Acta Cryst. (2009). E65, o2626 [ doi:10.1107/S1600536809039026 ]
In the cation of the title compound, C6H7N2O+·ClO4-, the amide group is oriented at a dihedral angle of 10.41 (17)° to the benzene ring. The crystal structure is stabilized by intermolecular N-H
O hydrogen bonding.
4-Carbamoylpyridine (2.44 g, 20 mmol) and 10% aqueous solution (15 ml) of HClO4 were dissolved in 30 ml water. The solution was heated at 343 K for 0.5 h, forming a clear solution. The reaction mixture was cooled slowly to room temperature, block crystals of the title compound were formed.
All H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined using a riding model with Uiso(H) = 1.2Ueq(C,N).
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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2591fig1thm.gif)
| Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level. |
| C6H7N2O+·ClO4− | F(000) = 456 |
| Mr = 222.59 | Dx = 1.657 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1421 reflections |
| a = 10.935 (2) Å | θ = 3.2–27.5° |
| b = 10.082 (2) Å | µ = 0.43 mm−1 |
| c = 8.2021 (16) Å | T = 293 K |
| β = 99.37 (3)° | Block, colorless |
| V = 892.2 (3) Å3 | 0.30 × 0.25 × 0.22 mm |
| Z = 4 |
| Rigaku SCXmini diffractometer | 2033 independent reflections |
| Radiation source: fine-focus sealed tube | 1421 reflections with I > 2σ(I) |
| graphite | Rint = 0.074 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
| ω scans | h = −14→14 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −13→13 |
| Tmin = 0.87, Tmax = 0.90 | l = −10→10 |
| 8863 measured reflections |
| 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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.176 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0844P)2 + 0.3072P] where P = (Fo2 + 2Fc2)/3 |
| 2033 reflections | (Δ/σ)max < 0.001 |
| 127 parameters | Δρmax = 0.42 e Å−3 |
| 0 restraints | Δρmin = −0.42 e Å−3 |
| C6H7N2O+·ClO4− | V = 892.2 (3) Å3 |
| Mr = 222.59 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.935 (2) Å | µ = 0.43 mm−1 |
| b = 10.082 (2) Å | T = 293 K |
| c = 8.2021 (16) Å | 0.30 × 0.25 × 0.22 mm |
| β = 99.37 (3)° |
| Rigaku SCXmini diffractometer | 2033 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1421 reflections with I > 2σ(I) |
| Tmin = 0.87, Tmax = 0.90 | Rint = 0.074 |
| 8863 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
| wR(F2) = 0.176 | Δρmax = 0.42 e Å−3 |
| S = 1.04 | Δρmin = −0.42 e Å−3 |
| 2033 reflections | Absolute structure: ? |
| 127 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.35049 (7) | 0.39747 (7) | 0.09900 (9) | 0.0473 (3) | |
| O5 | 0.0368 (2) | 0.8048 (2) | 0.2309 (3) | 0.0650 (7) | |
| N2 | −0.0251 (3) | 0.5945 (3) | 0.1873 (4) | 0.0698 (10) | |
| H2A | −0.0862 | 0.6169 | 0.1127 | 0.084* | |
| H2B | −0.0128 | 0.5123 | 0.2130 | 0.084* | |
| C6 | 0.0493 (3) | 0.6856 (3) | 0.2619 (4) | 0.0463 (7) | |
| C4 | 0.2469 (3) | 0.7332 (3) | 0.4470 (4) | 0.0479 (8) | |
| H4A | 0.2386 | 0.8205 | 0.4104 | 0.057* | |
| N1 | 0.3573 (2) | 0.5717 (3) | 0.6122 (3) | 0.0541 (8) | |
| H1A | 0.4218 | 0.5492 | 0.6813 | 0.065* | |
| C3 | 0.1569 (2) | 0.6406 (3) | 0.3883 (3) | 0.0399 (7) | |
| O4 | 0.4364 (2) | 0.2906 (2) | 0.1204 (3) | 0.0707 (8) | |
| O3 | 0.3944 (2) | 0.4992 (2) | 0.2176 (3) | 0.0653 (7) | |
| C2 | 0.1692 (3) | 0.5117 (3) | 0.4485 (4) | 0.0457 (8) | |
| H2C | 0.1096 | 0.4479 | 0.4117 | 0.055* | |
| C5 | 0.3479 (3) | 0.6961 (4) | 0.5590 (4) | 0.0549 (9) | |
| H5A | 0.4094 | 0.7575 | 0.5973 | 0.066* | |
| O2 | 0.3407 (3) | 0.4505 (3) | −0.0636 (3) | 0.0843 (9) | |
| O1 | 0.2315 (2) | 0.3517 (3) | 0.1231 (4) | 0.0759 (8) | |
| C1 | 0.2713 (3) | 0.4798 (3) | 0.5636 (4) | 0.0536 (9) | |
| H1B | 0.2803 | 0.3945 | 0.6072 | 0.064* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0405 (5) | 0.0430 (5) | 0.0519 (5) | 0.0012 (3) | −0.0116 (3) | 0.0000 (3) |
| O5 | 0.0581 (15) | 0.0403 (14) | 0.0867 (19) | 0.0094 (11) | −0.0176 (12) | 0.0095 (12) |
| N2 | 0.0575 (19) | 0.0488 (18) | 0.087 (2) | −0.0020 (13) | −0.0377 (17) | 0.0116 (15) |
| C6 | 0.0397 (17) | 0.0405 (18) | 0.0548 (19) | 0.0032 (13) | −0.0039 (13) | 0.0050 (14) |
| C4 | 0.0466 (18) | 0.0361 (16) | 0.057 (2) | −0.0056 (13) | −0.0036 (14) | 0.0033 (13) |
| N1 | 0.0460 (16) | 0.0565 (18) | 0.0509 (17) | 0.0061 (12) | −0.0187 (13) | −0.0010 (12) |
| C3 | 0.0346 (16) | 0.0371 (15) | 0.0448 (17) | 0.0021 (11) | −0.0030 (12) | −0.0012 (12) |
| O4 | 0.0550 (15) | 0.0510 (15) | 0.097 (2) | 0.0147 (11) | −0.0145 (14) | −0.0040 (13) |
| O3 | 0.0595 (16) | 0.0570 (15) | 0.0721 (17) | −0.0015 (11) | −0.0110 (12) | −0.0208 (12) |
| C2 | 0.0469 (18) | 0.0319 (15) | 0.0520 (19) | −0.0018 (12) | −0.0109 (14) | −0.0034 (12) |
| C5 | 0.0438 (19) | 0.055 (2) | 0.060 (2) | −0.0120 (15) | −0.0079 (15) | −0.0007 (16) |
| O2 | 0.106 (2) | 0.087 (2) | 0.0518 (17) | −0.0028 (17) | −0.0107 (15) | 0.0126 (14) |
| O1 | 0.0434 (15) | 0.0839 (19) | 0.096 (2) | −0.0120 (13) | −0.0021 (13) | −0.0088 (16) |
| C1 | 0.060 (2) | 0.0381 (17) | 0.055 (2) | 0.0063 (15) | −0.0145 (16) | −0.0002 (14) |
| Cl1—O4 | 1.421 (2) | C4—C3 | 1.385 (4) |
| Cl1—O2 | 1.424 (3) | C4—H4A | 0.9300 |
| Cl1—O1 | 1.425 (3) | N1—C5 | 1.327 (4) |
| Cl1—O3 | 1.441 (2) | N1—C1 | 1.334 (4) |
| O5—C6 | 1.231 (3) | N1—H1A | 0.8600 |
| N2—C6 | 1.310 (4) | C3—C2 | 1.389 (4) |
| N2—H2A | 0.8600 | C2—C1 | 1.377 (4) |
| N2—H2B | 0.8600 | C2—H2C | 0.9300 |
| C6—C3 | 1.507 (4) | C5—H5A | 0.9300 |
| C4—C5 | 1.369 (5) | C1—H1B | 0.9300 |
| O4—Cl1—O2 | 110.33 (19) | C5—N1—C1 | 123.0 (3) |
| O4—Cl1—O1 | 109.76 (17) | C5—N1—H1A | 118.5 |
| O2—Cl1—O1 | 108.68 (18) | C1—N1—H1A | 118.5 |
| O4—Cl1—O3 | 108.36 (15) | C4—C3—C2 | 119.0 (3) |
| O2—Cl1—O3 | 109.30 (18) | C4—C3—C6 | 117.9 (3) |
| O1—Cl1—O3 | 110.41 (17) | C2—C3—C6 | 123.1 (3) |
| C6—N2—H2A | 120.0 | C1—C2—C3 | 118.9 (3) |
| C6—N2—H2B | 120.0 | C1—C2—H2C | 120.6 |
| H2A—N2—H2B | 120.0 | C3—C2—H2C | 120.6 |
| O5—C6—N2 | 123.2 (3) | N1—C5—C4 | 119.3 (3) |
| O5—C6—C3 | 118.9 (3) | N1—C5—H5A | 120.3 |
| N2—C6—C3 | 117.8 (3) | C4—C5—H5A | 120.3 |
| C5—C4—C3 | 120.0 (3) | N1—C1—C2 | 119.7 (3) |
| C5—C4—H4A | 120.0 | N1—C1—H1B | 120.1 |
| C3—C4—H4A | 120.0 | C2—C1—H1B | 120.1 |
| C5—C4—C3—C2 | 1.9 (5) | C4—C3—C2—C1 | −0.6 (5) |
| C5—C4—C3—C6 | −178.4 (3) | C6—C3—C2—C1 | 179.7 (3) |
| O5—C6—C3—C4 | −9.0 (5) | C1—N1—C5—C4 | −1.0 (5) |
| N2—C6—C3—C4 | 169.5 (3) | C3—C4—C5—N1 | −1.2 (5) |
| O5—C6—C3—C2 | 170.7 (3) | C5—N1—C1—C2 | 2.4 (5) |
| N2—C6—C3—C2 | −10.9 (5) | C3—C2—C1—N1 | −1.5 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.86 | 2.10 | 2.932 (4) | 162 |
| N2—H2A···O1ii | 0.86 | 2.32 | 3.162 (4) | 168 |
| N2—H2B···O5iii | 0.86 | 2.17 | 3.004 (4) | 164 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) −x, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.86 | 2.10 | 2.932 (4) | 162 |
| N2—H2A···O1ii | 0.86 | 2.32 | 3.162 (4) | 168 |
| N2—H2B···O5iii | 0.86 | 2.17 | 3.004 (4) | 164 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) −x, y−1/2, −z+1/2. |
This work was supported by a start-up grant from Jiangsu University of Science and Technology, China.
Athimoolam, S. & Natarajan, S. (2007). Acta Cryst. C63, o263–o266.
Czupiński, O., Bator, G., Ciunik, Z., Jakubas, R., Medycki, W. & Świergiel, J. (2002). J. Phys. Condens. Matter, 14, 8497–8512.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Gholivand, K., Zare, K., Afshar, F., Shariatinia, Z. & Khavasi, H. R. (2007). Acta Cryst. E63, o4027.
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.
Recently much attention has been devoted to simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar 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 structures of 4-carbamoylpyridinium dihydrogen phosphate (Gholivand et al., 2007) and 3-(aminocarbonyl)pyridinium perchlorate (Athimoolam & Natarajan, 2007) have been reported previously. In our laboratory, a compound containing 4-carbamoylpyridinium cation and ClO4- anion has been synthesized, its crystal structure is reported herein.
The asymmetric unit of the title compound (Fig. 1) consists of one 4-carbamoylpyridinium cation and one ClO4- anion. The crystal structure is stabilized by intermolecular N—H···O hydrogen bonds (Table 1).