2-Hy­droxy­pyridinium p-toluene­sulfonate

Jin, Y.

doi:10.1107/S1600536812019873

organic compounds

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Volume 68| Part 6| June 2012| Page o1669

doi:10.1107/S1600536812019873

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2-Hydroxypyridinium p-toluenesulfonate

Yu Jin ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jinyunihao@yahoo.cn

(Received 16 April 2012; accepted 3 May 2012; online 12 May 2012)

In the title molecular salt, C₅H₆NO⁺·C₇H₇O₃S⁻, the cations and anions are connected by N—H⋯O and O—H⋯O hydrogen bonds, forming [100] chains.

Related literature

For general background on ferroelectric frameworks, see: Zhang et al. (2008 , 2009 , 2010 ). For related salts containing p-toluenesulfonate anions, see: Helvenston et al. (2006 ); Collier et al. (2006 ); Koshima et al. (2001 ).

Experimental

Crystal data

C₅H₆NO⁺·C₇H₇O₃S⁻
M_r = 267.29
Orthorhombic, P b c a
a = 10.293 (2) Å
b = 14.484 (3) Å
c = 15.708 (3) Å
V = 2341.8 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.3 × 0.3 × 0.2 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.489, T_max = 1.000
23178 measured reflections
2688 independent reflections
2239 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.111
S = 1.09
2688 reflections
169 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.89 (4)	1.66 (4)	2.523 (2)	160 (3)
N1—H1D⋯O4ⁱ	0.86	1.86	2.704 (2)	166
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812019873/bh2431sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019873/bh2431Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019873/bh2431Isup3.cml

checkCIF report

Comment top

Several crystal structures of p-toluenesulfonate have been reported previously (Helvenston et al., 2006; Collier et al., 2006; Koshima et al., 2001). As an extension of this research, we report here the synthesis and the crystal structure of the title complex.

Until now, researchers have found that molecular motion can cause a rotation of the local structure to give rise to the formation of reversible structural phase transition from high-temperature disordered fashion to low temperature ordered fashion. Reversible structural phase transition is caused by many kinds of factors. Hydrogen-bonding interactions come to be the most common factor. Transition for hydrogen-bonding interactions from high-temperature disordered state to low temperature ordered state allows reversible structural phase transition. The compound reported here could have a tendency to hold such transition as a result of numerous hydrogen-bonding interactions in its crystal structure. The transition from the disordered arrangement to the ordered one gives rise to sharp change in the physical properties of these compounds. Only few compounds in which the components can be arranged in a disordered status at a relative high temperature and in an ordered one at a relative low temperature have been found until now (Zhang et al., 2008, 2009, 2010). As part of our search for simple ferroelectric compounds we have investigated the title compound and report its room temperature structure.

The asymmetric unit, containing one anion and one cation, is shown in Fig. 1 with the hydrogen bonds listed in Table 1. The compound remains stable as a result of the existence of numerous hydrogen-bonding interactions formed in the crystal. These interactions tie the cations and anions together in a complex spatial geometry (Fig. 2).

Related literature top

For general background on ferroelectric frameworks, see: Zhang et al. (2008, 2009, 2010). For related salts including p-toluenesulfonate anions, see: Helvenston et al. (2006); Collier et al. (2006); Koshima et al. (2001).

Experimental top

C₅H₆ON⁺.C₇H₇O₃S^- was formed from a mixture of C₅H₅ON (95.1 mg, 1.00 mmol), C₇H₇SO₃H (172 mg, 1.00 mmol), and distilled water (5 mL), which was stirred a few minutes at room temperature, giving a clear transparent solution. After evaporation for a few days, block colourless crystals suitable for X-ray diffraction were obtained in about 71% yield and filtered and washed with distilled water.

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of the title compound viewed along the c axis. Intermolecular interactions are shown as dashed lines.

2-Hydroxypyridinium p-toluenesulfonate top

Crystal data top

C₅H₆NO⁺·C₇H₇O₃S⁻	F(000) = 1120
M_r = 267.29	D_x = 1.516 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3450 reflections
a = 10.293 (2) Å	θ = 6.2–55.3°
b = 14.484 (3) Å	µ = 0.28 mm⁻¹
c = 15.708 (3) Å	T = 293 K
V = 2341.8 (8) Å³	Block, colourless
Z = 8	0.3 × 0.3 × 0.2 mm

Data collection top

Rigaku Mercury CCD diffractometer	2688 independent reflections
Radiation source: fine-focus sealed tube	2239 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −13→13
T_min = 0.489, T_max = 1.000	k = −18→18
23178 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0362P)² + 1.2062P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2688 reflections	Δρ_max = 0.26 e Å⁻³
169 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0347 (16)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₅H₆NO⁺·C₇H₇O₃S⁻	V = 2341.8 (8) Å³
M_r = 267.29	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.293 (2) Å	µ = 0.28 mm⁻¹
b = 14.484 (3) Å	T = 293 K
c = 15.708 (3) Å	0.3 × 0.3 × 0.2 mm

Data collection top

Rigaku Mercury CCD diffractometer	2688 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2239 reflections with I > 2σ(I)
T_min = 0.489, T_max = 1.000	R_int = 0.075
23178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.26 e Å⁻³
2688 reflections	Δρ_min = −0.41 e Å⁻³
169 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.5889 (2)	0.09901 (16)	0.81599 (13)	0.0461 (6)
H1A	0.6382	0.0453	0.8315	0.069*
H1B	0.4989	0.0890	0.8291	0.069*
H1C	0.6203	0.1514	0.8473	0.069*
C2	0.6034 (2)	0.11654 (13)	0.72297 (12)	0.0322 (4)
C3	0.5108 (2)	0.08731 (14)	0.66618 (13)	0.0356 (5)
H3	0.4365	0.0580	0.6862	0.043*
C4	0.52611 (19)	0.10060 (14)	0.58087 (12)	0.0335 (5)
H4	0.4625	0.0804	0.5431	0.040*
C5	0.63523 (18)	0.14370 (13)	0.55080 (12)	0.0277 (4)
C6	0.72725 (19)	0.17508 (14)	0.60638 (12)	0.0318 (4)
H6	0.8007	0.2055	0.5863	0.038*
C7	0.7102 (2)	0.16122 (13)	0.69220 (13)	0.0342 (5)
H7	0.7728	0.1827	0.7301	0.041*
C8	0.53344 (18)	0.14460 (13)	0.19333 (12)	0.0309 (4)
C9	0.65239 (19)	0.10354 (14)	0.20266 (13)	0.0352 (5)
H9	0.6890	0.0961	0.2564	0.042*
C10	0.7158 (2)	0.07393 (14)	0.13220 (14)	0.0401 (5)
H10	0.7970	0.0464	0.1378	0.048*
C11	0.6624 (2)	0.08387 (17)	0.05305 (14)	0.0446 (5)
H11	0.7052	0.0622	0.0049	0.054*
C12	0.5470 (2)	0.12556 (16)	0.04656 (14)	0.0424 (5)
H12	0.5097	0.1342	−0.0068	0.051*
N1	0.48537 (16)	0.15481 (12)	0.11587 (10)	0.0344 (4)
H1D	0.4112	0.1814	0.1101	0.041*
O1	0.45846 (14)	0.17554 (12)	0.25338 (10)	0.0446 (4)
H1	0.498 (3)	0.167 (2)	0.303 (2)	0.095 (12)*
O2	0.53381 (14)	0.17679 (12)	0.40618 (9)	0.0477 (4)
O3	0.70545 (15)	0.06576 (10)	0.41196 (9)	0.0426 (4)
O4	0.75191 (14)	0.22574 (10)	0.42828 (8)	0.0397 (4)
S1	0.65917 (5)	0.15323 (3)	0.44102 (3)	0.03132 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0660 (16)	0.0449 (13)	0.0273 (11)	−0.0031 (11)	0.0006 (10)	−0.0002 (9)
C2	0.0433 (11)	0.0285 (10)	0.0247 (9)	0.0050 (8)	−0.0003 (8)	−0.0014 (7)
C3	0.0343 (11)	0.0397 (11)	0.0326 (10)	−0.0038 (9)	0.0056 (9)	−0.0006 (9)
C4	0.0306 (10)	0.0415 (11)	0.0286 (10)	−0.0020 (8)	−0.0021 (8)	−0.0025 (9)
C5	0.0277 (9)	0.0317 (10)	0.0238 (9)	0.0053 (7)	0.0003 (7)	−0.0008 (7)
C6	0.0293 (10)	0.0340 (10)	0.0322 (10)	−0.0016 (8)	0.0004 (8)	0.0006 (8)
C7	0.0358 (11)	0.0358 (10)	0.0310 (10)	−0.0011 (8)	−0.0075 (8)	−0.0037 (8)
C8	0.0290 (10)	0.0348 (10)	0.0290 (10)	−0.0036 (8)	0.0013 (8)	0.0003 (8)
C9	0.0335 (11)	0.0398 (11)	0.0321 (10)	0.0004 (8)	−0.0045 (8)	0.0026 (9)
C10	0.0370 (11)	0.0381 (11)	0.0451 (12)	0.0086 (9)	0.0020 (9)	0.0002 (10)
C11	0.0507 (13)	0.0492 (13)	0.0338 (11)	0.0092 (11)	0.0069 (10)	−0.0043 (10)
C12	0.0469 (13)	0.0534 (13)	0.0269 (10)	0.0036 (10)	−0.0019 (9)	−0.0005 (10)
N1	0.0289 (8)	0.0432 (10)	0.0309 (9)	0.0013 (7)	−0.0033 (7)	0.0022 (7)
O1	0.0335 (8)	0.0702 (11)	0.0302 (8)	0.0100 (7)	0.0000 (6)	−0.0018 (8)
O2	0.0349 (8)	0.0804 (12)	0.0276 (7)	0.0126 (8)	−0.0024 (6)	0.0046 (8)
O3	0.0529 (9)	0.0417 (9)	0.0331 (8)	0.0064 (7)	0.0033 (7)	−0.0075 (6)
O4	0.0386 (8)	0.0428 (8)	0.0377 (8)	0.0030 (6)	0.0099 (6)	0.0051 (7)
S1	0.0296 (3)	0.0402 (3)	0.0241 (3)	0.0057 (2)	0.00163 (18)	0.0007 (2)

Geometric parameters (Å, º) top

C1—C2	1.491 (3)	C8—N1	1.322 (2)
C1—H1A	0.9600	C8—C9	1.369 (3)
C1—H1B	0.9600	C9—C10	1.355 (3)
C1—H1C	0.9600	C9—H9	0.9300
C2—C7	1.364 (3)	C10—C11	1.367 (3)
C2—C3	1.373 (3)	C10—H10	0.9300
C3—C4	1.363 (3)	C11—C12	1.336 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.369 (3)	C12—N1	1.330 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.366 (3)	N1—H1D	0.8600
C5—S1	1.7474 (19)	O1—H1	0.89 (4)
C6—C7	1.374 (3)	O2—S1	1.4425 (15)
C6—H6	0.9300	O3—S1	1.4284 (15)
C7—H7	0.9300	O4—S1	1.4333 (16)
C8—O1	1.299 (2)

C2—C1—H1A	109.5	O1—C8—C9	127.14 (19)
C2—C1—H1B	109.5	N1—C8—C9	118.81 (18)
H1A—C1—H1B	109.5	C10—C9—C8	118.75 (19)
C2—C1—H1C	109.5	C10—C9—H9	120.6
H1A—C1—H1C	109.5	C8—C9—H9	120.6
H1B—C1—H1C	109.5	C9—C10—C11	121.1 (2)
C7—C2—C3	118.42 (18)	C9—C10—H10	119.5
C7—C2—C1	120.61 (19)	C11—C10—H10	119.5
C3—C2—C1	120.97 (19)	C12—C11—C10	118.3 (2)
C4—C3—C2	120.99 (19)	C12—C11—H11	120.8
C4—C3—H3	119.5	C10—C11—H11	120.8
C2—C3—H3	119.5	N1—C12—C11	120.4 (2)
C3—C4—C5	119.90 (18)	N1—C12—H12	119.8
C3—C4—H4	120.0	C11—C12—H12	119.8
C5—C4—H4	120.0	C8—N1—C12	122.64 (18)
C6—C5—C4	120.00 (18)	C8—N1—H1D	118.7
C6—C5—S1	120.44 (15)	C12—N1—H1D	118.7
C4—C5—S1	119.49 (15)	C8—O1—H1	109 (2)
C5—C6—C7	119.34 (19)	O3—S1—O4	112.53 (9)
C5—C6—H6	120.3	O3—S1—O2	112.76 (10)
C7—C6—H6	120.3	O4—S1—O2	111.68 (10)
C2—C7—C6	121.31 (18)	O3—S1—C5	107.00 (9)
C2—C7—H7	119.3	O4—S1—C5	106.83 (9)
C6—C7—H7	119.3	O2—S1—C5	105.48 (9)
O1—C8—N1	114.05 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.89 (4)	1.66 (4)	2.523 (2)	160 (3)
N1—H1D···O4ⁱ	0.86	1.86	2.704 (2)	166
O1—H1···S1	0.89 (4)	2.73 (4)	3.6139 (18)	169 (3)
N1—H1D···S1ⁱ	0.86	2.75	3.4747 (18)	143

Symmetry code: (i) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₆NO⁺·C₇H₇O₃S⁻
M_r	267.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.293 (2), 14.484 (3), 15.708 (3)
V (Å³)	2341.8 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.3 × 0.3 × 0.2

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.489, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23178, 2688, 2239
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.111, 1.09
No. of reflections	2688
No. of parameters	169
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.41

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.89 (4)	1.66 (4)	2.523 (2)	160 (3)
N1—H1D···O4ⁱ	0.86	1.86	2.704 (2)	166.1

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

The author thanks Southeast University for support.

References

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