4-Aza-1-azoniabicyclo­[2.2.2]octane eosinide

Harrison, W.T.A.; Ramadevi, P.; Seethalakshmi, P.G.; Kumaresan, S.

doi:10.1107/S1600536807041396

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4-Aza-1-azoniabicyclo[2.2.2]octane eosinide

W. T. A. Harrison, P. Ramadevi, P. G. Seethalakshmi and S. Kumaresan

The title compound, C₆H₁₃N₂⁺·C₂₀H₇Br₄O₅⁻, is a molecular salt of singly protonated 1,4-diazabicyclo[2.2.2]octane and the eosinide monoanion. Contrary to a handful of previous crystal structures which contain eosin in its dianionic form, here, the carboxyl group of the anion has retained its H atom. The dihedral angle between the triple ring system and the pendant benzene ring in the anion is 86.0 (2)°. In the crystal structure, the components interact by way of a bifurcated N—H

(O,Br) hydrogen bond linking cation and anion, and an O—H

O hydrogen bond which links the anions into infinite chains propagating in [001].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041396/lh2486sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041396/lh2486Isup2.hkl Contains datablock I

CCDC reference: 660368

checkCIF report

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

Comment top

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 C₂₀H₆Br₄O₅^2- 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.

Related literature top

For background, see: Willner et al. (1992); García-Granda et al. (1993); Jones (1997); Todd & Harrison (2007).

Experimental top

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.

Structure description top

The title molecular-salt arose from our synthetic and structural studies of organic supramolecular networks (Jones, 1997).

For background, see: Willner et al. (1992); García-Granda et al. (1993); Jones (1997); Todd & Harrison (2007).

Computing details top

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).

Figures top

	Fig. 1. View of the molecular structure showing 50% displacement ellipsoids and arbitrary spheres for the H atoms. The bifurcated N—H···(O,Br) hydrogen bond is indicated by double dashed lines.
	Fig. 2. Part of a [001] chain with hydrogen bonds shown as double-dashed lines and the C-bound H atoms omitted for clarity. Symmetry codes: (i) x, 3/2 - y, z - 1/2; (ii) x, y, z - 1.

4-Aza-1-azoniabicyclo[2.2.2]octane eosinide top

Crystal data top

C₆H₁₃N₂⁺·C₂₀H₇Br₄O₅⁻	F(000) = 1480
M_r = 760.08	D_x = 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

Data collection top

Nonius KappaCCD area-detector diffractometer	5734 independent reflections
Radiation source: fine-focus sealed tube	3468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.113
ω and φ scans	θ_max = 27.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −17→17
T_min = 0.625, T_max = 0.938	k = −15→15
28164 measured reflections	l = −21→21

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)] = 0.096	Hydrogen site location: difmap and geom
wR(F²) = 0.149	H-atom parameters constrained
S = 1.36	w = 1/[σ²(F_o²) + 19.6202P] where P = (F_o² + 2F_c²)/3
5734 reflections	(Δ/σ)_max = 0.001
334 parameters	Δρ_max = 1.04 e Å⁻³
18 restraints	Δρ_min = −1.11 e Å⁻³

Crystal data top

C₆H₁₃N₂⁺·C₂₀H₇Br₄O₅⁻	V = 2501.4 (2) Å³
M_r = 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)°

Data collection top

Nonius KappaCCD area-detector diffractometer	5734 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	3468 reflections with I > 2σ(I)
T_min = 0.625, T_max = 0.938	R_int = 0.113
28164 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.096	18 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.36	w = 1/[σ²(F_o²) + 19.6202P] where P = (F_o² + 2F_c²)/3
5734 reflections	Δρ_max = 1.04 e Å⁻³
334 parameters	Δρ_min = −1.11 e Å⁻³

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	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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⁻
M_r	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)
T_min, T_max	0.625, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	28164, 5734, 3468
R_int	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(F_o²) + 19.6202P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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.

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