Ionic cocrystals of di­thio­bis­pyridines: the role of I⋯I halogen bonds in the building of iodine frameworks and the stabilization of crystal structures

Wzgarda-Raj, K.; Nawrot, M.; Rybarczyk-Pirek, A.J.; Palusiak, M.

doi:10.1107/S2053229621006306

Ionic cocrystals of dithiobispyridines: the role of II halogen bonds in the building of iodine frameworks and the stabilization of crystal structures

K. Wzgarda-Raj, M. Nawrot, A. J. Rybarczyk-Pirek and M. Palusiak

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.

Keywords: pyridine; cocrystal; salt; hydrogen bonding; halogen bonding; supramolecular chemistry; quantum chemistry; proton transfer; crystal structure; proton sponge.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229621006306/dg3017sup1.cif Contains datablocks structure_I, structure_II, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229621006306/dg3017structure_Isup2.hkl Contains datablock structure_I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229621006306/dg3017structure_IIsup3.hkl Contains datablock structure_II
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229621006306/dg3017structure_Isup4.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229621006306/dg3017structure_IIsup5.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229621006306/dg3017sup6.pdf Additional figures and tables

CCDC references: 2090706; 2090705

Computing details top

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
M_r = 982.71	D_x = 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	R_int = 0.041
CrysAlisPro 1.171.39.15e (Rigaku Oxford Diffraction, 2015 scans	θ_max = 30.9°, θ_min = 3.4°
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2020), based on expressions derived by Clark & Reid (1995)]	h = −13→12
T_min = 0.992, T_max = 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(F_o²) + 6.2162P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.047	(Δ/σ)_max = 0.002
S = 1.13	Δρ_max = 0.81 e Å⁻³
5952 reflections	Δρ_min = −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	U_iso*/U_eq
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⁻	D_x = 3.341 Mg m⁻³
M_r = 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	R_int = 0.042
ω scans	θ_max = 31.1°, θ_min = 3.3°
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2020), based on expressions derived by Clark & Reid (1995)]	h = −14→14
T_min = 0.995, T_max = 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(F_o²) + (0.0136P)² + 4.2557P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
3592 reflections	Δρ_max = 0.76 e Å⁻³
101 parameters	Δρ_min = −0.93 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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, 2_z symmetry)	2.037	–	1.765	–	1.346	84.4

4,4'-Dithiopyridines
II	double cation (2_z symmetry)	2.0389 (14)	–	1.764 (3)	–	1.343 (4) 1.343 (4)	78.4 (2)
XIWNAS	neutral (2_y symmetry)	2.032	1.780	–	1.329 1.335	-	84.0

Total molecular energies estimated for all possible tautomers (E_tot 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) top

E_tot Tautomer A	-1292.3270839
E_tot Tautomer B	-1292.3270839
E_tot 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

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Ionic cocrystals of di­thio­bis­pyridines: the role of II halogen bonds in the building of iodine frameworks and the stabilization of crystal structures

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Ionic cocrystals of dithiobispyridines: the role of II halogen bonds in the building of iodine frameworks and the stabilization of crystal structures