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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2349.
Published online 2009 September 5. doi:  10.1107/S1600536809034916
PMCID: PMC2970240

Isonicotinium hydrogen sulfate

Abstract

The crystal structure of the title compound, C6H6NO2 +·HSO4 , is stabilized by inter­molecular N—H(...)O and O—H(...)O hydrogen bonds.

Related literature

For background to simple mol­ecular–ionic crystals containing organic cations and acidic anions (1:1 molar ratio), see: Czupiński et al. (2002 [triangle]); Katrusiak & Szafrański (1999 [triangle], 2006 [triangle]). For a related structure, see: Jebas et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2349-scheme1.jpg

Experimental

Crystal data

  • C6H6NO2 +·HSO4
  • M r = 221.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2349-efi1.jpg
  • a = 8.3816 (17) Å
  • b = 11.439 (2) Å
  • c = 9.4057 (19) Å
  • β = 109.12 (3)°
  • V = 852.0 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.39 mm−1
  • T = 293 K
  • 0.25 × 0.22 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.90, T max = 0.92
  • 8697 measured reflections
  • 1947 independent reflections
  • 1745 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.091
  • S = 1.14
  • 1947 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.38 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/S1600536809034916/pv2195sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034916/pv2195Isup2.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 (Czupiński et al., 2002; Katrusiak & Szafrański, 1999; Katrusiak & Szafrański, 2006). The crystal structure of isonicotinium nitrate monohydrate has been reported. (Jebas et al., 2006). In our laboratory, the title compound, (I), has been synthesized, its crystal structure is reported herein.

The asymmetric unit of the title compound consists of protoned isonicotinic acid C6H6NO2+ and HSO4-anions (Fig. 1). The isonicotinium cation is essentially planar. The crystal structure is stabilized by intermolecular N—H···O and O—H···O hydrogen bonds. The H-bonds form a two-dimensional network as presented in Fig 2. viewed along the a-axis.

Experimental

Isonicotinic acid (10 mmol) and 10% aqueous H2SO4 in a molar ratio of 1:1 were mixed and dissolved in water by heating to 353 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

Hydrogen atoms bonded to N and O were located from a difference map and were included at those positions (O—H = 0.85/0.95 Å and N—H = 0.86 Å), while the remaining H atoms were placed in calculated positions, with C—H = 0.93 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; the thermal elliposids have been drawn at 50% probability level.
Fig. 2.
The H-bonded two-dimensional network of the title compound viewed down the a axis. Hydrogen bonds are drawn as dashed lines

Crystal data

C6H6NO2+·HSO4F(000) = 456
Mr = 221.18Dx = 1.716 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1745 reflections
a = 8.3816 (17) Åθ = 3.1–27.5°
b = 11.439 (2) ŵ = 0.39 mm1
c = 9.4057 (19) ÅT = 293 K
β = 109.12 (3)°Block, colorless
V = 852.0 (3) Å30.25 × 0.22 × 0.2 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer1947 independent reflections
Radiation source: fine-focus sealed tube1745 reflections with I > 2σ(I)
graphiteRint = 0.043
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −14→14
Tmin = 0.90, Tmax = 0.92l = −12→12
8697 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.091w = 1/[σ2(Fo2) + (0.0324P)2 + 0.395P] where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1947 reflectionsΔρmax = 0.29 e Å3
128 parametersΔρmin = −0.38 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.164 (6)

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
S10.73722 (6)0.21100 (4)0.56236 (4)0.02476 (17)
O20.86500 (19)0.91218 (12)0.57234 (16)0.0404 (4)
H2B0.87230.98630.57270.061*
O60.88648 (17)0.14017 (12)0.62022 (16)0.0392 (4)
O10.71828 (19)0.93897 (12)0.32951 (16)0.0405 (4)
O50.72948 (19)0.26942 (12)0.42296 (14)0.0372 (4)
O40.58610 (18)0.15100 (13)0.55516 (17)0.0427 (4)
O30.7598 (2)0.31698 (11)0.67114 (15)0.0413 (4)
H30.73460.30190.75940.062*
C60.7789 (2)0.87673 (16)0.4359 (2)0.0293 (4)
C30.7616 (2)0.74617 (16)0.42727 (19)0.0270 (4)
C40.8443 (3)0.67611 (17)0.5487 (2)0.0354 (4)
H4A0.91520.70890.63740.042*
C20.6584 (2)0.69616 (17)0.2959 (2)0.0346 (4)
H2A0.60260.74270.21350.041*
N10.7200 (2)0.51277 (15)0.4078 (2)0.0423 (4)
H1A0.70670.43820.40190.051*
C50.8204 (3)0.55833 (18)0.5365 (2)0.0418 (5)
H5A0.87390.50990.61750.050*
C10.6393 (3)0.57727 (19)0.2881 (2)0.0409 (5)
H1B0.57070.54200.20020.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0360 (3)0.0205 (2)0.0191 (2)−0.00064 (16)0.01072 (17)−0.00045 (14)
O20.0547 (9)0.0241 (7)0.0376 (8)−0.0021 (6)0.0087 (6)−0.0019 (6)
O60.0381 (8)0.0309 (7)0.0407 (8)0.0034 (6)0.0023 (6)−0.0038 (6)
O10.0506 (9)0.0312 (7)0.0398 (8)0.0061 (6)0.0148 (7)0.0096 (6)
O50.0644 (10)0.0292 (7)0.0217 (7)−0.0011 (6)0.0194 (6)−0.0001 (5)
O40.0385 (8)0.0453 (9)0.0477 (9)−0.0067 (6)0.0185 (6)0.0008 (7)
O30.0794 (11)0.0246 (7)0.0280 (7)−0.0030 (7)0.0285 (7)−0.0051 (5)
C60.0293 (9)0.0258 (9)0.0345 (10)0.0018 (7)0.0128 (7)0.0022 (7)
C30.0284 (9)0.0258 (9)0.0294 (9)0.0011 (7)0.0130 (7)0.0014 (7)
C40.0413 (11)0.0296 (9)0.0332 (10)0.0013 (8)0.0094 (8)0.0017 (8)
C20.0341 (10)0.0337 (10)0.0343 (10)0.0003 (8)0.0090 (8)0.0002 (8)
N10.0540 (11)0.0234 (8)0.0569 (12)−0.0060 (7)0.0282 (9)−0.0041 (7)
C50.0550 (13)0.0302 (10)0.0412 (12)0.0032 (9)0.0171 (10)0.0065 (9)
C10.0397 (11)0.0389 (11)0.0437 (12)−0.0079 (9)0.0133 (9)−0.0110 (9)

Geometric parameters (Å, °)

S1—O41.4226 (15)C3—C41.382 (3)
S1—O61.4393 (14)C4—C51.361 (3)
S1—O51.4540 (13)C4—H4A0.9300
S1—O31.5574 (13)C2—C11.369 (3)
O2—C61.314 (2)C2—H2A0.9300
O2—H2B0.8500N1—C11.331 (3)
O1—C61.197 (2)N1—C51.334 (3)
O3—H30.9372N1—H1A0.8600
C6—C31.500 (3)C5—H5A0.9300
C3—C21.379 (3)C1—H1B0.9300
O4—S1—O6113.36 (9)C5—C4—H4A120.5
O4—S1—O5113.76 (9)C3—C4—H4A120.5
O6—S1—O5112.10 (9)C1—C2—C3119.23 (19)
O4—S1—O3108.75 (9)C1—C2—H2A120.4
O6—S1—O3106.64 (9)C3—C2—H2A120.4
O5—S1—O3101.22 (8)C1—N1—C5123.11 (18)
C6—O2—H2B109.1C1—N1—H1A118.4
S1—O3—H3115.1C5—N1—H1A118.4
O1—C6—O2125.44 (18)N1—C5—C4119.67 (19)
O1—C6—C3122.68 (17)N1—C5—H5A120.2
O2—C6—C3111.87 (15)C4—C5—H5A120.2
C2—C3—C4119.86 (18)N1—C1—C2119.18 (19)
C2—C3—C6118.85 (16)N1—C1—H1B120.4
C4—C3—C6121.28 (16)C2—C1—H1B120.4
C5—C4—C3118.95 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2B···O6i0.851.812.6425 (19)166
O3—H3···O5ii0.941.752.6543 (18)160
N1—H1A···O50.861.942.787 (2)167

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2195).

References

  • Czupiński, O., Bator, G., Ciunik, Z., Jakubas, R., Medycki, W. & Świergiel, J. (2002). J. Phys. Condens. Matter, 14, 8497–8512.
  • Jebas, S. R., Balasubramanian, T. & Light, M. E. (2006). Acta Cryst E62, o3481–o3482.
  • 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