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It is possible that fluorous compounds could be utilized as directing forces in crystal engineering for applications in materials chemistry or catalysis. Although numerous fluorous compounds have been used for various applications, their structures in the solid state remains a lively matter for debate. The reaction of 4-[(2,2,2-tri­fluoro­eth­oxy)meth­yl]pyridine with HX (X = I or Cl) yielded new fluorous ponytailed pyridinium halide salts, namely 4-[(2,2,2-tri­fluoro­eth­oxy)meth­yl]pyridinium iodide, C8H9F3NO+·I, (1), and 4-[(2,2,2-tri­fluoro­eth­oxy)meth­yl]pyridinium chloride, C8H9F3NO+·Cl, (2), which were characterized by IR spectroscopy, multinuclei (1H, 13C and 19F) NMR spectroscopy and single-crystal X-ray diffraction. Structure analysis showed that there are two types of hydrogen bonds, namely N—H...X and C—H...X. The iodide anion in salt (1) is hydrogen bonded to three 4-[(2,2,2-tri­fluoro­eth­oxy)meth­yl]pyridinium cations in the crystal packing, while the chloride ion in salt (2) is involved in six hydrogen bonds to five 4-[(2,2,2-tri­fluoro­eth­oxy)meth­yl]pyridinium cations, which is attributed to the smaller size and reduced polarizability of the chloride ion compared to the iodide ion. In the IR spectra, the pyridinium N—H stretching band for salt (1) exhibited a blue shift compared with that of salt (2).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616018428/ku3190sup1.cif
Contains datablocks i16196, i16195

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616018428/ku3190i16196sup2.hkl
Contains datablock i16196

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616018428/ku3190i16195sup3.hkl
Contains datablock i16195

CCDC references: 1517711; 1517710

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: shelXle (Hübschle et al., 2011) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015b) and WinGX (Farrugia, 2012).

(i16196) 4-[(2,2,2-Trifluoroethoxy)methyl]pyridinium iodide top
Crystal data top
C8H9F3NO+·IF(000) = 608
Mr = 319.06Dx = 2.005 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.8651 (3) ÅCell parameters from 9913 reflections
b = 9.2595 (3) Åθ = 2.6–27.3°
c = 14.7958 (5) ŵ = 3.04 mm1
β = 101.151 (1)°T = 100 K
V = 1057.19 (6) Å3Prism, colourless
Z = 40.44 × 0.3 × 0.22 mm
Data collection top
Bruker APEXII CCD
diffractometer
2325 reflections with I > 2σ(I)
φ and ω scansRint = 0.026
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
θmax = 27.1°, θmin = 2.6°
Tmin = 0.673, Tmax = 0.971h = 1010
41459 measured reflectionsk = 1111
2334 independent reflectionsl = 1818
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.012 w = 1/[σ2(Fo2) + (0.005P)2 + 0.8874P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.028(Δ/σ)max = 0.002
S = 1.21Δρmax = 0.37 e Å3
2334 reflectionsΔρmin = 0.26 e Å3
164 parametersExtinction correction: SHELXL2013 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0084 (3)
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.55550 (2)0.18787 (2)0.60106 (2)0.01697 (5)
F10.53198 (12)0.89861 (11)0.14989 (7)0.0263 (2)
F20.25938 (12)0.90209 (10)0.09319 (8)0.0277 (2)
F30.44127 (15)0.84459 (11)0.00801 (7)0.0299 (2)
O10.55327 (13)0.61073 (11)0.11764 (7)0.0164 (2)
N10.57467 (18)0.25969 (17)0.37582 (10)0.0235 (3)
C10.5954 (2)0.4026 (2)0.37325 (11)0.0222 (3)
C20.58878 (19)0.47115 (18)0.29023 (10)0.0171 (3)
C30.55746 (18)0.39042 (16)0.20962 (10)0.0143 (3)
C40.5348 (2)0.24154 (17)0.21537 (11)0.0202 (3)
C50.5452 (2)0.17803 (19)0.29976 (12)0.0241 (3)
C60.5508 (2)0.45735 (16)0.11656 (10)0.0167 (3)
C70.3901 (2)0.67462 (16)0.11850 (11)0.0166 (3)
C80.4061 (2)0.83010 (16)0.09243 (11)0.0175 (3)
H1A0.578 (3)0.221 (3)0.4284 (17)0.041 (6)*
H10.614 (2)0.453 (2)0.4302 (14)0.024 (5)*
H20.602 (2)0.569 (2)0.2885 (12)0.017 (4)*
H40.515 (3)0.183 (2)0.1622 (15)0.029 (5)*
H50.531 (3)0.078 (2)0.3074 (14)0.028 (5)*
H6A0.655 (2)0.425 (2)0.0941 (12)0.017 (4)*
H6B0.449 (2)0.423 (2)0.0749 (13)0.019 (5)*
H7A0.359 (2)0.673 (2)0.1800 (14)0.022 (5)*
H7B0.295 (3)0.630 (2)0.0728 (13)0.023 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02272 (7)0.01525 (6)0.01325 (6)0.00010 (4)0.00425 (4)0.00119 (3)
F10.0203 (5)0.0203 (5)0.0367 (6)0.0055 (4)0.0016 (4)0.0077 (4)
F20.0193 (5)0.0188 (5)0.0444 (6)0.0059 (4)0.0050 (4)0.0007 (4)
F30.0487 (7)0.0203 (5)0.0239 (5)0.0018 (5)0.0150 (5)0.0079 (4)
O10.0152 (5)0.0132 (5)0.0218 (5)0.0014 (4)0.0059 (4)0.0046 (4)
N10.0192 (7)0.0352 (8)0.0176 (7)0.0087 (6)0.0076 (5)0.0127 (6)
C10.0159 (7)0.0349 (9)0.0159 (7)0.0039 (7)0.0037 (6)0.0003 (7)
C20.0154 (7)0.0196 (8)0.0165 (7)0.0020 (6)0.0037 (6)0.0011 (6)
C30.0110 (6)0.0169 (7)0.0153 (7)0.0026 (5)0.0034 (5)0.0019 (5)
C40.0239 (8)0.0166 (7)0.0203 (8)0.0022 (6)0.0047 (6)0.0020 (6)
C50.0238 (8)0.0213 (8)0.0288 (9)0.0042 (7)0.0085 (7)0.0094 (7)
C60.0230 (8)0.0132 (7)0.0146 (7)0.0021 (6)0.0051 (6)0.0009 (5)
C70.0144 (7)0.0160 (7)0.0198 (7)0.0002 (6)0.0044 (6)0.0022 (6)
C80.0165 (7)0.0166 (7)0.0194 (7)0.0001 (6)0.0034 (6)0.0010 (6)
Geometric parameters (Å, º) top
F1—C81.3341 (18)C2—H20.91 (2)
F2—C81.3346 (18)C3—C41.395 (2)
F3—C81.3373 (18)C3—C61.502 (2)
O1—C71.4154 (18)C4—C51.368 (2)
O1—C61.4204 (18)C4—H40.94 (2)
N1—C11.335 (2)C5—H50.95 (2)
N1—C51.338 (2)C6—H6A0.985 (18)
N1—H1A0.85 (2)C6—H6B0.964 (19)
C1—C21.374 (2)C7—C81.502 (2)
C1—H10.95 (2)C7—H7A0.99 (2)
C2—C31.389 (2)C7—H7B1.00 (2)
C7—O1—C6114.06 (12)O1—C6—C3113.85 (12)
C1—N1—C5122.58 (15)O1—C6—H6A107.3 (11)
C1—N1—H1A117.5 (16)C3—C6—H6A107.5 (11)
C5—N1—H1A119.9 (16)O1—C6—H6B110.1 (11)
N1—C1—C2119.96 (15)C3—C6—H6B109.1 (11)
N1—C1—H1117.2 (12)H6A—C6—H6B108.8 (15)
C2—C1—H1122.9 (12)O1—C7—C8106.09 (12)
C1—C2—C3119.27 (15)O1—C7—H7A113.0 (11)
C1—C2—H2119.9 (12)C8—C7—H7A107.3 (11)
C3—C2—H2120.8 (12)O1—C7—H7B112.7 (11)
C2—C3—C4118.89 (14)C8—C7—H7B108.2 (11)
C2—C3—C6122.30 (14)H7A—C7—H7B109.3 (16)
C4—C3—C6118.79 (14)F1—C8—F2107.07 (12)
C5—C4—C3119.65 (16)F1—C8—F3106.59 (13)
C5—C4—H4119.1 (13)F2—C8—F3107.05 (13)
C3—C4—H4121.2 (13)F1—C8—C7112.38 (13)
N1—C5—C4119.64 (16)F2—C8—C7111.16 (13)
N1—C5—H5117.4 (12)F3—C8—C7112.26 (13)
C4—C5—H5122.9 (12)
Hydrogen-bond geometry (Å, º) top
(a) a synthon hydrogen bond and (b) a bifurcated hydrogen bond.
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.85 (3)2.61 (2)3.430 (1)161 (2)
C2—H2···I1i0.91 (2)3.17 (2)3.814 (2)129 (1)
C5—H5···I1ii0.94 (2)2.95 (2)3.835 (2)157 (2)
C4—H4···F1iii0.94 (2)2.65 (2)3.319 (2)129 (2)
C4—H4···F3iv0.94 (2)2.62 (2)3.440 (2)146 (2)
C8—F1···C1v1.33 (1)3.02 (1)124 (1)
C8—F1···C2v1.33 (1)3.02 (1)150 (1)
C8—F2···C1vi1.34 (1)2.93 (1)149 (1)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z+1; (iii) x, y1, z; (iv) x+1, y+1, z; (v) x+3/2, y+1/2, z+1/2; (vi) x+1/2, y+1/2, z+1/2.
(i16195) 4-[(2,2,2-Trifluoroethoxy)methyl]pyridinium chloride top
Crystal data top
C8H9F3NO+·ClDx = 1.523 Mg m3
Mr = 227.61Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 9946 reflections
a = 9.2236 (3) Åθ = 2.6–26.1°
b = 13.5704 (5) ŵ = 0.40 mm1
c = 15.8600 (5) ÅT = 100 K
V = 1985.16 (12) Å3Prism, colourless
Z = 80.22 × 0.18 × 0.12 mm
F(000) = 928
Data collection top
Bruker APEXII CCD
diffractometer
1927 reflections with I > 2σ(I)
φ and ω scansRint = 0.050
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
θmax = 27.1°, θmin = 2.6°
Tmin = 0.922, Tmax = 0.971h = 1111
63957 measured reflectionsk = 1717
2189 independent reflectionsl = 2020
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025All H-atom parameters refined
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.0255P)2 + 1.0937P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2189 reflectionsΔρmax = 0.28 e Å3
163 parametersΔρmin = 0.23 e Å3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.05957 (3)0.15913 (2)0.10192 (2)0.01914 (9)
F10.62467 (11)0.35557 (6)0.09652 (5)0.0328 (2)
F20.68077 (8)0.40956 (6)0.21971 (5)0.02548 (19)
F30.45867 (9)0.37504 (6)0.19017 (6)0.0309 (2)
O10.53248 (10)0.18040 (7)0.16109 (6)0.0213 (2)
N10.26627 (12)0.08440 (8)0.02742 (7)0.0177 (2)
C10.39350 (14)0.12504 (10)0.04880 (8)0.0185 (3)
C20.48867 (14)0.07384 (9)0.09915 (8)0.0173 (3)
C30.45331 (13)0.02072 (9)0.12647 (7)0.0159 (2)
C40.31866 (14)0.05944 (9)0.10412 (8)0.0180 (3)
C50.22692 (14)0.00532 (10)0.05434 (8)0.0193 (3)
C60.55635 (14)0.07928 (9)0.17978 (8)0.0183 (3)
C70.62181 (14)0.24287 (9)0.20975 (8)0.0171 (3)
C80.59554 (14)0.34516 (9)0.17858 (8)0.0194 (3)
H1A0.2052 (19)0.1167 (13)0.0078 (11)0.037 (5)*
H10.4144 (16)0.1877 (11)0.0281 (9)0.019 (4)*
H20.5773 (16)0.1027 (11)0.1124 (9)0.020 (4)*
H40.2881 (16)0.1212 (12)0.1221 (9)0.022 (4)*
H50.1349 (17)0.0282 (11)0.0377 (9)0.021 (4)*
H6A0.5379 (15)0.0666 (11)0.2397 (10)0.020 (4)*
H6B0.6549 (18)0.0616 (11)0.1670 (9)0.023 (4)*
H7A0.7214 (16)0.2299 (10)0.2016 (8)0.017 (4)*
H7B0.5952 (15)0.2414 (11)0.2692 (9)0.017 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01730 (16)0.01961 (16)0.02051 (16)0.00136 (11)0.00131 (11)0.00397 (11)
F10.0531 (6)0.0259 (5)0.0194 (4)0.0062 (4)0.0023 (4)0.0056 (3)
F20.0275 (4)0.0185 (4)0.0304 (4)0.0073 (3)0.0003 (3)0.0042 (3)
F30.0222 (4)0.0228 (4)0.0477 (5)0.0047 (3)0.0028 (4)0.0005 (4)
O10.0270 (5)0.0121 (4)0.0247 (5)0.0027 (4)0.0091 (4)0.0009 (4)
N10.0181 (5)0.0170 (5)0.0180 (5)0.0030 (4)0.0020 (4)0.0003 (4)
C10.0230 (6)0.0148 (6)0.0178 (6)0.0017 (5)0.0007 (5)0.0003 (5)
C20.0176 (6)0.0165 (6)0.0179 (6)0.0029 (5)0.0008 (5)0.0022 (5)
C30.0190 (6)0.0156 (6)0.0129 (5)0.0014 (5)0.0015 (5)0.0025 (5)
C40.0189 (6)0.0143 (6)0.0207 (6)0.0019 (5)0.0016 (5)0.0001 (5)
C50.0158 (6)0.0198 (6)0.0223 (6)0.0013 (5)0.0006 (5)0.0033 (5)
C60.0218 (6)0.0139 (6)0.0193 (6)0.0004 (5)0.0032 (5)0.0014 (5)
C70.0169 (6)0.0175 (6)0.0170 (6)0.0023 (5)0.0007 (5)0.0011 (5)
C80.0206 (6)0.0185 (6)0.0192 (6)0.0024 (5)0.0018 (5)0.0018 (5)
Geometric parameters (Å, º) top
F1—C81.3365 (15)C2—H20.931 (15)
F2—C81.3444 (14)C3—C41.3943 (17)
F3—C81.3387 (15)C3—C61.4999 (17)
O1—C71.4118 (15)C4—C51.3706 (18)
O1—C61.4210 (15)C4—H40.929 (16)
N1—C51.3403 (17)C5—H50.942 (16)
N1—C11.3403 (17)C6—H6A0.980 (15)
N1—H1A0.906 (18)C6—H6B0.961 (16)
C1—C21.3752 (18)C7—C81.4933 (18)
C1—H10.931 (15)C7—H7A0.944 (15)
C2—C31.3932 (17)C7—H7B0.975 (15)
C7—O1—C6112.05 (9)O1—C6—C3107.21 (10)
C5—N1—C1122.03 (11)O1—C6—H6A110.2 (9)
C5—N1—H1A117.9 (11)C3—C6—H6A110.1 (9)
C1—N1—H1A120.1 (11)O1—C6—H6B110.1 (9)
N1—C1—C2119.86 (12)C3—C6—H6B110.4 (9)
N1—C1—H1117.9 (9)H6A—C6—H6B108.9 (12)
C2—C1—H1122.3 (9)O1—C7—C8106.41 (10)
C1—C2—C3119.77 (12)O1—C7—H7A112.4 (9)
C1—C2—H2118.7 (9)C8—C7—H7A106.6 (9)
C3—C2—H2121.5 (9)O1—C7—H7B111.7 (8)
C2—C3—C4118.46 (12)C8—C7—H7B107.4 (9)
C2—C3—C6120.99 (11)H7A—C7—H7B111.9 (12)
C4—C3—C6120.54 (11)F1—C8—F3106.94 (11)
C5—C4—C3119.63 (12)F1—C8—F2106.63 (10)
C5—C4—H4118.2 (9)F3—C8—F2106.73 (10)
C3—C4—H4122.1 (9)F1—C8—C7112.83 (11)
N1—C5—C4120.20 (12)F3—C8—C7112.90 (11)
N1—C5—H5117.0 (9)F2—C8—C7110.42 (10)
C4—C5—H5122.8 (9)
C5—N1—C1—C20.68 (18)C7—O1—C6—C3178.44 (10)
N1—C1—C2—C31.10 (19)C2—C3—C6—O1149.91 (11)
C1—C2—C3—C42.32 (18)C4—C3—C6—O131.00 (16)
C1—C2—C3—C6178.58 (12)C6—O1—C7—C8175.04 (10)
C2—C3—C4—C51.84 (18)O1—C7—C8—F158.56 (14)
C6—C3—C4—C5179.06 (11)O1—C7—C8—F362.84 (13)
C1—N1—C5—C41.17 (19)O1—C7—C8—F2177.77 (10)
C3—C4—C5—N10.13 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl10.91 (2)2.09 (2)2.979 (1)167 (2)
C1—H1···Cl1i0.93 (2)2.74 (2)3.411 (1)130 (1)
C5—H5···Cl1ii0.94 (2)2.72 (2)3.451 (1)135 (1)
C6—H6A···Cl1iii0.98 (2)2.95 (2)3.782 (1)144 (1)
C7—H7A···Cl1iv0.94 (2)2.74 (1)3.585 (1)150 (1)
C7—H7B···Cl1iii0.98 (1)2.73 (1)3.585 (1)150 (1)
C5—H5···F1v0.94 (2)2.65 (2)3.190 (2)117 (1)
C8—F2···C3vi1.34 (1)3.12 (1)118 (1)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y, z; (iii) x+1/2, y, z+1/2; (iv) x+1, y, z; (v) x1/2, y+1/2, z; (vi) x+1, y+1/2, z+1/2.
 

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