Acta Cryst. (2008). E64, o1764 [ doi:10.1107/S1600536808025312 ]
In the title compound, C6H14N2+·C8H4O42-, the protonated 1,4-diazoniabicyclo[2.2.2]octane cations and the deprotonated terephthalate anions are alternately linked by N-H
O hydrogen bonds into chains.
A mixture of 1,4-diazoniabicyclo[2.2.2]octane (0.072 g), terephthalic acid (0.08 g) and H2O (10 ml) was sealed in a 25 ml stainless-steel reactor with a Teflon-lined stainless steel reactor and was heated at 373 K for 3 d. On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving collorless single crystals suitable for X-ray analysis.
The H atoms bonded to C atoms were placed at calculated positions at C—H distances 0.93 and 0.97 Å for the aryl and methylene H-atoms, respectively, and Uiso(H) = 1.2Ueq(C) using a riding model. The H atoms bonded to N atoms were refined freely.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pv2092fig1thm.gif)
| Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids. |
![[Figure 2]](./pv2092fig2thm.gif)
| Fig. 2. The unit-cell packing of the title compound, showing the hydrogen bonding chains (symmetry code: a = 2 + x, -1 + y, z). |
| C6H14N22+·C8H4O42– | Z = 2 |
| Mr = 278.30 | F000 = 296 |
| Triclinic, P1 | Dx = 1.375 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.8046 (10) Å | Cell parameters from 98 reflections |
| b = 9.5482 (2) Å | θ = 2.1–25.0º |
| c = 10.8075 (2) Å | µ = 0.10 mm−1 |
| α = 65.990 (10)º | T = 293 (2) K |
| β = 78.436 (10)º | Prism, colorless |
| γ = 66.180 (10)º | 0.23 × 0.13 × 0.08 mm |
| V = 672.39 (2) Å3 |
| Siemens SMART 1K CCD area-detector diffractometer | 2377 independent reflections |
| Radiation source: fine-focus sealed tube | 1779 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.026 |
| T = 293(2) K | θmax = 25.0º |
| φ and ω scans | θmin = 2.1º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
| Tmin = 0.900, Tmax = 0.950 | k = −11→11 |
| 7312 measured reflections | l = −12→12 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0633P)2 + 0.1475P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max = 0.002 |
| 2377 reflections | Δρmax = 0.21 e Å−3 |
| 188 parameters | Δρmin = −0.26 e Å−3 |
| 2 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.023 (4) |
| C6H14N22+·C8H4O42– | γ = 66.180 (10)º |
| Mr = 278.30 | V = 672.39 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.8046 (10) Å | Mo Kα |
| b = 9.5482 (2) Å | µ = 0.10 mm−1 |
| c = 10.8075 (2) Å | T = 293 (2) K |
| α = 65.990 (10)º | 0.23 × 0.13 × 0.08 mm |
| β = 78.436 (10)º |
| Siemens SMART 1K CCD area-detector diffractometer | 2377 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1779 reflections with I > 2σ(I) |
| Tmin = 0.900, Tmax = 0.950 | Rint = 0.026 |
| 7312 measured reflections |
| R[F2 > 2σ(F2)] = 0.043 | 2 restraints |
| wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.21 e Å−3 |
| 2377 reflections | Δρmin = −0.26 e Å−3 |
| 188 parameters |
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 | ||
| O1 | 0.2883 (2) | 0.8953 (2) | 0.60534 (16) | 0.0691 (5) | |
| O2 | 0.25555 (18) | 0.84559 (17) | 0.82616 (14) | 0.0489 (4) | |
| O3 | 1.1805 (2) | 0.27977 (19) | 0.89737 (15) | 0.0629 (5) | |
| O4 | 1.23265 (18) | 0.40326 (18) | 0.67751 (14) | 0.0519 (4) | |
| N1 | −0.0871 (2) | 1.03609 (18) | 0.77218 (15) | 0.0328 (4) | |
| H1N | 0.040 (2) | 0.964 (2) | 0.7898 (18) | 0.039* | |
| N2 | −0.4239 (2) | 1.21700 (18) | 0.72154 (14) | 0.0317 (4) | |
| H2N | −0.553 (2) | 1.285 (2) | 0.7069 (18) | 0.038* | |
| C1 | 0.5526 (2) | 0.7124 (2) | 0.73811 (18) | 0.0315 (4) | |
| C2 | 0.6233 (2) | 0.6175 (2) | 0.86638 (18) | 0.0345 (4) | |
| H2A | 0.5455 | 0.6256 | 0.9425 | 0.041* | |
| C3 | 0.8080 (3) | 0.5111 (2) | 0.88253 (18) | 0.0354 (4) | |
| H3A | 0.8524 | 0.4464 | 0.9692 | 0.042* | |
| C4 | 0.9270 (2) | 0.5006 (2) | 0.77020 (17) | 0.0303 (4) | |
| C5 | 0.8571 (3) | 0.5980 (2) | 0.64181 (18) | 0.0352 (4) | |
| H5A | 0.9362 | 0.5932 | 0.5657 | 0.042* | |
| C6 | 0.6722 (3) | 0.7017 (2) | 0.62577 (19) | 0.0376 (5) | |
| H6A | 0.6273 | 0.7649 | 0.5391 | 0.045* | |
| C7 | 0.3509 (3) | 0.8265 (2) | 0.71843 (19) | 0.0376 (5) | |
| C8 | 1.1275 (3) | 0.3846 (2) | 0.78670 (19) | 0.0356 (4) | |
| C9 | −0.3943 (3) | 1.0480 (2) | 0.7369 (2) | 0.0389 (5) | |
| H9A | −0.4315 | 1.0493 | 0.6559 | 0.047* | |
| H9B | −0.4709 | 1.0034 | 0.8132 | 0.047* | |
| C10 | −0.1869 (3) | 0.9399 (2) | 0.7601 (2) | 0.0407 (5) | |
| H10A | −0.1752 | 0.8438 | 0.8422 | 0.049* | |
| H10B | −0.1322 | 0.9032 | 0.6847 | 0.049* | |
| C11 | −0.3778 (3) | 1.2165 (3) | 0.84800 (19) | 0.0419 (5) | |
| H11A | −0.4643 | 1.1827 | 0.9213 | 0.050* | |
| H11B | −0.3897 | 1.3264 | 0.8360 | 0.050* | |
| C12 | −0.1769 (3) | 1.0977 (2) | 0.88353 (18) | 0.0377 (5) | |
| H12A | −0.1062 | 1.1538 | 0.8965 | 0.045* | |
| H12B | −0.1781 | 1.0064 | 0.9672 | 0.045* | |
| C13 | −0.3010 (3) | 1.2820 (2) | 0.60835 (19) | 0.0404 (5) | |
| H13A | −0.3256 | 1.3954 | 0.5939 | 0.048* | |
| H13B | −0.3262 | 1.2783 | 0.5256 | 0.048* | |
| C14 | −0.0959 (3) | 1.1773 (2) | 0.64345 (19) | 0.0411 (5) | |
| H14A | −0.0299 | 1.1377 | 0.5711 | 0.049* | |
| H14B | −0.0356 | 1.2435 | 0.6526 | 0.049* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0381 (9) | 0.0919 (13) | 0.0523 (10) | 0.0164 (8) | −0.0141 (7) | −0.0364 (9) |
| O2 | 0.0265 (7) | 0.0596 (10) | 0.0459 (8) | 0.0020 (7) | 0.0000 (6) | −0.0230 (7) |
| O3 | 0.0341 (8) | 0.0626 (10) | 0.0484 (9) | 0.0015 (7) | −0.0034 (7) | 0.0032 (8) |
| O4 | 0.0259 (7) | 0.0630 (10) | 0.0413 (8) | 0.0009 (7) | 0.0016 (6) | −0.0126 (7) |
| N1 | 0.0195 (8) | 0.0335 (9) | 0.0379 (9) | −0.0030 (7) | −0.0017 (6) | −0.0122 (7) |
| N2 | 0.0203 (8) | 0.0342 (9) | 0.0353 (8) | −0.0016 (7) | −0.0034 (6) | −0.0145 (7) |
| C1 | 0.0242 (9) | 0.0320 (10) | 0.0394 (10) | −0.0070 (8) | −0.0002 (8) | −0.0177 (8) |
| C2 | 0.0277 (10) | 0.0387 (11) | 0.0348 (10) | −0.0085 (8) | 0.0063 (8) | −0.0181 (8) |
| C3 | 0.0316 (10) | 0.0363 (10) | 0.0305 (9) | −0.0076 (8) | −0.0022 (8) | −0.0091 (8) |
| C4 | 0.0248 (9) | 0.0272 (9) | 0.0360 (10) | −0.0076 (8) | 0.0007 (8) | −0.0116 (8) |
| C5 | 0.0270 (10) | 0.0388 (11) | 0.0329 (10) | −0.0059 (8) | 0.0043 (8) | −0.0149 (8) |
| C6 | 0.0297 (10) | 0.0403 (11) | 0.0325 (10) | −0.0027 (8) | −0.0048 (8) | −0.0115 (8) |
| C7 | 0.0270 (10) | 0.0403 (11) | 0.0456 (11) | −0.0045 (8) | −0.0033 (9) | −0.0226 (9) |
| C8 | 0.0263 (10) | 0.0344 (10) | 0.0399 (11) | −0.0069 (8) | −0.0030 (8) | −0.0108 (9) |
| C9 | 0.0333 (11) | 0.0375 (11) | 0.0475 (11) | −0.0130 (9) | −0.0045 (9) | −0.0156 (9) |
| C10 | 0.0378 (11) | 0.0316 (10) | 0.0518 (12) | −0.0081 (9) | −0.0050 (9) | −0.0173 (9) |
| C11 | 0.0308 (11) | 0.0532 (13) | 0.0422 (11) | −0.0041 (9) | −0.0019 (8) | −0.0285 (10) |
| C12 | 0.0311 (10) | 0.0438 (11) | 0.0365 (10) | −0.0076 (9) | −0.0059 (8) | −0.0170 (9) |
| C13 | 0.0360 (11) | 0.0348 (11) | 0.0397 (10) | −0.0087 (9) | −0.0027 (8) | −0.0068 (9) |
| C14 | 0.0303 (10) | 0.0420 (11) | 0.0414 (11) | −0.0105 (9) | 0.0028 (8) | −0.0104 (9) |
| O1—C7 | 1.221 (2) | C4—C8 | 1.503 (2) |
| O2—C7 | 1.288 (2) | C5—C6 | 1.378 (3) |
| O3—C8 | 1.222 (2) | C5—H5A | 0.9300 |
| O4—C8 | 1.287 (2) | C6—H6A | 0.9300 |
| N1—C10 | 1.478 (2) | C9—C10 | 1.533 (3) |
| N1—C12 | 1.480 (2) | C9—H9A | 0.9700 |
| N1—C14 | 1.482 (2) | C9—H9B | 0.9700 |
| N1—H1N | 0.954 (15) | C10—H10A | 0.9700 |
| N2—C9 | 1.477 (2) | C10—H10B | 0.9700 |
| N2—C11 | 1.479 (2) | C11—C12 | 1.531 (3) |
| N2—C13 | 1.481 (2) | C11—H11A | 0.9700 |
| N2—H2N | 0.959 (15) | C11—H11B | 0.9700 |
| C1—C6 | 1.388 (2) | C12—H12A | 0.9700 |
| C1—C2 | 1.388 (3) | C12—H12B | 0.9700 |
| C1—C7 | 1.507 (2) | C13—C14 | 1.532 (3) |
| C2—C3 | 1.383 (3) | C13—H13A | 0.9700 |
| C2—H2A | 0.9300 | C13—H13B | 0.9700 |
| C3—C4 | 1.385 (2) | C14—H14A | 0.9700 |
| C3—H3A | 0.9300 | C14—H14B | 0.9700 |
| C4—C5 | 1.390 (2) | ||
| C10—N1—C12 | 109.46 (14) | N2—C9—C10 | 109.63 (14) |
| C10—N1—C14 | 109.60 (14) | N2—C9—H9A | 109.7 |
| C12—N1—C14 | 109.29 (14) | C10—C9—H9A | 109.7 |
| C10—N1—H1N | 106.8 (11) | N2—C9—H9B | 109.7 |
| C12—N1—H1N | 111.5 (11) | C10—C9—H9B | 109.7 |
| C14—N1—H1N | 110.1 (11) | H9A—C9—H9B | 108.2 |
| C9—N2—C11 | 109.82 (14) | N1—C10—C9 | 109.09 (14) |
| C9—N2—C13 | 109.48 (14) | N1—C10—H10A | 109.9 |
| C11—N2—C13 | 109.17 (15) | C9—C10—H10A | 109.9 |
| C9—N2—H2N | 109.9 (11) | N1—C10—H10B | 109.9 |
| C11—N2—H2N | 106.9 (11) | C9—C10—H10B | 109.9 |
| C13—N2—H2N | 111.5 (11) | H10A—C10—H10B | 108.3 |
| C6—C1—C2 | 118.69 (16) | N2—C11—C12 | 109.40 (14) |
| C6—C1—C7 | 119.60 (16) | N2—C11—H11A | 109.8 |
| C2—C1—C7 | 121.71 (16) | C12—C11—H11A | 109.8 |
| C3—C2—C1 | 120.90 (16) | N2—C11—H11B | 109.8 |
| C3—C2—H2A | 119.6 | C12—C11—H11B | 109.8 |
| C1—C2—H2A | 119.6 | H11A—C11—H11B | 108.2 |
| C2—C3—C4 | 120.26 (17) | N1—C12—C11 | 109.31 (14) |
| C2—C3—H3A | 119.9 | N1—C12—H12A | 109.8 |
| C4—C3—H3A | 119.9 | C11—C12—H12A | 109.8 |
| C3—C4—C5 | 118.80 (16) | N1—C12—H12B | 109.8 |
| C3—C4—C8 | 120.66 (16) | C11—C12—H12B | 109.8 |
| C5—C4—C8 | 120.54 (16) | H12A—C12—H12B | 108.3 |
| C6—C5—C4 | 120.92 (16) | N2—C13—C14 | 108.99 (15) |
| C6—C5—H5A | 119.5 | N2—C13—H13A | 109.9 |
| C4—C5—H5A | 119.5 | C14—C13—H13A | 109.9 |
| C5—C6—C1 | 120.40 (17) | N2—C13—H13B | 109.9 |
| C5—C6—H6A | 119.8 | C14—C13—H13B | 109.9 |
| C1—C6—H6A | 119.8 | H13A—C13—H13B | 108.3 |
| O1—C7—O2 | 124.21 (17) | N1—C14—C13 | 109.66 (14) |
| O1—C7—C1 | 120.01 (17) | N1—C14—H14A | 109.7 |
| O2—C7—C1 | 115.77 (16) | C13—C14—H14A | 109.7 |
| O3—C8—O4 | 124.30 (17) | N1—C14—H14B | 109.7 |
| O3—C8—C4 | 120.41 (17) | C13—C14—H14B | 109.7 |
| O4—C8—C4 | 115.28 (16) | H14A—C14—H14B | 108.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O2 | 0.954 (15) | 1.623 (15) | 2.5757 (19) | 176.8 (17) |
| N2—H2N···O4i | 0.959 (15) | 1.600 (15) | 2.5589 (19) | 177.9 (18) |
| Symmetry codes: (i) x−2, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O2 | 0.954 (15) | 1.623 (15) | 2.5757 (19) | 176.8 (17) |
| N2—H2N···O4i | 0.959 (15) | 1.600 (15) | 2.5589 (19) | 177.9 (18) |
| Symmetry codes: (i) x−2, y+1, z. |
The authors acknowledge the financial support from the Natural Science Foundation of Fujian Province (No. 2006 F3042).
Bergerhoff, G., Berndt, M. & Brandenburg, K. (1996). J. Res. Natl Inst. Stand. Technol. 101, 221–225.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
The asymmetric unit of the title compound, (I), consists of a protonated 1,4-diazoniabicyclo[2.2.2]octane cation, C6H14N2+, and a deprotonated terephthalate anion, C8H4O42-, (Figure 1). Single N—H···O hydrogen bond was formed between the protonated N end of the cation and the deprotonated carboxylate group of the anion, which generates the hydrogen bonding chains (Table 1 & Figure 2).