It has been confirmed that mercaptopyridines undergo spontaneous condensation in redox reaction with iodine-forming dithiopyridines. In the solid state, these compounds are protonated at the N atoms and cocrystallize with iodine forming salt structures, namely, 2-[(pyridin-2-yl)disulfanyl]pyridinium triiodide sesquiiodine, C10H9N2S2+·I3−·1.5I2, and 4,4′-(disulfanediyl)dipyridinium pentaiodide triiodide, C10H10N2S22+·I5−·I3−. Dithiopyridine cations are packed among three-dimensional frameworks built from iodide anions and neutral iodine molecules, and are linked by hydrogen, halogen and chalcogen interactions. Quantum chemical computations indicated that dithiopyridines exhibit anomalously high nitrogen basicity which qualify them as potential proton sponges.
Supporting information
CCDC references: 2090706; 2090705
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b).
2-[(Pyridin-2-yl)disulfanyl]pyridinium triiodide sesquiiodine (structure_I)
top
Crystal data top
C10H9N2S2+·I3−·1.5I2 | F(000) = 1732 |
Mr = 982.71 | Dx = 3.028 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3273 (1) Å | Cell parameters from 22640 reflections |
b = 18.2114 (3) Å | θ = 3.5–30.8° |
c = 12.6897 (2) Å | µ = 8.83 mm−1 |
β = 90.607 (2)° | T = 150 K |
V = 2155.39 (5) Å3 | Plate, brown |
Z = 4 | 0.28 × 0.12 × 0.09 mm |
Data collection top
XtaLAB Synergy Dualflex HyPix diffractometer | 5952 independent reflections |
Radiation source: micro-focus sealed X-ray tube | 5295 reflections with I > 2σ(I) |
Detector resolution: 10.0000 pixels mm-1 | Rint = 0.041 |
CrysAlisPro 1.171.39.15e (Rigaku Oxford Diffraction, 2015 scans | θmax = 30.9°, θmin = 3.4° |
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2020), based on expressions derived by
Clark & Reid (1995)] | h = −13→12 |
Tmin = 0.992, Tmax = 0.997 | k = −25→25 |
38980 measured reflections | l = −17→17 |
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)] = 0.025 | w = 1/[σ2(Fo2) + 6.2162P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max = 0.002 |
S = 1.13 | Δρmax = 0.81 e Å−3 |
5952 reflections | Δρmin = −0.70 e Å−3 |
186 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00040 (2) |
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 | |
I2 | 0.25666 (3) | 0.78880 (2) | 0.75539 (2) | 0.02501 (6) | |
I5 | 0.61028 (3) | 0.44782 (2) | 0.87305 (2) | 0.02634 (6) | |
I4 | 0.90683 (2) | 0.44386 (2) | 0.87004 (2) | 0.02521 (6) | |
I3 | 0.26456 (3) | 0.64265 (2) | 0.82050 (2) | 0.02916 (7) | |
I6 | 0.41625 (3) | 0.48540 (2) | 0.58567 (2) | 0.03083 (7) | |
I1 | 0.25331 (2) | 0.45269 (2) | 0.82763 (2) | 0.02387 (6) | |
S2 | 0.08143 (11) | 0.60000 (5) | 0.41905 (7) | 0.0270 (2) | |
S1 | 0.04639 (11) | 0.58596 (6) | 0.57703 (7) | 0.0286 (2) | |
N1 | −0.1387 (4) | 0.69899 (19) | 0.5576 (3) | 0.0270 (7) | |
N2 | 0.0986 (3) | 0.74440 (19) | 0.4558 (3) | 0.0264 (7) | |
C24 | 0.2983 (5) | 0.8217 (3) | 0.4179 (3) | 0.0361 (10) | |
H24 | 0.341569 | 0.868923 | 0.419832 | 0.043* | |
C22 | 0.3065 (4) | 0.6932 (3) | 0.3771 (3) | 0.0355 (10) | |
H22 | 0.355428 | 0.651562 | 0.350183 | 0.043* | |
C25 | 0.1615 (4) | 0.8106 (2) | 0.4568 (3) | 0.0312 (9) | |
H25 | 0.110850 | 0.851181 | 0.485058 | 0.037* | |
C11 | −0.1193 (4) | 0.6312 (2) | 0.5973 (3) | 0.0244 (8) | |
C21 | 0.1716 (4) | 0.6869 (2) | 0.4178 (3) | 0.0254 (8) | |
C14 | −0.3658 (5) | 0.7077 (3) | 0.6363 (3) | 0.0355 (10) | |
H14 | −0.450792 | 0.734768 | 0.649405 | 0.043* | |
C15 | −0.2597 (5) | 0.7369 (2) | 0.5742 (3) | 0.0333 (9) | |
H15 | −0.272289 | 0.783950 | 0.543136 | 0.040* | |
C23 | 0.3694 (5) | 0.7623 (3) | 0.3764 (4) | 0.0402 (11) | |
H23 | 0.461963 | 0.768669 | 0.347124 | 0.048* | |
C12 | −0.2244 (5) | 0.5995 (2) | 0.6590 (3) | 0.0328 (9) | |
H12 | −0.212035 | 0.551464 | 0.686964 | 0.039* | |
C13 | −0.3474 (5) | 0.6392 (3) | 0.6789 (3) | 0.0376 (10) | |
H13 | −0.419572 | 0.618911 | 0.722323 | 0.045* | |
H1 | −0.077 (7) | 0.715 (4) | 0.526 (5) | 0.07 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I2 | 0.02425 (12) | 0.02310 (12) | 0.02773 (12) | 0.00142 (9) | 0.00332 (9) | 0.00102 (9) |
I5 | 0.01976 (11) | 0.03428 (15) | 0.02503 (12) | 0.00099 (10) | 0.00339 (9) | 0.00204 (10) |
I4 | 0.02021 (11) | 0.03030 (14) | 0.02509 (12) | 0.00128 (9) | −0.00085 (9) | −0.00121 (9) |
I3 | 0.03537 (14) | 0.02270 (13) | 0.02945 (13) | 0.00368 (10) | 0.00247 (10) | 0.00287 (10) |
I6 | 0.02870 (13) | 0.03772 (16) | 0.02609 (13) | 0.00470 (11) | 0.00121 (10) | 0.00151 (11) |
I1 | 0.01683 (11) | 0.01955 (12) | 0.03532 (13) | −0.00014 (9) | 0.00346 (9) | −0.00073 (9) |
S2 | 0.0333 (5) | 0.0233 (5) | 0.0243 (4) | 0.0036 (4) | 0.0031 (4) | −0.0039 (4) |
S1 | 0.0338 (5) | 0.0280 (5) | 0.0241 (4) | 0.0077 (4) | −0.0007 (4) | 0.0013 (4) |
N1 | 0.0259 (17) | 0.0274 (18) | 0.0277 (17) | 0.0019 (14) | 0.0071 (14) | 0.0020 (13) |
N2 | 0.0260 (16) | 0.0247 (17) | 0.0284 (16) | 0.0019 (13) | 0.0047 (13) | −0.0020 (13) |
C24 | 0.033 (2) | 0.034 (2) | 0.041 (2) | −0.0113 (19) | 0.0041 (19) | −0.0008 (19) |
C22 | 0.028 (2) | 0.037 (3) | 0.041 (2) | 0.0075 (18) | 0.0082 (18) | −0.0027 (19) |
C25 | 0.030 (2) | 0.027 (2) | 0.036 (2) | 0.0003 (17) | 0.0075 (17) | −0.0056 (17) |
C11 | 0.0293 (19) | 0.025 (2) | 0.0189 (17) | 0.0012 (15) | −0.0020 (14) | −0.0028 (14) |
C21 | 0.0257 (18) | 0.028 (2) | 0.0223 (18) | 0.0047 (16) | 0.0013 (15) | −0.0003 (15) |
C14 | 0.026 (2) | 0.045 (3) | 0.035 (2) | 0.0032 (18) | 0.0074 (17) | −0.0035 (19) |
C15 | 0.033 (2) | 0.030 (2) | 0.038 (2) | 0.0049 (17) | 0.0079 (18) | 0.0038 (17) |
C23 | 0.025 (2) | 0.045 (3) | 0.051 (3) | −0.0014 (19) | 0.0134 (19) | 0.002 (2) |
C12 | 0.042 (2) | 0.027 (2) | 0.029 (2) | −0.0053 (18) | 0.0081 (18) | −0.0001 (16) |
C13 | 0.038 (2) | 0.040 (3) | 0.035 (2) | −0.010 (2) | 0.0126 (19) | −0.0055 (19) |
Geometric parameters (Å, º) top
I2—I3 | 2.7877 (4) | C22—C21 | 1.370 (5) |
I5—I4 | 2.7676 (3) | C22—C23 | 1.390 (7) |
I6—I6i | 2.7428 (5) | C22—H22 | 0.9500 |
S2—C21 | 1.793 (4) | C25—H25 | 0.9500 |
S2—S1 | 2.0506 (13) | C11—C12 | 1.387 (5) |
S1—C11 | 1.773 (4) | C14—C13 | 1.369 (7) |
N1—C15 | 1.341 (5) | C14—C15 | 1.378 (6) |
N1—C11 | 1.344 (5) | C14—H14 | 0.9500 |
N1—H1 | 0.76 (6) | C15—H15 | 0.9500 |
N2—C25 | 1.340 (5) | C23—H23 | 0.9500 |
N2—C21 | 1.341 (5) | C12—C13 | 1.382 (6) |
C24—C23 | 1.376 (7) | C12—H12 | 0.9500 |
C24—C25 | 1.388 (6) | C13—H13 | 0.9500 |
C24—H24 | 0.9500 | | |
| | | |
C21—S2—S1 | 101.46 (13) | N2—C21—C22 | 122.9 (4) |
C11—S1—S2 | 103.42 (13) | N2—C21—S2 | 116.5 (3) |
C15—N1—C11 | 121.6 (4) | C22—C21—S2 | 120.6 (3) |
C15—N1—H1 | 122 (5) | C13—C14—C15 | 119.3 (4) |
C11—N1—H1 | 116 (5) | C13—C14—H14 | 120.3 |
C25—N2—C21 | 118.8 (3) | C15—C14—H14 | 120.3 |
C23—C24—C25 | 118.0 (4) | N1—C15—C14 | 120.1 (4) |
C23—C24—H24 | 121.0 | N1—C15—H15 | 120.0 |
C25—C24—H24 | 121.0 | C14—C15—H15 | 120.0 |
C21—C22—C23 | 117.9 (4) | C24—C23—C22 | 120.3 (4) |
C21—C22—H22 | 121.1 | C24—C23—H23 | 119.9 |
C23—C22—H22 | 121.1 | C22—C23—H23 | 119.9 |
N2—C25—C24 | 122.1 (4) | C13—C12—C11 | 118.5 (4) |
N2—C25—H25 | 118.9 | C13—C12—H12 | 120.8 |
C24—C25—H25 | 118.9 | C11—C12—H12 | 120.8 |
N1—C11—C12 | 120.1 (4) | C14—C13—C12 | 120.4 (4) |
N1—C11—S1 | 119.1 (3) | C14—C13—H13 | 119.8 |
C12—C11—S1 | 120.7 (3) | C12—C13—H13 | 119.8 |
| | | |
C21—N2—C25—C24 | 1.3 (6) | S1—S2—C21—N2 | −60.6 (3) |
C23—C24—C25—N2 | 0.6 (7) | S1—S2—C21—C22 | 121.0 (3) |
C15—N1—C11—C12 | −1.4 (6) | C11—N1—C15—C14 | 2.3 (6) |
C15—N1—C11—S1 | −177.3 (3) | C13—C14—C15—N1 | −1.3 (7) |
S2—S1—C11—N1 | −47.8 (3) | C25—C24—C23—C22 | −2.0 (7) |
S2—S1—C11—C12 | 136.4 (3) | C21—C22—C23—C24 | 1.5 (7) |
C25—N2—C21—C22 | −1.8 (6) | N1—C11—C12—C13 | −0.5 (6) |
C25—N2—C21—S2 | 179.8 (3) | S1—C11—C12—C13 | 175.3 (3) |
C23—C22—C21—N2 | 0.4 (7) | C15—C14—C13—C12 | −0.6 (7) |
C23—C22—C21—S2 | 178.7 (3) | C11—C12—C13—C14 | 1.5 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
4,4'-(Disulfanediyl)dipyridinium pentaiodide triiodide (structure_II)
top
Crystal data top
C10H10N2S22+·I5−·I3− | Dx = 3.341 Mg m−3 |
Mr = 618.76 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 26294 reflections |
a = 10.1352 (2) Å | θ = 3.4–31.0° |
b = 11.8427 (2) Å | µ = 10.25 mm−1 |
c = 20.4986 (4) Å | T = 150 K |
V = 2460.41 (8) Å3 | Plate, brown |
Z = 8 | 0.22 × 0.09 × 0.05 mm |
F(000) = 2160 | |
Data collection top
XtaLAB Synergy Dualflex HyPix diffractometer | 3057 reflections with I > 2σ(I) |
Detector resolution: 10.0000 pixels mm-1 | Rint = 0.042 |
ω scans | θmax = 31.1°, θmin = 3.3° |
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2020), based on expressions derived by
Clark & Reid (1995)] | h = −14→14 |
Tmin = 0.995, Tmax = 0.999 | k = −16→15 |
42621 measured reflections | l = −29→26 |
3592 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.042 | w = 1/[σ2(Fo2) + (0.0136P)2 + 4.2557P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3592 reflections | Δρmax = 0.76 e Å−3 |
101 parameters | Δρmin = −0.93 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 | |
I2 | 0.34946 (2) | 0.42061 (2) | 0.44882 (2) | 0.02310 (5) | |
I3 | 0.40040 (2) | 0.57975 (2) | 0.35192 (2) | 0.02661 (5) | |
I5 | 0.750000 | 0.750000 | 0.22742 (2) | 0.02781 (7) | |
I1 | 0.250000 | 0.250000 | 0.55790 (2) | 0.02797 (7) | |
I4 | 0.46262 (2) | 0.77992 (2) | 0.22919 (2) | 0.03019 (6) | |
S1 | 0.84660 (7) | 0.27400 (6) | 0.50607 (4) | 0.02160 (14) | |
N1 | 0.9030 (3) | 0.5190 (2) | 0.34185 (13) | 0.0268 (6) | |
H1 | 0.917497 | 0.565850 | 0.309335 | 0.032* | |
C12 | 0.7537 (3) | 0.4092 (2) | 0.40243 (14) | 0.0222 (6) | |
H12 | 0.666202 | 0.383859 | 0.410359 | 0.027* | |
C13 | 0.8573 (3) | 0.3717 (2) | 0.44135 (14) | 0.0193 (5) | |
C11 | 0.7793 (3) | 0.4829 (3) | 0.35264 (15) | 0.0261 (6) | |
H11 | 0.709327 | 0.508597 | 0.325600 | 0.031* | |
C15 | 1.0053 (3) | 0.4861 (3) | 0.37888 (16) | 0.0288 (7) | |
H15 | 1.091363 | 0.514125 | 0.370127 | 0.035* | |
C14 | 0.9854 (3) | 0.4122 (3) | 0.42922 (16) | 0.0260 (6) | |
H14 | 1.057240 | 0.388592 | 0.455670 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I2 | 0.01728 (9) | 0.02644 (10) | 0.02558 (10) | 0.00023 (7) | −0.00158 (7) | −0.00429 (7) |
I3 | 0.02531 (10) | 0.02598 (10) | 0.02855 (11) | −0.00112 (7) | 0.00412 (8) | −0.00195 (8) |
I5 | 0.04360 (17) | 0.02162 (14) | 0.01820 (13) | 0.00083 (11) | 0.000 | 0.000 |
I1 | 0.03826 (16) | 0.02346 (14) | 0.02218 (14) | −0.00322 (11) | 0.000 | 0.000 |
I4 | 0.03840 (12) | 0.02561 (11) | 0.02654 (11) | −0.00444 (8) | −0.00446 (8) | 0.00171 (8) |
S1 | 0.0190 (3) | 0.0238 (4) | 0.0220 (3) | −0.0013 (3) | −0.0032 (3) | 0.0019 (3) |
N1 | 0.0288 (13) | 0.0272 (14) | 0.0243 (14) | −0.0017 (10) | 0.0035 (11) | 0.0045 (11) |
C12 | 0.0192 (13) | 0.0244 (15) | 0.0231 (14) | 0.0007 (11) | 0.0001 (11) | 0.0004 (12) |
C13 | 0.0214 (13) | 0.0183 (13) | 0.0183 (14) | −0.0005 (10) | 0.0002 (11) | −0.0039 (11) |
C11 | 0.0243 (15) | 0.0289 (16) | 0.0251 (16) | 0.0032 (12) | −0.0002 (12) | −0.0004 (13) |
C15 | 0.0236 (15) | 0.0304 (17) | 0.0326 (17) | −0.0040 (12) | 0.0015 (13) | 0.0000 (13) |
C14 | 0.0195 (14) | 0.0290 (16) | 0.0296 (16) | −0.0019 (11) | −0.0032 (12) | 0.0031 (13) |
Geometric parameters (Å, º) top
I2—I3 | 2.7863 (3) | C12—C11 | 1.368 (4) |
I5—I4 | 2.9344 (2) | C12—C13 | 1.392 (4) |
I5—I4i | 2.9344 (2) | C12—H12 | 0.9500 |
S1—C13 | 1.764 (3) | C13—C14 | 1.406 (4) |
S1—S1ii | 2.0389 (14) | C11—H11 | 0.9500 |
N1—C15 | 1.343 (4) | C15—C14 | 1.368 (5) |
N1—C11 | 1.343 (4) | C15—H15 | 0.9500 |
N1—H1 | 0.8800 | C14—H14 | 0.9500 |
| | | |
I4—I5—I4i | 178.576 (13) | C14—C13—S1 | 114.5 (2) |
C13—S1—S1ii | 104.02 (10) | N1—C11—C12 | 120.2 (3) |
C15—N1—C11 | 122.4 (3) | N1—C11—H11 | 119.9 |
C15—N1—H1 | 118.8 | C12—C11—H11 | 119.9 |
C11—N1—H1 | 118.8 | N1—C15—C14 | 119.8 (3) |
C11—C12—C13 | 119.2 (3) | N1—C15—H15 | 120.1 |
C11—C12—H12 | 120.4 | C14—C15—H15 | 120.1 |
C13—C12—H12 | 120.4 | C15—C14—C13 | 119.2 (3) |
C12—C13—C14 | 119.1 (3) | C15—C14—H14 | 120.4 |
C12—C13—S1 | 126.4 (2) | C13—C14—H14 | 120.4 |
| | | |
C11—C12—C13—C14 | 1.2 (4) | C13—C12—C11—N1 | −0.4 (5) |
C11—C12—C13—S1 | −177.9 (2) | C11—N1—C15—C14 | 0.8 (5) |
S1ii—S1—C13—C12 | 2.7 (3) | N1—C15—C14—C13 | 0.0 (5) |
S1ii—S1—C13—C14 | −176.4 (2) | C12—C13—C14—C15 | −1.0 (5) |
C15—N1—C11—C12 | −0.6 (5) | S1—C13—C14—C15 | 178.2 (3) |
Symmetry codes: (i) −x+3/2, −y+3/2, z; (ii) −x+3/2, −y+1/2, z. |
Selected geometric parameters (Å, °) defining the structure of disulfide
bridge in the dithiopyridine moiety top | Charge | S—S | S—C—(N) | S—C—(NH) | C—N | (S)—C—N(H) | C—S—S—C |
2,2'-Dithiopyridines | | | | | | | |
I | cation | 2.0506 (13) | 1.793 (4) | 1.773 (4) | 1.341 (5) | 1.344 (5) | 87.3 (2) |
HAJWUL | cation (disorder) | 2.052 | 1.781 | 1.754 | 1.348 | 1.351 | 87.3 |
DPYSUL | neutral | 2.016 | 1.786 | 1.785 | 1.329 | 1.358 | 87.1 |
FARWIF: A B C D | cation | 2.009 2.051 2.002 2.060 | 1.779 1.644 1.853 1.707 | 1.746 1.775 1.766 1.687 | 1.342 1.349 1.337 1.345 | 1.343 1.339 1.333 1.340 | 90.0 83.4 90. 0 86.7 |
FARWIF01 | cation (disorder, 2z symmetry) | 2.037 | – | 1.765 | – | 1.346 | 84.4 |
| | | | | | | |
4,4'-Dithiopyridines | | | | | | | |
II | double cation (2z symmetry) | 2.0389 (14) | – | 1.764 (3) | – | 1.343 (4) 1.343 (4) | 78.4 (2) |
XIWNAS | neutral (2y symmetry) | 2.032 | 1.780 | – | 1.329 1.335 | - | 84.0 |
Total molecular energies estimated for all possible tautomers
(Etot in Hartrees) and the relative energies estimated as a
difference between a given tautomer and the one of lowest energy (ΔE in
kcal mol-1) topEtot Tautomer A | -1292.3270839 |
Etot Tautomer B | -1292.3270839 |
Etot Transition state | -1292.3236721 |
ΔE (PT barrier) | 2.14 |
Geometric parameters (Å, °) of hydrogen bonds top | Hydrogen bonds (HB) | D—H | H···A | D···A | D—H···A | Symmetry code |
I | | | | | | |
part1* | N1—H1···N2 | 0.76 (7) | 1.95 (7) | 2.704 (5) | 171 (7) | x, y, z |
| C12—H12···I4 | 0.95 | 3.23 | 4.079 (5) | 150 | x-1, y, z |
| C13—H13···I1 | 0.95 | 3.35 | 3.748 (5) | 108 | x-1, y, z |
| C13—H13···I3 | 0.95 | 3.24 | 4.058 (5) | 146 | x-1, y, z |
| C14—H14···I2 | 0.95 | 3.21 | 4.120 (5) | 161 | x-1, y, z |
| C15—H15···I3 | 0.95 | 3.15 | 3.904 (5) | 138 | x-1/2, y+3/2, z-1/2 |
| C15—H15···I4 | 0.95 | 3.36 | 4.076 (5) | 134 | -x+1/2, y+1/2, -z+3/2 |
part2* | C22—H22···I1 | 0.95 | 3.37 | 4.179 (5) | 144 | -x+1, -y+1, -z+1 |
| C23—H23···I2 | 0.95 | 3.17 | 4.048 (5) | 154 | x+1/2, -y+3/2, z-1/2 |
| C23—H23···I3 | 0.95 | 3.27 | 4.140 (5) | 153 | x+1/2, -y+3/2, z-1/2 |
| C25—H25···I5 | 0.95 | 3.27 | 4.177 (5) | 161 | -x+1/2, y+1/2, -z+3/2 |
| C25—H25···I6 | 0.95 | 3.26 | 3.842 (4) | 122 | -x+1/2, y+1/2, -z+3/2 |
II | | | | | | |
| N1—H1···I4 | 0.86 (4) | 2.76 (4) | 3.587 (3) | 160 (3) | -x+3/2, -y+3/2, z |
| N1—H1···I5 | 0.86 (4) | 3.25 (4) | 3.924 (3) | 137 (2) | -x+3/2, -y+3/2, z |
| C12—H12···I2 | 0.95 | 3.34 | 3.802 (3) | 154 | -x, y+1/2, -z+1/2 |
| C14—H14···I2 | 0.95 | 2.99 | 3.850 (3) | 134 | -x+1, y+1/2, -z+1/2 |
| C14—H14···I3 | 0.95 | 3.30 | 4.225 (3) | 164 | -x+1, y+1/2, -z+1/2 |
| C15—H15···I2 | 0.95 | 3.27 | 3.850 (3) | 122 | -x+1, y+1/2, -z+1/2 |
| C15—H15···I1 | 0.95 | 3.25 | 4.192 (3) | 172 | -x+1, y+1/2, -z+1/2 |
Note: (*) each part of the molecule consist of one pyridine ring and one
neighbouring S atom. |
Geometric parameters (Å, °) for halogen and chalcogen interactions top | | I/S···Y | R—I/S···X | Symmetry | |
Halogen bonds (XB) | | | | | |
I | | I3—I2···I6 | 3.166 (2) | 178 (1) | I3- anion |
| | I2—I3···I6 | 3.462 (5) | 164 (1) | x, y, z |
| | I5—–I4···I6 | 3.286 (3) | 170 (1) | x+1, y, z |
| | I4-I5···I6 | 3.374 (3) | 169 (1) | x, y, z |
| | I1i—I1···I6 | 3.492 (4) | 171 (1) | x, y, z |
II | | I3—I2···I1 | 3.178 (4) | 172 (1) | I5- anion |
| | I2—I4···I3 | 3.514 (5) | 180 (1) | x, y, z |
| | | | | |
Chalcogen bonds (ChB) | | | | | |
I | part1* | C11—S1···I1 | 3.91 (2) | 170 (1) | x, y, z |
II | part2* | C12—S2···S1 | 3.59 (2) | 171 (1) | x, -y+1, -z+1 |
| | C11—S1···I3 | 3.75 (9) | 168 (1) | x+1/2, y-1/2, -z+1 |
| | | | | |
I···I contacts | | | | | |
II | | I2···I2 | 4.153 (4) | | -x+1, -y+1, -z+1 |
| | I3···I4 | 4.159 (4) | | x, y, z |
| | I5···I2 | 4.260 (4) | | x, y, z |
| | I4···I4 | 4.368 (4) | | x, y, z |
Note: (*) each part of the molecule consists of one pyridine ring and one
neighbouring S atom. |
Percentage (%) of various atomic contacts to disulfide molecule surface top | H···N | H···I | H···all | S···I | S···S | S···all | all···I |
| N/C—H···N | N/C—H···I | | C—S···I | C—S···S | | |
| Hydrogen bonds | | | Chalcogen bonds | | | |
I | 1.1 | 34.8 | 54.7 | 9.4 | 4.3 | 16.6 | 51.1 |
II | 0 | 49.2 | 59.1 | 9.8 | 0 | 15.2 | 74.3 |
FARWIF | 0.6 | 22.3 | 57.1 | 5.1 | 4.9 | 16.8 | 36.3 |
FARWIF01 | 0.6 | 21.9 | 56.9 | 5.8 | 0.6 | 18.8 | 33.8 |
HAJWUL | 0.6 | 20.2 | 57.6 | 9.3 | 4.4 | 16.8 | 35.0 |