 (4)
C7—C2—C3—C4	−178.9 (4)	C2—C1—C6—C5	−4.1 (7)
C2—C3—C4—C5	−1.6 (6)	C4—C5—C6—C1	2.9 (6)
C2—C3—C4—C8	−178.1 (5)	N1—C5—C6—C1	−177.8 (3)
C3—C4—C5—C6	−0.1 (5)	C5—N1—C9—O1	6.1 (5)
C8—C4—C5—C6	176.5 (4)	C5—N1—C9—N2	−174.4 (3)
C3—C4—C5—N1	−179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.23	2.941 (3)	140
N2—H2A···O1ⁱ	0.86 (1)	2.24 (2)	2.985 (3)	145 (3)
N2—H2B···O1ⁱⁱ	0.86 (1)	2.12 (1)	2.977 (3)	173 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.23	2.941 (3)	140
N2—H2A···O1ⁱ	0.86 (1)	2.24 (2)	2.985 (3)	145 (3)
N2—H2B···O1ⁱⁱ	0.86 (1)	2.12 (1)	2.977 (3)	173 (4)

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

Acknowledgements

CR and SS thank the Vice Chancellor and the management of Kalasalingam University, Krishnankoil, for their support and encouragement.

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