N Hydro­xy­piperidinium chloride

Acta Cryst.(2002). E58, o509±o510 DOI: 10.1107/S1600536802005792 Wolfgang Kliegelet al. C₅H₁₂NO+Clÿ

o509

organic papers

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

N

-Hydroxypiperidinium chloride

Wolfgang Kliegel,a_{Ulf Riebe,}a

Brian O. Patrick,b_{Steven J.}

Rettigb_{and James Trotter}b_*

a_{Institut fuÈr Pharmazeutische Chemie,}

Technische UniversitaÈt Braunschweig, Beethovenstrasse 55, 38106 Braunschweig, Germany, andb_{Department of Chemistry,} University of British Columbia, Vancouver, BC, Canada V6T 1Z1

Correspondence e-mail: brian@xray1.chem.ubc.ca

Key indicators Single-crystal X-ray study

T= 173 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.028

wRfactor = 0.061

Data-to-parameter ratio = 18.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

[(CH2)5NHOH]+Clÿ contains a six-membered piperidinium

ring with a chair conformation, linked to chloride ions by NÐ

H Cl and OÐH Cl hydrogen bonds. The hydroxy

substituent is in an equatorial site.

Comment

Crystals of a by-product isolated during the synthesis of a chloral adduct by reaction ofN-hydroxypiperidine and chloral hydrate (Zinneret al., 1965; Kliegelet al., 2001) proved to be

N-hydroxypiperidine hydrochloride (N-hydroxypiperidinium chloride), (I) (Fig. 1). The salt, which has been well known for a long time (Wernick & Wolffenstein, 1898; Thesing & Mayer, 1956), probably originates from the formation of HCl during the reaction by partial decomposition of chloral hydrate, the mechanism of which is not clear. The presence of water and the basic reagent (N-hydroxypiperidine) might produce HCl and dichloroacetic acid, or chloroform, which could be the source for HCl (Fairbrother, 1973; Lutnitskii, 1975).

The cation contains a six-membered piperidinium ring with a normal chair conformation (dihedral angle magnitudes 56.4± 57.8_{), and the hydroxy substituent in the equatorial site. Bond}

lengths and angles differ slightly from those in piperidinium chloride (ReÂrat, 1960; Dattagupta & Saha, 1975; Gaudetet al., 1989). In particular, there is some asymmetry in the molecular dimensions as a result of the presence of the OH H atom, which has a staggered conformation about the NÐO bond. The two OÐNÐC angles differ signi®cantly [111.4 (1) and 106.3 (1)_{], the distortion presumably resulting from}

intra-molecular (the OH H atom is on the side of the larger angle) or intermolecular (hydrogen bonds) steric interactions. There is also a slight alternation in the values of the endocyclic bond angles, with those at C1, C3, and C5 being exactly tetrahedral [109.6 (1)_{] and those at C2, C4 [111.3 (1)] and especially at N}

[112.9 (1)_{] being slightly larger. The NÐO bond length}

[1.418 (2) AÊ] is similar to that in protonated hydroxylamine (H2NOHHCl) [1.411 (2) AÊ; Shiet al., 1987].

510

anions are linked about a centre of inversion by OÐH Cl and NÐH Cl hydrogen bonds, to produce a ten-membered hydrogen-bonded ring: O Cl = 2.967 (1), OÐH = 0.92 (2), H Cl = 2.05 (2) AÊ, OÐH Cl = 170 (2)_{; N Cl = 3.044 (1),}

NÐH = 0.91 (2), H Cl = 2.14 (2) AÊ, NÐH Cl = 170 (1)_;

O Cl N = 112.0 (1)_{. These units are linked by weaker}

(van der Waals) forces, with a possible intermolecular CÐ H O bond, C O = 3.374 (2), H O = 2.44 AÊ, CÐH O = 159_{, and a possible CÐH Cl bond [C Cl = 3.624 (2),}

H Cl = 2.71 AÊ and CÐH Cl = 156_].

Experimental

Crystals were obtained as a by-product of the reaction of chloral hydrate andN-hydroxypiperidine (Kliegelet al., 2001).

Crystal data C5H12NO+Clÿ Mr= 137.61 Monoclinic,P21=c a= 7.1304 (5) AÊ b= 7.0213 (5) AÊ c= 14.4857 (9) AÊ

= 93.333 (4) V= 724.00 (7) AÊ3 Z= 4

Dx= 1.262 Mg mÿ3

Mo Kradiation Cell parameters from 4174

re¯ections

= 2.9±27.8

= 0.44 mmÿ1 T= 173 K Block, colorless 0.200.200.20 mm Data collection

Quantum CCD diffractometer

'and!scans

Absorption correction: multi-scan (d*TREK; Molecular Structure Corporation, 2001)

Tmin= 0.86,Tmax= 0.92

6650 measured re¯ections

1526 independent re¯ections 1230 re¯ections withI> 3(I) Rint= 0.029

max= 27 h=ÿ8!9 k=ÿ8!8 l=ÿ17!15 Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.028} wR(F2_{) = 0.061} S= 1.63 1526 re¯ections 81 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(Fo)]

(/)max= 0.001

max= 0.26 e AÊÿ3

min=ÿ0.29 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1ÐN1 1.418 (2)

N1ÐC1 1.484 (2)

N1ÐC5 1.490 (2)

C1ÐC2 1.515 (2)

C2ÐC3 1.524 (2)

C3ÐC4 1.516 (2)

C4ÐC5 1.514 (2)

O1ÐN1ÐC1 111.4 (1)

O1ÐN1ÐC5 106.3 (1)

C1ÐN1ÐC5 112.9 (1)

N1ÐC1ÐC2 109.6 (1)

C1ÐC2ÐC3 111.2 (1)

C2ÐC3ÐC4 109.6 (1)

C3ÐC4ÐC5 111.3 (1)

N1ÐC5ÐC4 109.6 (1)

Data collection: d*TREK (Molecular Structure Corporation, 2001); cell re®nement: d*TREK; data reduction: d*TREK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to re®ne structure:TEXSAN(Molecular Structure Corporation, 1997); software used to prepare material for publica-tion:TEXSAN.

We thank the Natural Sciences and Engineering Research Council of Canada and the Fonds der Chemische Industrie, Frankfurt am Main, for ®nancial support

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115±119.

Dattagupta, J. K. & Saha, N. N. (1975).J. Cryst. Mol. Struct.5, 177±189. Fairbrother, J. E. (1973).Analytical Pro®les of Drug Substances, Vol. 2, edited

by K. Florey, pp. 85±143. New York: Academic Press.

Gaudet, M. V., Zaworotko, M. J. & White, P. S. (1989).Inorg. Chem.28, 1191± 1193.

Kliegel, W., Riebe, U., Patrick, B. O., Rettig, S. J. & Trotter, J. (2001).Acta Cryst.E57, o1173±o1174.

Lutnitskii, F. I. (1975).Chem. Rev.75, 259±290.

Molecular Structure Corporation (1997).TEXSAN.Version 1.8. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

Molecular Structure Corporation (2001).d*TREK. Version 7.11. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

ReÂrat, C. (1960).Acta Cryst.13, 72±80.

Shi, K.-L., Wang, R.-Q. & Mak, T. C. W. (1987).J. Mol. Struct.160, 109±116. Thesing, I. & Mayer, H. (1956).Chem. Ber.89, 2159±2167.

Wernick, W. & Wolffenstein, R. (1898).Ber. Dtsch. Chem. Ges.31, 1553±1561. Zinner, G., Ritter, W. & Kliegel, W. (1965).Pharmazie,20, 291±296. Figure 1

supporting information

sup-1

supporting information

Acta Cryst. (2002). E58, o509–o510 [doi:10.1107/S1600536802005792]

N

-Hydroxypiperidinium chloride

Wolfgang Kliegel, Ulf Riebe, Brian O. Patrick, Steven J. Rettig and James Trotter

S1. Comment

Crystals of a by-product isolated during the synthesis of a chloral adduct by reaction of N-hydroxypiperidine and chloral

hydrate (Zinner et al., 1965; Kliegel et al., 2001) proved to be N-hydroxypiperidine hydrochloride (N

-hydroxy-piperidinium chloride), (I) (Fig. 1). The salt, which has been well known for a long time (Wernick & Wolffenstein, 1898;

Thesing & Mayer, 1956), probably originates from the formation of HCl during the reaction by partial decomposition of

chloral hydrate, the mechanism of which is not clear. The presence of water and the basic reagent (N-hydroxypiperidine)

might produce HCl and dichloroacetic acid, or chloroform which could be the source for HCl (Fairbrother, 1973;

Lutnitskii, 1975).

The cation contains a six-membered piperidinium ring with a normal chair conformation (dihedral angle magnitudes

56.4–57.8°), and the hydroxy substituent in the equatorial site. Bond lengths and angles differ slightly from those in

piperidinium chloride (Rérat, 1960; Dattagupta & Saha, 1975; Gaudet et al., 1989). In particular, there is some

asymmetry in the molecular dimensions as a result of the presence of the OH H atom, which has a staggered

conformation about the N—O bond. The two O—N—C angles differ significantly [111.4 (1) and 106.3 (1)°], the

distortion presumably resulting from intramolecular (the OH H atom is on the side of the larger angle) or intermolecular

(hydrogen bonds) steric interactions. There is also a slight alternation in the values of the endocyclic bond angles, with

those at C1, C3, and C5 being exactly tetrahedral [109.6 (1)°], and those at C2, C4 [111.3 (1)°] and especially at N

[112.9 (1)°] being slightly larger. The N—O bond length, 1.418 (2) Å, is similar to that in protonated hydroxylamine

(H2NOH·HCl), 1.411 (2) Å (Shi et al., 1987).

Two cations and two anions are linked about a centre of inversion by O—H···Cl and N—H···Cl hydrogen bonds, to

produce a ten-membered hydrogen-bonded ring: O···Cl = 2.967 (1), O—H = 0.92 (2), H···Cl = 2.05 (2) Å, O—H···Cl =

170 (2)°; N···Cl = 3.044 (1), N—H = 0.91 (2), H···Cl = 2.14 (2) Å, N—H···Cl = 170 (1)°; O···Cl···N = 112.0 (1)°. These

units are linked by weaker (van der Waals) forces, with a possible intermolecular C—H···O bond, C···O = 3.374 (2), H···O

= 2.44 Å, C—H···O = 159°, and a possible C—H···Cl bond [C···Cl = 3.624 (2), H···Cl = 2.71 Å and C—H···Cl = 156°].

S2. Experimental

Figure 1

View of the title structure shown with 50% ellipsoids.

(I)

Crystal data C5H12NO+·Cl−

Mr = 137.61 Monoclinic, P21/c

a = 7.1304 (5) Å b = 7.0213 (5) Å c = 14.4857 (9) Å β = 93.333 (4)° V = 724.00 (7) Å3

Z = 4

F(000) = 296 Dx = 1.262 Mg m−3

Mo Kα radiation, λ = 0.7107 Å Cell parameters from 4174 reflections θ = 2.9–27.8°

µ = 0.44 mm−1

T = 173 K Block, colorless 0.20 × 0.20 × 0.20 mm

Data collection Quantum CCD diffractometer

Radiation source: X-ray tube Graphite monochromator area detector scans

Absorption correction: multi-scan

(D*TREK; Molecular Structure Corporation,

2001)

Tmin = 0.86, Tmax = 0.92

6650 measured reflections 1526 independent reflections 1230 reflections with I > 3σ(I) Rint = 0.029

θmax = 27°, θmin = 2.9°

h = −8→9

k = −8→8

supporting information

sup-3

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.028}

wR(F2_{) = 0.061}

S = 1.63 1526 reflections 81 parameters 0 restraints

0 constraints

H atoms treated by a mixture of independent and constrained refinement

Weighting scheme based on measured s.u.'s w = 1/[σ2_(F

o)]

(Δ/σ)max = 0.001

Δρmax = 0.26 e Å−3

Δρmin = −0.29 e Å−3

Special details

Experimental. Data were collected in 0.50° oscillations with 60.0 s exposures. A sweep of data was done using φ oscillations from 0.0 to 190.0° at χ = -90° and a second sweep was performed using ω oscillations between -23.0 and 18.0° at χ = -90.0°. The crystal-to-detector distance was 38.83 mm. The detector swing angle was -10.0°. The absorption correction is based on a three-dimensional analysis of symmetry-equivalent data and is performed along with batch scaling in a single step.

Refinement. H11 and H12 (bonded to N and O respectively) were refined isotropically; the other H atoms were fixed in idealized sites.

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

x y z Uiso*/Ueq

Cl1 0.24319 (5) 0.09979 (6) 1.08369 (2) 0.0288 (1)

O1 0.1190 (2) −0.0039 (2) 0.83651 (7) 0.0312 (3)

N1 0.1981 (2) 0.1649 (2) 0.87582 (8) 0.0177 (3)

C1 0.0638 (2) 0.3262 (2) 0.86723 (9) 0.0237 (4)

C2 0.1571 (2) 0.5054 (2) 0.9058 (1) 0.0289 (4)

C3 0.3365 (2) 0.5492 (2) 0.8576 (1) 0.0298 (4)

C4 0.4680 (2) 0.3798 (2) 0.8663 (1) 0.0285 (4)

C5 0.3741 (2) 0.2008 (2) 0.82795 (9) 0.0231 (4)

H1 0.0249 0.3458 0.8019 0.028*

H2 −0.0468 0.2972 0.9019 0.028*

H3 0.0698 0.6125 0.8967 0.035*

H4 0.1880 0.4879 0.9720 0.035*

H5 0.3053 0.5756 0.7921 0.036*

H6 0.3980 0.6609 0.8865 0.036*

H7 0.5796 0.4062 0.8321 0.034*

H8 0.5055 0.3597 0.9318 0.034*

H9 0.4595 0.0924 0.8379 0.028*

H10 0.3438 0.2167 0.7615 0.028*

H11 0.227 (2) 0.142 (3) 0.937 (1) 0.044 (5)*

H12 0.007 (3) −0.020 (3) 0.865 (1) 0.067 (7)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cl1 0.0277 (2) 0.0386 (2) 0.0195 (2) −0.0037 (2) −0.0034 (1) 0.0078 (2)

O1 0.0382 (7) 0.0242 (6) 0.0317 (6) −0.0101 (6) 0.0064 (5) −0.0127 (5)

N1 0.0217 (6) 0.0176 (6) 0.0137 (6) 0.0008 (5) 0.0010 (4) −0.0006 (4)

C2 0.0330 (9) 0.0173 (8) 0.0379 (9) 0.0047 (8) 0.0143 (7) 0.0035 (7)

C3 0.0321 (9) 0.0237 (9) 0.0344 (9) −0.0055 (7) 0.0078 (7) 0.0043 (6)

C4 0.0203 (8) 0.035 (1) 0.0306 (8) −0.0022 (8) 0.0042 (6) 0.0058 (7)

C5 0.0197 (7) 0.0282 (9) 0.0221 (7) 0.0066 (7) 0.0064 (5) 0.0018 (6)

Geometric parameters (Å, º)

O1—N1 1.418 (2) C2—H4 0.98

O1—H12 0.92 (2) C3—C4 1.516 (2)

N1—C1 1.484 (2) C3—H5 0.98

N1—C5 1.490 (2) C3—H6 0.98

N1—H11 0.91 (2) C4—C5 1.514 (2)

C1—C2 1.515 (2) C4—H7 0.98

C1—H1 0.98 C4—H8 0.98

C1—H2 0.98 C5—H9 0.98

C2—C3 1.524 (2) C5—H10 0.98

C2—H3 0.98

CL1···O1i _{2.967 (1) O1···C3}iii _{3.506 (2)}

CL1···N1 3.044 (1) O1···C2iii _{3.595 (2)}

O1···C1ii _{3.374 (2)}

N1—O1—H12 105 (1) C2—C3—C4 109.6 (1)

O1—N1—C1 111.4 (1) C2—C3—H5 109.4

O1—N1—C5 106.3 (1) C2—C3—H6 109.4

O1—N1—H11 108 (1) C4—C3—H5 109.4

C1—N1—C5 112.9 (1) C4—C3—H6 109.4

C1—N1—H11 109 (1) H5—C3—H6 109.5

C5—N1—H11 109 (1) C3—C4—C5 111.3 (1)

N1—C1—C2 109.6 (1) C3—C4—H7 109.0

N1—C1—H1 109.4 C3—C4—H8 109.0

N1—C1—H2 109.4 C5—C4—H7 109.0

C2—C1—H1 109.4 C5—C4—H8 109.0

C2—C1—H2 109.4 H7—C4—H8 109.5

H1—C1—H2 109.5 N1—C5—C4 109.6 (1)

C1—C2—C3 111.2 (1) N1—C5—H9 109.4

C1—C2—H3 109.0 N1—C5—H10 109.4

C1—C2—H4 109.0 C4—C5—H9 109.4

C3—C2—H3 109.0 C4—C5—H10 109.4

C3—C2—H4 109.0 H9—C5—H10 109.5

H3—C2—H4 109.5

O1—N1—C1—C2 −177.3 (1) C1—N1—C5—C4 57.7 (1)

O1—N1—C5—C4 −179.9 (1) C1—C2—C3—C4 −56.4 (2)

N1—C1—C2—C3 56.6 (2) C2—C1—N1—C5 −57.8 (1)

N1—C5—C4—C3 −56.5 (2) C2—C3—C4—C5 56.4 (2)