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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2350.
Published online 2009 September 5. doi:  10.1107/S1600536809034928
PMCID: PMC2970485

Nicotinium hydrogen sulfate

Abstract

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 [triangle]); Katrusiak & Szafrański (1999 [triangle], 2006 [triangle]). For the structure of dinicotinium sulfate, see: Athimoolam & Rajaram (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2350-scheme1.jpg

Experimental

Crystal data

  • C6H6NO2 +·HSO4
  • M r = 221.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2350-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.090
  • S = 1.14
  • 1949 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.49 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034928/bx2233sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed in calculated positions, with C—H = 0.93 Å, O—H = 0.85 Å and N—H = 0.86 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(O).

Figures

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

Crystal data

C6H6NO2+·HSO4F(000) = 456
Mr = 221.19Dx = 1.725 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1788 reflections
a = 8.2654 (17) Åθ = 3.2–27.5°
b = 11.545 (2) ŵ = 0.39 mm1
c = 9.4669 (19) ÅT = 293 K
β = 109.43 (3)°Block, colorless
V = 851.9 (3) Å30.25 × 0.2 × 0.2 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer1949 independent reflections
Radiation source: fine-focus sealed tube1788 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scansh = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −14→14
Tmin = 0.91, Tmax = 0.93l = −12→12
8643 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0405P)2 + 0.3479P] where P = (Fo2 + 2Fc2)/3
1949 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = −0.49 e Å3

Special details

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)

xyzUiso*/Ueq
S10.75328 (5)0.70391 (3)0.56623 (4)0.02440 (13)
O10.71400 (17)0.45258 (11)0.34210 (15)0.0396 (3)
O20.87198 (17)0.40764 (11)0.57869 (13)0.0382 (3)
H2B0.88390.48070.58770.057*
O30.90270 (15)0.63375 (11)0.64101 (13)0.0340 (3)
O40.59511 (16)0.64255 (12)0.54911 (14)0.0391 (3)
O50.75643 (18)0.75578 (12)0.42787 (13)0.0395 (3)
O60.76089 (19)0.81232 (11)0.66597 (13)0.0414 (4)
H10.75970.79750.75810.062*
N10.60598 (19)0.10546 (14)0.25572 (17)0.0366 (4)
H1B0.53610.08400.17010.044*
C40.75053 (19)0.25493 (14)0.41590 (17)0.0259 (3)
C50.6393 (2)0.21802 (15)0.27984 (19)0.0312 (4)
H5A0.58770.27150.20500.037*
C30.8265 (2)0.17308 (15)0.52470 (19)0.0334 (4)
H3A0.90310.19600.61690.040*
C20.7879 (3)0.05679 (16)0.4957 (2)0.0422 (4)
H2A0.83720.00130.56850.051*
C60.7770 (2)0.38299 (15)0.43965 (18)0.0282 (3)
C10.6761 (3)0.02450 (16)0.3583 (2)0.0414 (4)
H1A0.6494−0.05320.33700.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0327 (2)0.0247 (2)0.01610 (19)0.00166 (15)0.00847 (15)−0.00001 (13)
O10.0447 (7)0.0301 (7)0.0398 (7)0.0039 (6)0.0083 (6)0.0078 (5)
O20.0476 (7)0.0270 (6)0.0332 (7)−0.0027 (5)0.0044 (5)−0.0032 (5)
O30.0314 (6)0.0327 (6)0.0306 (6)0.0016 (5)0.0007 (5)−0.0031 (5)
O40.0306 (6)0.0493 (8)0.0370 (7)−0.0028 (6)0.0104 (5)0.0001 (6)
O50.0642 (9)0.0384 (7)0.0199 (6)0.0022 (6)0.0195 (6)0.0021 (5)
O60.0776 (10)0.0271 (6)0.0241 (6)0.0051 (6)0.0230 (6)−0.0019 (5)
N10.0338 (8)0.0376 (8)0.0334 (8)−0.0030 (6)0.0045 (6)−0.0106 (6)
C40.0231 (7)0.0274 (8)0.0265 (8)0.0008 (6)0.0073 (6)−0.0005 (6)
C50.0295 (8)0.0336 (9)0.0274 (8)0.0029 (7)0.0051 (6)0.0002 (7)
C30.0338 (9)0.0312 (9)0.0291 (8)0.0010 (7)0.0025 (7)0.0018 (7)
C20.0512 (11)0.0281 (9)0.0417 (11)0.0031 (8)0.0079 (8)0.0069 (8)
C60.0251 (7)0.0280 (8)0.0309 (8)0.0007 (6)0.0086 (6)0.0016 (6)
C10.0461 (11)0.0268 (9)0.0501 (11)−0.0043 (8)0.0145 (9)−0.0059 (8)

Geometric parameters (Å, °)

S1—O41.4478 (13)N1—H1B0.8600
S1—O51.4483 (12)C4—C51.377 (2)
S1—O31.4493 (13)C4—C31.385 (2)
S1—O61.5565 (12)C4—C61.500 (2)
O1—C61.204 (2)C5—H5A0.9300
O2—C61.320 (2)C3—C21.386 (3)
O2—H2B0.8501C3—H3A0.9300
O6—H10.8921C2—C11.373 (3)
N1—C51.332 (2)C2—H2A0.9300
N1—C11.334 (2)C1—H1A0.9300
O4—S1—O5112.85 (8)N1—C5—H5A120.1
O4—S1—O3111.86 (8)C4—C5—H5A120.1
O5—S1—O3113.83 (8)C4—C3—C2119.75 (16)
O4—S1—O6108.30 (8)C4—C3—H3A120.1
O5—S1—O6101.94 (7)C2—C3—H3A120.1
O3—S1—O6107.28 (8)C1—C2—C3119.25 (17)
C6—O2—H2B108.9C1—C2—H2A120.4
S1—O6—H1115.3C3—C2—H2A120.4
C5—N1—C1122.94 (16)O1—C6—O2125.66 (16)
C5—N1—H1B118.5O1—C6—C4122.57 (15)
C1—N1—H1B118.5O2—C6—C4111.75 (14)
C5—C4—C3118.73 (16)N1—C1—C2119.48 (17)
C5—C4—C6117.62 (15)N1—C1—H1A120.3
C3—C4—C6123.61 (15)C2—C1—H1A120.3
N1—C5—C4119.85 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2B···O30.851.832.6697 (18)169
O6—H1···O5i0.891.732.6129 (17)170
N1—H1B···O4ii0.862.112.843 (2)143

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2233).

References

  • Athimoolam, S. & Rajaram, R. K. (2005). Acta Cryst. E61, o2764–o2767.
  • Czupiński, O., Bator, G., Ciunik, Z., Jakubas, R., Medycki, W. & Świergiel, J. (2002). J. Phys. Condens. Matter, 14, 8497–8512.
  • Katrusiak, A. & Szafrański, M. (1999). Phys. Rev. Lett.82, 576–579.
  • Katrusiak, A. & Szafrański, M. (2006). J. Am. Chem. Soc.128, 15775–15785. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography