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

The asymmetric unit of the title structure, C(14)H(30)N(2)O(4) (2+)·2PF(6) (-), contains the anion and half of the cation, the latter being completed by a crystallographic twofold axis. 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 ▶). 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+·2PF6 −

M = 580.34

Monoclinic,

a = 10.8297 (16) Å

b = 16.485 (2) Å

c = 12.6846 (19) Å

β = 95.538 (2)°

V = 2254.0 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 296 K

0.24 × 0.06 × 0.02 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.977, T max = 0.994

9756 measured reflections

2785 independent reflections

2002 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.095

S = 1.03

2785 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.34 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 ▶) and WinGX (Farrugia, 1999 ▶); 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/S1600536811025992/fy2005sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025992/fy2005Isup2.hkl

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

C14H30N2O42+·2PF6−	F(000) = 1192
Mr = 580.34	Dx = 1.710 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1782 reflections
a = 10.8297 (16) Å	θ = 2.3–28.9°
b = 16.485 (2) Å	µ = 0.32 mm−1
c = 12.6846 (19) Å	T = 296 K
β = 95.538 (2)°	Needle, colourless
V = 2254.0 (6) Å3	0.24 × 0.06 × 0.02 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2785 independent reflections
Radiation source: sealed tube	2002 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 28.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −14→14
Tmin = 0.977, Tmax = 0.994	k = −22→21
9756 measured reflections	l = −17→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0378P)2 + 1.6619P] where P = (Fo2 + 2Fc2)/3
2785 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.34 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
P1	0.47273 (5)	0.15573 (3)	0.99505 (4)	0.02088 (14)
O1	0.56230 (12)	0.43242 (8)	0.89074 (10)	0.0200 (3)
F1	0.46836 (11)	0.12944 (8)	1.11636 (9)	0.0315 (3)
F2	0.35902 (11)	0.09625 (8)	0.96176 (9)	0.0316 (3)
O2	0.39311 (12)	0.59898 (8)	0.80510 (11)	0.0222 (3)
F6	0.58658 (11)	0.21576 (7)	1.02955 (10)	0.0334 (3)
F5	0.37765 (11)	0.22713 (7)	1.01299 (11)	0.0366 (3)
F3	0.56899 (12)	0.08506 (8)	0.98002 (11)	0.0379 (3)
F4	0.47690 (13)	0.18356 (9)	0.87520 (10)	0.0421 (4)
N1	0.31687 (14)	0.44308 (9)	0.79332 (12)	0.0180 (3)
H0	0.3874	0.4684	0.7775	0.022*
C6	0.46254 (18)	0.40126 (12)	0.94552 (15)	0.0217 (4)
H6A	0.4339	0.4429	0.9914	0.026*
H6B	0.4917	0.3556	0.9893	0.026*
C5	0.35700 (18)	0.37461 (12)	0.86707 (15)	0.0203 (4)
H5A	0.3831	0.3289	0.8265	0.024*
H5B	0.2877	0.3573	0.9046	0.024*
C4	0.65712 (18)	0.37384 (12)	0.87734 (16)	0.0225 (4)
H4A	0.6216	0.3256	0.8426	0.027*
H4B	0.6988	0.3583	0.9455	0.027*
C1	0.24085 (18)	0.50610 (12)	0.84409 (16)	0.0218 (4)
H1A	0.1536	0.4921	0.8331	0.026*
H1B	0.2648	0.5079	0.9197	0.026*
C3	0.25267 (18)	0.41362 (13)	0.69006 (15)	0.0227 (4)
H3A	0.2131	0.4591	0.6518	0.027*
H3B	0.1887	0.3750	0.7040	0.027*
C7	0.43045 (19)	0.66749 (12)	0.74776 (17)	0.0257 (5)
H7A	0.4019	0.7170	0.7788	0.031*
H7B	0.3947	0.6646	0.6747	0.031*
C2	0.26190 (18)	0.58770 (12)	0.79590 (16)	0.0238 (4)
H2A	0.2286	0.5888	0.7221	0.029*
H2B	0.2222	0.6300	0.8336	0.029*

	U11	U22	U33	U12	U13	U23
P1	0.0180 (3)	0.0221 (3)	0.0230 (3)	0.0016 (2)	0.0041 (2)	0.0031 (2)
O1	0.0164 (7)	0.0203 (7)	0.0237 (7)	0.0008 (5)	0.0041 (5)	0.0034 (6)
F1	0.0293 (7)	0.0440 (8)	0.0210 (6)	−0.0057 (6)	0.0018 (5)	0.0048 (5)
F2	0.0312 (7)	0.0350 (7)	0.0281 (7)	−0.0101 (6)	−0.0007 (5)	−0.0018 (5)
O2	0.0215 (7)	0.0205 (7)	0.0249 (7)	0.0003 (6)	0.0034 (6)	0.0057 (6)
F6	0.0221 (6)	0.0305 (7)	0.0476 (8)	−0.0053 (5)	0.0031 (6)	0.0034 (6)
F5	0.0252 (7)	0.0270 (7)	0.0587 (9)	0.0080 (5)	0.0097 (6)	0.0028 (6)
F3	0.0338 (7)	0.0298 (7)	0.0523 (9)	0.0105 (6)	0.0158 (6)	−0.0002 (6)
F4	0.0452 (8)	0.0555 (9)	0.0260 (7)	−0.0063 (7)	0.0063 (6)	0.0133 (6)
N1	0.0143 (8)	0.0194 (8)	0.0208 (9)	−0.0003 (6)	0.0039 (6)	−0.0006 (7)
C6	0.0219 (10)	0.0252 (11)	0.0186 (10)	−0.0007 (8)	0.0047 (8)	0.0038 (8)
C5	0.0198 (10)	0.0182 (10)	0.0233 (10)	0.0004 (8)	0.0045 (8)	0.0029 (8)
C4	0.0197 (10)	0.0249 (11)	0.0228 (11)	0.0042 (8)	0.0012 (8)	0.0048 (8)
C1	0.0197 (10)	0.0212 (10)	0.0256 (11)	0.0047 (8)	0.0077 (8)	−0.0024 (8)
C3	0.0174 (10)	0.0281 (11)	0.0221 (10)	−0.0032 (8)	−0.0003 (8)	−0.0028 (8)
C7	0.0339 (12)	0.0160 (10)	0.0286 (11)	0.0049 (8)	0.0102 (9)	0.0021 (8)
C2	0.0205 (10)	0.0270 (11)	0.0240 (11)	0.0061 (8)	0.0030 (8)	0.0014 (8)

P1—F3	1.5871 (13)	C5—H5A	0.9700
P1—F4	1.5927 (13)	C5—H5B	0.9700
P1—F5	1.5946 (13)	C4—C3i	1.509 (3)
P1—F2	1.5987 (13)	C4—H4A	0.9700
P1—F1	1.6037 (13)	C4—H4B	0.9700
P1—F6	1.6083 (13)	C1—C2	1.504 (3)
O1—C4	1.432 (2)	C1—H1A	0.9700
O1—C6	1.435 (2)	C1—H1B	0.9700
O2—C7	1.423 (2)	C3—C4i	1.509 (3)
O2—C2	1.427 (2)	C3—H3A	0.9700
N1—C3	1.503 (2)	C3—H3B	0.9700
N1—C5	1.503 (2)	C7—C7i	1.502 (4)
N1—C1	1.508 (2)	C7—H7A	0.9700
N1—H0	0.9100	C7—H7B	0.9700
C6—C5	1.507 (3)	C2—H2A	0.9700
C6—H6A	0.9700	C2—H2B	0.9700
C6—H6B	0.9700
F3—P1—F4	91.00 (8)	C6—C5—H5B	109.6
F3—P1—F5	178.59 (8)	H5A—C5—H5B	108.1
F4—P1—F5	90.10 (8)	O1—C4—C3i	106.57 (15)
F3—P1—F2	90.93 (7)	O1—C4—H4A	110.4
F4—P1—F2	90.95 (7)	C3i—C4—H4A	110.4
F5—P1—F2	89.93 (7)	O1—C4—H4B	110.4
F3—P1—F1	89.85 (7)	C3i—C4—H4B	110.4
F4—P1—F1	178.93 (8)	H4A—C4—H4B	108.6
F5—P1—F1	89.04 (7)	C2—C1—N1	109.40 (15)
F2—P1—F1	89.68 (7)	C2—C1—H1A	109.8
F3—P1—F6	89.38 (7)	N1—C1—H1A	109.8
F4—P1—F6	89.48 (7)	C2—C1—H1B	109.8
F5—P1—F6	89.75 (7)	N1—C1—H1B	109.8
F2—P1—F6	179.46 (8)	H1A—C1—H1B	108.2
F1—P1—F6	89.88 (7)	N1—C3—C4i	111.34 (16)
C4—O1—C6	113.47 (14)	N1—C3—H3A	109.4
C7—O2—C2	113.05 (15)	C4i—C3—H3A	109.4
C3—N1—C5	112.42 (15)	N1—C3—H3B	109.4
C3—N1—C1	111.66 (15)	C4i—C3—H3B	109.4
C5—N1—C1	112.86 (15)	H3A—C3—H3B	108.0
C3—N1—H0	106.5	O2—C7—C7i	108.31 (15)
C5—N1—H0	106.5	O2—C7—H7A	110.0
C1—N1—H0	106.5	C7i—C7—H7A	110.0
O1—C6—C5	110.07 (15)	O2—C7—H7B	110.0
O1—C6—H6A	109.6	C7i—C7—H7B	110.0
C5—C6—H6A	109.6	H7A—C7—H7B	108.4
O1—C6—H6B	109.6	O2—C2—C1	105.79 (15)
C5—C6—H6B	109.6	O2—C2—H2A	110.6
H6A—C6—H6B	108.2	C1—C2—H2A	110.6
N1—C5—C6	110.33 (16)	O2—C2—H2B	110.6
N1—C5—H5A	109.6	C1—C2—H2B	110.6
C6—C5—H5A	109.6	H2A—C2—H2B	108.7
N1—C5—H5B	109.6
C4—O1—C6—C5	−96.35 (18)	C5—N1—C1—C2	149.57 (16)
C3—N1—C5—C6	156.50 (15)	C5—N1—C3—C4i	−71.3 (2)
C1—N1—C5—C6	−76.12 (19)	C1—N1—C3—C4i	160.72 (16)
O1—C6—C5—N1	−55.1 (2)	C2—O2—C7—C7i	−173.23 (18)
C6—O1—C4—C3i	174.66 (15)	C7—O2—C2—C1	170.30 (16)
C3—N1—C1—C2	−82.64 (19)	N1—C1—C2—O2	−53.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H0···O1	0.91	2.34	2.826 (2)	113
N1—H0···O2	0.91	2.18	2.699 (2)	115
N1—H0···O1i	0.91	2.33	2.790 (2)	111
C2—H2A···F2ii	0.97	2.43	3.405 (2)	178
C6—H6B···F5	0.97	2.48	3.157 (2)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H0⋯O1	0.91	2.34	2.826 (2)	113
N1—H0⋯O2	0.91	2.18	2.699 (2)	115
N1—H0⋯O1i	0.91	2.33	2.790 (2)	111
C2—H2A⋯F2ii	0.97	2.43	3.405 (2)	178
C6—H6B⋯F5	0.97	2.48	3.157 (2)	126

Symmetry codes: (i) ; (ii) .