1,4-Diazo-niabicyclo-[2.2.2]octane tetra-chloroiodate(III) chloride.

In the title compound, C(6)H(14)N(2) (2+)·Cl(4)I(-)·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 Cl(4)I(-) 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 inter-molecular N-H⋯Cl hydrogen bonds.

Related literature

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

Experimental

Crystal data

C6H14N2 2+·Cl4I−·Cl−

M = 418.34

Orthorhombic,

a = 8.1496 (16) Å

b = 21.904 (4) Å

c = 7.7184 (15) Å

V = 1377.8 (5) Å3

Z = 4

Mo Kα radiation

μ = 3.26 mm−1

T = 293 K

0.28 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.85, T max = 0.90

7175 measured reflections

908 independent reflections

882 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.045

S = 1.25

908 reflections

48 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.41 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007865/pv2257sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007865/pv2257Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H14N22+·Cl4I−·Cl−	F(000) = 808
Mr = 418.34	Dx = 2.017 Mg m−3
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 882 reflections
a = 8.1496 (16) Å	θ = 3.2–27.5°
b = 21.904 (4) Å	µ = 3.26 mm−1
c = 7.7184 (15) Å	T = 293 K
V = 1377.8 (5) Å3	Block, yellow
Z = 4	0.28 × 0.25 × 0.20 mm

Rigaku SCXmini diffractometer	908 independent reflections
Radiation source: fine-focus sealed tube	882 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −28→27
Tmin = 0.85, Tmax = 0.90	l = −9→10
7175 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.019	H-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 reflections	Δρmax = 0.44 e Å−3
48 parameters	Δρmin = −0.41 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (2)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.0000	0.34601 (10)	0.9105 (3)	0.0342 (5)
H1	0.0000	0.3460	1.0284	0.041*
C1	0.0000	0.41040 (14)	0.8486 (4)	0.0590 (10)
H1A	0.0965	0.4315	0.8915	0.071*	0.50
H1B	−0.0965	0.4315	0.8915	0.071*	0.50
C2	0.1498 (3)	0.31364 (11)	0.8488 (3)	0.0442 (5)
H2A	0.1502	0.2720	0.8917	0.053*
H2B	0.2472	0.3341	0.8917	0.053*
I1	0.5000	0.453833 (11)	0.2500	0.03008 (11)
Cl1	0.5000	0.56970 (5)	0.2500	0.0529 (3)
Cl2	0.5000	0.34147 (6)	0.2500	0.0918 (6)
Cl3	0.1864 (17)	0.4465 (8)	0.2500	0.0442 (7)	0.50
Cl3'	0.2037 (18)	0.4541 (8)	0.223 (2)	0.0442 (7)	0.25
Cl4	0.0000	0.27673 (5)	0.2500	0.0396 (2)

	U11	U22	U33	U12	U13	U23
N1	0.0441 (13)	0.0360 (12)	0.0226 (11)	0.000	0.000	0.0025 (9)
C1	0.109 (3)	0.0320 (15)	0.0356 (17)	0.000	0.000	−0.0016 (13)
C2	0.0339 (11)	0.0605 (14)	0.0381 (12)	0.0051 (10)	−0.0025 (9)	0.0047 (10)
I1	0.02875 (15)	0.03053 (15)	0.03098 (15)	0.000	0.000	0.000
Cl1	0.0619 (8)	0.0343 (5)	0.0624 (7)	0.000	0.000	0.000
Cl2	0.0792 (11)	0.0290 (6)	0.167 (2)	0.000	0.000	0.000
Cl3	0.025 (2)	0.055 (3)	0.052 (4)	−0.005 (3)	0.000	0.000
Cl3'	0.025 (2)	0.055 (3)	0.052 (4)	−0.005 (3)	0.000	0.000
Cl4	0.0516 (6)	0.0410 (5)	0.0261 (4)	0.000	0.000	0.000

N1—C1	1.489 (4)	I1—Cl3'	2.424 (16)
N1—C2	1.490 (2)	I1—Cl3'iii	2.424 (16)
N1—C2i	1.490 (2)	I1—Cl3'iv	2.424 (16)
N1—H1	0.9100	I1—Cl3'v	2.424 (16)
C1—C1ii	1.522 (7)	I1—Cl2	2.4612 (14)
C1—H1A	0.9700	I1—Cl1	2.5379 (13)
C1—H1B	0.9700	I1—Cl3	2.561 (15)
C2—C2ii	1.525 (4)	I1—Cl3iv	2.561 (15)
C2—H2A	0.9700	Cl3'—Cl3'v	0.42 (4)
C2—H2B	0.9700
C1—N1—C2	110.37 (15)	Cl3'iv—I1—Cl3'v	179.7 (8)
C1—N1—C2i	110.37 (15)	Cl3'—I1—Cl2	90.2 (4)
C2—N1—C2i	110.0 (2)	Cl3'iii—I1—Cl2	90.2 (4)
C1—N1—H1	108.7	Cl3'iv—I1—Cl2	90.2 (4)
C2—N1—H1	108.7	Cl3'v—I1—Cl2	90.2 (4)
C2i—N1—H1	108.7	Cl3'—I1—Cl1	89.8 (4)
N1—C1—C1ii	108.72 (16)	Cl3'iii—I1—Cl1	89.8 (4)
N1—C1—H1A	109.9	Cl3'iv—I1—Cl1	89.8 (4)
C1ii—C1—H1A	109.9	Cl3'v—I1—Cl1	89.8 (4)
N1—C1—H1B	109.9	Cl2—I1—Cl1	180.0
C1ii—C1—H1B	109.9	Cl3'iii—I1—Cl3	173.9 (4)
H1A—C1—H1B	108.3	Cl3'iv—I1—Cl3	173.9 (4)
N1—C2—C2ii	108.65 (12)	Cl2—I1—Cl3	86.4 (4)
N1—C2—H2A	110.0	Cl1—I1—Cl3	93.6 (4)
C2ii—C2—H2A	110.0	Cl3'—I1—Cl3iv	173.9 (4)
N1—C2—H2B	110.0	Cl3'v—I1—Cl3iv	173.9 (4)
C2ii—C2—H2B	110.0	Cl2—I1—Cl3iv	86.4 (4)
H2A—C2—H2B	108.3	Cl1—I1—Cl3iv	93.6 (4)
Cl3'—I1—Cl3'iii	179.7 (9)	Cl3—I1—Cl3iv	172.8 (7)
Cl3'—I1—Cl3'iv	170.0 (8)	Cl3'v—Cl3'—I1	85.0 (4)
Cl3'iii—I1—Cl3'v	170.0 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl4vi	0.91	2.29	3.028 (2)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl4i	0.91	2.29	3.028 (2)	138

Symmetry code: (i) .