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Neutralization of 4-[(2,2,3,3-tetra­fluoro­prop­oxy)meth­yl]pyridine with hydro­halo acids HX (X = Cl and Br) yielded the pyridinium salts 4-[(2,2,3,3-tetra­fluoro­prop­oxy)meth­yl]pyridinium chloride, C9H10F4NO+·Cl, (1), and 4-[(2,2,3,3-tetra­fluoro­prop­oxy)meth­yl]pyridinium bromide, C9H10F4NO+·Br, (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single-crystal X-ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N—H, ortho-C—H and CF2—H groups. Two cations and two anions form a centrosymmetric dimeric building block, utilizing complimentary N—H...X...H—Csp3 connections. These dimers are further crosslinked, utilizing another complimentary Csp2—H...X...H—Csp2 connection. The pyridinium rings are π-stacked, forming columns running parallel to the a axis that make angles of ca 44–45° with the normal to the pyridinium plane. There are also supra­molecular C—H...F—C inter­actions, namely bifurcated C—H...F and bifurcated C—F...H inter­actions; additionally, one type II C—F...F—C halogen bond has been observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617004016/ku3194sup1.cif
Contains datablocks i16197, i16318

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229617004016/ku3194i16197sup2.hkl
Contains datablock i16197

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229617004016/ku3194i16318sup3.hkl
Contains datablock i16318

CCDC references: 1537616; 1537615

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b) and SIR92 (Altomare et al., 1993) for i16197; SHELXL2013 (Sheldrick, 2015b) for i16318. Molecular graphics: shelXle (Hübschle et al., 2011) for i16197; shelXle (Hübschle et al., 2011) and for i16318. Software used to prepare material for publication: SHELXTL (Sheldrick, 2008) for i16197; WinGX (Farrugia, 2012) for i16318.

(i16197) 4-[(2,2,3,3-Tetrafluoropropoxy)methyl]pyridinium chloride top
Crystal data top
C9H10F4NO+·ClF(000) = 528
Mr = 259.63Dx = 1.610 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 4.7874 (4) ÅCell parameters from 2075 reflections
b = 8.2086 (6) Åθ = 2.6–27.1°
c = 27.2894 (18) ŵ = 0.39 mm1
β = 92.803 (4)°T = 100 K
V = 1071.13 (14) Å3Plate, colourless
Z = 40.32 × 0.30 × 0.02 mm
Data collection top
Bruker APEXII CCD
diffractometer
2007 reflections with I > 2σ(I)
φ and ω scansRint = 0.064
Absorption correction: multi-scan
(SADABS; Bruker, 1996)
θmax = 27.1°, θmin = 2.6°
Tmin = 0.875, Tmax = 0.971h = 66
31900 measured reflectionsk = 1010
2356 independent reflectionsl = 3434
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031All H-atom parameters refined
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0275P)2 + 0.541P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2356 reflectionsΔρmax = 0.33 e Å3
185 parametersΔρmin = 0.25 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.

Refinement. The diffraction data were collected at 100 (1) K, employing a Bruker CCD diffractometer SMART (Bruker, 2001); the refinement was performed with the SHELXL-2013 program package (Sheldrick, 2015). Cell refinement: SMART; absorption correction: SADABS (Sheldrick, 2015); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl11.06998 (8)0.23740 (4)0.54207 (2)0.01628 (11)
F10.41306 (18)0.71203 (11)0.25298 (3)0.0192 (2)
F20.03030 (19)0.70185 (13)0.27420 (3)0.0251 (2)
F30.5332 (2)0.77524 (13)0.34747 (4)0.0291 (3)
F40.2340 (3)0.94451 (12)0.31776 (4)0.0396 (3)
O10.0587 (2)0.46628 (12)0.34176 (4)0.0181 (3)
N10.6283 (3)0.23528 (16)0.46065 (5)0.0152 (3)
C10.4980 (3)0.10408 (19)0.44159 (5)0.0165 (3)
C20.2848 (3)0.12348 (19)0.40664 (5)0.0146 (3)
C30.2051 (3)0.27954 (18)0.39149 (5)0.0116 (3)
C40.3417 (3)0.41255 (19)0.41306 (5)0.0134 (3)
C50.5562 (3)0.3868 (2)0.44760 (5)0.0151 (3)
C60.0204 (3)0.29861 (18)0.35182 (5)0.0128 (3)
C70.2588 (3)0.49700 (19)0.30287 (5)0.0148 (3)
C80.2283 (3)0.67391 (19)0.29078 (5)0.0143 (3)
C90.2666 (4)0.78916 (19)0.33344 (6)0.0194 (4)
H10.566 (3)0.001 (2)0.4526 (6)0.016 (4)*
H1A0.762 (4)0.224 (2)0.4819 (7)0.028 (5)*
H20.196 (3)0.031 (2)0.3934 (6)0.017 (4)*
H40.294 (3)0.516 (2)0.4043 (6)0.013 (4)*
H50.662 (3)0.472 (2)0.4628 (6)0.016 (4)*
H6A0.032 (3)0.243 (2)0.3220 (6)0.015 (4)*
H6B0.191 (4)0.250 (2)0.3620 (6)0.013 (4)*
H7A0.446 (4)0.476 (2)0.3124 (6)0.017 (4)*
H7B0.219 (3)0.435 (2)0.2737 (6)0.017 (4)*
H90.140 (4)0.769 (2)0.3610 (6)0.015 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0179 (2)0.01525 (19)0.01528 (18)0.00206 (15)0.00332 (13)0.00042 (14)
F10.0186 (5)0.0230 (5)0.0153 (4)0.0031 (4)0.0055 (4)0.0053 (4)
F20.0141 (5)0.0362 (6)0.0250 (5)0.0048 (4)0.0023 (4)0.0116 (4)
F30.0267 (6)0.0338 (6)0.0270 (5)0.0082 (5)0.0026 (4)0.0106 (4)
F40.0646 (8)0.0112 (5)0.0414 (6)0.0043 (5)0.0122 (5)0.0038 (4)
O10.0242 (6)0.0099 (5)0.0189 (5)0.0010 (5)0.0120 (4)0.0010 (4)
N10.0127 (7)0.0211 (7)0.0116 (6)0.0026 (5)0.0000 (5)0.0014 (5)
C10.0192 (8)0.0142 (8)0.0165 (7)0.0044 (6)0.0040 (6)0.0040 (6)
C20.0169 (8)0.0121 (7)0.0148 (7)0.0008 (6)0.0024 (6)0.0003 (6)
C30.0110 (7)0.0142 (7)0.0099 (6)0.0010 (6)0.0043 (5)0.0001 (5)
C40.0169 (8)0.0111 (8)0.0125 (7)0.0013 (6)0.0028 (6)0.0007 (6)
C50.0159 (8)0.0171 (8)0.0125 (7)0.0015 (6)0.0028 (6)0.0023 (6)
C60.0157 (8)0.0098 (7)0.0130 (7)0.0005 (6)0.0001 (6)0.0002 (6)
C70.0148 (8)0.0153 (8)0.0137 (7)0.0003 (6)0.0043 (6)0.0002 (6)
C80.0099 (7)0.0197 (8)0.0129 (7)0.0009 (6)0.0029 (6)0.0049 (6)
C90.0243 (9)0.0113 (8)0.0221 (8)0.0006 (7)0.0053 (7)0.0018 (6)
Geometric parameters (Å, º) top
F1—C81.3621 (15)C3—C41.389 (2)
F2—C81.3581 (17)C3—C61.499 (2)
F3—C91.355 (2)C4—C51.376 (2)
F4—C91.3565 (18)C4—H40.907 (18)
O1—C61.4137 (18)C5—H50.949 (17)
O1—C71.4171 (17)C6—H6A0.976 (17)
N1—C51.334 (2)C6—H6B0.963 (17)
N1—C11.337 (2)C7—C81.498 (2)
N1—H1A0.85 (2)C7—H7A0.962 (17)
C1—C21.372 (2)C7—H7B0.970 (17)
C1—H10.954 (18)C8—C91.518 (2)
C2—C31.394 (2)C9—H90.957 (18)
C2—H20.933 (18)
C6—O1—C7113.28 (11)O1—C6—H6B110.8 (10)
C5—N1—C1122.50 (14)C3—C6—H6B109.8 (10)
C5—N1—H1A117.3 (13)H6A—C6—H6B107.8 (14)
C1—N1—H1A120.3 (13)O1—C7—C8105.53 (12)
N1—C1—C2119.61 (15)O1—C7—H7A111.9 (10)
N1—C1—H1116.6 (10)C8—C7—H7A109.4 (10)
C2—C1—H1123.7 (10)O1—C7—H7B111.7 (10)
C1—C2—C3119.77 (15)C8—C7—H7B107.6 (10)
C1—C2—H2119.0 (10)H7A—C7—H7B110.5 (14)
C3—C2—H2121.2 (10)F2—C8—F1106.12 (11)
C4—C3—C2118.72 (13)F2—C8—C7109.72 (13)
C4—C3—C6122.10 (13)F1—C8—C7108.83 (12)
C2—C3—C6119.16 (13)F2—C8—C9107.26 (13)
C5—C4—C3119.32 (14)F1—C8—C9109.82 (12)
C5—C4—H4119.6 (10)C7—C8—C9114.73 (13)
C3—C4—H4121.1 (10)F3—C9—F4107.04 (13)
N1—C5—C4120.05 (14)F3—C9—C8108.37 (12)
N1—C5—H5116.6 (10)F4—C9—C8108.90 (13)
C4—C5—H5123.3 (10)F3—C9—H9109.6 (10)
O1—C6—C3108.90 (12)F4—C9—H9109.2 (10)
O1—C6—H6A109.3 (10)C8—C9—H9113.5 (10)
C3—C6—H6A110.3 (10)
(i16318) 4-[(2,2,3,3-Tetrafluoropropoxy)methyl]pyridinium bromide top
Crystal data top
C9H10F4NO+·BrF(000) = 600
Mr = 304.09Dx = 1.828 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 4.7977 (3) ÅCell parameters from 6743 reflections
b = 8.3123 (6) Åθ = 2.9–27.1°
c = 27.739 (2) ŵ = 3.75 mm1
β = 92.646 (3)°T = 100 K
V = 1105.04 (13) Å3Niddle, colourless
Z = 40.36 × 0.08 × 0.06 mm
Data collection top
Bruker APEXII CCD
diffractometer
2166 reflections with I > 2σ(I)
φ and ω scansRint = 0.041
Absorption correction: multi-scan
(SADABS; Bruker, 1996)
θmax = 27.1°, θmin = 2.6°
Tmin = 0.735, Tmax = 0.971h = 66
21424 measured reflectionsk = 1010
2446 independent reflectionsl = 3335
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021All H-atom parameters refined
wR(F2) = 0.047 w = 1/[σ2(Fo2) + (0.0179P)2 + 0.7397P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.003
2446 reflectionsΔρmax = 0.39 e Å3
185 parametersΔρmin = 0.31 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
C10.4699 (4)0.1025 (2)0.43760 (7)0.0173 (4)
C20.2618 (4)0.1251 (2)0.40283 (6)0.0145 (4)
C30.1886 (3)0.2801 (2)0.38822 (6)0.0116 (3)
C40.3268 (4)0.4105 (2)0.41008 (6)0.0136 (4)
C50.5350 (4)0.3818 (2)0.44457 (6)0.0155 (4)
C60.0345 (4)0.3020 (2)0.34910 (6)0.0127 (3)
C70.2648 (4)0.4990 (2)0.30097 (6)0.0146 (4)
C80.2301 (3)0.6737 (2)0.28885 (6)0.0141 (4)
C90.2679 (4)0.7886 (2)0.33060 (7)0.0202 (4)
N10.6027 (3)0.23085 (18)0.45707 (5)0.0155 (3)
O10.0669 (3)0.46736 (14)0.33916 (5)0.0184 (3)
F10.4116 (2)0.71197 (13)0.25147 (4)0.0191 (2)
F20.0300 (2)0.69929 (14)0.27276 (4)0.0251 (3)
F30.5340 (3)0.77647 (15)0.34442 (4)0.0315 (3)
F40.2321 (3)0.94153 (14)0.31507 (5)0.0407 (3)
Br11.06227 (4)0.23738 (2)0.54243 (2)0.01457 (6)
H10.529 (4)0.001 (2)0.4487 (7)0.015 (5)*
H1A0.732 (5)0.217 (3)0.4777 (8)0.025 (6)*
H20.174 (4)0.035 (2)0.3897 (7)0.014 (5)*
H40.280 (4)0.517 (2)0.4020 (6)0.011 (5)*
H50.640 (4)0.463 (2)0.4591 (7)0.012 (5)*
H6A0.019 (4)0.245 (2)0.3201 (8)0.017 (5)*
H6B0.209 (4)0.256 (2)0.3581 (7)0.015 (5)*
H7A0.457 (4)0.479 (2)0.3110 (7)0.011 (5)*
H7B0.232 (4)0.437 (2)0.2725 (7)0.014 (5)*
H90.145 (4)0.767 (2)0.3576 (8)0.016 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0204 (10)0.0138 (9)0.0179 (9)0.0032 (7)0.0034 (8)0.0046 (7)
C20.0155 (9)0.0117 (8)0.0163 (9)0.0001 (7)0.0012 (7)0.0004 (7)
C30.0113 (8)0.0139 (8)0.0097 (8)0.0016 (6)0.0034 (6)0.0006 (6)
C40.0162 (9)0.0112 (8)0.0136 (9)0.0006 (7)0.0034 (7)0.0006 (7)
C50.0158 (9)0.0172 (9)0.0137 (9)0.0025 (7)0.0023 (7)0.0018 (7)
C60.0144 (9)0.0093 (8)0.0144 (9)0.0007 (7)0.0003 (7)0.0005 (7)
C70.0166 (10)0.0145 (9)0.0123 (9)0.0000 (7)0.0042 (7)0.0004 (7)
C80.0099 (8)0.0195 (9)0.0126 (8)0.0012 (7)0.0028 (7)0.0050 (7)
C90.0263 (11)0.0128 (9)0.0210 (10)0.0001 (8)0.0054 (8)0.0003 (7)
N10.0121 (8)0.0222 (8)0.0122 (7)0.0032 (6)0.0003 (6)0.0036 (6)
O10.0250 (7)0.0100 (6)0.0190 (7)0.0003 (5)0.0119 (5)0.0008 (5)
F10.0189 (6)0.0233 (6)0.0145 (5)0.0028 (4)0.0059 (4)0.0052 (4)
F20.0142 (5)0.0362 (7)0.0248 (6)0.0050 (5)0.0015 (4)0.0112 (5)
F30.0284 (7)0.0369 (7)0.0292 (7)0.0083 (5)0.0027 (5)0.0117 (5)
F40.0679 (9)0.0116 (6)0.0408 (8)0.0033 (6)0.0158 (7)0.0034 (5)
Br10.01588 (10)0.01375 (9)0.01384 (9)0.00135 (7)0.00178 (6)0.00000 (7)
Geometric parameters (Å, º) top
C1—N11.343 (2)C6—H6B0.97 (2)
C1—C21.369 (3)C7—O11.414 (2)
C1—H10.94 (2)C7—C81.502 (2)
C2—C31.391 (2)C7—H7A0.989 (18)
C2—H20.92 (2)C7—H7B0.96 (2)
C3—C41.394 (2)C8—F11.3605 (19)
C3—C61.500 (2)C8—F21.361 (2)
C4—C51.372 (3)C8—C91.518 (3)
C4—H40.939 (19)C9—F31.354 (2)
C5—N11.338 (2)C9—F41.356 (2)
C5—H50.92 (2)C9—H90.95 (2)
C6—O11.409 (2)N1—H1A0.83 (2)
C6—H6A0.98 (2)
N1—C1—C2119.46 (17)O1—C7—H7A111.0 (11)
N1—C1—H1116.7 (12)C8—C7—H7A110.1 (11)
C2—C1—H1123.8 (12)O1—C7—H7B112.7 (11)
C1—C2—C3119.89 (17)C8—C7—H7B107.9 (11)
C1—C2—H2118.1 (12)H7A—C7—H7B109.4 (15)
C3—C2—H2122.0 (12)F1—C8—F2106.13 (13)
C2—C3—C4118.98 (16)F1—C8—C7108.85 (14)
C2—C3—C6119.03 (15)F2—C8—C7109.72 (15)
C4—C3—C6121.98 (15)F1—C8—C9109.84 (15)
C5—C4—C3118.99 (17)F2—C8—C9107.18 (15)
C5—C4—H4119.3 (11)C7—C8—C9114.77 (15)
C3—C4—H4121.7 (11)F3—C9—F4107.13 (16)
N1—C5—C4120.27 (17)F3—C9—C8108.46 (15)
N1—C5—H5116.8 (12)F4—C9—C8109.03 (16)
C4—C5—H5122.9 (12)F3—C9—H9108.9 (13)
O1—C6—C3109.18 (14)F4—C9—H9110.0 (12)
O1—C6—H6A110.1 (11)C8—C9—H9113.1 (12)
C3—C6—H6A109.3 (12)C5—N1—C1122.38 (16)
O1—C6—H6B110.4 (11)C5—N1—H1A118.0 (15)
C3—C6—H6B111.3 (12)C1—N1—H1A119.6 (15)
H6A—C6—H6B106.5 (16)C6—O1—C7113.08 (13)
O1—C7—C8105.66 (14)
Hydrogen-bond geometry for (1) and (2) (Å, °) top
SaltD—H···ASymmetry codeD—HH···AD···AD—H···A
(1)N1—H1A···Cl10.85 (2)2.16 (2)2.992 (2)168 (2)
C1—H1···Cl1-x+2, -y, -z+10.95 (2)2.72 (2)3.571 (2)150 (1)
C5—H5···Cl1-x+2, -y+1, -z+10.95 (2)2.62 (2)3.499 (2)154 (1)
C9—H9···Cl1-x+1, -y+1, -z+10.96 (2)2.65 (2)3.487 (2)146 (2)
C2—H4···O1*0.91 (2)2.38 (2)2.700 (2)100 (1)
(2)N1—H1A···Br10.83 (2)2.35 (2)3.161 (2)166 (2)
C1—H1···Br1-x+2, -y, -z+10.94 (2)2.79 (2)3.635 (2)150 (2)
C5—H5···Br1-x+2, -y+1, -z+10.92 (2)2.87 (2)3.717 (2)153 (2)
C9—H9···Br1-x+1, -y+1, -z+10.95 (2)2.78 (2)3.620 (2)148 (2)
C4—H4···O1*0.94 (2)2.39 (2)2.705 (2)99 (2)
Note: (*) intramolecular hydrogen bond.
C—H···F—C and C—F···F—C weak interactions for (1) and (2) (Å, °) top
SaltD—H(F)···ASymmetry codeD—H(F)H(F)···AD···AD—H(F)···A
(1)C6—H6A···F2-x, y-1/2, -z+1/20.98 (2)2.65 (2)3.528 (2)149 (1)
C7—H7B···F1-x-1, y+1/2, -z+1/20.97 (2)2.62 (2)3.167 (2)116 (1)
C7—H7B···F2-x, y-1/2, -z+1/20.97 (2)2.51 (2)3.423 (2)156 (1)
C8—F1···F2x-1, y, z1.362 (2)2.756 (1)3.563 (2)115.6 (1)
C8—F2···F1x+1, y, z1.358 (2)2.756 (1)4.097 (2)169.0 (1)
C8—F2···F3x+1, y, z1.358 (2)2.884 (1)3.695 (2)116.5 (1)
C9—F3···F2x-1, y, z1.355 (2)2.884 (1)3.732 (2)118.8 (1)
(2)C6—H6A···F2-x, y-1/2, -z+1/20.98 (2)2.60 (2)3.487 (2)150 (2)
C7—H7B···F1-x-1, y+1/2, -z+1/20.96 (2)2.60 (2)3.164 (2)118 (1)
C7—H7B···F2-x, y-1/2, -z+1/20.96 (2)2.56 (2)3.445 (2)154 (2)
C8—F1···F2x-1, y, z1.361 (2)2.772 (1)3.564 (2)114.8 (1)
C8—F2···F1x+1, y, z1.361 (2)2.772 (1)4.120 (1)170.2 (1)
C8—F2···F3x+1, y, z1.361 (2)2.890 (2)3.713 (1)117.0 (1)
C9—F3···F2x-1, y, z1.354 (2)2.890 (2)3.738 (1)118.9 (1)
 

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