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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o160.
Published online 2007 December 6. doi:  10.1107/S1600536807064756
PMCID: PMC2915228

N-(4-Bromo­benzo­yl)-N,N′-dicyclo­hexyl­urea

Abstract

In the title compound, C20H27BrN2O2, mol­ecules are linked into one-dimensional chains through (amide)N—H(...)O=C(amide) inter­molecular hydrogen bonds.

Related literature

For related literature, see: Bohne et al. (2005 [triangle]); Bondy et al. (2004 [triangle]); Bruker (2000 [triangle]); Ślebioda (1995 [triangle]). For literature on related crystal structures, see: Ball et al. (1990 [triangle]); Chérioux et al. (2002 [triangle]); Gallagher et al. (1999 [triangle]); Govindasamy & Subramanian (1997 [triangle]); Toniolo et al. (1990 [triangle]); Wu et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o160-scheme1.jpg

Experimental

Crystal data

  • C20H27BrN2O2
  • M r = 407.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o160-efi1.jpg
  • a = 13.501 (2) Å
  • b = 9.5621 (10) Å
  • c = 16.306 (2) Å
  • β = 114.443 (6)°
  • V = 1916.3 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.16 mm−1
  • T = 113 (2) K
  • 0.38 × 0.16 × 0.14 mm

Data collection

  • Rigaku Saturn CCD diffractometer
  • Absorption correction: multi-scan (REQABS; Jacobson, 1998 [triangle]) T min = 0.484, T max = 0.739
  • 17461 measured reflections
  • 4526 independent reflections
  • 3651 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.078
  • S = 1.06
  • 4526 reflections
  • 231 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: CrystalClear (Jacobson, 1999 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: CrystalStructure (Rigaku, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807064756/pk2071sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064756/pk2071Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the Research Fund for New Faculty at the State Key Laboratory of Applied Organic Chemistry.

supplementary crystallographic information

Comment

The first conscious total synthesis of a natural product was that of urea in 1828 by Wohler, which marks the beginnings of organic synthesis. Since then, many urea derivatives have been prepared and have demonstrated a wide range of uses, including fluorescence probes (Bohne et al., 2005) and anion receptors (Bondy et al., 2004).

The title compound, an N-acylurea derivative, can be conveniently prepared from dicyclohexylcarbodiimide (DCC) and p-bromobenzoic acid according to reported methods (Ślebioda, 1995). The molecular structure is shown in Fig.1. Each cyclohexyl group adopts the chair conformation, as is required for energy minimization. The two carbonyl groups are twisted substantially at the central atom, N1, with a dihedral angle of 66.43 (10)° between the O1/C7/N1 and O2/C14/N2 planes, which increases the distance between atoms O1 and N2. As a result, no intramolecular N2–H2A···O1 hydrogen bond is formed. However, molecules are linked into chains through (amide) N–H···O=C (amide) intermolecular hydrogen bonds, reinforced by C–H···O=C interactions. Surprisingly, this supramolecular arrangement is not observed in a closely related X-ray structure (Gallagher et al., 1999).

Experimental

p-bromobenzoic acid (201 mg, 1 mmol) was dissolved in CHCl3 (5 ml) and DCC (206 mg, 1 mmol) and N,N-dimethylpyridin-4-amine (122 mg, 1 mmol) were added to the solution. The resulting mixture was stirred for 1 h at 298 K. After evaporation of the solvent, a colorless solid was isolated. Single crystals suitable for X-ray structure determination were obtained by slow evaporation of a EtOAc solution over a period of several days.

Refinement

The H atom bonded to N2 was found in a difference map and refined freely to obtain an unbiased geometry for the hydrogen bonding scheme. The H atoms bonded to C were placed geometrically (C—H values were set to 1.00, 0.99 and 0.95 A° for atoms CH2 and CH, respectively) and refined with a riding model, with Uiso(H) = 1.2 times Ueq(C).

Figures

Fig. 1.
An ellipsoid plot of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C20H27BrN2O2F000 = 848
Mr = 407.35Dx = 1.412 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71070 Å
Hall symbol: -P 2ynCell parameters from 4164 reflections
a = 13.501 (2) Åθ = 1.7–27.9º
b = 9.5621 (10) ŵ = 2.16 mm1
c = 16.306 (2) ÅT = 113 (2) K
β = 114.443 (6)ºPrism, colorless
V = 1916.3 (4) Å30.38 × 0.16 × 0.14 mm
Z = 4

Data collection

Rigaku Saturn CCD diffractometer4526 independent reflections
Radiation source: Rotating anode3651 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.044
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113(2) Kθmin = 1.7º
ω scansh = −17→17
Absorption correction: multi-scan(REQABS; Jacobson, 1998)k = −12→12
Tmin = 0.484, Tmax = 0.739l = −21→20
17461 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078  w = 1/[σ2(Fo2) + (0.0381P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.003
4526 reflectionsΔρmax = 0.45 e Å3
231 parametersΔρmin = −0.44 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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 > 2σ(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)

xyzUiso*/Ueq
Br10.615319 (17)0.39160 (2)1.092233 (14)0.03591 (9)
N10.86443 (11)0.53780 (15)0.80694 (9)0.0172 (3)
N20.67615 (11)0.53992 (16)0.73657 (10)0.0180 (3)
O10.95485 (9)0.68643 (13)0.92419 (8)0.0226 (3)
O20.76754 (10)0.34042 (13)0.73292 (8)0.0234 (3)
C10.69576 (14)0.4583 (2)1.02792 (12)0.0233 (4)
C20.69278 (15)0.5987 (2)1.00682 (13)0.0267 (4)
H20.65080.66241.02400.032*
C30.75215 (15)0.6450 (2)0.96011 (13)0.0246 (4)
H30.75190.74140.94600.029*
C40.81235 (13)0.55047 (19)0.93373 (11)0.0176 (4)
C50.81418 (14)0.40955 (19)0.95585 (12)0.0205 (4)
H50.85510.34500.93810.025*
C60.75616 (14)0.3634 (2)1.00396 (12)0.0223 (4)
H60.75810.26771.02020.027*
C70.88221 (13)0.60122 (18)0.88777 (12)0.0179 (4)
C80.94261 (14)0.55666 (19)0.76516 (12)0.0199 (4)
H80.99070.63720.79630.024*
C91.01578 (15)0.4287 (2)0.77921 (14)0.0259 (4)
H9A0.97020.34520.75310.031*
H9B1.05740.41220.84450.031*
C101.09504 (16)0.4493 (2)0.73482 (14)0.0331 (5)
H10A1.14620.52600.76560.040*
H10B1.13800.36280.74150.040*
C111.03445 (17)0.4842 (2)0.63510 (14)0.0361 (5)
H11A0.98780.40430.60320.043*
H11B1.08740.50070.60860.043*
C120.96424 (17)0.6143 (2)0.62288 (14)0.0341 (5)
H12A0.92380.63380.55780.041*
H12B1.01170.69560.65070.041*
C130.88348 (15)0.5955 (2)0.66570 (13)0.0268 (4)
H13A0.84240.68340.65990.032*
H13B0.83080.52100.63350.032*
C140.76568 (14)0.4618 (2)0.75616 (11)0.0180 (4)
C150.56540 (13)0.48403 (19)0.69141 (12)0.0180 (4)
H150.57020.38530.67330.022*
C160.50196 (16)0.5682 (2)0.60708 (13)0.0313 (5)
H16A0.53920.56390.56610.038*
H16B0.49870.66730.62330.038*
C170.38642 (16)0.5099 (2)0.55931 (15)0.0399 (6)
H17A0.34520.56680.50510.048*
H17B0.38990.41280.53960.048*
C180.32755 (16)0.5114 (2)0.62076 (18)0.0509 (7)
H18A0.31890.60910.63680.061*
H18B0.25420.47020.58900.061*
C190.39104 (16)0.4288 (2)0.70547 (16)0.0403 (6)
H19A0.39340.32930.68960.048*
H19B0.35350.43440.74620.048*
C200.50804 (16)0.4842 (2)0.75473 (14)0.0296 (5)
H20A0.50630.58050.77640.036*
H20B0.54870.42450.80770.036*
H2A0.6851 (15)0.6326 (10)0.7456 (12)0.023 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.03720 (13)0.04748 (17)0.03229 (13)−0.01255 (10)0.02362 (10)−0.00410 (10)
N10.0147 (7)0.0164 (8)0.0206 (8)−0.0024 (6)0.0075 (6)−0.0004 (6)
N20.0154 (7)0.0136 (9)0.0238 (8)−0.0013 (6)0.0070 (6)−0.0024 (7)
O10.0190 (6)0.0223 (7)0.0233 (7)−0.0054 (6)0.0056 (5)−0.0015 (6)
O20.0213 (6)0.0140 (7)0.0322 (8)0.0006 (5)0.0084 (6)−0.0032 (6)
C10.0217 (9)0.0320 (12)0.0174 (9)−0.0071 (8)0.0093 (8)−0.0027 (9)
C20.0257 (10)0.0269 (12)0.0320 (11)−0.0048 (8)0.0165 (9)−0.0102 (9)
C30.0259 (10)0.0198 (11)0.0297 (10)−0.0034 (8)0.0132 (8)−0.0030 (9)
C40.0141 (8)0.0212 (10)0.0151 (8)−0.0030 (7)0.0037 (7)−0.0019 (8)
C50.0164 (8)0.0239 (11)0.0194 (9)0.0003 (8)0.0057 (7)0.0005 (8)
C60.0218 (9)0.0244 (11)0.0191 (9)−0.0012 (8)0.0067 (8)0.0040 (8)
C70.0145 (8)0.0166 (10)0.0198 (9)0.0026 (7)0.0045 (7)0.0037 (8)
C80.0171 (9)0.0203 (10)0.0252 (10)−0.0019 (7)0.0117 (8)−0.0001 (8)
C90.0188 (9)0.0267 (11)0.0306 (11)0.0044 (8)0.0087 (8)0.0030 (9)
C100.0221 (10)0.0396 (13)0.0405 (12)0.0087 (9)0.0159 (9)0.0002 (11)
C110.0321 (11)0.0479 (14)0.0351 (12)0.0045 (10)0.0209 (10)−0.0050 (11)
C120.0348 (11)0.0463 (14)0.0290 (11)0.0046 (10)0.0210 (10)0.0048 (10)
C130.0245 (10)0.0332 (12)0.0264 (10)0.0058 (9)0.0144 (8)0.0065 (9)
C140.0176 (9)0.0184 (10)0.0179 (9)−0.0019 (7)0.0074 (7)0.0019 (8)
C150.0141 (8)0.0162 (10)0.0219 (9)−0.0008 (7)0.0055 (7)−0.0019 (8)
C160.0314 (11)0.0229 (11)0.0270 (11)−0.0040 (9)−0.0006 (9)0.0023 (9)
C170.0268 (11)0.0284 (13)0.0408 (13)0.0028 (9)−0.0096 (10)0.0015 (10)
C180.0150 (10)0.0391 (14)0.0841 (19)0.0034 (10)0.0060 (12)−0.0301 (14)
C190.0277 (11)0.0528 (15)0.0518 (15)−0.0179 (10)0.0279 (11)−0.0276 (12)
C200.0262 (10)0.0367 (13)0.0304 (11)−0.0088 (9)0.0163 (9)−0.0101 (10)

Geometric parameters (Å, °)

Br1—C11.9048 (18)C10—H10A0.9900
N1—C71.379 (2)C10—H10B0.9900
N1—C141.441 (2)C11—C121.526 (3)
N1—C81.485 (2)C11—H11A0.9900
N2—C141.342 (2)C11—H11B0.9900
N2—C151.467 (2)C12—C131.529 (2)
N2—H2A0.898 (9)C12—H12A0.9900
O1—C71.223 (2)C12—H12B0.9900
O2—C141.225 (2)C13—H13A0.9900
C1—C61.380 (3)C13—H13B0.9900
C1—C21.382 (3)C15—C161.516 (2)
C2—C31.387 (3)C15—C201.526 (2)
C2—H20.9500C15—H151.0000
C3—C41.397 (3)C16—C171.531 (3)
C3—H30.9500C16—H16A0.9900
C4—C51.393 (3)C16—H16B0.9900
C4—C71.507 (2)C17—C181.515 (3)
C5—C61.390 (2)C17—H17A0.9900
C5—H50.9500C17—H17B0.9900
C6—H60.9500C18—C191.512 (3)
C8—C131.528 (2)C18—H18A0.9900
C8—C91.529 (3)C18—H18B0.9900
C8—H81.0000C19—C201.540 (3)
C9—C101.532 (3)C19—H19A0.9900
C9—H9A0.9900C19—H19B0.9900
C9—H9B0.9900C20—H20A0.9900
C10—C111.524 (3)C20—H20B0.9900
C7—N1—C14121.65 (14)C11—C12—C13111.49 (17)
C7—N1—C8120.63 (14)C11—C12—H12A109.3
C14—N1—C8117.50 (14)C13—C12—H12A109.3
C14—N2—C15123.18 (15)C11—C12—H12B109.3
C14—N2—H2A117.5 (12)C13—C12—H12B109.3
C15—N2—H2A118.8 (12)H12A—C12—H12B108.0
C6—C1—C2121.85 (17)C8—C13—C12110.81 (16)
C6—C1—Br1118.30 (15)C8—C13—H13A109.5
C2—C1—Br1119.85 (14)C12—C13—H13A109.5
C1—C2—C3118.86 (18)C8—C13—H13B109.5
C1—C2—H2120.6C12—C13—H13B109.5
C3—C2—H2120.6H13A—C13—H13B108.1
C2—C3—C4120.33 (18)O2—C14—N2125.83 (16)
C2—C3—H3119.8O2—C14—N1121.54 (16)
C4—C3—H3119.8N2—C14—N1112.60 (16)
C5—C4—C3119.75 (17)N2—C15—C16109.75 (14)
C5—C4—C7119.52 (16)N2—C15—C20110.93 (14)
C3—C4—C7120.56 (17)C16—C15—C20111.03 (16)
C6—C5—C4119.98 (17)N2—C15—H15108.3
C6—C5—H5120.0C16—C15—H15108.3
C4—C5—H5120.0C20—C15—H15108.3
C1—C6—C5119.22 (18)C15—C16—C17110.02 (16)
C1—C6—H6120.4C15—C16—H16A109.7
C5—C6—H6120.4C17—C16—H16A109.7
O1—C7—N1122.99 (16)C15—C16—H16B109.7
O1—C7—C4120.93 (16)C17—C16—H16B109.7
N1—C7—C4115.88 (15)H16A—C16—H16B108.2
N1—C8—C13110.98 (14)C18—C17—C16111.28 (18)
N1—C8—C9111.83 (15)C18—C17—H17A109.4
C13—C8—C9112.02 (16)C16—C17—H17A109.4
N1—C8—H8107.2C18—C17—H17B109.4
C13—C8—H8107.2C16—C17—H17B109.4
C9—C8—H8107.2H17A—C17—H17B108.0
C8—C9—C10111.13 (16)C19—C18—C17110.18 (17)
C8—C9—H9A109.4C19—C18—H18A109.6
C10—C9—H9A109.4C17—C18—H18A109.6
C8—C9—H9B109.4C19—C18—H18B109.6
C10—C9—H9B109.4C17—C18—H18B109.6
H9A—C9—H9B108.0H18A—C18—H18B108.1
C11—C10—C9111.13 (16)C18—C19—C20111.59 (18)
C11—C10—H10A109.4C18—C19—H19A109.3
C9—C10—H10A109.4C20—C19—H19A109.3
C11—C10—H10B109.4C18—C19—H19B109.3
C9—C10—H10B109.4C20—C19—H19B109.3
H10A—C10—H10B108.0H19A—C19—H19B108.0
C10—C11—C12110.37 (17)C15—C20—C19110.18 (16)
C10—C11—H11A109.6C15—C20—H20A109.6
C12—C11—H11A109.6C19—C20—H20A109.6
C10—C11—H11B109.6C15—C20—H20B109.6
C12—C11—H11B109.6C19—C20—H20B109.6
H11A—C11—H11B108.1H20A—C20—H20B108.1
C6—C1—C2—C30.1 (3)C13—C8—C9—C1054.1 (2)
Br1—C1—C2—C3179.88 (14)C8—C9—C10—C11−55.5 (2)
C1—C2—C3—C41.0 (3)C9—C10—C11—C1257.0 (2)
C2—C3—C4—C5−1.1 (3)C10—C11—C12—C13−57.3 (2)
C2—C3—C4—C7−176.41 (17)N1—C8—C13—C12−179.79 (15)
C3—C4—C5—C60.0 (3)C9—C8—C13—C12−54.0 (2)
C7—C4—C5—C6175.39 (15)C11—C12—C13—C855.7 (2)
C2—C1—C6—C5−1.2 (3)C15—N2—C14—O26.6 (3)
Br1—C1—C6—C5179.06 (13)C15—N2—C14—N1−175.26 (14)
C4—C5—C6—C11.1 (3)C7—N1—C14—O2−125.42 (18)
C14—N1—C7—O1−166.44 (16)C8—N1—C14—O260.0 (2)
C8—N1—C7—O17.9 (2)C7—N1—C14—N256.4 (2)
C14—N1—C7—C418.6 (2)C8—N1—C14—N2−118.19 (17)
C8—N1—C7—C4−167.06 (14)C14—N2—C15—C16−124.11 (18)
C5—C4—C7—O1−117.18 (19)C14—N2—C15—C20112.83 (19)
C3—C4—C7—O158.1 (2)N2—C15—C16—C17179.70 (16)
C5—C4—C7—N157.9 (2)C20—C15—C16—C17−57.3 (2)
C3—C4—C7—N1−126.75 (18)C15—C16—C17—C1857.9 (2)
C7—N1—C8—C13−131.60 (17)C16—C17—C18—C19−57.3 (2)
C14—N1—C8—C1343.0 (2)C17—C18—C19—C2056.3 (2)
C7—N1—C8—C9102.52 (19)N2—C15—C20—C19178.56 (17)
C14—N1—C8—C9−82.87 (19)C16—C15—C20—C1956.2 (2)
N1—C8—C9—C10179.38 (15)C18—C19—C20—C15−55.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O2i0.898 (10)2.072 (11)2.961 (2)170 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2071).

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