supplementary materials
Nicotinium hydrogen sulfate
The structure of title compound, C6H6NO2+·HSO4-, comprises discrete ions which are interconected by N-H
O and O-HO 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.
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.
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).
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).
Nicotinium hydrogen sulfate
top
Crystal data top
| C6H6NO2+·HSO4− | F(000) = 456 |
| Mr = 221.19 | Dx = 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 | Rint = 0.029 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
| ω scans | h = −10→10 |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005) | k = −14→14 |
| Tmin = 0.91, Tmax = 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(Fo2) + (0.0405P)2 + 0.3479P]
where P = (Fo2 + 2Fc2)/3 |
| 1949 reflections | (Δ/σ)max = 0.001 |
| 127 parameters | Δρmax = 0.21 e Å−3 |
| 0 restraints | Δρmin = −0.49 e Å−3 |
Crystal data top
| C6H6NO2+·HSO4− | V = 851.9 (3) Å3 |
| Mr = 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) |
| Tmin = 0.91, Tmax = 0.93 | Rint = 0.029 |
| 8643 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.090 | Δρmax = 0.21 e Å−3 |
| S = 1.14 | Δρmin = −0.49 e Å−3 |
| 1949 reflections | Absolute structure: ? |
| 127 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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, °) 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. |
Table 1
Hydrogen-bond geometry (Å, °) 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. |
This work was supported by a start-up grant from Southeast University to
Professor Ren-Gen Xiong.
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
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./bx2233fig1thm.gif)
![[Figure 2]](./bx2233fig2thm.gif)
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.