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, C
8H
10F
2NO
+·I
−, (1), has a –CH
2OCH
2CF
2H substituent at the
para position of the pyridinium ring and 4-[(3-chloro-2,2,3,3-tetrafluoropropoxy)methyl]pyridinium iodide, C
9H
9ClF
4NO
+·I
−, (2), has a –CH
2OCH
2CF
2CF
2Cl 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
CCDC references: 1565383; 1565382
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+·I− | F(000) = 576 |
Mr = 301.07 | Dx = 1.982 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9221 (1) Å | Cell parameters from 9922 reflections |
b = 8.4974 (2) Å | θ = 2.5–27.2° |
c = 24.1323 (7) Å | µ = 3.17 mm−1 |
β = 91.610 (1)° | T = 100 K |
V = 1008.94 (4) Å3 | Plate, colourless |
Z = 4 | 0.34 × 0.30 × 0.08 mm |
Data collection top
Bruker APEXII CCD diffractometer | 2208 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.024 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | θmax = 27.1°, θmin = 1.7° |
Tmin = 0.819, Tmax = 0.971 | h = −6→6 |
34955 measured reflections | k = −10→10 |
2231 independent reflections | l = −30→30 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H 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 = 1.28 | Δρmax = 0.38 e Å−3 |
2231 reflections | Δρmin = −0.37 e Å−3 |
122 parameters | Extinction correction: SHELXL2013 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction 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 | x | y | z | Uiso*/Ueq | |
I1 | 1.07331 (2) | 0.78331 (2) | 0.55794 (2) | 0.01406 (5) | |
F1 | 0.0012 (3) | 0.79498 (15) | 0.20001 (5) | 0.0375 (3) | |
F2 | 0.0776 (3) | 0.54453 (16) | 0.20994 (5) | 0.0412 (4) | |
O1 | −0.1092 (3) | 0.70739 (15) | 0.30691 (5) | 0.0188 (3) | |
N1 | 0.6050 (3) | 0.78417 (19) | 0.44880 (6) | 0.0164 (3) | |
H1A | 0.721 (4) | 0.821 (3) | 0.4720 (9) | 0.020* | |
C1 | 0.5972 (4) | 0.6274 (2) | 0.44283 (7) | 0.0157 (3) | |
H1 | 0.7182 | 0.5626 | 0.4640 | 0.019* | |
C2 | 0.4137 (3) | 0.5610 (2) | 0.40595 (7) | 0.0147 (3) | |
H2 | 0.4073 | 0.4501 | 0.4012 | 0.018* | |
C3 | 0.2361 (3) | 0.6582 (2) | 0.37544 (7) | 0.0119 (3) | |
C4 | 0.2454 (3) | 0.8192 (2) | 0.38426 (7) | 0.0145 (3) | |
H4 | 0.1227 | 0.8868 | 0.3646 | 0.017* | |
C5 | 0.4336 (4) | 0.8807 (2) | 0.42166 (8) | 0.0170 (4) | |
H5 | 0.4414 | 0.9910 | 0.4281 | 0.020* | |
C6 | 0.0439 (3) | 0.5855 (2) | 0.33335 (7) | 0.0146 (3) | |
H6A | 0.1471 | 0.5263 | 0.3056 | 0.018* | |
H6B | −0.0797 | 0.5113 | 0.3518 | 0.018* | |
C7 | −0.2744 (4) | 0.6572 (2) | 0.26140 (8) | 0.0230 (4) | |
H7A | −0.4325 | 0.7287 | 0.2573 | 0.028* | |
H7B | −0.3441 | 0.5503 | 0.2691 | 0.028* | |
C8 | −0.1251 (5) | 0.6544 (2) | 0.20825 (8) | 0.0287 (5) | |
H8 | −0.2545 | 0.6318 | 0.1766 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01415 (6) | 0.01339 (6) | 0.01443 (6) | −0.00003 (4) | −0.00318 (4) | 0.00007 (4) |
F1 | 0.0574 (9) | 0.0256 (7) | 0.0298 (7) | −0.0105 (6) | 0.0058 (6) | 0.0051 (5) |
F2 | 0.0712 (10) | 0.0341 (7) | 0.0186 (6) | 0.0168 (7) | 0.0054 (6) | −0.0041 (5) |
O1 | 0.0202 (6) | 0.0183 (6) | 0.0175 (6) | 0.0033 (5) | −0.0076 (5) | −0.0012 (5) |
N1 | 0.0131 (7) | 0.0215 (8) | 0.0145 (7) | −0.0018 (6) | −0.0010 (6) | −0.0035 (6) |
C1 | 0.0148 (8) | 0.0192 (9) | 0.0131 (8) | 0.0021 (7) | 0.0009 (6) | 0.0021 (7) |
C2 | 0.0159 (8) | 0.0146 (8) | 0.0136 (8) | 0.0006 (7) | 0.0016 (7) | 0.0011 (7) |
C3 | 0.0118 (7) | 0.0149 (8) | 0.0092 (7) | −0.0004 (6) | 0.0040 (6) | 0.0008 (6) |
C4 | 0.0145 (8) | 0.0133 (8) | 0.0158 (8) | 0.0008 (6) | 0.0010 (6) | 0.0023 (6) |
C5 | 0.0167 (8) | 0.0146 (9) | 0.0199 (9) | −0.0004 (7) | 0.0023 (7) | −0.0022 (7) |
C6 | 0.0150 (8) | 0.0148 (8) | 0.0139 (8) | 0.0019 (7) | −0.0010 (6) | 0.0002 (7) |
C7 | 0.0215 (9) | 0.0226 (9) | 0.0241 (10) | −0.0044 (8) | −0.0121 (8) | 0.0029 (8) |
C8 | 0.0467 (13) | 0.0182 (10) | 0.0206 (10) | −0.0012 (9) | −0.0107 (9) | 0.0003 (8) |
Geometric parameters (Å, º) top
F1—C8 | 1.363 (2) | C3—C4 | 1.385 (2) |
F2—C8 | 1.366 (3) | C3—C6 | 1.502 (2) |
O1—C7 | 1.414 (2) | C4—C5 | 1.378 (2) |
O1—C6 | 1.421 (2) | C4—H4 | 0.9500 |
N1—C5 | 1.335 (2) | C5—H5 | 0.9500 |
N1—C1 | 1.340 (2) | C6—H6A | 0.9900 |
N1—H1A | 0.85 (2) | C6—H6B | 0.9900 |
C1—C2 | 1.371 (2) | C7—C8 | 1.496 (3) |
C1—H1 | 0.9500 | C7—H7A | 0.9900 |
C2—C3 | 1.397 (2) | C7—H7B | 0.9900 |
C2—H2 | 0.9500 | C8—H8 | 1.0000 |
| | | |
C7—O1—C6 | 114.51 (14) | O1—C6—C3 | 108.64 (14) |
C5—N1—C1 | 122.83 (16) | O1—C6—H6A | 110.0 |
C5—N1—H1A | 120.2 (15) | C3—C6—H6A | 110.0 |
C1—N1—H1A | 117.0 (15) | O1—C6—H6B | 110.0 |
N1—C1—C2 | 119.66 (17) | C3—C6—H6B | 110.0 |
N1—C1—H1 | 120.2 | H6A—C6—H6B | 108.3 |
C2—C1—H1 | 120.2 | O1—C7—C8 | 112.64 (16) |
C1—C2—C3 | 119.33 (17) | O1—C7—H7A | 109.1 |
C1—C2—H2 | 120.3 | C8—C7—H7A | 109.1 |
C3—C2—H2 | 120.3 | O1—C7—H7B | 109.1 |
C4—C3—C2 | 119.04 (16) | C8—C7—H7B | 109.1 |
C4—C3—C6 | 121.87 (15) | H7A—C7—H7B | 107.8 |
C2—C3—C6 | 119.09 (16) | F1—C8—F2 | 105.53 (18) |
C5—C4—C3 | 119.62 (16) | F1—C8—C7 | 110.37 (17) |
C5—C4—H4 | 120.2 | F2—C8—C7 | 111.16 (16) |
C3—C4—H4 | 120.2 | F1—C8—H8 | 109.9 |
N1—C5—C4 | 119.46 (17) | F2—C8—H8 | 109.9 |
N1—C5—H5 | 120.3 | C7—C8—H8 | 109.9 |
C4—C5—H5 | 120.3 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I1 | 0.85 (2) | 2.69 (2) | 3.4501 (15) | 151 (2) |
C1—H1···I1i | 0.95 | 3.16 | 3.8487 (18) | 131 |
C5—H5···I1i | 0.95 | 3.07 | 3.7705 (18) | 131 |
C8—H8···I1ii | 1.00 | 3.05 | 3.917 (2) | 146 |
C6—H6A···F1iii | 0.98 | 2.63 | 3.443 (2) | 140 |
C7—H7B···F1iv | 0.99 | 2.43 | 3.413 (2) | 173 |
C6—H6A···F2 | 0.99 | 2.33 | 3.008 (2) | 125 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−3/2, −y+3/2, z−1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x−1/2, y−1/2, −z+1/2. |
4-[(3-Chloro-2,2,3,3-tetrafluoropropoxy)methyl]pyridinium iodide (i16319)
top
Crystal data top
C9H9ClF4NO+·I− | F(000) = 736 |
Mr = 385.52 | Dx = 2.100 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3299 (2) Å | Cell parameters from 9996 reflections |
b = 27.5016 (7) Å | θ = 2.6–27.2° |
c = 8.3227 (2) Å | µ = 2.88 mm−1 |
β = 91.813 (2)° | T = 100 K |
V = 1219.34 (6) Å3 | Plate, colourless |
Z = 4 | 0.44 × 0.36 × 0.04 mm |
Data collection top
Bruker APEXII CCD diffractometer | 2631 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.032 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | θmax = 27.1°, θmin = 2.6° |
Tmin = 0.742, Tmax = 0.971 | h = −6→6 |
23618 measured reflections | k = −35→35 |
2687 independent reflections | l = −10→10 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.018 | H 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 reflections | Δρmax = 0.50 e Å−3 |
158 parameters | Δρmin = −0.43 e Å−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 | x | y | z | Uiso*/Ueq | |
I1 | −0.07294 (2) | 0.54576 (2) | 0.78282 (2) | 0.01335 (4) | |
Cl1 | 0.93422 (10) | 0.15860 (2) | 0.70756 (6) | 0.01902 (11) | |
F1 | 0.7905 (2) | 0.26201 (4) | 0.67304 (14) | 0.0149 (2) | |
F2 | 1.0714 (2) | 0.25388 (4) | 0.86687 (14) | 0.0180 (3) | |
F3 | 1.0913 (2) | 0.20815 (4) | 0.47562 (14) | 0.0210 (3) | |
F4 | 1.3589 (2) | 0.19877 (4) | 0.67401 (17) | 0.0236 (3) | |
O1 | 1.0798 (3) | 0.34294 (5) | 0.69182 (17) | 0.0150 (3) | |
N1 | 0.3803 (3) | 0.45367 (6) | 0.8043 (2) | 0.0152 (3) | |
C1 | 0.3836 (4) | 0.45246 (7) | 0.6427 (3) | 0.0165 (4) | |
H1 | 0.2658 | 0.4710 | 0.5805 | 0.020* | |
C2 | 0.5576 (4) | 0.42433 (7) | 0.5680 (2) | 0.0143 (4) | |
H2 | 0.5615 | 0.4234 | 0.4540 | 0.017* | |
C4 | 0.7296 (4) | 0.39695 (7) | 0.6611 (2) | 0.0116 (4) | |
C5 | 0.7249 (4) | 0.40050 (7) | 0.8278 (2) | 0.0134 (4) | |
H5 | 0.8435 | 0.3831 | 0.8932 | 0.016* | |
C6 | 0.5467 (4) | 0.42942 (7) | 0.8975 (3) | 0.0159 (4) | |
H6 | 0.5423 | 0.4321 | 1.0112 | 0.019* | |
C7 | 0.9082 (4) | 0.36433 (7) | 0.5774 (2) | 0.0146 (4) | |
H7A | 0.8134 | 0.3385 | 0.5191 | 0.017* | |
H7B | 1.0019 | 0.3833 | 0.4980 | 0.017* | |
C8 | 1.1868 (4) | 0.29899 (7) | 0.6391 (3) | 0.0143 (4) | |
H8A | 1.3642 | 0.2970 | 0.6775 | 0.017* | |
H8B | 1.1825 | 0.2980 | 0.5202 | 0.017* | |
C9 | 1.0403 (4) | 0.25630 (7) | 0.7042 (2) | 0.0118 (4) | |
C10 | 1.1159 (4) | 0.20667 (7) | 0.6368 (2) | 0.0141 (4) | |
H1A | 0.267 (5) | 0.4713 (9) | 0.841 (3) | 0.019 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01386 (7) | 0.01387 (7) | 0.01234 (7) | 0.00388 (5) | 0.00054 (5) | 0.00106 (5) |
Cl1 | 0.0182 (3) | 0.0135 (2) | 0.0256 (3) | −0.00237 (18) | 0.0049 (2) | 0.00308 (19) |
F1 | 0.0076 (5) | 0.0182 (6) | 0.0190 (6) | 0.0026 (4) | 0.0006 (4) | 0.0000 (5) |
F2 | 0.0209 (6) | 0.0229 (6) | 0.0102 (6) | −0.0009 (5) | −0.0006 (5) | 0.0007 (5) |
F3 | 0.0305 (7) | 0.0185 (6) | 0.0144 (6) | −0.0010 (5) | 0.0076 (5) | −0.0028 (5) |
F4 | 0.0100 (6) | 0.0178 (6) | 0.0430 (8) | 0.0040 (5) | 0.0022 (5) | 0.0030 (6) |
O1 | 0.0158 (7) | 0.0126 (7) | 0.0164 (7) | 0.0048 (6) | −0.0013 (6) | −0.0016 (5) |
N1 | 0.0134 (9) | 0.0135 (8) | 0.0189 (9) | 0.0025 (7) | 0.0025 (7) | −0.0023 (7) |
C1 | 0.0163 (10) | 0.0129 (9) | 0.0201 (11) | 0.0008 (8) | −0.0033 (8) | 0.0011 (8) |
C2 | 0.0162 (10) | 0.0134 (9) | 0.0132 (10) | −0.0004 (8) | −0.0023 (8) | 0.0006 (7) |
C4 | 0.0116 (9) | 0.0077 (8) | 0.0154 (10) | −0.0018 (7) | 0.0008 (7) | 0.0011 (7) |
C5 | 0.0136 (10) | 0.0121 (9) | 0.0146 (10) | 0.0006 (7) | 0.0001 (8) | 0.0027 (7) |
C6 | 0.0176 (10) | 0.0143 (10) | 0.0159 (10) | −0.0011 (8) | 0.0016 (8) | −0.0006 (8) |
C7 | 0.0167 (10) | 0.0130 (9) | 0.0140 (10) | 0.0035 (8) | 0.0007 (8) | 0.0013 (8) |
C8 | 0.0121 (10) | 0.0120 (9) | 0.0189 (10) | 0.0033 (7) | 0.0038 (8) | 0.0000 (8) |
C9 | 0.0096 (9) | 0.0156 (9) | 0.0102 (9) | 0.0016 (7) | −0.0009 (7) | 0.0005 (7) |
C10 | 0.0121 (10) | 0.0135 (9) | 0.0169 (10) | 0.0007 (7) | 0.0025 (8) | 0.0020 (8) |
Geometric parameters (Å, º) top
Cl1—C10 | 1.751 (2) | C2—H2 | 0.9500 |
F1—C9 | 1.357 (2) | C4—C5 | 1.392 (3) |
F2—C9 | 1.360 (2) | C4—C7 | 1.496 (3) |
F3—C10 | 1.345 (2) | C5—C6 | 1.380 (3) |
F4—C10 | 1.340 (2) | C5—H5 | 0.9500 |
O1—C8 | 1.412 (2) | C6—H6 | 0.9500 |
O1—C7 | 1.426 (2) | C7—H7A | 0.9900 |
N1—C6 | 1.338 (3) | C7—H7B | 0.9900 |
N1—C1 | 1.346 (3) | C8—C9 | 1.519 (3) |
N1—H1A | 0.84 (3) | C8—H8A | 0.9900 |
C1—C2 | 1.372 (3) | C8—H8B | 0.9900 |
C1—H1 | 0.9500 | C9—C10 | 1.534 (3) |
C2—C4 | 1.401 (3) | | |
| | | |
C8—O1—C7 | 113.73 (15) | O1—C7—H7B | 109.7 |
C6—N1—C1 | 122.52 (19) | C4—C7—H7B | 109.7 |
C6—N1—H1A | 123.1 (17) | H7A—C7—H7B | 108.2 |
C1—N1—H1A | 114.4 (17) | O1—C8—C9 | 109.48 (16) |
N1—C1—C2 | 119.81 (19) | O1—C8—H8A | 109.8 |
N1—C1—H1 | 120.1 | C9—C8—H8A | 109.8 |
C2—C1—H1 | 120.1 | O1—C8—H8B | 109.8 |
C1—C2—C4 | 119.51 (19) | C9—C8—H8B | 109.8 |
C1—C2—H2 | 120.2 | H8A—C8—H8B | 108.2 |
C4—C2—H2 | 120.2 | F1—C9—F2 | 106.50 (15) |
C5—C4—C2 | 118.76 (18) | F1—C9—C8 | 110.76 (16) |
C5—C4—C7 | 122.59 (18) | F2—C9—C8 | 110.16 (16) |
C2—C4—C7 | 118.64 (18) | F1—C9—C10 | 107.49 (16) |
C6—C5—C4 | 119.59 (19) | F2—C9—C10 | 107.16 (15) |
C6—C5—H5 | 120.2 | C8—C9—C10 | 114.41 (16) |
C4—C5—H5 | 120.2 | F4—C10—F3 | 107.35 (16) |
N1—C6—C5 | 119.73 (19) | F4—C10—C9 | 108.85 (16) |
N1—C6—H6 | 120.1 | F3—C10—C9 | 108.63 (16) |
C5—C6—H6 | 120.1 | F4—C10—Cl1 | 109.92 (14) |
O1—C7—C4 | 109.88 (16) | F3—C10—Cl1 | 108.70 (14) |
O1—C7—H7A | 109.7 | C9—C10—Cl1 | 113.22 (14) |
C4—C7—H7A | 109.7 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I1 | 0.84 (3) | 2.77 (3) | 3.501 (2) | 147 (2) |
C6—H6···I1i | 0.95 | 3.14 | 3.788 (2) | 127 |
C7—H7B···I1ii | 0.99 | 3.08 | 4.005 (2) | 157 |
C10—Cl1···I1iii | 1.75 (1) | 3.65 (1) | 5.341 (2) | 161 (1) |
C8—H8A···F1iv | 0.99 | 2.47 | 3.378 (2) | 152 |
C9—F1···F4v | 1.36 (1) | 2.88 (1) | 3.962 (2) | 135 (1) |
C9—F1···F2vi | 1.36 (1) | 2.80 (1) | 3.710 (2) | 122 (1) |
C9—F1···F3vii | 1.36 (1) | 2.88 (1) | 3.483 (2) | 105 (1) |
C9—F2···F1vii | 1.36 (1) | 2.80 (1) | 4.114 (2) | 161 (1) |
C9—F2···F3vii | 1.36 (1) | 2.93 (1) | 3.483 (2) | 102 (1) |
C10—F3···F1viii | 1.34 (1) | 2.88 (1) | 4.091 (2) | 149 (1) |
C10—F3···F2viii | 1.34 (1) | 2.93 (1) | 3.530 (2) | 105 (1) |
C10—F4···F1iv | 1.34 (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, y−1/2, −z+3/2; (iv) x+1, y, z; (v) x−1, y, z; (vi) x−1/2, −y+1/2, z−1/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) x+1/2, −y+1/2, z−1/2. |