(4,7,13,16,21,24-Hexaoxa-1,10-di-aza-bicyclo-[8.8.8]hexa-cosa-ne)sodium iodide-1,1,2,2,tetra-fluoro-1,2-diiodo-ethane (2/3).

The title complex (CX1), [Na(C18H36N2O6)]I·1.5C2F4I2, is a three-component adduct containing a [2.2.2]-cryptand, sodium iodide and 1,1,2,2-tetra-fluoro-1,2-di-iodo-ethane. The di-iodo-ethane works as a bidentate halogen-bonding (XB) donor, the [2.2.2]-cryptand chelates the sodium cation, and the iodide counter-ion acts as a tridentate XB acceptor. A (6,3) network is formed in which iodide anions are the nodes and halocarbons the sides. The network symmetry is C 3i and the I⋯I(-) XB distance is 3.4492 (5) Å. This network is strongly deformed and wrinkled. It forms a layer 9.6686 (18) Å high and the inter-layer distance is 4.4889 (10) Å. The cations, inter-acting with each other via weak O⋯H hydrogen bonds, are confined between two anionic layers and also form a (6,3) net. The structure of CX1 is closely related to that of the KI homologue (CX2). The 1,1,2,2,-tetrafluoro-1,2-diiodoethane molecule is rotationally disordered around the I⋯I axis, resulting in an 1:1 disorder of the C2F4 moiety.

Related literature

For other K2.2.2./salt/haloperfluoro­carbon complexes, see: Fox et al. (2004 ▶); Metrangolo et al. (2004 ▶); Liantonio et al. (2003 ▶, 2006 ▶).

Experimental

Crystal data

[Na(C18H36N2O6)]I−·1.5C2F4I2

M = 1057.11

Trigonal,

a = 11.634 (2) Å

c = 84.945 (15) Å

V = 9957 (4) Å3

Z = 12

Mo Kα radiation

μ = 3.84 mm−1

T = 93 K

0.28 × 0.25 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.676, T max = 1.000

47282 measured reflections

2994 independent reflections

2604 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.076

S = 1.07

2994 reflections

148 parameters

44 restraints

H-atom parameters constrained

Δρmax = 1.64 e Å−3

Δρmin = −0.58 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008) ▶; molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL2012.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813016085/kj2225sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016085/kj2225Isup2.hkl

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

[Na(C18H36N2O6)]I−·1.5C2F4I2	Dx = 2.116 Mg m−3
Mr = 1057.11	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 20222 reflections
a = 11.634 (2) Å	θ = 2.2–29.8°
c = 84.945 (15) Å	µ = 3.84 mm−1
V = 9957 (4) Å3	T = 93 K
Z = 12	Hexagonal table, colourless
F(000) = 6012	0.28 × 0.25 × 0.03 mm

Bruker APEXII CCD diffractometer	2604 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.035
φ and ω scans	θmax = 30.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
Tmin = 0.676, Tmax = 1.000	k = −15→15
47282 measured reflections	l = −114→114
2994 independent reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3
2994 reflections	(Δ/σ)max = 0.001
148 parameters	Δρmax = 1.64 e Å−3
44 restraints	Δρmin = −0.58 e Å−3

Experimental. OXFORD low temperature device.

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. The tetrafluorodiiodoethane molecule was rotationally disordered. The split model was refined with restraints on geometric parameters and ADPs. The rotation of this molecule around the I···I axis, was so large that SHELXL suggested a second splitting of two F atoms. We considered not useful and even dangerous the suggestion, because the largest correlations between split atoms parameters, already high (<0.87), would be larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
I2	0.0000	0.0000	0.47358 (2)	0.01498 (10)
I1	0.22447 (2)	0.05878 (2)	0.44381 (2)	0.02001 (9)
C7	0.3618 (9)	0.1058 (7)	0.42456 (12)	0.029 (2)	0.5
F1	0.4634 (7)	0.2274 (9)	0.42658 (10)	0.065 (3)	0.5
F2	0.4115 (9)	0.0252 (9)	0.42395 (11)	0.080 (3)	0.5
C8	0.3016 (8)	0.1016 (6)	0.40861 (12)	0.028 (2)	0.5
F3	0.2439 (9)	0.1750 (10)	0.40947 (12)	0.074 (3)	0.5
F4	0.2054 (7)	−0.0222 (8)	0.40618 (10)	0.083 (4)	0.5
Na	0.3333	0.6667	0.48841 (2)	0.0176 (4)
N1	0.3333	0.6667	0.52071 (5)	0.0147 (9)
C1	0.2462 (3)	0.5297 (3)	0.52603 (3)	0.0167 (6)
H1A	0.1525	0.5071	0.5248	0.020*
H1B	0.2622	0.5232	0.5374	0.020*
C2	0.2684 (3)	0.4311 (3)	0.51696 (4)	0.0174 (6)
H2A	0.3585	0.4461	0.5191	0.021*
H2B	0.2029	0.3397	0.5202	0.021*
O1	0.2542 (2)	0.44777 (19)	0.50055 (2)	0.0159 (4)
C3	0.2593 (3)	0.3468 (3)	0.49158 (3)	0.0186 (6)
H3A	0.1802	0.2595	0.4938	0.022*
H3B	0.3394	0.3422	0.4944	0.022*
C4	0.2632 (3)	0.3789 (3)	0.47452 (4)	0.0186 (6)
H4A	0.2602	0.3067	0.4680	0.022*
H4B	0.1857	0.3884	0.4718	0.022*
O2	0.3838 (2)	0.5009 (2)	0.47155 (3)	0.0180 (5)
C5	0.4235 (3)	0.5180 (3)	0.45540 (4)	0.0198 (6)
H5A	0.4210	0.4363	0.4516	0.024*
H5B	0.5162	0.5918	0.4546	0.024*
C6	0.3357 (3)	0.5475 (3)	0.44487 (3)	0.0191 (6)
H6A	0.3687	0.5597	0.4339	0.023*
H6B	0.2442	0.4708	0.4450	0.023*
N2	0.3333	0.6667	0.44990 (5)	0.0173 (9)

	U11	U22	U33	U12	U13	U23
I2	0.01522 (13)	0.01522 (13)	0.01451 (17)	0.00761 (6)	0.000	0.000
I1	0.01636 (13)	0.02578 (14)	0.01665 (12)	0.00961 (9)	0.00183 (7)	0.00086 (8)
C7	0.028 (5)	0.051 (6)	0.021 (5)	0.030 (5)	0.005 (4)	0.002 (4)
F1	0.025 (3)	0.080 (6)	0.025 (3)	−0.022 (4)	0.007 (2)	−0.019 (5)
F2	0.114 (8)	0.145 (7)	0.058 (6)	0.122 (7)	0.058 (5)	0.066 (5)
C8	0.017 (5)	0.048 (6)	0.020 (5)	0.017 (4)	0.004 (4)	0.003 (4)
F3	0.086 (7)	0.137 (7)	0.060 (6)	0.101 (6)	0.046 (5)	0.063 (6)
F4	0.033 (4)	0.089 (7)	0.028 (3)	−0.043 (4)	0.009 (3)	−0.022 (5)
Na	0.0162 (7)	0.0162 (7)	0.0204 (10)	0.0081 (3)	0.000	0.000
N1	0.0115 (13)	0.0115 (13)	0.021 (2)	0.0057 (6)	0.000	0.000
C1	0.0148 (14)	0.0158 (15)	0.0172 (14)	0.0058 (13)	0.0007 (11)	0.0012 (11)
C2	0.0184 (16)	0.0147 (15)	0.0184 (15)	0.0078 (13)	−0.0009 (12)	0.0023 (11)
O1	0.0194 (11)	0.0140 (11)	0.0163 (10)	0.0099 (9)	0.0001 (8)	0.0004 (8)
C3	0.0219 (16)	0.0120 (15)	0.0211 (15)	0.0079 (13)	0.0002 (12)	−0.0011 (11)
C4	0.0167 (15)	0.0135 (15)	0.0221 (15)	0.0049 (13)	0.0016 (12)	−0.0015 (12)
O2	0.0182 (11)	0.0143 (11)	0.0185 (11)	0.0058 (9)	0.0000 (8)	−0.0003 (8)
C5	0.0192 (16)	0.0188 (16)	0.0207 (15)	0.0091 (13)	0.0038 (13)	0.0002 (12)
C6	0.0197 (16)	0.0195 (16)	0.0168 (14)	0.0089 (13)	0.0001 (12)	−0.0016 (12)
N2	0.0167 (14)	0.0167 (14)	0.018 (2)	0.0084 (7)	0.000	0.000

I1—C8i	2.153 (11)	O1—C3	1.427 (4)
I1—C7	2.156 (11)	C3—C4	1.492 (4)
C7—F1	1.325 (5)	C3—H3A	0.9900
C7—F2	1.327 (5)	C3—H3B	0.9900
C7—C8	1.514 (7)	C4—O2	1.434 (4)
C8—F4	1.325 (5)	C4—H4A	0.9900
C8—F3	1.327 (5)	C4—H4B	0.9900
N1—C1ii	1.468 (3)	O2—C5	1.430 (4)
N1—C1	1.468 (3)	C5—C6	1.520 (4)
N1—C1iii	1.468 (3)	C5—H5A	0.9900
C1—C2	1.508 (4)	C5—H5B	0.9900
C1—H1A	0.9900	C6—N2	1.464 (3)
C1—H1B	0.9900	C6—H6A	0.9900
C2—O1	1.428 (4)	C6—H6B	0.9900
C2—H2A	0.9900	N2—C6iii	1.464 (3)
C2—H2B	0.9900	N2—C6ii	1.464 (4)
F1—C7—F2	106.7 (7)	O1—C3—C4	108.7 (2)
F1—C7—C8	107.6 (5)	O1—C3—H3A	109.9
F2—C7—C8	107.4 (5)	C4—C3—H3A	109.9
F1—C7—I1	109.0 (5)	O1—C3—H3B	109.9
F2—C7—I1	112.3 (6)	C4—C3—H3B	109.9
C8—C7—I1	113.5 (4)	H3A—C3—H3B	108.3
F4—C8—F3	106.5 (7)	O2—C4—C3	108.1 (2)
F4—C8—C7	107.5 (5)	O2—C4—H4A	110.1
F3—C8—C7	107.7 (5)	C3—C4—H4A	110.1
F1i—C8—I1i	118.8 (9)	O2—C4—H4B	110.1
F4—C8—I1i	110.4 (6)	C3—C4—H4B	110.1
F3—C8—I1i	110.5 (6)	H4A—C4—H4B	108.4
C7—C8—I1i	114.0 (4)	C5—O2—C4	113.2 (2)
C1ii—N1—C1	110.97 (18)	O2—C5—C6	112.9 (3)
C1ii—N1—C1iii	110.97 (18)	O2—C5—H5A	109.0
C1—N1—C1iii	110.97 (18)	C6—C5—H5A	109.0
N1—C1—C2	112.3 (2)	O2—C5—H5B	109.0
N1—C1—H1A	109.1	C6—C5—H5B	109.0
C2—C1—H1A	109.1	H5A—C5—H5B	107.8
N1—C1—H1B	109.1	N2—C6—C5	112.0 (3)
C2—C1—H1B	109.1	N2—C6—H6A	109.2
H1A—C1—H1B	107.9	C5—C6—H6A	109.2
O1—C2—C1	108.6 (2)	N2—C6—H6B	109.2
O1—C2—H2A	110.0	C5—C6—H6B	109.2
C1—C2—H2A	110.0	H6A—C6—H6B	107.9
O1—C2—H2B	110.0	C6iii—N2—C6ii	111.84 (19)
C1—C2—H2B	110.0	C6iii—N2—C6	111.84 (19)
H2A—C2—H2B	108.3	C6ii—N2—C6	111.84 (18)
C3—O1—C2	110.8 (2)
F1—C7—C8—F4	176.1 (9)	C1iii—N1—C1—C2	162.6 (3)
F2—C7—C8—F4	61.5 (8)	N1—C1—C2—O1	−54.8 (3)
I1—C7—C8—F4	−63.3 (8)	C1—C2—O1—C3	−173.3 (2)
F1—C7—C8—F3	−69.6 (8)	C2—O1—C3—C4	−172.2 (2)
F2—C7—C8—F3	175.9 (7)	O1—C3—C4—O2	63.8 (3)
I1—C7—C8—F3	51.1 (7)	C3—C4—O2—C5	158.4 (2)
F1—C7—C8—I1i	53.4 (8)	C4—O2—C5—C6	71.9 (3)
F2—C7—C8—I1i	−61.2 (7)	O2—C5—C6—N2	58.0 (3)
I1—C7—C8—I1i	174.0 (2)	C5—C6—N2—C6iii	−154.9 (3)
C1ii—N1—C1—C2	−73.6 (4)	C5—C6—N2—C6ii	78.7 (4)

	CX1	CX2
Hole side1	11.634 (2)	11.7478 (15)
Layer height2	9.6686 (18)	9.6380 (13)
h3	4.4889 (10)	4.5343 (7)
V3	303.79 (7)	312.89 (6)
M+—O1	2.460 (2)	2.6650 (12)
M+—O2	2.692 (2)	2.7737 (13)
M+—N1	2.744 (5)	2.941 (2)
M+—N2	3.271 (5)	2.985 (3)

X···Y—C	CX1 X···Y	CX1 C—X···Y	CX2 X···Y	CX2 C—X···Y
I2···I1—C7	3.4492 (5)	175.99 (17)	3.4492 (5)	176.30 (16)
I2···I1—C8i	3.4492 (5)	168.30 (16)	3.4492 (5)	166.40 (16)
O1···(H3B—C3)ii	2.63	147.9	2.60	147.6

Table 1

Some parameters (Å, Å3) of the anionic layer and of the cation in the structures CX1 and CX2

	CX1	CX2
Hole side1	11.634 (2)	11.7478 (15)
Layer height2	9.6686 (18)	9.6380 (13)
h 3	4.4889 (10)	4.5343 (7)
V 3	303.79 (7)	312.89 (6)
M +—O1	2.460 (2)	2.6650 (12)
M +—O2	2.692 (2)	2.7737 (13)
M +—N1	2.744 (5)	2.941 (2)
M +—N2	3.271 (5)	2.985 (3)

Notes: (1) Distance between the nearest iodide anions on the same side of the anionic layer, equal to the cell parameter a; (2) distance between the planes through the iodide anions on the opposite sides of the anionic layer; (3) h = distance between the nearest planes through iodide anions of contiguous layers. (4) V = a 2 h/2, volume of the trigonal prism whose vertices are the three iodide anions on a layer and the same faced on the contiguous one.

Table 2

Halogen and hydrogen bonds (Å, °) in CX1 and CX2

In CX2, the cell origin and the atom numbering are different, so that atom labels and symmetry code refer only to CX1; for CX2 the reported values refer to the equivalent atoms and values.

X⋯Y—C	CX1 X⋯Y	CX1 C—X⋯Y	CX2 X⋯Y	CX2 C—X⋯Y
I2⋯I1—C7	3.4492 (5)	175.99 (17)	3.4492 (5)	176.30 (16)
I2⋯I1—C8i	3.4492 (5)	168.30 (16)	3.4492 (5)	166.40 (16)
O1⋯(H3B—C3)ii	2.63	147.9	2.60	147.6

Symmetry codes: (i) ; (ii) .