N,N′-Bis(4-chloro­phen­yl)urea

Abstract

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,

• a = 27.093 (3) Å

• b = 4.5768 (5) Å

• c = 9.901 (1) Å

• β = 96.389 (2)°

• V = 1220.1 (2) ų

• 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[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U_eq(C).

The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.88±0.01 Å; its temperature factor was freely refined.

Figures

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.

Crystal data

C13H10Cl2N2O	F000 = 576
Mr = 281.13	Dx = 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 = 3.0–28.2º
b = 4.5768 (5) Å	µ = 0.52 mm−1
c = 9.901 (1) Å	T = 100 (2) K
β = 96.389 (2)º	Block, colorless
V = 1220.1 (2) Å3	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEXII diffractometer	1386 independent reflections
Radiation source: fine-focus sealed tube	1210 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.020
T = 100(2) K	θmax = 27.5º
ω scans	θmin = 1.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −34→27
Tmin = 0.862, Tmax = 0.950	k = −5→5
3703 measured reflections	l = −10→12

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0445P)2 + 1.607P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max < 0.001
1386 reflections	Δρmax = 0.31 e Å−3
87 parameters	Δρmin = −0.29 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

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 codes: (ii) x, y−1, z.