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ISSN: 2056-9890

Di­methyl cis-4-hy­droxy­methyl­piperidine-2,6-di­carboxyl­ate

aFachbereich Chemie, Organische Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Strasse, D-67663 Kaiserslautern, Germany
*Correspondence e-mail: hartung@chemie.uni-kl.de

(Received 13 January 2010; accepted 23 March 2010; online 2 April 2010)

The heterocyclic core of the title compound, C10H17NO5, adopts a chair conformation with its three C substituents positioned equatorially. In the crystal, inter­molecular O—H⋯N hydrogen bonds between neighbouring mol­ecules lead to chains along b. These chains are connected by hydro­phobic inter­actions, forming infinite layers and N—H⋯O=C contacts between mol­ecules of adjacent layers give rise to a three-dimensional structure.

Related literature

For structures of related N-heterocyclic compounds, see: Parkin et al. (2004[Parkin, A., Oswald, I. D. H. & Parsons, S. (2004). Acta Cryst. B60, 219-227.]). For the synthetic procedure, see: Tang et al. (2006[Tang, R.-R., Zaho, Q., Yan, Z.-E. & Luo, Y.-M. (2006). Synth. Commun. 36, 2027-3034.]).

[Scheme 1]

Experimental

Crystal data
  • C10H17NO5

  • Mr = 231.25

  • Monoclinic, P 21 /c

  • a = 9.1403 (4) Å

  • b = 7.9153 (3) Å

  • c = 16.0199 (6) Å

  • β = 90.503 (4)°

  • V = 1158.97 (8) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 150 K

  • 0.35 × 0.25 × 0.20 mm

Data collection
  • Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector

  • 9123 measured reflections

  • 3542 independent reflections

  • 1862 reflections with I > 2σ(I)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.146

  • S = 0.89

  • 3542 reflections

  • 149 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.41 e Å−3

  • Δρmin = −0.40 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O91—H91⋯N1i 0.82 2.07 2.883 (2) 171
N1—H1⋯O4ii 0.98 (2) 2.19 (2) 3.144 (2) 165 (2)
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

The all-cis-isomer of 4-(hydroxymethyl)-piperidine-2,6-dicarboxylic acid dimethyl ester, (I), represents a potential tridentate ONO-donor ligand for development of a new generation of solid phase-bound oxidation catalysts. Its three C substituents were equatorially attached to piperidine adopting a 1C4-chair conformation (Figure 1). A quartett structure (J = 12.4 Hz) in the nuclear magnetic resonance (NMR) spectrum for axially connected protons to C3 and C5 provided evidence that this arrangement corresponded to the most significantly populated conformer of (I) in solution (CDCl3, 298 K). The amino H-atom was found in axial position. The arrangement that is thermodynamically favored, i.e. equatorial NH positioning, was reported for the crystal structure of piperidine and its structurally closely related derivatives morpholine and piperazine (Parkin et al., 2004).

Intermolecular O–H···N bridges between proximate molecules lead to chains along b. The chains are additionally connected by hydrophobic interactions to form layers. N–H···OC contacts between molecules of adjascent layers give rise to a three dimensional structure (Figure 2).

Related literature top

For structures of related N-heterocyclic compounds, see: Parkin et al. (2004). For the synthetic procedure, see: Tang et al. (2006).

Experimental top

Pd/C [200 mg, 10 % (w/w)] was added to a solution of dimethyl 4-(hydroxymethyl)-pyridine-2,5-dicarboxylate (400 mg, 1.78 mmol; Tang et al., 2006) in AcOEt (100 ml). The mixture was transferred into a hydrogenating apparatus and stirred at a pressure of 3.5 bar for 14 h at 298 K in an atmosphere of H2. The hydrogen pressure constantly decrased until a constant value of 2.4 bar was reached when the reaction stopped. The reaction mixture was filtrated through a short pad of celite. The filtrate was concentrated under reduced pressure. The remaining oil was covered with a layer of AcOEt (5 ml) and allowed to rest for 1 h at 277 K. Colorless crystals that deposited were collected by filtration. Yield: 139 mg (34 %); mp 372 K. 1H NMR (400 MHz, CDCl3, δH p.p.m.): 1.15 (q, J = 12.4 Hz, 2H), 1.78 (m, 1H), 2.13 (d, J = 12.4 Hz, 2H), 3.43 (dd, J = 11.7 Hz, 2.5 Hz, 2H), 3.55 (d, J = 6.3 Hz, 2H), 3.74 (s, 6H). 13C NMR (101 MHz, CDCl3 δC p.p.m.): 31.7, 38.7, 52.1, 57.9, 67.4, 172.7. Analytical data calculated for all-cis-4-(hydroxymethyl)-piperidine-2,6-dicarboxylic acid dimethyl ester: C, 51.94; H, 7.41; N, 6.06; found: C, 52.34; H, 7.46; N, 6.02.

Refinement top

The hydrogen bonded to N1 was refined freely. The hydrogen bonded to O91 was positioned as idealized OH group with C—O—H angle tetrahedral and as riding atom with Uiso(H)=1.5 times Ueq(O91). All other H Atoms were positioned geometrically and treated as riding atoms (C—H = 0.97-0.98 Å), with Uiso(H)=1.2 or 1.5 times Ueq(C).

Structure description top

The all-cis-isomer of 4-(hydroxymethyl)-piperidine-2,6-dicarboxylic acid dimethyl ester, (I), represents a potential tridentate ONO-donor ligand for development of a new generation of solid phase-bound oxidation catalysts. Its three C substituents were equatorially attached to piperidine adopting a 1C4-chair conformation (Figure 1). A quartett structure (J = 12.4 Hz) in the nuclear magnetic resonance (NMR) spectrum for axially connected protons to C3 and C5 provided evidence that this arrangement corresponded to the most significantly populated conformer of (I) in solution (CDCl3, 298 K). The amino H-atom was found in axial position. The arrangement that is thermodynamically favored, i.e. equatorial NH positioning, was reported for the crystal structure of piperidine and its structurally closely related derivatives morpholine and piperazine (Parkin et al., 2004).

Intermolecular O–H···N bridges between proximate molecules lead to chains along b. The chains are additionally connected by hydrophobic interactions to form layers. N–H···OC contacts between molecules of adjascent layers give rise to a three dimensional structure (Figure 2).

For structures of related N-heterocyclic compounds, see: Parkin et al. (2004). For the synthetic procedure, see: Tang et al. (2006).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis CCD (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Version 1.08; Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of (I) (50% probability displacement ellipsoids)
[Figure 2] Fig. 2. Three dimensional structure of (I) in the solid state with intermolecular O–H···N bridges and N–H···OC contacts (50% probability displacement ellipsoids for all non H-atoms).
Dimethyl cis-4-hydroxymethylpiperidine-2,6-dicarboxylate top
Crystal data top
C10H17NO5F(000) = 496
Mr = 231.25Dx = 1.325 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2439 reflections
a = 9.1403 (4) Åθ = 3.6–31.2°
b = 7.9153 (3) ŵ = 0.11 mm1
c = 16.0199 (6) ÅT = 150 K
β = 90.503 (4)°Prism, colourless
V = 1158.97 (8) Å30.35 × 0.25 × 0.20 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
1862 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.045
Graphite monochromatorθmax = 31.1°, θmin = 3.6°
Detector resolution: 16.1399 pixels mm-1h = 1313
Rotation method data acquisition using ω and phi scansk = 1111
9123 measured reflectionsl = 2323
3542 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.044 w = 1/[σ2(Fo2) + (0.0827P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.146(Δ/σ)max < 0.001
S = 0.89Δρmax = 0.41 e Å3
3542 reflectionsΔρmin = 0.40 e Å3
149 parameters
Crystal data top
C10H17NO5V = 1158.97 (8) Å3
Mr = 231.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.1403 (4) ŵ = 0.11 mm1
b = 7.9153 (3) ÅT = 150 K
c = 16.0199 (6) Å0.35 × 0.25 × 0.20 mm
β = 90.503 (4)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
1862 reflections with I > 2σ(I)
9123 measured reflectionsRint = 0.045
3542 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 0.89Δρmax = 0.41 e Å3
3542 reflectionsΔρmin = 0.40 e Å3
149 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.74419 (16)0.02707 (16)0.01230 (8)0.0237 (3)
C20.64855 (17)0.13614 (18)0.06151 (9)0.0220 (3)
H20.55070.1330.03610.026*
O40.94904 (13)0.11150 (15)0.09219 (7)0.0312 (3)
C80.85668 (18)0.01946 (19)0.12238 (10)0.0249 (3)
C70.63717 (18)0.0686 (2)0.14932 (9)0.0255 (3)
O10.51869 (14)0.13296 (16)0.18655 (7)0.0320 (3)
C50.80958 (17)0.27664 (19)0.07663 (10)0.0241 (3)
H5A0.90910.28310.05540.029*
H5B0.80930.31540.13410.029*
C40.71060 (17)0.39036 (18)0.02456 (9)0.0223 (3)
H40.61260.38870.04980.027*
O910.67225 (15)0.67327 (15)0.02363 (8)0.0405 (3)
H910.70150.77120.02310.061*
O30.72305 (16)0.02473 (18)0.18282 (8)0.0434 (4)
C60.75608 (17)0.09224 (19)0.07327 (9)0.0226 (3)
H60.65880.08730.09940.027*
C30.69913 (18)0.32103 (19)0.06401 (9)0.0244 (3)
H3A0.62980.3880.09540.029*
H3B0.79360.32840.09180.029*
O20.83440 (15)0.00053 (17)0.20437 (7)0.0370 (3)
C90.7656 (2)0.5714 (2)0.02568 (11)0.0312 (4)
H9A0.86470.5760.00360.037*
H9B0.76670.61320.08260.037*
C100.4996 (2)0.0889 (3)0.27333 (10)0.0396 (5)
H10A0.41180.14060.29370.059*
H10B0.5820.12850.30530.059*
H10C0.49210.03160.27860.059*
C110.9277 (2)0.1006 (3)0.25831 (11)0.0452 (5)
H11A0.9030.07820.31560.068*
H11B0.91360.21840.24670.068*
H11C1.02820.07120.24820.068*
H10.844 (2)0.032 (2)0.0344 (10)0.029 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0317 (7)0.0181 (6)0.0214 (6)0.0003 (5)0.0046 (5)0.0005 (5)
C20.0248 (7)0.0212 (7)0.0200 (7)0.0011 (6)0.0032 (5)0.0000 (6)
O40.0339 (7)0.0266 (6)0.0333 (6)0.0032 (5)0.0035 (5)0.0026 (5)
C80.0287 (8)0.0208 (7)0.0251 (7)0.0036 (6)0.0040 (6)0.0041 (6)
C70.0321 (8)0.0213 (7)0.0232 (7)0.0057 (7)0.0031 (6)0.0016 (6)
O10.0380 (7)0.0373 (7)0.0207 (5)0.0014 (5)0.0079 (5)0.0013 (5)
C50.0274 (8)0.0190 (7)0.0259 (7)0.0013 (6)0.0064 (6)0.0014 (6)
C40.0253 (7)0.0184 (7)0.0231 (7)0.0027 (6)0.0043 (6)0.0002 (6)
O910.0442 (8)0.0196 (5)0.0581 (8)0.0000 (5)0.0194 (6)0.0033 (6)
O30.0477 (8)0.0485 (8)0.0339 (7)0.0122 (7)0.0056 (6)0.0150 (6)
C60.0251 (7)0.0217 (7)0.0212 (7)0.0027 (6)0.0033 (5)0.0021 (6)
C30.0313 (9)0.0189 (7)0.0230 (7)0.0006 (6)0.0033 (6)0.0009 (6)
O20.0438 (7)0.0435 (7)0.0237 (6)0.0123 (6)0.0059 (5)0.0065 (5)
C90.0373 (9)0.0213 (7)0.0352 (9)0.0015 (7)0.0100 (7)0.0010 (7)
C100.0503 (11)0.0494 (11)0.0193 (7)0.0053 (9)0.0072 (7)0.0037 (8)
C110.0501 (12)0.0546 (12)0.0312 (9)0.0183 (10)0.0096 (8)0.0111 (9)
Geometric parameters (Å, º) top
N1—C21.4640 (19)C4—C31.526 (2)
N1—C61.4696 (19)C4—H40.98
N1—H10.98 (2)O91—C91.420 (2)
C2—C71.509 (2)O91—H910.82
C2—C31.535 (2)C6—H60.98
C2—H20.98C3—H3A0.97
O4—C81.212 (2)C3—H3B0.97
C8—O21.3358 (19)O2—C111.454 (2)
C8—C61.503 (2)C9—H9A0.97
C7—O31.201 (2)C9—H9B0.97
C7—O11.341 (2)C10—H10A0.96
O1—C101.4452 (18)C10—H10B0.96
C5—C41.529 (2)C10—H10C0.96
C5—C61.540 (2)C11—H11A0.96
C5—H5A0.97C11—H11B0.96
C5—H5B0.97C11—H11C0.96
C4—C91.519 (2)
C2—N1—C6110.16 (12)N1—C6—C5113.04 (12)
C2—N1—H1110.1 (10)C8—C6—C5110.08 (12)
C6—N1—H1104.3 (10)N1—C6—H6108.1
N1—C2—C7109.83 (12)C8—C6—H6108.1
N1—C2—C3113.27 (12)C5—C6—H6108.1
C7—C2—C3109.67 (12)C4—C3—C2109.98 (12)
N1—C2—H2108C4—C3—H3A109.7
C7—C2—H2108C2—C3—H3A109.7
C3—C2—H2108C4—C3—H3B109.7
O4—C8—O2124.00 (14)C2—C3—H3B109.7
O4—C8—C6124.87 (14)H3A—C3—H3B108.2
O2—C8—C6111.10 (14)C8—O2—C11115.98 (14)
O3—C7—O1124.19 (14)O91—C9—C4109.19 (13)
O3—C7—C2125.75 (15)O91—C9—H9A109.8
O1—C7—C2110.01 (13)C4—C9—H9A109.8
C7—O1—C10116.17 (14)O91—C9—H9B109.8
C4—C5—C6110.44 (12)C4—C9—H9B109.8
C4—C5—H5A109.6H9A—C9—H9B108.3
C6—C5—H5A109.6O1—C10—H10A109.5
C4—C5—H5B109.6O1—C10—H10B109.5
C6—C5—H5B109.6H10A—C10—H10B109.5
H5A—C5—H5B108.1O1—C10—H10C109.5
C9—C4—C3112.07 (13)H10A—C10—H10C109.5
C9—C4—C5110.57 (13)H10B—C10—H10C109.5
C3—C4—C5109.96 (13)O2—C11—H11A109.5
C9—C4—H4108O2—C11—H11B109.5
C3—C4—H4108H11A—C11—H11B109.5
C5—C4—H4108O2—C11—H11C109.5
C9—O91—H91109.5H11A—C11—H11C109.5
N1—C6—C8109.41 (13)H11B—C11—H11C109.5
C6—N1—C2—C7179.88 (13)O2—C8—C6—N1159.66 (13)
C6—N1—C2—C356.88 (17)O4—C8—C6—C5102.51 (18)
N1—C2—C7—O321.3 (2)O2—C8—C6—C575.56 (17)
C3—C2—C7—O3103.81 (18)C4—C5—C6—N155.54 (18)
N1—C2—C7—O1160.97 (13)C4—C5—C6—C8178.22 (13)
C3—C2—C7—O173.94 (16)C9—C4—C3—C2177.93 (13)
O3—C7—O1—C102.2 (2)C5—C4—C3—C254.53 (17)
C2—C7—O1—C10175.62 (14)N1—C2—C3—C457.03 (17)
C6—C5—C4—C9178.34 (13)C7—C2—C3—C4179.89 (13)
C6—C5—C4—C354.06 (17)O4—C8—O2—C110.9 (2)
C2—N1—C6—C8179.01 (13)C6—C8—O2—C11178.96 (15)
C2—N1—C6—C555.96 (17)C3—C4—C9—O9156.50 (19)
O4—C8—C6—N122.3 (2)C5—C4—C9—O91179.57 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O91—H91···N1i0.822.072.883 (2)171
N1—H1···O4ii0.98 (2)2.19 (2)3.144 (2)165 (2)
Symmetry codes: (i) x, y+1, z; (ii) x+2, y, z.

Experimental details

Crystal data
Chemical formulaC10H17NO5
Mr231.25
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)9.1403 (4), 7.9153 (3), 16.0199 (6)
β (°) 90.503 (4)
V3)1158.97 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.35 × 0.25 × 0.20
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9123, 3542, 1862
Rint0.045
(sin θ/λ)max1)0.726
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.146, 0.89
No. of reflections3542
No. of parameters149
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.41, 0.40

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Version 1.08; Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O91—H91···N1i0.822.072.883 (2)170.9
N1—H1···O4ii0.98 (2)2.19 (2)3.144 (2)165 (2)
Symmetry codes: (i) x, y+1, z; (ii) x+2, y, z.
 

Acknowledgements

This work was supported by the Deutsche Forschungsgemeinschaft (grant Ha1705/8-2).

References

First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationOxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.  Google Scholar
First citationParkin, A., Oswald, I. D. H. & Parsons, S. (2004). Acta Cryst. B60, 219–227.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTang, R.-R., Zaho, Q., Yan, Z.-E. & Luo, Y.-M. (2006). Synth. Commun. 36, 2027–3034.  Web of Science CrossRef CAS Google Scholar

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