1-(3-Phenyl­prop­yl)urea

Li, Y.; Hua, G.; Slawin, A.M.Z.; Woollins, J.D.

doi:10.1107/S1600536809038501

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2556

doi:10.1107/S1600536809038501

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1-(3-Phenylpropyl)urea

Yang Li,^a Guoxiong Hua,^a Alexandra M. Z. Slawin ^a and J. Derek Woollins ^a ^*

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: jdw3@st-and.ac.uk

(Received 22 September 2009; accepted 23 September 2009; online 26 September 2009)

In the crystal of the title compound, C₁₀H₁₄N₂O, double supramolecular layers of PhCH₂CH₂CH₂NHC(O)NH₂ are formed parallel to the bc plane by intermolecular N—H⋯O hydrogen bonding, with R₂²(8) and R₂¹(6) motifs in the b- and c-axis directions, respectively. The mean plane of the C_ar—C—C group makes a dihedral angle of 84.8 (2)° with the benzene ring.

Related literature

For related structural information see Bernstein et al. (1995 ). For background chemistry, see: Gray et al. (2005 ); Hua & Woollins (2009 ); Renodon-Cornière et al. (2002 ).

Experimental

Crystal data

C₁₀H₁₄N₂O
M_r = 178.23
Monoclinic, P 2₁ /c
a = 17.002 (4) Å
b = 6.4953 (15) Å
c = 9.171 (2) Å
β = 91.401 (8)°
V = 1012.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 93 K
0.25 × 0.04 × 0.03 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004 ) T_min = 0.981, T_max = 0.998
6696 measured reflections
2126 independent reflections
1360 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.144
S = 1.03
2126 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88	2.10	2.936 (2)	159
N1—H1B⋯O1ⁱⁱ	0.88	2.09	2.8788 (19)	148
N2—H2⋯O1ⁱⁱ	0.863 (18)	2.127 (19)	2.9240 (19)	153.2 (17)
Symmetry codes: (i) -x+1, -y+3, -z+1; (ii) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038501/bt5070sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038501/bt5070Isup2.hkl

checkCIF report

Comment top

2,4-Bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide [PhP(Se)(µ-Se)]₂, which is known as Woollins reagent, WR, has received increasing attention due to its relatively unpleasant chemical properties and since it can be prepared readily and safely handled (Gray et al. 2005). Now it is becoming a very useful selenium source or reagent in synthetic chemistry (Hua et al. 2009; Hua & Woollins, 2009). We report here the synthesis and X-ray structure of C₆H₄(CH₂)₃NHCONH₂. The title compound was prepared by the reaction of Woollins' reagent with 3-phenylpropan-1-amine.

Double supramolecular layers of the title compound (Fig. 2), PhCH₂CH₂CH₂NHC(O)NH₂, are formed parallel to the bc plane by intermolecular N—H···O hydrogen bonding (see Table 1), with R₂²(8) and R₂¹(6) motifs in approximately b and c directions respectively (Bernstein et al., 1995). The mean plane of the C3—C5 group makes dihedral angle of 84.8 (2)° with the benzene ring.

Related literature top

For related structural information see Bernstein et al. (1995). For background chemistry, see: Gray et al. (2005); Hua & Woollins (2009); Renodon-Cornière et al. (2002).

Experimental top

A toluene suspension of Woollins reagent (0.54 g, 1.0 mmol) and Ph(CH₂)₃NHCN (0.29 g, 2.0 mmol), which were prepared from cyanogen bromide with primary or secondary amine in dry methanol in the presence of excess of anhydrous CH₃COONa at room temperature in almost quantitative yield (Renodon-Cornière et al. 2002), was refluxed for 4 h under nitrogen during which time the mixtures became a clear reddish brown solution. After cooling and addition of water (1 cm³) the reflux was continued for another 1 h. The solvent was removed in vacuum, and the residue was purified by column chromatography (silica gel, 9:1 dichloromethane/ethyl acetate as eluant) to afford the title compound in the yield of 95%. The single crystals of the title compound for the X-ray crystallographic analysis were obtained by recrystallization from dichloromethane/hexane as colorless blocks.

Computing details top

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. View along the b direction of the crystal packing of the title compound with hydrogen bonding shown as dashed lines.

1-(3-Phenylpropyl)urea top

Crystal data top

C₁₀H₁₄N₂O	F(000) = 384
M_r = 178.23	D_x = 1.169 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.002 (4) Å	Cell parameters from 2697 reflections
b = 6.4953 (15) Å	θ = 2.4–28.1°
c = 9.171 (2) Å	µ = 0.08 mm⁻¹
β = 91.401 (8)°	T = 93 K
V = 1012.5 (4) Å³	Platelet, colorless
Z = 4	0.25 × 0.04 × 0.03 mm

Data collection top

Rigaku Mercury CCD diffractometer	2126 independent reflections
Radiation source: rotating anode	1360 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.038
Detector resolution: 0.83 pixels mm^-1	θ_max = 28.5°, θ_min = 3.4°
ω scans	h = −16→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004)	k = −8→7
T_min = 0.981, T_max = 0.998	l = −9→11
6696 measured reflections

Refinement top

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0607P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2126 reflections	Δρ_max = 0.23 e Å⁻³
122 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (5)

Crystal data top

C₁₀H₁₄N₂O	V = 1012.5 (4) Å³
M_r = 178.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.002 (4) Å	µ = 0.08 mm⁻¹
b = 6.4953 (15) Å	T = 93 K
c = 9.171 (2) Å	0.25 × 0.04 × 0.03 mm
β = 91.401 (8)°

Data collection top

Rigaku Mercury CCD diffractometer	2126 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004)	1360 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.998	R_int = 0.038
6696 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.23 e Å⁻³
2126 reflections	Δρ_min = −0.20 e Å⁻³
122 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.

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

	x	y	z	U_iso*/U_eq
O1	0.56839 (7)	1.2854 (2)	0.55596 (11)	0.0367 (4)
N2	0.61033 (9)	1.1114 (2)	0.35832 (16)	0.0321 (4)
C5	0.81085 (11)	0.5672 (3)	0.32854 (16)	0.0325 (5)
N1	0.54532 (10)	1.4186 (3)	0.33030 (14)	0.0401 (5)
H1A	0.5219	1.5274	0.3665	0.048*
H1B	0.5499	1.4060	0.2353	0.048*
C2	0.64786 (11)	0.9469 (3)	0.44128 (17)	0.0342 (5)
H2A	0.6075	0.8490	0.4749	0.041*
H2B	0.6756	1.0048	0.5282	0.041*
C10	0.79059 (12)	0.3888 (3)	0.25485 (18)	0.0396 (5)
H10	0.7413	0.3258	0.2721	0.047*
C6	0.88327 (12)	0.6552 (3)	0.3003 (2)	0.0451 (6)
H6	0.8987	0.7777	0.3497	0.054*
C3	0.70581 (11)	0.8358 (3)	0.34725 (18)	0.0338 (5)
H3A	0.7425	0.9378	0.3063	0.041*
H3B	0.6768	0.7703	0.2646	0.041*
C4	0.75349 (11)	0.6713 (3)	0.42853 (18)	0.0354 (5)
H4A	0.7828	0.7353	0.5114	0.042*
H4B	0.7174	0.5671	0.4684	0.042*
C9	0.84088 (13)	0.3000 (3)	0.1561 (2)	0.0457 (6)
H9	0.8259	0.1765	0.1074	0.055*
C8	0.91183 (13)	0.3890 (4)	0.1284 (2)	0.0475 (6)
H8	0.9459	0.3288	0.0598	0.057*
C7	0.93348 (13)	0.5670 (4)	0.2009 (2)	0.0533 (6)
H7	0.9828	0.6294	0.1828	0.064*
C1	0.57407 (10)	1.2717 (3)	0.42002 (17)	0.0305 (5)
H2	0.6095 (11)	1.110 (3)	0.264 (2)	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0480 (9)	0.0409 (8)	0.0211 (7)	0.0078 (6)	0.0029 (5)	−0.0016 (5)
N2	0.0408 (10)	0.0356 (9)	0.0199 (8)	0.0082 (7)	0.0011 (6)	−0.0016 (6)
C5	0.0355 (11)	0.0340 (11)	0.0280 (9)	0.0034 (8)	0.0013 (7)	0.0026 (7)
N1	0.0575 (12)	0.0397 (10)	0.0232 (8)	0.0145 (8)	0.0041 (7)	−0.0004 (6)
C2	0.0405 (12)	0.0357 (11)	0.0264 (9)	0.0050 (8)	0.0023 (7)	0.0009 (7)
C10	0.0426 (13)	0.0348 (11)	0.0415 (11)	−0.0006 (9)	0.0055 (8)	−0.0006 (8)
C6	0.0402 (13)	0.0472 (13)	0.0480 (12)	−0.0050 (10)	0.0030 (9)	−0.0113 (9)
C3	0.0385 (12)	0.0351 (11)	0.0281 (10)	0.0043 (8)	0.0043 (7)	−0.0005 (7)
C4	0.0397 (12)	0.0363 (11)	0.0303 (10)	0.0037 (8)	0.0008 (8)	0.0013 (7)
C9	0.0541 (14)	0.0392 (12)	0.0440 (12)	0.0029 (10)	0.0029 (9)	−0.0079 (9)
C8	0.0447 (14)	0.0572 (15)	0.0408 (12)	0.0130 (11)	0.0071 (9)	−0.0058 (10)
C7	0.0388 (13)	0.0659 (16)	0.0557 (13)	−0.0033 (11)	0.0092 (10)	−0.0079 (11)
C1	0.0327 (11)	0.0361 (11)	0.0228 (10)	0.0010 (8)	0.0022 (7)	0.0001 (7)

Geometric parameters (Å, º) top

O1—C1	1.2559 (18)	C10—H10	0.9500
N2—C1	1.342 (2)	C6—C7	1.387 (3)
N2—C2	1.450 (2)	C6—H6	0.9500
N2—H2	0.863 (18)	C3—C4	1.525 (2)
C5—C10	1.380 (3)	C3—H3A	0.9900
C5—C6	1.388 (3)	C3—H3B	0.9900
C5—C4	1.514 (3)	C4—H4A	0.9900
N1—C1	1.344 (2)	C4—H4B	0.9900
N1—H1A	0.8800	C9—C8	1.367 (3)
N1—H1B	0.8800	C9—H9	0.9500
C2—C3	1.509 (2)	C8—C7	1.379 (3)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C7—H7	0.9500
C10—C9	1.386 (3)

C1—N2—C2	123.43 (14)	C4—C3—H3A	108.8
C1—N2—H2	115.5 (12)	C2—C3—H3B	108.8
C2—N2—H2	121.1 (12)	C4—C3—H3B	108.8
C10—C5—C6	117.78 (17)	H3A—C3—H3B	107.7
C10—C5—C4	120.97 (17)	C5—C4—C3	111.07 (14)
C6—C5—C4	121.11 (17)	C5—C4—H4A	109.4
C1—N1—H1A	120.0	C3—C4—H4A	109.4
C1—N1—H1B	120.0	C5—C4—H4B	109.4
H1A—N1—H1B	120.0	C3—C4—H4B	109.4
N2—C2—C3	109.73 (13)	H4A—C4—H4B	108.0
N2—C2—H2A	109.7	C8—C9—C10	120.42 (19)
C3—C2—H2A	109.7	C8—C9—H9	119.8
N2—C2—H2B	109.7	C10—C9—H9	119.8
C3—C2—H2B	109.7	C9—C8—C7	119.43 (18)
H2A—C2—H2B	108.2	C9—C8—H8	120.3
C5—C10—C9	121.23 (19)	C7—C8—H8	120.3
C5—C10—H10	119.4	C8—C7—C6	120.1 (2)
C9—C10—H10	119.4	C8—C7—H7	120.0
C7—C6—C5	121.1 (2)	C6—C7—H7	120.0
C7—C6—H6	119.5	O1—C1—N2	121.38 (15)
C5—C6—H6	119.5	O1—C1—N1	121.44 (16)
C2—C3—C4	113.74 (14)	N2—C1—N1	117.17 (14)
C2—C3—H3A	108.8

C1—N2—C2—C3	−160.22 (17)	C2—C3—C4—C5	−179.52 (16)
C6—C5—C10—C9	0.2 (3)	C5—C10—C9—C8	−0.6 (3)
C4—C5—C10—C9	175.84 (17)	C10—C9—C8—C7	0.8 (3)
C10—C5—C6—C7	0.2 (3)	C9—C8—C7—C6	−0.4 (3)
C4—C5—C6—C7	−175.50 (18)	C5—C6—C7—C8	0.0 (3)
N2—C2—C3—C4	175.12 (15)	C2—N2—C1—O1	−2.2 (3)
C10—C5—C4—C3	−92.9 (2)	C2—N2—C1—N1	176.63 (16)
C6—C5—C4—C3	82.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	2.10	2.936 (2)	159
N1—H1B···O1ⁱⁱ	0.88	2.09	2.8788 (19)	148
N2—H2···O1ⁱⁱ	0.863 (18)	2.127 (19)	2.9240 (19)	153.2 (17)

Symmetry codes: (i) −x+1, −y+3, −z+1; (ii) x, −y+5/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₂O
M_r	178.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	17.002 (4), 6.4953 (15), 9.171 (2)
β (°)	91.401 (8)
V (Å³)	1012.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.04 × 0.03

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2004)
T_min, T_max	0.981, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	6696, 2126, 1360
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.144, 1.03
No. of reflections	2126
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	2.10	2.936 (2)	159.3
N1—H1B···O1ⁱⁱ	0.88	2.09	2.8788 (19)	148.4
N2—H2···O1ⁱⁱ	0.863 (18)	2.127 (19)	2.9240 (19)	153.2 (17)

Symmetry codes: (i) −x+1, −y+3, −z+1; (ii) x, −y+5/2, z−1/2.

Acknowledgements

The authors are grateful to the University of St Andrews and the Engineering and Physical Science Research Council (EPRSC, UK) for financial support.

References

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