4,7,13,18-Tetra-oxa-1,10-diazo-nia-bicyclo-[8.5.5]icosane hexa-fluorido-silicate.

The asymmetric unit of the title molecular salt, C(14)H(30)N(2)O(4) (2+)·SiF(6) (2-), contains half of both the anion and the cation, both ions being completed by a crystallographic twofold axis passing through the Si atom. The cation has a cage structure with the ammonium H atoms pointing into the cage. These H atoms are shielded from inter-molecular inter-actions and form only intra-molecular contacts. There are short inter-molecular C-H⋯F inter-actions in the structure, but no conventional inter-molecular hydrogen bonds.

Related literature

For related structures, see: Cos et al. (1982 ▶); Rehder & Wang (2003 ▶); Luger et al. (1991 ▶); Sen Gupta et al. (2011 ▶); Anderson et al. (2006 ▶); Braband et al. (2003 ▶); Llusar et al. (2001 ▶). For discussion of a cryptand as a mol­ecular automatic titrator, see: Alibrandi et al. (2009 ▶). For NMR data, see: Macchioni et al. (2001 ▶); Christe & Wilson (1990 ▶).

Experimental

Crystal data

C14H30N2O4 2+·SiF6 2−

M = 432.49

Orthorhombic,

a = 10.050 (5) Å

b = 23.218 (5) Å

c = 8.031 (5) Å

V = 1874.0 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 293 K

0.11 × 0.10 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.977, T max = 0.990

9809 measured reflections

2305 independent reflections

1467 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.116

S = 1.02

2305 reflections

123 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026006/fy2006sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026006/fy2006Isup2.hkl

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

C14H30N2O42+·SiF62−	F(000) = 912
Mr = 432.49	Dx = 1.533 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2312 reflections
a = 10.050 (5) Å	θ = 2.2–28.0°
b = 23.218 (5) Å	µ = 0.21 mm−1
c = 8.031 (5) Å	T = 293 K
V = 1874.0 (15) Å3	Block, colourless
Z = 4	0.11 × 0.10 × 0.05 mm

Bruker SMART CCD area-detector diffractometer	2305 independent reflections
Radiation source: sealed tube	1467 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 28.8°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→13
Tmin = 0.977, Tmax = 0.990	k = −29→31
9809 measured reflections	l = −10→10

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0509P)2 + 0.6523P] where P = (Fo2 + 2Fc2)/3
2305 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Si1	0.5000	0.14596 (3)	0.2500	0.02931 (19)
F3	0.61848 (13)	0.19715 (5)	0.25800 (17)	0.0524 (3)
O2	0.86157 (15)	0.02390 (6)	0.76498 (17)	0.0421 (4)
F004	0.50972 (13)	0.14736 (7)	0.04208 (16)	0.0729 (5)
F005	0.61920 (12)	0.09635 (5)	0.2602 (2)	0.0668 (4)
O1	0.97909 (13)	0.14163 (5)	0.97904 (18)	0.0391 (3)
N1	0.79018 (16)	0.13502 (6)	0.72125 (19)	0.0341 (4)
H1	0.8702	0.1174	0.7367	0.041*
C5	0.9322 (2)	−0.02623 (8)	0.7128 (3)	0.0403 (5)
H5A	0.9389	−0.0267	0.5923	0.048*
H5B	0.8844	−0.0605	0.7477	0.048*
C1	0.6852 (2)	0.08871 (8)	0.7376 (3)	0.0450 (5)
H1A	0.6581	0.0853	0.8531	0.054*
H1B	0.6076	0.0991	0.6722	0.054*
C3	0.7786 (2)	0.18006 (8)	0.8537 (3)	0.0394 (5)
H3A	0.6854	0.1879	0.8757	0.047*
H3B	0.8200	0.2155	0.8160	0.047*
C011	0.9254 (2)	0.18663 (9)	0.5104 (2)	0.0412 (5)
H01A	0.9253	0.2032	0.3996	0.049*
H01B	0.9459	0.2168	0.5901	0.049*
C4	0.8453 (2)	0.15967 (10)	1.0105 (3)	0.0429 (5)
H4A	0.8456	0.1906	1.0917	0.051*
H4B	0.7952	0.1278	1.0569	0.051*
C2	0.7402 (2)	0.03213 (9)	0.6775 (3)	0.0483 (6)
H2A	0.6785	0.0011	0.7013	0.058*
H2B	0.7560	0.0333	0.5584	0.058*
C014	0.7927 (2)	0.16036 (9)	0.5484 (2)	0.0424 (5)
H01C	0.7736	0.1304	0.4677	0.051*
H01D	0.7241	0.1896	0.5391	0.051*

	U11	U22	U33	U12	U13	U23
Si1	0.0274 (4)	0.0258 (3)	0.0347 (4)	0.000	0.0017 (3)	0.000
F3	0.0491 (8)	0.0408 (6)	0.0671 (8)	−0.0155 (6)	−0.0126 (6)	0.0053 (6)
O2	0.0468 (8)	0.0332 (7)	0.0463 (8)	0.0034 (6)	−0.0072 (7)	−0.0068 (6)
F004	0.0457 (8)	0.1356 (14)	0.0373 (7)	−0.0124 (8)	0.0033 (6)	−0.0186 (8)
F005	0.0401 (7)	0.0406 (7)	0.1199 (13)	0.0122 (6)	−0.0051 (8)	−0.0097 (8)
O1	0.0357 (8)	0.0381 (8)	0.0435 (8)	−0.0003 (6)	0.0016 (6)	0.0001 (6)
N1	0.0268 (8)	0.0330 (8)	0.0426 (9)	0.0010 (6)	0.0007 (7)	0.0030 (7)
C5	0.0537 (13)	0.0267 (9)	0.0406 (11)	−0.0044 (9)	0.0065 (9)	−0.0041 (7)
C1	0.0293 (10)	0.0426 (12)	0.0632 (14)	−0.0069 (9)	−0.0008 (10)	0.0046 (11)
C3	0.0383 (11)	0.0346 (10)	0.0454 (11)	0.0042 (9)	0.0074 (9)	0.0007 (8)
C011	0.0448 (12)	0.0429 (11)	0.0358 (10)	0.0049 (9)	0.0023 (9)	0.0081 (9)
C4	0.0388 (11)	0.0510 (13)	0.0390 (11)	0.0033 (9)	0.0084 (9)	0.0014 (9)
C2	0.0457 (13)	0.0414 (12)	0.0578 (13)	−0.0097 (10)	−0.0078 (11)	−0.0001 (10)
C014	0.0380 (11)	0.0505 (12)	0.0386 (11)	0.0045 (9)	−0.0064 (9)	0.0067 (9)

Si1—F005i	1.6640 (13)	C1—C2	1.505 (3)
Si1—F005	1.6640 (13)	C1—H1A	0.9700
Si1—F004i	1.6730 (17)	C1—H1B	0.9700
Si1—F004	1.6730 (17)	C3—C4	1.503 (3)
Si1—F3	1.6836 (13)	C3—H3A	0.9700
Si1—F3i	1.6836 (13)	C3—H3B	0.9700
O2—C2	1.421 (3)	C011—O1ii	1.421 (2)
O2—C5	1.426 (2)	C011—C014	1.498 (3)
O1—C011ii	1.421 (2)	C011—H01A	0.9700
O1—C4	1.431 (2)	C011—H01B	0.9700
N1—C3	1.496 (2)	C4—H4A	0.9700
N1—C014	1.508 (2)	C4—H4B	0.9700
N1—C1	1.512 (2)	C2—H2A	0.9700
N1—H1	0.9100	C2—H2B	0.9700
C5—C5ii	1.488 (4)	C014—H01C	0.9700
C5—H5A	0.9700	C014—H01D	0.9700
C5—H5B	0.9700
F005i—Si1—F005	92.38 (10)	N1—C1—H1B	109.7
F005i—Si1—F004i	91.18 (8)	H1A—C1—H1B	108.2
F005—Si1—F004i	90.36 (8)	N1—C3—C4	109.91 (16)
F005i—Si1—F004	90.36 (8)	N1—C3—H3A	109.7
F005—Si1—F004	91.18 (8)	C4—C3—H3A	109.7
F004i—Si1—F004	177.77 (13)	N1—C3—H3B	109.7
F005i—Si1—F3	178.75 (7)	C4—C3—H3B	109.7
F005—Si1—F3	88.72 (7)	H3A—C3—H3B	108.2
F004i—Si1—F3	89.40 (7)	O1ii—C011—C014	106.85 (16)
F004—Si1—F3	89.03 (7)	O1ii—C011—H01A	110.4
F005i—Si1—F3i	88.72 (7)	C014—C011—H01A	110.4
F005—Si1—F3i	178.75 (7)	O1ii—C011—H01B	110.4
F004i—Si1—F3i	89.03 (7)	C014—C011—H01B	110.4
F004—Si1—F3i	89.40 (7)	H01A—C011—H01B	108.6
F3—Si1—F3i	90.18 (10)	O1—C4—C3	111.31 (16)
C2—O2—C5	113.08 (16)	O1—C4—H4A	109.4
C011ii—O1—C4	114.14 (15)	C3—C4—H4A	109.4
C3—N1—C014	112.51 (15)	O1—C4—H4B	109.4
C3—N1—C1	112.39 (16)	C3—C4—H4B	109.4
C014—N1—C1	111.66 (16)	H4A—C4—H4B	108.0
C3—N1—H1	106.6	O2—C2—C1	105.91 (17)
C014—N1—H1	106.6	O2—C2—H2A	110.6
C1—N1—H1	106.6	C1—C2—H2A	110.6
O2—C5—C5ii	109.75 (13)	O2—C2—H2B	110.6
O2—C5—H5A	109.7	C1—C2—H2B	110.6
C5ii—C5—H5A	109.7	H2A—C2—H2B	108.7
O2—C5—H5B	109.7	C011—C014—N1	111.18 (16)
C5ii—C5—H5B	109.7	C011—C014—H01C	109.4
H5A—C5—H5B	108.2	N1—C014—H01C	109.4
C2—C1—N1	109.68 (17)	C011—C014—H01D	109.4
C2—C1—H1A	109.7	N1—C014—H01D	109.4
N1—C1—H1A	109.7	H01C—C014—H01D	108.0
C2—C1—H1B	109.7
C2—O2—C5—C5ii	169.93 (19)	N1—C3—C4—O1	53.0 (2)
C3—N1—C1—C2	−148.05 (17)	C5—O2—C2—C1	−175.52 (16)
C014—N1—C1—C2	84.4 (2)	N1—C1—C2—O2	52.4 (2)
C014—N1—C3—C4	−150.55 (16)	O1ii—C011—C014—N1	60.8 (2)
C1—N1—C3—C4	82.4 (2)	C3—N1—C014—C011	76.0 (2)
C011ii—O1—C4—C3	88.0 (2)	C1—N1—C014—C011	−156.55 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.91	2.19	2.701 (2)	115
N1—H1···O1	0.91	2.30	2.813 (2)	115
N1—H1···O1ii	0.91	2.37	2.826 (2)	111
C1—H1B···F004i	0.97	2.37	3.277 (3)	156
C011—H01B···F3iii	0.97	2.50	3.381 (3)	151
C2—H2A···F005iv	0.97	2.39	3.289 (3)	155
C014—H01C···F005	0.97	2.41	3.257 (3)	146
C3—H3A···F004v	0.97	2.41	3.189 (3)	137
C3—H3B···F3iii	0.97	2.17	3.129 (3)	169
C014—H01D···F3	0.97	2.50	3.039 (3)	115
C4—H4B···F005v	0.97	2.52	3.368 (3)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.91	2.19	2.701 (2)	115
N1—H1⋯O1	0.91	2.30	2.813 (2)	115
N1—H1⋯O1i	0.91	2.37	2.826 (2)	111
C1—H1B⋯F004ii	0.97	2.37	3.277 (3)	156
C011—H01B⋯F3iii	0.97	2.50	3.381 (3)	151
C2—H2A⋯F005iv	0.97	2.39	3.289 (3)	155
C014—H01C⋯F005	0.97	2.41	3.257 (3)	146
C3—H3A⋯F004v	0.97	2.41	3.189 (3)	137
C3—H3B⋯F3iii	0.97	2.17	3.129 (3)	169
C014—H01D⋯F3	0.97	2.50	3.039 (3)	115
C4—H4B⋯F005v	0.97	2.52	3.368 (3)	147

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .