Nicotinium hydrogen sulfate

Chen, L.-Z.

doi:10.1107/S1600536809034928

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2350

doi:10.1107/S1600536809034928

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Nicotinium hydrogen sulfate

Li-Zhuang Chen ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

(Received 10 August 2009; accepted 31 August 2009; online 5 September 2009)

The structure of title compound, C₆H₆NO₂⁺·HSO₄⁻, comprises discrete ions which are interconected by N—H⋯O and O—H⋯O hydrogen bonds, leading to a neutral one-dimensional network along [001]. These hydrogen bonds appear to complement the Coulombic interaction and help to stabilize the structure further.

Related literature

For simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Czupiński et al. (2002 ); Katrusiak & Szafrański (1999 , 2006 ). For the structure of dinicotinium sulfate, see: Athimoolam & Rajaram (2005 ).

Experimental

Crystal data

C₆H₆NO₂⁺·HSO₄⁻
M_r = 221.19
Monoclinic, P 2₁ /c
a = 8.2654 (17) Å
b = 11.545 (2) Å
c = 9.4669 (19) Å
β = 109.43 (3)°
V = 851.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 293 K
0.25 × 0.2 × 0.2 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.91, T_max = 0.93
8643 measured reflections
1949 independent reflections
1788 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.14
1949 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯O3	0.85	1.83	2.6697 (18)	169
O6—H1⋯O5ⁱ	0.89	1.73	2.6129 (17)	170
N1—H1B⋯O4ⁱⁱ	0.86	2.11	2.843 (2)	143
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536809034928/bx2233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034928/bx2233Isup2.hkl

checkCIF report

Comment top

Recently, much attention has been devoted to simple molecular–ionic crystals containing organic cations and acid radicals (1:1molar ratio) due to the tunability of their special structural features and their interesting physical properties. (e.g. Czupiński et al., 2002; Katrusiak & Szafrański, 1999; Katrusiak & Szafrański, 2006) the crystal structure of dinicotinium sulfate compound have been reported (Athimoolam et al., 2005). In our laboratory, a compound containing protoned nicotinic acid and HSO₄^-anions has been synthesized, its crystal structure is reported herein.

The asymmetric unit of the title compound, C₆H₆NO₂⁺.HSO₄^-, (Fig.1) consists of protoned nicotinic acid and HSO₄^-anions, the nicotinium cation is essentially planar. The protonation of the N site of the pyridine ring is demonstrated by the C—N bond distances and C—N—C bond angle. Usually, protonation on the aromatic ring leads to a slightly larger C—N—C bond angle (122.9 (2)°). Cations and anions are placed alternately and linked through intermolecular hydrogen bonds (Fig. 2 and Table 1). The structure of title compound C₆H₆NO₂⁺.HSO₄^-, comprises discrete ions which are placed alternately and interconected by N—H···O and O—H···O hydrogen bonds leading to a neutral one-dimensional network along [001] direction. These hydrogen bonds appear to complement the Coulombic interaction and help to stabilize the structure further.

Related literature top

For simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Czupiński et al. (2002); Katrusiak & Szafrański (1999,2006). For the structure of

dinicotinium sulfate, see: Athimoolam et al. (2005).

Experimental top

Nicotinic acid (10 mmol) and 10% aqueous H₂SO₄ in a molar ratio of 1:1 were mixed and dissolved in water by heating to 323 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed, collected and washed with dilute aqueous H₂SO₄.

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 asymmetric unit of the title compound with atom labels
	Fig. 2. The packing viewed along the a axis. Hydrogen bonds are drawn as dashed lines

Nicotinium hydrogen sulfate top

Crystal data top

C₆H₆NO₂⁺·HSO₄⁻	F(000) = 456
M_r = 221.19	D_x = 1.725 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1788 reflections
a = 8.2654 (17) Å	θ = 3.2–27.5°
b = 11.545 (2) Å	µ = 0.39 mm⁻¹
c = 9.4669 (19) Å	T = 293 K
β = 109.43 (3)°	Block, colorless
V = 851.9 (3) Å³	0.25 × 0.2 × 0.2 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1949 independent reflections
Radiation source: fine-focus sealed tube	1788 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.91, T_max = 0.93	l = −12→12
8643 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0405P)² + 0.3479P] where P = (F_o² + 2F_c²)/3
1949 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₆H₆NO₂⁺·HSO₄⁻	V = 851.9 (3) Å³
M_r = 221.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2654 (17) Å	µ = 0.39 mm⁻¹
b = 11.545 (2) Å	T = 293 K
c = 9.4669 (19) Å	0.25 × 0.2 × 0.2 mm
β = 109.43 (3)°

Data collection top

Rigaku SCXmini diffractometer	1949 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1788 reflections with I > 2σ(I)
T_min = 0.91, T_max = 0.93	R_int = 0.029
8643 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.14	Δρ_max = 0.21 e Å⁻³
1949 reflections	Δρ_min = −0.49 e Å⁻³
127 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
S1	0.75328 (5)	0.70391 (3)	0.56623 (4)	0.02440 (13)
O1	0.71400 (17)	0.45258 (11)	0.34210 (15)	0.0396 (3)
O2	0.87198 (17)	0.40764 (11)	0.57869 (13)	0.0382 (3)
H2B	0.8839	0.4807	0.5877	0.057*
O3	0.90270 (15)	0.63375 (11)	0.64101 (13)	0.0340 (3)
O4	0.59511 (16)	0.64255 (12)	0.54911 (14)	0.0391 (3)
O5	0.75643 (18)	0.75578 (12)	0.42787 (13)	0.0395 (3)
O6	0.76089 (19)	0.81232 (11)	0.66597 (13)	0.0414 (4)
H1	0.7597	0.7975	0.7581	0.062*
N1	0.60598 (19)	0.10546 (14)	0.25572 (17)	0.0366 (4)
H1B	0.5361	0.0840	0.1701	0.044*
C4	0.75053 (19)	0.25493 (14)	0.41590 (17)	0.0259 (3)
C5	0.6393 (2)	0.21802 (15)	0.27984 (19)	0.0312 (4)
H5A	0.5877	0.2715	0.2050	0.037*
C3	0.8265 (2)	0.17308 (15)	0.52470 (19)	0.0334 (4)
H3A	0.9031	0.1960	0.6169	0.040*
C2	0.7879 (3)	0.05679 (16)	0.4957 (2)	0.0422 (4)
H2A	0.8372	0.0013	0.5685	0.051*
C6	0.7770 (2)	0.38299 (15)	0.43965 (18)	0.0282 (3)
C1	0.6761 (3)	0.02450 (16)	0.3583 (2)	0.0414 (4)
H1A	0.6494	−0.0532	0.3370	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0327 (2)	0.0247 (2)	0.01610 (19)	0.00166 (15)	0.00847 (15)	−0.00001 (13)
O1	0.0447 (7)	0.0301 (7)	0.0398 (7)	0.0039 (6)	0.0083 (6)	0.0078 (5)
O2	0.0476 (7)	0.0270 (6)	0.0332 (7)	−0.0027 (5)	0.0044 (5)	−0.0032 (5)
O3	0.0314 (6)	0.0327 (6)	0.0306 (6)	0.0016 (5)	0.0007 (5)	−0.0031 (5)
O4	0.0306 (6)	0.0493 (8)	0.0370 (7)	−0.0028 (6)	0.0104 (5)	0.0001 (6)
O5	0.0642 (9)	0.0384 (7)	0.0199 (6)	0.0022 (6)	0.0195 (6)	0.0021 (5)
O6	0.0776 (10)	0.0271 (6)	0.0241 (6)	0.0051 (6)	0.0230 (6)	−0.0019 (5)
N1	0.0338 (8)	0.0376 (8)	0.0334 (8)	−0.0030 (6)	0.0045 (6)	−0.0106 (6)
C4	0.0231 (7)	0.0274 (8)	0.0265 (8)	0.0008 (6)	0.0073 (6)	−0.0005 (6)
C5	0.0295 (8)	0.0336 (9)	0.0274 (8)	0.0029 (7)	0.0051 (6)	0.0002 (7)
C3	0.0338 (9)	0.0312 (9)	0.0291 (8)	0.0010 (7)	0.0025 (7)	0.0018 (7)
C2	0.0512 (11)	0.0281 (9)	0.0417 (11)	0.0031 (8)	0.0079 (8)	0.0069 (8)
C6	0.0251 (7)	0.0280 (8)	0.0309 (8)	0.0007 (6)	0.0086 (6)	0.0016 (6)
C1	0.0461 (11)	0.0268 (9)	0.0501 (11)	−0.0043 (8)	0.0145 (9)	−0.0059 (8)

Geometric parameters (Å, º) top

S1—O4	1.4478 (13)	N1—H1B	0.8600
S1—O5	1.4483 (12)	C4—C5	1.377 (2)
S1—O3	1.4493 (13)	C4—C3	1.385 (2)
S1—O6	1.5565 (12)	C4—C6	1.500 (2)
O1—C6	1.204 (2)	C5—H5A	0.9300
O2—C6	1.320 (2)	C3—C2	1.386 (3)
O2—H2B	0.8501	C3—H3A	0.9300
O6—H1	0.8921	C2—C1	1.373 (3)
N1—C5	1.332 (2)	C2—H2A	0.9300
N1—C1	1.334 (2)	C1—H1A	0.9300

O4—S1—O5	112.85 (8)	N1—C5—H5A	120.1
O4—S1—O3	111.86 (8)	C4—C5—H5A	120.1
O5—S1—O3	113.83 (8)	C4—C3—C2	119.75 (16)
O4—S1—O6	108.30 (8)	C4—C3—H3A	120.1
O5—S1—O6	101.94 (7)	C2—C3—H3A	120.1
O3—S1—O6	107.28 (8)	C1—C2—C3	119.25 (17)
C6—O2—H2B	108.9	C1—C2—H2A	120.4
S1—O6—H1	115.3	C3—C2—H2A	120.4
C5—N1—C1	122.94 (16)	O1—C6—O2	125.66 (16)
C5—N1—H1B	118.5	O1—C6—C4	122.57 (15)
C1—N1—H1B	118.5	O2—C6—C4	111.75 (14)
C5—C4—C3	118.73 (16)	N1—C1—C2	119.48 (17)
C5—C4—C6	117.62 (15)	N1—C1—H1A	120.3
C3—C4—C6	123.61 (15)	C2—C1—H1A	120.3
N1—C5—C4	119.85 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3	0.85	1.83	2.6697 (18)	169
O6—H1···O5ⁱ	0.89	1.73	2.6129 (17)	170
N1—H1B···O4ⁱⁱ	0.86	2.11	2.843 (2)	143

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

Experimental details

Crystal data
Chemical formula	C₆H₆NO₂⁺·HSO₄⁻
M_r	221.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.2654 (17), 11.545 (2), 9.4669 (19)
β (°)	109.43 (3)
V (Å³)	851.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.25 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.91, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	8643, 1949, 1788
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.14
No. of reflections	1949
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.49

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
O2—H2B···O3	0.85	1.83	2.6697 (18)	169.1
O6—H1···O5ⁱ	0.89	1.73	2.6129 (17)	170.2
N1—H1B···O4ⁱⁱ	0.86	2.11	2.843 (2)	143.1

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

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

References

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