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Acta Cryst. (2010). E66, o788    [ doi:10.1107/S1600536810007865 ]

1,4-Diazoniabicyclo[2.2.2]octane tetrachloroiodate(III) chloride

L.-Z. Chen

Abstract top

In the title compound, C6H14N22+·Cl4I-·Cl-, the dication and the anions lie on special positions. The dication has mm2 symmetry with two bonded C atoms and the two N atoms located on a crystallographic mirror plane parallel to bc, and with a mirror plane parallel to ab passing through the mid points of the three C-C bonds. In the square-planar Cl4I- anion, two Cl atoms and the I atom are located on the mm2 axis; the other two Cl atoms are disordered over two postions of equal occupancy (0.25) across the mirror parallel to the ab plane. The Cl- anion is located on the mm2 axis. The crystal structure is stabilized by intermolecular N-H...Cl hydrogen bonds.

Comment top

Ferroelectric materials continue to attract much attention due to their potential applications in memory devices (Scott, 2007). Recently, diazabicyclo[2.2.2]octane (dabco) salts with inorganic tetrahedral anions having potassium dihydrophosphate-type (KDP-type) structures have been found to exhibit exceptional dielectric properties (Katrusiak & Szafrański, 2006). In our laboratory, the title compound containing a diprotonated cation, C6H14N22+, a tetrachloroiodate and a Cl- anions, has been synthesized. In this article, the crystal structure of the title compound is reported.

In the title compound (Fig. 1), all the species lie on special positions with only one quarter of each being part of the asymmetric unit. The I(III) ion in a square-planar coordination environment. The Cl3 atom is disordered. The crystal structure is stabilized by intermolecular N—H···Cl hydrogen bonds (Table 1).

Related literature top

For ferroelectric materials, see: Scott (2007); Katrusiak & Szafrański (2006).

Experimental top

KI (0.5 g) and I2 (0.7 g) were dissolved in a solution of ethanol (30 ml) and conc. HCl (13 ml) (36%). After addition of 1,4-diazoniabicyclo[2.2.2]octane (1 g) to the above solution, the mixture was stirred for 1 h and then filtered. The filtrate was left at room temperature to allow the solvent to evaporate. Yellow transparent block crystals were obtained after one weeks.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.97 Å and N—H = 0.91 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C/N). The Cl3 atom was disordered over two sites

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The title compound with atomic labels; displacement ellipsoids were drawn at the 30% probability level.
1,4-Diazoniabicyclo[2.2.2]octane tetrachloroiodate(III) chloride top
Crystal data top
C6H14N22+·Cl4I−·Cl−F(000) = 808
Mr = 418.34Dx = 2.017 Mg m−3
Orthorhombic, CmcmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2Cell parameters from 882 reflections
a = 8.1496 (16) Åθ = 3.2–27.5°
b = 21.904 (4) ŵ = 3.26 mm−1
c = 7.7184 (15) ÅT = 293 K
V = 1377.8 (5) Å3Block, yellow
Z = 40.28 × 0.25 × 0.20 mm
Data collection top
Rigaku SCXmini
diffractometer		908 independent reflections
Radiation source: fine-focus sealed tube882 reflections with I > 2σ(I)
graphiteRint = 0.028
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scansh = −10→10
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −28→27
Tmin = 0.85, Tmax = 0.90l = −9→10
7175 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.019H-atom parameters constrained
wR(F2) = 0.045 w = 1/[σ2(Fo2) + (0.0179P)2 + 1.0795P]
where P = (Fo2 + 2Fc2)/3
S = 1.25(Δ/σ)max < 0.001
908 reflectionsΔρmax = 0.44 e Å−3
48 parametersΔρmin = −0.41 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0042 (2)
Crystal data top
C6H14N22+·Cl4I−·Cl−V = 1377.8 (5) Å3
Mr = 418.34Z = 4
Orthorhombic, CmcmMo Kα radiation
a = 8.1496 (16) ŵ = 3.26 mm−1
b = 21.904 (4) ÅT = 293 K
c = 7.7184 (15) Å0.28 × 0.25 × 0.20 mm
Data collection top
Rigaku SCXmini
diffractometer		908 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		882 reflections with I > 2σ(I)
Tmin = 0.85, Tmax = 0.90Rint = 0.028
7175 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.019H-atom parameters constrained
wR(F2) = 0.045Δρmax = 0.44 e Å−3
S = 1.25Δρmin = −0.41 e Å−3
908 reflectionsAbsolute structure: ?
48 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
N10.00000.34601 (10)0.9105 (3)0.0342 (5)
H10.00000.34601.02840.041*
C10.00000.41040 (14)0.8486 (4)0.0590 (10)
H1A0.09650.43150.89150.071*0.50
H1B−0.09650.43150.89150.071*0.50
C20.1498 (3)0.31364 (11)0.8488 (3)0.0442 (5)
H2A0.15020.27200.89170.053*
H2B0.24720.33410.89170.053*
I10.50000.453833 (11)0.25000.03008 (11)
Cl10.50000.56970 (5)0.25000.0529 (3)
Cl20.50000.34147 (6)0.25000.0918 (6)
Cl30.1864 (17)0.4465 (8)0.25000.0442 (7)0.50
Cl3'0.2037 (18)0.4541 (8)0.223 (2)0.0442 (7)0.25
Cl40.00000.27673 (5)0.25000.0396 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0441 (13)0.0360 (12)0.0226 (11)0.0000.0000.0025 (9)
C10.109 (3)0.0320 (15)0.0356 (17)0.0000.000−0.0016 (13)
C20.0339 (11)0.0605 (14)0.0381 (12)0.0051 (10)−0.0025 (9)0.0047 (10)
I10.02875 (15)0.03053 (15)0.03098 (15)0.0000.0000.000
Cl10.0619 (8)0.0343 (5)0.0624 (7)0.0000.0000.000
Cl20.0792 (11)0.0290 (6)0.167 (2)0.0000.0000.000
Cl30.025 (2)0.055 (3)0.052 (4)−0.005 (3)0.0000.000
Cl3'0.025 (2)0.055 (3)0.052 (4)−0.005 (3)0.0000.000
Cl40.0516 (6)0.0410 (5)0.0261 (4)0.0000.0000.000
Geometric parameters (Å, °) top
N1—C11.489 (4)I1—Cl3'2.424 (16)
N1—C21.490 (2)I1—Cl3'iii2.424 (16)
N1—C2i1.490 (2)I1—Cl3'iv2.424 (16)
N1—H10.9100I1—Cl3'v2.424 (16)
C1—C1ii1.522 (7)I1—Cl22.4612 (14)
C1—H1A0.9700I1—Cl12.5379 (13)
C1—H1B0.9700I1—Cl32.561 (15)
C2—C2ii1.525 (4)I1—Cl3iv2.561 (15)
C2—H2A0.9700Cl3'—Cl3'v0.42 (4)
C2—H2B0.9700
C1—N1—C2110.37 (15)Cl3'iv—I1—Cl3'v179.7 (8)
C1—N1—C2i110.37 (15)Cl3'—I1—Cl290.2 (4)
C2—N1—C2i110.0 (2)Cl3'iii—I1—Cl290.2 (4)
C1—N1—H1108.7Cl3'iv—I1—Cl290.2 (4)
C2—N1—H1108.7Cl3'v—I1—Cl290.2 (4)
C2i—N1—H1108.7Cl3'—I1—Cl189.8 (4)
N1—C1—C1ii108.72 (16)Cl3'iii—I1—Cl189.8 (4)
N1—C1—H1A109.9Cl3'iv—I1—Cl189.8 (4)
C1ii—C1—H1A109.9Cl3'v—I1—Cl189.8 (4)
N1—C1—H1B109.9Cl2—I1—Cl1180.0
C1ii—C1—H1B109.9Cl3'iii—I1—Cl3173.9 (4)
H1A—C1—H1B108.3Cl3'iv—I1—Cl3173.9 (4)
N1—C2—C2ii108.65 (12)Cl2—I1—Cl386.4 (4)
N1—C2—H2A110.0Cl1—I1—Cl393.6 (4)
C2ii—C2—H2A110.0Cl3'—I1—Cl3iv173.9 (4)
N1—C2—H2B110.0Cl3'v—I1—Cl3iv173.9 (4)
C2ii—C2—H2B110.0Cl2—I1—Cl3iv86.4 (4)
H2A—C2—H2B108.3Cl1—I1—Cl3iv93.6 (4)
Cl3'—I1—Cl3'iii179.7 (9)Cl3—I1—Cl3iv172.8 (7)
Cl3'—I1—Cl3'iv170.0 (8)Cl3'v—Cl3'—I185.0 (4)
Cl3'iii—I1—Cl3'v170.0 (8)
Symmetry codes: (i) −x, y, z; (ii) x, y, −z+3/2; (iii) −x+1, y, −z+1/2; (iv) −x+1, y, z; (v) x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl4vi0.912.293.028 (2)138
Symmetry codes: (vi) x, y, z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl4i0.912.293.028 (2)138
Symmetry codes: (i) x, y, z+1.
Acknowledgements top

This work was supported by a start-up grant from Jiangsu University of Science and Technology

references
References top

Katrusiak, A. & Szafrański, M. (2006). J. Am. Chem. Soc. 128, 15775–15785

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Scott, J. F. (2007). Science, 315, 954–959.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.