3,5-Dicarb­oxy-2,6-dimethyl­pyridinium chloride dihydrate

Yao, J.-Y.

doi:10.1107/S1600536810017423

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1365

https://doi.org/10.1107/S1600536810017423

Open

access

3,5-Dicarboxy-2,6-dimethylpyridinium chloride dihydrate

Ji-Yuan Yao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: yaojiyuan520@163.com

(Received 5 May 2010; accepted 12 May 2010; online 15 May 2010)

In the title compound, C₉H₁₀NO₄⁺·Cl⁻·2H₂O, both the cation and the anion have crystallographic twofold rotation symmetry; in the former, one N and one C atom lie on the rotation axis. In the crystal structure, the ions and water molecules are linked via O—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds into layers parallel to (101).

Related literature

For the structure of a related 3,5-dicarboxy-2,6-dimethylpyridinium salt, see: Rowan & Holt (1997 ). For the ferroelectric properties of supramolecular compounds, see: Ye et al. (2008 ); Hang et al. (2009 ). For a description of the Cambridge Structural Database, see: Allen et al. (2002 ).

Experimental

Crystal data

C₉H₁₀NO₄⁺·Cl⁻·2H₂O
M_r = 267.66
Monoclinic, C 2/c
a = 8.2301 (10) Å
b = 10.7825 (10) Å
c = 13.882 (2) Å
β = 98.11 (3)°
V = 1219.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.50 × 0.50 × 0.50 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.938, T_max = 1.000
5826 measured reflections
1353 independent reflections
1204 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.120
S = 1.11
1353 reflections
91 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1Wⁱ	0.82	1.72	2.537 (2)	173
N1—H1A⋯Cl1ⁱⁱ	0.95 (4)	2.21 (4)	3.160 (2)	180 (1)
O1W—H2⋯O2ⁱⁱⁱ	0.79 (4)	1.95 (4)	2.720 (2)	166 (3)
O1W—H2A⋯Cl1ⁱⁱ	0.81 (4)	2.29 (4)	3.096 (2)	177 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) x+1, y, z; (iii) x, y-1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810017423/rz2448sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017423/rz2448Isup2.hkl

checkCIF report

Comment top

Organic and inorganic complexes or salts can develop supramolecular structures via multiple hydrogen-bonding systems by self-assembly of components which contain abundant hydrogen-bonding sites (Rowan & Holt, 1997). The present study is a part of systematic investigation of ferroelectric materials (Ye et al., 2008; Hang et al., 2009) that include metal-organic coordination compounds with organic ligands or compounds whose structures consist both of organic and inorganic building fragments.

The asymmetric unit of the title compound is composed of a half of a 3,5-dicarboxy-2,6-dimethylpyridinium cation, a half of a chloride anion and a water molecule. Both cation and anion have crystallographically imposed twofold rotation symmetry (Fig. 1). In the cation, the C—O bond lengths in the carboxylic group (C1—O1 = 1.300 (2) Å; C1—O2 = 1.218 (2) Å) conform to the expected values (Allen, 2002). The C3—N1—C3 angle of 126.6 (2) ° corresponds closely to the average value found in protonated pyridinium ions (122.0 (2) °). In the crystal structure (Fig. 2), the 3,5-dicarboxy-2,6-dimethylpyridinium cations, the chloride anions and the water molecules are linked via O—H···O, O—H···Cl and N—H···Cl hydrogen bonds (Table 1) to form two-dimensional layers parallel to the (101) plane. Dielectric studies (capacitance and dielectric loss measurements) were performed on powder samples of the title compound pressed into tablets on the surfaces of which a conducting carbon glue was deposited. The automatic impedance TongHui 2828 Analyzer has been used. In the measured temperature ranges (80 to 480 K, m.p. > 480 K), the structure showed no dielectric anomaly.

Related literature top

For the structure of a related 3,5-dicarboxy-2,6-dimethylpyridinium salt, see: Rowan & Holt (1997). For the ferroelectric properties of supramolecular compounds, see: Ye et al. (2008); Hang et al. (2009). For a description of the Cambridge Structural Database, see: Allen et al. (2002).

Experimental top

2,6-Dimethylpyridine-3,5-dicarboxylic acid (1.95 g , 10 mmol) and concentrated hydrochloric acid (10 mmol) were dissolved in methanol (25 ml). The solution was filtered and left at room temperature for 5 days. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent.

Structure description top

For the structure of a related 3,5-dicarboxy-2,6-dimethylpyridinium salt, see: Rowan & Holt (1997). For the ferroelectric properties of supramolecular compounds, see: Ye et al. (2008); Hang et al. (2009). For a description of the Cambridge Structural Database, see: Allen et al. (2002).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms with suffix A are generated by the symmetry operation (2-x, y, 0.5-z).
	Fig. 2. Crystal packing of the title compound viewed along the b axis. Dashed lines indicate hydrogen bonds.

3,5-Dicarboxy-2,6-dimethylpyridinium chloride dihydrate top

Crystal data top

C₉H₁₀NO₄⁺·Cl⁻·2H₂O	F(000) = 560
M_r = 267.66	D_x = 1.458 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1418 reflections
a = 8.2301 (10) Å	θ = 3.3–27.1°
b = 10.7825 (10) Å	µ = 0.33 mm⁻¹
c = 13.882 (2) Å	T = 293 K
β = 98.11 (3)°	Prism, colourless
V = 1219.5 (3) Å³	0.50 × 0.50 × 0.50 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1353 independent reflections
Radiation source: fine-focus sealed tube	1204 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.1°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.938, T_max = 1.000	l = −17→17
5826 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0618P)² + 0.5934P] where P = (F_o² + 2F_c²)/3
1353 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₁₀NO₄⁺·Cl⁻·2H₂O	V = 1219.5 (3) Å³
M_r = 267.66	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 8.2301 (10) Å	µ = 0.33 mm⁻¹
b = 10.7825 (10) Å	T = 293 K
c = 13.882 (2) Å	0.50 × 0.50 × 0.50 mm
β = 98.11 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1353 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1204 reflections with I > 2σ(I)
T_min = 0.938, T_max = 1.000	R_int = 0.022
5826 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.26 e Å⁻³
1353 reflections	Δρ_min = −0.21 e Å⁻³
91 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.

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	0.0000	0.47434 (6)	0.2500	0.0491 (2)
O1	0.80009 (19)	0.97343 (12)	0.46240 (10)	0.0527 (4)
H1	0.7609	1.0230	0.4976	0.079*
N1	1.0000	0.76737 (19)	0.2500	0.0380 (4)
O1W	0.8401 (3)	0.38706 (18)	0.42729 (16)	0.0882 (8)
C1	0.8456 (2)	1.03196 (17)	0.38880 (13)	0.0440 (4)
O2	0.8329 (2)	1.14346 (13)	0.37602 (13)	0.0691 (5)
C2	0.9224 (2)	0.95307 (16)	0.31833 (12)	0.0388 (4)
C3	0.9200 (2)	0.82364 (16)	0.31650 (12)	0.0387 (4)
C4	0.8353 (3)	0.73948 (19)	0.37910 (16)	0.0569 (5)
H4A	0.8362	0.6563	0.3545	0.085*
H4B	0.7240	0.7664	0.3784	0.085*
H4C	0.8915	0.7417	0.4446	0.085*
C5	1.0000	1.0148 (2)	0.2500	0.0395 (5)
H5	1.0000	1.1011	0.2500	0.047*
H1A	1.0000	0.679 (4)	0.2500	0.066 (9)*
H2	0.844 (4)	0.315 (4)	0.422 (2)	0.097 (11)*
H2A	0.880 (4)	0.409 (3)	0.380 (3)	0.094 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0579 (4)	0.0409 (4)	0.0525 (4)	0.000	0.0217 (3)	0.000
O1	0.0749 (9)	0.0434 (8)	0.0461 (8)	0.0062 (6)	0.0306 (7)	−0.0030 (5)
N1	0.0476 (11)	0.0288 (10)	0.0412 (11)	0.000	0.0183 (8)	0.000
O1W	0.152 (2)	0.0408 (9)	0.0924 (14)	−0.0033 (10)	0.0889 (15)	−0.0088 (8)
C1	0.0525 (10)	0.0364 (9)	0.0466 (10)	−0.0028 (7)	0.0190 (8)	−0.0070 (7)
O2	0.1067 (13)	0.0324 (7)	0.0792 (11)	−0.0005 (7)	0.0505 (9)	−0.0073 (7)
C2	0.0440 (9)	0.0346 (8)	0.0403 (9)	−0.0001 (6)	0.0149 (7)	−0.0022 (6)
C3	0.0455 (9)	0.0335 (9)	0.0399 (9)	−0.0003 (6)	0.0160 (7)	−0.0009 (6)
C4	0.0809 (14)	0.0382 (10)	0.0607 (12)	−0.0052 (9)	0.0414 (11)	0.0003 (8)
C5	0.0453 (12)	0.0294 (11)	0.0459 (13)	0.000	0.0137 (10)	0.000

Geometric parameters (Å, º) top

O1—C1	1.300 (2)	C2—C5	1.386 (2)
O1—H1	0.8200	C2—C3	1.396 (3)
N1—C3	1.3513 (18)	C3—C4	1.495 (2)
N1—C3ⁱ	1.3513 (18)	C4—H4A	0.9600
N1—H1A	0.95 (4)	C4—H4B	0.9600
O1W—H2	0.79 (4)	C4—H4C	0.9600
O1W—H2A	0.81 (4)	C5—C2ⁱ	1.386 (2)
C1—O2	1.218 (2)	C5—H5	0.9300
C1—C2	1.501 (2)

C1—O1—H1	109.5	N1—C3—C4	115.88 (16)
C3—N1—C3ⁱ	126.6 (2)	C2—C3—C4	127.09 (15)
C3—N1—H1A	116.68 (10)	C3—C4—H4A	109.5
C3ⁱ—N1—H1A	116.68 (11)	C3—C4—H4B	109.5
H2—O1W—H2A	101 (3)	H4A—C4—H4B	109.5
O2—C1—O1	124.43 (16)	C3—C4—H4C	109.5
O2—C1—C2	120.00 (16)	H4A—C4—H4C	109.5
O1—C1—C2	115.55 (16)	H4B—C4—H4C	109.5
C5—C2—C3	118.33 (15)	C2ⁱ—C5—C2	122.6 (2)
C5—C2—C1	116.78 (16)	C2ⁱ—C5—H5	118.7
C3—C2—C1	124.89 (15)	C2—C5—H5	118.7
N1—C3—C2	117.01 (15)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1Wⁱⁱ	0.82	1.72	2.537 (2)	173
N1—H1A···Cl1ⁱⁱⁱ	0.95 (4)	2.21 (4)	3.160 (2)	180 (1)
O1W—H2···O2^iv	0.79 (4)	1.95 (4)	2.720 (2)	166 (3)
O1W—H2A···Cl1ⁱⁱⁱ	0.81 (4)	2.29 (4)	3.096 (2)	177 (3)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀NO₄⁺·Cl⁻·2H₂O
M_r	267.66
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	8.2301 (10), 10.7825 (10), 13.882 (2)
β (°)	98.11 (3)
V (Å³)	1219.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.50 × 0.50 × 0.50

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.938, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5826, 1353, 1204
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.120, 1.11
No. of reflections	1353
No. of parameters	91
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1Wⁱ	0.82	1.72	2.537 (2)	172.8
N1—H1A···Cl1ⁱⁱ	0.95 (4)	2.21 (4)	3.160 (2)	180.000 (1)
O1W—H2···O2ⁱⁱⁱ	0.79 (4)	1.95 (4)	2.720 (2)	166 (3)
O1W—H2A···Cl1ⁱⁱ	0.81 (4)	2.29 (4)	3.096 (2)	177 (3)

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

Acknowledgements

The author is grateful to the starter fund of Southeast University for financial support topurchase a single-crystal X-ray diffractometer.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 5, 2026–2029. Web of Science CSD CrossRef Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rowan, K. R. & Holt, E. M. (1997). Acta Cryst. C53, 106–108. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, Q., Hang, T., Fu, D. W., Xu, G. H. & Xiong, R. G. (2008). Cryst. Growth Des. 8, 3501–3503. Web of Science CSD CrossRef CAS Google Scholar