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The title compound, C
6H
14N
22+·2C
7H
4NO
4−·2.17H
2O, is a hydrated molecular salt. The cation has crystallographic twofold rotation symmetry, and the component species interact by way of bifurcated N—H
(O, N) hydrogen bonds to result in associations of two anions and one cation. The anion is stabilized by an intramolecular O—H
O bond. The water molecules are disordered and occupy [001]
pseudo channels in the structure.
Supporting information
CCDC reference: 673036
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
Some non-H atoms missing
- Disorder in main residue
- R factor = 0.051
- wR factor = 0.155
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT430_ALERT_2_A Short Inter D...A Contact O11 .. O13 .. 1.81 Ang.
| Author Response: this is a disorder artefact
|
PLAT430_ALERT_2_A Short Inter D...A Contact O11 .. O13 .. 2.38 Ang.
| Author Response: this is a disorder artefact
|
PLAT430_ALERT_2_A Short Inter D...A Contact O12 .. O12 .. 1.95 Ang.
| Author Response: this is a disorder artefact
|
Alert level C
CHEMW01_ALERT_1_C The difference between the given and expected weight for
compound is greater 1 mass unit. Check that all hydrogen
atoms have been taken into account.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.16
PLAT301_ALERT_3_C Main Residue Disorder ......................... 6.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O11
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <O12
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C8 - C10 ... 1.53 Ang.
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C20 H26.34 N4 O10.17
Atom count from the _atom_site data: C20 H22 N4 O10.342
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
symmetry error - see SYMMG tests
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C20 H26.34 N4 O10.17
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 80.00 80.00 0.00
H 105.36 88.00 17.36
N 16.00 16.00 0.00
O 40.68 41.37 -0.69
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
3 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
10 ALERT level C = Check and explain
5 ALERT level G = General alerts; check
8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
9 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Pyridine-2,3-dicarboxylic acid (0.0835 g, 0.5 mmol) was dissolved in hot water.
To the resulting clear solution was added an aqueous solution of
diazabicyclo[2.2.2]octane (0.056 g, 0.5 mmol). The mixture was allowed to
crystallize at room temperature. Colourless blocks of (I) were obtained after
six weeks. The crystals were washed with doubly distilled water and finally
with ether and then air dried.
The carboxylic acid hydrogen atom was located in a difference map and refined as
riding in its as-found relative position. The C– and N-bound H atoms were
geometrically placed (C—H = 0.93–0.97 Å, N—H = 0.91 Å) and refined as
riding. The constraint Uiso(H) = 1.2Ueq(carrier) was applied
in all cases. The H atoms of the disordered water molecules could not be
located in difference maps, nor could they be geometrically placed in an
unambiguous manner.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
1,4-Diazoniabicyclo[2.2.2]octane bis(3-carboxypyridine-2-carboxylate)
2.17-hydrate
top
Crystal data top
C6H14N22+·2C7H4NO4−·2.17H2O | F(000) = 1030 |
Mr = 488.62 | Dx = 1.525 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 35550 reflections |
a = 19.4117 (6) Å | θ = 1.0–29.5° |
b = 8.1486 (3) Å | µ = 0.12 mm−1 |
c = 13.4528 (4) Å | T = 293 K |
V = 2127.94 (12) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.15 × 0.15 mm |
Data collection top
Bruker SMART1000 CCD diffractometer | 2239 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 29.5°, θmin = 3.0° |
ω scans | h = −26→26 |
46987 measured reflections | k = −11→11 |
2958 independent reflections | l = −18→18 |
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)] = 0.051 | Hydrogen site location: difmap and geom |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0738P)2 + 0.9232P] where P = (Fo2 + 2Fc2)/3 |
2958 reflections | (Δ/σ)max = 0.001 |
169 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C6H14N22+·2C7H4NO4−·2.17H2O | V = 2127.94 (12) Å3 |
Mr = 488.62 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 19.4117 (6) Å | µ = 0.12 mm−1 |
b = 8.1486 (3) Å | T = 293 K |
c = 13.4528 (4) Å | 0.20 × 0.15 × 0.15 mm |
Data collection top
Bruker SMART1000 CCD diffractometer | 2239 reflections with I > 2σ(I) |
46987 measured reflections | Rint = 0.034 |
2958 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.40 e Å−3 |
2958 reflections | Δρmin = −0.27 e Å−3 |
169 parameters | |
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 | Occ. (<1) |
N1 | 0.44586 (6) | 0.05154 (17) | 0.79953 (9) | 0.0365 (3) | |
H1 | 0.4062 | 0.0516 | 0.8357 | 0.044* | |
C1 | 0.50208 (8) | −0.0217 (2) | 0.85972 (12) | 0.0452 (4) | |
H1A | 0.4877 | −0.1272 | 0.8858 | 0.054* | |
H1B | 0.5132 | 0.0496 | 0.9152 | 0.054* | |
C2 | 0.43507 (8) | −0.0429 (3) | 0.70684 (12) | 0.0478 (4) | |
H2A | 0.3942 | −0.0036 | 0.6729 | 0.057* | |
H2B | 0.4286 | −0.1581 | 0.7223 | 0.057* | |
C3 | 0.46380 (10) | 0.2233 (2) | 0.77198 (16) | 0.0548 (5) | |
H3A | 0.4622 | 0.2932 | 0.8303 | 0.066* | |
H3B | 0.4311 | 0.2650 | 0.7236 | 0.066* | |
C4 | 0.26026 (9) | −0.0092 (2) | 0.78806 (12) | 0.0441 (4) | |
H4 | 0.2796 | −0.0662 | 0.7351 | 0.053* | |
C5 | 0.18977 (9) | 0.0058 (2) | 0.79217 (13) | 0.0485 (4) | |
H5 | 0.1619 | −0.0386 | 0.7427 | 0.058* | |
C6 | 0.16167 (8) | 0.0881 (2) | 0.87141 (13) | 0.0452 (4) | |
H6 | 0.1141 | 0.0991 | 0.8760 | 0.054* | |
C7 | 0.20344 (7) | 0.15523 (19) | 0.94498 (11) | 0.0362 (3) | |
C8 | 0.27499 (7) | 0.13568 (18) | 0.93433 (10) | 0.0322 (3) | |
C9 | 0.16358 (9) | 0.2440 (2) | 1.02636 (15) | 0.0509 (4) | |
C10 | 0.33207 (8) | 0.1987 (2) | 1.00263 (11) | 0.0385 (3) | |
N2 | 0.30195 (6) | 0.05417 (17) | 0.85635 (9) | 0.0382 (3) | |
O1 | 0.19488 (7) | 0.3047 (2) | 1.10082 (11) | 0.0672 (4) | |
H2 | 0.2447 | 0.2903 | 1.0970 | 0.081* | |
O2 | 0.10145 (8) | 0.2546 (3) | 1.01790 (17) | 0.1080 (9) | |
O3 | 0.31596 (7) | 0.26887 (19) | 1.08370 (9) | 0.0575 (4) | |
O4 | 0.39173 (6) | 0.1798 (2) | 0.97738 (10) | 0.0616 (4) | |
O11 | 0.0514 (5) | 0.0498 (6) | 0.6190 (5) | 0.111 (2) | 0.555 (12) |
O12 | 0.0227 (3) | 0.0523 (6) | 0.5563 (8) | 0.090 (3) | 0.445 (12) |
O13 | 0.0231 (5) | 0.0986 (13) | 0.7440 (9) | 0.083 (5)* | 0.171 (6) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0252 (5) | 0.0537 (8) | 0.0305 (6) | 0.0001 (5) | 0.0049 (4) | −0.0032 (5) |
C1 | 0.0332 (7) | 0.0738 (12) | 0.0287 (7) | 0.0002 (7) | 0.0002 (5) | 0.0085 (7) |
C2 | 0.0293 (7) | 0.0765 (13) | 0.0378 (8) | −0.0089 (7) | −0.0013 (6) | −0.0109 (8) |
C3 | 0.0560 (11) | 0.0510 (10) | 0.0575 (11) | 0.0076 (8) | 0.0185 (9) | 0.0002 (8) |
C4 | 0.0429 (9) | 0.0551 (10) | 0.0344 (7) | −0.0073 (7) | 0.0047 (6) | −0.0058 (7) |
C5 | 0.0417 (8) | 0.0624 (11) | 0.0412 (8) | −0.0146 (8) | −0.0032 (7) | −0.0016 (8) |
C6 | 0.0308 (7) | 0.0547 (10) | 0.0500 (9) | −0.0038 (7) | 0.0006 (6) | 0.0052 (8) |
C7 | 0.0329 (7) | 0.0386 (7) | 0.0371 (7) | 0.0025 (6) | 0.0060 (5) | 0.0056 (6) |
C8 | 0.0317 (6) | 0.0369 (7) | 0.0281 (6) | 0.0017 (5) | 0.0034 (5) | 0.0050 (5) |
C9 | 0.0385 (8) | 0.0566 (11) | 0.0577 (10) | 0.0048 (7) | 0.0142 (7) | −0.0071 (8) |
C10 | 0.0356 (7) | 0.0502 (9) | 0.0296 (7) | 0.0030 (6) | 0.0012 (5) | 0.0006 (6) |
N2 | 0.0336 (6) | 0.0495 (8) | 0.0314 (6) | 0.0000 (5) | 0.0046 (5) | −0.0012 (5) |
O1 | 0.0485 (7) | 0.1003 (12) | 0.0527 (8) | 0.0172 (7) | 0.0088 (6) | −0.0245 (8) |
O2 | 0.0375 (8) | 0.155 (2) | 0.1312 (17) | 0.0157 (10) | 0.0101 (9) | −0.0741 (15) |
O3 | 0.0473 (7) | 0.0861 (10) | 0.0391 (6) | 0.0092 (7) | −0.0016 (5) | −0.0194 (6) |
O4 | 0.0326 (6) | 0.1067 (12) | 0.0457 (7) | −0.0007 (7) | 0.0017 (5) | −0.0208 (7) |
O11 | 0.151 (5) | 0.095 (3) | 0.085 (3) | −0.052 (3) | 0.005 (4) | 0.012 (2) |
O12 | 0.052 (2) | 0.081 (3) | 0.137 (7) | 0.0051 (18) | 0.017 (3) | 0.020 (3) |
Geometric parameters (Å, º) top
N1—C2 | 1.480 (2) | C4—H4 | 0.9300 |
N1—C1 | 1.484 (2) | C5—C6 | 1.372 (3) |
N1—C3 | 1.489 (2) | C5—H5 | 0.9300 |
N1—H1 | 0.9100 | C6—C7 | 1.392 (2) |
C1—C2i | 1.523 (2) | C6—H6 | 0.9300 |
C1—H1A | 0.9700 | C7—C8 | 1.4052 (19) |
C1—H1B | 0.9700 | C7—C9 | 1.523 (2) |
C2—C1i | 1.523 (2) | C8—N2 | 1.3475 (18) |
C2—H2A | 0.9700 | C8—C10 | 1.528 (2) |
C2—H2B | 0.9700 | C9—O2 | 1.214 (2) |
C3—C3i | 1.525 (4) | C9—O1 | 1.272 (2) |
C3—H3A | 0.9700 | C10—O4 | 1.2168 (19) |
C3—H3B | 0.9700 | C10—O3 | 1.2704 (18) |
C4—N2 | 1.329 (2) | O1—H2 | 0.9750 |
C4—C5 | 1.375 (2) | | |
| | | |
C2—N1—C1 | 110.77 (13) | N2—C4—C5 | 122.96 (16) |
C2—N1—C3 | 108.18 (14) | N2—C4—H4 | 118.5 |
C1—N1—C3 | 109.98 (14) | C5—C4—H4 | 118.5 |
C2—N1—H1 | 109.3 | C6—C5—C4 | 118.04 (16) |
C1—N1—H1 | 109.3 | C6—C5—H5 | 121.0 |
C3—N1—H1 | 109.3 | C4—C5—H5 | 121.0 |
N1—C1—C2i | 108.29 (12) | C5—C6—C7 | 120.86 (15) |
N1—C1—H1A | 110.0 | C5—C6—H6 | 119.6 |
C2i—C1—H1A | 110.0 | C7—C6—H6 | 119.6 |
N1—C1—H1B | 110.0 | C6—C7—C8 | 117.31 (14) |
C2i—C1—H1B | 110.0 | C6—C7—C9 | 113.70 (14) |
H1A—C1—H1B | 108.4 | C8—C7—C9 | 128.98 (15) |
N1—C2—C1i | 108.83 (12) | N2—C8—C7 | 121.28 (13) |
N1—C2—H2A | 109.9 | N2—C8—C10 | 110.61 (12) |
C1i—C2—H2A | 109.9 | C7—C8—C10 | 128.11 (13) |
N1—C2—H2B | 109.9 | O2—C9—O1 | 121.37 (18) |
C1i—C2—H2B | 109.9 | O2—C9—C7 | 118.09 (19) |
H2A—C2—H2B | 108.3 | O1—C9—C7 | 120.54 (16) |
N1—C3—C3i | 108.18 (9) | O4—C10—O3 | 122.07 (15) |
N1—C3—H3A | 110.1 | O4—C10—C8 | 118.66 (13) |
C3i—C3—H3A | 110.1 | O3—C10—C8 | 119.27 (13) |
N1—C3—H3B | 110.1 | C4—N2—C8 | 119.54 (13) |
C3i—C3—H3B | 110.1 | C9—O1—H2 | 112.7 |
H3A—C3—H3B | 108.4 | | |
| | | |
C2—N1—C1—C2i | 51.54 (17) | C9—C7—C8—C10 | 0.2 (3) |
C3—N1—C1—C2i | −68.01 (18) | C6—C7—C9—O2 | −3.3 (3) |
C1—N1—C2—C1i | −67.61 (16) | C8—C7—C9—O2 | 175.6 (2) |
C3—N1—C2—C1i | 53.01 (18) | C6—C7—C9—O1 | 176.68 (18) |
C2—N1—C3—C3i | −71.0 (2) | C8—C7—C9—O1 | −4.5 (3) |
C1—N1—C3—C3i | 50.1 (2) | N2—C8—C10—O4 | 4.8 (2) |
N2—C4—C5—C6 | −0.9 (3) | C7—C8—C10—O4 | −174.75 (17) |
C4—C5—C6—C7 | 0.4 (3) | N2—C8—C10—O3 | −175.20 (15) |
C5—C6—C7—C8 | 0.2 (2) | C7—C8—C10—O3 | 5.3 (2) |
C5—C6—C7—C9 | 179.21 (16) | C5—C4—N2—C8 | 0.7 (3) |
C6—C7—C8—N2 | −0.4 (2) | C7—C8—N2—C4 | 0.0 (2) |
C9—C7—C8—N2 | −179.25 (15) | C10—C8—N2—C4 | −179.56 (14) |
C6—C7—C8—C10 | 179.01 (15) | | |
Symmetry code: (i) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2···O3 | 0.98 | 1.41 | 2.3796 (18) | 176 |
N1—H1···N2 | 0.91 | 2.04 | 2.8963 (17) | 156 |
N1—H1···O4 | 0.91 | 2.19 | 2.8143 (17) | 125 |
Experimental details
Crystal data |
Chemical formula | C6H14N22+·2C7H4NO4−·2.17H2O |
Mr | 488.62 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 19.4117 (6), 8.1486 (3), 13.4528 (4) |
V (Å3) | 2127.94 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.20 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 46987, 2958, 2239 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.693 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.155, 1.03 |
No. of reflections | 2958 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.27 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2···O3 | 0.98 | 1.41 | 2.3796 (18) | 176 |
N1—H1···N2 | 0.91 | 2.04 | 2.8963 (17) | 156 |
N1—H1···O4 | 0.91 | 2.19 | 2.8143 (17) | 125 |
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As part of our investigations of supramolecular networks (Harrison et al., 2007), the title compound, (I), a hydrated molecular salt, has been prepared and structurally characterized. The complete C6H14N22+ cation is generated by crystallographic 2-fold symmetry, with the rotation axis bisecting the C3—C3i (i = 1 - x, y, 3/2 - z) bond. The C—O bond distances of the C7H4NO4- anion suggest charge localization (i.e. well defined single and double bonds) in the deprotonated carboxylate group. The dihedral angles between the mean plane of the pyridine ring (N2/C4—C8) and the planes of the C9/O1/O2 and C10/O3/O4 groups are 3.7 (3)° and 5.0 (2)°, respectively. The anion is stabilized by an intramolecular O—H···O hydrogen bond (Table 2).
In the crystal of (I), associations of two anions and one cation occur, linked by bifurcated N—H···(N,O) hydrogen bonds arising from the symmetry equivalent N—H groupings of the cation. These trimolecular associations form a pseudo framework delimiting [001] channels containing the disordered water molecules (Fig. 2). There are no significant π-π stacking interactions, the shortest centroid-centroid separation involving the pyridine rings being longer than 4.13 Å.