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In the crystal structure of the title compound, C8H18N22+·2I·CH3CN, the dication lies on a mirror plane containing the mol­ecular dication threefold axis. The structure displays C—H...I inter­actions between H atoms of the 1,4-dimethyl-1,4-diazo­nia­bicyclo­[2.2.2]octane dication and the iodide anions. The H...I distances are in the range 2.96–3.18 (4) Å. The dications pack forming channels along the b axis, which contain the iodide anions and acetonitrile solvent mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105028763/hj1071sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105028763/hj1071Isup2.hkl
Contains datablock I

CCDC reference: 290568

Comment top

The 1,4-dimethyl-1,4-diazaniabicyclo[2.2.2]octane dication has been used as a non-coordinating divalent cation in salts of mono- and polynuclear transition metal complexes, and as the counter-ion for organic charge transfer salts. Several structures have been determined that contain the 1,4-dimethyl-1,4-diazaniabicyclo[2.2.2]octane dication, including transition metal complex salts (Christoph & Goedken, 1973; Bond & Willett, 1991), silicate clusters (Breu et al., 2004; Wiebcke et al., 1994) and calixarenes (Mansikkamaki et al., 2002, 2004, 2005), but only one simple salt of any diquaternary alkyl diazabicyclooctane dication has been determined with octadecyl n-alkyl groups [Cambridge Structural Database (Allen, 2002) refcode QETLEG (Ishioka et al., 2000)]. We report here the structure of the title compound (I), an acetonitrile solvate of 1,4-dimethyl-1,4-diazaniabicyclo[2.2.2]octane diiodide.

The structure of (I) is presented in Fig. 1. The asymmetric unit consists of part of one 1,4-dimethyl-1,4-diazaniabicyclo[2.2.2]octane dication and two iodide counter-ions. Atoms C1, C2, C5, C6, N1 and N2 all lie on special positions with mirror symmetry. Atoms C3 and C4 are on general positions. The mirror plane generates the third ethylene strap of the dication moiety. Both of the two unique I atoms are located on special positions with mirror site symmetry and near the methyl groups of the dication. Additionally, a disordered solvent molecule of acetonitrile is present.

Molecules of (I) show intermolecular C—H···I interactions between the H atoms of the dication and the I atoms (Table 1). Fig. 2 shows a view of these interactions. Atoms I1 and I2 each participate in three unique C—H···I interactions with the dication. Atom I1 also participates in a C—H···I interaction with the acetonitrile solvent molecule. In the overall structure, I1 and I2 are each within van der Waals contact of six H atoms. The I atoms are not within van der Waals contact of H1A, H1B, H2A and H2B of the ethylene strap that lies on a mirror plane. Note that as the positions of the H atoms bonded to the disordered acetonitrile solvate molecule were constrained as riding atoms, the C8—H8B···I1 hydrogen-bonding interaction listed in Table 1 may be suspect.

These C—H···I interactions are considered non-classical hydrogen bonds, as they involve combinations of weak donors (C—H) with strong acceptors (I). Comparison of the normalized C—H···I distances of the C—H···I interactions in the structure of I (RHX = 0.94–1.01) with the mean normalized distances of C—H···I interactions in the hydrogen-bonding analysis of Brammer et al. (2001) (RHX = 0.982) suggests these interactions are typical of C—H···I hydrogen bonding. The angular relation of the C—H···I interactions [C—H···I = 152.0–159 (3)°] are also reasonable for C—H···I hydrogen bonding. The proximity of the C-atom donors that form these C—H···I interactions to the positively charged N atoms perhaps enhance their ability to participate in hydrogen bonding (Palusiak et al., 2005).

A packing diagram of the structure (Fig. 3) reveals that the dication moieties as well as the iodide anions and acetonitrile solvate molecules are packed in layers perpendicular to the b axis at 0.25b and 0.75b. Perpendicular to the layers, the dication moieties form roughly hexagonal channels, though no crystallographic three- or sixfold symmetry is present. Iodide anions and acetonitrile solvent molecules fill these channels in the structure.

Experimental top

The sample of 1,4-dimethyl-1,4-diazaniabicyclo[2.2.2]octane diiodide was synthesized by the method used to make the analogous N-methylpyridinium iodide (Wiley et al., 1972). Crystals of (I) were grown by slow evaporation from a solution containing 1,4-dimethyl-1,4-diazaniabicyclo[2.2.2]octane diiodide, 3',4'-dibutyl-5,5"-bis(dicyanomethylene)-5,5"-dihydro- 2,2':5',2"-terthiophene, water and acetonitrile.

Refinement top

The coordinates of all H atoms were refined, except atom H8A, H8B and H8C. These H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98 Å and Uiso(H) values of 1.5Ueq(C). Attempts to refine the coordinates of the H atoms on the disordered acetonitrile molecule were unsuccessful. The acetonitrile solvent molecule is disordered over a mirror plane. Refinement of this disorder required restraint of the N3—C7 bond length at 1.136 (3) Å, restraint of the C7—C8 bond length at 1.470 (3) Å, and restraint of the total distance between N3 and C8 at 2.606 (3) Å.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. A view of the structure of (I), showing the intermolecular C—H···I interactions. Only H atoms participating in C—H···I interactions are shown with labels. I atoms are labeled with symmetry codes identifying the location relative to the dication asymmetric unit. [Symmetry codes: (i) 1 − x, −1/2 + y, 1 − z; (ii) 1/2 − x, 1 − y, −1/2 + z; (iii) x, y − 1, z − 1; (iv) x, y, z − 1.]
(I) top
Crystal data top
C8H18N22+·2I·C2H3NF(000) = 832
Mr = 437.10Dx = 1.846 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2nCell parameters from 2300 reflections
a = 20.174 (3) Åθ = 2.0–25.0°
b = 7.343 (1) ŵ = 3.98 mm1
c = 10.6140 (14) ÅT = 173 K
V = 1572.3 (4) Å3Plate, yellow
Z = 40.25 × 0.04 × 0.04 mm
Data collection top
Siemens SMART platform CCD
diffractometer
1508 independent reflections
Radiation source: normal-focus sealed tube1297 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
h = 2224
Tmin = 0.592, Tmax = 0.85k = 88
11185 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: difference Fourier map
wR(F2) = 0.045H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0111P)2 + 1.9299P]
where P = (Fo2 + 2Fc2)/3
1508 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.50 e Å3
3 restraintsΔρmin = 0.59 e Å3
Crystal data top
C8H18N22+·2I·C2H3NV = 1572.3 (4) Å3
Mr = 437.10Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 20.174 (3) ŵ = 3.98 mm1
b = 7.343 (1) ÅT = 173 K
c = 10.6140 (14) Å0.25 × 0.04 × 0.04 mm
Data collection top
Siemens SMART platform CCD
diffractometer
1508 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995)
1297 reflections with I > 2σ(I)
Tmin = 0.592, Tmax = 0.85Rint = 0.047
11185 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0293 restraints
wR(F2) = 0.045H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.50 e Å3
1508 reflectionsΔρmin = 0.59 e Å3
121 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
xyzUiso*/UeqOcc. (<1)
I10.446123 (18)0.75000.77407 (3)0.03368 (12)
I20.17904 (2)0.75000.97122 (4)0.03812 (12)
N10.27879 (19)0.25000.0689 (4)0.0269 (10)
N20.39204 (19)0.25000.0362 (4)0.0232 (9)
C10.2711 (3)0.25000.0732 (5)0.0298 (13)
H1A0.2439 (17)0.139 (5)0.096 (3)0.041 (11)*
H2A0.3443 (17)0.139 (5)0.183 (3)0.035 (11)*
C20.3391 (3)0.25000.1352 (5)0.0361 (15)
C30.31703 (18)0.4167 (5)0.1081 (4)0.0280 (9)
H3A0.3235 (17)0.413 (5)0.201 (4)0.045 (12)*
H3B0.2924 (15)0.524 (5)0.086 (3)0.022 (9)*
C40.3846 (2)0.4163 (6)0.0454 (4)0.0312 (9)
H4A0.4181 (17)0.412 (5)0.103 (3)0.036 (11)*
H4B0.3891 (18)0.516 (6)0.012 (3)0.045 (12)*
C50.2114 (3)0.25000.1304 (7)0.0374 (15)
H5A0.1876 (16)0.138 (5)0.102 (3)0.034 (10)*
H5B0.220 (3)0.25000.220 (5)0.043 (17)*
C60.4589 (3)0.25000.0984 (6)0.0309 (14)
H6A0.4601 (17)0.147 (5)0.151 (3)0.038 (11)*
H6B0.491 (3)0.25000.038 (5)0.028 (15)*
N30.1149 (3)0.243 (4)0.7302 (4)0.0453 (14)0.50
C70.0797 (3)0.265 (3)0.8120 (5)0.0453 (14)0.50
C80.0325 (3)0.3002 (10)0.9146 (6)0.0453 (14)0.50
H8A0.01570.42500.90760.068*0.50
H8B0.05490.28510.99590.068*0.50
H8C0.00450.21420.90880.068*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0330 (2)0.0369 (2)0.03105 (19)0.0000.00545 (17)0.000
I20.0429 (2)0.0350 (2)0.0365 (2)0.0000.00193 (19)0.000
N10.016 (2)0.034 (3)0.031 (3)0.0000.0019 (19)0.000
N20.021 (2)0.025 (2)0.024 (2)0.0000.0001 (19)0.000
C10.027 (3)0.035 (4)0.028 (3)0.0000.005 (3)0.000
C20.036 (4)0.046 (4)0.026 (3)0.0000.007 (3)0.000
C30.027 (2)0.021 (2)0.036 (2)0.0017 (18)0.0003 (19)0.0055 (18)
C40.030 (2)0.025 (2)0.039 (2)0.0035 (18)0.006 (2)0.0074 (19)
C50.023 (3)0.034 (4)0.056 (4)0.0000.010 (3)0.000
C60.030 (4)0.033 (4)0.030 (3)0.0000.005 (3)0.000
N30.052 (3)0.039 (4)0.044 (2)0.004 (4)0.0048 (17)0.009 (4)
C70.052 (3)0.039 (4)0.044 (2)0.004 (4)0.0048 (17)0.009 (4)
C80.052 (3)0.039 (4)0.044 (2)0.004 (4)0.0048 (17)0.009 (4)
Geometric parameters (Å, º) top
N1—C31.505 (4)C3—H3B0.96 (3)
N1—C3i1.505 (4)C4—H4A0.91 (3)
N1—C51.507 (7)C4—H4B0.96 (4)
N1—C11.517 (7)C5—H5A1.00 (3)
N2—C21.499 (7)C5—H5B0.97 (5)
N2—C61.501 (7)C6—H6A0.94 (3)
N2—C41.505 (4)C6—H6B0.92 (5)
N2—C4i1.505 (4)N3—C71.133 (3)
C1—C21.520 (8)C7—C81.470 (3)
C1—H1A1.01 (3)C8—H8A0.9800
C2—H2A0.97 (3)C8—H8B0.9800
C3—C41.516 (5)C8—H8C0.9800
C3—H3A0.99 (4)
C3—N1—C3i108.8 (4)N1—C3—H3A109 (2)
C3—N1—C5110.0 (3)C4—C3—H3A108 (2)
C3i—N1—C5110.0 (3)N1—C3—H3B109.6 (19)
C3—N1—C1109.1 (3)C4—C3—H3B111.1 (19)
C3i—N1—C1109.1 (3)H3A—C3—H3B109 (3)
C5—N1—C1109.8 (4)N2—C4—C3110.1 (3)
C2—N2—C6109.4 (4)N2—C4—H4A106 (2)
C2—N2—C4109.4 (3)C3—C4—H4A112 (2)
C6—N2—C4110.1 (3)N2—C4—H4B104 (2)
C2—N2—C4i109.4 (3)C3—C4—H4B111 (2)
C6—N2—C4i110.1 (3)H4A—C4—H4B113 (3)
C4—N2—C4i108.5 (4)N1—C5—H5A108 (2)
N1—C1—C2109.8 (4)N1—C5—H5B106 (3)
N1—C1—H1A107 (2)H5A—C5—H5B112 (3)
C2—C1—H1A113 (2)N2—C6—H6A107 (2)
N2—C2—C1109.8 (4)N2—C6—H6B109 (3)
N2—C2—H2A107 (2)H6A—C6—H6B114 (3)
C1—C2—H2A109 (2)N3—C7—C8177 (2)
N1—C3—C4109.8 (3)
C3—N1—C1—C259.4 (2)C3i—N1—C3—C459.6 (5)
C3i—N1—C1—C259.4 (2)C5—N1—C3—C4179.7 (4)
C5—N1—C1—C2180.0C1—N1—C3—C459.2 (4)
C6—N2—C2—C1180.0C2—N2—C4—C359.6 (5)
C4—N2—C2—C159.4 (3)C6—N2—C4—C3179.9 (4)
C4i—N2—C2—C159.4 (3)C4i—N2—C4—C359.6 (5)
N1—C1—C2—N20.0N1—C3—C4—N20.1 (5)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···I2ii0.99 (4)3.11 (4)4.045 (4)157 (3)
C4—H4B···I1iii0.96 (4)3.07 (4)3.980 (4)159 (3)
C6—H6A···I1iv0.94 (3)3.04 (4)3.921 (2)157 (3)
C6—H6B···I1v0.92 (5)3.07 (5)3.940 (7)159 (4)
C8—H8B···I1vi0.982.963.857 (7)152
C3—H3B···I2iii0.96 (3)3.08 (3)3.981 (4)157 (2)
C5—H5A···I2iv1.00 (3)3.18 (4)4.094 (3)154 (2)
Symmetry codes: (ii) x+1/2, y1/2, z1/2; (iii) x, y, z1; (iv) x, y1, z1; (v) x+1, y1/2, z+1; (vi) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC8H18N22+·2I·C2H3N
Mr437.10
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)173
a, b, c (Å)20.174 (3), 7.343 (1), 10.6140 (14)
V3)1572.3 (4)
Z4
Radiation typeMo Kα
µ (mm1)3.98
Crystal size (mm)0.25 × 0.04 × 0.04
Data collection
DiffractometerSiemens SMART platform CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Blessing, 1995)
Tmin, Tmax0.592, 0.85
No. of measured, independent and
observed [I > 2σ(I)] reflections
11185, 1508, 1297
Rint0.047
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.045, 1.11
No. of reflections1508
No. of parameters121
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.50, 0.59

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···I2i0.99 (4)3.11 (4)4.045 (4)157 (3)
C4—H4B···I1ii0.96 (4)3.07 (4)3.980 (4)159 (3)
C6—H6A···I1iii0.94 (3)3.04 (4)3.921 (2)157 (3)
C6—H6B···I1iv0.92 (5)3.07 (5)3.940 (7)159 (4)
C8—H8B···I1v0.982.963.857 (7)152
C3—H3B···I2ii0.96 (3)3.08 (3)3.981 (4)157 (2)
C5—H5A···I2iii1.00 (3)3.18 (4)4.094 (3)154 (2)
Symmetry codes: (i) x+1/2, y1/2, z1/2; (ii) x, y, z1; (iii) x, y1, z1; (iv) x+1, y1/2, z+1; (v) x+1/2, y1/2, z+1/2.
 

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