N,N,2,4,6-Penta-methyl-anilinium hexa-fluoro-phosphate-1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane (2/1).

In the title compound, 2C11H18N(+)·2PF6 (-)·C12H24O6, the 18-crown-6 mol-ecule has crystallographically imposed inversion symmetry. In the crystal, it inter-acts with the cation through weak C-H⋯O hydrogen bonds. The cations and anions are further linked via N-H⋯F and C-H⋯F hydrogen bonds, leading to a sandwich structure .

Related literature

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling (1999 ▶); Homes et al. (2001 ▶). For the structure of a related compound, see: Zhang (2013 ▶).

Experimental

Crystal data

2C11H18N+·2PF6 −·C12H24O6

M = 882.78

Monoclinic,

a = 8.9122 (18) Å

b = 16.775 (3) Å

c = 15.136 (3) Å

β = 103.71 (3)°

V = 2198.4 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.19 mm−1

T = 293 K

0.40 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.832, T max = 1.000

18170 measured reflections

3858 independent reflections

2524 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.083

wR(F 2) = 0.195

S = 1.20

3858 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.30 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: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813033734/rz5098sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033734/rz5098Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813033734/rz5098Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C11H18N+·2PF6−·C12H24O6	F(000) = 928
Mr = 882.78	Dx = 1.334 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3858 reflections
a = 8.9122 (18) Å	θ = 2.6–25.0°
b = 16.775 (3) Å	µ = 0.19 mm−1
c = 15.136 (3) Å	T = 293 K
β = 103.71 (3)°	Prism, colourless
V = 2198.4 (8) Å3	0.40 × 0.30 × 0.20 mm
Z = 2

Rigaku Mercury2 (2x2 bin mode) diffractometer	3858 independent reflections
Radiation source: fine-focus sealed tube	2524 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 13.6612 pixels mm-1	θmax = 25.0°, θmin = 3.0°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
Tmin = 0.832, Tmax = 1.000	l = −17→17
18170 measured 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)] = 0.083	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.195	H-atom parameters constrained
S = 1.20	w = 1/[σ2(Fo2) + (0.0528P)2 + 2.P] where P = (Fo2 + 2Fc2)/3
3858 reflections	(Δ/σ)max = 0.003
253 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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. 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
P1	0.47256 (14)	0.24011 (8)	0.74636 (8)	0.0722 (4)
F6	0.4805 (5)	0.2762 (2)	0.6529 (2)	0.1280 (12)
F5	0.3159 (4)	0.2840 (2)	0.7412 (3)	0.1289 (12)
F4	0.3770 (4)	0.16651 (18)	0.6942 (2)	0.1268 (12)
F3	0.4597 (5)	0.2030 (2)	0.8388 (2)	0.1461 (15)
F2	0.5602 (5)	0.3133 (2)	0.7981 (3)	0.1507 (15)
F1	0.6268 (5)	0.1971 (3)	0.7510 (3)	0.1725 (19)
O3	0.2823 (3)	1.00490 (16)	0.45178 (17)	0.0589 (7)
O2	0.1340 (3)	0.85340 (16)	0.45499 (17)	0.0612 (7)
O1	−0.1059 (3)	0.85014 (16)	0.55077 (17)	0.0609 (7)
C6	0.2987 (5)	1.0742 (3)	0.4023 (3)	0.0651 (11)
H6A	0.2276	1.0722	0.3429	0.078*
H6B	0.4029	1.0771	0.3936	0.078*
C4	0.2945 (5)	0.8633 (3)	0.4624 (3)	0.0673 (11)
H4A	0.3358	0.8166	0.4386	0.081*
H4B	0.3480	0.8696	0.5257	0.081*
C5	0.3191 (5)	0.9355 (3)	0.4095 (3)	0.0647 (11)
H5A	0.4261	0.9378	0.4056	0.078*
H5B	0.2548	0.9321	0.3482	0.078*
C2	−0.0682 (5)	0.7856 (2)	0.5001 (3)	0.0616 (11)
H2A	−0.1249	0.7899	0.4371	0.074*
H2B	−0.0961	0.7357	0.5243	0.074*
C3	0.1010 (5)	0.7875 (2)	0.5061 (3)	0.0630 (11)
H3A	0.1573	0.7927	0.5691	0.076*
H3B	0.1329	0.7384	0.4821	0.076*
C1	−0.2661 (5)	0.8535 (3)	0.5475 (3)	0.0664 (11)
H1A	−0.2971	0.8060	0.5751	0.080*
H1B	−0.3247	0.8560	0.4848	0.080*
C7	0.0742 (4)	0.0080 (2)	0.7882 (2)	0.0501 (9)
N1	0.1899 (4)	0.0220 (2)	0.7330 (2)	0.0679 (10)
H1C	0.1970	0.0761	0.7327	0.081*
C9	−0.1049 (5)	0.0657 (3)	0.8628 (3)	0.0647 (11)
H9A	−0.1532	0.1104	0.8797	0.078*
C12	0.0381 (5)	−0.0678 (2)	0.8125 (3)	0.0616 (11)
C11	−0.0714 (6)	−0.0732 (3)	0.8639 (3)	0.0726 (13)
H11A	−0.0971	−0.1235	0.8816	0.087*
C8	0.0030 (4)	0.0760 (2)	0.8112 (2)	0.0537 (10)
C10	−0.1433 (5)	−0.0085 (3)	0.8899 (3)	0.0675 (12)
C13	0.0349 (6)	0.1585 (2)	0.7817 (3)	0.0774 (13)
H13A	−0.0270	0.1963	0.8049	0.116*
H13B	0.0099	0.1611	0.7164	0.116*
H13C	0.1422	0.1709	0.8048	0.116*
C16	0.1342 (6)	0.0025 (3)	0.6344 (3)	0.0709 (12)
H16A	0.2140	0.0142	0.6035	0.106*
H16B	0.0443	0.0338	0.6087	0.106*
H16C	0.1085	−0.0531	0.6277	0.106*
C17	0.3506 (5)	−0.0026 (3)	0.7753 (4)	0.0873 (15)
H17A	0.3774	0.0142	0.8377	0.131*
H17B	0.4196	0.0217	0.7433	0.131*
H17C	0.3588	−0.0595	0.7724	0.131*
C15	0.1046 (7)	−0.1451 (3)	0.7880 (4)	0.1037 (18)
H15A	0.0592	−0.1889	0.8131	0.156*
H15B	0.2144	−0.1452	0.8123	0.156*
H15C	0.0827	−0.1503	0.7230	0.156*
C14	−0.2611 (6)	−0.0173 (4)	0.9466 (3)	0.109 (2)
H14A	−0.2989	0.0344	0.9579	0.164*
H14B	−0.2137	−0.0423	1.0034	0.164*
H14C	−0.3455	−0.0496	0.9144	0.164*

	U11	U22	U33	U12	U13	U23
P1	0.0737 (8)	0.0786 (9)	0.0619 (7)	0.0147 (7)	0.0115 (6)	−0.0153 (6)
F6	0.166 (3)	0.134 (3)	0.090 (2)	−0.004 (2)	0.044 (2)	0.010 (2)
F5	0.105 (2)	0.129 (3)	0.155 (3)	0.044 (2)	0.035 (2)	−0.003 (2)
F4	0.177 (3)	0.088 (2)	0.106 (2)	−0.022 (2)	0.017 (2)	−0.0247 (18)
F3	0.202 (4)	0.166 (4)	0.074 (2)	0.046 (3)	0.041 (2)	0.022 (2)
F2	0.155 (3)	0.151 (3)	0.140 (3)	−0.030 (3)	0.023 (2)	−0.065 (3)
F1	0.126 (3)	0.232 (5)	0.158 (3)	0.101 (3)	0.031 (3)	−0.019 (3)
O3	0.0604 (17)	0.0714 (18)	0.0509 (15)	−0.0010 (14)	0.0253 (13)	−0.0022 (14)
O2	0.0529 (16)	0.0711 (18)	0.0599 (16)	0.0049 (14)	0.0138 (12)	0.0084 (14)
O1	0.0557 (17)	0.0676 (18)	0.0605 (16)	−0.0109 (14)	0.0164 (13)	−0.0133 (14)
C6	0.053 (2)	0.090 (3)	0.057 (2)	−0.012 (2)	0.0249 (19)	0.003 (2)
C4	0.054 (3)	0.079 (3)	0.070 (3)	0.011 (2)	0.019 (2)	−0.001 (2)
C5	0.050 (2)	0.092 (3)	0.058 (2)	0.004 (2)	0.0234 (19)	−0.004 (2)
C2	0.076 (3)	0.054 (2)	0.054 (2)	−0.009 (2)	0.013 (2)	0.0014 (19)
C3	0.075 (3)	0.055 (2)	0.056 (2)	0.007 (2)	0.011 (2)	−0.003 (2)
C1	0.061 (3)	0.074 (3)	0.066 (3)	−0.019 (2)	0.018 (2)	0.000 (2)
C7	0.054 (2)	0.059 (2)	0.0350 (18)	−0.0008 (19)	0.0063 (16)	0.0018 (17)
N1	0.065 (2)	0.083 (3)	0.055 (2)	0.0083 (18)	0.0140 (17)	0.0001 (18)
C9	0.067 (3)	0.078 (3)	0.046 (2)	0.014 (2)	0.006 (2)	−0.008 (2)
C12	0.081 (3)	0.053 (2)	0.046 (2)	0.001 (2)	0.005 (2)	−0.0007 (19)
C11	0.089 (3)	0.069 (3)	0.052 (2)	−0.019 (3)	0.002 (2)	0.008 (2)
C8	0.061 (2)	0.055 (2)	0.040 (2)	0.0030 (19)	0.0023 (18)	−0.0010 (17)
C10	0.052 (2)	0.105 (4)	0.040 (2)	−0.010 (3)	0.0013 (18)	0.006 (2)
C13	0.110 (4)	0.049 (3)	0.075 (3)	0.005 (2)	0.026 (3)	0.001 (2)
C16	0.087 (3)	0.085 (3)	0.045 (2)	−0.004 (2)	0.023 (2)	−0.006 (2)
C17	0.067 (3)	0.090 (4)	0.100 (4)	0.011 (3)	0.010 (3)	0.010 (3)
C15	0.164 (6)	0.057 (3)	0.091 (4)	0.021 (3)	0.032 (4)	0.001 (3)
C14	0.073 (3)	0.187 (6)	0.070 (3)	−0.025 (4)	0.024 (3)	0.011 (3)

P1—F1	1.539 (3)	C7—C8	1.390 (5)
P1—F6	1.556 (3)	C7—N1	1.492 (5)
P1—F3	1.560 (3)	N1—C17	1.482 (5)
P1—F2	1.562 (4)	N1—C16	1.493 (5)
P1—F5	1.564 (3)	N1—H1C	0.9100
P1—F4	1.598 (3)	C9—C10	1.380 (6)
O3—C5	1.404 (5)	C9—C8	1.385 (6)
O3—C6	1.409 (5)	C9—H9A	0.9300
O2—C4	1.418 (4)	C12—C11	1.389 (6)
O2—C3	1.419 (4)	C12—C15	1.507 (6)
O1—C2	1.412 (4)	C11—C10	1.364 (6)
O1—C1	1.418 (4)	C11—H11A	0.9300
C6—C1i	1.495 (6)	C8—C13	1.503 (5)
C6—H6A	0.9700	C10—C14	1.512 (6)
C6—H6B	0.9700	C13—H13A	0.9600
C4—C5	1.497 (6)	C13—H13B	0.9600
C4—H4A	0.9700	C13—H13C	0.9600
C4—H4B	0.9700	C16—H16A	0.9600
C5—H5A	0.9700	C16—H16B	0.9600
C5—H5B	0.9700	C16—H16C	0.9600
C2—C3	1.490 (6)	C17—H17A	0.9600
C2—H2A	0.9700	C17—H17B	0.9600
C2—H2B	0.9700	C17—H17C	0.9600
C3—H3A	0.9700	C15—H15A	0.9600
C3—H3B	0.9700	C15—H15B	0.9600
C1—C6i	1.495 (6)	C15—H15C	0.9600
C1—H1A	0.9700	C14—H14A	0.9600
C1—H1B	0.9700	C14—H14B	0.9600
C7—C12	1.382 (5)	C14—H14C	0.9600
F1—P1—F6	89.5 (2)	C12—C7—C8	122.7 (4)
F1—P1—F3	91.6 (2)	C12—C7—N1	122.0 (4)
F6—P1—F3	178.3 (2)	C8—C7—N1	115.4 (3)
F1—P1—F2	90.6 (3)	C17—N1—C7	116.1 (3)
F6—P1—F2	91.4 (2)	C17—N1—C16	115.4 (4)
F3—P1—F2	89.9 (2)	C7—N1—C16	114.5 (3)
F1—P1—F5	179.7 (2)	C17—N1—H1C	102.6
F6—P1—F5	90.2 (2)	C7—N1—H1C	102.6
F3—P1—F5	88.7 (2)	C16—N1—H1C	102.6
F2—P1—F5	89.4 (2)	C10—C9—C8	122.3 (4)
F1—P1—F4	91.5 (2)	C10—C9—H9A	118.9
F6—P1—F4	89.15 (19)	C8—C9—H9A	118.9
F3—P1—F4	89.5 (2)	C7—C12—C11	116.6 (4)
F2—P1—F4	177.8 (2)	C7—C12—C15	126.6 (4)
F5—P1—F4	88.5 (2)	C11—C12—C15	116.9 (4)
C5—O3—C6	112.2 (3)	C10—C11—C12	123.4 (4)
C4—O2—C3	112.6 (3)	C10—C11—H11A	118.3
C2—O1—C1	112.3 (3)	C12—C11—H11A	118.3
O3—C6—C1i	110.0 (3)	C9—C8—C7	117.3 (4)
O3—C6—H6A	109.7	C9—C8—C13	119.2 (4)
C1i—C6—H6A	109.7	C7—C8—C13	123.5 (4)
O3—C6—H6B	109.7	C11—C10—C9	117.7 (4)
C1i—C6—H6B	109.7	C11—C10—C14	121.5 (5)
H6A—C6—H6B	108.2	C9—C10—C14	120.7 (5)
O2—C4—C5	109.0 (3)	C8—C13—H13A	109.5
O2—C4—H4A	109.9	C8—C13—H13B	109.5
C5—C4—H4A	109.9	H13A—C13—H13B	109.5
O2—C4—H4B	109.9	C8—C13—H13C	109.5
C5—C4—H4B	109.9	H13A—C13—H13C	109.5
H4A—C4—H4B	108.3	H13B—C13—H13C	109.5
O3—C5—C4	110.4 (3)	N1—C16—H16A	109.5
O3—C5—H5A	109.6	N1—C16—H16B	109.5
C4—C5—H5A	109.6	H16A—C16—H16B	109.5
O3—C5—H5B	109.6	N1—C16—H16C	109.5
C4—C5—H5B	109.6	H16A—C16—H16C	109.5
H5A—C5—H5B	108.1	H16B—C16—H16C	109.5
O1—C2—C3	108.6 (3)	N1—C17—H17A	109.5
O1—C2—H2A	110.0	N1—C17—H17B	109.5
C3—C2—H2A	110.0	H17A—C17—H17B	109.5
O1—C2—H2B	110.0	N1—C17—H17C	109.5
C3—C2—H2B	110.0	H17A—C17—H17C	109.5
H2A—C2—H2B	108.4	H17B—C17—H17C	109.5
O2—C3—C2	108.7 (3)	C12—C15—H15A	109.5
O2—C3—H3A	109.9	C12—C15—H15B	109.5
C2—C3—H3A	109.9	H15A—C15—H15B	109.5
O2—C3—H3B	109.9	C12—C15—H15C	109.5
C2—C3—H3B	109.9	H15A—C15—H15C	109.5
H3A—C3—H3B	108.3	H15B—C15—H15C	109.5
O1—C1—C6i	109.3 (3)	C10—C14—H14A	109.5
O1—C1—H1A	109.8	C10—C14—H14B	109.5
C6i—C1—H1A	109.8	H14A—C14—H14B	109.5
O1—C1—H1B	109.8	C10—C14—H14C	109.5
C6i—C1—H1B	109.8	H14A—C14—H14C	109.5
H1A—C1—H1B	108.3	H14B—C14—H14C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···F4	0.91	2.38	3.077 (5)	134
C16—H16A···O3ii	0.96	2.52	3.334 (5)	143
C16—H16B···O2iii	0.96	2.51	3.443 (5)	164
C16—H16C···O1ii	0.96	2.57	3.381 (5)	143
C17—H17B···F4	0.96	2.54	3.122 (6)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯F4	0.91	2.38	3.077 (5)	134
C16—H16A⋯O3i	0.96	2.52	3.334 (5)	143
C16—H16B⋯O2ii	0.96	2.51	3.443 (5)	164
C16—H16C⋯O1i	0.96	2.57	3.381 (5)	143
C17—H17B⋯F4	0.96	2.54	3.122 (6)	119

Symmetry codes: (i) ; (ii) .