N,N′-Bis(4-chloro­phen­yl)urea

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536808011069

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o922

doi:10.1107/S1600536808011069

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N,N′-Bis(4-chlorophenyl)urea

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 March 2008; accepted 20 April 2008; online 26 April 2008)

The carbonyl unit of the title compound, C₁₃H₁₀Cl₂N₂O, lies on a twofold rotation axis. The ring is aligned at 51.6 (1)° with respect to the N—C(=O)—N fragment. The two –NH– fragments of one molecule form hydrogen bonds [2.845 (2) Å] to the C=O fragment of an adjacent molecule, giving rise to the formation of a linear hydrogen-bonded chain.

Related literature

For isostructural N,N′-bis(4-bromophenyl)urea, see: Lin et al. (2004 ). N,N′-Bis-(4-chlorophenyl)urea has been isolated as a co-crystal with a phthalazinium chloride; see: Wamhoff et al. (1994 ). For the self-condensation of 4-chlorophenyl isocyanate to yield the title symmetrical urea, see: Fu et al. (2007 ); Jimenez Blanco et al. (1999 ).

Experimental

Crystal data

C₁₃H₁₀Cl₂N₂O
M_r = 281.13
Monoclinic, C 2/c
a = 27.093 (3) Å
b = 4.5768 (5) Å
c = 9.901 (1) Å
β = 96.389 (2)°
V = 1220.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 100 (2) K
0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.862, T_max = 0.950
3703 measured reflections
1386 independent reflections
1210 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.096
S = 1.11
1386 reflections
87 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (1)	2.05 (1)	2.845 (2)	152 (2)
Symmetry code: (i) x, y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011069/tk2256sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011069/tk2256Isup2.hkl

checkCIF report

Comment top

The title compound, a symmetrical urea derivative, was the unexpected product from the reaction of 4-chlorophenyl isocyanate with p-tolylsulfonic acid in ethanol. The carbonyl unit of (Cl-4-C₆H₄)NH–C(=O)–NH(C₆H₄-4-Cl) lies on a twofold rotation axis, Fig. 1, that relates one aromatic ring to the other. The ring is aligned at 51.6 (1) ° with respect to the N–C(=O)–N fragment. The two –NH– fragments of one molecule forms hydrogen bonds to the C=O fragment of an adjacent molecule, giving rise to the formation of a linear hydrogen-bonded chain (Table 1). The compound has previously been synthesized from the self-condensation of 4-chlorophenyl isocyanate in acetone (Fu et al., 2007) and in water catalyzed by pyridine (Jimenez Blanco et al., 1999).

Related literature top

For isostructural N,N'-bis(4-bromophenyl)urea, see: Lin et al. (2004). N,N'-Bis-(4-chlorophenyl)urea has been isolated as a co-crystal with a phthalazinium chloride; see: Wamhoff et al. (1994). For the self-condensation of 4-chlorophenyl isocyanate to yield the title symmetrical urea, see: Fu et al. (2007); Jimenez Blanco et al. (1999).

Experimental top

4-Chlorophenyl isocyanate (1.0 g, 6.5 mmol) and p-toluenesulfonic acid (1.2 g, 6.5 mmol) were heated in ethanol (100 ml) for 1 h. The solution was filtered; evaporation of the solvent gave plates of the symmetrical urea.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing the atom-numbering scheme and 70% probability displacement ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radius. The unlablled atoms related by a 2-fold axis of symmetry.

N,N'-Bis(4-chlorophenyl)urea top

Crystal data top

C₁₃H₁₀Cl₂N₂O	F(000) = 576
M_r = 281.13	D_x = 1.530 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1510 reflections
a = 27.093 (3) Å	θ = 3.0–28.2°
b = 4.5768 (5) Å	µ = 0.52 mm⁻¹
c = 9.901 (1) Å	T = 100 K
β = 96.389 (2)°	Block, colorless
V = 1220.1 (2) Å³	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	1386 independent reflections
Radiation source: fine-focus sealed tube	1210 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −34→27
T_min = 0.862, T_max = 0.950	k = −5→5
3703 measured reflections	l = −10→12

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0445P)² + 1.607P] where P = (F_o² + 2F_c²)/3
1386 reflections	(Δ/σ)_max < 0.001
87 parameters	Δρ_max = 0.31 e Å⁻³
1 restraint	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₃H₁₀Cl₂N₂O	V = 1220.1 (2) Å³
M_r = 281.13	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 27.093 (3) Å	µ = 0.52 mm⁻¹
b = 4.5768 (5) Å	T = 100 K
c = 9.901 (1) Å	0.20 × 0.20 × 0.10 mm
β = 96.389 (2)°

Data collection top

Bruker SMART APEXII diffractometer	1386 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1210 reflections with I > 2σ(I)
T_min = 0.862, T_max = 0.950	R_int = 0.020
3703 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.31 e Å⁻³
1386 reflections	Δρ_min = −0.29 e Å⁻³
87 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.293344 (15)	0.99597 (10)	0.33207 (4)	0.02417 (17)
O1	0.5000	0.9101 (4)	0.7500	0.0163 (4)
N1	0.46380 (5)	0.4789 (3)	0.67795 (15)	0.0149 (3)
H1	0.4640 (8)	0.292 (2)	0.691 (2)	0.024 (5)*
C1	0.5000	0.6399 (5)	0.7500	0.0130 (4)
C2	0.42311 (6)	0.6073 (3)	0.59591 (15)	0.0131 (3)
C3	0.43093 (6)	0.8150 (4)	0.49760 (16)	0.0152 (3)
H3	0.4638	0.8730	0.4854	0.018*
C4	0.39102 (6)	0.9373 (4)	0.41754 (17)	0.0175 (4)
H4	0.3963	1.0823	0.3520	0.021*
C5	0.34334 (6)	0.8455 (4)	0.43438 (16)	0.0162 (3)
C6	0.33491 (6)	0.6357 (4)	0.52957 (17)	0.0183 (4)
H6	0.3021	0.5729	0.5391	0.022*
C7	0.37498 (6)	0.5180 (4)	0.61096 (17)	0.0176 (4)
H7	0.3695	0.3754	0.6774	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0159 (2)	0.0299 (3)	0.0249 (3)	0.00200 (17)	−0.00584 (17)	0.00510 (17)
O1	0.0173 (8)	0.0094 (8)	0.0207 (8)	0.000	−0.0037 (6)	0.000
N1	0.0146 (7)	0.0082 (6)	0.0208 (7)	−0.0002 (5)	−0.0028 (6)	0.0007 (5)
C1	0.0128 (10)	0.0123 (11)	0.0141 (10)	0.000	0.0025 (8)	0.000
C2	0.0141 (7)	0.0104 (7)	0.0142 (7)	0.0001 (6)	−0.0006 (6)	−0.0027 (6)
C3	0.0124 (7)	0.0162 (8)	0.0167 (8)	−0.0028 (6)	0.0004 (6)	−0.0013 (6)
C4	0.0184 (8)	0.0178 (8)	0.0159 (8)	−0.0013 (6)	−0.0001 (6)	0.0016 (6)
C5	0.0138 (8)	0.0189 (8)	0.0152 (8)	0.0018 (6)	−0.0023 (6)	−0.0017 (6)
C6	0.0118 (8)	0.0233 (9)	0.0199 (8)	−0.0016 (6)	0.0024 (6)	−0.0009 (7)
C7	0.0176 (8)	0.0174 (8)	0.0178 (8)	−0.0019 (6)	0.0026 (6)	0.0026 (6)

Geometric parameters (Å, º) top

Cl1—C5	1.741 (2)	C3—C4	1.386 (2)
O1—C1	1.237 (3)	C3—H3	0.9500
N1—C1	1.363 (2)	C4—C5	1.386 (2)
N1—C2	1.422 (2)	C4—H4	0.9500
N1—H1	0.87 (1)	C5—C6	1.382 (2)
C1—N1ⁱ	1.363 (2)	C6—C7	1.387 (2)
C2—C7	1.390 (2)	C6—H6	0.9500
C2—C3	1.393 (2)	C7—H7	0.9500

C1—N1—C2	122.9 (1)	C5—C4—C3	119.2 (2)
C1—N1—H1	118 (1)	C5—C4—H4	120.4
C2—N1—H1	119 (1)	C3—C4—H4	120.4
O1—C1—N1	122.7 (1)	C4—C5—C6	121.3 (2)
O1—C1—N1ⁱ	122.7 (1)	C4—C5—Cl1	119.0 (1)
N1—C1—N1ⁱ	114.6 (2)	C6—C5—Cl1	119.65 (13)
C7—C2—C3	119.5 (2)	C7—C6—C5	119.21 (15)
C7—C2—N1	119.6 (1)	C7—C6—H6	120.4
C3—C2—N1	120.8 (1)	C5—C6—H6	120.4
C4—C3—C2	120.4 (2)	C6—C7—C2	120.42 (15)
C4—C3—H3	119.8	C6—C7—H7	119.8
C2—C3—H3	119.8	C2—C7—H7	119.8

C2—N1—C1—O1	0.4 (2)	C3—C4—C5—C6	0.3 (3)
C2—N1—C1—N1ⁱ	−179.6 (2)	C3—C4—C5—Cl1	−179.1 (1)
C1—N1—C2—C7	−129.4 (2)	C4—C5—C6—C7	0.9 (3)
C1—N1—C2—C3	52.6 (2)	Cl1—C5—C6—C7	−179.8 (1)
C7—C2—C3—C4	1.6 (2)	C5—C6—C7—C2	−0.8 (3)
N1—C2—C3—C4	179.6 (2)	C3—C2—C7—C6	−0.5 (2)
C2—C3—C4—C5	−1.5 (2)	N1—C2—C7—C6	−178.5 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.87 (1)	2.05 (1)	2.845 (2)	152 (2)

Symmetry code: (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀Cl₂N₂O
M_r	281.13
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	27.093 (3), 4.5768 (5), 9.901 (1)
β (°)	96.389 (2)
V (Å³)	1220.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.862, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	3703, 1386, 1210
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.096, 1.11
No. of reflections	1386
No. of parameters	87
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (1)	2.05 (1)	2.845 (2)	152 (2)

Symmetry code: (i) x, y−1, z.

Acknowledgements

We thank the University of Malaya for funding this study (SF022155/2007 A) and also for the purchase of the diffractometer.

References

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