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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2233.
Published online 2008 October 31. doi:  10.1107/S1600536808034922
PMCID: PMC2959576

2-(Hydroxy­meth­yl)pyridinium chloride

Abstract

In the title molecular salt, C6H8NO+·Cl, the packing is consolidated by N—H(...)Cl and O—H(...)Cl hydrogen bonds, resulting in the formation of [010] chains of alternating cations and anions.

Related literature

The title compound was initially isolated by Boyle et al. (2008 [triangle]). Only the di-substituted pyridine carbonyl HCl salt has been reported previously (Fites et al., 2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2233-scheme1.jpg

Experimental

Crystal data

  • C6H8NO+·Cl
  • M r = 145.58
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2233-efi1.jpg
  • a = 7.0689 (9) Å
  • b = 8.0833 (11) Å
  • c = 12.1304 (16) Å
  • β = 102.078 (2)°
  • V = 677.79 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.47 mm−1
  • T = 173 (2) K
  • 0.25 × 0.22 × 0.20 mm

Data collection

  • Bruker APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1999 [triangle]) T min = 0.867, T max = 0.909
  • 4681 measured reflections
  • 1227 independent reflections
  • 1202 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.092
  • S = 1.26
  • 1227 reflections
  • 87 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XSHELL (Bruker, 2000 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034922/kj2102sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034922/kj2102Isup2.hkl

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

Acknowledgments

For support of this research, the authors thank the Office of Basic Energy Science and the US Department of Energy under Contract DE—AC04–94 A L85000. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy.

supplementary crystallographic information

Comment

Figure 1 shows an atomic displacement ellipsoid plot of 2(hydroxymethyl)pyridinium chloride. The title compound was synthesized through the dissolution of bis(pyridine carbonoxide)titanium(dichloride), (OPy)2TiCl2, in H2O/HCl(5%). The synthesis was optimized by dissolving HOPy in H2O/HCl(5%). Fites, et al. (2006) reported the disubstituted salt structure which was isolated from a vanadium 2,6-pyridinedimethanol complex at low pH solutions. This is in agreement to what Boyle et al.(2008) found, where the title compound was isolated from low pH aqueous solutions of the titanium monosubstituted pyridinemethanol complex.

Figure 2 displays the packing arrangement of four molecules of the title compound with the Cl···H interactions that occur between adjacent molecules. The Cl interacts with the pyridinium (N1—H7···Cl1) and alcohol protons (O1—H1···Cl1), with a greater interaction observed with the alcohol, as listed in Table 1. The hydrogen bond angles for O1—H1···Cl1 and N1—H7···Cl1 are in agreement with literature angles and intermolecular interactions. In comparison, the disubstituted structure by Fites, et al. (2006) showed a stronger Cl binding potential with respect to the pyridinium proton (H···Cl = 2.208 Å) and a slightly weaker interaction with the alcohol (H···Cl 2.37 Å). Figure 2 also displays the pattern of H···Cl bonding throughout the unit cells. The individual molecules are related by a 21 screw axis parallel to the b axis of the structure. The alternating interaction of the Cl between the pyridinium proton and the alcohol proton yields a intermolecular chain along the b axis.

Experimental

2(Hydroxymethyl)pyridinium chloride was isolated by Boyle et al.(2008) through the dissolution of a titanium precursor, bis(pyridine carbonoxide)titanium(dichloride) or (OPy)2TiCl2, (where OPy = pyridine carbonoxide) in acidified water (5% of conc. HCl in water). In order to optimize the synthesis of this salt, crystal were grown via HOPy in acidified water (5% of conc. HCl in water). After slow evaporation, X-ray quality crystals were isolated and characterized by single-crystal X-ray, FTIR, NMR, and EA.

Refinement

H1 (which is bound to O1 of the methanol group) was placed on ideal position, allowed to rotate around the C—O bond and refined via a riding model while H7 was located on difference Fourier maps and allowed to refine freely.

Figures

Fig. 1.
The molecular structure of the title compound, with atom labels and 50% probability atomic displacement ellipsoids for non-H atoms. The Cl atom has been translated to clarify interaction with the OH group.
Fig. 2.
Packing of the title compound on the b-c plane illustrating the NH—Cl—OH intermolecular chain interaction which proceeds parallel to the b axis via the 21 screw axis.

Crystal data

C6H8NO+·ClF(000) = 304
Mr = 145.58Dx = 1.427 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 200 reflections
a = 7.0689 (9) Åθ = 3.1–25.2°
b = 8.0833 (11) ŵ = 0.48 mm1
c = 12.1304 (16) ÅT = 173 K
β = 102.078 (2)°Irregular, colorless
V = 677.79 (15) Å30.25 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer1227 independent reflections
Radiation source: fine-focus sealed tube1202 reflections with I > 2σ(I)
graphiteRint = 0.020
[var phi] and ω scansθmax = 25.2°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)h = −8→8
Tmin = 0.867, Tmax = 0.909k = −9→9
4681 measured reflectionsl = −14→13

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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.26w = 1/[σ2(Fo2) + (0.0271P)2 + 0.6606P] where P = (Fo2 + 2Fc2)/3
1227 reflections(Δ/σ)max < 0.001
87 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
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
Cl10.10702 (9)0.46272 (7)0.68760 (4)0.0311 (2)
N10.2053 (3)0.4526 (2)−0.05399 (16)0.0213 (4)
O10.0732 (2)0.1503 (2)−0.10825 (13)0.0292 (4)
H10.14980.1040−0.14030.044*
C10.2214 (3)0.3472 (3)0.03263 (18)0.0220 (5)
C40.3390 (3)0.6739 (3)0.0620 (2)0.0299 (5)
H40.37730.78400.07150.036*
C50.2628 (3)0.6116 (3)−0.04288 (19)0.0264 (5)
H50.25090.6789−0.10620.032*
C30.3576 (3)0.5680 (3)0.1541 (2)0.0312 (6)
H30.41040.60740.22600.037*
C20.2989 (3)0.4061 (3)0.14015 (19)0.0271 (5)
H20.31090.33640.20220.033*
C60.1592 (3)0.1715 (3)0.00685 (18)0.0273 (5)
H6A0.27080.09930.02660.033*
H6B0.06740.14020.05240.033*
H70.165 (4)0.414 (3)−0.118 (2)0.027 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0410 (4)0.0293 (3)0.0204 (3)−0.0037 (2)0.0005 (2)0.0035 (2)
N10.0213 (9)0.0237 (10)0.0181 (9)0.0011 (8)0.0023 (7)−0.0017 (8)
O10.0326 (9)0.0303 (9)0.0229 (8)−0.0027 (7)0.0015 (7)−0.0028 (7)
C10.0194 (11)0.0260 (11)0.0209 (11)0.0026 (9)0.0050 (8)0.0030 (9)
C40.0264 (12)0.0236 (12)0.0391 (14)−0.0003 (10)0.0052 (10)−0.0071 (10)
C50.0266 (12)0.0228 (12)0.0305 (12)0.0038 (9)0.0076 (9)0.0029 (10)
C30.0271 (12)0.0382 (14)0.0266 (12)0.0034 (11)0.0018 (9)−0.0102 (11)
C20.0273 (12)0.0340 (13)0.0197 (11)0.0033 (10)0.0038 (9)0.0012 (10)
C60.0323 (13)0.0260 (12)0.0223 (11)−0.0020 (10)0.0026 (9)0.0028 (9)

Geometric parameters (Å, °)

N1—C11.339 (3)C4—C31.392 (4)
N1—C51.347 (3)C4—H40.9300
N1—H70.83 (3)C5—H50.9300
O1—C61.412 (3)C3—C21.372 (3)
O1—H10.8200C3—H30.9300
C1—C21.389 (3)C2—H20.9300
C1—C61.500 (3)C6—H6A0.9700
C4—C51.370 (3)C6—H6B0.9700
C1—N1—C5123.7 (2)C2—C3—C4120.8 (2)
C1—N1—H7116.8 (18)C2—C3—H3119.6
C5—N1—H7119.3 (18)C4—C3—H3119.6
C6—O1—H1109.5C3—C2—C1119.5 (2)
N1—C1—C2118.1 (2)C3—C2—H2120.2
N1—C1—C6117.76 (19)C1—C2—H2120.2
C2—C1—C6124.2 (2)O1—C6—C1111.60 (18)
C5—C4—C3118.2 (2)O1—C6—H6A109.3
C5—C4—H4120.9C1—C6—H6A109.3
C3—C4—H4120.9O1—C6—H6B109.3
N1—C5—C4119.7 (2)C1—C6—H6B109.3
N1—C5—H5120.1H6A—C6—H6B108.0
C4—C5—H5120.1

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···Cl1i0.822.243.0409 (18)167
N1—H7···Cl1ii0.83 (3)2.34 (3)3.067 (2)146 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2102).

References

  • Boyle, T. J., Ottley, L. M., Rodriguez, M. A., Sewell, R. M., Alam, T. M. & McIntyre, S. K. (2008). Inorg. Chem Submitted. [PubMed]
  • Bruker (1998). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2000). XSHELL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2001). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fites, R. J., Yeager, A. T., Sarvela, T. L., Howard, W. A., Zhu, G. & Pang, K. (2006). Inorg. Chim. Acta, 359, 248–256.
  • Sheldrick, G. M. (1999). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography