4-Methyl-anilinium tetra-fluoro-borate 18-crown-6 clathrate.

In the title compound, C(7)H(10)N(+)·BF(4) (-)·C(12)H(24)O(6), the proton-ated 4-methyl-anilinium cation inter-acts with 18-crown-6 forming a rotator-stator structure, (C(6)H(4)CH(3)NH(3) (+))(18-crown-6), through three bifurcated N-H⋯(O,O) hydrogen bonds between the ammonium groups of the cations (-NH(3)) and the O atoms of the crown ether mol-ecule. The BF(4) (-) anions, the methyl group and the protonated -NH(3) groups of the 4-methylanilinium lie on a dual axis of rotation. The 18-crown-6 unit is perpendicular to the dual axis of rotation and the mirror plane which contains the dual axis of rotation. The benzene ring of 4-methylanilinium is perpendicular to the mirror plane and parallel to the dual axis.

Related literature

For a similar 18-crown-6 clathrate, see: Pedersen et al. (1967 ▶). For ferroelectric properties, see: Fu et al. (2007 ▶); Ye et al. (2009 ▶).; Zhang et al. (2009 ▶).

Experimental

Crystal data

C7H10N+·BF4 −·C12H24O6

M = 459.28

Orthorhombic,

a = 15.439 (3) Å

b = 11.616 (2) Å

c = 13.071 (3) Å

V = 2344.2 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.977, T max = 0.977

23254 measured reflections

2816 independent reflections

1541 reflections with I > 2σ(I)

R int = 0.086

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.209

S = 1.02

2816 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.23 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: PRPKAPPA (Ferguson, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810019033/jh2160sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810019033/jh2160Isup2.hkl

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

C7H10N+·BF4−·C12H24O6	F(000) = 976
Mr = 459.28	Dx = 1.301 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2816 reflections
a = 15.439 (3) Å	θ = 3.1–27.5°
b = 11.616 (2) Å	µ = 0.11 mm−1
c = 13.071 (3) Å	T = 293 K
V = 2344.2 (8) Å3	Block, pale yellow
Z = 4	0.20 × 0.20 × 0.20 mm

Rigaku SCXmini diffractometer	2816 independent reflections
Radiation source: fine-focus sealed tube	1541 reflections with I > 2σ(I)
graphite	Rint = 0.086
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
Tmin = 0.977, Tmax = 0.977	l = −16→16
23254 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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.209	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0947P)2 + 0.766P] where P = (Fo2 + 2Fc2)/3
2816 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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)
O1	0.45735 (17)	0.2500	0.85026 (19)	0.0531 (7)
O2	0.39198 (12)	0.03619 (16)	0.78258 (14)	0.0548 (5)
O3	0.30174 (13)	0.04501 (16)	0.59530 (15)	0.0607 (6)
O4	0.21893 (18)	0.2500	0.5296 (2)	0.0630 (8)
C5	0.4704 (2)	0.0478 (3)	0.8399 (2)	0.0615 (8)
H5A	0.5189	0.0592	0.7937	0.074*
H5B	0.4809	−0.0217	0.8792	0.074*
C3	0.3162 (2)	−0.0608 (2)	0.6496 (2)	0.0640 (8)
H3A	0.3188	−0.1245	0.6017	0.077*
H3B	0.2689	−0.0747	0.6968	0.077*
C4	0.3988 (2)	−0.0519 (3)	0.7065 (2)	0.0617 (8)
H4A	0.4118	−0.1250	0.7390	0.074*
H4B	0.4455	−0.0337	0.6596	0.074*
C2	0.2237 (2)	0.0450 (3)	0.5374 (3)	0.0719 (9)
H2A	0.1742	0.0476	0.5831	0.086*
H2B	0.2199	−0.0249	0.4971	0.086*
C6	0.4625 (2)	0.1481 (2)	0.9098 (2)	0.0587 (8)
H6A	0.4109	0.1403	0.9516	0.070*
H6B	0.5124	0.1517	0.9548	0.070*
C1	0.2230 (2)	0.1471 (3)	0.4689 (2)	0.0770 (10)
H1A	0.2750	0.1478	0.4273	0.092*
H1B	0.1732	0.1435	0.4236	0.092*
N1	0.29810 (18)	0.2500	0.7297 (2)	0.0432 (7)
H1C	0.3138	0.3222	0.7167	0.065*	0.50
H1D	0.2860	0.2142	0.6712	0.065*	0.50
H1E	0.3412	0.2136	0.7613	0.065*	0.50
C7	0.2212 (2)	0.2500	0.7954 (2)	0.0406 (8)
C8	0.18519 (19)	0.1469 (3)	0.8255 (2)	0.0566 (7)
H8A	0.2099	0.0775	0.8054	0.068*
C10	0.0727 (2)	0.2500	0.9169 (3)	0.0562 (11)
C9	0.11146 (19)	0.1480 (3)	0.8863 (2)	0.0624 (8)
H9A	0.0874	0.0784	0.9071	0.075*
C11	−0.0088 (3)	0.2500	0.9817 (4)	0.0863 (15)
H11A	−0.0260	0.3279	0.9954	0.129*	0.50
H11B	0.0023	0.2110	1.0450	0.129*	0.50
H11C	−0.0544	0.2111	0.9455	0.129*	0.50
B1	0.3985 (3)	0.2500	0.2064 (4)	0.0572 (12)
F3	0.48142 (17)	0.2500	0.1644 (2)	0.0831 (8)
F1	0.38646 (15)	0.1522 (2)	0.2638 (2)	0.1101 (8)
F2	0.3400 (2)	0.2500	0.1254 (2)	0.0999 (10)

	U11	U22	U33	U12	U13	U23
O1	0.0597 (17)	0.0518 (15)	0.0479 (15)	0.000	−0.0094 (12)	0.000
O2	0.0579 (12)	0.0441 (10)	0.0624 (12)	0.0055 (8)	0.0011 (9)	−0.0021 (9)
O3	0.0587 (12)	0.0543 (12)	0.0692 (13)	−0.0104 (9)	−0.0082 (10)	−0.0084 (10)
O4	0.0669 (19)	0.080 (2)	0.0418 (15)	0.000	−0.0083 (13)	0.000
C5	0.0575 (18)	0.0592 (18)	0.0677 (19)	0.0124 (14)	−0.0051 (15)	0.0141 (15)
C3	0.074 (2)	0.0441 (16)	0.074 (2)	−0.0127 (14)	0.0129 (16)	−0.0112 (14)
C4	0.071 (2)	0.0456 (16)	0.0688 (19)	0.0061 (14)	0.0090 (16)	−0.0020 (14)
C2	0.061 (2)	0.080 (2)	0.074 (2)	−0.0116 (16)	−0.0106 (17)	−0.0257 (19)
C6	0.0621 (18)	0.0637 (19)	0.0503 (15)	0.0038 (14)	−0.0086 (13)	0.0117 (15)
C1	0.070 (2)	0.109 (3)	0.0524 (17)	−0.0058 (19)	−0.0146 (15)	−0.020 (2)
N1	0.0446 (17)	0.0441 (16)	0.0411 (16)	0.000	−0.0027 (13)	0.000
C7	0.0379 (19)	0.047 (2)	0.0374 (18)	0.000	−0.0074 (15)	0.000
C8	0.0599 (18)	0.0526 (17)	0.0574 (17)	−0.0035 (13)	0.0064 (14)	−0.0007 (13)
C10	0.040 (2)	0.086 (3)	0.042 (2)	0.000	−0.0028 (17)	0.000
C9	0.0597 (19)	0.068 (2)	0.0599 (17)	−0.0157 (15)	0.0048 (14)	0.0030 (15)
C11	0.067 (3)	0.122 (4)	0.070 (3)	0.000	0.009 (3)	0.000
B1	0.049 (3)	0.047 (3)	0.076 (3)	0.000	−0.010 (2)	0.000
F3	0.0672 (17)	0.0736 (18)	0.109 (2)	0.000	0.0040 (15)	0.000
F1	0.1019 (17)	0.0984 (17)	0.1301 (18)	−0.0018 (13)	0.0172 (14)	0.0433 (15)
F2	0.081 (2)	0.114 (2)	0.105 (2)	0.000	−0.0178 (17)	0.000

O1—C6i	1.419 (3)	C1—H1A	0.9700
O1—C6	1.419 (3)	C1—H1B	0.9700
O2—C5	1.431 (3)	N1—C7	1.465 (4)
O2—C4	1.431 (3)	N1—H1C	0.8900
O3—C2	1.423 (3)	N1—H1D	0.8900
O3—C3	1.436 (4)	N1—H1E	0.8900
O4—C1	1.436 (4)	C7—C8	1.378 (3)
O4—C1i	1.436 (4)	C7—C8i	1.378 (3)
C5—C6	1.486 (4)	C8—C9	1.388 (4)
C5—H5A	0.9700	C8—H8A	0.9300
C5—H5B	0.9700	C10—C9i	1.386 (4)
C3—C4	1.480 (4)	C10—C9	1.386 (4)
C3—H3A	0.9700	C10—C11	1.517 (6)
C3—H3B	0.9700	C9—H9A	0.9300
C4—H4A	0.9700	C11—H11A	0.9600
C4—H4B	0.9700	C11—H11B	0.9600
C2—C1	1.487 (5)	C11—H11C	0.9600
C2—H2A	0.9700	B1—F1	1.374 (4)
C2—H2B	0.9700	B1—F1i	1.374 (4)
C6—H6A	0.9700	B1—F3	1.392 (5)
C6—H6B	0.9700	B1—F2	1.393 (5)
C6i—O1—C6	113.0 (3)	O4—C1—H1A	109.8
C5—O2—C4	111.7 (2)	C2—C1—H1A	109.8
C2—O3—C3	113.2 (2)	O4—C1—H1B	109.8
C1—O4—C1i	112.7 (3)	C2—C1—H1B	109.8
O2—C5—C6	109.0 (2)	H1A—C1—H1B	108.2
O2—C5—H5A	109.9	C7—N1—H1C	109.5
C6—C5—H5A	109.9	C7—N1—H1D	109.5
O2—C5—H5B	109.9	H1C—N1—H1D	109.5
C6—C5—H5B	109.9	C7—N1—H1E	109.5
H5A—C5—H5B	108.3	H1C—N1—H1E	109.5
O3—C3—C4	108.8 (2)	H1D—N1—H1E	109.5
O3—C3—H3A	109.9	C8—C7—C8i	120.7 (3)
C4—C3—H3A	109.9	C8—C7—N1	119.65 (17)
O3—C3—H3B	109.9	C8i—C7—N1	119.65 (17)
C4—C3—H3B	109.9	C7—C8—C9	119.1 (3)
H3A—C3—H3B	108.3	C7—C8—H8A	120.4
O2—C4—C3	109.6 (2)	C9—C8—H8A	120.4
O2—C4—H4A	109.7	C9i—C10—C9	117.4 (4)
C3—C4—H4A	109.7	C9i—C10—C11	121.28 (18)
O2—C4—H4B	109.7	C9—C10—C11	121.28 (18)
C3—C4—H4B	109.7	C10—C9—C8	121.8 (3)
H4A—C4—H4B	108.2	C10—C9—H9A	119.1
O3—C2—C1	109.0 (3)	C8—C9—H9A	119.1
O3—C2—H2A	109.9	C10—C11—H11A	109.5
C1—C2—H2A	109.9	C10—C11—H11B	109.5
O3—C2—H2B	109.9	H11A—C11—H11B	109.5
C1—C2—H2B	109.9	C10—C11—H11C	109.5
H2A—C2—H2B	108.3	H11A—C11—H11C	109.5
O1—C6—C5	108.7 (2)	H11B—C11—H11C	109.5
O1—C6—H6A	109.9	F1—B1—F1i	111.6 (4)
C5—C6—H6A	109.9	F1—B1—F3	109.9 (2)
O1—C6—H6B	109.9	F1i—B1—F3	109.9 (2)
C5—C6—H6B	109.9	F1—B1—F2	109.1 (3)
H6A—C6—H6B	108.3	F1i—B1—F2	109.1 (3)
O4—C1—C2	109.4 (2)	F3—B1—F2	107.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2i	0.89	2.21	2.958 (2)	141
N1—H1C···O3i	0.89	2.22	2.960 (2)	140
N1—H1D···O4	0.89	2.16	2.887 (4)	138
N1—H1D···O3	0.89	2.22	2.960 (2)	141
N1—H1E···O1	0.89	2.18	2.920 (4)	140
N1—H1E···O2	0.89	2.22	2.958 (2)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O2i	0.89	2.21	2.958 (2)	141
N1—H1C⋯O3i	0.89	2.22	2.960 (2)	140
N1—H1D⋯O4	0.89	2.16	2.887 (4)	138
N1—H1D⋯O3	0.89	2.22	2.960 (2)	141
N1—H1E⋯O1	0.89	2.18	2.920 (4)	140
N1—H1E⋯O2	0.89	2.22	2.958 (2)	140

Symmetry code: (i) .