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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3096.
Published online 2010 November 6. doi:  10.1107/S1600536810044958
PMCID: PMC3011642

Dicyclo­hexyl­ammonium 3-[(hy­droxy­meth­yl)carbamo­yl]propano­ate

Abstract

The title compound, C12H24N+·C5H8NO4 , contains one dicyclo­hexyl­ammonium cation and one 3-[(hy­droxy­meth­yl)carbamo­yl]propano­ate anion in the asymmetric unit. In the crystal, the ions are linked by inter­molecular N—H(...)O and O—H(...)O hydrogen bonds, forming chains propagating along [100].

Related literature

For the biological activity of succinimide derivatives, see: Argay et al. (1999 [triangle]). For the preparation of the Mannich base 1-[(dicyclo­hexyl­amino)­meth­yl]pyrrolidine-2,5-dione, see: Tra­montini (1973 [triangle]); Tramontini & Angliolini (1990 [triangle]). For standard bond lengths, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3096-scheme1.jpg

Experimental

Crystal data

  • C12H24N+·C5H8NO4
  • M r = 328.45
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3096-efi1.jpg
  • a = 5.6844 (5) Å
  • b = 17.7967 (12) Å
  • c = 18.4264 (16) Å
  • β = 95.495 (7)°
  • V = 1855.5 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 173 K
  • 0.45 × 0.45 × 0.13 mm

Data collection

  • Stoe IPDS-2 diffractometer
  • Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009 [triangle]) T min = 0.714, T max = 1.000
  • 11855 measured reflections
  • 3941 independent reflections
  • 2568 reflections with I > 2σ(I)
  • R int = 0.055

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.095
  • S = 0.93
  • 3941 reflections
  • 225 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: X-AREA (Stoe & Cie, 2009 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2009 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 [triangle]) and publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810044958/fj2363sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044958/fj2363Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge Dr Panchanathee­swaran for his support and many helpful discussions. HSE thanks the X-Ray Application LAB, CSEM, Neuchâtel, for access to the X-ray diffraction equipment.

supplementary crystallographic information

Comment

The pyrrolidine skeleton occurs in many families of biologically important compounds, and several succinimide derivatives are important in biology due to their antepileptic, anticonvulsive, fungicidal and other pharmalogical properties (Argay et al. 1999). The title compound was obtained during our attempts to prepare the Mannich base 1-((dicyclohexylamino)methyl)pyrrolidine-2,5-dione according to the reported procedure (Tramontini, 1973; Tramontini & Angliolini, 1990). The anion is probably formed by the hydrolysis of succinimide to yield the amino acid, i.e. NH2COCH2CH2COOH. The formation of the the title compound can be accounted for by the reaction of this amino acid with formaldehyde and the subsequent protonation of dicyclohexylamine.

The molecular structure of the title compound is illustrated in Fig. 1. It is compossed of a dicyclohexylammonium cation and a 4-(hydroxymethylamino)-4-oxobutanoate anion. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal the cations and anions are linked via N—H···O and O—H···O hydrogen bonds involving both the cation and the anion. In this manner hydrogen bonded polymer chains are formed propagating in [100]; see Fig. 2 and Table 1 for details.

Experimental

Dicyclohexylamine (36.2 ml, 0.2M) was added slowly to a solution of succinimide in ethanol (19.8 g, 0.2M). A solution of formaldehyde (40%, 15 ml) was added in drops with continuous stirring of the solution. The yellowish brown compound formed was initially sticky in nature and slowly turned into a stony mass, which was then crushed to form a fine powder. This product was washed several times with acetone and was then dried in the air in an oven at 333 K and recrystallized using water.

Refinement

The H-atoms could all be located in difference electron-density maps. The NH2, NH and OH H-atoms were freely refined. O—H = 0.88 (2) Å, N—H = 0.829 (17) - 0.95 (2) Å. The C-bound H-atoms were included in calculated positions and treated as riding: C—H = 0.99 and 1.0 Å for CH2 and CH H-atoms, respectively, with Uiso(H) = 1.2Ueq (parent C-atom).

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
A partial view of the crystal packing of the title compound, showing the formation of the N—H···O and O—H···O hydrogen bonded (dashed cyan lines) polymer chain propagating in [100]; see Table ...

Crystal data

C12H24N+·C5H8NO4F(000) = 720
Mr = 328.45Dx = 1.176 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7150 reflections
a = 5.6844 (5) Åθ = 1.6–27.2°
b = 17.7967 (12) ŵ = 0.08 mm1
c = 18.4264 (16) ÅT = 173 K
β = 95.495 (7)°Plate, colourless
V = 1855.5 (3) Å30.45 × 0.45 × 0.13 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer3941 independent reflections
Radiation source: fine-focus sealed tube2568 reflections with I > 2σ(I)
graphiteRint = 0.055
[var phi] and ω scansθmax = 26.7°, θmin = 1.6°
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)h = −6→7
Tmin = 0.714, Tmax = 1.000k = −22→21
11855 measured reflectionsl = −23→23

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095w = 1/[σ2(Fo2) + (0.0463P)2] where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
3941 reflectionsΔρmax = 0.19 e Å3
225 parametersΔρmin = −0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0046 (12)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. The H-atoms could all be located in difference electron-density maps. The NH2, NH and OH H-atoms were freely refined. O—H = 0.88 (2) Å, N—H = 0.829 (17) - 0.95 (2) Å. The C-bound H-atoms were included in calculated positions and treated as riding: C—H = 0.99 and 1.0 Å for CH2 and CH H-atoms, respectively, with Uiso(H) = 1.2Ueq (parent C-atom).

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

xyzUiso*/Ueq
N10.1835 (3)0.16377 (7)0.26459 (6)0.0231 (4)
C10.1626 (3)0.15553 (8)0.18284 (7)0.0240 (4)
C20.3908 (3)0.17650 (9)0.15118 (7)0.0302 (5)
C30.3685 (3)0.16325 (9)0.06882 (8)0.0337 (5)
C40.2964 (3)0.08243 (9)0.05011 (8)0.0376 (5)
C50.0679 (3)0.06210 (9)0.08250 (8)0.0360 (5)
C60.0916 (3)0.07455 (8)0.16494 (7)0.0295 (5)
C70.2441 (3)0.24038 (8)0.29523 (7)0.0268 (5)
C80.2700 (3)0.23401 (9)0.37808 (8)0.0342 (5)
C90.3228 (3)0.31025 (10)0.41315 (9)0.0418 (6)
C100.1112 (5)0.37352 (10)0.30517 (10)0.0554 (7)
C110.1319 (4)0.36647 (10)0.38784 (9)0.0461 (6)
C120.0575 (4)0.29729 (9)0.26847 (8)0.0402 (6)
O10.7522 (2)0.63034 (6)0.19198 (6)0.0350 (3)
O21.02645 (19)0.55189 (6)0.16058 (6)0.0358 (3)
O30.5058 (2)0.35217 (7)0.07565 (8)0.0589 (5)
O4−0.0493 (2)0.31104 (7)0.07088 (6)0.0382 (4)
N20.1841 (2)0.42193 (8)0.08447 (7)0.0317 (4)
C130.8158 (3)0.57440 (8)0.15773 (7)0.0256 (4)
C140.6297 (3)0.52971 (9)0.11060 (8)0.0292 (5)
C150.5506 (3)0.46122 (9)0.15209 (8)0.0334 (5)
C160.4109 (3)0.40679 (9)0.10178 (8)0.0324 (5)
C170.0415 (3)0.37297 (9)0.03501 (8)0.0341 (5)
H10.034100.189500.161500.0290*
H1A0.290 (3)0.1313 (10)0.2847 (8)0.027 (4)*
H1B0.038 (4)0.1508 (10)0.2824 (10)0.046 (5)*
H2A0.522300.145900.174600.0360*
H2B0.427400.230100.161500.0360*
H3A0.249100.198000.045000.0400*
H3B0.521800.174200.049700.0400*
H4A0.274300.07640−0.003500.0450*
H4B0.423800.047900.069400.0450*
H5A0.028900.008800.071800.0430*
H5B−0.062800.093400.059600.0430*
H6A−0.060900.063300.184500.0350*
H6B0.212400.040000.188400.0350*
H70.399100.256400.278800.0320*
H8A0.122100.213700.394700.0410*
H8B0.399700.198700.393500.0410*
H9A0.331900.305300.466900.0500*
H9B0.477600.328600.400000.0500*
H10A0.261000.393600.289700.0670*
H10B−0.016500.409400.289400.0670*
H11A0.171000.416100.410200.0550*
H11B−0.021200.349900.403800.0550*
H12A−0.099900.279500.279800.0480*
H12B0.054300.302800.214900.0480*
H2N0.124 (3)0.4572 (10)0.1056 (9)0.034 (5)*
H4O−0.195 (4)0.3219 (13)0.0796 (11)0.068 (7)*
H14A0.696100.513000.065500.0350*
H14B0.491600.562200.096400.0350*
H15A0.691300.435400.176200.0400*
H15B0.451900.478000.190500.0400*
H17A−0.091400.402200.010500.0410*
H17B0.139000.35450−0.003000.0410*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0259 (7)0.0221 (7)0.0210 (6)0.0028 (6)0.0002 (5)0.0016 (5)
C10.0289 (8)0.0222 (7)0.0202 (7)0.0021 (7)−0.0007 (6)−0.0006 (5)
C20.0358 (9)0.0276 (8)0.0276 (7)−0.0042 (7)0.0051 (6)−0.0013 (6)
C30.0427 (10)0.0324 (9)0.0273 (8)−0.0034 (8)0.0104 (7)−0.0013 (6)
C40.0526 (11)0.0335 (9)0.0278 (8)0.0002 (8)0.0096 (7)−0.0069 (7)
C50.0478 (11)0.0306 (9)0.0293 (8)−0.0065 (8)0.0019 (7)−0.0077 (6)
C60.0362 (9)0.0245 (8)0.0277 (7)−0.0039 (7)0.0021 (6)−0.0008 (6)
C70.0314 (9)0.0245 (8)0.0248 (7)−0.0036 (7)0.0041 (6)−0.0039 (6)
C80.0418 (10)0.0342 (9)0.0254 (7)0.0073 (8)−0.0033 (7)−0.0040 (6)
C90.0476 (11)0.0452 (10)0.0319 (8)−0.0037 (9)−0.0003 (7)−0.0125 (8)
C100.0968 (18)0.0235 (9)0.0439 (10)0.0069 (10)−0.0043 (10)−0.0039 (7)
C110.0669 (14)0.0300 (9)0.0411 (9)0.0003 (9)0.0038 (9)−0.0121 (7)
C120.0623 (12)0.0257 (9)0.0305 (8)0.0080 (9)−0.0069 (8)0.0000 (6)
O10.0304 (6)0.0338 (6)0.0409 (6)−0.0011 (5)0.0038 (5)−0.0132 (5)
O20.0265 (6)0.0311 (6)0.0485 (6)0.0006 (5)−0.0026 (5)−0.0113 (5)
O30.0329 (7)0.0372 (8)0.1074 (12)−0.0028 (6)0.0107 (7)−0.0271 (7)
O40.0313 (7)0.0291 (6)0.0540 (7)−0.0021 (6)0.0033 (6)−0.0010 (5)
N20.0303 (8)0.0277 (7)0.0366 (7)−0.0019 (6)0.0011 (6)−0.0095 (6)
C130.0273 (8)0.0243 (8)0.0251 (7)−0.0030 (7)0.0017 (6)0.0007 (6)
C140.0288 (9)0.0250 (8)0.0325 (8)−0.0037 (7)−0.0040 (6)0.0005 (6)
C150.0316 (9)0.0309 (9)0.0368 (8)−0.0074 (8)−0.0020 (7)0.0026 (7)
C160.0300 (9)0.0236 (8)0.0441 (9)−0.0056 (7)0.0060 (7)−0.0008 (7)
C170.0357 (9)0.0335 (9)0.0330 (8)−0.0047 (8)0.0023 (7)−0.0056 (7)

Geometric parameters (Å, °)

O1—C131.2505 (18)C3—H3A0.9900
O2—C131.259 (2)C4—H4B0.9900
O3—C161.232 (2)C4—H4A0.9900
O4—C171.408 (2)C5—H5A0.9900
O4—H4O0.88 (2)C5—H5B0.9900
N1—C11.5068 (17)C6—H6B0.9900
N1—C71.5030 (19)C6—H6A0.9900
N1—H1A0.892 (17)C7—H71.0000
N1—H1B0.95 (2)C8—H8B0.9900
N2—C161.326 (2)C8—H8A0.9900
N2—C171.451 (2)C9—H9B0.9900
N2—H2N0.829 (17)C9—H9A0.9900
C1—C61.524 (2)C10—H10B0.9900
C1—C21.519 (2)C10—H10A0.9900
C2—C31.529 (2)C11—H11B0.9900
C3—C41.526 (2)C11—H11A0.9900
C4—C51.524 (2)C12—H12B0.9900
C5—C61.528 (2)C12—H12A0.9900
C7—C121.515 (2)C13—C141.526 (2)
C7—C81.524 (2)C14—C151.529 (2)
C8—C91.520 (2)C15—C161.512 (2)
C9—C111.516 (3)C14—H14A0.9900
C10—C121.533 (2)C14—H14B0.9900
C10—C111.522 (2)C15—H15A0.9900
C1—H11.0000C15—H15B0.9900
C2—H2A0.9900C17—H17A0.9900
C2—H2B0.9900C17—H17B0.9900
C3—H3B0.9900
C17—O4—H4O107.9 (15)C5—C6—H6A110.00
C1—N1—C7117.20 (11)N1—C7—H7109.00
C7—N1—H1A108.0 (11)C8—C7—H7109.00
C1—N1—H1A109.8 (10)C12—C7—H7109.00
C1—N1—H1B109.6 (11)C7—C8—H8B109.00
C7—N1—H1B105.5 (11)C9—C8—H8A109.00
H1A—N1—H1B106.2 (16)C7—C8—H8A109.00
C16—N2—C17120.06 (14)C9—C8—H8B109.00
C16—N2—H2N118.4 (12)H8A—C8—H8B108.00
C17—N2—H2N121.3 (12)C11—C9—H9B109.00
N1—C1—C2111.81 (13)H9A—C9—H9B108.00
C2—C1—C6111.55 (13)C8—C9—H9A110.00
N1—C1—C6107.59 (11)C8—C9—H9B110.00
C1—C2—C3110.53 (13)C11—C9—H9A109.00
C2—C3—C4111.38 (13)C11—C10—H10B109.00
C3—C4—C5110.84 (13)C12—C10—H10A109.00
C4—C5—C6110.95 (13)C12—C10—H10B109.00
C1—C6—C5110.40 (12)C11—C10—H10A109.00
N1—C7—C8107.79 (11)H10A—C10—H10B108.00
N1—C7—C12110.86 (13)C9—C11—H11B110.00
C8—C7—C12111.92 (13)H11A—C11—H11B108.00
C7—C8—C9110.83 (13)C10—C11—H11A110.00
C8—C9—C11110.60 (14)C9—C11—H11A110.00
C11—C10—C12111.20 (14)C10—C11—H11B110.00
C9—C11—C10110.29 (16)C10—C12—H12B110.00
C7—C12—C10110.15 (16)H12A—C12—H12B108.00
N1—C1—H1109.00C7—C12—H12B110.00
C6—C1—H1109.00C10—C12—H12A110.00
C2—C1—H1109.00C7—C12—H12A110.00
C3—C2—H2B110.00O1—C13—O2123.51 (14)
C3—C2—H2A110.00O1—C13—C14118.94 (15)
H2A—C2—H2B108.00O2—C13—C14117.55 (13)
C1—C2—H2B110.00C13—C14—C15110.60 (12)
C1—C2—H2A110.00C14—C15—C16111.49 (12)
C2—C3—H3B109.00O3—C16—N2121.23 (15)
H3A—C3—H3B108.00O3—C16—C15121.41 (15)
C4—C3—H3B109.00N2—C16—C15117.30 (14)
C2—C3—H3A109.00O4—C17—N2112.52 (12)
C4—C3—H3A109.00C13—C14—H14A110.00
C5—C4—H4B109.00C13—C14—H14B110.00
H4A—C4—H4B108.00C15—C14—H14A110.00
C5—C4—H4A109.00C15—C14—H14B110.00
C3—C4—H4A109.00H14A—C14—H14B108.00
C3—C4—H4B109.00C14—C15—H15A109.00
C4—C5—H5B109.00C14—C15—H15B109.00
H5A—C5—H5B108.00C16—C15—H15A109.00
C4—C5—H5A109.00C16—C15—H15B109.00
C6—C5—H5B109.00H15A—C15—H15B108.00
C6—C5—H5A109.00O4—C17—H17A109.00
C1—C6—H6B110.00O4—C17—H17B109.00
H6A—C6—H6B108.00N2—C17—H17A109.00
C5—C6—H6B110.00N2—C17—H17B109.00
C1—C6—H6A110.00H17A—C17—H17B108.00
C7—N1—C1—C259.28 (18)C4—C5—C6—C156.57 (17)
C7—N1—C1—C6−177.90 (14)N1—C7—C8—C9−177.94 (14)
C1—N1—C7—C8−176.66 (14)C8—C7—C12—C1054.9 (2)
C1—N1—C7—C1260.53 (19)C12—C7—C8—C9−55.78 (19)
C16—N2—C17—O484.82 (17)N1—C7—C12—C10175.30 (14)
C17—N2—C16—O31.2 (2)C7—C8—C9—C1156.73 (18)
C17—N2—C16—C15178.48 (13)C8—C9—C11—C10−57.9 (2)
N1—C1—C2—C3176.74 (12)C12—C10—C11—C957.7 (3)
C2—C1—C6—C5−56.83 (17)C11—C10—C12—C7−55.9 (2)
C6—C1—C2—C356.21 (16)O1—C13—C14—C15−96.94 (16)
N1—C1—C6—C5−179.81 (14)O2—C13—C14—C1582.16 (17)
C1—C2—C3—C4−55.54 (17)C13—C14—C15—C16−166.86 (13)
C2—C3—C4—C555.81 (17)C14—C15—C16—O395.92 (18)
C3—C4—C5—C6−56.27 (17)C14—C15—C16—N2−81.33 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.892 (17)2.597 (17)3.285 (2)134.7 (14)
N1—H1A···O2i0.892 (17)1.975 (17)2.8546 (18)168.7 (15)
N1—H1B···O1ii0.95 (2)1.80 (2)2.740 (2)174.3 (17)
N2—H2N···O2iii0.829 (17)2.069 (17)2.8914 (18)171.1 (16)
O4—H4O···O3iii0.88 (2)1.78 (2)2.6423 (16)166.4 (19)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2363).

References

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