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

Xu, Jie

Zhao, Min-Min

English

PubMed

In the title compound, C6H7ClN+&amp;#183;BF4&amp;#8722;&amp;#183;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 &amp;#8211;NH3+ group of the cation inserts into the crown-ether ring and forms bifurcated N&amp;#8212;H...(O,O) hydrogen bonds. The H atoms of the &amp;#8211;NH3+ group were modelled as disordered across the mirror plane

Jie Xu

Min-Min Zhao

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4-Chloroanilinium tetrafluoroborate 18-crown-6 clathrate

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4-Chloroanilinium tetrafluoroborate18-crown-6 clathrateJie Xu* and Min-Min ZhaoOrdered Matter Science Research Center, College of Chemistry and ChemicalEngineering, Southeast University, Nanjing 210096, People’s Republic of ChinaCorrespondence e-mail: chemcrystal66@yahoo.com.cnReceived 25 December 2011; accepted 12 February 2012Key indicators: single-crystal X-ray study; T = 298 K; mean (C–C) = 0.004 Å;R factor = 0.068; wR factor = 0.176; data-to-parameter ratio = 17.9.In the title compound, C6H7ClN+BF4C12H24O6, thecomplete cation is generated by crystallographic mirrorsymmetry, with two C atoms and the N and Cl atoms lyingon the mirror plane. The complete crown ether is alsogenerated by mirror symmetry, as is the anion (in which the Band two F atoms lie on the mirror plane). The –NH3+ group ofthe cation inserts into the crown-ether ring and formsbifurcated N—H  (O,O) hydrogen bonds. The H atoms ofthe –NH3+ group were modelled as disordered across themirror plane.Related literatureFor the ferroelectric properties of related compounds, see: Fuet al. (2011)ExperimentalCrystal dataC6H7ClN+BF4C12H24O6Mr = 479.70Orthorhombic, Pnmaa = 15.619 (3) Åb = 11.374 (2) Åc = 12.956 (3) ÅV = 2301.6 (8) Å3Z = 4Mo K radiation = 0.23 mm1T = 298 K0.10  0.03  0.03 mmData collectionRigaku Mercury2 CCDdiffractometerAbsorption correction: multi-scan(CrystalClear; Rigaku, 2005)Tmin = 0.910, Tmax = 1.00022855 measured reflections2772 independent reflections1466 reflections with I > 2(I)Rint = 0.112RefinementR[F 2 > 2(F 2)] = 0.068wR(F 2) = 0.176S = 1.042772 reflections155 parametersH-atom parameters constrainedmax = 0.24 e Å3min = 0.26 e Å3Table 1Hydrogen-bond geometry (Å, ).D—H  A D—H H  A D  A D—H  AN1—H1A  O2 0.89 2.12 2.897 (3) 146N1—H1A  O3 0.89 2.24 2.927 (3) 134N1—H1B  O3i 0.89 2.25 2.927 (3) 133N1—H1B  O4 0.89 2.10 2.891 (4) 147N1—H1C  O1 0.89 2.21 2.865 (4) 130N1—H1C  O2i 0.89 2.10 2.897 (3) 148Symmetry code: (i) x;yþ 12; z.Data collection: CrystalClear (Rigaku, 2005); cell refinement:CrystalClear; data reduction: CrystalClear; program(s) used to solvestructure: SHELXS97 (Sheldrick, 2008); program(s) used to refinestructure: SHELXL97 (Sheldrick, 2008); molecular graphics:SHELXTL (Sheldrick, 2008); software used to prepare material forpublication: SHELXTL.This work was supported by a start-up grant from SoutheastUniversity, China.Supplementary data and figures for this paper are available from theIUCr electronic archives (Reference: HB6580).ReferencesFu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011).Adv. Mater. 23, 5658–5662.Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.organic compoundso738 Xu and Zhao doi:10.1107/S1600536812006216 Acta Cryst. (2012). E68, o738Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supporting informationsup-1Acta Cryst. (2012). E68, o738    supporting informationActa Cryst. (2012). E68, o738    [doi:10.1107/S1600536812006216]4-Chloroanilinium tetrafluoroborate 18-crown-6 clathrateJie Xu and Min-Min ZhaoS1. Comment 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-chloro-anilium 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).S2. Experimental 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).S3. Refinement All H atoms attached to C atoms were fixed geometrically and treated as riding with C–H = 0.93 Å (Caromatic) or 0.97 Å (Cmethylene).The positional parameters of the H atoms (N1) were intially refined freely, subsequently restrained using a distance of N–H = 0.89 (2) Å, and in the final refinements treated in riding motion of their parent nitrogen atom with Uiso(H)=1.5Ueq(N).supporting informationsup-2Acta Cryst. (2012). E68, o738    Figure 1A view of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity. Figure 2The 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 Crystal data C6H7ClN+·BF4−·C12H24O6Mr = 479.70Orthorhombic, PnmaHall symbol: -P 2ac 2na = 15.619 (3) Åb = 11.374 (2) Åc = 12.956 (3) ÅV = 2301.6 (8) Å3supporting informationsup-3Acta Cryst. (2012). E68, o738    Z = 4F(000) = 1008Dx = 1.384 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 2772 reflectionsθ = 3.1–27.5°µ = 0.23 mm−1T = 298 KBlock, colorless0.10 × 0.03 × 0.03 mmData collection Rigaku Mercury2 CCD diffractometerRadiation source: fine-focus sealed tubeGraphite monochromatorDetector resolution: 13.6612 pixels mm-1CCD profile fitting scansAbsorption correction: multi-scan (CrystalClear; Rigaku, 2005)Tmin = 0.910, Tmax = 1.00022855 measured reflections2772 independent reflections1466 reflections with I > 2σ(I)Rint = 0.112θmax = 27.5°, θmin = 3.1°h = −20→20k = −14→14l = −16→16Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.068wR(F2) = 0.176S = 1.042772 reflections155 parameters0 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0645P)2 + 0.8791P] where P = (Fo2 + 2Fc2)/3(Δ/σ)max < 0.001Δρmax = 0.24 e Å−3Δρmin = −0.26 e Å−3Special details 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) x y z Uiso*/Ueq 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* 0.50H1B 0.6495 0.2811 0.2451 0.064* 0.50H1C 0.7033 0.2924 0.3360 0.064* 0.50O1 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)supporting informationsup-4Acta Cryst. (2012). E68, o738    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) U11 U22 U33 U12 U13 U23Cl1 0.0634 (9) 0.1501 (15) 0.0924 (11) 0.000 0.0263 (8) 0.000O4 0.0613 (18) 0.0453 (17) 0.0421 (16) 0.000 −0.0095 (13) 0.000O2 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) 0.000O1 0.068 (2) 0.063 (2) 0.0418 (16) 0.000 −0.0087 (14) 0.000O3 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) 0.000C5 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) 0.000C1 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) 0.000F2 0.075 (2) 0.102 (2) 0.105 (2) 0.000 0.0133 (18) 0.000supporting informationsup-5Acta Cryst. (2012). E68, o738    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) 0.000Geometric parameters (Å, º) Cl1—C10 1.735 (5) C3—C4 1.490 (4)O4—C6 1.415 (3) C3—H3A 0.9700O4—C6i 1.415 (3) C3—H3B 0.9700O2—C2 1.421 (4) C6—H6A 0.9700O2—C3 1.424 (4) C6—H6B 0.9700N1—C7 1.457 (5) C4—H4A 0.9700N1—H1A 0.8900 C4—H4B 0.9700N1—H1B 0.8900 C2—C1 1.484 (4)N1—H1C 0.8900 C2—H2A 0.9700O1—C1i 1.427 (3) C2—H2B 0.9700O1—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 0.9700C7—C8 1.375 (3) C1—H1E 0.9700C7—C8i 1.375 (3) C9—H9A 0.9300C5—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 0.9300C6—O4—C6i 112.8 (3) C5—C6—H6B 110.0C2—O2—C3 113.4 (2) H6A—C6—H6B 108.4C7—N1—H1A 109.5 O3—C4—C3 109.4 (2)C7—N1—H1B 109.5 O3—C4—H4A 109.8H1A—N1—H1B 109.5 C3—C4—H4A 109.8C7—N1—H1C 109.5 O3—C4—H4B 109.8H1A—N1—H1C 109.5 C3—C4—H4B 109.8H1B—N1—H1C 109.5 H4A—C4—H4B 108.2C1i—O1—C1 112.8 (3) O2—C2—C1 108.8 (3)C4—O3—C5 112.0 (2) O2—C2—H2A 109.9C8—C7—C8i 120.8 (4) C1—C2—H2A 109.9C8—C7—N1 119.62 (19) O2—C2—H2B 109.9C8i—C7—N1 119.62 (19) C1—C2—H2B 109.9O3—C5—C6 109.1 (2) H2A—C2—H2B 108.3O3—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 109.8C9—C8—C7 119.6 (3) C2—C1—H1D 109.8C9—C8—H8A 120.2 O1—C1—H1E 109.8C7—C8—H8A 120.2 C2—C1—H1E 109.8supporting informationsup-6Acta Cryst. (2012). E68, o738    O2—C3—C4 108.6 (2) H1D—C1—H1E 108.3O2—C3—H3A 110.0 C8—C9—C10 119.9 (3)C4—C3—H3A 110.0 C8—C9—H9A 120.1O2—C3—H3B 110.0 C10—C9—H9A 120.1C4—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) D—H···A D—H H···A D···A D—H···AN1—H1A···O2 0.89 2.12 2.897 (3) 146N1—H1A···O3 0.89 2.24 2.927 (3) 134N1—H1B···O3i 0.89 2.25 2.927 (3) 133N1—H1B···O4 0.89 2.10 2.891 (4) 147N1—H1C···O1 0.89 2.21 2.865 (4) 130N1—H1C···O2i 0.89 2.10 2.897 (3) 148Symmetry code: (i) x, −y+1/2, z.

Acta Crystallographica Section E Structure Reports Online

Acta Cryst. A64, 112–122. organic compounds o738 Xu and Zhao doi:10.1107/S1600536812006216 Acta Cryst.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) xyzU iso*/Ueq Occ.

https://journals.iucr.org/e/issues/2012/03/00/hb6580/hb6580.pdf

4-Chloroanilinium tetrafluoroborate 18-crown-6 clathrate

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4-Chloro­anilinium tetra­fluoro­borate 18-crown-6 clathrate

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4-Chloroanilinium tetrafluoroborate 18-crown-6 clathrate