2-(Hydroxy­meth­yl)pyridinium chloride

Ottley, L.A.M.; Rodriguez, M.A.; Boyle, T.J.

doi:10.1107/S1600536808034922

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2233

doi:10.1107/S1600536808034922

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2-(Hydroxymethyl)pyridinium chloride

Leigh Anna M. Ottley,^a ^* Mark A. Rodriguez ^b and Timothy J. Boyle ^a

^aSandia National Laboratories, Advanced Materials Laboratories, 1001 University Blvd. SE, Albuquerque, NM 87106, USA, and ^bPO Box 5800, MS 1411, Sandia National Laboratories, Albuquerque, NM 87185, USA
^*Correspondence e-mail: laottle@sandia.gov

(Received 2 September 2008; accepted 27 October 2008; online 31 October 2008)

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 ). Only the di-substituted pyridine carbonyl HCl salt has been reported previously (Fites et al., 2006 ).

Experimental

Crystal data

C₆H₈NO⁺·Cl⁻
M_r = 145.58
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.092
S = 1.26
1227 reflections
87 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1ⁱ	0.82	2.24	3.0409 (18)	167
N1—H7⋯Cl1ⁱⁱ	0.83 (3)	2.34 (3)	3.067 (2)	146 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y, z-1.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

2-(Hydroxymethyl)pyridinium chloride top

Crystal data top

C₆H₈NO⁺·Cl⁻	F(000) = 304
M_r = 145.58	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 200 reflections
a = 7.0689 (9) Å	θ = 3.1–25.2°
b = 8.0833 (11) Å	µ = 0.48 mm⁻¹
c = 12.1304 (16) Å	T = 173 K
β = 102.078 (2)°	Irregular, colorless
V = 677.79 (15) Å³	0.25 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	1227 independent reflections
Radiation source: fine-focus sealed tube	1202 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.2°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −8→8
T_min = 0.867, T_max = 0.909	k = −9→9
4681 measured reflections	l = −14→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ²(F_o²) + (0.0271P)² + 0.6606P] where P = (F_o² + 2F_c²)/3
1227 reflections	(Δ/σ)_max < 0.001
87 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₆H₈NO⁺·Cl⁻	V = 677.79 (15) Å³
M_r = 145.58	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0689 (9) Å	µ = 0.48 mm⁻¹
b = 8.0833 (11) Å	T = 173 K
c = 12.1304 (16) Å	0.25 × 0.22 × 0.20 mm
β = 102.078 (2)°

Data collection top

Bruker APEX CCD area-detector diffractometer	1227 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	1202 reflections with I > 2σ(I)
T_min = 0.867, T_max = 0.909	R_int = 0.020
4681 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	Δρ_max = 0.28 e Å⁻³
1227 reflections	Δρ_min = −0.23 e Å⁻³
87 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.10702 (9)	0.46272 (7)	0.68760 (4)	0.0311 (2)
N1	0.2053 (3)	0.4526 (2)	−0.05399 (16)	0.0213 (4)
O1	0.0732 (2)	0.1503 (2)	−0.10825 (13)	0.0292 (4)
H1	0.1498	0.1040	−0.1403	0.044*
C1	0.2214 (3)	0.3472 (3)	0.03263 (18)	0.0220 (5)
C4	0.3390 (3)	0.6739 (3)	0.0620 (2)	0.0299 (5)
H4	0.3773	0.7840	0.0715	0.036*
C5	0.2628 (3)	0.6116 (3)	−0.04288 (19)	0.0264 (5)
H5	0.2509	0.6789	−0.1062	0.032*
C3	0.3576 (3)	0.5680 (3)	0.1541 (2)	0.0312 (6)
H3	0.4104	0.6074	0.2260	0.037*
C2	0.2989 (3)	0.4061 (3)	0.14015 (19)	0.0271 (5)
H2	0.3109	0.3364	0.2022	0.033*
C6	0.1592 (3)	0.1715 (3)	0.00685 (18)	0.0273 (5)
H6A	0.2708	0.0993	0.0266	0.033*
H6B	0.0674	0.1402	0.0524	0.033*
H7	0.165 (4)	0.414 (3)	−0.118 (2)	0.027 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0410 (4)	0.0293 (3)	0.0204 (3)	−0.0037 (2)	0.0005 (2)	0.0035 (2)
N1	0.0213 (9)	0.0237 (10)	0.0181 (9)	0.0011 (8)	0.0023 (7)	−0.0017 (8)
O1	0.0326 (9)	0.0303 (9)	0.0229 (8)	−0.0027 (7)	0.0015 (7)	−0.0028 (7)
C1	0.0194 (11)	0.0260 (11)	0.0209 (11)	0.0026 (9)	0.0050 (8)	0.0030 (9)
C4	0.0264 (12)	0.0236 (12)	0.0391 (14)	−0.0003 (10)	0.0052 (10)	−0.0071 (10)
C5	0.0266 (12)	0.0228 (12)	0.0305 (12)	0.0038 (9)	0.0076 (9)	0.0029 (10)
C3	0.0271 (12)	0.0382 (14)	0.0266 (12)	0.0034 (11)	0.0018 (9)	−0.0102 (11)
C2	0.0273 (12)	0.0340 (13)	0.0197 (11)	0.0033 (10)	0.0038 (9)	0.0012 (10)
C6	0.0323 (13)	0.0260 (12)	0.0223 (11)	−0.0020 (10)	0.0026 (9)	0.0028 (9)

Geometric parameters (Å, º) top

N1—C1	1.339 (3)	C4—C3	1.392 (4)
N1—C5	1.347 (3)	C4—H4	0.9300
N1—H7	0.83 (3)	C5—H5	0.9300
O1—C6	1.412 (3)	C3—C2	1.372 (3)
O1—H1	0.8200	C3—H3	0.9300
C1—C2	1.389 (3)	C2—H2	0.9300
C1—C6	1.500 (3)	C6—H6A	0.9700
C4—C5	1.370 (3)	C6—H6B	0.9700

C1—N1—C5	123.7 (2)	C2—C3—C4	120.8 (2)
C1—N1—H7	116.8 (18)	C2—C3—H3	119.6
C5—N1—H7	119.3 (18)	C4—C3—H3	119.6
C6—O1—H1	109.5	C3—C2—C1	119.5 (2)
N1—C1—C2	118.1 (2)	C3—C2—H2	120.2
N1—C1—C6	117.76 (19)	C1—C2—H2	120.2
C2—C1—C6	124.2 (2)	O1—C6—C1	111.60 (18)
C5—C4—C3	118.2 (2)	O1—C6—H6A	109.3
C5—C4—H4	120.9	C1—C6—H6A	109.3
C3—C4—H4	120.9	O1—C6—H6B	109.3
N1—C5—C4	119.7 (2)	C1—C6—H6B	109.3
N1—C5—H5	120.1	H6A—C6—H6B	108.0
C4—C5—H5	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.82	2.24	3.0409 (18)	167
N1—H7···Cl1ⁱⁱ	0.83 (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.

Experimental details

Crystal data
Chemical formula	C₆H₈NO⁺·Cl⁻
M_r	145.58
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	7.0689 (9), 8.0833 (11), 12.1304 (16)
β (°)	102.078 (2)
V (Å³)	677.79 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.25 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1999)
T_min, T_max	0.867, 0.909
No. of measured, independent and observed [I > 2σ(I)] reflections	4681, 1227, 1202
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.093, 1.26
No. of reflections	1227
No. of parameters	87
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.23

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XSHELL (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.82	2.24	3.0409 (18)	166.9
N1—H7···Cl1ⁱⁱ	0.83 (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.

Acknowledgements

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.

References

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