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To enable a comparison between a C—H...X hydrogen bond and a halogen bond, the structures of two fluorous-substituted pyridinium iodide salts have been determined. 4-[(2,2-Di­fluoro­eth­oxy)meth­yl]pyridinium iodide, C8H10F2NO+·I, (1), has a –CH2OCH2CF2H substituent at the para position of the pyridinium ring and 4-[(3-chloro-2,2,3,3-tetra­fluoro­prop­oxy)meth­yl]pyridinium iodide, C9H9ClF4NO+·I, (2), has a –CH2OCH2CF2CF2Cl substituent at the para position of the pyridinium ring. In salt (1), the iodide anion is involved in one N—H...I and three C—H...I hydrogen bonds, which, together with C—H...F hydrogen bonds, link the cations and anions into a three-dimensional network. For salt (2), the iodide anion is involved in one N—H...I hydrogen bond, two C—H...I hydrogen bonds and one C—Cl...I halogen bond; additional C—H...F and C—F...F inter­actions link the cations and anions into a three-dimensional arrangement.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617011172/ku3200sup1.cif
Contains datablocks global, i16183, i16319

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229617011172/ku3200i16183sup2.hkl
Contains datablock i16183

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229617011172/ku3200i16319sup3.hkl
Contains datablock i16319

CCDC references: 1565383; 1565382

Computing details top

Data collection: APEX2 (Bruker, 2015) for i16183; Bruker Instrument Service v2012.12.0.3 for i16319. For both structures, cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015). Program(s) used to solve structure: SHELXS97 (Sheldrick 2008) for i16183; SHELXT (Sheldrick, 2015a) for i16319. For both structures, program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b). Molecular graphics: SHELXTL (Sheldrick 2008) for i16183; shelXle (Hübschle et al., 2011) for i16319. Software used to prepare material for publication: SHELXTL (Sheldrick 2008) for i16183; WinGX (Farrugia, 2012) for i16319.

4-[(2,2-Difluoroethoxy)methyl]pyridinium iodide (i16183) top
Crystal data top
C8H10F2NO+·IF(000) = 576
Mr = 301.07Dx = 1.982 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 4.9221 (1) ÅCell parameters from 9922 reflections
b = 8.4974 (2) Åθ = 2.5–27.2°
c = 24.1323 (7) ŵ = 3.17 mm1
β = 91.610 (1)°T = 100 K
V = 1008.94 (4) Å3Plate, colourless
Z = 40.34 × 0.30 × 0.08 mm
Data collection top
Bruker APEXII CCD
diffractometer
2208 reflections with I > 2σ(I)
φ and ω scansRint = 0.024
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
θmax = 27.1°, θmin = 1.7°
Tmin = 0.819, Tmax = 0.971h = 66
34955 measured reflectionsk = 1010
2231 independent reflectionsl = 3030
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.014 w = 1/[σ2(Fo2) + 1.0459P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.029(Δ/σ)max = 0.002
S = 1.28Δρmax = 0.38 e Å3
2231 reflectionsΔρmin = 0.37 e Å3
122 parametersExtinction correction: SHELXL2013 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00303 (13)
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
I11.07331 (2)0.78331 (2)0.55794 (2)0.01406 (5)
F10.0012 (3)0.79498 (15)0.20001 (5)0.0375 (3)
F20.0776 (3)0.54453 (16)0.20994 (5)0.0412 (4)
O10.1092 (3)0.70739 (15)0.30691 (5)0.0188 (3)
N10.6050 (3)0.78417 (19)0.44880 (6)0.0164 (3)
H1A0.721 (4)0.821 (3)0.4720 (9)0.020*
C10.5972 (4)0.6274 (2)0.44283 (7)0.0157 (3)
H10.71820.56260.46400.019*
C20.4137 (3)0.5610 (2)0.40595 (7)0.0147 (3)
H20.40730.45010.40120.018*
C30.2361 (3)0.6582 (2)0.37544 (7)0.0119 (3)
C40.2454 (3)0.8192 (2)0.38426 (7)0.0145 (3)
H40.12270.88680.36460.017*
C50.4336 (4)0.8807 (2)0.42166 (8)0.0170 (4)
H50.44140.99100.42810.020*
C60.0439 (3)0.5855 (2)0.33335 (7)0.0146 (3)
H6A0.14710.52630.30560.018*
H6B0.07970.51130.35180.018*
C70.2744 (4)0.6572 (2)0.26140 (8)0.0230 (4)
H7A0.43250.72870.25730.028*
H7B0.34410.55030.26910.028*
C80.1251 (5)0.6544 (2)0.20825 (8)0.0287 (5)
H80.25450.63180.17660.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01415 (6)0.01339 (6)0.01443 (6)0.00003 (4)0.00318 (4)0.00007 (4)
F10.0574 (9)0.0256 (7)0.0298 (7)0.0105 (6)0.0058 (6)0.0051 (5)
F20.0712 (10)0.0341 (7)0.0186 (6)0.0168 (7)0.0054 (6)0.0041 (5)
O10.0202 (6)0.0183 (6)0.0175 (6)0.0033 (5)0.0076 (5)0.0012 (5)
N10.0131 (7)0.0215 (8)0.0145 (7)0.0018 (6)0.0010 (6)0.0035 (6)
C10.0148 (8)0.0192 (9)0.0131 (8)0.0021 (7)0.0009 (6)0.0021 (7)
C20.0159 (8)0.0146 (8)0.0136 (8)0.0006 (7)0.0016 (7)0.0011 (7)
C30.0118 (7)0.0149 (8)0.0092 (7)0.0004 (6)0.0040 (6)0.0008 (6)
C40.0145 (8)0.0133 (8)0.0158 (8)0.0008 (6)0.0010 (6)0.0023 (6)
C50.0167 (8)0.0146 (9)0.0199 (9)0.0004 (7)0.0023 (7)0.0022 (7)
C60.0150 (8)0.0148 (8)0.0139 (8)0.0019 (7)0.0010 (6)0.0002 (7)
C70.0215 (9)0.0226 (9)0.0241 (10)0.0044 (8)0.0121 (8)0.0029 (8)
C80.0467 (13)0.0182 (10)0.0206 (10)0.0012 (9)0.0107 (9)0.0003 (8)
Geometric parameters (Å, º) top
F1—C81.363 (2)C3—C41.385 (2)
F2—C81.366 (3)C3—C61.502 (2)
O1—C71.414 (2)C4—C51.378 (2)
O1—C61.421 (2)C4—H40.9500
N1—C51.335 (2)C5—H50.9500
N1—C11.340 (2)C6—H6A0.9900
N1—H1A0.85 (2)C6—H6B0.9900
C1—C21.371 (2)C7—C81.496 (3)
C1—H10.9500C7—H7A0.9900
C2—C31.397 (2)C7—H7B0.9900
C2—H20.9500C8—H81.0000
C7—O1—C6114.51 (14)O1—C6—C3108.64 (14)
C5—N1—C1122.83 (16)O1—C6—H6A110.0
C5—N1—H1A120.2 (15)C3—C6—H6A110.0
C1—N1—H1A117.0 (15)O1—C6—H6B110.0
N1—C1—C2119.66 (17)C3—C6—H6B110.0
N1—C1—H1120.2H6A—C6—H6B108.3
C2—C1—H1120.2O1—C7—C8112.64 (16)
C1—C2—C3119.33 (17)O1—C7—H7A109.1
C1—C2—H2120.3C8—C7—H7A109.1
C3—C2—H2120.3O1—C7—H7B109.1
C4—C3—C2119.04 (16)C8—C7—H7B109.1
C4—C3—C6121.87 (15)H7A—C7—H7B107.8
C2—C3—C6119.09 (16)F1—C8—F2105.53 (18)
C5—C4—C3119.62 (16)F1—C8—C7110.37 (17)
C5—C4—H4120.2F2—C8—C7111.16 (16)
C3—C4—H4120.2F1—C8—H8109.9
N1—C5—C4119.46 (17)F2—C8—H8109.9
N1—C5—H5120.3C7—C8—H8109.9
C4—C5—H5120.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.85 (2)2.69 (2)3.4501 (15)151 (2)
C1—H1···I1i0.953.163.8487 (18)131
C5—H5···I1i0.953.073.7705 (18)131
C8—H8···I1ii1.003.053.917 (2)146
C6—H6A···F1iii0.982.633.443 (2)140
C7—H7B···F1iv0.992.433.413 (2)173
C6—H6A···F20.992.333.008 (2)125
Symmetry codes: (i) x+2, y+1, z+1; (ii) x3/2, y+3/2, z1/2; (iii) x+1/2, y1/2, z+1/2; (iv) x1/2, y1/2, z+1/2.
4-[(3-Chloro-2,2,3,3-tetrafluoropropoxy)methyl]pyridinium iodide (i16319) top
Crystal data top
C9H9ClF4NO+·IF(000) = 736
Mr = 385.52Dx = 2.100 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 5.3299 (2) ÅCell parameters from 9996 reflections
b = 27.5016 (7) Åθ = 2.6–27.2°
c = 8.3227 (2) ŵ = 2.88 mm1
β = 91.813 (2)°T = 100 K
V = 1219.34 (6) Å3Plate, colourless
Z = 40.44 × 0.36 × 0.04 mm
Data collection top
Bruker APEXII CCD
diffractometer
2631 reflections with I > 2σ(I)
φ and ω scansRint = 0.032
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
θmax = 27.1°, θmin = 2.6°
Tmin = 0.742, Tmax = 0.971h = 66
23618 measured reflectionsk = 3535
2687 independent reflectionsl = 1010
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.018H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.037 w = 1/[σ2(Fo2) + (0.0042P)2 + 1.4046P]
where P = (Fo2 + 2Fc2)/3
S = 1.20(Δ/σ)max = 0.003
2687 reflectionsΔρmax = 0.50 e Å3
158 parametersΔρmin = 0.43 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
I10.07294 (2)0.54576 (2)0.78282 (2)0.01335 (4)
Cl10.93422 (10)0.15860 (2)0.70756 (6)0.01902 (11)
F10.7905 (2)0.26201 (4)0.67304 (14)0.0149 (2)
F21.0714 (2)0.25388 (4)0.86687 (14)0.0180 (3)
F31.0913 (2)0.20815 (4)0.47562 (14)0.0210 (3)
F41.3589 (2)0.19877 (4)0.67401 (17)0.0236 (3)
O11.0798 (3)0.34294 (5)0.69182 (17)0.0150 (3)
N10.3803 (3)0.45367 (6)0.8043 (2)0.0152 (3)
C10.3836 (4)0.45246 (7)0.6427 (3)0.0165 (4)
H10.26580.47100.58050.020*
C20.5576 (4)0.42433 (7)0.5680 (2)0.0143 (4)
H20.56150.42340.45400.017*
C40.7296 (4)0.39695 (7)0.6611 (2)0.0116 (4)
C50.7249 (4)0.40050 (7)0.8278 (2)0.0134 (4)
H50.84350.38310.89320.016*
C60.5467 (4)0.42942 (7)0.8975 (3)0.0159 (4)
H60.54230.43211.01120.019*
C70.9082 (4)0.36433 (7)0.5774 (2)0.0146 (4)
H7A0.81340.33850.51910.017*
H7B1.00190.38330.49800.017*
C81.1868 (4)0.29899 (7)0.6391 (3)0.0143 (4)
H8A1.36420.29700.67750.017*
H8B1.18250.29800.52020.017*
C91.0403 (4)0.25630 (7)0.7042 (2)0.0118 (4)
C101.1159 (4)0.20667 (7)0.6368 (2)0.0141 (4)
H1A0.267 (5)0.4713 (9)0.841 (3)0.019 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01386 (7)0.01387 (7)0.01234 (7)0.00388 (5)0.00054 (5)0.00106 (5)
Cl10.0182 (3)0.0135 (2)0.0256 (3)0.00237 (18)0.0049 (2)0.00308 (19)
F10.0076 (5)0.0182 (6)0.0190 (6)0.0026 (4)0.0006 (4)0.0000 (5)
F20.0209 (6)0.0229 (6)0.0102 (6)0.0009 (5)0.0006 (5)0.0007 (5)
F30.0305 (7)0.0185 (6)0.0144 (6)0.0010 (5)0.0076 (5)0.0028 (5)
F40.0100 (6)0.0178 (6)0.0430 (8)0.0040 (5)0.0022 (5)0.0030 (6)
O10.0158 (7)0.0126 (7)0.0164 (7)0.0048 (6)0.0013 (6)0.0016 (5)
N10.0134 (9)0.0135 (8)0.0189 (9)0.0025 (7)0.0025 (7)0.0023 (7)
C10.0163 (10)0.0129 (9)0.0201 (11)0.0008 (8)0.0033 (8)0.0011 (8)
C20.0162 (10)0.0134 (9)0.0132 (10)0.0004 (8)0.0023 (8)0.0006 (7)
C40.0116 (9)0.0077 (8)0.0154 (10)0.0018 (7)0.0008 (7)0.0011 (7)
C50.0136 (10)0.0121 (9)0.0146 (10)0.0006 (7)0.0001 (8)0.0027 (7)
C60.0176 (10)0.0143 (10)0.0159 (10)0.0011 (8)0.0016 (8)0.0006 (8)
C70.0167 (10)0.0130 (9)0.0140 (10)0.0035 (8)0.0007 (8)0.0013 (8)
C80.0121 (10)0.0120 (9)0.0189 (10)0.0033 (7)0.0038 (8)0.0000 (8)
C90.0096 (9)0.0156 (9)0.0102 (9)0.0016 (7)0.0009 (7)0.0005 (7)
C100.0121 (10)0.0135 (9)0.0169 (10)0.0007 (7)0.0025 (8)0.0020 (8)
Geometric parameters (Å, º) top
Cl1—C101.751 (2)C2—H20.9500
F1—C91.357 (2)C4—C51.392 (3)
F2—C91.360 (2)C4—C71.496 (3)
F3—C101.345 (2)C5—C61.380 (3)
F4—C101.340 (2)C5—H50.9500
O1—C81.412 (2)C6—H60.9500
O1—C71.426 (2)C7—H7A0.9900
N1—C61.338 (3)C7—H7B0.9900
N1—C11.346 (3)C8—C91.519 (3)
N1—H1A0.84 (3)C8—H8A0.9900
C1—C21.372 (3)C8—H8B0.9900
C1—H10.9500C9—C101.534 (3)
C2—C41.401 (3)
C8—O1—C7113.73 (15)O1—C7—H7B109.7
C6—N1—C1122.52 (19)C4—C7—H7B109.7
C6—N1—H1A123.1 (17)H7A—C7—H7B108.2
C1—N1—H1A114.4 (17)O1—C8—C9109.48 (16)
N1—C1—C2119.81 (19)O1—C8—H8A109.8
N1—C1—H1120.1C9—C8—H8A109.8
C2—C1—H1120.1O1—C8—H8B109.8
C1—C2—C4119.51 (19)C9—C8—H8B109.8
C1—C2—H2120.2H8A—C8—H8B108.2
C4—C2—H2120.2F1—C9—F2106.50 (15)
C5—C4—C2118.76 (18)F1—C9—C8110.76 (16)
C5—C4—C7122.59 (18)F2—C9—C8110.16 (16)
C2—C4—C7118.64 (18)F1—C9—C10107.49 (16)
C6—C5—C4119.59 (19)F2—C9—C10107.16 (15)
C6—C5—H5120.2C8—C9—C10114.41 (16)
C4—C5—H5120.2F4—C10—F3107.35 (16)
N1—C6—C5119.73 (19)F4—C10—C9108.85 (16)
N1—C6—H6120.1F3—C10—C9108.63 (16)
C5—C6—H6120.1F4—C10—Cl1109.92 (14)
O1—C7—C4109.88 (16)F3—C10—Cl1108.70 (14)
O1—C7—H7A109.7C9—C10—Cl1113.22 (14)
C4—C7—H7A109.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.84 (3)2.77 (3)3.501 (2)147 (2)
C6—H6···I1i0.953.143.788 (2)127
C7—H7B···I1ii0.993.084.005 (2)157
C10—Cl1···I1iii1.75 (1)3.65 (1)5.341 (2)161 (1)
C8—H8A···F1iv0.992.473.378 (2)152
C9—F1···F4v1.36 (1)2.88 (1)3.962 (2)135 (1)
C9—F1···F2vi1.36 (1)2.80 (1)3.710 (2)122 (1)
C9—F1···F3vii1.36 (1)2.88 (1)3.483 (2)105 (1)
C9—F2···F1vii1.36 (1)2.80 (1)4.114 (2)161 (1)
C9—F2···F3vii1.36 (1)2.93 (1)3.483 (2)102 (1)
C10—F3···F1viii1.34 (1)2.88 (1)4.091 (2)149 (1)
C10—F3···F2viii1.34 (1)2.93 (1)3.530 (2)105 (1)
C10—F4···F1iv1.34 (1)2.88 (1)3.907 (2)132 (1)
Symmetry codes: (i) x, y+1, z+2; (ii) x+1, y+1, z+1; (iii) x+1/2, y1/2, z+3/2; (iv) x+1, y, z; (v) x1, y, z; (vi) x1/2, y+1/2, z1/2; (vii) x1/2, y+1/2, z+1/2; (viii) x+1/2, y+1/2, z1/2.
 

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