PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1764.
Published online 2008 August 16. doi:  10.1107/S1600536808025312
PMCID: PMC2960572

1,4-Diazo­niabicyclo­[2.2.2]octane terephthalate

Abstract

In the title compound, C6H14N2+·C8H4O4 2−, 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.

An external file that holds a picture, illustration, etc.
Object name is e-64-o1764-scheme1.jpg

Experimental

Crystal data

  • C6H14N2 2+·C8H4O4 2−
  • M r = 278.30
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1764-efi1.jpg
  • a = 7.8046 (10) Å
  • b = 9.5482 (2) Å
  • c = 10.8075 (2) Å
  • α = 65.900 (10)°
  • β = 78.360 (10)°
  • γ = 66.800 (10)°
  • V = 672.39 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 (2) K
  • 0.23 × 0.13 × 0.08 mm

Data collection

  • Siemens SMART 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.900, T max = 0.950
  • 7312 measured reflections
  • 2377 independent reflections
  • 1779 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.125
  • S = 1.04
  • 2377 reflections
  • 188 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Bergerhoff et al., 1996 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025312/pv2092sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025312/pv2092Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the financial support from the Natural Science Foundation of Fujian Province (No. 2006 F3042).

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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.

Figures

Fig. 1.
A view of the title compound, showing 30% probability displacement ellipsoids.
Fig. 2.
The unit-cell packing of the title compound, showing the hydrogen bonding chains (symmetry code: a = 2 + x, -1 + y, z).

Crystal data

C6H14N22+·C8H4O42–Z = 2
Mr = 278.30F000 = 296
Triclinic, P1Dx = 1.375 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.8046 (10) ÅCell parameters from 98 reflections
b = 9.5482 (2) Åθ = 2.1–25.0º
c = 10.8075 (2) ŵ = 0.10 mm1
α = 65.990 (10)ºT = 293 (2) K
β = 78.436 (10)ºPrism, colorless
γ = 66.180 (10)º0.23 × 0.13 × 0.08 mm
V = 672.39 (2) Å3

Data collection

Siemens SMART 1K CCD area-detector diffractometer2377 independent reflections
Radiation source: fine-focus sealed tube1779 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 293(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.900, Tmax = 0.950k = −11→11
7312 measured reflectionsl = −12→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H 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 reflectionsΔρmax = 0.21 e Å3
188 parametersΔρmin = −0.26 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.023 (4)

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
O10.2883 (2)0.8953 (2)0.60534 (16)0.0691 (5)
O20.25555 (18)0.84559 (17)0.82616 (14)0.0489 (4)
O31.1805 (2)0.27977 (19)0.89737 (15)0.0629 (5)
O41.23265 (18)0.40326 (18)0.67751 (14)0.0519 (4)
N1−0.0871 (2)1.03609 (18)0.77218 (15)0.0328 (4)
H1N0.040 (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*
C10.5526 (2)0.7124 (2)0.73811 (18)0.0315 (4)
C20.6233 (2)0.6175 (2)0.86638 (18)0.0345 (4)
H2A0.54550.62560.94250.041*
C30.8080 (3)0.5111 (2)0.88253 (18)0.0354 (4)
H3A0.85240.44640.96920.042*
C40.9270 (2)0.5006 (2)0.77020 (17)0.0303 (4)
C50.8571 (3)0.5980 (2)0.64181 (18)0.0352 (4)
H5A0.93620.59320.56570.042*
C60.6722 (3)0.7017 (2)0.62577 (19)0.0376 (5)
H6A0.62730.76490.53910.045*
C70.3509 (3)0.8265 (2)0.71843 (19)0.0376 (5)
C81.1275 (3)0.3846 (2)0.78670 (19)0.0356 (4)
C9−0.3943 (3)1.0480 (2)0.7369 (2)0.0389 (5)
H9A−0.43151.04930.65590.047*
H9B−0.47091.00340.81320.047*
C10−0.1869 (3)0.9399 (2)0.7601 (2)0.0407 (5)
H10A−0.17520.84380.84220.049*
H10B−0.13220.90320.68470.049*
C11−0.3778 (3)1.2165 (3)0.84800 (19)0.0419 (5)
H11A−0.46431.18270.92130.050*
H11B−0.38971.32640.83600.050*
C12−0.1769 (3)1.0977 (2)0.88353 (18)0.0377 (5)
H12A−0.10621.15380.89650.045*
H12B−0.17811.00640.96720.045*
C13−0.3010 (3)1.2820 (2)0.60835 (19)0.0404 (5)
H13A−0.32561.39540.59390.048*
H13B−0.32621.27830.52560.048*
C14−0.0959 (3)1.1773 (2)0.64345 (19)0.0411 (5)
H14A−0.02991.13770.57110.049*
H14B−0.03561.24350.65260.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0381 (9)0.0919 (13)0.0523 (10)0.0164 (8)−0.0141 (7)−0.0364 (9)
O20.0265 (7)0.0596 (10)0.0459 (8)0.0020 (7)0.0000 (6)−0.0230 (7)
O30.0341 (8)0.0626 (10)0.0484 (9)0.0015 (7)−0.0034 (7)0.0032 (8)
O40.0259 (7)0.0630 (10)0.0413 (8)0.0009 (7)0.0016 (6)−0.0126 (7)
N10.0195 (8)0.0335 (9)0.0379 (9)−0.0030 (7)−0.0017 (6)−0.0122 (7)
N20.0203 (8)0.0342 (9)0.0353 (8)−0.0016 (7)−0.0034 (6)−0.0145 (7)
C10.0242 (9)0.0320 (10)0.0394 (10)−0.0070 (8)−0.0002 (8)−0.0177 (8)
C20.0277 (10)0.0387 (11)0.0348 (10)−0.0085 (8)0.0063 (8)−0.0181 (8)
C30.0316 (10)0.0363 (10)0.0305 (9)−0.0076 (8)−0.0022 (8)−0.0091 (8)
C40.0248 (9)0.0272 (9)0.0360 (10)−0.0076 (8)0.0007 (8)−0.0116 (8)
C50.0270 (10)0.0388 (11)0.0329 (10)−0.0059 (8)0.0043 (8)−0.0149 (8)
C60.0297 (10)0.0403 (11)0.0325 (10)−0.0027 (8)−0.0048 (8)−0.0115 (8)
C70.0270 (10)0.0403 (11)0.0456 (11)−0.0045 (8)−0.0033 (9)−0.0226 (9)
C80.0263 (10)0.0344 (10)0.0399 (11)−0.0069 (8)−0.0030 (8)−0.0108 (9)
C90.0333 (11)0.0375 (11)0.0475 (11)−0.0130 (9)−0.0045 (9)−0.0156 (9)
C100.0378 (11)0.0316 (10)0.0518 (12)−0.0081 (9)−0.0050 (9)−0.0173 (9)
C110.0308 (11)0.0532 (13)0.0422 (11)−0.0041 (9)−0.0019 (8)−0.0285 (10)
C120.0311 (10)0.0438 (11)0.0365 (10)−0.0076 (9)−0.0059 (8)−0.0170 (9)
C130.0360 (11)0.0348 (11)0.0397 (10)−0.0087 (9)−0.0027 (8)−0.0068 (9)
C140.0303 (10)0.0420 (11)0.0414 (11)−0.0105 (9)0.0028 (8)−0.0104 (9)

Geometric parameters (Å, °)

O1—C71.221 (2)C4—C81.503 (2)
O2—C71.288 (2)C5—C61.378 (3)
O3—C81.222 (2)C5—H5A0.9300
O4—C81.287 (2)C6—H6A0.9300
N1—C101.478 (2)C9—C101.533 (3)
N1—C121.480 (2)C9—H9A0.9700
N1—C141.482 (2)C9—H9B0.9700
N1—H1N0.954 (15)C10—H10A0.9700
N2—C91.477 (2)C10—H10B0.9700
N2—C111.479 (2)C11—C121.531 (3)
N2—C131.481 (2)C11—H11A0.9700
N2—H2N0.959 (15)C11—H11B0.9700
C1—C61.388 (2)C12—H12A0.9700
C1—C21.388 (3)C12—H12B0.9700
C1—C71.507 (2)C13—C141.532 (3)
C2—C31.383 (3)C13—H13A0.9700
C2—H2A0.9300C13—H13B0.9700
C3—C41.385 (2)C14—H14A0.9700
C3—H3A0.9300C14—H14B0.9700
C4—C51.390 (2)
C10—N1—C12109.46 (14)N2—C9—C10109.63 (14)
C10—N1—C14109.60 (14)N2—C9—H9A109.7
C12—N1—C14109.29 (14)C10—C9—H9A109.7
C10—N1—H1N106.8 (11)N2—C9—H9B109.7
C12—N1—H1N111.5 (11)C10—C9—H9B109.7
C14—N1—H1N110.1 (11)H9A—C9—H9B108.2
C9—N2—C11109.82 (14)N1—C10—C9109.09 (14)
C9—N2—C13109.48 (14)N1—C10—H10A109.9
C11—N2—C13109.17 (15)C9—C10—H10A109.9
C9—N2—H2N109.9 (11)N1—C10—H10B109.9
C11—N2—H2N106.9 (11)C9—C10—H10B109.9
C13—N2—H2N111.5 (11)H10A—C10—H10B108.3
C6—C1—C2118.69 (16)N2—C11—C12109.40 (14)
C6—C1—C7119.60 (16)N2—C11—H11A109.8
C2—C1—C7121.71 (16)C12—C11—H11A109.8
C3—C2—C1120.90 (16)N2—C11—H11B109.8
C3—C2—H2A119.6C12—C11—H11B109.8
C1—C2—H2A119.6H11A—C11—H11B108.2
C2—C3—C4120.26 (17)N1—C12—C11109.31 (14)
C2—C3—H3A119.9N1—C12—H12A109.8
C4—C3—H3A119.9C11—C12—H12A109.8
C3—C4—C5118.80 (16)N1—C12—H12B109.8
C3—C4—C8120.66 (16)C11—C12—H12B109.8
C5—C4—C8120.54 (16)H12A—C12—H12B108.3
C6—C5—C4120.92 (16)N2—C13—C14108.99 (15)
C6—C5—H5A119.5N2—C13—H13A109.9
C4—C5—H5A119.5C14—C13—H13A109.9
C5—C6—C1120.40 (17)N2—C13—H13B109.9
C5—C6—H6A119.8C14—C13—H13B109.9
C1—C6—H6A119.8H13A—C13—H13B108.3
O1—C7—O2124.21 (17)N1—C14—C13109.66 (14)
O1—C7—C1120.01 (17)N1—C14—H14A109.7
O2—C7—C1115.77 (16)C13—C14—H14A109.7
O3—C8—O4124.30 (17)N1—C14—H14B109.7
O3—C8—C4120.41 (17)C13—C14—H14B109.7
O4—C8—C4115.28 (16)H14A—C14—H14B108.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.954 (15)1.623 (15)2.5757 (19)176.8 (17)
N2—H2N···O4i0.959 (15)1.600 (15)2.5589 (19)177.9 (18)

Symmetry codes: (i) x−2, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2092).

References

  • 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. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography