Why are reactions of 2- and 8-thio­quinoline derivatives with iodine different?

The crystal structures of 1,2-di­hydro-1,1′-bi[thia­zolo[3,2-a]quinoline]-10a,10a′-diium diiodide hemihydrate, C₂₂H₁₆N₂S₂²⁺·2I⁻·0.5H₂O, and 1,2-di­hydro-1,1′-bi[thia­zolo[3,2-a]quinoline]-10a,10a′-diium iodide triiodide, C₂₂H₁₆N₂S₂²⁺·I⁻·I₃⁻, obtained during the reaction of 1,4-bis­(quinolin-2-ylsulfan­yl)but-2-yne (2TQB) with iodine, have been determined at 120 K. The crystalline products contain the dication as a result of the reaction proceeding along the iodo­cyclization pathway. This is fundamentally different from the previously observed reaction of 1,4-bis­(quinolin-8-ylsulfan­yl)but-2-yne (8TQB) with iodine under similar conditions. A comparative analysis of the possible conformational states indicates dif­ferences in the relative stabilities and free rotation for the 2- and 8-thio­quinoline derivatives which lead to a disparity in the convergence of the potential reaction centres for 2TQB and 8TQB.

Computing details

For both structures, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2013).

1,2-Dihydro-1,1'-bi[thiazolo[3,2-a]quinoline]-10a,10a'-diium diiodide hemihydrate (kb06)

Crystal data

C22H16N2S2^2+·2I^−·0.5H2O	F(000) = 2440
Mr = 635.29	Dx = 1.975 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.3218 (16) Å	Cell parameters from 6680 reflections
b = 8.6006 (6) Å	θ = 2.6–32.0°
c = 25.2773 (19) Å	µ = 3.15 mm^−1
β = 112.768 (2)°	T = 120 K
V = 4274.2 (5) Å^3	Prism, red
Z = 8	0.21 × 0.14 × 0.14 mm

Data collection

Bruker SMART APEX DUO diffractometer	7369 reflections with I > 2σ(I)
ω scan	Rint = 0.054
Absorption correction: analytical (SADABS; Bruker, 2013)	θmax = 36.3°, θmin = 2.1°
Tmin = 0.637, Tmax = 0.762	h = −35→35
38462 measured reflections	k = −14→14
10030 independent reflections	l = −41→41

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0579P)^2 + 6.0287P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.003
10030 reflections	Δρmax = 2.34 e Å^−3
259 parameters	Δρmin = −1.57 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.

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

	x	y	z	Uiso*/Ueq
I1	0.12530 (2)	−0.11371 (2)	0.71511 (2)	0.01845 (5)
I2	0.33136 (2)	0.57033 (3)	0.48198 (2)	0.02524 (6)
S1	0.33277 (4)	0.25899 (9)	0.59378 (4)	0.02274 (16)
S2	0.16065 (4)	0.29419 (9)	0.68456 (3)	0.02015 (14)
O1	0.0000	−0.3133 (5)	0.7500	0.0380 (10)
H1	0.0279	−0.2514	0.7435	0.043 (15)*
N1	0.30928 (13)	0.5223 (3)	0.63007 (11)	0.0155 (4)
N2	0.12470 (13)	0.3910 (3)	0.58006 (11)	0.0152 (4)
C1	0.36036 (16)	0.4334 (4)	0.62626 (14)	0.0194 (5)
C2	0.42893 (17)	0.4810 (4)	0.64724 (14)	0.0222 (6)
H2	0.4632	0.4149	0.6444	0.027*
C3	0.44465 (17)	0.6233 (5)	0.67155 (14)	0.0238 (6)
H3	0.4907	0.6570	0.6867	0.029*
C4	0.39299 (16)	0.7228 (4)	0.67469 (13)	0.0197 (6)
C5	0.40962 (17)	0.8750 (4)	0.69685 (14)	0.0225 (6)
H5	0.4554	0.9096	0.7095	0.027*
C6	0.36055 (19)	0.9740 (4)	0.70040 (14)	0.0242 (6)
H6	0.3723	1.0758	0.7156	0.029*
C7	0.29355 (18)	0.9228 (4)	0.68138 (14)	0.0214 (6)
H7	0.2596	0.9908	0.6838	0.026*
C8	0.27510 (16)	0.7751 (3)	0.65904 (13)	0.0177 (5)
H8	0.2291	0.7426	0.6466	0.021*
C9	0.32432 (15)	0.6735 (3)	0.65467 (12)	0.0166 (5)
C10	0.24586 (15)	0.4438 (3)	0.60695 (13)	0.0167 (5)
C11	0.25155 (17)	0.3020 (4)	0.58600 (14)	0.0206 (6)
H11	0.2142	0.2336	0.5688	0.025*
C12	0.18136 (15)	0.4988 (3)	0.61246 (13)	0.0161 (5)
H12	0.1702	0.6071	0.5973	0.019*
C13	0.18691 (16)	0.4907 (4)	0.67502 (13)	0.0175 (5)
H131	0.1568	0.5687	0.6819	0.021*
H132	0.2343	0.5105	0.7020	0.021*
C14	0.11069 (15)	0.2825 (3)	0.61238 (13)	0.0170 (5)
C15	0.05745 (16)	0.1750 (4)	0.58746 (14)	0.0199 (6)
H152	0.0486	0.0962	0.6100	0.024*
C16	0.01884 (17)	0.1868 (4)	0.53019 (15)	0.0223 (6)
H162	−0.0189	0.1192	0.5133	0.027*
C17	0.03404 (16)	0.2979 (4)	0.49552 (13)	0.0188 (5)
C18	−0.00462 (17)	0.3094 (4)	0.43564 (14)	0.0230 (6)
H182	−0.0421	0.2415	0.4179	0.028*
C19	0.01165 (19)	0.4173 (4)	0.40338 (15)	0.0252 (7)
H192	−0.0138	0.4231	0.3632	0.030*
C20	0.06647 (19)	0.5205 (4)	0.43002 (14)	0.0245 (6)
H202	0.0769	0.5964	0.4074	0.029*
C21	0.10509 (17)	0.5134 (4)	0.48800 (14)	0.0202 (6)
H212	0.1422	0.5825	0.5052	0.024*
C22	0.08863 (15)	0.4025 (3)	0.52109 (13)	0.0161 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01832 (9)	0.01474 (9)	0.02153 (9)	−0.00045 (6)	0.00687 (7)	−0.00018 (6)
I2	0.02916 (12)	0.01579 (10)	0.02553 (11)	−0.00440 (8)	0.00483 (8)	−0.00022 (7)
S1	0.0249 (4)	0.0145 (3)	0.0327 (4)	0.0041 (3)	0.0153 (3)	−0.0003 (3)
S2	0.0258 (4)	0.0156 (3)	0.0179 (3)	−0.0014 (3)	0.0072 (3)	0.0004 (2)
O1	0.0270 (19)	0.0188 (18)	0.075 (3)	0.000	0.027 (2)	0.000
N1	0.0147 (10)	0.0124 (10)	0.0184 (11)	0.0015 (8)	0.0053 (9)	0.0010 (8)
N2	0.0170 (10)	0.0094 (9)	0.0171 (11)	−0.0015 (8)	0.0042 (8)	−0.0022 (8)
C1	0.0198 (13)	0.0172 (13)	0.0216 (14)	0.0046 (10)	0.0085 (11)	0.0028 (10)
C2	0.0178 (13)	0.0275 (16)	0.0223 (14)	0.0042 (12)	0.0086 (11)	0.0024 (12)
C3	0.0173 (13)	0.0337 (18)	0.0200 (14)	−0.0037 (12)	0.0069 (11)	−0.0001 (12)
C4	0.0191 (13)	0.0208 (14)	0.0183 (13)	−0.0040 (11)	0.0062 (10)	0.0005 (10)
C5	0.0213 (14)	0.0269 (16)	0.0194 (13)	−0.0103 (12)	0.0079 (11)	−0.0028 (11)
C6	0.0340 (18)	0.0187 (14)	0.0192 (14)	−0.0098 (13)	0.0096 (13)	−0.0036 (11)
C7	0.0274 (15)	0.0129 (12)	0.0215 (14)	−0.0026 (11)	0.0067 (12)	−0.0022 (10)
C8	0.0175 (12)	0.0115 (12)	0.0202 (13)	−0.0015 (9)	0.0031 (10)	−0.0004 (9)
C9	0.0191 (13)	0.0126 (12)	0.0161 (12)	−0.0022 (9)	0.0045 (10)	0.0009 (9)
C10	0.0163 (12)	0.0126 (12)	0.0205 (13)	0.0013 (9)	0.0064 (10)	0.0011 (10)
C11	0.0230 (14)	0.0144 (12)	0.0262 (15)	−0.0014 (11)	0.0117 (12)	−0.0035 (11)
C12	0.0173 (12)	0.0120 (12)	0.0175 (12)	−0.0020 (9)	0.0052 (10)	−0.0013 (9)
C13	0.0184 (13)	0.0130 (12)	0.0204 (13)	−0.0005 (10)	0.0068 (10)	−0.0024 (10)
C14	0.0166 (12)	0.0137 (12)	0.0206 (13)	−0.0012 (9)	0.0069 (10)	−0.0002 (10)
C15	0.0205 (14)	0.0128 (13)	0.0273 (15)	−0.0043 (10)	0.0102 (12)	−0.0008 (10)
C16	0.0187 (13)	0.0164 (14)	0.0295 (16)	−0.0030 (10)	0.0067 (12)	−0.0030 (11)
C17	0.0181 (13)	0.0153 (12)	0.0206 (13)	0.0013 (10)	0.0049 (10)	−0.0033 (10)
C18	0.0193 (14)	0.0213 (15)	0.0220 (14)	0.0029 (11)	0.0009 (11)	−0.0049 (11)
C19	0.0257 (16)	0.0268 (17)	0.0187 (14)	0.0087 (13)	0.0039 (12)	−0.0013 (12)
C20	0.0337 (18)	0.0194 (14)	0.0203 (14)	0.0085 (13)	0.0102 (13)	0.0023 (11)
C21	0.0245 (14)	0.0145 (13)	0.0198 (13)	0.0034 (11)	0.0066 (11)	−0.0003 (10)
C22	0.0167 (12)	0.0110 (11)	0.0195 (12)	0.0029 (9)	0.0058 (10)	0.0002 (9)

Geometric parameters (Å, º)

I1—S2	3.7312 (9)	C7—H7	0.9500
I2—S1	3.8846 (9)	C8—C9	1.403 (4)
S1—C1	1.702 (3)	C8—H8	0.9500
S1—C11	1.706 (3)	C10—C11	1.353 (4)
S2—C14	1.723 (3)	C10—C12	1.511 (4)
S2—C13	1.826 (3)	C11—H11	0.9500
O1—H1	0.8605	C12—C13	1.541 (4)
N1—C1	1.364 (4)	C12—H12	1.0000
N1—C10	1.419 (4)	C13—H131	0.9900
N1—C9	1.424 (4)	C13—H132	0.9900
N2—C14	1.348 (4)	C14—C15	1.409 (4)
N2—C22	1.391 (4)	C15—C16	1.364 (5)
N2—C12	1.491 (4)	C15—H152	0.9500
C1—C2	1.409 (5)	C16—C17	1.416 (5)
C2—C3	1.352 (5)	C16—H162	0.9500
C2—H2	0.9500	C17—C22	1.414 (4)
C3—C4	1.421 (5)	C17—C18	1.419 (4)
C3—H3	0.9500	C18—C19	1.366 (5)
C4—C5	1.414 (5)	C18—H182	0.9500
C4—C9	1.416 (4)	C19—C20	1.413 (5)
C5—C6	1.379 (5)	C19—H192	0.9500
C5—H5	0.9500	C20—C21	1.377 (5)
C6—C7	1.391 (5)	C20—H202	0.9500
C6—H6	0.9500	C21—C22	1.400 (4)
C7—C8	1.384 (4)	C21—H212	0.9500
C1—S1—C11	90.59 (16)	C10—C11—S1	113.0 (2)
C1—S1—I2	69.35 (11)	C10—C11—H11	123.5
C11—S1—I2	92.57 (12)	S1—C11—H11	123.5
C14—S2—C13	90.55 (14)	N2—C12—C10	109.1 (2)
C14—S2—I1	94.17 (10)	N2—C12—C13	105.0 (2)
C13—S2—I1	174.06 (11)	C10—C12—C13	111.7 (2)
C1—N1—C10	111.3 (3)	N2—C12—H12	110.3
C1—N1—C9	119.5 (3)	C10—C12—H12	110.3
C10—N1—C9	129.2 (3)	C13—C12—H12	110.3
C14—N2—C22	122.6 (3)	C12—C13—S2	105.8 (2)
C14—N2—C12	114.8 (2)	C12—C13—H131	110.6
C22—N2—C12	122.6 (2)	S2—C13—H131	110.6
N1—C1—C2	123.4 (3)	C12—C13—H132	110.6
N1—C1—S1	113.1 (2)	S2—C13—H132	110.6
C2—C1—S1	123.5 (3)	H131—C13—H132	108.7
C3—C2—C1	118.2 (3)	N2—C14—C15	120.8 (3)
C3—C2—H2	120.9	N2—C14—S2	114.2 (2)
C1—C2—H2	120.9	C15—C14—S2	124.9 (2)
C2—C3—C4	120.6 (3)	C16—C15—C14	118.5 (3)
C2—C3—H3	119.7	C16—C15—H152	120.8
C4—C3—H3	119.7	C14—C15—H152	120.8
C5—C4—C9	119.0 (3)	C15—C16—C17	121.2 (3)
C5—C4—C3	119.9 (3)	C15—C16—H162	119.4
C9—C4—C3	121.1 (3)	C17—C16—H162	119.4
C6—C5—C4	121.2 (3)	C22—C17—C16	119.4 (3)
C6—C5—H5	119.4	C22—C17—C18	118.6 (3)
C4—C5—H5	119.4	C16—C17—C18	122.0 (3)
C5—C6—C7	119.1 (3)	C19—C18—C17	120.5 (3)
C5—C6—H6	120.5	C19—C18—H182	119.8
C7—C6—H6	120.5	C17—C18—H182	119.8
C8—C7—C6	121.6 (3)	C18—C19—C20	119.8 (3)
C8—C7—H7	119.2	C18—C19—H192	120.1
C6—C7—H7	119.2	C20—C19—H192	120.1
C7—C8—C9	120.1 (3)	C21—C20—C19	121.6 (3)
C7—C8—H8	120.0	C21—C20—H202	119.2
C9—C8—H8	120.0	C19—C20—H202	119.2
C8—C9—C4	119.1 (3)	C20—C21—C22	118.7 (3)
C8—C9—N1	123.7 (3)	C20—C21—H212	120.6
C4—C9—N1	117.2 (3)	C22—C21—H212	120.6
C11—C10—N1	112.0 (3)	N2—C22—C21	121.7 (3)
C11—C10—C12	122.8 (3)	N2—C22—C17	117.4 (3)
N1—C10—C12	124.7 (3)	C21—C22—C17	120.8 (3)
C10—N1—C1—C2	−178.3 (3)	C14—N2—C12—C13	−21.5 (3)
C9—N1—C1—C2	2.1 (5)	C22—N2—C12—C13	157.9 (3)
C10—N1—C1—S1	1.4 (3)	C11—C10—C12—N2	−12.5 (4)
C9—N1—C1—S1	−178.1 (2)	N1—C10—C12—N2	176.9 (3)
C11—S1—C1—N1	−1.1 (3)	C11—C10—C12—C13	103.2 (3)
I2—S1—C1—N1	91.4 (2)	N1—C10—C12—C13	−67.4 (4)
C11—S1—C1—C2	178.7 (3)	N2—C12—C13—S2	30.8 (3)
I2—S1—C1—C2	−88.8 (3)	C10—C12—C13—S2	−87.3 (3)
N1—C1—C2—C3	−1.2 (5)	C14—S2—C13—C12	−27.0 (2)
S1—C1—C2—C3	179.1 (3)	C22—N2—C14—C15	−0.7 (5)
C1—C2—C3—C4	−1.2 (5)	C12—N2—C14—C15	178.7 (3)
C2—C3—C4—C5	−175.9 (3)	C22—N2—C14—S2	−178.4 (2)
C2—C3—C4—C9	2.6 (5)	C12—N2—C14—S2	1.0 (3)
C9—C4—C5—C6	1.5 (5)	C13—S2—C14—N2	16.0 (2)
C3—C4—C5—C6	180.0 (3)	I1—S2—C14—N2	−160.4 (2)
C4—C5—C6—C7	−0.5 (5)	C13—S2—C14—C15	−161.5 (3)
C5—C6—C7—C8	0.0 (5)	I1—S2—C14—C15	22.1 (3)
C6—C7—C8—C9	−0.6 (5)	N2—C14—C15—C16	−2.3 (5)
C7—C8—C9—C4	1.6 (5)	S2—C14—C15—C16	175.2 (3)
C7—C8—C9—N1	−177.3 (3)	C14—C15—C16—C17	3.8 (5)
C5—C4—C9—C8	−2.0 (4)	C15—C16—C17—C22	−2.4 (5)
C3—C4—C9—C8	179.5 (3)	C15—C16—C17—C18	178.5 (3)
C5—C4—C9—N1	176.9 (3)	C22—C17—C18—C19	1.3 (5)
C3—C4—C9—N1	−1.6 (4)	C16—C17—C18—C19	−179.6 (3)
C1—N1—C9—C8	178.2 (3)	C17—C18—C19—C20	−1.3 (5)
C10—N1—C9—C8	−1.3 (5)	C18—C19—C20—C21	1.1 (5)
C1—N1—C9—C4	−0.7 (4)	C19—C20—C21—C22	−0.9 (5)
C10—N1—C9—C4	179.9 (3)	C14—N2—C22—C21	−178.3 (3)
C1—N1—C10—C11	−1.1 (4)	C12—N2—C22—C21	2.3 (4)
C9—N1—C10—C11	178.4 (3)	C14—N2—C22—C17	2.0 (4)
C1—N1—C10—C12	170.3 (3)	C12—N2—C22—C17	−177.3 (3)
C9—N1—C10—C12	−10.2 (5)	C20—C21—C22—N2	−178.7 (3)
N1—C10—C11—S1	0.3 (4)	C20—C21—C22—C17	0.9 (5)
C12—C10—C11—S1	−171.3 (2)	C16—C17—C22—N2	−0.5 (4)
C1—S1—C11—C10	0.4 (3)	C18—C17—C22—N2	178.6 (3)
I2—S1—C11—C10	−68.9 (2)	C16—C17—C22—C21	179.8 (3)
C14—N2—C12—C10	98.3 (3)	C18—C17—C22—C21	−1.1 (4)
C22—N2—C12—C10	−82.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···I1	0.86	2.72	3.5618 (19)	167

1,2-Dihydro-1,1'-bi[thiazolo[3,2-a]quinoline]-10a,10a'-diium iodide triiodide (kb07)

Crystal data

C22H16N2S2·I^−·I3^−	Z = 2
Mr = 880.09	F(000) = 812
Triclinic, P1	Dx = 2.251 Mg m^−3
a = 8.4090 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1793 (5) Å	Cell parameters from 5766 reflections
c = 15.0322 (7) Å	θ = 2.5–33.0°
α = 100.233 (1)°	µ = 4.97 mm^−1
β = 105.798 (1)°	T = 120 K
γ = 100.372 (1)°	Prism, red
V = 1298.61 (10) Å^3	0.15 × 0.15 × 0.12 mm

Data collection

Bruker SMART APEX DUO diffractometer	8210 reflections with I > 2σ(I)
ω –scan	Rint = 0.035
Absorption correction: numerical SADABS-2014/5 - Bruker AXS area detector scaling and absorption correction	θmax = 36.4°, θmin = 1.9°
Tmin = 0.565, Tmax = 0.674	h = −13→14
24022 measured reflections	k = −18→18
11866 independent reflections	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 0.9437P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
11866 reflections	Δρmax = 3.29 e Å^−3
271 parameters	Δρmin = −3.21 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.

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

	x	y	z	Uiso*/Ueq
I1	1.31557 (4)	1.17568 (3)	0.95960 (2)	0.01842 (6)
I2	0.90839 (4)	0.72026 (3)	0.34349 (2)	0.02575 (7)
I3	0.70401 (4)	0.46557 (3)	0.32289 (2)	0.02392 (7)
I4	1.11002 (5)	0.96411 (4)	0.36229 (3)	0.04094 (10)
S1	0.84466 (19)	0.62217 (15)	0.57145 (9)	0.0329 (3)
S2	1.20723 (14)	0.84259 (10)	0.92626 (9)	0.0208 (2)
N1	0.6960 (5)	0.7440 (3)	0.6722 (3)	0.0182 (6)
N2	0.9596 (4)	0.6436 (3)	0.8785 (2)	0.0155 (6)
C1	0.6881 (6)	0.6991 (5)	0.5798 (3)	0.0230 (9)
C2	0.5618 (7)	0.7115 (5)	0.5012 (3)	0.0284 (10)
H2	0.5585	0.6770	0.4380	0.034*
C3	0.4450 (7)	0.7737 (5)	0.5178 (4)	0.0304 (11)
H3	0.3569	0.7813	0.4655	0.037*
C4	0.4524 (6)	0.8276 (5)	0.6118 (3)	0.0245 (9)
C5	0.3351 (7)	0.8978 (6)	0.6294 (4)	0.0315 (11)
H5	0.2467	0.9054	0.5773	0.038*
C6	0.3465 (7)	0.9549 (5)	0.7202 (4)	0.0311 (11)
H6	0.2663	1.0011	0.7307	0.037*
C7	0.4770 (6)	0.9448 (4)	0.7975 (3)	0.0212 (8)
H7	0.4854	0.9853	0.8603	0.025*
C8	0.5925 (6)	0.8774 (4)	0.7836 (3)	0.0184 (7)
H8	0.6809	0.8720	0.8366	0.022*
C9	0.5811 (5)	0.8162 (4)	0.6914 (3)	0.0171 (7)
C10	0.8278 (6)	0.7106 (4)	0.7374 (3)	0.0187 (7)
C11	0.9158 (7)	0.6475 (5)	0.6918 (3)	0.0292 (10)
H11A	1.0102	0.6193	0.7244	0.035*
C12	0.8692 (5)	0.7385 (4)	0.8445 (3)	0.0160 (7)
H12A	0.7618	0.7318	0.8619	0.019*
C13	0.9926 (6)	0.8666 (4)	0.8973 (3)	0.0218 (8)
H131	0.9678	0.9006	0.9561	0.026*
H132	0.9805	0.9268	0.8563	0.026*
C14	1.1300 (5)	0.6842 (4)	0.9139 (3)	0.0168 (7)
C15	1.2322 (6)	0.6006 (4)	0.9337 (3)	0.0201 (8)
H15	1.3526	0.6296	0.9591	0.024*
C16	1.1557 (6)	0.4760 (4)	0.9159 (3)	0.0192 (8)
H16	1.2243	0.4181	0.9273	0.023*
C17	0.9781 (6)	0.4325 (4)	0.8811 (3)	0.0175 (7)
C18	0.8939 (6)	0.3042 (4)	0.8626 (3)	0.0227 (8)
H18	0.9593	0.2440	0.8727	0.027*
C19	0.7197 (7)	0.2661 (4)	0.8304 (4)	0.0281 (10)
H19	0.6654	0.1802	0.8192	0.034*
C20	0.6209 (6)	0.3538 (5)	0.8137 (4)	0.0289 (10)
H20	0.5003	0.3261	0.7914	0.035*
C21	0.6959 (6)	0.4793 (4)	0.8293 (4)	0.0234 (9)
H21	0.6283	0.5378	0.8178	0.028*
C22	0.8749 (5)	0.5184 (4)	0.8627 (3)	0.0164 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01814 (12)	0.01580 (12)	0.02318 (13)	0.00530 (9)	0.00869 (10)	0.00471 (9)
I2	0.02249 (14)	0.03118 (16)	0.02359 (14)	0.00392 (12)	0.00755 (11)	0.00872 (12)
I3	0.01888 (13)	0.02608 (15)	0.02563 (14)	0.00545 (11)	0.00703 (11)	0.00317 (11)
I4	0.03099 (19)	0.0359 (2)	0.0518 (2)	−0.00088 (15)	0.00492 (16)	0.02192 (17)
S1	0.0430 (7)	0.0488 (8)	0.0179 (5)	0.0302 (7)	0.0143 (5)	0.0084 (5)
S2	0.0169 (5)	0.0154 (4)	0.0301 (6)	0.0020 (4)	0.0085 (4)	0.0058 (4)
N1	0.0193 (16)	0.0189 (16)	0.0183 (16)	0.0065 (13)	0.0078 (13)	0.0041 (13)
N2	0.0159 (15)	0.0144 (15)	0.0169 (15)	0.0047 (12)	0.0051 (12)	0.0044 (12)
C1	0.025 (2)	0.031 (2)	0.0169 (18)	0.0089 (18)	0.0088 (16)	0.0076 (17)
C2	0.033 (3)	0.033 (3)	0.018 (2)	0.014 (2)	0.0031 (18)	0.0047 (18)
C3	0.029 (2)	0.041 (3)	0.019 (2)	0.015 (2)	0.0026 (18)	0.005 (2)
C4	0.022 (2)	0.030 (2)	0.021 (2)	0.0088 (18)	0.0041 (17)	0.0071 (17)
C5	0.022 (2)	0.047 (3)	0.028 (2)	0.016 (2)	0.0058 (19)	0.011 (2)
C6	0.025 (2)	0.040 (3)	0.036 (3)	0.021 (2)	0.012 (2)	0.012 (2)
C7	0.0202 (19)	0.0196 (19)	0.027 (2)	0.0068 (15)	0.0108 (17)	0.0049 (16)
C8	0.0199 (18)	0.0195 (18)	0.0206 (18)	0.0086 (15)	0.0101 (15)	0.0065 (15)
C9	0.0169 (17)	0.0176 (17)	0.0193 (18)	0.0070 (14)	0.0062 (14)	0.0071 (14)
C10	0.0229 (19)	0.0205 (19)	0.0179 (18)	0.0092 (16)	0.0103 (15)	0.0073 (15)
C11	0.035 (3)	0.041 (3)	0.018 (2)	0.022 (2)	0.0085 (19)	0.0102 (19)
C12	0.0182 (17)	0.0172 (17)	0.0165 (17)	0.0075 (14)	0.0082 (14)	0.0064 (14)
C13	0.021 (2)	0.0178 (19)	0.027 (2)	0.0058 (15)	0.0083 (17)	0.0050 (16)
C14	0.0165 (17)	0.0164 (17)	0.0163 (17)	0.0021 (14)	0.0056 (14)	0.0022 (14)
C15	0.0167 (18)	0.0201 (19)	0.026 (2)	0.0062 (15)	0.0076 (16)	0.0092 (16)
C16	0.0211 (19)	0.0192 (18)	0.0213 (19)	0.0098 (15)	0.0085 (15)	0.0065 (15)
C17	0.0214 (19)	0.0135 (16)	0.0175 (17)	0.0059 (14)	0.0048 (15)	0.0041 (13)
C18	0.027 (2)	0.0127 (17)	0.026 (2)	0.0042 (15)	0.0056 (17)	0.0022 (15)
C19	0.026 (2)	0.0153 (19)	0.034 (3)	−0.0006 (16)	0.0003 (19)	0.0038 (18)
C20	0.019 (2)	0.025 (2)	0.035 (3)	−0.0014 (17)	−0.0001 (18)	0.009 (2)
C21	0.0174 (19)	0.0187 (19)	0.030 (2)	0.0028 (15)	0.0022 (17)	0.0063 (17)
C22	0.0167 (17)	0.0148 (16)	0.0171 (17)	0.0024 (13)	0.0049 (14)	0.0043 (13)

Geometric parameters (Å, º)

I1—S2	3.5796 (11)	C7—H7	0.9500
I2—I4	2.8613 (5)	C8—C9	1.401 (6)
I2—I3	2.9651 (5)	C8—H8	0.9500
I3—S1	3.5985 (13)	C10—C11	1.345 (6)
S1—C11	1.697 (5)	C10—C12	1.513 (6)
S1—C1	1.717 (5)	C11—H11A	0.9500
S2—C14	1.731 (4)	C12—C13	1.540 (6)
S2—C13	1.819 (5)	C12—H12A	1.0000
N1—C1	1.369 (6)	C13—H131	0.9900
N1—C10	1.420 (6)	C13—H132	0.9900
N1—C9	1.421 (5)	C14—C15	1.397 (6)
N2—C14	1.344 (5)	C15—C16	1.370 (6)
N2—C22	1.398 (5)	C15—H15	0.9500
N2—C12	1.495 (5)	C16—C17	1.401 (6)
C1—C2	1.404 (7)	C16—H16	0.9500
C2—C3	1.352 (7)	C17—C22	1.420 (6)
C2—H2	0.9500	C17—C18	1.422 (6)
C3—C4	1.415 (7)	C18—C19	1.370 (7)
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.416 (7)	C19—C20	1.408 (7)
C4—C9	1.421 (6)	C19—H19	0.9500
C5—C6	1.369 (8)	C20—C21	1.379 (7)
C5—H5	0.9500	C20—H20	0.9500
C6—C7	1.401 (7)	C21—C22	1.408 (6)
C6—H6	0.9500	C21—H21	0.9500
C7—C8	1.369 (6)
I4—I2—I3	178.982 (16)	N1—C10—C12	126.7 (4)
I2—I3—S1	72.59 (3)	C10—C11—S1	114.6 (4)
C11—S1—C1	89.9 (2)	C10—C11—H11A	122.7
C11—S1—I3	161.0 (2)	S1—C11—H11A	122.7
C1—S1—I3	102.52 (16)	N2—C12—C10	107.3 (3)
C14—S2—C13	91.2 (2)	N2—C12—C13	105.4 (3)
C14—S2—I1	172.17 (15)	C10—C12—C13	114.1 (4)
C13—S2—I1	81.85 (15)	N2—C12—H12A	109.9
C1—N1—C10	111.7 (4)	C10—C12—H12A	109.9
C1—N1—C9	119.4 (4)	C13—C12—H12A	109.9
C10—N1—C9	128.9 (4)	C12—C13—S2	107.3 (3)
C14—N2—C22	122.7 (4)	C12—C13—H131	110.3
C14—N2—C12	114.8 (3)	S2—C13—H131	110.3
C22—N2—C12	122.0 (3)	C12—C13—H132	110.3
N1—C1—C2	123.2 (4)	S2—C13—H132	110.3
N1—C1—S1	112.5 (3)	H131—C13—H132	108.5
C2—C1—S1	124.2 (4)	N2—C14—C15	120.8 (4)
C3—C2—C1	118.3 (5)	N2—C14—S2	114.7 (3)
C3—C2—H2	120.9	C15—C14—S2	124.4 (3)
C1—C2—H2	120.9	C16—C15—C14	118.7 (4)
C2—C3—C4	120.9 (5)	C16—C15—H15	120.6
C2—C3—H3	119.6	C14—C15—H15	120.6
C4—C3—H3	119.6	C15—C16—C17	121.3 (4)
C3—C4—C5	121.1 (4)	C15—C16—H16	119.4
C3—C4—C9	120.9 (4)	C17—C16—H16	119.4
C5—C4—C9	117.9 (4)	C16—C17—C22	119.6 (4)
C6—C5—C4	121.3 (5)	C16—C17—C18	122.9 (4)
C6—C5—H5	119.4	C22—C17—C18	117.4 (4)
C4—C5—H5	119.4	C19—C18—C17	120.9 (4)
C5—C6—C7	119.8 (4)	C19—C18—H18	119.5
C5—C6—H6	120.1	C17—C18—H18	119.5
C7—C6—H6	120.1	C18—C19—C20	120.3 (4)
C8—C7—C6	120.8 (4)	C18—C19—H19	119.9
C8—C7—H7	119.6	C20—C19—H19	119.9
C6—C7—H7	119.6	C21—C20—C19	121.3 (5)
C7—C8—C9	120.3 (4)	C21—C20—H20	119.4
C7—C8—H8	119.8	C19—C20—H20	119.4
C9—C8—H8	119.8	C20—C21—C22	118.4 (4)
C8—C9—C4	119.8 (4)	C20—C21—H21	120.8
C8—C9—N1	123.1 (4)	C22—C21—H21	120.8
C4—C9—N1	117.1 (4)	N2—C22—C21	121.6 (4)
C11—C10—N1	111.2 (4)	N2—C22—C17	116.8 (4)
C11—C10—C12	122.2 (4)	C21—C22—C17	121.6 (4)
C10—N1—C1—C2	175.5 (5)	C22—N2—C12—C10	−72.2 (5)
C9—N1—C1—C2	−5.6 (7)	C14—N2—C12—C13	−22.3 (5)
C10—N1—C1—S1	−2.5 (5)	C22—N2—C12—C13	165.8 (4)
C9—N1—C1—S1	176.4 (3)	C11—C10—C12—N2	−23.3 (6)
C11—S1—C1—N1	1.5 (4)	N1—C10—C12—N2	156.1 (4)
I3—S1—C1—N1	167.0 (3)	C11—C10—C12—C13	93.1 (6)
C11—S1—C1—C2	−176.5 (5)	N1—C10—C12—C13	−87.5 (5)
I3—S1—C1—C2	−11.0 (5)	N2—C12—C13—S2	26.4 (4)
N1—C1—C2—C3	1.8 (8)	C10—C12—C13—S2	−91.1 (4)
S1—C1—C2—C3	179.5 (4)	C14—S2—C13—C12	−20.3 (3)
C1—C2—C3—C4	1.5 (9)	I1—S2—C13—C12	163.2 (3)
C2—C3—C4—C5	177.1 (6)	C22—N2—C14—C15	2.3 (6)
C2—C3—C4—C9	−0.9 (8)	C12—N2—C14—C15	−169.5 (4)
C3—C4—C5—C6	−177.0 (6)	C22—N2—C14—S2	179.4 (3)
C9—C4—C5—C6	1.1 (8)	C12—N2—C14—S2	7.5 (5)
C4—C5—C6—C7	0.4 (9)	C13—S2—C14—N2	8.2 (3)
C5—C6—C7—C8	−0.7 (8)	C13—S2—C14—C15	−174.9 (4)
C6—C7—C8—C9	−0.6 (7)	N2—C14—C15—C16	0.4 (7)
C7—C8—C9—C4	2.0 (7)	S2—C14—C15—C16	−176.4 (3)
C7—C8—C9—N1	−179.5 (4)	C14—C15—C16—C17	−1.9 (7)
C3—C4—C9—C8	175.8 (5)	C15—C16—C17—C22	0.8 (7)
C5—C4—C9—C8	−2.3 (7)	C15—C16—C17—C18	−179.4 (4)
C3—C4—C9—N1	−2.8 (7)	C16—C17—C18—C19	178.7 (5)
C5—C4—C9—N1	179.2 (4)	C22—C17—C18—C19	−1.5 (7)
C1—N1—C9—C8	−172.7 (4)	C17—C18—C19—C20	0.9 (8)
C10—N1—C9—C8	6.1 (7)	C18—C19—C20—C21	0.0 (9)
C1—N1—C9—C4	5.8 (6)	C19—C20—C21—C22	−0.2 (8)
C10—N1—C9—C4	−175.4 (4)	C14—N2—C22—C21	177.3 (4)
C1—N1—C10—C11	2.5 (6)	C12—N2—C22—C21	−11.4 (6)
C9—N1—C10—C11	−176.4 (5)	C14—N2—C22—C17	−3.3 (6)
C1—N1—C10—C12	−177.0 (4)	C12—N2—C22—C17	167.9 (4)
C9—N1—C10—C12	4.2 (7)	C20—C21—C22—N2	178.8 (4)
N1—C10—C11—S1	−1.4 (6)	C20—C21—C22—C17	−0.5 (7)
C12—C10—C11—S1	178.1 (4)	C16—C17—C22—N2	1.7 (6)
C1—S1—C11—C10	0.0 (5)	C18—C17—C22—N2	−178.1 (4)
I3—S1—C11—C10	−131.5 (5)	C16—C17—C22—C21	−178.9 (4)
C14—N2—C12—C10	99.7 (4)	C18—C17—C22—C21	1.3 (6)