Acta Cryst. (2007). E63, o3356 [ doi:10.1107/S1600536807031170 ]
Anions and cations of the title compound, C5H8N3+·C4HO4-, are connected by moderately strong intermolecular N-H
O hydrogen bonds into an infinite three-dimensional network. Hydrogen squarate anions form dimers through strong O-HO interactions.
3,4-diaminopyridinium hydrogensquarate was obtained by mixing an equimolar ratio of 3,4-diaminopyridine (Merck) and squaric acid (Sigma-Aldrich) in 10 ml e thanol. Suitable crystals for X-ray analysis, were grown by allowing the solution to slowly evaporate for 10 days, and were subsequently filtered off, washed with methanol and dried under air.
H atoms were constrained to idealized positions and refined using a riding model, with C—H distances of 0.93 Å [Uiso(H) = 1.2 Uiso(C)], NH distances of 0.86 Å [Uiso(H) = 1.5 Uiso(N) and O—H distances of 0.82 Å [Uiso(H) = 1.5 Uiso(O)].
Data collection: R3m/V (Siemens, 1989); cell refinement: R3m/V; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.
![[Figure 1]](./bt2412fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./bt2412fig2thm.gif)
| Fig. 2. Hydrogen bonding between the anions and cations of (I). |
| C5H8N3+·C4HO4− | F(000) = 464 |
| Mr = 223.19 | Dx = 1.529 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 27 reflections |
| a = 10.069 (2) Å | θ = 7.5–15° |
| b = 7.1925 (14) Å | µ = 0.12 mm−1 |
| c = 13.480 (3) Å | T = 294 K |
| β = 96.56 (3)° | Prsim, colourless |
| V = 969.8 (3) Å3 | 0.58 × 0.48 × 0.46 mm |
| Z = 4 |
| Siemens P4 four-circle diffractometer | 1172 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.044 |
| graphite | θmax = 25.0°, θmin = 2.0° |
| ω scans | h = −1→11 |
| Absorption correction: ψ scan (XPREP; Sheldrick, 1995) | k = −1→8 |
| Tmin = 0.844, Tmax = 0.938 | l = −16→16 |
| 2310 measured reflections | 3 standard reflections every 100 reflections |
| 1698 independent reflections | intensity decay: 1% |
| 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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.189 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0946P)2 + 0.5492P] where P = (Fo2 + 2Fc2)/3 |
| 1698 reflections | (Δ/σ)max = 0.001 |
| 154 parameters | Δρmax = 0.24 e Å−3 |
| 0 restraints | Δρmin = −0.37 e Å−3 |
| C5H8N3+·C4HO4− | V = 969.8 (3) Å3 |
| Mr = 223.19 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.069 (2) Å | µ = 0.12 mm−1 |
| b = 7.1925 (14) Å | T = 294 K |
| c = 13.480 (3) Å | 0.58 × 0.48 × 0.46 mm |
| β = 96.56 (3)° |
| Siemens P4 four-circle diffractometer | 1172 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (XPREP; Sheldrick, 1995) | Rint = 0.044 |
| Tmin = 0.844, Tmax = 0.938 | θmax = 25.0° |
| 2310 measured reflections | 3 standard reflections every 100 reflections |
| 1698 independent reflections | intensity decay: 1% |
| R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
| wR(F2) = 0.189 | Δρmax = 0.24 e Å−3 |
| S = 1.09 | Δρmin = −0.37 e Å−3 |
| 1698 reflections | Absolute structure: ? |
| 154 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 | ||
| N1 | 0.7328 (3) | 0.3740 (5) | 1.0145 (2) | 0.0559 (9) | |
| H1 | 0.6586 | 0.3990 | 1.0375 | 0.067* | |
| C2 | 0.8249 (3) | 0.2759 (5) | 1.0705 (3) | 0.0520 (9) | |
| H2 | 0.8086 | 0.2368 | 1.1338 | 0.062* | |
| C3 | 0.9425 (3) | 0.2325 (5) | 1.0359 (2) | 0.0472 (9) | |
| H3 | 1.0057 | 0.1624 | 1.0754 | 0.057* | |
| N2 | 1.0874 (2) | 0.2506 (4) | 0.9064 (2) | 0.0498 (8) | |
| H21 | 1.1031 | 0.2865 | 0.8480 | 0.060* | |
| H22 | 1.1465 | 0.1877 | 0.9434 | 0.060* | |
| C4 | 0.9699 (3) | 0.2929 (5) | 0.9401 (2) | 0.0400 (8) | |
| N3 | 0.8886 (3) | 0.4537 (5) | 0.7857 (2) | 0.0568 (9) | |
| H31 | 0.8270 | 0.5150 | 0.7503 | 0.068* | |
| H32 | 0.9620 | 0.4277 | 0.7619 | 0.068* | |
| C5 | 0.8693 (3) | 0.3965 (5) | 0.8816 (2) | 0.0403 (8) | |
| C6 | 0.7522 (3) | 0.4362 (5) | 0.9219 (3) | 0.0511 (9) | |
| H6 | 0.6860 | 0.5061 | 0.8854 | 0.061* | |
| C1' | 0.2926 (3) | 0.0429 (5) | 0.2041 (2) | 0.0429 (8) | |
| O1' | 0.1804 (2) | 0.0879 (4) | 0.22347 (18) | 0.0579 (8) | |
| C2' | 0.3618 (3) | 0.0417 (5) | 0.1124 (2) | 0.0417 (8) | |
| O2' | 0.3283 (2) | 0.0894 (4) | 0.02326 (16) | 0.0519 (7) | |
| C3' | 0.4780 (3) | −0.0317 (5) | 0.1697 (2) | 0.0414 (8) | |
| O3' | 0.5998 (2) | −0.0799 (4) | 0.15119 (17) | 0.0576 (8) | |
| H3' | 0.6030 | −0.0814 | 0.0907 | 0.086* | |
| C4' | 0.4173 (3) | −0.0327 (5) | 0.2619 (3) | 0.0465 (9) | |
| O4' | 0.4548 (2) | −0.0753 (4) | 0.34977 (18) | 0.0589 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0358 (14) | 0.072 (2) | 0.062 (2) | −0.0045 (15) | 0.0139 (13) | −0.0134 (18) |
| C2 | 0.049 (2) | 0.060 (2) | 0.048 (2) | −0.0107 (18) | 0.0109 (16) | −0.0025 (18) |
| C3 | 0.0440 (17) | 0.052 (2) | 0.0449 (19) | −0.0018 (16) | 0.0021 (14) | −0.0001 (17) |
| N2 | 0.0357 (14) | 0.063 (2) | 0.0504 (17) | 0.0070 (13) | 0.0061 (12) | 0.0012 (15) |
| C4 | 0.0335 (15) | 0.0413 (18) | 0.0444 (18) | −0.0026 (14) | 0.0012 (13) | −0.0080 (15) |
| N3 | 0.0509 (17) | 0.076 (2) | 0.0430 (17) | 0.0126 (16) | 0.0020 (13) | 0.0090 (16) |
| C5 | 0.0364 (16) | 0.0447 (19) | 0.0389 (17) | −0.0023 (14) | −0.0003 (13) | −0.0048 (15) |
| C6 | 0.0375 (17) | 0.056 (2) | 0.058 (2) | 0.0015 (16) | −0.0040 (15) | −0.0087 (19) |
| C1' | 0.0296 (15) | 0.053 (2) | 0.0465 (18) | −0.0003 (14) | 0.0043 (13) | −0.0021 (16) |
| O1' | 0.0304 (11) | 0.090 (2) | 0.0544 (14) | 0.0110 (12) | 0.0107 (10) | 0.0002 (14) |
| C2' | 0.0284 (15) | 0.053 (2) | 0.0438 (18) | 0.0011 (14) | 0.0040 (13) | −0.0060 (16) |
| O2' | 0.0322 (11) | 0.0770 (18) | 0.0462 (14) | 0.0142 (11) | 0.0023 (9) | −0.0022 (13) |
| C3' | 0.0277 (14) | 0.056 (2) | 0.0415 (18) | 0.0034 (14) | 0.0076 (12) | −0.0001 (16) |
| O3' | 0.0303 (11) | 0.094 (2) | 0.0500 (14) | 0.0170 (12) | 0.0092 (10) | 0.0092 (14) |
| C4' | 0.0272 (15) | 0.059 (2) | 0.053 (2) | 0.0003 (15) | 0.0026 (14) | −0.0006 (18) |
| O4' | 0.0330 (12) | 0.095 (2) | 0.0495 (14) | 0.0065 (12) | 0.0070 (10) | 0.0134 (14) |
| N1—C2 | 1.330 (5) | N3—H32 | 0.8600 |
| N1—C6 | 1.360 (5) | C5—C6 | 1.383 (4) |
| N1—H1 | 0.8600 | C6—H6 | 0.9300 |
| C2—C3 | 1.358 (5) | C1'—O1' | 1.232 (4) |
| C2—H2 | 0.9300 | C1'—C2' | 1.486 (4) |
| C3—C4 | 1.420 (5) | C1'—C4' | 1.501 (4) |
| C3—H3 | 0.9300 | C2'—O2' | 1.259 (4) |
| N2—C4 | 1.349 (4) | C2'—C3' | 1.427 (4) |
| N2—H21 | 0.8600 | C3'—O3' | 1.325 (3) |
| N2—H22 | 0.8600 | C3'—C4' | 1.446 (4) |
| C4—C5 | 1.421 (4) | O3'—H3' | 0.8200 |
| N3—C5 | 1.391 (4) | C4'—O4' | 1.241 (4) |
| N3—H31 | 0.8600 | ||
| C2—N1—C6 | 122.1 (3) | C6—C5—C4 | 118.4 (3) |
| C2—N1—H1 | 118.9 | N3—C5—C4 | 120.3 (3) |
| C6—N1—H1 | 118.9 | N1—C6—C5 | 120.7 (3) |
| N1—C2—C3 | 120.4 (3) | N1—C6—H6 | 119.7 |
| N1—C2—H2 | 119.8 | C5—C6—H6 | 119.7 |
| C3—C2—H2 | 119.8 | O1'—C1'—C2' | 134.9 (3) |
| C2—C3—C4 | 120.7 (3) | O1'—C1'—C4' | 135.9 (3) |
| C2—C3—H3 | 119.7 | C2'—C1'—C4' | 89.2 (2) |
| C4—C3—H3 | 119.7 | O2'—C2'—C3' | 137.0 (3) |
| C4—N2—H21 | 120.0 | O2'—C2'—C1' | 133.8 (3) |
| C4—N2—H22 | 120.0 | C3'—C2'—C1' | 89.2 (3) |
| H21—N2—H22 | 120.0 | O3'—C3'—C2' | 135.6 (3) |
| N2—C4—C5 | 121.9 (3) | O3'—C3'—C4' | 130.7 (3) |
| N2—C4—C3 | 120.4 (3) | C2'—C3'—C4' | 93.8 (2) |
| C5—C4—C3 | 117.7 (3) | C3'—O3'—H3' | 109.5 |
| C5—N3—H31 | 120.0 | O4'—C4'—C3' | 135.2 (3) |
| C5—N3—H32 | 120.0 | O4'—C4'—C1' | 136.9 (3) |
| H31—N3—H32 | 120.0 | C3'—C4'—C1' | 87.9 (3) |
| C6—C5—N3 | 121.3 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3'—H3'···O2'i | 0.82 | 1.76 | 2.539 (3) | 159 |
| N2—H21···O1'ii | 0.86 | 2.13 | 2.972 (4) | 166 |
| N1—H1···O4'iii | 0.86 | 2.01 | 2.799 (4) | 152 |
| N2—H22···O2'iv | 0.86 | 2.14 | 2.973 (3) | 164 |
| Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x+1, y, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3'—H3'···O2'i | 0.82 | 1.76 | 2.539 (3) | 159 |
| N2—H21···O1'ii | 0.86 | 2.13 | 2.972 (4) | 166 |
| N1—H1···O4'iii | 0.86 | 2.01 | 2.799 (4) | 152 |
| N2—H22···O2'iv | 0.86 | 2.14 | 2.973 (3) | 164 |
| Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x+1, y, z+1. |
BK thanks the Alexander von Humboldt Foundation for a Fellowship and TK thanks the DAAD and the Alexander von Humboldt Foundation for a grant within the priority programme `Stability Pact South-Eastern Europe'.
Kolev, T., Fiser, S. S., Spiteller, M., Sheldrick, W. S. & Mayer-Figge, H. (2005). Acta Cryst. E61, o1469–o1471.
Kolev, T., Koleva, B. B., Spassov, T., Cherneva, E., Spiteller, M., Sheldrick, W. S. & Mayer-Figge, H. (2007). J. Phys. Chem. B In the press. Update?
Kolev, T., Wortmann, R., Spiteller, M., Sheldrick, W. S. & Heller, M. (2004). Acta Cryst. E60, o956–o957.
Kolev, T., Wortmann, R., Spiteller, M., Sheldrick, W. S. & Mayer-Figge, H. (2005). Acta Cryst. E61, o1090–o1092.
Sheldrick, G. M. (1995). SHELXTL (Release 5.03 for Siemens R3 crystallographic research system). Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Siemens (1989). R3m/V (Version 3.2). Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
In the course of our spectroscopic and structural studies of pyridine derivatives (Kolev et al., 2004; Kolev, Wortmann et al.,2005; Kolev, Fiser et al., 2005; Kolev et al., 2007), the crystal structure of 3,4-diaminopyridinium hydrogensquarate is reported. Its molecular structure is depicted in Fig. 1. The crystal structure consists of chains of cations and anions connected by moderate hydrogen bonds (Fig. 2) with N···O lengths of 2.799 (4), 2.972 (4) and 2.973 (4) Å, respectively. Hydrogensquarate anions are linked into centrosymmetric dimers by strong O—H···O [O···O = 2.539 (3) Å] interactions.