The reaction of thio­urea and 1,3-di­methyl­thio­urea towards organoiodines: oxidative bond formation and halogen bonding

By varying the halogen-bond-donor mol­ecule, 11 new halogen-bonding co­crys­tals involving thio­urea or 1,3-di­methyl­thio­urea were obtained, namely, 1,3-di­­methyl­thio­urea–1,2-di­iodo-3,4,5,6-tetra­fluoro­ben­zene (1/1), C₆F₄I₂·C₃H₈N₂S, 1, thio­­urea–1,3-di­iodo-2,4,5,6-tetra­fluoro­ben­zene (1/1), C₆F₄I₂·CH₄N₂S, 2, 1,3-di­methyl­thio­urea–1,3-di­iodo-2,4,5,6-tetra­fluoro­ben­zene (1/1), C₆F₄I₂·C₃H₈N₂S, 3, 1,3-di­methyl­thio­urea–1,3-di­iodo-2,4,5,6-tetra­fluoro­ben­zene–methanol (1/1/1), C₆F₄I₂·C₃H₈N₂S·CH₄O, 4, 1,3-di­methyl­thio­urea–1,3-di­iodo-2,4,5,6-tetra­fluoro­ben­zene–ethanol (1/1/1), C₆F₄I₂·C₃H₈N₂S·C₂H₆O, 5, 1,3-di­methyl­thio­urea–1,4-di­iodo-2,3,5,6-tetra­fluoro­ben­zene (1/1), C₆F₄I₂·C₃H₈N₂S, 6, 1,3-di­methyl­thio­urea–1,3,5-tri­fluoro-2,4,6-tri­iodo­ben­zene (1/1), C₆F₃I₃·C₃H₈N₂S, 7, 1,3-di­methyl­thio­urea–1,1,2,2-tetra­iodo­ethene (1/1), C₆H₁₆N₄S₂·C₂I₄, 8, [(di­methylamino)­methyl­idene](1,2,2-tri­iodo­ethen­yl)sulfonium iodide–1,1,2,2-tetra­iodo­ethene–acetone (1/1/1), C₅H₈I₃N₂S⁺·I⁻·C₃H₆O·C₂I₄, 9, 2-amino-4-methyl-1,3-thia­zol-3-ium iodide–1,1,2,2-tetra­iodo­ethene (2/3), 2C₄H₇N₂S⁺·2I⁻·3C₂I₄, 10, and 4,4-dimethyl-4H-1,3,5-thia­diazine-3,5-diium diiodide–1,1,2,2-tetra­iodo­ethene (2/3), 2C₅H₁₂N₄S²⁺·4I⁻·3C₂I₄, 11. When utilizing the common halogen-bond-donor mol­ecules 1,2-, 1,3-, and 1,4-di­iodo­tetra­fluoro­ben­zene, as well as 1,3,5-tri­fluoro-2,4,6-tri­iodo­ben­zene, bifurcated I...S...I inter­actions were observed, resulting in the formation of isolated rings, chains, and sheets. Tetra­iodo­ethyl­ene (TIE) provided I...S...I cocrystals as well, but further yielded a sulfonium-containing product through the reaction of the S atom with TIE. This particular sulfonium motif is the first of its kind to be structurally characterized, and is stabilized in the solid state through a three-dimensional I...I halogen-bonding network. Thio­urea reacted with acetone in the presence of TIE to provide two novel heterocyclic products, again stabilized in the solid state through I...I halogen bonding.

Computing details

Data collection: APEX3 (Bruker, 2017) for (1), (2), (3), (4), (5), (6), (7), (10), (11); CrysAlis PRO (Rigaku OD, 2020) for (8), (9). Cell refinement: SAINT (Bruker, 2017) for (1), (2), (3), (4), (5), (6), (7), (10), (11); CrysAlis PRO (Rigaku OD, 2020) for (8), (9). Data reduction: SAINT (Bruker, 2017) for (1), (2), (3), (4), (5), (6), (7), (10), (11); CrysAlis PRO (Rigaku OD, 2020) for (8), (9). For all structures, program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010) and OLEX2 (Dolomanov et al., 2009).

1,3-Dimethylthiourea–1,2-diiodo-3,4,5,6-tetrafluorobenzene (1/1) (1)

Crystal data

C6F4I2·C3H8N2S	F(000) = 936
Mr = 506.03	Dx = 2.462 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1701 (4) Å	Cell parameters from 8185 reflections
b = 7.9283 (3) Å	θ = 3.1–26.4°
c = 14.3228 (4) Å	µ = 4.79 mm^−1
β = 98.898 (1)°	T = 100 K
V = 1365.35 (8) Å^3	Plate, colourless
Z = 4	0.24 × 0.21 × 0.12 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3193 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.021
φ and ω scans	θmax = 28.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −16→16
Tmin = 0.595, Tmax = 0.745	k = −10→10
11592 measured reflections	l = −19→17
3328 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.015	Hydrogen site location: mixed
wR(F^2) = 0.032	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0068P)^2 + 0.7322P] where P = (Fo^2 + 2Fc^2)/3
3328 reflections	(Δ/σ)max = 0.002
173 parameters	Δρmax = 0.40 e Å^−3
2 restraints	Δρmin = −0.32 e Å^−3

Special details

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. 1. Fixed Uiso At 1.5 times of: All C(H,H,H) groups 2. Restrained distances H1N2-N2 = H1N1-N1 0.87 with sigma of 0.02 3.a Idealised Me refined as rotating group: C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.68526 (2)	0.43826 (2)	0.34599 (2)	0.01454 (4)
I2	0.68508 (2)	0.91268 (2)	0.36555 (2)	0.01440 (4)
F1	0.44702 (9)	1.00806 (13)	0.40403 (8)	0.0192 (2)
F2	0.26300 (9)	0.83115 (14)	0.41833 (8)	0.0203 (2)
F3	0.26260 (9)	0.49045 (14)	0.40307 (8)	0.0216 (2)
F4	0.44736 (10)	0.32658 (13)	0.37401 (9)	0.0220 (2)
C1	0.54789 (15)	0.5830 (2)	0.37247 (12)	0.0133 (3)
C2	0.54812 (15)	0.7589 (2)	0.38083 (12)	0.0130 (3)
C3	0.45180 (16)	0.8393 (2)	0.39706 (13)	0.0143 (3)
C4	0.35618 (15)	0.7505 (2)	0.40477 (12)	0.0149 (3)
C5	0.35571 (15)	0.5771 (2)	0.39634 (13)	0.0154 (4)
C6	0.45121 (16)	0.4955 (2)	0.38086 (13)	0.0156 (3)
S1	0.11856 (4)	0.82437 (6)	0.68872 (3)	0.01816 (10)
N2	−0.08338 (13)	0.8022 (2)	0.58644 (11)	0.0176 (3)
N1	0.06267 (14)	0.7483 (2)	0.50747 (11)	0.0200 (3)
C7	0.02646 (15)	0.7895 (2)	0.58804 (13)	0.0151 (3)
C8	−0.00758 (17)	0.7148 (3)	0.41781 (14)	0.0246 (4)
H8A	−0.047350	0.815454	0.396036	0.037*
H8B	−0.059595	0.627044	0.426005	0.037*
H8C	0.037788	0.679776	0.372135	0.037*
C9	−0.13552 (16)	0.8376 (3)	0.66947 (14)	0.0209 (4)
H9A	−0.214573	0.846388	0.651024	0.031*
H9B	−0.107126	0.941899	0.697532	0.031*
H9C	−0.119166	0.747877	0.714471	0.031*
H1N2	−0.1260 (18)	0.787 (3)	0.5348 (13)	0.024 (6)*
H1N1	0.1308 (14)	0.746 (3)	0.5100 (17)	0.026 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01526 (6)	0.01392 (6)	0.01417 (6)	0.00206 (4)	0.00142 (4)	−0.00056 (4)
I2	0.01310 (6)	0.01374 (6)	0.01611 (6)	−0.00219 (4)	0.00147 (4)	0.00009 (4)
F1	0.0200 (6)	0.0108 (5)	0.0271 (6)	0.0014 (4)	0.0049 (5)	−0.0002 (5)
F2	0.0143 (5)	0.0217 (6)	0.0257 (6)	0.0030 (4)	0.0058 (5)	−0.0004 (5)
F3	0.0168 (6)	0.0217 (6)	0.0266 (6)	−0.0082 (5)	0.0045 (5)	−0.0004 (5)
F4	0.0245 (6)	0.0108 (5)	0.0305 (6)	−0.0024 (4)	0.0034 (5)	0.0007 (5)
C1	0.0146 (8)	0.0128 (8)	0.0121 (8)	0.0015 (6)	0.0009 (7)	−0.0001 (6)
C2	0.0135 (8)	0.0129 (8)	0.0123 (8)	−0.0017 (7)	0.0005 (6)	0.0006 (7)
C3	0.0169 (9)	0.0119 (8)	0.0139 (8)	−0.0006 (7)	0.0017 (7)	−0.0006 (7)
C4	0.0132 (8)	0.0180 (9)	0.0133 (8)	0.0015 (7)	0.0021 (7)	−0.0001 (7)
C5	0.0148 (9)	0.0167 (9)	0.0144 (8)	−0.0055 (7)	0.0015 (7)	0.0021 (7)
C6	0.0204 (9)	0.0108 (8)	0.0151 (8)	−0.0008 (7)	0.0010 (7)	0.0012 (7)
S1	0.0120 (2)	0.0264 (2)	0.0160 (2)	−0.00103 (17)	0.00183 (17)	−0.00110 (18)
N2	0.0125 (8)	0.0252 (8)	0.0152 (7)	0.0004 (6)	0.0022 (6)	−0.0012 (7)
N1	0.0110 (8)	0.0338 (10)	0.0154 (7)	0.0017 (7)	0.0028 (6)	0.0000 (7)
C7	0.0132 (8)	0.0154 (8)	0.0169 (8)	−0.0006 (7)	0.0030 (7)	0.0027 (7)
C8	0.0200 (10)	0.0384 (12)	0.0152 (9)	0.0043 (9)	0.0022 (8)	−0.0023 (9)
C9	0.0147 (9)	0.0287 (10)	0.0207 (9)	0.0020 (8)	0.0069 (8)	−0.0038 (8)

Geometric parameters (Å, º)

I1—C1	2.1102 (18)	N2—C7	1.337 (2)
I2—C2	2.1037 (17)	N2—C9	1.459 (2)
F1—C3	1.343 (2)	N2—H1N2	0.843 (16)
F2—C4	1.342 (2)	N1—C7	1.338 (2)
F3—C5	1.341 (2)	N1—C8	1.453 (3)
F4—C6	1.343 (2)	N1—H1N1	0.824 (16)
C1—C2	1.399 (2)	C8—H8A	0.9600
C1—C6	1.387 (3)	C8—H8B	0.9600
C2—C3	1.385 (2)	C8—H8C	0.9600
C3—C4	1.379 (3)	C9—H9A	0.9600
C4—C5	1.380 (3)	C9—H9B	0.9600
C5—C6	1.378 (3)	C9—H9C	0.9600
S1—C7	1.7064 (19)
C2—C1—I1	124.49 (13)	C9—N2—H1N2	117.1 (16)
C6—C1—I1	116.70 (13)	C7—N1—C8	125.44 (16)
C6—C1—C2	118.80 (16)	C7—N1—H1N1	115.5 (17)
C1—C2—I2	124.03 (13)	C8—N1—H1N1	119.0 (17)
C3—C2—I2	117.09 (13)	N2—C7—S1	121.78 (14)
C3—C2—C1	118.85 (16)	N2—C7—N1	117.72 (17)
F1—C3—C2	121.22 (16)	N1—C7—S1	120.50 (14)
F1—C3—C4	117.13 (16)	N1—C8—H8A	109.5
C4—C3—C2	121.64 (16)	N1—C8—H8B	109.5
F2—C4—C3	120.69 (16)	N1—C8—H8C	109.5
F2—C4—C5	119.70 (16)	H8A—C8—H8B	109.5
C3—C4—C5	119.60 (17)	H8A—C8—H8C	109.5
F3—C5—C4	119.73 (17)	H8B—C8—H8C	109.5
F3—C5—C6	120.95 (16)	N2—C9—H9A	109.5
C6—C5—C4	119.33 (17)	N2—C9—H9B	109.5
F4—C6—C1	120.88 (16)	N2—C9—H9C	109.5
F4—C6—C5	117.34 (16)	H9A—C9—H9B	109.5
C5—C6—C1	121.78 (16)	H9A—C9—H9C	109.5
C7—N2—C9	124.06 (17)	H9B—C9—H9C	109.5
C7—N2—H1N2	118.9 (16)
I1—C1—C2—I2	1.4 (2)	C2—C1—C6—F4	−179.52 (16)
I1—C1—C2—C3	179.14 (13)	C2—C1—C6—C5	0.6 (3)
I1—C1—C6—F4	1.2 (2)	C2—C3—C4—F2	−178.46 (16)
I1—C1—C6—C5	−178.74 (14)	C2—C3—C4—C5	0.1 (3)
I2—C2—C3—F1	−0.9 (2)	C3—C4—C5—F3	−179.48 (16)
I2—C2—C3—C4	177.68 (14)	C3—C4—C5—C6	0.4 (3)
F1—C3—C4—F2	0.2 (3)	C4—C5—C6—F4	179.38 (16)
F1—C3—C4—C5	178.76 (16)	C4—C5—C6—C1	−0.7 (3)
F2—C4—C5—F3	−0.9 (3)	C6—C1—C2—I2	−177.85 (13)
F2—C4—C5—C6	178.93 (16)	C6—C1—C2—C3	−0.1 (3)
F3—C5—C6—F4	−0.8 (3)	C8—N1—C7—S1	179.62 (17)
F3—C5—C6—C1	179.15 (16)	C8—N1—C7—N2	−0.4 (3)
C1—C2—C3—F1	−178.85 (16)	C9—N2—C7—S1	−3.3 (3)
C1—C2—C3—C4	−0.2 (3)	C9—N2—C7—N1	176.79 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···I2^i	0.96	3.31	4.018 (2)	132
C8—H8C···S1^ii	0.96	2.94	3.844 (2)	157
N2—H1N2···I2^i	0.84 (2)	3.23 (2)	3.9949 (17)	152 (2)
N1—H1N1···I1^iii	0.82 (2)	3.16 (2)	3.7433 (17)	130 (2)
N1—H1N1···F2	0.82 (2)	2.33 (2)	2.9947 (19)	138 (2)

Symmetry codes: (i) x−1, y, z; (ii) x, −y+3/2, z−1/2; (iii) −x+1, −y+1, −z+1.

Thiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1) (2)

Crystal data

C6F4I2·CH4N2S	Dx = 2.702 Mg m^−3
Mr = 477.98	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9885 reflections
a = 8.5853 (5) Å	θ = 2.9–28.3°
b = 11.6911 (7) Å	µ = 5.56 mm^−1
c = 23.4148 (17) Å	T = 100 K
V = 2350.2 (3) Å^3	Needle, colourless
Z = 8	0.71 × 0.14 × 0.06 mm
F(000) = 1744

Data collection

Bruker D8 Venture Photon 2 diffractometer	2216 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.049
φ and ω scans	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −10→10
Tmin = 0.539, Tmax = 0.746	k = −14→14
19936 measured reflections	l = −29→25
2390 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: difference Fourier map
wR(F^2) = 0.046	All H-atom parameters refined
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0159P)^2 + 1.4818P] where P = (Fo^2 + 2Fc^2)/3
2390 reflections	(Δ/σ)max = 0.002
161 parameters	Δρmax = 0.63 e Å^−3
4 restraints	Δρmin = −0.87 e Å^−3

Special details

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. 1. Restrained distances N1-H1N1 = N1-H2N1 = N2-H1N2 = N2-H2N2 0.87 with sigma of 0.02

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.49699 (2)	0.64348 (2)	0.35989 (2)	0.01252 (7)
I2	0.48591 (2)	0.59659 (2)	0.10171 (2)	0.01365 (7)
F1	0.57601 (15)	0.67590 (12)	0.22765 (6)	0.0145 (3)
F2	0.26164 (17)	0.39328 (12)	0.14214 (6)	0.0170 (3)
F3	0.17367 (16)	0.31964 (12)	0.24596 (7)	0.0174 (3)
F4	0.28440 (17)	0.41971 (13)	0.34057 (7)	0.0181 (3)
C1	0.4305 (3)	0.5530 (2)	0.28645 (11)	0.0119 (5)
C2	0.4751 (3)	0.5877 (2)	0.23227 (12)	0.0119 (5)
C3	0.4230 (3)	0.5364 (2)	0.18259 (11)	0.0123 (5)
C4	0.3205 (3)	0.4451 (2)	0.18840 (11)	0.0123 (5)
C5	0.2746 (3)	0.4065 (2)	0.24136 (11)	0.0121 (5)
C6	0.3305 (3)	0.4597 (2)	0.28950 (11)	0.0124 (5)
S1	0.41741 (6)	0.21797 (5)	0.51991 (3)	0.01215 (13)
N1	0.5517 (3)	0.3874 (2)	0.46289 (11)	0.0159 (5)
H1N1	0.636 (3)	0.351 (3)	0.4705 (15)	0.032 (10)*
H2N1	0.551 (3)	0.441 (2)	0.4389 (11)	0.014 (7)*
N2	0.2854 (2)	0.39241 (19)	0.46591 (10)	0.0158 (5)
H1N2	0.198 (2)	0.363 (2)	0.4732 (14)	0.026 (9)*
H2N2	0.286 (3)	0.4534 (19)	0.4451 (12)	0.022 (8)*
C7	0.4185 (3)	0.3407 (2)	0.47968 (11)	0.0120 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01478 (10)	0.01182 (11)	0.01096 (11)	0.00087 (5)	−0.00204 (5)	−0.00065 (6)
I2	0.01521 (9)	0.01498 (11)	0.01076 (11)	0.00306 (6)	0.00116 (5)	0.00204 (6)
F1	0.0147 (7)	0.0120 (7)	0.0168 (8)	−0.0048 (6)	0.0012 (6)	0.0006 (6)
F2	0.0211 (8)	0.0145 (8)	0.0153 (8)	−0.0003 (6)	−0.0057 (6)	−0.0039 (6)
F3	0.0166 (7)	0.0111 (7)	0.0246 (9)	−0.0064 (6)	−0.0018 (6)	0.0014 (6)
F4	0.0226 (7)	0.0178 (8)	0.0138 (8)	−0.0033 (6)	0.0039 (6)	0.0025 (6)
C1	0.0113 (11)	0.0108 (12)	0.0136 (13)	0.0023 (9)	−0.0020 (9)	−0.0016 (10)
C2	0.0113 (11)	0.0065 (12)	0.0181 (15)	0.0007 (9)	0.0000 (9)	0.0019 (10)
C3	0.0120 (11)	0.0135 (13)	0.0114 (13)	0.0038 (9)	0.0013 (9)	0.0036 (10)
C4	0.0131 (10)	0.0123 (12)	0.0113 (13)	0.0034 (9)	−0.0043 (9)	−0.0030 (10)
C5	0.0096 (10)	0.0075 (12)	0.0190 (13)	−0.0006 (9)	−0.0003 (9)	0.0019 (9)
C6	0.0120 (11)	0.0129 (12)	0.0123 (13)	0.0032 (9)	0.0024 (9)	0.0041 (10)
S1	0.0114 (3)	0.0136 (3)	0.0113 (3)	0.0001 (2)	0.0007 (2)	0.0025 (2)
N1	0.0133 (10)	0.0135 (12)	0.0209 (13)	0.0014 (9)	0.0018 (9)	0.0059 (10)
N2	0.0122 (10)	0.0174 (12)	0.0178 (12)	0.0001 (9)	0.0011 (9)	0.0068 (9)
C7	0.0146 (12)	0.0147 (13)	0.0066 (12)	0.0024 (9)	0.0007 (9)	−0.0014 (9)

Geometric parameters (Å, º)

I1—C1	2.098 (3)	C4—C5	1.377 (4)
I2—C3	2.092 (2)	C5—C6	1.374 (4)
F1—C2	1.351 (3)	S1—C7	1.716 (3)
F2—C4	1.340 (3)	N1—H1N1	0.860 (18)
F3—C5	1.340 (3)	N1—H2N1	0.845 (18)
F4—C6	1.344 (3)	N1—C7	1.327 (3)
C1—C2	1.386 (4)	N2—H1N2	0.842 (17)
C1—C6	1.390 (3)	N2—H2N2	0.864 (17)
C2—C3	1.383 (4)	N2—C7	1.332 (3)
C3—C4	1.389 (3)
C2—C1—I1	121.83 (18)	C6—C5—C4	119.4 (2)
C2—C1—C6	116.6 (2)	F4—C6—C1	120.0 (2)
C6—C1—I1	121.45 (19)	F4—C6—C5	118.0 (2)
F1—C2—C1	118.3 (2)	C5—C6—C1	121.9 (2)
F1—C2—C3	118.1 (2)	H1N1—N1—H2N1	121 (3)
C3—C2—C1	123.6 (2)	C7—N1—H1N1	118 (2)
C2—C3—I2	122.12 (18)	C7—N1—H2N1	119.9 (19)
C2—C3—C4	117.1 (2)	H1N2—N2—H2N2	117 (3)
C4—C3—I2	120.72 (19)	C7—N2—H1N2	122 (2)
F2—C4—C3	120.4 (2)	C7—N2—H2N2	120 (2)
F2—C4—C5	118.2 (2)	N1—C7—S1	120.77 (19)
C5—C4—C3	121.4 (2)	N1—C7—N2	118.7 (2)
F3—C5—C4	120.4 (2)	N2—C7—S1	120.49 (19)
F3—C5—C6	120.2 (2)
I1—C1—C2—F1	6.3 (3)	C1—C2—C3—I2	177.22 (18)
I1—C1—C2—C3	−174.26 (18)	C1—C2—C3—C4	0.0 (4)
I1—C1—C6—F4	−5.5 (3)	C2—C1—C6—F4	178.8 (2)
I1—C1—C6—C5	173.74 (18)	C2—C1—C6—C5	−2.0 (3)
I2—C3—C4—F2	0.8 (3)	C2—C3—C4—F2	178.1 (2)
I2—C3—C4—C5	−178.19 (18)	C2—C3—C4—C5	−0.9 (4)
F1—C2—C3—I2	−3.4 (3)	C3—C4—C5—F3	178.9 (2)
F1—C2—C3—C4	179.4 (2)	C3—C4—C5—C6	0.4 (4)
F2—C4—C5—F3	−0.1 (3)	C4—C5—C6—F4	−179.6 (2)
F2—C4—C5—C6	−178.6 (2)	C4—C5—C6—C1	1.1 (4)
F3—C5—C6—F4	1.9 (3)	C6—C1—C2—F1	−178.0 (2)
F3—C5—C6—C1	−177.4 (2)	C6—C1—C2—C3	1.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1^i	0.86 (2)	2.56 (2)	3.397 (2)	166 (3)
N1—H2N1···I1	0.85 (2)	3.04 (2)	3.873 (2)	171 (2)
N2—H1N2···S1^ii	0.84 (2)	2.59 (2)	3.429 (2)	171 (3)
N2—H2N2···I2^iii	0.86 (2)	3.27 (3)	3.849 (2)	127 (2)
N2—H2N2···F4	0.86 (2)	2.48 (3)	2.952 (3)	115 (2)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z+1; (iii) x−1/2, y, −z+1/2.

1,3-Dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1) (3)

Crystal data

C6F4I2·C3H8N2S	Z = 2
Mr = 506.03	F(000) = 468
Triclinic, P1	Dx = 2.398 Mg m^−3
a = 7.1432 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8452 (6) Å	Cell parameters from 9938 reflections
c = 13.7688 (12) Å	θ = 2.8–28.4°
α = 83.922 (3)°	µ = 4.66 mm^−1
β = 76.598 (3)°	T = 100 K
γ = 69.092 (3)°	Plate, colourless
V = 700.94 (10) Å^3	0.21 × 0.13 × 0.02 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3065 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.028
φ and ω scans	θmax = 28.4°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −9→9
Tmin = 0.585, Tmax = 0.746	k = −10→10
13521 measured reflections	l = −18→18
3503 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.021	Hydrogen site location: mixed
wR(F^2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	w = 1/[σ^2(Fo^2) + 0.9448P] where P = (Fo^2 + 2Fc^2)/3
3503 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −0.76 e Å^−3

Special details

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. 1. Fixed Uiso At 1.5 times of: All C(H,H,H) groups 2.a Idealised Me refined as rotating group: C9(H2A,H2B,H2C), C8(H3A,H3B,H3C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.59583 (3)	0.62999 (3)	0.69302 (2)	0.01779 (5)
I2	0.78968 (3)	0.80193 (3)	0.25003 (2)	0.01946 (5)
F1	0.6682 (3)	0.8398 (2)	0.48582 (14)	0.0249 (4)
F2	0.9205 (3)	0.3655 (2)	0.25585 (13)	0.0210 (4)
F3	0.9085 (3)	0.1207 (2)	0.40756 (14)	0.0279 (4)
F4	0.7691 (3)	0.2312 (2)	0.59777 (14)	0.0272 (4)
C1	0.7160 (4)	0.5396 (4)	0.5463 (2)	0.0164 (6)
C2	0.7272 (4)	0.6621 (4)	0.4659 (2)	0.0175 (6)
C3	0.7939 (4)	0.6081 (4)	0.3677 (2)	0.0165 (6)
C4	0.8555 (4)	0.4253 (4)	0.3496 (2)	0.0165 (5)
C5	0.8503 (4)	0.2976 (4)	0.4272 (2)	0.0185 (6)
C6	0.7794 (4)	0.3564 (4)	0.5242 (2)	0.0176 (6)
S1	0.70630 (10)	0.17301 (10)	1.09889 (5)	0.01806 (14)
N1	0.7832 (4)	0.0555 (3)	0.91559 (19)	0.0167 (5)
H1N1	0.899 (5)	0.002 (4)	0.926 (3)	0.014 (8)*
N2	0.4593 (4)	0.2538 (3)	0.9684 (2)	0.0187 (5)
H1N2	0.442 (5)	0.243 (5)	0.911 (3)	0.021 (9)*
C7	0.6445 (4)	0.1598 (4)	0.9874 (2)	0.0149 (5)
C9	0.7500 (4)	0.0439 (4)	0.8165 (2)	0.0199 (6)
H2A	0.644886	−0.011572	0.821804	0.030*
H2B	0.878296	−0.031181	0.774686	0.030*
H2C	0.704606	0.166711	0.786381	0.030*
C8	0.2879 (4)	0.3777 (4)	1.0364 (2)	0.0245 (7)
H3A	0.224094	0.306624	1.087309	0.037*
H3B	0.186574	0.456251	0.998730	0.037*
H3C	0.337939	0.453344	1.068782	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01489 (9)	0.02297 (10)	0.01382 (10)	−0.00421 (7)	−0.00178 (7)	−0.00423 (7)
I2	0.02072 (9)	0.02260 (10)	0.01641 (10)	−0.00924 (7)	−0.00519 (7)	0.00306 (7)
F1	0.0331 (10)	0.0160 (8)	0.0223 (10)	−0.0058 (7)	−0.0023 (8)	−0.0038 (7)
F2	0.0225 (8)	0.0246 (9)	0.0133 (9)	−0.0058 (7)	−0.0003 (7)	−0.0061 (7)
F3	0.0394 (11)	0.0144 (8)	0.0238 (10)	−0.0028 (7)	−0.0033 (8)	−0.0054 (7)
F4	0.0384 (10)	0.0203 (9)	0.0168 (9)	−0.0054 (8)	−0.0038 (8)	0.0045 (7)
C1	0.0120 (12)	0.0205 (14)	0.0142 (14)	−0.0027 (10)	−0.0014 (10)	−0.0035 (11)
C2	0.0142 (12)	0.0165 (13)	0.0199 (15)	−0.0022 (10)	−0.0043 (11)	−0.0020 (11)
C3	0.0134 (12)	0.0200 (14)	0.0155 (14)	−0.0056 (10)	−0.0035 (10)	0.0025 (11)
C4	0.0123 (12)	0.0217 (14)	0.0139 (14)	−0.0037 (10)	−0.0017 (10)	−0.0035 (11)
C5	0.0150 (12)	0.0170 (13)	0.0212 (15)	−0.0026 (10)	−0.0025 (11)	−0.0041 (11)
C6	0.0162 (12)	0.0198 (14)	0.0143 (14)	−0.0038 (10)	−0.0034 (11)	0.0020 (11)
S1	0.0167 (3)	0.0217 (3)	0.0123 (3)	−0.0022 (3)	−0.0032 (3)	−0.0008 (3)
N1	0.0127 (11)	0.0194 (12)	0.0159 (12)	−0.0028 (9)	−0.0033 (9)	−0.0005 (9)
N2	0.0156 (11)	0.0219 (13)	0.0150 (13)	−0.0007 (9)	−0.0046 (10)	−0.0022 (10)
C7	0.0160 (12)	0.0147 (13)	0.0147 (13)	−0.0064 (10)	−0.0041 (10)	0.0025 (10)
C9	0.0191 (13)	0.0235 (15)	0.0162 (15)	−0.0061 (11)	−0.0019 (11)	−0.0054 (12)
C8	0.0174 (13)	0.0241 (15)	0.0224 (16)	0.0027 (11)	−0.0008 (12)	−0.0017 (12)

Geometric parameters (Å, º)

I1—C1	2.095 (3)	N1—H1N1	0.82 (3)
I2—C3	2.099 (3)	N1—C7	1.330 (4)
F1—C2	1.343 (3)	N1—C9	1.455 (4)
F2—C4	1.340 (3)	N2—H1N2	0.85 (4)
F3—C5	1.337 (3)	N2—C7	1.337 (3)
F4—C6	1.342 (3)	N2—C8	1.460 (4)
C1—C2	1.394 (4)	C9—H2A	0.9800
C1—C6	1.389 (4)	C9—H2B	0.9800
C2—C3	1.383 (4)	C9—H2C	0.9800
C3—C4	1.374 (4)	C8—H3A	0.9800
C4—C5	1.388 (4)	C8—H3B	0.9800
C5—C6	1.380 (4)	C8—H3C	0.9800
S1—C7	1.715 (3)
C2—C1—I1	121.3 (2)	C9—N1—H1N1	118 (2)
C6—C1—I1	121.6 (2)	C7—N2—H1N2	117 (2)
C6—C1—C2	117.0 (3)	C7—N2—C8	125.9 (3)
F1—C2—C1	117.9 (3)	C8—N2—H1N2	118 (2)
F1—C2—C3	119.4 (3)	N1—C7—S1	120.3 (2)
C3—C2—C1	122.7 (3)	N1—C7—N2	117.4 (3)
C2—C3—I2	120.6 (2)	N2—C7—S1	122.3 (2)
C4—C3—I2	121.2 (2)	N1—C9—H2A	109.5
C4—C3—C2	118.1 (3)	N1—C9—H2B	109.5
F2—C4—C3	120.6 (3)	N1—C9—H2C	109.5
F2—C4—C5	118.1 (3)	H2A—C9—H2B	109.5
C3—C4—C5	121.3 (3)	H2A—C9—H2C	109.5
F3—C5—C4	120.2 (3)	H2B—C9—H2C	109.5
F3—C5—C6	120.7 (3)	N2—C8—H3A	109.5
C6—C5—C4	119.1 (3)	N2—C8—H3B	109.5
F4—C6—C1	120.2 (3)	N2—C8—H3C	109.5
F4—C6—C5	118.1 (3)	H3A—C8—H3B	109.5
C5—C6—C1	121.7 (3)	H3A—C8—H3C	109.5
C7—N1—H1N1	117 (2)	H3B—C8—H3C	109.5
C7—N1—C9	124.5 (2)
I1—C1—C2—F1	3.4 (3)	C2—C1—C6—F4	−178.7 (2)
I1—C1—C2—C3	−175.9 (2)	C2—C1—C6—C5	0.0 (4)
I1—C1—C6—F4	−1.5 (4)	C2—C3—C4—F2	179.7 (2)
I1—C1—C6—C5	177.1 (2)	C2—C3—C4—C5	0.4 (4)
I2—C3—C4—F2	2.0 (4)	C3—C4—C5—F3	179.1 (2)
I2—C3—C4—C5	−177.3 (2)	C3—C4—C5—C6	0.8 (4)
F1—C2—C3—I2	−3.0 (4)	C4—C5—C6—F4	177.7 (3)
F1—C2—C3—C4	179.3 (2)	C4—C5—C6—C1	−1.0 (4)
F2—C4—C5—F3	−0.2 (4)	C6—C1—C2—F1	−179.5 (2)
F2—C4—C5—C6	−178.5 (2)	C6—C1—C2—C3	1.3 (4)
F3—C5—C6—F4	−0.6 (4)	C9—N1—C7—S1	−176.0 (2)
F3—C5—C6—C1	−179.3 (3)	C9—N1—C7—N2	3.2 (4)
C1—C2—C3—I2	176.2 (2)	C8—N2—C7—S1	0.2 (4)
C1—C2—C3—C4	−1.5 (4)	C8—N2—C7—N1	−178.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1^i	0.82 (3)	2.61 (3)	3.409 (2)	163 (3)
N2—H1N2···I2^ii	0.85 (4)	3.17 (4)	3.964 (3)	157 (3)
C9—H2A···I2^ii	0.98	3.28	3.904 (3)	123
C9—H2B···F2^iii	0.98	2.53	3.323 (3)	138
C9—H2B···F3^iii	0.98	2.64	3.499 (3)	147
C9—H2C···F4	0.98	2.56	3.204 (4)	123

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y, −z+1.

1,3-Dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–methanol (1/1/1) (4)

Crystal data

C6F4I2·C3H8N2S·CH4O	F(000) = 2016
Mr = 538.08	Dx = 2.227 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.3088 (13) Å	Cell parameters from 9389 reflections
b = 7.3062 (5) Å	θ = 2.7–28.3°
c = 22.8048 (15) Å	µ = 4.09 mm^−1
β = 93.930 (4)°	T = 100 K
V = 3209.6 (4) Å^3	Block, colourless
Z = 8	0.47 × 0.31 × 0.17 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3215 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.028
φ and ω scans	θmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −24→24
Tmin = 0.525, Tmax = 0.746	k = −9→9
49572 measured reflections	l = −28→28
3257 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.015	Hydrogen site location: mixed
wR(F^2) = 0.033	H atoms treated by a mixture of independent and constrained refinement
S = 1.31	w = 1/[σ^2(Fo^2) + 9.4854P] where P = (Fo^2 + 2Fc^2)/3
3257 reflections	(Δ/σ)max = 0.004
196 parameters	Δρmax = 0.47 e Å^−3
2 restraints	Δρmin = −0.54 e Å^−3

Special details

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. 1. Fixed Uiso At 1.5 times of: All C(H,H,H) groups 2. Restrained distances N1-H1N1 = N2-H1N2 0.88 with sigma of 0.02 3.a Idealised Me refined as rotating group: C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.69299 (2)	−0.08748 (2)	0.36122 (2)	0.01434 (4)
I2	0.69254 (2)	0.08093 (2)	0.62305 (2)	0.01309 (4)
F1	0.64299 (6)	−0.0076 (2)	0.48957 (6)	0.0201 (3)
F2	0.85509 (7)	0.0734 (2)	0.60133 (6)	0.0210 (3)
F3	0.92479 (7)	−0.0028 (2)	0.50567 (6)	0.0266 (3)
F4	0.85557 (7)	−0.0777 (2)	0.40225 (6)	0.0220 (3)
C1	0.74718 (11)	−0.0429 (3)	0.44336 (9)	0.0132 (4)
C2	0.71305 (11)	−0.0057 (3)	0.49353 (10)	0.0142 (4)
C3	0.74693 (11)	0.0328 (3)	0.54750 (9)	0.0132 (4)
C4	0.81883 (11)	0.0347 (3)	0.55030 (10)	0.0152 (4)
C5	0.85518 (11)	−0.0036 (3)	0.50172 (10)	0.0179 (5)
C6	0.81890 (12)	−0.0422 (3)	0.44885 (10)	0.0159 (4)
O1	0.51260 (11)	0.1828 (3)	0.16413 (9)	0.0317 (5)
C10	0.49978 (14)	0.1456 (4)	0.10290 (12)	0.0288 (6)
H10A	0.488154	0.259835	0.081949	0.043*
H10B	0.460978	0.059559	0.097122	0.043*
H10C	0.541405	0.091898	0.087583	0.043*
H1O1	0.5255 (19)	0.095 (5)	0.1793 (17)	0.047 (11)*
S1	0.61084 (3)	0.86192 (8)	0.23566 (2)	0.01583 (11)
N1	0.64726 (12)	0.5183 (3)	0.25782 (9)	0.0223 (4)
N2	0.55414 (10)	0.5519 (3)	0.19146 (9)	0.0165 (4)
C7	0.60294 (12)	0.6276 (3)	0.22693 (9)	0.0168 (5)
C8	0.64639 (14)	0.3192 (3)	0.25496 (11)	0.0241 (5)
H8A	0.648356	0.280017	0.214006	0.036*
H8B	0.603621	0.273254	0.270502	0.036*
H8C	0.686607	0.270301	0.278441	0.036*
C9	0.50573 (12)	0.6551 (3)	0.15256 (11)	0.0223 (5)
H9A	0.530632	0.709653	0.120852	0.034*
H9B	0.484455	0.752280	0.174887	0.034*
H9C	0.469479	0.573009	0.135733	0.034*
H1N1	0.6762 (14)	0.573 (4)	0.2814 (12)	0.036 (9)*
H1N2	0.5523 (16)	0.433 (2)	0.1891 (13)	0.030 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01746 (7)	0.01245 (7)	0.01277 (7)	0.00019 (5)	−0.00149 (5)	0.00007 (5)
I2	0.01364 (7)	0.01251 (7)	0.01303 (7)	0.00015 (5)	0.00016 (5)	0.00018 (5)
F1	0.0092 (6)	0.0318 (8)	0.0187 (7)	0.0002 (6)	−0.0018 (5)	−0.0023 (6)
F2	0.0160 (6)	0.0296 (8)	0.0167 (7)	−0.0022 (6)	−0.0049 (5)	−0.0030 (6)
F3	0.0105 (6)	0.0418 (9)	0.0275 (8)	−0.0011 (6)	0.0003 (5)	−0.0068 (7)
F4	0.0188 (7)	0.0284 (8)	0.0197 (7)	0.0006 (6)	0.0070 (5)	−0.0039 (6)
C1	0.0161 (10)	0.0102 (10)	0.0128 (10)	−0.0012 (8)	−0.0020 (8)	0.0016 (8)
C2	0.0110 (10)	0.0122 (11)	0.0193 (11)	0.0001 (8)	−0.0004 (8)	0.0015 (9)
C3	0.0157 (10)	0.0103 (10)	0.0139 (10)	−0.0001 (8)	0.0017 (8)	0.0021 (8)
C4	0.0155 (10)	0.0141 (11)	0.0155 (10)	−0.0020 (8)	−0.0033 (8)	0.0005 (8)
C5	0.0119 (10)	0.0191 (12)	0.0226 (12)	−0.0003 (9)	0.0005 (9)	0.0007 (9)
C6	0.0176 (11)	0.0138 (11)	0.0169 (11)	−0.0003 (9)	0.0042 (9)	0.0009 (9)
O1	0.0397 (11)	0.0169 (10)	0.0360 (11)	0.0006 (8)	−0.0152 (9)	0.0019 (8)
C10	0.0224 (12)	0.0270 (14)	0.0357 (15)	0.0010 (11)	−0.0062 (11)	0.0011 (12)
S1	0.0216 (3)	0.0128 (3)	0.0128 (2)	−0.0011 (2)	−0.0008 (2)	−0.0001 (2)
N1	0.0319 (12)	0.0145 (10)	0.0190 (10)	−0.0023 (9)	−0.0083 (9)	−0.0011 (8)
N2	0.0192 (10)	0.0123 (10)	0.0180 (10)	0.0000 (8)	0.0004 (7)	−0.0008 (8)
C7	0.0208 (11)	0.0188 (12)	0.0110 (10)	−0.0010 (9)	0.0027 (8)	−0.0004 (9)
C8	0.0336 (14)	0.0129 (11)	0.0241 (13)	−0.0007 (10)	−0.0101 (10)	−0.0001 (10)
C9	0.0176 (11)	0.0203 (12)	0.0282 (13)	0.0014 (10)	−0.0053 (10)	−0.0034 (10)

Geometric parameters (Å, º)

I1—C1	2.107 (2)	C10—H10B	0.9800
I2—C3	2.108 (2)	C10—H10C	0.9800
F1—C2	1.350 (2)	S1—C7	1.729 (2)
F2—C4	1.346 (3)	N1—C7	1.336 (3)
F3—C5	1.341 (3)	N1—C8	1.456 (3)
F4—C6	1.342 (3)	N1—H1N1	0.847 (18)
C1—C2	1.386 (3)	N2—C7	1.320 (3)
C1—C6	1.382 (3)	N2—C9	1.455 (3)
C2—C3	1.383 (3)	N2—H1N2	0.873 (18)
C3—C4	1.385 (3)	C8—H8A	0.9800
C4—C5	1.380 (3)	C8—H8B	0.9800
C5—C6	1.381 (3)	C8—H8C	0.9800
O1—C10	1.428 (3)	C9—H9A	0.9800
O1—H1O1	0.76 (4)	C9—H9B	0.9800
C10—H10A	0.9800	C9—H9C	0.9800
C2—C1—I1	121.94 (16)	H10A—C10—H10C	109.5
C6—C1—I1	120.97 (16)	H10B—C10—H10C	109.5
C6—C1—C2	117.0 (2)	C7—N1—C8	124.7 (2)
F1—C2—C1	118.29 (19)	C7—N1—H1N1	115 (2)
F1—C2—C3	118.20 (19)	C8—N1—H1N1	120 (2)
C3—C2—C1	123.5 (2)	C7—N2—C9	123.9 (2)
C2—C3—I2	121.99 (16)	C7—N2—H1N2	119 (2)
C2—C3—C4	117.0 (2)	C9—N2—H1N2	117 (2)
C4—C3—I2	120.96 (16)	N1—C7—S1	118.90 (18)
F2—C4—C3	120.1 (2)	N2—C7—S1	122.61 (18)
F2—C4—C5	118.3 (2)	N2—C7—N1	118.5 (2)
C5—C4—C3	121.6 (2)	N1—C8—H8A	109.5
F3—C5—C4	120.5 (2)	N1—C8—H8B	109.5
F3—C5—C6	120.4 (2)	N1—C8—H8C	109.5
C4—C5—C6	119.1 (2)	H8A—C8—H8B	109.5
F4—C6—C1	120.5 (2)	H8A—C8—H8C	109.5
F4—C6—C5	117.8 (2)	H8B—C8—H8C	109.5
C5—C6—C1	121.7 (2)	N2—C9—H9A	109.5
C10—O1—H1O1	108 (3)	N2—C9—H9B	109.5
O1—C10—H10A	109.5	N2—C9—H9C	109.5
O1—C10—H10B	109.5	H9A—C9—H9B	109.5
O1—C10—H10C	109.5	H9A—C9—H9C	109.5
H10A—C10—H10B	109.5	H9B—C9—H9C	109.5
I1—C1—C2—F1	3.4 (3)	C2—C1—C6—F4	179.8 (2)
I1—C1—C2—C3	−176.79 (17)	C2—C1—C6—C5	−0.9 (3)
I1—C1—C6—F4	−2.8 (3)	C2—C3—C4—F2	179.2 (2)
I1—C1—C6—C5	176.50 (18)	C2—C3—C4—C5	−1.2 (3)
I2—C3—C4—F2	−2.2 (3)	C3—C4—C5—F3	−179.3 (2)
I2—C3—C4—C5	177.44 (18)	C3—C4—C5—C6	0.9 (4)
F1—C2—C3—I2	1.7 (3)	C4—C5—C6—F4	179.6 (2)
F1—C2—C3—C4	−179.70 (19)	C4—C5—C6—C1	0.2 (4)
F2—C4—C5—F3	0.3 (3)	C6—C1—C2—F1	−179.28 (19)
F2—C4—C5—C6	−179.5 (2)	C6—C1—C2—C3	0.6 (3)
F3—C5—C6—F4	−0.2 (3)	C8—N1—C7—S1	179.7 (2)
F3—C5—C6—C1	−179.6 (2)	C8—N1—C7—N2	0.6 (4)
C1—C2—C3—I2	−178.19 (17)	C9—N2—C7—S1	5.2 (3)
C1—C2—C3—C4	0.4 (3)	C9—N2—C7—N1	−175.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···I2^i	0.98	3.23	4.071 (3)	145
O1—H1O1···S1^ii	0.76 (4)	2.64 (4)	3.366 (2)	160 (4)
C8—H8C···I1	0.98	3.22	3.900 (2)	128
C8—H8C···I2^iii	0.98	3.31	4.094 (2)	138
C9—H9B···S1^iv	0.98	2.95	3.825 (3)	149
C9—H9C···F2^v	0.98	2.53	3.485 (3)	165
N1—H1N1···I1^vi	0.85 (2)	3.08 (2)	3.788 (2)	142 (3)
N2—H1N2···O1	0.87 (2)	2.05 (2)	2.870 (3)	157 (3)

Symmetry codes: (i) x, −y, z−1/2; (ii) x, y−1, z; (iii) −x+3/2, −y+1/2, −z+1; (iv) −x+1, y, −z+1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) x, y+1, z.

1,3-Dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–ethanol (1/1/1) (5)

Crystal data

C6F4I2·C3H8N2S·C2H6O	F(000) = 2080
Mr = 552.10	Dx = 2.137 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.3027 (6) Å	Cell parameters from 9883 reflections
b = 7.5161 (2) Å	θ = 2.6–28.3°
c = 22.5373 (7) Å	µ = 3.83 mm^−1
β = 93.872 (1)°	T = 100 K
V = 3431.28 (17) Å^3	Needle, colourless
Z = 8	0.71 × 0.13 × 0.11 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3184 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.030
φ and ω scans	θmax = 26.4°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −25→25
Tmin = 0.557, Tmax = 0.746	k = −9→9
19838 measured reflections	l = −28→28
3503 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: mixed
wR(F^2) = 0.040	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0096P)^2 + 9.6716P] where P = (Fo^2 + 2Fc^2)/3
3503 reflections	(Δ/σ)max = 0.003
205 parameters	Δρmax = 0.76 e Å^−3
4 restraints	Δρmin = −0.72 e Å^−3

Special details

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. 1. Fixed Uiso At 1.2 times of: All C(H,H) groups At 1.5 times of: All C(H,H,H) groups 2. Restrained distances H1N1-N1 = H1N2-N2 0.86 with sigma of 0.02 H1O1-O1 0.98 with sigma of 0.02 H1O1-C11 1.82 with sigma of 0.04 3.a Secondary CH2 refined with riding coordinates: C11(H11A,H11B) 3.b Idealised Me refined as rotating group: C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.20033 (2)	0.38219 (2)	0.36229 (2)	0.01850 (5)
I2	0.19459 (2)	0.60809 (2)	0.62173 (2)	0.01944 (5)
F1	0.14979 (7)	0.4940 (2)	0.48826 (7)	0.0267 (3)
F2	0.34941 (8)	0.5854 (2)	0.60315 (7)	0.0310 (4)
F3	0.41776 (8)	0.4901 (3)	0.50981 (8)	0.0405 (4)
F4	0.35388 (7)	0.4008 (2)	0.40545 (7)	0.0303 (4)
C1	0.24995 (12)	0.4456 (3)	0.44455 (12)	0.0186 (5)
C2	0.21655 (12)	0.4936 (3)	0.49368 (12)	0.0194 (5)
C3	0.24747 (12)	0.5417 (3)	0.54762 (12)	0.0194 (5)
C4	0.31598 (13)	0.5404 (3)	0.55186 (12)	0.0223 (5)
C5	0.35129 (13)	0.4916 (4)	0.50433 (13)	0.0255 (6)
C6	0.31815 (13)	0.4451 (3)	0.45144 (12)	0.0221 (5)
S1	0.37863 (3)	0.80902 (8)	0.26243 (3)	0.02194 (13)
N1	0.34026 (11)	0.4758 (3)	0.24367 (11)	0.0228 (5)
H1N1	0.3102 (12)	0.527 (4)	0.2219 (13)	0.033 (9)*
N2	0.43628 (11)	0.5079 (3)	0.30155 (11)	0.0251 (5)
H1N2	0.4381 (17)	0.396 (2)	0.3026 (16)	0.040 (10)*
C7	0.38636 (12)	0.5819 (3)	0.27005 (11)	0.0197 (5)
C8	0.34055 (15)	0.2823 (3)	0.24757 (14)	0.0294 (6)
H8A	0.300280	0.235019	0.226901	0.044*
H8B	0.342348	0.246318	0.289446	0.044*
H8C	0.379226	0.235388	0.228998	0.044*
C9	0.48727 (15)	0.6067 (4)	0.33605 (15)	0.0365 (7)
H9A	0.506899	0.694784	0.310469	0.055*
H9B	0.521536	0.524349	0.351837	0.055*
H9C	0.467694	0.667533	0.369059	0.055*
O1	0.48604 (16)	0.1480 (5)	0.31261 (13)	0.0715 (10)
H1O1	0.516 (2)	0.148 (10)	0.2822 (17)	0.23 (4)*
C10	0.49799 (19)	0.1374 (6)	0.41953 (18)	0.0558 (10)
H10A	0.477138	0.254948	0.416500	0.084*
H10B	0.537389	0.143345	0.447080	0.084*
H10C	0.466782	0.051248	0.434325	0.084*
C11	0.5164 (2)	0.0830 (5)	0.36227 (17)	0.0578 (11)
H11A	0.564020	0.109476	0.360624	0.069*
H11B	0.511784	−0.047999	0.360440	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02101 (8)	0.01546 (8)	0.01880 (9)	0.00158 (6)	−0.00048 (6)	0.00123 (6)
I2	0.02346 (9)	0.01542 (8)	0.01928 (9)	−0.00058 (6)	0.00028 (6)	0.00124 (6)
F1	0.0176 (7)	0.0373 (9)	0.0250 (9)	0.0027 (6)	−0.0001 (6)	−0.0044 (7)
F2	0.0266 (8)	0.0424 (10)	0.0230 (9)	−0.0068 (7)	−0.0056 (7)	−0.0028 (7)
F3	0.0168 (8)	0.0683 (13)	0.0360 (11)	−0.0032 (8)	−0.0006 (7)	−0.0080 (9)
F4	0.0226 (8)	0.0425 (10)	0.0262 (9)	0.0008 (7)	0.0059 (7)	−0.0032 (7)
C1	0.0209 (12)	0.0138 (11)	0.0206 (13)	−0.0012 (9)	−0.0012 (10)	0.0028 (9)
C2	0.0186 (12)	0.0156 (12)	0.0238 (14)	0.0010 (9)	−0.0005 (10)	0.0028 (10)
C3	0.0243 (13)	0.0145 (12)	0.0194 (13)	−0.0009 (9)	0.0017 (10)	0.0031 (9)
C4	0.0246 (13)	0.0208 (13)	0.0206 (14)	−0.0032 (10)	−0.0052 (11)	0.0033 (10)
C5	0.0169 (12)	0.0294 (14)	0.0299 (16)	−0.0017 (10)	−0.0008 (11)	0.0043 (11)
C6	0.0221 (13)	0.0219 (13)	0.0226 (14)	−0.0012 (10)	0.0035 (11)	0.0031 (10)
S1	0.0294 (3)	0.0181 (3)	0.0180 (3)	−0.0009 (2)	−0.0008 (3)	0.0009 (2)
N1	0.0259 (12)	0.0187 (11)	0.0233 (12)	0.0007 (9)	−0.0015 (10)	0.0016 (9)
N2	0.0231 (11)	0.0257 (13)	0.0263 (13)	0.0003 (9)	0.0012 (10)	0.0090 (10)
C7	0.0233 (12)	0.0211 (12)	0.0156 (13)	0.0012 (10)	0.0067 (10)	0.0029 (10)
C8	0.0371 (16)	0.0175 (13)	0.0339 (17)	−0.0030 (11)	0.0046 (13)	−0.0008 (11)
C9	0.0265 (15)	0.0446 (18)	0.0370 (19)	−0.0038 (13)	−0.0083 (13)	0.0138 (14)
O1	0.076 (2)	0.104 (2)	0.0348 (15)	0.0625 (18)	0.0025 (14)	0.0046 (15)
C10	0.049 (2)	0.074 (3)	0.043 (2)	0.0136 (19)	−0.0079 (17)	0.0009 (19)
C11	0.080 (3)	0.048 (2)	0.046 (2)	0.040 (2)	0.005 (2)	0.0068 (17)

Geometric parameters (Å, º)

I1—C1	2.104 (3)	N2—C7	1.320 (3)
I2—C3	2.106 (3)	N2—C9	1.456 (4)
F1—C2	1.353 (3)	C8—H8A	0.9800
F2—C4	1.344 (3)	C8—H8B	0.9800
F3—C5	1.347 (3)	C8—H8C	0.9800
F4—C6	1.347 (3)	C9—H9A	0.9800
C1—C2	1.385 (4)	C9—H9B	0.9800
C1—C6	1.383 (3)	C9—H9C	0.9800
C2—C3	1.378 (4)	O1—H1O1	0.94 (2)
C3—C4	1.388 (4)	O1—C11	1.333 (4)
C4—C5	1.378 (4)	C10—H10A	0.9800
C5—C6	1.374 (4)	C10—H10B	0.9800
S1—C7	1.722 (3)	C10—H10C	0.9800
N1—H1N1	0.850 (18)	C10—C11	1.427 (5)
N1—C7	1.338 (3)	C11—H11A	0.9900
N1—C8	1.457 (3)	C11—H11B	0.9900
N2—H1N2	0.840 (18)
C2—C1—I1	122.16 (18)	N2—C7—N1	118.5 (2)
C6—C1—I1	120.96 (19)	N1—C8—H8A	109.5
C6—C1—C2	116.9 (2)	N1—C8—H8B	109.5
F1—C2—C1	118.0 (2)	N1—C8—H8C	109.5
F1—C2—C3	118.2 (2)	H8A—C8—H8B	109.5
C3—C2—C1	123.7 (2)	H8A—C8—H8C	109.5
C2—C3—I2	122.38 (19)	H8B—C8—H8C	109.5
C2—C3—C4	117.0 (2)	N2—C9—H9A	109.5
C4—C3—I2	120.62 (19)	N2—C9—H9B	109.5
F2—C4—C3	120.2 (2)	N2—C9—H9C	109.5
F2—C4—C5	118.5 (2)	H9A—C9—H9B	109.5
C5—C4—C3	121.3 (2)	H9A—C9—H9C	109.5
F3—C5—C4	120.1 (3)	H9B—C9—H9C	109.5
F3—C5—C6	120.4 (2)	C11—O1—H1O1	109 (3)
C6—C5—C4	119.5 (2)	H10A—C10—H10B	109.5
F4—C6—C1	120.1 (2)	H10A—C10—H10C	109.5
F4—C6—C5	118.2 (2)	H10B—C10—H10C	109.5
C5—C6—C1	121.6 (2)	C11—C10—H10A	109.5
C7—N1—H1N1	116 (2)	C11—C10—H10B	109.5
C7—N1—C8	124.6 (2)	C11—C10—H10C	109.5
C8—N1—H1N1	119 (2)	O1—C11—C10	121.3 (3)
C7—N2—H1N2	118 (2)	O1—C11—H11A	107.0
C7—N2—C9	124.4 (2)	O1—C11—H11B	107.0
C9—N2—H1N2	118 (2)	C10—C11—H11A	107.0
N1—C7—S1	119.4 (2)	C10—C11—H11B	107.0
N2—C7—S1	122.2 (2)	H11A—C11—H11B	106.7
I1—C1—C2—F1	1.9 (3)	C2—C1—C6—F4	−179.6 (2)
I1—C1—C2—C3	−177.73 (19)	C2—C1—C6—C5	−0.6 (4)
I1—C1—C6—F4	−1.1 (3)	C2—C3—C4—F2	−179.9 (2)
I1—C1—C6—C5	177.9 (2)	C2—C3—C4—C5	−0.6 (4)
I2—C3—C4—F2	−1.5 (3)	C3—C4—C5—F3	−179.4 (2)
I2—C3—C4—C5	177.8 (2)	C3—C4—C5—C6	0.7 (4)
F1—C2—C3—I2	1.8 (3)	C4—C5—C6—F4	178.9 (2)
F1—C2—C3—C4	−179.9 (2)	C4—C5—C6—C1	−0.1 (4)
F2—C4—C5—F3	−0.1 (4)	C6—C1—C2—F1	−179.6 (2)
F2—C4—C5—C6	−180.0 (2)	C6—C1—C2—C3	0.8 (4)
F3—C5—C6—F4	−0.9 (4)	C8—N1—C7—S1	−178.9 (2)
F3—C5—C6—C1	−180.0 (2)	C8—N1—C7—N2	0.7 (4)
C1—C2—C3—I2	−178.57 (18)	C9—N2—C7—S1	4.2 (4)
C1—C2—C3—C4	−0.2 (4)	C9—N2—C7—N1	−175.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···I1^i	0.85 (2)	3.27 (3)	3.930 (2)	136 (3)
N1—H1N1···I2^ii	0.85 (2)	3.31 (3)	3.950 (2)	135 (3)
N2—H1N2···O1	0.84 (2)	2.11 (2)	2.892 (4)	155 (3)
C8—H8A···I1^iii	0.98	3.33	3.948 (3)	123
C8—H8A···I2^ii	0.98	3.31	4.046 (3)	134
O1—H1O1···O1^iv	0.94 (2)	2.13 (4)	2.916 (6)	139 (5)
C11—H11A···I1^v	0.99	3.25	4.028 (4)	137

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, −y+1, z−1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, y, −z+1/2; (v) x+1/2, y−1/2, z.

1,3-Dimethylthiourea–1,4-diiodo-2,3,5,6-tetrafluorobenzene (1/1) (6)

Crystal data

C6F4I2·C3H8N2S	F(000) = 1872
Mr = 506.03	Dx = 2.425 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 26.134 (3) Å	Cell parameters from 9827 reflections
b = 7.4435 (7) Å	θ = 2.9–27.1°
c = 14.7320 (15) Å	µ = 4.72 mm^−1
β = 104.650 (4)°	T = 100 K
V = 2772.6 (5) Å^3	Block, colourless
Z = 8	0.29 × 0.26 × 0.25 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3269 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.041
φ and ω scans	θmax = 28.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −34→34
Tmin = 0.553, Tmax = 0.746	k = −9→9
33517 measured reflections	l = −19→19
3437 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	Hydrogen site location: mixed
wR(F^2) = 0.036	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0031P)^2 + 6.3061P] where P = (Fo^2 + 2Fc^2)/3
3437 reflections	(Δ/σ)max = 0.003
171 parameters	Δρmax = 0.45 e Å^−3
2 restraints	Δρmin = −0.50 e Å^−3

Special details

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. 1. Fixed Uiso At 1.2 times of: All C(H,H) groups At 1.5 times of: All C(H,H,H) groups 2. Restrained distances H1N2-N2 = HN2-N1 0.86 with sigma of 0.02 3.a Idealised Me refined as rotating group: C9(H7A,H7B,H7C), C8(H9A,H9B,H9C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.63937 (2)	0.39490 (2)	0.52958 (2)	0.01536 (4)
I2	0.38319 (2)	0.23670 (2)	0.25384 (2)	0.01541 (4)
F1	0.57149 (6)	0.03964 (19)	0.47245 (12)	0.0324 (4)
F2	0.47434 (6)	−0.02057 (19)	0.36575 (12)	0.0338 (4)
F3	0.45086 (5)	0.60257 (18)	0.30995 (11)	0.0258 (3)
F4	0.54797 (6)	0.66288 (18)	0.41875 (11)	0.0277 (3)
C1	0.56177 (8)	0.3531 (3)	0.44991 (15)	0.0154 (4)
C2	0.54163 (9)	0.1809 (3)	0.43461 (17)	0.0195 (5)
C3	0.49160 (9)	0.1494 (3)	0.37897 (17)	0.0195 (5)
C4	0.45947 (9)	0.2899 (3)	0.33646 (15)	0.0161 (4)
C5	0.47963 (9)	0.4620 (3)	0.35099 (15)	0.0164 (4)
C6	0.53006 (9)	0.4932 (3)	0.40700 (16)	0.0169 (4)
S1	0.26387 (2)	−0.09732 (7)	0.64014 (4)	0.01520 (10)
N2	0.31816 (8)	0.1777 (3)	0.59372 (14)	0.0196 (4)
N1	0.27648 (7)	−0.0063 (2)	0.47348 (13)	0.0159 (4)
C9	0.33236 (11)	0.2472 (3)	0.68943 (18)	0.0276 (6)
H7A	0.342977	0.373332	0.688743	0.041*
H7B	0.361806	0.176957	0.727380	0.041*
H7C	0.301828	0.237909	0.716440	0.041*
C7	0.28792 (8)	0.0336 (3)	0.56445 (15)	0.0140 (4)
C8	0.29985 (10)	0.0837 (3)	0.40590 (17)	0.0217 (5)
H9A	0.287783	0.025348	0.344579	0.033*
H9B	0.338488	0.076283	0.427034	0.033*
H9C	0.289021	0.210145	0.400613	0.033*
H1N2	0.3295 (11)	0.238 (3)	0.5543 (17)	0.026*
HN2	0.2598 (10)	−0.101 (3)	0.455 (2)	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01263 (7)	0.01554 (7)	0.01666 (7)	−0.00109 (5)	0.00137 (5)	−0.00121 (5)
I2	0.01264 (7)	0.01754 (7)	0.01515 (7)	−0.00110 (5)	0.00188 (5)	0.00024 (5)
F1	0.0207 (7)	0.0151 (7)	0.0510 (10)	0.0025 (6)	−0.0103 (7)	0.0051 (7)
F2	0.0235 (7)	0.0137 (7)	0.0542 (10)	−0.0046 (6)	−0.0083 (7)	0.0026 (7)
F3	0.0209 (7)	0.0144 (6)	0.0358 (8)	0.0035 (5)	−0.0044 (6)	0.0043 (6)
F4	0.0237 (7)	0.0112 (6)	0.0415 (9)	−0.0027 (5)	−0.0040 (6)	−0.0011 (6)
C1	0.0119 (9)	0.0184 (10)	0.0152 (10)	−0.0006 (8)	0.0019 (8)	−0.0030 (8)
C2	0.0158 (10)	0.0143 (10)	0.0259 (12)	0.0031 (8)	0.0009 (9)	0.0037 (9)
C3	0.0178 (11)	0.0128 (10)	0.0261 (12)	−0.0035 (8)	0.0024 (9)	−0.0002 (9)
C4	0.0136 (10)	0.0173 (10)	0.0169 (10)	−0.0016 (8)	0.0033 (8)	−0.0010 (8)
C5	0.0152 (10)	0.0144 (10)	0.0188 (10)	0.0025 (8)	0.0031 (8)	0.0016 (8)
C6	0.0169 (10)	0.0116 (9)	0.0217 (11)	−0.0013 (8)	0.0037 (8)	−0.0030 (8)
S1	0.0141 (2)	0.0170 (2)	0.0134 (2)	−0.00255 (19)	0.00140 (19)	0.00076 (19)
N2	0.0206 (10)	0.0150 (9)	0.0213 (10)	−0.0058 (7)	0.0021 (8)	0.0011 (8)
N1	0.0186 (9)	0.0132 (8)	0.0161 (9)	−0.0031 (7)	0.0047 (7)	0.0005 (7)
C9	0.0317 (14)	0.0193 (12)	0.0255 (13)	−0.0059 (10)	−0.0046 (10)	−0.0058 (10)
C7	0.0108 (9)	0.0124 (9)	0.0172 (10)	0.0015 (7)	0.0007 (8)	0.0012 (8)
C8	0.0269 (12)	0.0199 (11)	0.0205 (11)	0.0027 (9)	0.0097 (9)	0.0053 (9)

Geometric parameters (Å, º)

I1—C1	2.093 (2)	N2—C9	1.459 (3)
I2—C4	2.094 (2)	N2—C7	1.337 (3)
F1—C2	1.344 (2)	N2—H1N2	0.844 (17)
F2—C3	1.341 (3)	N1—C7	1.331 (3)
F3—C5	1.340 (2)	N1—C8	1.456 (3)
F4—C6	1.343 (2)	N1—HN2	0.835 (17)
C1—C2	1.382 (3)	C9—H7A	0.9800
C1—C6	1.382 (3)	C9—H7B	0.9800
C2—C3	1.376 (3)	C9—H7C	0.9800
C3—C4	1.387 (3)	C8—H9A	0.9800
C4—C5	1.381 (3)	C8—H9B	0.9800
C5—C6	1.386 (3)	C8—H9C	0.9800
S1—C7	1.715 (2)
C2—C1—I1	120.29 (16)	C7—N2—H1N2	119 (2)
C2—C1—C6	117.76 (19)	C7—N1—C8	124.04 (19)
C6—C1—I1	121.87 (16)	C7—N1—HN2	118 (2)
F1—C2—C1	120.05 (19)	C8—N1—HN2	116 (2)
F1—C2—C3	118.6 (2)	N2—C9—H7A	109.5
C3—C2—C1	121.4 (2)	N2—C9—H7B	109.5
F2—C3—C2	118.8 (2)	N2—C9—H7C	109.5
F2—C3—C4	120.2 (2)	H7A—C9—H7B	109.5
C2—C3—C4	121.0 (2)	H7A—C9—H7C	109.5
C3—C4—I2	119.88 (16)	H7B—C9—H7C	109.5
C5—C4—I2	122.36 (16)	N2—C7—S1	121.99 (17)
C5—C4—C3	117.76 (19)	N1—C7—S1	120.14 (16)
F3—C5—C4	120.40 (19)	N1—C7—N2	117.9 (2)
F3—C5—C6	118.55 (19)	N1—C8—H9A	109.5
C4—C5—C6	121.0 (2)	N1—C8—H9B	109.5
F4—C6—C1	120.12 (19)	N1—C8—H9C	109.5
F4—C6—C5	118.85 (19)	H9A—C8—H9B	109.5
C1—C6—C5	121.0 (2)	H9A—C8—H9C	109.5
C9—N2—H1N2	115 (2)	H9B—C8—H9C	109.5
C7—N2—C9	125.5 (2)
I1—C1—C2—F1	1.3 (3)	C2—C1—C6—F4	−179.3 (2)
I1—C1—C2—C3	−177.01 (19)	C2—C1—C6—C5	0.4 (3)
I1—C1—C6—F4	−2.7 (3)	C2—C3—C4—I2	−179.14 (19)
I1—C1—C6—C5	177.02 (17)	C2—C3—C4—C5	0.7 (4)
I2—C4—C5—F3	−1.7 (3)	C3—C4—C5—F3	178.4 (2)
I2—C4—C5—C6	179.21 (17)	C3—C4—C5—C6	−0.7 (3)
F1—C2—C3—F2	0.9 (4)	C4—C5—C6—F4	179.8 (2)
F1—C2—C3—C4	−178.6 (2)	C4—C5—C6—C1	0.1 (4)
F2—C3—C4—I2	1.4 (3)	C6—C1—C2—F1	178.0 (2)
F2—C3—C4—C5	−178.8 (2)	C6—C1—C2—C3	−0.3 (4)
F3—C5—C6—F4	0.6 (3)	C9—N2—C7—S1	−3.2 (3)
F3—C5—C6—C1	−179.0 (2)	C9—N2—C7—N1	176.5 (2)
C1—C2—C3—F2	179.3 (2)	C8—N1—C7—S1	−172.61 (17)
C1—C2—C3—C4	−0.2 (4)	C8—N1—C7—N2	7.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H7A···I2^i	0.98	3.15	4.097 (2)	162
C9—H7B···I2^ii	0.98	3.14	3.873 (3)	133
C8—H9A···S1^iii	0.98	2.97	3.790 (2)	142
C8—H9B···F1^iv	0.98	2.59	3.509 (3)	156
N2—H1N2···I1^v	0.84 (2)	3.19 (2)	3.959 (2)	153 (2)
N1—HN2···S1^vi	0.84 (2)	2.64 (2)	3.4246 (19)	157 (3)

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y, z+1/2; (iii) x, −y, z−1/2; (iv) −x+1, −y, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1/2, −y−1/2, −z+1.

1,3-Dimethylthiourea–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1) (7)

Crystal data

C6F3I3·C3H8N2S	Z = 2
Mr = 613.93	F(000) = 556
Triclinic, P1	Dx = 2.664 Mg m^−3
a = 7.5014 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1065 (8) Å	Cell parameters from 9841 reflections
c = 11.8534 (10) Å	θ = 2.4–26.4°
α = 79.871 (3)°	µ = 6.28 mm^−1
β = 83.011 (3)°	T = 100 K
γ = 74.410 (3)°	Block, colourless
V = 765.41 (11) Å^3	0.16 × 0.16 × 0.11 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3075 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.024
φ and ω scans	θmax = 26.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −9→9
Tmin = 0.660, Tmax = 0.745	k = −11→11
19222 measured reflections	l = −14→14
3136 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.011	Hydrogen site location: mixed
wR(F^2) = 0.024	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0027P)^2 + 0.5036P] where P = (Fo^2 + 2Fc^2)/3
3136 reflections	(Δ/σ)max = 0.003
173 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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. 1. Fixed Uiso At 1.5 times of: All C(H,H,H) groups 2.a Idealised Me refined as rotating group: C9(H7A,H7B,H7C), C8(H9A,H9B,H9C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.75725 (2)	0.31998 (2)	0.81611 (2)	0.01463 (3)
I2	0.79515 (2)	0.87867 (2)	0.45987 (2)	0.01644 (3)
I3	0.72964 (2)	0.29766 (2)	0.30857 (2)	0.01354 (3)
F1	0.79845 (14)	0.65146 (12)	0.69756 (9)	0.0170 (2)
F2	0.75836 (15)	0.63852 (12)	0.30796 (9)	0.0192 (2)
F3	0.70683 (15)	0.21127 (12)	0.58317 (9)	0.0173 (2)
C1	0.7551 (2)	0.4277 (2)	0.64448 (15)	0.0130 (3)
C2	0.7765 (2)	0.5763 (2)	0.61403 (15)	0.0133 (3)
C3	0.7750 (2)	0.65157 (19)	0.50197 (15)	0.0135 (3)
C4	0.7571 (2)	0.5695 (2)	0.41807 (15)	0.0133 (3)
C5	0.7379 (2)	0.4196 (2)	0.44187 (15)	0.0127 (3)
C6	0.7335 (2)	0.35391 (19)	0.55622 (15)	0.0132 (3)
S1	0.24620 (6)	0.85328 (5)	0.91900 (4)	0.01561 (9)
N2	0.4476 (2)	1.05856 (19)	0.85184 (13)	0.0156 (3)
H1N1	0.459 (3)	1.144 (3)	0.8489 (19)	0.020 (6)*
N1	0.1924 (2)	1.13121 (18)	0.97550 (14)	0.0164 (3)
H1N2	0.099 (3)	1.113 (3)	1.0041 (19)	0.019 (6)*
C9	0.5780 (2)	0.9580 (2)	0.77948 (15)	0.0171 (4)
H7A	0.535590	0.978718	0.701895	0.026*
H7B	0.585126	0.850100	0.812051	0.026*
H7C	0.701019	0.977451	0.775811	0.026*
C7	0.2992 (2)	1.0268 (2)	0.91426 (15)	0.0142 (3)
C8	0.2193 (3)	1.2827 (2)	0.97788 (17)	0.0197 (4)
H9A	0.199510	1.345672	0.902228	0.030*
H9B	0.346003	1.272022	0.997090	0.030*
H9C	0.130395	1.332740	1.035916	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01697 (6)	0.01593 (6)	0.01194 (6)	−0.00672 (4)	−0.00179 (4)	−0.00015 (4)
I2	0.01838 (6)	0.00930 (6)	0.02090 (6)	−0.00306 (4)	−0.00109 (4)	−0.00125 (4)
I3	0.01542 (6)	0.01303 (6)	0.01307 (6)	−0.00442 (4)	−0.00170 (4)	−0.00268 (4)
F1	0.0222 (5)	0.0149 (5)	0.0161 (5)	−0.0060 (4)	−0.0026 (4)	−0.0052 (4)
F2	0.0297 (6)	0.0152 (5)	0.0123 (5)	−0.0069 (4)	−0.0026 (4)	0.0016 (4)
F3	0.0247 (6)	0.0127 (5)	0.0168 (5)	−0.0096 (4)	−0.0025 (4)	0.0003 (4)
C1	0.0111 (8)	0.0144 (8)	0.0131 (8)	−0.0031 (6)	−0.0008 (6)	−0.0008 (7)
C2	0.0119 (8)	0.0138 (8)	0.0145 (8)	−0.0019 (6)	−0.0015 (6)	−0.0049 (7)
C3	0.0123 (8)	0.0094 (8)	0.0185 (9)	−0.0028 (6)	−0.0003 (7)	−0.0015 (7)
C4	0.0130 (8)	0.0135 (8)	0.0118 (8)	−0.0026 (6)	−0.0011 (6)	0.0011 (6)
C5	0.0124 (8)	0.0120 (8)	0.0142 (8)	−0.0027 (6)	−0.0019 (6)	−0.0035 (6)
C6	0.0123 (8)	0.0103 (8)	0.0166 (9)	−0.0033 (6)	−0.0009 (7)	−0.0005 (7)
S1	0.0190 (2)	0.0163 (2)	0.0134 (2)	−0.00835 (17)	0.00163 (16)	−0.00306 (16)
N2	0.0166 (8)	0.0138 (8)	0.0173 (8)	−0.0062 (6)	0.0010 (6)	−0.0024 (6)
N1	0.0150 (8)	0.0187 (8)	0.0168 (8)	−0.0062 (6)	0.0015 (6)	−0.0044 (6)
C9	0.0160 (9)	0.0204 (9)	0.0148 (9)	−0.0058 (7)	0.0025 (7)	−0.0031 (7)
C7	0.0147 (8)	0.0180 (9)	0.0103 (8)	−0.0043 (7)	−0.0044 (6)	0.0000 (7)
C8	0.0239 (10)	0.0169 (9)	0.0198 (9)	−0.0061 (7)	−0.0011 (7)	−0.0055 (7)

Geometric parameters (Å, º)

I1—C1	2.0975 (17)	N2—H1N1	0.80 (2)
I2—C3	2.0821 (17)	N2—C9	1.457 (2)
I3—C5	2.1007 (17)	N2—C7	1.330 (2)
F1—C2	1.3470 (19)	N1—H1N2	0.78 (2)
F2—C4	1.346 (2)	N1—C7	1.328 (2)
F3—C6	1.3445 (19)	N1—C8	1.453 (2)
C1—C2	1.385 (2)	C9—H7A	0.9800
C1—C6	1.386 (2)	C9—H7B	0.9800
C2—C3	1.383 (2)	C9—H7C	0.9800
C3—C4	1.384 (2)	C8—H9A	0.9800
C4—C5	1.386 (2)	C8—H9B	0.9800
C5—C6	1.382 (2)	C8—H9C	0.9800
S1—C7	1.7200 (18)
C2—C1—I1	121.34 (13)	C7—N2—C9	125.76 (16)
C2—C1—C6	116.81 (16)	C7—N1—H1N2	115.5 (16)
C6—C1—I1	121.85 (13)	C7—N1—C8	125.52 (16)
F1—C2—C1	118.46 (15)	C8—N1—H1N2	118.2 (17)
F1—C2—C3	118.46 (15)	N2—C9—H7A	109.5
C3—C2—C1	123.08 (16)	N2—C9—H7B	109.5
C2—C3—I2	122.17 (13)	N2—C9—H7C	109.5
C2—C3—C4	116.88 (16)	H7A—C9—H7B	109.5
C4—C3—I2	120.95 (13)	H7A—C9—H7C	109.5
F2—C4—C3	118.33 (15)	H7B—C9—H7C	109.5
F2—C4—C5	118.43 (15)	N2—C7—S1	121.44 (14)
C3—C4—C5	123.24 (16)	N1—C7—S1	119.86 (14)
C4—C5—I3	120.86 (13)	N1—C7—N2	118.69 (17)
C6—C5—I3	122.43 (12)	N1—C8—H9A	109.5
C6—C5—C4	116.64 (15)	N1—C8—H9B	109.5
F3—C6—C1	118.35 (15)	N1—C8—H9C	109.5
F3—C6—C5	118.38 (15)	H9A—C8—H9B	109.5
C5—C6—C1	123.27 (16)	H9A—C8—H9C	109.5
C9—N2—H1N1	117.6 (16)	H9B—C8—H9C	109.5
C7—N2—H1N1	116.3 (16)
I1—C1—C2—F1	−0.2 (2)	C2—C1—C6—F3	−178.02 (15)
I1—C1—C2—C3	−179.69 (13)	C2—C1—C6—C5	1.9 (3)
I1—C1—C6—F3	2.4 (2)	C2—C3—C4—F2	−178.87 (15)
I1—C1—C6—C5	−177.70 (13)	C2—C3—C4—C5	1.1 (3)
I2—C3—C4—F2	1.9 (2)	C3—C4—C5—I3	−175.80 (13)
I2—C3—C4—C5	−178.13 (13)	C3—C4—C5—C6	1.3 (3)
I3—C5—C6—F3	−5.9 (2)	C4—C5—C6—F3	177.09 (15)
I3—C5—C6—C1	174.17 (13)	C4—C5—C6—C1	−2.8 (3)
F1—C2—C3—I2	−2.4 (2)	C6—C1—C2—F1	−179.79 (15)
F1—C2—C3—C4	178.36 (15)	C6—C1—C2—C3	0.7 (3)
F2—C4—C5—I3	4.2 (2)	C9—N2—C7—S1	1.6 (2)
F2—C4—C5—C6	−178.76 (15)	C9—N2—C7—N1	−179.53 (16)
C1—C2—C3—I2	177.08 (13)	C8—N1—C7—S1	−178.90 (14)
C1—C2—C3—C4	−2.1 (3)	C8—N1—C7—N2	2.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N1···I1^i	0.80 (2)	3.04 (2)	3.6907 (16)	140.8 (19)
N1—H1N2···S1^ii	0.78 (2)	2.60 (2)	3.3493 (17)	162 (2)
C9—H7A···I2^iii	0.98	3.17	4.0382 (19)	148
C9—H7B···F1	0.98	2.54	3.090 (2)	115
C8—H9A···F2^iii	0.98	2.46	3.331 (2)	148

Symmetry codes: (i) x, y+1, z; (ii) −x, −y+2, −z+2; (iii) −x+1, −y+2, −z+1.

1,3-Dimethylthiourea–1,1,2,2-tetraiodoethene (1/1) (8)

Crystal data

C6H16N4S2·C2I4	F(000) = 1120
Mr = 635.79	Dx = 3.110 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.3783 (3) Å	Cell parameters from 37161 reflections
b = 4.32943 (5) Å	θ = 1.4–29.2°
c = 14.67541 (19) Å	µ = 9.30 mm^−1
β = 107.2430 (14)°	T = 100 K
V = 1357.93 (3) Å^3	Block, colourless
Z = 4	0.22 × 0.16 × 0.14 mm

Data collection

XtaLAB Synergy HyPix3000 diffractometer	1797 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	1776 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.052
Detector resolution: 10.0000 pixels mm^-1	θmax = 29.1°, θmin = 1.9°
ω scans	h = −30→30
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −5→5
Tmin = 0.430, Tmax = 1.000	l = −20→19
43887 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.015	Hydrogen site location: mixed
wR(F^2) = 0.037	H atoms treated by a mixture of independent and constrained refinement
S = 1.23	w = 1/[σ^2(Fo^2) + (0.0137P)^2 + 3.9553P] where P = (Fo^2 + 2Fc^2)/3
1797 reflections	(Δ/σ)max = 0.003
85 parameters	Δρmax = 0.88 e Å^−3
2 restraints	Δρmin = −1.01 e Å^−3

Special details

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. 1. Fixed Uiso At 1.2 times of: All N(H) groups At 1.5 times of: All C(H,H,H) groups 2. Restrained distances H1N1-N1 0.86 with sigma of 0.02 N2-H1N2 0.86 with sigma of 0.02 3. Others Fixed Sof: N1(0.5) H1N1(0.5) N2(0.5) H1N2(0.5) C2(0.5) C3(0.5) H3A(0.5) H3B(0.5) H3C(0.5) C4(0.5) H4A(0.5) H4B(0.5) H4C(0.5) 4.a Me refined with riding coordinates: C3(H3A,H3B,H3C), C4(H4A,H4B,H4C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	0.36502 (2)	0.37698 (4)	0.52220 (2)	0.01435 (5)
I2	0.26092 (2)	0.51778 (4)	0.65643 (2)	0.01395 (5)
C1	0.27321 (11)	0.3197 (6)	0.53236 (17)	0.0141 (5)
S1	0.500000	0.500000	0.500000	0.0385 (3)
N1	0.5420 (2)	0.0670 (13)	0.6392 (4)	0.0225 (10)	0.5
H1N1	0.529 (3)	−0.058 (14)	0.592 (4)	0.027*	0.5
N2	0.5657 (2)	0.5580 (13)	0.6987 (4)	0.0256 (11)	0.5
H1N2	0.584 (3)	0.466 (16)	0.752 (3)	0.031*	0.5
C2	0.5394 (2)	0.3734 (14)	0.6253 (4)	0.0205 (11)	0.5
C3	0.5765 (7)	−0.081 (4)	0.7279 (8)	0.034 (3)	0.5
H3A	0.571723	−0.300528	0.721438	0.051*	0.5
H3B	0.620053	−0.028150	0.742732	0.051*	0.5
H3C	0.560676	−0.010635	0.778399	0.051*	0.5
C4	0.5669 (6)	0.897 (4)	0.6936 (8)	0.035 (3)	0.5
H4A	0.588450	0.978598	0.755401	0.053*	0.5
H4B	0.588231	0.958376	0.648646	0.053*	0.5
H4C	0.524827	0.973899	0.673502	0.053*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01081 (8)	0.01760 (9)	0.01482 (9)	−0.00162 (5)	0.00410 (6)	0.00070 (6)
I2	0.01581 (8)	0.01620 (9)	0.01060 (8)	−0.00133 (6)	0.00507 (6)	−0.00118 (5)
C1	0.0140 (10)	0.0160 (11)	0.0139 (11)	0.0010 (9)	0.0067 (9)	0.0022 (9)
S1	0.0118 (4)	0.0368 (7)	0.0664 (9)	0.0008 (4)	0.0107 (5)	0.0246 (6)
N1	0.019 (2)	0.028 (3)	0.015 (2)	0.004 (2)	−0.0038 (18)	0.000 (2)
N2	0.022 (2)	0.032 (3)	0.018 (2)	0.001 (2)	−0.0011 (19)	−0.002 (2)
C2	0.013 (2)	0.028 (3)	0.021 (3)	−0.001 (2)	0.006 (2)	−0.002 (2)
C3	0.028 (4)	0.030 (5)	0.033 (6)	0.008 (3)	−0.009 (5)	0.005 (5)
C4	0.030 (6)	0.031 (4)	0.042 (7)	−0.001 (4)	0.008 (6)	−0.007 (6)

Geometric parameters (Å, º)

I1—C1	2.118 (2)	N2—C2	1.330 (7)
I2—C1	2.103 (2)	N2—C4	1.468 (17)
C1—C1^i	1.327 (5)	C3—H3A	0.9600
S1—C2	1.871 (6)	C3—H3B	0.9600
N1—H1N1	0.86 (2)	C3—H3C	0.9600
N1—C2	1.341 (8)	C4—H4A	0.9600
N1—C3	1.451 (12)	C4—H4B	0.9600
N2—H1N2	0.86 (2)	C4—H4C	0.9600
I2—C1—I1	113.06 (11)	N1—C3—H3A	109.5
C1^i—C1—I1	124.9 (2)	N1—C3—H3B	109.5
C1^i—C1—I2	122.0 (2)	N1—C3—H3C	109.5
C2—N1—H1N1	121 (5)	H3A—C3—H3B	109.5
C2—N1—C3	124.0 (7)	H3A—C3—H3C	109.5
C3—N1—H1N1	114 (5)	H3B—C3—H3C	109.5
C2—N2—H1N2	116 (5)	N2—C4—H4A	109.5
C2—N2—C4	124.7 (7)	N2—C4—H4B	109.5
C4—N2—H1N2	120 (5)	N2—C4—H4C	109.5
N1—C2—S1	115.2 (4)	H4A—C4—H4B	109.5
N2—C2—S1	125.9 (5)	H4A—C4—H4C	109.5
N2—C2—N1	118.9 (5)	H4B—C4—H4C	109.5
C3—N1—C2—S1	172.7 (9)	C4—N2—C2—S1	1.5 (11)
C3—N1—C2—N2	−5.5 (12)	C4—N2—C2—N1	179.4 (8)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

[(Dimethylamino)methylidene](1,2,2-triiodoethenyl)sulfonium iodide–1,1,2,2-tetraiodoethene–acetone (1/1/1) (9)

Crystal data

C5H8I3N2S^+·I^−·C3H6O·C2I4	Z = 2
Mr = 1225.49	F(000) = 1072
Triclinic, P1	Dx = 3.195 Mg m^−3
a = 7.7715 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3862 (1) Å	Cell parameters from 46229 reflections
c = 14.1290 (1) Å	θ = 1.5–29.0°
α = 78.476 (1)°	µ = 9.82 mm^−1
β = 79.610 (1)°	T = 100 K
γ = 74.766 (1)°	Plate, yellow
V = 1273.99 (2) Å^3	0.14 × 0.09 × 0.06 mm

Data collection

XtaLAB Synergy HyPix3000 diffractometer	6721 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	5812 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.062
Detector resolution: 10.0000 pixels mm^-1	θmax = 29.2°, θmin = 1.5°
ω scans	h = −10→10
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2020)	k = −16→16
Tmin = 0.837, Tmax = 1.000	l = −19→18
88855 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: mixed
wR(F^2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0085P)^2 + 2.1923P] where P = (Fo^2 + 2Fc^2)/3
6721 reflections	(Δ/σ)max = 0.001
230 parameters	Δρmax = 0.88 e Å^−3
38 restraints	Δρmin = −1.30 e Å^−3

Special details

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. 1. Fixed Uiso At 1.5 times of: All C(H,H,H) groups 2. Restrained distances H1N1-N1 0.86 with sigma of 0.02 N2-H1N2 0.86 with sigma of 0.02 3. Uiso/Uaniso restraints and constraints C3A ~ C3B ~ C4A ~ C4B: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004 within 2A 4. Others Sof(C3B)=Sof(C4B)=1-FVAR(1) Sof(C3A)=Sof(C4A)=FVAR(1) 5.a Idealised Me refined as rotating group: C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	0.25732 (3)	1.10461 (2)	−0.10627 (2)	0.01629 (6)
I2	0.26531 (3)	0.90940 (2)	0.11207 (2)	0.01724 (6)
C1	0.4149 (5)	1.0024 (4)	0.0011 (3)	0.0154 (8)
I3	0.25482 (4)	0.57355 (2)	0.13231 (2)	0.01938 (6)
I4	0.31762 (4)	0.36334 (2)	−0.01360 (2)	0.02112 (7)
I8	0.00937 (4)	0.74134 (2)	0.30640 (2)	0.01689 (6)
C2	0.4230 (6)	0.4879 (4)	0.0221 (3)	0.0189 (9)
I5	0.13017 (4)	0.75556 (3)	0.52631 (2)	0.02139 (7)
I6	0.10641 (4)	0.96818 (2)	0.67277 (2)	0.02226 (7)
I7	0.19942 (4)	0.75181 (3)	0.87622 (2)	0.02715 (7)
S1	0.25528 (15)	0.56728 (9)	0.72323 (8)	0.0213 (2)
N1	0.5644 (5)	0.6081 (3)	0.6184 (3)	0.0209 (8)
H1N1	0.528 (6)	0.6767 (19)	0.626 (3)	0.018 (13)*
N2	0.5384 (5)	0.4237 (3)	0.6509 (3)	0.0182 (8)
H1N2	0.651 (3)	0.399 (4)	0.636 (3)	0.024 (13)*
C3A	0.2006 (10)	0.7138 (6)	0.6746 (5)	0.0151 (10)	0.573 (6)
C3B	0.2060 (13)	0.7171 (9)	0.7302 (8)	0.0155 (11)	0.427 (6)
C4A	0.1753 (10)	0.7917 (6)	0.7302 (5)	0.0160 (10)	0.573 (6)
C4B	0.1611 (13)	0.7976 (8)	0.6578 (7)	0.0156 (11)	0.427 (6)
C5	0.4717 (6)	0.5320 (4)	0.6579 (3)	0.0165 (9)
C6	0.7412 (6)	0.5803 (4)	0.5606 (4)	0.0317 (12)
H6A	0.735633	0.537860	0.511840	0.048*
H6B	0.827556	0.535871	0.602441	0.048*
H6C	0.776515	0.649019	0.529680	0.048*
C7	0.4477 (6)	0.3325 (4)	0.6940 (3)	0.0233 (10)
H7A	0.507810	0.265809	0.665755	0.035*
H7B	0.324906	0.355434	0.681480	0.035*
H7C	0.450897	0.316342	0.763086	0.035*
O1	0.5630 (4)	0.8354 (3)	0.6017 (2)	0.0263 (7)
C8	0.5912 (6)	1.0136 (4)	0.6261 (3)	0.0261 (10)
H8A	0.709384	1.027184	0.618650	0.039*
H8B	0.514532	1.052910	0.675965	0.039*
H8C	0.542572	1.040669	0.565576	0.039*
C9	0.6024 (6)	0.8895 (4)	0.6542 (3)	0.0227 (10)
C10	0.6596 (7)	0.8339 (4)	0.7517 (3)	0.0318 (12)
H10A	0.569928	0.863345	0.802359	0.048*
H10B	0.772288	0.849207	0.756425	0.048*
H10C	0.673040	0.753494	0.758721	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01445 (13)	0.01737 (14)	0.01756 (13)	−0.00434 (11)	−0.00641 (10)	0.00066 (11)
I2	0.01426 (13)	0.01949 (15)	0.01764 (13)	−0.00715 (11)	−0.00105 (10)	0.00106 (11)
C1	0.020 (2)	0.015 (2)	0.0114 (19)	−0.0044 (17)	−0.0009 (16)	−0.0031 (16)
I3	0.02281 (15)	0.02037 (15)	0.01537 (13)	−0.00399 (12)	−0.00242 (11)	−0.00544 (11)
I4	0.02624 (16)	0.02023 (15)	0.02006 (14)	−0.00836 (12)	−0.00484 (11)	−0.00517 (11)
I8	0.01645 (13)	0.01901 (15)	0.01449 (13)	−0.00311 (11)	−0.00312 (10)	−0.00152 (11)
C2	0.028 (2)	0.015 (2)	0.015 (2)	−0.0053 (19)	−0.0081 (18)	−0.0021 (17)
I5	0.02456 (15)	0.02547 (16)	0.01730 (14)	−0.01064 (13)	0.00008 (11)	−0.00702 (12)
I6	0.01891 (15)	0.01437 (14)	0.03266 (17)	−0.00037 (11)	−0.00427 (12)	−0.00582 (12)
I7	0.03469 (18)	0.02724 (18)	0.01828 (15)	−0.00393 (14)	−0.01029 (12)	0.00076 (12)
S1	0.0231 (6)	0.0130 (5)	0.0236 (6)	−0.0027 (4)	−0.0004 (4)	0.0023 (4)
N1	0.0174 (19)	0.015 (2)	0.029 (2)	−0.0074 (16)	−0.0043 (16)	0.0038 (17)
N2	0.020 (2)	0.0147 (19)	0.0207 (19)	−0.0069 (16)	−0.0019 (15)	−0.0006 (15)
C3A	0.015 (2)	0.015 (2)	0.015 (2)	−0.0026 (19)	−0.001 (2)	−0.003 (2)
C3B	0.015 (2)	0.015 (2)	0.016 (2)	−0.002 (2)	−0.001 (2)	−0.003 (3)
C4A	0.016 (2)	0.015 (2)	0.016 (2)	−0.003 (2)	−0.0012 (19)	−0.002 (2)
C4B	0.015 (2)	0.015 (2)	0.016 (2)	−0.003 (2)	−0.001 (2)	−0.003 (2)
C5	0.020 (2)	0.017 (2)	0.014 (2)	−0.0063 (17)	−0.0057 (16)	−0.0009 (17)
C6	0.024 (3)	0.026 (3)	0.042 (3)	−0.010 (2)	0.001 (2)	0.001 (2)
C7	0.025 (2)	0.019 (2)	0.026 (2)	−0.0088 (19)	−0.0022 (19)	−0.0021 (19)
O1	0.0258 (17)	0.0174 (17)	0.0348 (19)	−0.0054 (14)	−0.0043 (14)	−0.0012 (14)
C8	0.032 (3)	0.016 (2)	0.031 (3)	−0.011 (2)	−0.008 (2)	0.002 (2)
C9	0.016 (2)	0.018 (2)	0.030 (2)	−0.0033 (18)	0.0009 (18)	0.0026 (19)
C10	0.033 (3)	0.027 (3)	0.032 (3)	−0.010 (2)	−0.003 (2)	0.004 (2)

Geometric parameters (Å, º)

I1—C1	2.120 (4)	N2—C5	1.322 (5)
I2—C1	2.112 (4)	N2—C7	1.460 (5)
C1—C1^i	1.304 (8)	C3A—C4A	1.317 (11)
I3—C2	2.111 (4)	C3B—C4B	1.305 (14)
I4—C2	2.104 (4)	C6—H6A	0.9600
C2—C2^ii	1.326 (8)	C6—H6B	0.9600
I5—C3A	2.188 (7)	C6—H6C	0.9600
I5—C4B	2.096 (9)	C7—H7A	0.9600
I6—C4A	2.135 (8)	C7—H7B	0.9600
I6—C4B	2.089 (10)	C7—H7C	0.9600
I7—C3B	2.178 (10)	O1—C9	1.217 (5)
I7—C4A	2.054 (7)	C8—H8A	0.9600
S1—C3A	1.774 (8)	C8—H8B	0.9600
S1—C3B	1.813 (11)	C8—H8C	0.9600
S1—C5	1.757 (4)	C8—C9	1.493 (6)
N1—H1N1	0.844 (19)	C9—C10	1.501 (6)
N1—C5	1.311 (5)	C10—H10A	0.9600
N1—C6	1.460 (6)	C10—H10B	0.9600
N2—H1N2	0.852 (19)	C10—H10C	0.9600
I2—C1—I1	112.49 (17)	N2—C5—S1	116.5 (3)
C1^i—C1—I1	123.7 (4)	N1—C6—H6A	109.5
C1^i—C1—I2	123.8 (4)	N1—C6—H6B	109.5
I4—C2—I3	113.18 (19)	N1—C6—H6C	109.5
C2^ii—C2—I3	123.4 (4)	H6A—C6—H6B	109.5
C2^ii—C2—I4	123.4 (4)	H6A—C6—H6C	109.5
C5—S1—C3A	98.0 (3)	H6B—C6—H6C	109.5
C5—S1—C3B	107.1 (3)	N2—C7—H7A	109.5
C5—N1—H1N1	123 (3)	N2—C7—H7B	109.5
C5—N1—C6	122.8 (4)	N2—C7—H7C	109.5
C6—N1—H1N1	115 (3)	H7A—C7—H7B	109.5
C5—N2—H1N2	120 (3)	H7A—C7—H7C	109.5
C5—N2—C7	125.2 (4)	H7B—C7—H7C	109.5
C7—N2—H1N2	113 (3)	H8A—C8—H8B	109.5
S1—C3A—I5	115.8 (4)	H8A—C8—H8C	109.5
C4A—C3A—I5	122.1 (6)	H8B—C8—H8C	109.5
C4A—C3A—S1	121.2 (6)	C9—C8—H8A	109.5
S1—C3B—I7	113.6 (5)	C9—C8—H8B	109.5
C4B—C3B—I7	122.2 (8)	C9—C8—H8C	109.5
C4B—C3B—S1	123.8 (8)	O1—C9—C8	121.9 (4)
I7—C4A—I6	116.0 (3)	O1—C9—C10	120.8 (4)
C3A—C4A—I6	121.4 (6)	C8—C9—C10	117.2 (4)
C3A—C4A—I7	122.5 (6)	C9—C10—H10A	109.5
I6—C4B—I5	119.3 (5)	C9—C10—H10B	109.5
C3B—C4B—I5	119.6 (8)	C9—C10—H10C	109.5
C3B—C4B—I6	121.1 (8)	H10A—C10—H10B	109.5
N1—C5—S1	122.4 (3)	H10A—C10—H10C	109.5
N1—C5—N2	121.1 (4)	H10B—C10—H10C	109.5
I5—C3A—C4A—I6	−10.8 (9)	C3B—S1—C5—N1	−4.3 (5)
I5—C3A—C4A—I7	169.3 (3)	C3B—S1—C5—N2	175.2 (4)
I7—C3B—C4B—I5	−169.9 (4)	C5—S1—C3A—I5	75.6 (4)
I7—C3B—C4B—I6	6.9 (12)	C5—S1—C3A—C4A	−115.3 (6)
S1—C3A—C4A—I6	−179.3 (3)	C5—S1—C3B—I7	−110.1 (4)
S1—C3A—C4A—I7	0.8 (9)	C5—S1—C3B—C4B	76.3 (9)
S1—C3B—C4B—I5	3.1 (12)	C6—N1—C5—S1	−177.4 (3)
S1—C3B—C4B—I6	179.9 (5)	C6—N1—C5—N2	3.1 (6)
C3A—S1—C5—N1	20.5 (4)	C7—N2—C5—S1	−0.9 (5)
C3A—S1—C5—N2	−159.9 (4)	C7—N2—C5—N1	178.6 (4)

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.84 (2)	2.01 (3)	2.775 (5)	151 (4)
N2—H1N2···I8^iii	0.85 (2)	2.91 (3)	3.659 (4)	149 (4)
N2—H1N2···I5^iii	0.85 (2)	3.24 (4)	3.837 (4)	130 (4)
C7—H7B···I8^iv	0.96	3.10	3.895 (4)	141
C7—H7C···I4^v	0.96	3.26	4.142 (4)	154
C8—H8A···I6^vi	0.96	3.18	4.050 (5)	152
C10—H10B···I6^vi	0.96	3.24	4.119 (5)	153

Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) x, y, z+1; (vi) x+1, y, z.

2-Amino-4-methyl-1,3-thiazol-3-ium iodide–1,1,2,2-tetraiodoethene (2/3) (10)

Crystal data

2C4H7N2S^+·2I^−·3C2I4	F(000) = 1800
Mr = 2079.01	Dx = 3.456 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.813 (4) Å	Cell parameters from 9831 reflections
b = 30.677 (12) Å	θ = 2.5–26.4°
c = 9.085 (5) Å	µ = 10.96 mm^−1
β = 113.429 (15)°	T = 100 K
V = 1998.1 (16) Å^3	Plate, yellow
Z = 2	0.25 × 0.08 × 0.07 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	3780 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.033
φ and ω scans	θmax = 26.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −9→9
Tmin = 0.456, Tmax = 0.745	k = −38→38
22733 measured reflections	l = −11→11
4061 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: mixed
wR(F^2) = 0.038	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0104P)^2 + 2.8813P] where P = (Fo^2 + 2Fc^2)/3
4061 reflections	(Δ/σ)max = 0.002
167 parameters	Δρmax = 1.21 e Å^−3
0 restraints	Δρmin = −0.82 e Å^−3

Special details

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. 1. Fixed Uiso At 1.2 times of: All C(H) groups At 1.5 times of: All C(H,H,H) groups 2.a Aromatic/amide H refined with riding coordinates: C3(H3) 2.b Idealised Me refined as rotating group: C4(H4A,H4B,H4C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.82019 (4)	0.23695 (2)	0.18833 (3)	0.01979 (6)
I2	0.91809 (3)	0.33753 (2)	0.39053 (3)	0.01647 (6)
I3	0.32674 (4)	0.24975 (2)	0.10720 (3)	0.02303 (6)
I4	0.42633 (3)	0.34759 (2)	0.32731 (3)	0.01780 (6)
C5	0.7125 (5)	0.29019 (11)	0.2702 (4)	0.0162 (8)
C6	0.5340 (5)	0.29459 (11)	0.2423 (4)	0.0148 (7)
S1	1.04644 (15)	0.39442 (4)	0.84076 (13)	0.0261 (2)
N1	0.6976 (5)	0.40400 (10)	0.7433 (4)	0.0174 (7)
N2	0.8248 (5)	0.44303 (11)	0.5881 (4)	0.0216 (7)
C1	0.8401 (5)	0.41675 (12)	0.7079 (5)	0.0176 (8)
C2	0.7446 (6)	0.37579 (12)	0.8745 (5)	0.0220 (8)
C3	0.9269 (6)	0.36744 (13)	0.9402 (5)	0.0252 (9)
H3	0.984927	0.349003	1.030481	0.030*
C4	0.5896 (7)	0.35962 (15)	0.9181 (6)	0.0342 (11)
H4A	0.486837	0.349005	0.821467	0.051*
H4B	0.545008	0.383479	0.965334	0.051*
H4C	0.635619	0.335803	0.995863	0.051*
H1N1	0.584 (7)	0.4143 (16)	0.687 (6)	0.040 (15)*
H1N2	0.717 (8)	0.4510 (17)	0.524 (7)	0.046 (16)*
H2N2	0.920 (8)	0.4476 (15)	0.555 (6)	0.040 (15)*
I5	0.36445 (3)	0.47479 (2)	0.19862 (3)	0.01611 (6)
I6	0.17936 (3)	0.53013 (2)	−0.17297 (3)	0.01678 (6)
C7	0.4194 (6)	0.50099 (13)	0.0056 (5)	0.0233 (9)
I7	0.23358 (3)	0.42935 (2)	0.50201 (3)	0.01519 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01620 (13)	0.02074 (13)	0.02201 (14)	0.00149 (9)	0.00716 (11)	−0.00566 (10)
I2	0.01283 (12)	0.01621 (12)	0.01926 (13)	−0.00279 (8)	0.00522 (10)	−0.00148 (9)
I3	0.01407 (13)	0.02683 (14)	0.02607 (15)	−0.00528 (10)	0.00573 (11)	−0.00996 (11)
I4	0.01458 (12)	0.01569 (12)	0.02302 (14)	0.00201 (8)	0.00736 (11)	−0.00084 (9)
C5	0.0168 (19)	0.0153 (18)	0.0133 (19)	0.0002 (14)	0.0024 (16)	−0.0004 (14)
C6	0.0128 (18)	0.0143 (18)	0.0155 (19)	−0.0014 (13)	0.0035 (16)	−0.0021 (14)
S1	0.0152 (5)	0.0364 (6)	0.0219 (6)	0.0067 (4)	0.0023 (4)	−0.0014 (4)
N1	0.0149 (17)	0.0199 (16)	0.0149 (17)	0.0032 (13)	0.0034 (14)	0.0018 (13)
N2	0.0179 (19)	0.0254 (18)	0.024 (2)	0.0032 (14)	0.0113 (17)	0.0054 (14)
C1	0.0141 (19)	0.0179 (19)	0.020 (2)	0.0025 (14)	0.0052 (17)	−0.0056 (15)
C2	0.025 (2)	0.020 (2)	0.015 (2)	−0.0005 (16)	0.0024 (18)	0.0011 (15)
C3	0.027 (2)	0.022 (2)	0.021 (2)	0.0058 (16)	0.0033 (19)	0.0028 (16)
C4	0.033 (3)	0.039 (3)	0.028 (3)	−0.011 (2)	0.009 (2)	0.008 (2)
I5	0.01566 (12)	0.01666 (12)	0.01788 (13)	−0.00053 (9)	0.00863 (10)	0.00142 (9)
I6	0.01155 (12)	0.01953 (12)	0.01801 (13)	0.00377 (9)	0.00454 (10)	0.00280 (9)
C7	0.024 (2)	0.021 (2)	0.023 (2)	0.0015 (16)	0.0075 (19)	−0.0003 (16)
I7	0.01152 (12)	0.01684 (12)	0.01710 (13)	0.00073 (8)	0.00558 (10)	0.00024 (9)

Geometric parameters (Å, º)

I1—C5	2.104 (4)	N2—H1N2	0.85 (6)
I2—C5	2.119 (4)	N2—H2N2	0.92 (5)
I3—C6	2.107 (4)	C2—C3	1.332 (6)
I4—C6	2.113 (4)	C2—C4	1.500 (6)
C5—C6	1.321 (5)	C3—H3	0.9500
S1—C1	1.726 (4)	C4—H4A	0.9800
S1—C3	1.745 (5)	C4—H4B	0.9800
N1—C1	1.334 (5)	C4—H4C	0.9800
N1—C2	1.399 (5)	I5—C7	2.123 (4)
N1—H1N1	0.89 (5)	I6—C7	2.128 (4)
N2—C1	1.321 (5)	C7—C7^i	1.304 (8)
I1—C5—I2	112.76 (17)	N1—C2—C4	117.6 (4)
C6—C5—I1	123.5 (3)	C3—C2—N1	111.8 (4)
C6—C5—I2	123.7 (3)	C3—C2—C4	130.5 (4)
I3—C6—I4	112.92 (17)	S1—C3—H3	124.0
C5—C6—I3	123.6 (3)	C2—C3—S1	112.0 (3)
C5—C6—I4	123.5 (3)	C2—C3—H3	124.0
C1—S1—C3	90.4 (2)	C2—C4—H4A	109.5
C1—N1—C2	115.2 (3)	C2—C4—H4B	109.5
C1—N1—H1N1	120 (3)	C2—C4—H4C	109.5
C2—N1—H1N1	125 (3)	H4A—C4—H4B	109.5
C1—N2—H1N2	119 (4)	H4A—C4—H4C	109.5
C1—N2—H2N2	123 (3)	H4B—C4—H4C	109.5
H1N2—N2—H2N2	116 (5)	I5—C7—I6	112.48 (19)
N1—C1—S1	110.6 (3)	C7^i—C7—I5	124.4 (4)
N2—C1—S1	124.9 (3)	C7^i—C7—I6	123.1 (4)
N2—C1—N1	124.5 (4)
I1—C5—C6—I3	−1.3 (5)	C1—N1—C2—C4	−178.8 (4)
I1—C5—C6—I4	179.07 (17)	C2—N1—C1—S1	−0.8 (4)
I2—C5—C6—I3	175.13 (17)	C2—N1—C1—N2	179.5 (4)
I2—C5—C6—I4	−4.5 (5)	C3—S1—C1—N1	0.7 (3)
N1—C2—C3—S1	0.0 (5)	C3—S1—C1—N2	−179.7 (4)
C1—S1—C3—C2	−0.3 (3)	C4—C2—C3—S1	179.2 (4)
C1—N1—C2—C3	0.6 (5)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···I7	0.89 (5)	2.62 (5)	3.498 (4)	169 (4)
N2—H1N2···I5	0.85 (6)	3.22 (6)	4.036 (4)	162 (5)
N2—H2N2···I6^i	0.92 (5)	3.31 (5)	3.848 (4)	120 (4)
N2—H2N2···I7^ii	0.92 (5)	2.74 (5)	3.602 (4)	158 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z.

4,4-Dimethyl-4H-1,3,5-thiadiazine-3,5-diium diiodide–1,1,2,2-tetraiodoethene (2/3) (11)

Crystal data

2C5H12N4S^2+·4I^−·3C2I4	F(000) = 2112
Mr = 2422.95	Dx = 3.378 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6879 (1) Å	Cell parameters from 9831 reflections
b = 16.2822 (3) Å	θ = 2.5–26.4°
c = 19.0763 (3) Å	µ = 10.50 mm^−1
β = 94.074 (1)°	T = 100 K
V = 2381.86 (7) Å^3	Plate, colourless
Z = 2	0.11 × 0.07 × 0.04 mm

Data collection

Bruker D8 Venture Photon 2 diffractometer	4315 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	Rint = 0.032
φ and ω scans	θmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −9→9
Tmin = 0.456, Tmax = 0.745	k = −20→20
32862 measured reflections	l = −23→23
4882 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: mixed
wR(F^2) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0156P)^2 + 6.246P] where P = (Fo^2 + 2Fc^2)/3
4882 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 1.67 e Å^−3
42 restraints	Δρmin = −2.13 e Å^−3

Special details

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. 1. Fixed Uiso At 1.2 times of: All C(H,H,H,H,H,H) groups At 1.5 times of: All C(H,H,H) groups 2. Restrained distances H2N1-N1 = H1N1-N1 = H2N2-N2 = H1N2-N2 = H1N3-N3 = H1N4-N4 0.86 with sigma of 0.02 3. Uiso/Uaniso restraints and constraints C6B ~ C7A ~ C7B ~ C6A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A 4. Others Sof(C6B)=Sof(C7B)=1-FVAR(1) Sof(C6A)=Sof(C7A)=FVAR(1) 5.a Idealised Me refined as rotating group: C4(H4A,H4B,H4C), C5(H5A,H5B,H5C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	−0.03937 (4)	0.51360 (2)	0.28036 (2)	0.01768 (8)
I2	0.54350 (4)	0.32122 (2)	0.19721 (2)	0.01464 (7)
I3	0.70673 (4)	0.42818 (2)	0.40829 (2)	0.02078 (8)
I4	0.77223 (4)	0.32029 (2)	0.56903 (2)	0.02259 (8)
I5	0.30595 (4)	0.31473 (2)	0.58495 (2)	0.02681 (9)
I6	0.23968 (4)	0.41607 (2)	0.42041 (2)	0.02110 (8)
C6A	0.5899 (10)	0.3707 (4)	0.4936 (4)	0.0179 (15)	0.711 (10)
C7A	0.4207 (9)	0.3686 (4)	0.4977 (4)	0.0168 (15)	0.711 (10)
C6B	0.493 (2)	0.3891 (10)	0.4667 (10)	0.015 (3)	0.289 (10)
C7B	0.524 (2)	0.3530 (10)	0.5290 (9)	0.014 (3)	0.289 (10)
I7	0.28020 (4)	0.06878 (2)	0.57364 (2)	0.01586 (7)
I8	0.24697 (4)	−0.05728 (2)	0.42265 (2)	0.01667 (7)
C8	0.4152 (6)	0.0025 (3)	0.4992 (3)	0.0215 (11)
S1	0.19978 (14)	0.17006 (7)	0.26574 (6)	0.0163 (2)
N1	0.0769 (5)	0.0218 (2)	0.2407 (2)	0.0194 (9)
N2	0.0884 (5)	0.3173 (2)	0.2309 (2)	0.0198 (9)
N3	−0.0872 (5)	0.2480 (2)	0.3041 (2)	0.0148 (8)
N4	−0.0934 (5)	0.1026 (2)	0.3086 (2)	0.0146 (8)
C1	0.0449 (5)	0.0904 (3)	0.2726 (2)	0.0149 (10)
C2	0.0526 (5)	0.2534 (3)	0.2675 (2)	0.0147 (10)
C3	−0.1212 (6)	0.1774 (3)	0.3498 (3)	0.0174 (10)
C4	−0.3122 (6)	0.1800 (3)	0.3659 (3)	0.0213 (11)
H4A	−0.339718	0.131331	0.393302	0.032*
H4B	−0.385825	0.180612	0.321804	0.032*
H4C	−0.334091	0.229581	0.392986	0.032*
C5	−0.0018 (6)	0.1785 (3)	0.4162 (2)	0.0228 (11)
H5A	−0.024176	0.228050	0.443301	0.034*
H5B	0.119846	0.178398	0.403953	0.034*
H5C	−0.023660	0.129772	0.444423	0.034*
H2N1	0.015 (5)	−0.021 (2)	0.249 (3)	0.027*
H1N1	0.175 (4)	0.015 (3)	0.222 (2)	0.027*
H2N2	0.037 (6)	0.3632 (18)	0.240 (3)	0.027*
H1N2	0.185 (4)	0.318 (3)	0.210 (3)	0.027*
H1N3	−0.172 (5)	0.282 (2)	0.295 (3)	0.027*
H1N4	−0.179 (4)	0.071 (3)	0.294 (3)	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01671 (15)	0.01716 (16)	0.01927 (16)	0.00103 (12)	0.00192 (12)	0.00108 (13)
I2	0.01373 (15)	0.01548 (16)	0.01487 (15)	0.00226 (12)	0.00203 (11)	0.00267 (12)
I3	0.02667 (17)	0.01775 (17)	0.01853 (16)	−0.00294 (13)	0.00591 (13)	−0.00033 (13)
I4	0.01984 (17)	0.03013 (19)	0.01746 (17)	0.00661 (14)	−0.00109 (13)	0.00474 (14)
I5	0.03052 (19)	0.02089 (18)	0.0306 (2)	0.00114 (14)	0.01353 (15)	0.00625 (14)
I6	0.01842 (16)	0.02361 (18)	0.02039 (17)	0.00087 (13)	−0.00472 (12)	0.00236 (14)
C6A	0.025 (4)	0.016 (3)	0.013 (3)	0.000 (3)	0.000 (3)	0.004 (3)
C7A	0.021 (4)	0.015 (3)	0.014 (3)	0.005 (3)	−0.002 (3)	0.009 (3)
C6B	0.022 (6)	0.009 (5)	0.014 (6)	0.003 (5)	−0.001 (5)	0.002 (5)
C7B	0.018 (6)	0.012 (5)	0.011 (6)	0.002 (5)	−0.003 (5)	0.006 (5)
I7	0.01399 (15)	0.01814 (16)	0.01566 (15)	0.00204 (12)	0.00258 (11)	−0.00272 (12)
I8	0.01248 (14)	0.02149 (17)	0.01571 (16)	−0.00154 (12)	−0.00137 (11)	−0.00476 (13)
C8	0.025 (2)	0.020 (3)	0.018 (3)	0.000 (2)	−0.001 (2)	0.002 (2)
S1	0.0131 (5)	0.0127 (6)	0.0234 (6)	0.0001 (5)	0.0038 (5)	0.0004 (5)
N1	0.020 (2)	0.013 (2)	0.027 (2)	−0.0003 (18)	0.0085 (18)	−0.0041 (19)
N2	0.020 (2)	0.011 (2)	0.030 (2)	0.0031 (17)	0.0124 (19)	0.0026 (19)
N3	0.016 (2)	0.0083 (19)	0.020 (2)	0.0024 (15)	0.0031 (16)	0.0038 (16)
N4	0.017 (2)	0.012 (2)	0.014 (2)	−0.0014 (16)	0.0036 (16)	−0.0043 (16)
C1	0.014 (2)	0.015 (2)	0.015 (2)	−0.0002 (19)	−0.0040 (18)	0.005 (2)
C2	0.013 (2)	0.014 (2)	0.017 (2)	0.0025 (19)	0.0008 (18)	−0.003 (2)
C3	0.019 (2)	0.012 (2)	0.022 (3)	−0.0013 (19)	0.005 (2)	0.003 (2)
C4	0.023 (3)	0.018 (3)	0.024 (3)	0.001 (2)	0.008 (2)	−0.002 (2)
C5	0.027 (3)	0.025 (3)	0.017 (3)	0.002 (2)	0.002 (2)	0.000 (2)

Geometric parameters (Å, º)

I3—C6A	2.130 (7)	N2—C2	1.294 (6)
I3—C6B	2.144 (18)	N2—H2N2	0.869 (19)
I4—C6A	2.104 (7)	N2—H1N2	0.860 (19)
I4—C7B	2.074 (16)	N3—C2	1.325 (5)
I5—C7A	2.127 (7)	N3—C3	1.477 (5)
I5—C7B	2.143 (17)	N3—H1N3	0.857 (19)
I6—C7A	2.102 (7)	N4—C1	1.321 (5)
I6—C6B	2.128 (18)	N4—C3	1.473 (6)
C6A—C7A	1.309 (11)	N4—H1N4	0.863 (19)
C6B—C7B	1.33 (3)	C3—C4	1.522 (6)
I7—C8	2.113 (5)	C3—C5	1.511 (7)
I8—C8	2.118 (5)	C4—H4A	0.9800
C8—C8^i	1.305 (9)	C4—H4B	0.9800
S1—C1	1.772 (4)	C4—H4C	0.9800
S1—C2	1.768 (4)	C5—H5A	0.9800
N1—C1	1.303 (6)	C5—H5B	0.9800
N1—H2N1	0.858 (19)	C5—H5C	0.9800
N1—H1N1	0.863 (19)
I4—C6A—I3	113.4 (3)	C1—N4—H1N4	111 (3)
C7A—C6A—I3	122.2 (6)	C3—N4—H1N4	122 (3)
C7A—C6A—I4	124.4 (6)	N1—C1—S1	116.3 (3)
I6—C7A—I5	114.2 (3)	N1—C1—N4	123.9 (4)
C6A—C7A—I5	121.8 (6)	N4—C1—S1	119.8 (3)
C6A—C7A—I6	124.0 (6)	N2—C2—S1	116.5 (3)
I6—C6B—I3	115.8 (8)	N2—C2—N3	123.3 (4)
C7B—C6B—I3	120.1 (14)	N3—C2—S1	120.2 (3)
C7B—C6B—I6	124.1 (14)	N3—C3—C4	108.2 (4)
I4—C7B—I5	118.3 (8)	N3—C3—C5	111.3 (4)
C6B—C7B—I4	122.8 (14)	N4—C3—N3	106.8 (4)
C6B—C7B—I5	118.5 (14)	N4—C3—C4	108.0 (4)
I7—C8—I8	113.2 (2)	N4—C3—C5	110.8 (4)
C8^i—C8—I7	123.6 (5)	C5—C3—C4	111.6 (4)
C8^i—C8—I8	123.2 (5)	C3—C4—H4A	109.5
C2—S1—C1	97.3 (2)	C3—C4—H4B	109.5
C1—N1—H2N1	119 (3)	C3—C4—H4C	109.5
C1—N1—H1N1	120 (3)	H4A—C4—H4B	109.5
H2N1—N1—H1N1	119 (5)	H4A—C4—H4C	109.5
C2—N2—H2N2	118 (3)	H4B—C4—H4C	109.5
C2—N2—H1N2	119 (3)	C3—C5—H5A	109.5
H2N2—N2—H1N2	120 (5)	C3—C5—H5B	109.5
C2—N3—C3	123.2 (4)	C3—C5—H5C	109.5
C2—N3—H1N3	119 (3)	H5A—C5—H5B	109.5
C3—N3—H1N3	117 (3)	H5A—C5—H5C	109.5
C1—N4—C3	123.7 (4)	H5B—C5—H5C	109.5
I3—C6A—C7A—I5	−177.8 (3)	C1—N4—C3—C4	164.1 (4)
I3—C6A—C7A—I6	2.8 (9)	C1—N4—C3—C5	−73.4 (5)
I3—C6B—C7B—I4	−7.0 (19)	C2—S1—C1—N1	147.7 (4)
I3—C6B—C7B—I5	−179.8 (7)	C2—S1—C1—N4	−32.3 (4)
I4—C6A—C7A—I5	1.4 (9)	C2—N3—C3—N4	−47.8 (5)
I4—C6A—C7A—I6	−178.0 (3)	C2—N3—C3—C4	−163.8 (4)
I6—C6B—C7B—I4	175.5 (7)	C2—N3—C3—C5	73.2 (5)
I6—C6B—C7B—I5	2.8 (19)	C3—N3—C2—S1	5.5 (6)
C1—S1—C2—N2	−146.8 (4)	C3—N3—C2—N2	−175.4 (4)
C1—S1—C2—N3	32.3 (4)	C3—N4—C1—S1	−5.7 (6)
C1—N4—C3—N3	48.0 (6)	C3—N4—C1—N1	174.3 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···I2^ii	0.98	3.32	4.046 (5)	133
C4—H4C···I3^ii	0.98	3.26	4.122 (5)	148
C5—H5A···I4^ii	0.98	3.32	4.191 (5)	150
C5—H5B···S1	0.98	2.75	3.360 (5)	121
N1—H2N1···I2^iii	0.86 (2)	2.82 (3)	3.618 (4)	155 (4)
N1—H1N1···I1^iii	0.86 (2)	2.80 (3)	3.609 (4)	156 (4)
N1—H1N1···I6^iii	0.86 (2)	3.27 (4)	3.874 (4)	129 (4)
N2—H2N2···I1	0.87 (2)	2.65 (2)	3.493 (4)	165 (4)
N2—H1N2···I2	0.86 (2)	2.79 (3)	3.602 (4)	158 (5)
N2—H1N2···I8^iv	0.86 (2)	3.32 (4)	3.857 (4)	123 (4)
N3—H1N3···I2^ii	0.86 (2)	2.85 (3)	3.580 (4)	144 (4)
N4—H1N4···I1^v	0.86 (2)	2.67 (2)	3.503 (4)	162 (4)

Symmetry codes: (ii) x−1, y, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x−1/2, y−1/2, −z+1/2.