Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041396/lh2486sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041396/lh2486Isup2.hkl |
CCDC reference: 660368
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.015 Å
- R factor = 0.096
- wR factor = 0.149
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
Alert level C RADNW01_ALERT_1_C The radiation wavelength lies outside the expected range for the supplied radiation type. Expected range 0.71065-0.71075 Wavelength given = 0.70173 RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.113 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT213_ALERT_2_C Atom C3 has ADP max/min Ratio ............. 3.30 oblat PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 15 PLAT431_ALERT_2_C Short Inter HL..A Contact Br2 .. N2 .. 3.33 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact Br2 .. C25 .. 3.33 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 18
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 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
Equimolar quantities of eosin and 1,4-diazoniabicyclo[2.2.2]octane (also known as DABCO) were each dissolved in a mixture of acetone and ethanol (2:1 v/v). The two solutions were mixed and allowed to stand at room temperature and very dark, fragile, rods of the title compound formed after four days. When smeared onto a glass slide, an orange colour was apparent.
The tiny crystal used for data collection was a weak scatterer, which may correlate with the rather high residuals. Atoms C1, C3 and C10 gave highly aniostropic displacements and their Uij values were restrained to approximate to isotropic behaviour.
The O-bound H was located in a difference map and refined as riding in its as-found relative position. The other hydrogen atoms were geometrically placed (N—H = 0.93 Å, C—H = 0.93–0.99 Å) and refined as riding. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases.
The title molecular-salt arose from our synthetic and structural studies of organic supramolecular networks (Jones, 1997).
The compound contains 4-aza-1-azoniabicyclo[2.2.2]octane (C6H13N2+) monocations and eosinide (C20H7Br4O5-) monoanions. The eosin proton has been lost from the phenol group of the triple ring system (either O1 or O2). When deprotonated, resonance forms can be drawn which delocalize the charge and make these two O atoms equvalent, hence their equal (within experimental error) C—O bond lengths [C3—O1 = 1.266 (11) Å, C11—O2 = 1.256 (10) Å] in the crystal of (I).
Contrary to previous crystal structures containing the C20H6Br4O52- eosin dianion (Willner et al., 1992; García-Granda et al., 1993), the C20/O4/O5 carboxylic acid group has retained its proton, as indicated by the strong contrast between the single [C20—O5 = 1.322 (11) Å] and double [C20—O4 = 1.201 (11) Å] bonds and the formation of an O—H···O hydrogen bond (see below). The dihedral angle between the mean planes of the triple ring system and the pendant C14–C19 benzene ring is 86.0 (2)°, indicating that they are almost perpendicular. Conversely, the C20/O4/O5 group is almost co-planar with its benzene ring [dihedral angle = 4.6 (17)°]. The C6H13N2+ cation in displays unexceptional geometrical parameters (Todd & Harrison, 2007).
The component species in are linked together by hydrogen bonds. The cation forms a bifurcated N—H···(O,Br) hydrogen bond to one side of the eosin triple ring system (bond-angle sum for H1 = 359°). Then, anions are linked into [001] chains by way of an inter-anion O—H···O link (Fig. 2) to the O atom at the other side of the fused ring. There are no significant π–π stacking interactions, as the closest separation of aromatic ring centoids is greater than 4.1 Å.
For background, see: Willner et al. (1992); García-Granda et al. (1993); Jones (1997); Todd & Harrison (2007).
Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); 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).
C6H13N2+·C20H7Br4O5− | F(000) = 1480 |
Mr = 760.08 | Dx = 2.018 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.70173 Å |
Hall symbol: -P 2ybc | Cell parameters from 5684 reflections |
a = 13.4675 (8) Å | θ = 2.9–27.5° |
b = 12.3257 (7) Å | µ = 6.48 mm−1 |
c = 16.2266 (6) Å | T = 120 K |
β = 111.771 (3)° | Shard, orange |
V = 2501.4 (2) Å3 | 0.08 × 0.05 × 0.01 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 5734 independent reflections |
Radiation source: fine-focus sealed tube | 3468 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.113 |
ω and φ scans | θmax = 27.3°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −17→17 |
Tmin = 0.625, Tmax = 0.938 | k = −15→15 |
28164 measured reflections | l = −21→21 |
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)] = 0.096 | Hydrogen site location: difmap and geom |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.36 | w = 1/[σ2(Fo2) + 19.6202P] where P = (Fo2 + 2Fc2)/3 |
5734 reflections | (Δ/σ)max = 0.001 |
334 parameters | Δρmax = 1.04 e Å−3 |
18 restraints | Δρmin = −1.11 e Å−3 |
C6H13N2+·C20H7Br4O5− | V = 2501.4 (2) Å3 |
Mr = 760.08 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4675 (8) Å | µ = 6.48 mm−1 |
b = 12.3257 (7) Å | T = 120 K |
c = 16.2266 (6) Å | 0.08 × 0.05 × 0.01 mm |
β = 111.771 (3)° |
Nonius KappaCCD area-detector diffractometer | 5734 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3468 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.938 | Rint = 0.113 |
28164 measured reflections |
R[F2 > 2σ(F2)] = 0.096 | 18 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.36 | w = 1/[σ2(Fo2) + 19.6202P] where P = (Fo2 + 2Fc2)/3 |
5734 reflections | Δρmax = 1.04 e Å−3 |
334 parameters | Δρmin = −1.11 e Å−3 |
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 | ||
C1 | 0.2077 (7) | 0.5378 (7) | 0.4770 (6) | 0.016 (2) | |
C2 | 0.2177 (7) | 0.6283 (8) | 0.5314 (6) | 0.018 (2) | |
C3 | 0.1308 (8) | 0.7015 (8) | 0.5185 (6) | 0.021 (2) | |
C4 | 0.0304 (8) | 0.6698 (8) | 0.4494 (6) | 0.024 (2) | |
C5 | 0.0208 (8) | 0.5828 (8) | 0.3963 (6) | 0.022 (2) | |
H5 | −0.0465 | 0.5676 | 0.3510 | 0.027* | |
C6 | 0.1091 (8) | 0.5134 (8) | 0.4066 (6) | 0.021 (2) | |
C7 | 0.1050 (8) | 0.4252 (8) | 0.3511 (6) | 0.019 (2) | |
C8 | 0.1947 (7) | 0.3599 (8) | 0.3689 (6) | 0.019 (2) | |
C9 | 0.1963 (8) | 0.2659 (7) | 0.3188 (6) | 0.021 (2) | |
H9 | 0.1337 | 0.2463 | 0.2699 | 0.025* | |
C10 | 0.2849 (8) | 0.2036 (7) | 0.3391 (6) | 0.019 (2) | |
C11 | 0.3837 (8) | 0.2254 (7) | 0.4122 (6) | 0.018 (2) | |
C12 | 0.3815 (8) | 0.3230 (7) | 0.4605 (6) | 0.021 (2) | |
C13 | 0.2907 (8) | 0.3859 (8) | 0.4410 (6) | 0.021 (2) | |
C14 | 0.0028 (7) | 0.3984 (8) | 0.2759 (6) | 0.022 (2) | |
C15 | −0.0648 (8) | 0.3250 (8) | 0.2928 (6) | 0.022 (2) | |
H15 | −0.0447 | 0.2941 | 0.3503 | 0.027* | |
C16 | −0.1609 (8) | 0.2956 (9) | 0.2279 (7) | 0.031 (3) | |
H16 | −0.2071 | 0.2461 | 0.2409 | 0.037* | |
C17 | −0.1891 (8) | 0.3390 (9) | 0.1436 (7) | 0.029 (2) | |
H17 | −0.2544 | 0.3185 | 0.0980 | 0.034* | |
C18 | −0.1215 (8) | 0.4125 (8) | 0.1261 (7) | 0.028 (2) | |
H18 | −0.1416 | 0.4421 | 0.0681 | 0.033* | |
C19 | −0.0257 (8) | 0.4442 (8) | 0.1906 (6) | 0.024 (2) | |
C20 | 0.0451 (8) | 0.5252 (8) | 0.1720 (6) | 0.021 (2) | |
O1 | 0.1412 (5) | 0.7877 (5) | 0.5633 (4) | 0.0225 (15) | |
O2 | 0.4645 (5) | 0.1652 (5) | 0.4323 (4) | 0.0216 (15) | |
O3 | 0.2952 (5) | 0.4734 (5) | 0.4927 (4) | 0.0206 (15) | |
O4 | 0.1318 (5) | 0.5485 (6) | 0.2249 (4) | 0.0296 (17) | |
O5 | 0.0031 (5) | 0.5656 (6) | 0.0909 (4) | 0.0315 (18) | |
H2 | 0.0458 | 0.6093 | 0.0805 | 0.038* | |
Br1 | 0.34956 (8) | 0.65689 (8) | 0.62238 (6) | 0.0270 (3) | |
Br2 | −0.09106 (9) | 0.75531 (9) | 0.43160 (7) | 0.0365 (3) | |
Br3 | 0.28147 (9) | 0.08005 (9) | 0.26922 (7) | 0.0344 (3) | |
Br4 | 0.50931 (8) | 0.36284 (8) | 0.55491 (6) | 0.0238 (2) | |
N1 | 0.5498 (6) | 0.0147 (7) | 0.3626 (5) | 0.0227 (19) | |
H1 | 0.5004 | 0.0584 | 0.3745 | 0.027* | |
N2 | 0.6838 (7) | −0.1054 (7) | 0.3322 (5) | 0.028 (2) | |
C21 | 0.5153 (8) | −0.1002 (8) | 0.3589 (6) | 0.022 (2) | |
H21A | 0.4448 | −0.1103 | 0.3107 | 0.026* | |
H21B | 0.5092 | −0.1212 | 0.4157 | 0.026* | |
C22 | 0.6572 (8) | 0.0274 (8) | 0.4362 (6) | 0.026 (2) | |
H22A | 0.6535 | 0.0043 | 0.4934 | 0.031* | |
H22B | 0.6801 | 0.1043 | 0.4415 | 0.031* | |
C23 | 0.5557 (9) | 0.0482 (8) | 0.2767 (6) | 0.028 (2) | |
H23A | 0.5816 | 0.1239 | 0.2802 | 0.033* | |
H23B | 0.4844 | 0.0434 | 0.2285 | 0.033* | |
C24 | 0.6000 (10) | −0.1709 (9) | 0.3418 (7) | 0.039 (3) | |
H24A | 0.6314 | −0.2220 | 0.3918 | 0.047* | |
H24B | 0.5654 | −0.2140 | 0.2871 | 0.047* | |
C25 | 0.7368 (8) | −0.0440 (9) | 0.4131 (7) | 0.032 (3) | |
H25A | 0.7928 | 0.0024 | 0.4055 | 0.039* | |
H25B | 0.7721 | −0.0948 | 0.4626 | 0.039* | |
C26 | 0.6349 (9) | −0.0305 (9) | 0.2588 (7) | 0.033 (3) | |
H26A | 0.5966 | −0.0724 | 0.2042 | 0.039* | |
H26B | 0.6918 | 0.0120 | 0.2487 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.022 (5) | 0.015 (4) | 0.018 (4) | −0.002 (4) | 0.014 (4) | 0.005 (4) |
C2 | 0.013 (5) | 0.023 (5) | 0.015 (5) | 0.008 (4) | 0.002 (4) | 0.009 (4) |
C3 | 0.027 (6) | 0.019 (5) | 0.015 (5) | 0.005 (4) | 0.006 (4) | 0.014 (4) |
C4 | 0.021 (5) | 0.026 (6) | 0.023 (5) | 0.012 (4) | 0.005 (4) | 0.000 (4) |
C5 | 0.018 (5) | 0.024 (6) | 0.024 (5) | 0.008 (4) | 0.007 (4) | 0.012 (4) |
C6 | 0.022 (5) | 0.018 (5) | 0.023 (5) | 0.004 (4) | 0.008 (4) | 0.001 (4) |
C7 | 0.025 (5) | 0.017 (5) | 0.010 (5) | 0.001 (4) | 0.001 (4) | 0.004 (4) |
C8 | 0.017 (5) | 0.025 (6) | 0.016 (5) | 0.001 (4) | 0.005 (4) | 0.001 (4) |
C9 | 0.030 (6) | 0.015 (5) | 0.015 (5) | 0.001 (4) | 0.004 (4) | 0.001 (4) |
C10 | 0.027 (5) | 0.018 (5) | 0.009 (4) | 0.002 (4) | 0.005 (4) | −0.006 (3) |
C11 | 0.023 (5) | 0.019 (5) | 0.018 (5) | −0.002 (4) | 0.016 (4) | 0.000 (4) |
C12 | 0.029 (6) | 0.012 (5) | 0.019 (5) | 0.003 (4) | 0.006 (4) | −0.002 (4) |
C13 | 0.027 (6) | 0.019 (5) | 0.016 (5) | −0.005 (4) | 0.008 (4) | −0.007 (4) |
C14 | 0.019 (5) | 0.023 (6) | 0.026 (6) | 0.007 (4) | 0.012 (4) | −0.002 (4) |
C15 | 0.024 (6) | 0.017 (5) | 0.026 (5) | 0.003 (4) | 0.010 (4) | 0.004 (4) |
C16 | 0.030 (6) | 0.025 (6) | 0.045 (7) | −0.010 (5) | 0.023 (5) | −0.007 (5) |
C17 | 0.018 (5) | 0.035 (6) | 0.029 (6) | −0.013 (5) | 0.004 (4) | −0.009 (5) |
C18 | 0.027 (6) | 0.021 (5) | 0.032 (6) | 0.001 (5) | 0.006 (5) | 0.001 (5) |
C19 | 0.025 (6) | 0.023 (6) | 0.028 (6) | 0.002 (4) | 0.013 (5) | −0.002 (4) |
C20 | 0.025 (6) | 0.018 (5) | 0.019 (5) | 0.001 (4) | 0.008 (4) | 0.001 (4) |
O1 | 0.023 (4) | 0.018 (4) | 0.028 (4) | 0.004 (3) | 0.012 (3) | 0.002 (3) |
O2 | 0.021 (4) | 0.020 (4) | 0.026 (4) | 0.008 (3) | 0.011 (3) | −0.001 (3) |
O3 | 0.023 (4) | 0.025 (4) | 0.013 (3) | 0.007 (3) | 0.006 (3) | 0.001 (3) |
O4 | 0.021 (4) | 0.037 (5) | 0.030 (4) | −0.008 (3) | 0.008 (3) | −0.001 (3) |
O5 | 0.027 (4) | 0.037 (5) | 0.027 (4) | −0.009 (3) | 0.005 (3) | 0.006 (3) |
Br1 | 0.0270 (6) | 0.0228 (6) | 0.0250 (5) | 0.0056 (5) | 0.0026 (4) | −0.0046 (4) |
Br2 | 0.0321 (6) | 0.0345 (7) | 0.0409 (7) | 0.0097 (5) | 0.0115 (5) | −0.0064 (5) |
Br3 | 0.0304 (6) | 0.0299 (6) | 0.0374 (6) | 0.0042 (5) | 0.0063 (5) | −0.0100 (5) |
Br4 | 0.0217 (5) | 0.0220 (5) | 0.0241 (5) | 0.0031 (4) | 0.0042 (4) | −0.0020 (4) |
N1 | 0.020 (5) | 0.025 (5) | 0.020 (4) | 0.001 (4) | 0.004 (4) | 0.002 (3) |
N2 | 0.034 (5) | 0.022 (5) | 0.027 (5) | 0.003 (4) | 0.011 (4) | −0.002 (4) |
C21 | 0.025 (6) | 0.023 (6) | 0.019 (5) | −0.002 (4) | 0.010 (4) | 0.000 (4) |
C22 | 0.031 (6) | 0.018 (5) | 0.030 (6) | −0.005 (5) | 0.013 (5) | −0.004 (4) |
C23 | 0.041 (7) | 0.020 (6) | 0.030 (6) | 0.002 (5) | 0.022 (5) | 0.002 (4) |
C24 | 0.055 (8) | 0.019 (6) | 0.042 (7) | 0.007 (6) | 0.017 (6) | −0.005 (5) |
C25 | 0.026 (6) | 0.035 (7) | 0.034 (6) | 0.013 (5) | 0.010 (5) | −0.003 (5) |
C26 | 0.031 (6) | 0.037 (7) | 0.032 (6) | 0.001 (5) | 0.016 (5) | −0.004 (5) |
C1—O3 | 1.364 (10) | C17—C18 | 1.387 (13) |
C1—C2 | 1.398 (13) | C17—H17 | 0.9500 |
C1—C6 | 1.426 (13) | C18—C19 | 1.382 (13) |
C2—C3 | 1.429 (13) | C18—H18 | 0.9500 |
C2—Br1 | 1.874 (9) | C19—C20 | 1.486 (13) |
C3—O1 | 1.266 (11) | C20—O4 | 1.201 (11) |
C3—C4 | 1.454 (13) | C20—O5 | 1.322 (11) |
C4—C5 | 1.352 (13) | O5—H2 | 0.8497 |
C4—Br2 | 1.876 (9) | N1—C21 | 1.485 (12) |
C5—C6 | 1.423 (13) | N1—C23 | 1.485 (12) |
C5—H5 | 0.9500 | N1—C22 | 1.504 (12) |
C6—C7 | 1.401 (13) | N1—H1 | 0.9300 |
C7—C8 | 1.389 (13) | N2—C24 | 1.441 (14) |
C7—C14 | 1.500 (12) | N2—C25 | 1.453 (12) |
C8—C9 | 1.421 (13) | N2—C26 | 1.457 (13) |
C8—C13 | 1.422 (12) | C21—C24 | 1.540 (14) |
C9—C10 | 1.352 (13) | C21—H21A | 0.9900 |
C9—H9 | 0.9500 | C21—H21B | 0.9900 |
C10—C11 | 1.442 (12) | C22—C25 | 1.538 (13) |
C10—Br3 | 1.889 (9) | C22—H22A | 0.9900 |
C11—O2 | 1.256 (10) | C22—H22B | 0.9900 |
C11—C12 | 1.442 (12) | C23—C26 | 1.547 (14) |
C12—C13 | 1.382 (13) | C23—H23A | 0.9900 |
C12—Br4 | 1.896 (9) | C23—H23B | 0.9900 |
C13—O3 | 1.354 (10) | C24—H24A | 0.9900 |
C14—C15 | 1.381 (13) | C24—H24B | 0.9900 |
C14—C19 | 1.410 (13) | C25—H25A | 0.9900 |
C15—C16 | 1.380 (13) | C25—H25B | 0.9900 |
C15—H15 | 0.9500 | C26—H26A | 0.9900 |
C16—C17 | 1.384 (14) | C26—H26B | 0.9900 |
C16—H16 | 0.9500 | ||
O3—C1—C2 | 118.2 (8) | C18—C19—C14 | 117.8 (9) |
O3—C1—C6 | 120.7 (8) | C18—C19—C20 | 121.7 (9) |
C2—C1—C6 | 121.1 (8) | C14—C19—C20 | 120.5 (9) |
C1—C2—C3 | 121.9 (8) | O4—C20—O5 | 124.4 (9) |
C1—C2—Br1 | 119.2 (7) | O4—C20—C19 | 122.9 (9) |
C3—C2—Br1 | 118.8 (7) | O5—C20—C19 | 112.6 (8) |
O1—C3—C2 | 122.3 (9) | C13—O3—C1 | 120.7 (7) |
O1—C3—C4 | 122.8 (9) | C20—O5—H2 | 111.4 |
C2—C3—C4 | 114.9 (9) | C21—N1—C23 | 110.7 (7) |
C5—C4—C3 | 123.1 (9) | C21—N1—C22 | 109.0 (7) |
C5—C4—Br2 | 118.4 (7) | C23—N1—C22 | 110.2 (8) |
C3—C4—Br2 | 118.5 (7) | C21—N1—H1 | 109.0 |
C4—C5—C6 | 121.6 (9) | C23—N1—H1 | 109.0 |
C4—C5—H5 | 119.2 | C22—N1—H1 | 109.0 |
C6—C5—H5 | 119.2 | C24—N2—C25 | 109.7 (8) |
C7—C6—C5 | 124.0 (9) | C24—N2—C26 | 108.0 (8) |
C7—C6—C1 | 118.7 (9) | C25—N2—C26 | 109.3 (8) |
C5—C6—C1 | 117.2 (9) | N1—C21—C24 | 107.8 (8) |
C8—C7—C6 | 119.5 (8) | N1—C21—H21A | 110.2 |
C8—C7—C14 | 120.4 (8) | C24—C21—H21A | 110.2 |
C6—C7—C14 | 120.0 (8) | N1—C21—H21B | 110.2 |
C7—C8—C9 | 123.4 (8) | C24—C21—H21B | 110.2 |
C7—C8—C13 | 119.8 (9) | H21A—C21—H21B | 108.5 |
C9—C8—C13 | 116.9 (9) | N1—C22—C25 | 107.4 (8) |
C10—C9—C8 | 121.5 (9) | N1—C22—H22A | 110.2 |
C10—C9—H9 | 119.2 | C25—C22—H22A | 110.2 |
C8—C9—H9 | 119.2 | N1—C22—H22B | 110.2 |
C9—C10—C11 | 123.8 (8) | C25—C22—H22B | 110.2 |
C9—C10—Br3 | 119.2 (7) | H22A—C22—H22B | 108.5 |
C11—C10—Br3 | 117.0 (7) | N1—C23—C26 | 106.4 (8) |
O2—C11—C10 | 123.4 (8) | N1—C23—H23A | 110.4 |
O2—C11—C12 | 122.8 (8) | C26—C23—H23A | 110.4 |
C10—C11—C12 | 113.9 (8) | N1—C23—H23B | 110.4 |
C13—C12—C11 | 122.5 (8) | C26—C23—H23B | 110.4 |
C13—C12—Br4 | 120.0 (7) | H23A—C23—H23B | 108.6 |
C11—C12—Br4 | 117.4 (7) | N2—C24—C21 | 111.4 (8) |
O3—C13—C12 | 118.2 (8) | N2—C24—H24A | 109.3 |
O3—C13—C8 | 120.4 (8) | C21—C24—H24A | 109.3 |
C12—C13—C8 | 121.3 (8) | N2—C24—H24B | 109.3 |
C15—C14—C19 | 119.9 (9) | C21—C24—H24B | 109.3 |
C15—C14—C7 | 117.2 (8) | H24A—C24—H24B | 108.0 |
C19—C14—C7 | 122.9 (9) | N2—C25—C22 | 111.4 (8) |
C16—C15—C14 | 121.3 (9) | N2—C25—H25A | 109.3 |
C16—C15—H15 | 119.3 | C22—C25—H25A | 109.3 |
C14—C15—H15 | 119.3 | N2—C25—H25B | 109.3 |
C15—C16—C17 | 119.3 (9) | C22—C25—H25B | 109.3 |
C15—C16—H16 | 120.3 | H25A—C25—H25B | 108.0 |
C17—C16—H16 | 120.3 | N2—C26—C23 | 112.2 (8) |
C16—C17—C18 | 119.6 (9) | N2—C26—H26A | 109.2 |
C16—C17—H17 | 120.2 | C23—C26—H26A | 109.2 |
C18—C17—H17 | 120.2 | N2—C26—H26B | 109.2 |
C19—C18—C17 | 122.0 (9) | C23—C26—H26B | 109.2 |
C19—C18—H18 | 119.0 | H26A—C26—H26B | 107.9 |
C17—C18—H18 | 119.0 | ||
O3—C1—C2—C3 | 178.6 (8) | Br4—C12—C13—C8 | 178.1 (7) |
C6—C1—C2—C3 | −1.1 (13) | C7—C8—C13—O3 | 0.4 (14) |
O3—C1—C2—Br1 | 0.1 (11) | C9—C8—C13—O3 | −179.1 (8) |
C6—C1—C2—Br1 | −179.6 (7) | C7—C8—C13—C12 | −179.8 (9) |
C1—C2—C3—O1 | −174.9 (8) | C9—C8—C13—C12 | 0.7 (14) |
Br1—C2—C3—O1 | 3.6 (12) | C8—C7—C14—C15 | 85.0 (11) |
C1—C2—C3—C4 | 4.5 (13) | C6—C7—C14—C15 | −91.8 (11) |
Br1—C2—C3—C4 | −177.0 (7) | C8—C7—C14—C19 | −94.7 (12) |
O1—C3—C4—C5 | 174.3 (9) | C6—C7—C14—C19 | 88.5 (12) |
C2—C3—C4—C5 | −5.1 (14) | C19—C14—C15—C16 | −0.5 (15) |
O1—C3—C4—Br2 | −4.4 (13) | C7—C14—C15—C16 | 179.7 (9) |
C2—C3—C4—Br2 | 176.2 (7) | C14—C15—C16—C17 | 1.3 (15) |
C3—C4—C5—C6 | 2.1 (15) | C15—C16—C17—C18 | −1.1 (16) |
Br2—C4—C5—C6 | −179.2 (7) | C16—C17—C18—C19 | 0.2 (16) |
C4—C5—C6—C7 | −177.0 (9) | C17—C18—C19—C14 | 0.6 (15) |
C4—C5—C6—C1 | 1.6 (14) | C17—C18—C19—C20 | −178.4 (9) |
O3—C1—C6—C7 | −3.2 (13) | C15—C14—C19—C18 | −0.4 (14) |
C2—C1—C6—C7 | 176.6 (8) | C7—C14—C19—C18 | 179.3 (9) |
O3—C1—C6—C5 | 178.2 (8) | C15—C14—C19—C20 | 178.6 (9) |
C2—C1—C6—C5 | −2.1 (13) | C7—C14—C19—C20 | −1.7 (14) |
C5—C6—C7—C8 | −177.6 (9) | C18—C19—C20—O4 | −174.8 (10) |
C1—C6—C7—C8 | 3.9 (13) | C14—C19—C20—O4 | 6.2 (15) |
C5—C6—C7—C14 | −0.8 (14) | C18—C19—C20—O5 | 3.5 (13) |
C1—C6—C7—C14 | −179.3 (8) | C14—C19—C20—O5 | −175.4 (8) |
C6—C7—C8—C9 | 176.9 (9) | C12—C13—O3—C1 | −179.4 (8) |
C14—C7—C8—C9 | 0.1 (14) | C8—C13—O3—C1 | 0.4 (13) |
C6—C7—C8—C13 | −2.6 (14) | C2—C1—O3—C13 | −178.7 (8) |
C14—C7—C8—C13 | −179.4 (8) | C6—C1—O3—C13 | 1.0 (12) |
C7—C8—C9—C10 | −179.1 (9) | C23—N1—C21—C24 | 61.7 (10) |
C13—C8—C9—C10 | 0.4 (14) | C22—N1—C21—C24 | −59.6 (9) |
C8—C9—C10—C11 | 0.5 (15) | C21—N1—C22—C25 | 62.4 (10) |
C8—C9—C10—Br3 | −179.7 (7) | C23—N1—C22—C25 | −59.2 (10) |
C9—C10—C11—O2 | 177.7 (9) | C21—N1—C23—C26 | −57.7 (10) |
Br3—C10—C11—O2 | −2.1 (12) | C22—N1—C23—C26 | 62.9 (10) |
C9—C10—C11—C12 | −2.4 (13) | C25—N2—C24—C21 | 60.5 (11) |
Br3—C10—C11—C12 | 177.9 (6) | C26—N2—C24—C21 | −58.4 (11) |
O2—C11—C12—C13 | −176.6 (9) | N1—C21—C24—N2 | −1.6 (11) |
C10—C11—C12—C13 | 3.5 (13) | C24—N2—C25—C22 | −57.3 (11) |
O2—C11—C12—Br4 | 2.6 (12) | C26—N2—C25—C22 | 60.8 (11) |
C10—C11—C12—Br4 | −177.4 (6) | N1—C22—C25—N2 | −3.5 (11) |
C11—C12—C13—O3 | 177.0 (8) | C24—N2—C26—C23 | 62.4 (11) |
Br4—C12—C13—O3 | −2.1 (12) | C25—N2—C26—C23 | −56.8 (11) |
C11—C12—C13—C8 | −2.8 (15) | N1—C23—C26—N2 | −4.2 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.93 | 1.78 | 2.647 (10) | 153 |
N1—H1···Br3 | 0.93 | 2.82 | 3.455 (8) | 127 |
O5—H2···O1i | 0.85 | 1.90 | 2.748 (9) | 177 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H13N2+·C20H7Br4O5− |
Mr | 760.08 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 13.4675 (8), 12.3257 (7), 16.2266 (6) |
β (°) | 111.771 (3) |
V (Å3) | 2501.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.48 |
Crystal size (mm) | 0.08 × 0.05 × 0.01 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.625, 0.938 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28164, 5734, 3468 |
Rint | 0.113 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.096, 0.149, 1.36 |
No. of reflections | 5734 |
No. of parameters | 334 |
No. of restraints | 18 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + 19.6202P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.04, −1.11 |
Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.93 | 1.78 | 2.647 (10) | 153 |
N1—H1···Br3 | 0.93 | 2.82 | 3.455 (8) | 127 |
O5—H2···O1i | 0.85 | 1.90 | 2.748 (9) | 177 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
The title molecular-salt arose from our synthetic and structural studies of organic supramolecular networks (Jones, 1997).
The compound contains 4-aza-1-azoniabicyclo[2.2.2]octane (C6H13N2+) monocations and eosinide (C20H7Br4O5-) monoanions. The eosin proton has been lost from the phenol group of the triple ring system (either O1 or O2). When deprotonated, resonance forms can be drawn which delocalize the charge and make these two O atoms equvalent, hence their equal (within experimental error) C—O bond lengths [C3—O1 = 1.266 (11) Å, C11—O2 = 1.256 (10) Å] in the crystal of (I).
Contrary to previous crystal structures containing the C20H6Br4O52- eosin dianion (Willner et al., 1992; García-Granda et al., 1993), the C20/O4/O5 carboxylic acid group has retained its proton, as indicated by the strong contrast between the single [C20—O5 = 1.322 (11) Å] and double [C20—O4 = 1.201 (11) Å] bonds and the formation of an O—H···O hydrogen bond (see below). The dihedral angle between the mean planes of the triple ring system and the pendant C14–C19 benzene ring is 86.0 (2)°, indicating that they are almost perpendicular. Conversely, the C20/O4/O5 group is almost co-planar with its benzene ring [dihedral angle = 4.6 (17)°]. The C6H13N2+ cation in displays unexceptional geometrical parameters (Todd & Harrison, 2007).
The component species in are linked together by hydrogen bonds. The cation forms a bifurcated N—H···(O,Br) hydrogen bond to one side of the eosin triple ring system (bond-angle sum for H1 = 359°). Then, anions are linked into [001] chains by way of an inter-anion O—H···O link (Fig. 2) to the O atom at the other side of the fused ring. There are no significant π–π stacking interactions, as the closest separation of aromatic ring centoids is greater than 4.1 Å.