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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3162.
Published online 2010 November 13. doi:  10.1107/S1600536810045538
PMCID: PMC3011593

4-Carbamoylpiperidinium acetate monohydrate

Abstract

In the structure of the title compound, C6H13N2O+·C2H3O2 ·H2O, the amide H atoms of the cations form centrosymmetric cyclic hydrogen-bonding associations incorporating two water mol­ecules [graph set R 4 2(8)], which are conjoint with cyclic water-bridged amide–amide associations [R 4 4(12)] and larger R 4 4(20) associations involving the water mol­ecule and the acetate anions, which bridge through the piperidinium H-bond donors, giving an overall three-dimensional framework structure.

Related literature

For structural data on isonipecotamide salts, see: Smith et al. (2010 [triangle]); Smith & Wermuth (2010a [triangle],b [triangle]). For graph-set motifs, see: Etter et al. (1990 [triangle]).

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Object name is e-66-o3162-scheme1.jpg

Experimental

Crystal data

  • C6H13N2O+·C2H3O2 ·H2O
  • M r = 206.24
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3162-efi4.jpg
  • a = 5.8219 (2) Å
  • b = 7.7675 (3) Å
  • c = 12.4022 (5) Å
  • α = 81.088 (4)°
  • β = 78.763 (4)°
  • γ = 76.202 (4)°
  • V = 530.75 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 200 K
  • 0.40 × 0.35 × 0.15 mm

Data collection

  • Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 [triangle]) T min = 0.962, T max = 0.980
  • 6385 measured reflections
  • 2087 independent reflections
  • 1602 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.105
  • S = 0.93
  • 2087 reflections
  • 151 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]) within WinGX (Farrugia, 1999 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045538/nk2071sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045538/nk2071Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the Australian Research Council, the Faculty of Science and Technology, Queensland University of Technology and the School of Biomolecular and Physical Sciences, Griffith University.

supplementary crystallographic information

Comment

The amide 4-carbamoylpiperidine (isonipecotamide, INIPA) has proved to be a particularly useful synthon for the construction of crystalline salts with a range of aromatic carboxylic acids, enabling their structure determination (Smith & Wermuth, 2010a, 2010b). The structure of the 2:1 INIPA salt of biphenyl-4,4'-disulfonic acid has also been reported (Smith et al., 2010), and all reported compounds, prepared in aqueous ethanolic solution, have been anhydrous. No structures with aliphatic acids have previously been reported. However, our reaction of isonipecotamide with acetic acid in aqueous methanolic solution gave the title compound, the hydrate C6H13N2O+ C2H3O2-. H2O, (I) and the structure is reported here.

With (I) (Fig. 1) the amide H atoms of the cations form centrosymetric cyclic hydrogen-bonding associations which incorporate two water molecules [graph set R24(8) (Etter et al., 1990)], These are conjoint with cyclic water-bridged amide–amide associations [R44(12)] and larger R44(20) associations also involving the water molecule and the acetate anions (Table 1). These acetate groups bridge the cations through the piperidinium H donor atoms, giving an overall three-dimensional framework structure (Fig. 2).

Experimental

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of 4-carbamoylpiperidine (isonipecotamide) and acetic acid in 50 ml of 80% methanol–water. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave colourless plates of (I) (m.p. 409 K) from which a specimen was cleaved for the X-ray analysis.

Refinement

Hydrogen atoms involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. The N–H bond distance range is 0.899 (17)–0.949 (18) Å and the water O–H distances are 0.82 (2) and 0.92 (2) Å. Other H-atoms were included in the refinement at calculated positions [C–H = 0.96–0.97 Å and with Uiso(H) = 1.2Ueq(C), using a riding-model approximation.

Figures

Fig. 1.
Molecular configuration and atom naming scheme for the three INIPA cation the acetate anion and the water molecule of solvation in (I). Inter-species hydrogen bonds are shown as dashed lines and displacement ellipsoids are drawn at the 40% probability ...
Fig. 2.
The three-dimensional hydrogen-bonded framework structure of (I) viewed down the approximate b cell direction showing the cyclic R24(8), R44(12) and R44(20) hydrogen-bonding interactions in (I). Non-associative H atoms are omitted. For symmetry codes, ...

Crystal data

C6H13N2O+·C2H3O2·H2OZ = 2
Mr = 206.24F(000) = 224
Triclinic, P1Dx = 1.291 Mg m3
Hall symbol: -P 1Melting point: 409 K
a = 5.8219 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.7675 (3) ÅCell parameters from 3330 reflections
c = 12.4022 (5) Åθ = 3.4–28.8°
α = 81.088 (4)°µ = 0.10 mm1
β = 78.763 (4)°T = 200 K
γ = 76.202 (4)°Plate, colourless
V = 530.75 (4) Å30.40 × 0.35 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer2087 independent reflections
Radiation source: Enhance (Mo) X-ray source1602 reflections with I > 2σ(I)
graphiteRint = 0.021
Detector resolution: 16.977 pixels mm-1θmax = 26.0°, θmin = 3.4°
ω scansh = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)k = −9→9
Tmin = 0.962, Tmax = 0.980l = −15→15
6385 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 0.93w = 1/[σ2(Fo2) + (0.0733P)2 + 0.0214P] where P = (Fo2 + 2Fc2)/3
2087 reflections(Δ/σ)max < 0.001
151 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.19 e Å3

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. 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)

xyzUiso*/Ueq
O41A0.48609 (16)0.38864 (13)0.35243 (9)0.0344 (3)
N1A0.9204 (2)0.82745 (15)0.19803 (10)0.0274 (4)
N41A0.7954 (2)0.21185 (16)0.42814 (10)0.0297 (4)
C2A0.9917 (3)0.67001 (19)0.13552 (11)0.0290 (4)
C3A0.8415 (2)0.53343 (18)0.18703 (11)0.0264 (4)
C4A0.8642 (2)0.47820 (17)0.30875 (11)0.0223 (4)
C5A0.8010 (3)0.64377 (18)0.37045 (11)0.0283 (4)
C6A0.9525 (3)0.77742 (19)0.31557 (12)0.0319 (5)
C41A0.6994 (2)0.35378 (17)0.36412 (11)0.0236 (4)
O111.43436 (17)−0.04485 (13)0.19784 (8)0.0320 (3)
O121.14721 (18)0.09626 (14)0.10165 (9)0.0395 (4)
C11.3462 (2)0.08082 (17)0.12972 (11)0.0246 (4)
C21.4884 (3)0.2219 (2)0.08190 (13)0.0375 (5)
O1W1.31002 (18)0.08400 (15)0.40367 (9)0.0314 (3)
H4A1.030300.416900.313800.0270*
H11A1.005 (3)0.917 (2)0.1664 (15)0.050 (5)*
H12A0.757 (3)0.882 (2)0.1956 (14)0.043 (5)*
H21A1.160000.616600.136100.0350*
H22A0.969500.707000.059200.0350*
H31A0.894200.429100.147200.0320*
H32A0.674800.583900.180700.0320*
H41A0.958 (3)0.178 (2)0.4274 (13)0.036 (4)*
H42A0.701 (3)0.138 (2)0.4646 (14)0.045 (5)*
H51A0.632700.699200.371600.0340*
H52A0.827100.608500.446400.0340*
H61A0.905200.883000.354200.0380*
H62A1.120100.725600.319400.0380*
H211.429400.286900.016900.0450*
H221.654500.166100.062700.0450*
H231.471800.302500.135700.0450*
H11W1.355 (4)0.031 (3)0.3388 (19)0.069 (7)*
H12W1.368 (4)0.175 (3)0.3891 (17)0.062 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O41A0.0236 (5)0.0304 (6)0.0475 (6)−0.0104 (4)−0.0061 (4)0.0086 (5)
N1A0.0228 (6)0.0200 (6)0.0383 (7)−0.0088 (5)−0.0057 (5)0.0076 (5)
N41A0.0279 (7)0.0236 (6)0.0349 (7)−0.0100 (5)−0.0026 (5)0.0083 (5)
C2A0.0309 (7)0.0300 (8)0.0250 (7)−0.0108 (6)−0.0021 (6)0.0039 (6)
C3A0.0310 (7)0.0259 (7)0.0235 (7)−0.0116 (6)−0.0025 (5)−0.0007 (6)
C4A0.0192 (6)0.0198 (6)0.0269 (7)−0.0060 (5)−0.0038 (5)0.0029 (5)
C5A0.0345 (8)0.0271 (7)0.0247 (7)−0.0124 (6)−0.0020 (6)−0.0016 (6)
C6A0.0391 (8)0.0270 (8)0.0336 (8)−0.0155 (6)−0.0057 (6)−0.0032 (6)
C41A0.0239 (7)0.0202 (7)0.0256 (7)−0.0065 (5)−0.0007 (5)−0.0008 (6)
O110.0274 (5)0.0289 (5)0.0362 (6)−0.0050 (4)−0.0060 (4)0.0061 (5)
O120.0333 (6)0.0339 (6)0.0535 (7)−0.0167 (5)−0.0175 (5)0.0165 (5)
C10.0250 (7)0.0227 (7)0.0257 (7)−0.0074 (5)−0.0012 (5)−0.0015 (6)
C20.0368 (8)0.0335 (8)0.0450 (9)−0.0182 (7)−0.0080 (7)0.0054 (7)
O1W0.0325 (6)0.0304 (6)0.0324 (6)−0.0149 (5)−0.0066 (4)0.0073 (5)

Geometric parameters (Å, °)

O41A—C41A1.2386 (16)C4A—C41A1.5186 (18)
O11—C11.2667 (16)C5A—C6A1.518 (2)
O12—C11.2473 (17)C2A—H21A0.9700
O1W—H12W0.84 (2)C2A—H22A0.9700
O1W—H11W0.92 (2)C3A—H32A0.9700
N1A—C6A1.4856 (19)C3A—H31A0.9700
N1A—C2A1.4816 (18)C4A—H4A0.9800
N41A—C41A1.3289 (18)C5A—H51A0.9700
N1A—H12A0.949 (18)C5A—H52A0.9700
N1A—H11A0.940 (17)C6A—H62A0.9700
N41A—H41A0.919 (18)C6A—H61A0.9700
N41A—H42A0.899 (17)C1—C21.509 (2)
C2A—C3A1.521 (2)C2—H230.9600
C3A—C4A1.5266 (19)C2—H210.9600
C4A—C5A1.5311 (19)C2—H220.9600
H11W—O1W—H12W104 (2)C2A—C3A—H32A109.00
C2A—N1A—C6A111.60 (11)C4A—C3A—H32A109.00
H11A—N1A—H12A104.9 (14)H31A—C3A—H32A108.00
C6A—N1A—H11A109.2 (11)C4A—C3A—H31A109.00
C2A—N1A—H11A112.5 (10)C5A—C4A—H4A109.00
C2A—N1A—H12A109.7 (10)C41A—C4A—H4A109.00
C6A—N1A—H12A108.8 (10)C3A—C4A—H4A109.00
C41A—N41A—H42A118.4 (11)C4A—C5A—H51A109.00
C41A—N41A—H41A121.8 (10)C6A—C5A—H51A109.00
H41A—N41A—H42A119.1 (15)C6A—C5A—H52A109.00
N1A—C2A—C3A110.23 (12)C4A—C5A—H52A109.00
C2A—C3A—C4A110.91 (11)H51A—C5A—H52A108.00
C3A—C4A—C41A111.67 (10)N1A—C6A—H62A110.00
C5A—C4A—C41A108.66 (11)C5A—C6A—H61A110.00
C3A—C4A—C5A109.87 (11)C5A—C6A—H62A110.00
C4A—C5A—C6A111.11 (12)H61A—C6A—H62A108.00
N1A—C6A—C5A109.84 (13)N1A—C6A—H61A110.00
O41A—C41A—C4A120.90 (12)O11—C1—O12123.79 (12)
O41A—C41A—N41A122.94 (12)O11—C1—C2117.89 (12)
N41A—C41A—C4A116.11 (11)O12—C1—C2118.31 (12)
N1A—C2A—H21A110.00C1—C2—H22109.00
C3A—C2A—H21A110.00C1—C2—H23109.00
C3A—C2A—H22A110.00C1—C2—H21109.00
H21A—C2A—H22A108.00H21—C2—H23109.00
N1A—C2A—H22A110.00H22—C2—H23109.00
C2A—C3A—H31A109.00H21—C2—H22109.00
C6A—N1A—C2A—C3A59.57 (16)C41A—C4A—C5A—C6A−177.38 (12)
C2A—N1A—C6A—C5A−59.60 (16)C3A—C4A—C41A—O41A−47.52 (17)
N1A—C2A—C3A—C4A−56.87 (15)C3A—C4A—C41A—N41A135.05 (12)
C2A—C3A—C4A—C5A54.57 (15)C5A—C4A—C41A—O41A73.82 (16)
C2A—C3A—C4A—C41A175.21 (11)C5A—C4A—C41A—N41A−103.61 (14)
C3A—C4A—C5A—C6A−54.94 (16)C4A—C5A—C6A—N1A57.10 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1A—H11A···O12i0.940 (17)1.793 (17)2.7311 (16)175.8 (17)
N1A—H12A···O11ii0.949 (18)1.824 (18)2.7666 (16)171.8 (14)
N41A—H41A···O1W0.919 (18)1.984 (18)2.8939 (17)170.2 (15)
N41A—H42A···O1Wiii0.899 (17)2.188 (16)2.9491 (16)142.1 (15)
O1W—H11W···O110.92 (2)1.87 (2)2.7871 (15)172 (2)
O1W—H12W···O41Aiv0.84 (2)1.90 (2)2.7370 (15)177 (2)
C2A—H22A···O12v0.972.423.3428 (18)158

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2071).

References

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  • Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. [PubMed]
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Oxford Diffraction (2010). CrysAlis PRO Oxford Diffraction Ltd, Yarnton, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smith, G. & Wermuth, U. D. (2010a). Acta Cryst. C66 Submitted. [FG3206]
  • Smith, G. & Wermuth, U. D. (2010b). Acta Cryst. C66 Accepted. [SU3056]
  • Smith, G., Wermuth, U. D. & Young, D. J. (2010). Acta Cryst. E66, o3160–o3161. [PMC free article] [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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