2-(Dihydroxy­meth­yl)pyridinium chloride

Qian, H.-F.; Huang, W.

doi:10.1107/S1600536810006604

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o695

doi:10.1107/S1600536810006604

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2-(Dihydroxymethyl)pyridinium chloride

Hui-Fen Qian ^a ^* and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn,

(Received 18 January 2010; accepted 20 February 2010; online 27 February 2010)

In the title compound, C₆H₈NO₂⁺·Cl⁻, intermolecular O—H⋯Cl and N—H⋯Cl hydrogen bonds are observed in which each chloride anion links three adjacent cations into a hydrogen-bond network.

Related literature

For a related compound, see Mantero et al. (2006 ).

Experimental

Crystal data

C₆H₈NO₂⁺·Cl⁻
M_r = 161.58
Monoclinic, P 2₁ /c
a = 4.6879 (7) Å
b = 15.557 (2) Å
c = 10.1199 (14) Å
β = 91.181 (2)°
V = 737.88 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 291 K
0.12 × 0.12 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.948, T_max = 0.956
3676 measured reflections
1303 independent reflections
842 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.075
S = 0.89
1303 reflections
99 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 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
O2—H2A⋯Cl1ⁱ	0.85 (1)	2.24 (1)	3.089 (2)	176 (2)
O1—H1A⋯Cl1ⁱⁱ	0.85 (1)	2.19 (1)	3.0374 (18)	177 (3)
N1—H1⋯Cl1ⁱⁱⁱ	0.86	2.33	3.115 (2)	151
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1; (iii) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006604/bg2326sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006604/bg2326Isup2.hkl

checkCIF report

Comment top

The crystal structure of pyridin-4-ylmethanediol, namely the hydrated form of isonicotinaldehyde has been previously reported (Mantero et al., 2006). In this paper, we report the X-ray single-crystal structure of pyridin-2-ylmethanediol-1-ium chloride (I).

The molecular structure of (I) is illustrated in Fig. 1. The two hydroxyl groups lie at the same side of the aromatic ring. In the crystal packing, intermolecular O—H···Cl and N—H···Cl hydrogen bonding interactions are observed where every chloride anion links three adjacent molecules into a hydrogen-bond sustained network (Fig. 2).

Related literature top

For a related compound, see Mantero et al. (2006).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Perspective view of the hydrogen bonding interactions in the crystal packing of (I), where the hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x - 1, -y+3/2, z + 1/2; (ii) x, y1/2, z + 1; (iii) x, -y+3/2, z + 1/2.]

2-(Dihydroxymethyl)pyridinium chloride top

Crystal data top

C₆H₈NO₂⁺·Cl⁻	F(000) = 336
M_r = 161.58	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 776 reflections
a = 4.6879 (7) Å	θ = 2.4–21.0°
b = 15.557 (2) Å	µ = 0.45 mm⁻¹
c = 10.1199 (14) Å	T = 291 K
β = 91.181 (2)°	Block, colourless
V = 737.88 (18) Å³	0.12 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1303 independent reflections
Radiation source: fine-focus sealed tube	842 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→5
T_min = 0.948, T_max = 0.956	k = −12→18
3676 measured reflections	l = −12→10

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.89	w = 1/[σ²(F_o²) + (0.0272P)²] where P = (F_o² + 2F_c²)/3
1303 reflections	(Δ/σ)_max = 0.001
99 parameters	Δρ_max = 0.22 e Å⁻³
2 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₆H₈NO₂⁺·Cl⁻	V = 737.88 (18) Å³
M_r = 161.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.6879 (7) Å	µ = 0.45 mm⁻¹
b = 15.557 (2) Å	T = 291 K
c = 10.1199 (14) Å	0.12 × 0.12 × 0.10 mm
β = 91.181 (2)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1303 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	842 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.956	R_int = 0.058
3676 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	2 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.89	Δρ_max = 0.22 e Å⁻³
1303 reflections	Δρ_min = −0.23 e Å⁻³
99 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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.

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
C1	0.0342 (4)	0.62701 (15)	0.8930 (2)	0.0395 (6)
C2	0.1167 (5)	0.54999 (16)	0.8429 (2)	0.0469 (6)
H2	0.2515	0.5168	0.8883	0.056*
C3	0.0002 (5)	0.52104 (16)	0.7246 (2)	0.0544 (7)
H3	0.0549	0.4681	0.6906	0.065*
C4	−0.1975 (5)	0.57099 (17)	0.6572 (2)	0.0553 (7)
H4	−0.2792	0.5519	0.5780	0.066*
C5	−0.2716 (5)	0.64860 (17)	0.7082 (2)	0.0504 (7)
H5	−0.4015	0.6836	0.6630	0.060*
C6	0.1322 (5)	0.66291 (15)	1.0257 (2)	0.0448 (6)
H6	0.0102	0.6382	1.0935	0.054*
Cl1	0.51126 (13)	0.65293 (4)	0.34503 (6)	0.0572 (2)
H1A	0.442 (6)	0.6405 (18)	1.1316 (11)	0.090 (11)*
H2A	0.211 (5)	0.7784 (16)	0.978 (2)	0.080 (11)*
N1	−0.1571 (4)	0.67433 (12)	0.82335 (17)	0.0424 (5)
H1	−0.2077	0.7233	0.8546	0.051*
O1	0.4092 (3)	0.63308 (12)	1.04924 (17)	0.0573 (5)
O2	0.1066 (4)	0.75152 (12)	1.03217 (17)	0.0567 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0371 (13)	0.0428 (15)	0.0389 (13)	−0.0011 (11)	0.0022 (11)	0.0061 (11)
C2	0.0486 (14)	0.0414 (15)	0.0508 (15)	0.0054 (12)	0.0005 (12)	0.0027 (12)
C3	0.0671 (17)	0.0424 (16)	0.0537 (17)	−0.0014 (14)	0.0030 (14)	−0.0052 (13)
C4	0.0661 (18)	0.0557 (18)	0.0439 (15)	−0.0126 (15)	−0.0050 (13)	−0.0025 (13)
C5	0.0529 (16)	0.0540 (17)	0.0441 (15)	−0.0023 (13)	−0.0062 (12)	0.0083 (13)
C6	0.0431 (14)	0.0467 (16)	0.0446 (14)	0.0032 (13)	0.0011 (11)	0.0031 (12)
Cl1	0.0683 (5)	0.0469 (4)	0.0559 (4)	−0.0043 (3)	−0.0107 (3)	−0.0036 (3)
N1	0.0464 (12)	0.0389 (12)	0.0418 (12)	0.0010 (10)	0.0008 (9)	0.0013 (9)
O1	0.0480 (11)	0.0753 (14)	0.0483 (12)	0.0133 (9)	−0.0086 (9)	−0.0063 (9)
O2	0.0670 (13)	0.0478 (12)	0.0551 (12)	0.0021 (10)	−0.0013 (10)	−0.0084 (9)

Geometric parameters (Å, º) top

C1—N1	1.348 (3)	C5—N1	1.334 (3)
C1—C2	1.360 (3)	C5—H5	0.9300
C1—C6	1.518 (3)	C6—O2	1.385 (3)
C2—C3	1.381 (3)	C6—O1	1.395 (3)
C2—H2	0.9300	C6—H6	0.9800
C3—C4	1.379 (3)	N1—H1	0.8600
C3—H3	0.9300	O1—H1A	0.852 (10)
C4—C5	1.361 (3)	O2—H2A	0.853 (10)
C4—H4	0.9300

N1—C1—C2	118.5 (2)	N1—C5—H5	120.1
N1—C1—C6	116.6 (2)	C4—C5—H5	120.1
C2—C1—C6	124.8 (2)	O2—C6—O1	113.84 (19)
C1—C2—C3	120.0 (2)	O2—C6—C1	112.52 (18)
C1—C2—H2	120.0	O1—C6—C1	106.99 (18)
C3—C2—H2	120.0	O2—C6—H6	107.7
C4—C3—C2	119.6 (2)	O1—C6—H6	107.7
C4—C3—H3	120.2	C1—C6—H6	107.7
C2—C3—H3	120.2	C5—N1—C1	123.0 (2)
C5—C4—C3	119.1 (2)	C5—N1—H1	118.5
C5—C4—H4	120.4	C1—N1—H1	118.5
C3—C4—H4	120.4	C6—O1—H1A	105.8 (19)
N1—C5—C4	119.7 (2)	C6—O2—H2A	114.0 (19)

N1—C1—C2—C3	−1.4 (3)	C2—C1—C6—O2	157.6 (2)
C6—C1—C2—C3	175.9 (2)	N1—C1—C6—O1	−150.91 (18)
C1—C2—C3—C4	0.6 (4)	C2—C1—C6—O1	31.8 (3)
C2—C3—C4—C5	0.8 (4)	C4—C5—N1—C1	0.7 (3)
C3—C4—C5—N1	−1.4 (4)	C2—C1—N1—C5	0.7 (3)
N1—C1—C6—O2	−25.2 (3)	C6—C1—N1—C5	−176.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Cl1ⁱ	0.85 (1)	2.24 (1)	3.089 (2)	176 (2)
O1—H1A···Cl1ⁱⁱ	0.85 (1)	2.19 (1)	3.0374 (18)	177 (3)
N1—H1···Cl1ⁱⁱⁱ	0.86	2.33	3.115 (2)	151

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y, z+1; (iii) x−1, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₈NO₂⁺·Cl⁻
M_r	161.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	4.6879 (7), 15.557 (2), 10.1199 (14)
β (°)	91.181 (2)
V (Å³)	737.88 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.12 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.948, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	3676, 1303, 842
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.075, 0.89
No. of reflections	1303
No. of parameters	99
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.23

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Cl1ⁱ	0.853 (10)	2.238 (10)	3.089 (2)	176 (2)
O1—H1A···Cl1ⁱⁱ	0.852 (10)	2.186 (10)	3.0374 (18)	177 (3)
N1—H1···Cl1ⁱⁱⁱ	0.86	2.33	3.115 (2)	151.1

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y, z+1; (iii) x−1, −y+3/2, z+1/2.

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (No. 20871065) and the Jiangsu Province Department of Science and Technology (No. BK2009226) for financial aid.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mantero, D. G., Altaf, M., Neels, A. & Stoeckli-Evans, H. (2006). Acta Cryst. E62, o5204–o5206. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar