4-Chloro­anilinium tetra­fluoro­borate 18-crown-6 clathrate

Xu, J.; Zhao, M.-M.

doi:10.1107/S1600536812006216

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o738

doi:10.1107/S1600536812006216

Open

access

4-Chloroanilinium tetrafluoroborate 18-crown-6 clathrate

Jie Xu ^a ^* and Min-Min Zhao ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chemcrystal66@yahoo.com.cn

(Received 25 December 2011; accepted 12 February 2012; online 17 February 2012)

In the title compound, C₆H₇ClN⁺·BF₄⁻·C₁₂H₂₄O₆, the complete cation is generated by crystallographic mirror symmetry, with two C atoms and the N and Cl atoms lying on the mirror plane. The complete crown ether is also generated by mirror symmetry, as is the anion (in which the B and two F atoms lie on the mirror plane). The –NH₃⁺ group of the cation inserts into the crown-ether ring and forms bifurcated N—H⋯(O,O) hydrogen bonds. The H atoms of the –NH₃⁺ group were modelled as disordered across the mirror plane.

Related literature

For the ferroelectric properties of related compounds, see: Fu et al. (2011 )

Experimental

Crystal data

C₆H₇ClN⁺·BF₄⁻·C₁₂H₂₄O₆
M_r = 479.70
Orthorhombic, P n m a
a = 15.619 (3) Å
b = 11.374 (2) Å
c = 12.956 (3) Å
V = 2301.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 298 K
0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
22855 measured reflections
2772 independent reflections
1466 reflections with I > 2σ(I)
R_int = 0.112

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.176
S = 1.04
2772 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.89	2.12	2.897 (3)	146
N1—H1A⋯O3	0.89	2.24	2.927 (3)	134
N1—H1B⋯O3ⁱ	0.89	2.25	2.927 (3)	133
N1—H1B⋯O4	0.89	2.10	2.891 (4)	147
N1—H1C⋯O1	0.89	2.21	2.865 (4)	130
N1—H1C⋯O2ⁱ	0.89	2.10	2.897 (3)	148
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812006216/hb6580sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006216/hb6580Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006216/hb6580Isup3.cml

checkCIF report

Comment top

With the purpose of obtaining phase transition crystals of amino compounds, various amines have been studied and we have elaborated a series of new materials with this organic molecules (Fu et al. 2011). In this study, we describe the crystal structure of the title compound.

The asymmetric unit is composed of one organic cation, one BF₄^- anion and one crown ether (Fig.1). The 4-chloroanilium cation and macrocyclic ether mlecule are associated vis hydrogen bonding with the -NH₃⁺ group forming bifurcated bonds with all six O atoms of 18-crown-6 molecule. Despite the disorder in the amino group, it is clear that in each orientation the cation forms three bifurcated hydrogen bonds. These H-bonding interactions link the cation and 18-crown-6 ether molecule into a 1:1 complex, [(C₆H₇ClN).(18-rown-6)]⁺ (Table 1 and Fig.2).

Related literature top

For the ferroelectric properties of related compounds, see: Fu et al. (2011)

Experimental top

18-Crown-6 (3 mmol), HBF₄ (5 mmol) and the organic amine (3 mmol) were dissolved in water/EtOH (1:1 v/v) solution. The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound.

The dielectric constant of title compound as a function of temperature indicates that the permittivity is basically temperature-independent, suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (405 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant ranging from 4.1 to 8.1).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of the title compound, showing the H-bonding interactions. H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

4-Chloroanilinium tetrafluoroborate 1,4,7,10,13,16-hexaoxacyclooctadecane top

Crystal data top

C₆H₇ClN⁺·BF₄⁻·C₁₂H₂₄O₆	F(000) = 1008
M_r = 479.70	D_x = 1.384 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2772 reflections
a = 15.619 (3) Å	θ = 3.1–27.5°
b = 11.374 (2) Å	µ = 0.23 mm⁻¹
c = 12.956 (3) Å	T = 298 K
V = 2301.6 (8) Å³	Block, colorless
Z = 4	0.10 × 0.03 × 0.03 mm

Data collection top

Rigaku Mercury2 CCD diffractometer	2772 independent reflections
Radiation source: fine-focus sealed tube	1466 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.112
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD profile fitting scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.910, T_max = 1.000	l = −16→16
22855 measured reflections

Refinement top

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0645P)² + 0.8791P] where P = (F_o² + 2F_c²)/3
2772 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₆H₇ClN⁺·BF₄⁻·C₁₂H₂₄O₆	V = 2301.6 (8) Å³
M_r = 479.70	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 15.619 (3) Å	µ = 0.23 mm⁻¹
b = 11.374 (2) Å	T = 298 K
c = 12.956 (3) Å	0.10 × 0.03 × 0.03 mm

Data collection top

Rigaku Mercury2 CCD diffractometer	2772 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1466 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.112
22855 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
2772 reflections	Δρ_min = −0.26 e Å⁻³
155 parameters

Special details top

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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	1.00491 (9)	0.2500	0.01849 (12)	0.1019 (6)
O4	0.54013 (18)	0.2500	0.1542 (2)	0.0496 (7)
O2	0.69794 (13)	0.04251 (17)	0.40917 (15)	0.0561 (6)
N1	0.6932 (2)	0.2500	0.2796 (2)	0.0430 (8)
H1A	0.6806	0.1765	0.2975	0.064*	0.50
H1B	0.6495	0.2811	0.2451	0.064*	0.50
H1C	0.7033	0.2924	0.3360	0.064*	0.50
O1	0.78267 (19)	0.2500	0.4727 (2)	0.0574 (8)
O3	0.60482 (13)	0.03256 (17)	0.22269 (15)	0.0518 (6)
C7	0.7692 (2)	0.2500	0.2142 (3)	0.0397 (9)
C5	0.5276 (2)	0.0445 (3)	0.1647 (2)	0.0555 (8)
H5A	0.4797	0.0563	0.2110	0.067*
H5B	0.5173	−0.0266	0.1251	0.067*
C8	0.8049 (2)	0.1449 (3)	0.1844 (2)	0.0533 (8)
H8A	0.7802	0.0743	0.2048	0.064*
C3	0.6806 (2)	−0.0649 (3)	0.3568 (3)	0.0588 (9)
H3A	0.6778	−0.1291	0.4060	0.071*
H3B	0.7259	−0.0816	0.3077	0.071*
C6	0.5358 (2)	0.1464 (3)	0.0940 (2)	0.0548 (8)
H6A	0.5871	0.1386	0.0525	0.066*
H6B	0.4868	0.1498	0.0481	0.066*
C4	0.5972 (2)	−0.0534 (3)	0.3018 (2)	0.0600 (9)
H4A	0.5813	−0.1285	0.2719	0.072*
H4B	0.5529	−0.0304	0.3501	0.072*
C2	0.7766 (2)	0.0415 (3)	0.4644 (3)	0.0642 (9)
H2A	0.8242	0.0441	0.4164	0.077*
H2B	0.7811	−0.0300	0.5048	0.077*
C10	0.9133 (3)	0.2500	0.0942 (3)	0.0620 (13)
C1	0.7793 (2)	0.1455 (3)	0.5335 (3)	0.0698 (10)
H1D	0.7287	0.1468	0.5770	0.084*
H1E	0.8293	0.1412	0.5777	0.084*
C9	0.8773 (2)	0.1450 (3)	0.1244 (2)	0.0633 (9)
H9A	0.9020	0.0743	0.1042	0.076*
F3	0.02293 (17)	0.2500	0.6646 (2)	0.0761 (8)
F2	0.16106 (19)	0.2500	0.6182 (3)	0.0941 (10)
F1	0.12000 (15)	0.1503 (2)	0.7597 (2)	0.1066 (8)
B1	0.1052 (3)	0.2500	0.7028 (5)	0.0574 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0634 (9)	0.1501 (15)	0.0924 (11)	0.000	0.0263 (8)	0.000
O4	0.0613 (18)	0.0453 (17)	0.0421 (16)	0.000	−0.0095 (13)	0.000
O2	0.0553 (13)	0.0470 (13)	0.0660 (14)	0.0079 (10)	−0.0087 (11)	0.0063 (10)
N1	0.046 (2)	0.0414 (18)	0.0417 (18)	0.000	−0.0073 (15)	0.000
O1	0.068 (2)	0.063 (2)	0.0418 (16)	0.000	−0.0087 (14)	0.000
O3	0.0574 (13)	0.0414 (11)	0.0567 (12)	−0.0060 (9)	−0.0027 (10)	0.0042 (10)
C7	0.041 (2)	0.044 (2)	0.034 (2)	0.000	−0.0091 (17)	0.000
C5	0.057 (2)	0.0509 (19)	0.058 (2)	−0.0101 (15)	−0.0079 (15)	−0.0093 (15)
C8	0.062 (2)	0.0459 (18)	0.0525 (18)	0.0046 (15)	0.0009 (16)	0.0024 (14)
C3	0.072 (2)	0.0397 (18)	0.065 (2)	0.0078 (15)	0.0068 (18)	0.0125 (16)
C6	0.061 (2)	0.056 (2)	0.0470 (17)	−0.0014 (15)	−0.0079 (14)	−0.0113 (15)
C4	0.071 (2)	0.0425 (19)	0.067 (2)	−0.0060 (15)	0.0026 (18)	0.0035 (16)
C2	0.061 (2)	0.067 (2)	0.064 (2)	0.0090 (17)	−0.0110 (17)	0.0142 (18)
C10	0.044 (3)	0.098 (4)	0.044 (3)	0.000	−0.005 (2)	0.000
C1	0.070 (2)	0.090 (3)	0.0490 (19)	0.0054 (19)	−0.0131 (17)	0.017 (2)
C9	0.065 (2)	0.070 (2)	0.0550 (19)	0.0169 (18)	0.0026 (17)	−0.0039 (18)
F3	0.0625 (18)	0.0647 (18)	0.101 (2)	0.000	−0.0047 (15)	0.000
F2	0.075 (2)	0.102 (2)	0.105 (2)	0.000	0.0133 (18)	0.000
F1	0.0994 (17)	0.0917 (17)	0.1288 (19)	0.0004 (13)	−0.0163 (15)	0.0429 (16)
B1	0.049 (3)	0.043 (3)	0.080 (4)	0.000	0.006 (3)	0.000

Geometric parameters (Å, º) top

Cl1—C10	1.735 (5)	C3—C4	1.490 (4)
O4—C6	1.415 (3)	C3—H3A	0.9700
O4—C6ⁱ	1.415 (3)	C3—H3B	0.9700
O2—C2	1.421 (4)	C6—H6A	0.9700
O2—C3	1.424 (4)	C6—H6B	0.9700
N1—C7	1.457 (5)	C4—H4A	0.9700
N1—H1A	0.8900	C4—H4B	0.9700
N1—H1B	0.8900	C2—C1	1.484 (4)
N1—H1C	0.8900	C2—H2A	0.9700
O1—C1ⁱ	1.427 (3)	C2—H2B	0.9700
O1—C1	1.427 (3)	C10—C9ⁱ	1.376 (4)
O3—C4	1.422 (3)	C10—C9	1.376 (4)
O3—C5	1.427 (3)	C1—H1D	0.9700
C7—C8	1.375 (3)	C1—H1E	0.9700
C7—C8ⁱ	1.375 (3)	C9—H9A	0.9300
C5—C6	1.482 (4)	F3—B1	1.377 (6)
C5—H5A	0.9700	F2—B1	1.401 (6)
C5—H5B	0.9700	F1—B1	1.372 (4)
C8—C9	1.371 (4)	B1—F1ⁱ	1.372 (4)
C8—H8A	0.9300

C6—O4—C6ⁱ	112.8 (3)	C5—C6—H6B	110.0
C2—O2—C3	113.4 (2)	H6A—C6—H6B	108.4
C7—N1—H1A	109.5	O3—C4—C3	109.4 (2)
C7—N1—H1B	109.5	O3—C4—H4A	109.8
H1A—N1—H1B	109.5	C3—C4—H4A	109.8
C7—N1—H1C	109.5	O3—C4—H4B	109.8
H1A—N1—H1C	109.5	C3—C4—H4B	109.8
H1B—N1—H1C	109.5	H4A—C4—H4B	108.2
C1ⁱ—O1—C1	112.8 (3)	O2—C2—C1	108.8 (3)
C4—O3—C5	112.0 (2)	O2—C2—H2A	109.9
C8—C7—C8ⁱ	120.8 (4)	C1—C2—H2A	109.9
C8—C7—N1	119.62 (19)	O2—C2—H2B	109.9
C8ⁱ—C7—N1	119.62 (19)	C1—C2—H2B	109.9
O3—C5—C6	109.1 (2)	H2A—C2—H2B	108.3
O3—C5—H5A	109.9	C9ⁱ—C10—C9	120.3 (4)
C6—C5—H5A	109.9	C9ⁱ—C10—Cl1	119.8 (2)
O3—C5—H5B	109.9	C9—C10—Cl1	119.8 (2)
C6—C5—H5B	109.9	O1—C1—C2	109.3 (2)
H5A—C5—H5B	108.3	O1—C1—H1D	109.8
C9—C8—C7	119.6 (3)	C2—C1—H1D	109.8
C9—C8—H8A	120.2	O1—C1—H1E	109.8
C7—C8—H8A	120.2	C2—C1—H1E	109.8
O2—C3—C4	108.6 (2)	H1D—C1—H1E	108.3
O2—C3—H3A	110.0	C8—C9—C10	119.9 (3)
C4—C3—H3A	110.0	C8—C9—H9A	120.1
O2—C3—H3B	110.0	C10—C9—H9A	120.1
C4—C3—H3B	110.0	F1ⁱ—B1—F1	111.5 (5)
H3A—C3—H3B	108.3	F1ⁱ—B1—F3	110.5 (3)
O4—C6—C5	108.4 (2)	F1—B1—F3	110.5 (3)
O4—C6—H6A	110.0	F1ⁱ—B1—F2	108.4 (3)
C5—C6—H6A	110.0	F1—B1—F2	108.4 (3)
O4—C6—H6B	110.0	F3—B1—F2	107.5 (4)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	2.12	2.897 (3)	146
N1—H1A···O3	0.89	2.24	2.927 (3)	134
N1—H1B···O3ⁱ	0.89	2.25	2.927 (3)	133
N1—H1B···O4	0.89	2.10	2.891 (4)	147
N1—H1C···O1	0.89	2.21	2.865 (4)	130
N1—H1C···O2ⁱ	0.89	2.10	2.897 (3)	148

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₆H₇ClN⁺·BF₄⁻·C₁₂H₂₄O₆
M_r	479.70
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	15.619 (3), 11.374 (2), 12.956 (3)
V (Å³)	2301.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Rigaku Mercury2 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22855, 2772, 1466
R_int	0.112
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.176, 1.04
No. of reflections	2772
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.26

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	2.12	2.897 (3)	146
N1—H1A···O3	0.89	2.24	2.927 (3)	134
N1—H1B···O3ⁱ	0.89	2.25	2.927 (3)	133
N1—H1B···O4	0.89	2.10	2.891 (4)	147
N1—H1C···O1	0.89	2.21	2.865 (4)	130
N1—H1C···O2ⁱ	0.89	2.10	2.897 (3)	148

Symmetry code: (i) x, −y+1/2, z.

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

References

Fu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011). Adv. Mater. 23, 5658–5662. Web of Science CSD CrossRef CAS PubMed Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o738

doi:10.1107/S1600536812006216

Open

access