(1Z,2Z)-1,2-Bis(3-methyl-2,3-di­hydro-1,3-benzo­thiazol-2-yl­idene)hydrazine

The title compound, C₁₆H₁₄N₄S₂, crystallizes in symmetry group C₂. The mol­ecule is planar with C_2h symmetry, with the inversion centre at the mid-point of the hydrazine N—N bond, and it has an N—N s-trans conformation and a Z,Z configuration. The particular crystal examined was a racemic twin, as suggested by the Flack parameter of 0.41 (2) [Flack (1983). Acta Cryst. A39, 876–881].

Comment

The mol­ecular structure of the title compound, (I), examined at 93 K is shown in Fig. 1. Selected bond distances and angles and the torsion angles relating to the >C=N—N=C< chain are listed in Table 1. The packing of the mol­ecules is indicated in Fig. 2. The particular crystal studied here proved to be a racemic twin, as suggested by the Flack parameter (Flack, 1983) of 0.41 (2). During the refinement, the structure was treated as a racemic twin.

Compound (I) was oxidized by air to a cation radical in acetonitrile or on silica gel. The cation radical is blue and stable for weeks. Its visible spectrum shows a broad band with three peaks at 659, 733 and 818 nm (Nakano & Mori, 2005; Sawicki et al., 1963). The spectrum is very similar to that of the cation radical of 2,2′-azinobis(3-ethyl­benzothia­zoline-6-sulfonic acid) [ABTS; systematic name: 2,2′-(hydrazine-1,2-diylidene)bis­(3-ethyl-2,3-dihydro­benzo[d]thia­zole-6-sulfonate)] which is a water-soluble analogue of the present compound (Henriquez & Lissi, 2002). Compound (I) was previously described in reaction with oxidants such as nitrite (Sawicki et al., 1963) and potassium ferricyanide (Bartsch et al., 1970). This electron-donating character to form the stable cation radical suggests that compound (I) would be useful for forming charge-transfer complexes with electron acceptors such as TCNQ (Guerin et al., 2002).

A recent point of concern regarding compounds with azine groups has appeared in the term `conjugate stopper' for heteroatoms in 1,3-diene systems including N atoms (Glaser et al., 1993; Zuman & Ludvik, 2000; Choytun et al., 2004). It was thought that the conjugation effect through the azine group was determined by the bond distances of =N1—N2= and —C1=N1— (—C9=N2—) and the torsion angle about the N—N bond of the >C=N—N=C< chain; the single-bond character of N—N and the double-bond character of C=N indicate a lack of delocalization of π electrons, while the planar structure of C=N—N=C indicates π conjugation.

The mol­ecular geometry of compound (I) including >C=N—N=C< is completely planar (torsion angle of less than 1°; Table 1). It has a Z,Z configuration, with angles of 111.0 and 110.2° for C1—N1—N2 and N1—N2—C9, respectively (Fig. 1). On the other hand, the bond distances of N1—N2 and C1=N1 (C9=N2) are 1.409 and 1.287 Å (1.294 Å), respectively (Table 1). The former indicates almost a single bond if compared with the value of 1.45 Å in NH₂NH₂ (Liminga & Olovsson, 1964), and the latter almost a double bond if compared with the value of 1.28 Å in imines (Allen et al., 1987). Additionally, these data are very similar to those of formaldehyde azine, where the distances for N—N and C=N are 1.418 and 1.277 Å, respectively, and the angles for C—N—N and H—C—N are 111.4 and 120.7°, respectively (Lide, 1993). These bond distances suggests less delocalization of π electrons, while the mol­ecule is completely flat, permitting inter­action between π bonds of the C=N groups.

The packing of the mol­ecules of (I) in the solid state indicates the lack of intra- and inter­molecular hydrogen bonds, suggesting no hydrogen-bonding effect on the lone-pair electrons of the azine group.

The concept of the `conjugation stopper' of the azine group relating to distances and geometry has not been convincing to date and the present structural results add to the knowledge in the field. The fact that the cation radical of compound (I) is stable gives additional information about the electronic structure of azine groups.

Figure 1 The mol­ecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2 NOT USED A view of the packing in the crystal of (I).

Experimental

Compound (I) was prepared by the oxidation of 3-methyl-2-benzo­thiazolinone hydrazone (MBTH; alternative name: 2-hydrazino-3-methyl-2,3-dihydro­benzo[d]thia­zole), (II), in air, catalyzed by a water-soluble iron porphyrin, FeTMPyPCl₅ {[5,10,15,20-tetra­kis(1-methyl-4-pyridyl)-21H,23H-porphine]iron(III) penta­chloride}, in a phosphate buffer solution (0.1 M; pH 7.0) (Nakano et al., 2005). Through the redox reaction of the iron porphyrin, the superoxide anion radical is released and the porphyrin peripheral eventually decomposes after 30 min. Reagent (II) acts not only as a reducing one-electron donor, but is also oxidized to form compound (I), and dinitro­gen is released from the system. In the present study, the reaction was performed under conditions of 7.0 × 10⁻⁴ M MBTH hydro­chloride and a catalytic concentration of hemin (1 × 10⁻⁵ M). The product, (I), was extracted from the reaction mixture into dichloro­methane, purified by column chromatography (silica gel, dichloromethane) and then crystallized from a solution in dichloro­methane–petroleum ether (1:1) by free evaporation of the solvents overnight. Crystals were collected on filter paper, washed with petroleum ether and dried. A single crystal was selected and used for the data collection. Analysis: m/z = 326.0661; ¹H NMR (300 MHz, acetonitrile-d₃): δ 7.44 (2H), 7.27 (2H), 7.20 (4H), 3.48 (6H); sublimation at 500–503 K (literature m.p. 534–535 K; Hünig & Quast, 1968).

Crystal data

• C₁₆H₁₄N₄S₂

• M_r = 326.43

• Monoclinic, C 2

• a = 16.0038 (17) Å

• b = 5.8679 (7) Å

• c = 15.9529 (18) Å

• β = 104.235 (8)°

• V = 1452.1 (3) ų

• Z = 4

• D_x = 1.493 Mg m⁻³

• Cu Kα radiation

• μ = 3.33 mm⁻¹

• T = 93 (1) K

• Block, pale yellow

• 0.15 × 0.15 × 0.10 mm

Data collection

• Rigaku R-AXIS RAPID diffractometer

• ω scans

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.597, T_max = 0.717

• 7214 measured reflections

• 2506 independent reflections

• 2352 reflections with F² > 2σ(F²)

• R_int = 0.039

• θ_max = 68.2°

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.033

• wR(F²) = 0.094

• S = 1.10

• 2506 reflections

• 203 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0356P)² + 2.2491P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max < 0.001

• Δρ_max = 0.35 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

• Absolute structure: Flack (1983), with 1044 Friedel pairs

• Flack parameter: 0.41 (2)

Table 1
Selected geometric parameters (Å, °)

S1—C1	1.765 (3)
S2—C9	1.762 (3)
N1—N2	1.409 (3)
N1—C1	1.287 (3)
N2—C9	1.294 (3)
N3—C1	1.384 (4)
N4—C9	1.375 (4)

N2—N1—C1	111.0 (2)
N1—N2—C9	110.2 (2)
C1—N3—C8	119.8 (2)
C9—N4—C16	120.2 (2)
S1—C1—N1	127.7 (2)
S1—C1—N3	110.7 (2)
N1—C1—N3	121.6 (3)
S2—C9—N2	127.3 (2)

C1—N1—N2—C9	−178.9 (3)
N1—N2—C9—N4	−179.5 (3)
N1—N2—C9—S2	0.6 (4)
N2—N1—C1—N3	−179.2 (3)
N2—N1—C1—S1	0.3 (4)

H atoms were refined using a riding model, with C—H distances in the range 0.95–0.98 Å and with U_iso(H) = 1.2U_eq(C).

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.

Supporting information

S1. Comment

The molecular structure of the title compound, (I), examined at 93 K is shown in Fig. 1. Selected bond distances and angles and the torsion angles relating to the >C═N—N═C< chain are listed in Table 1. The packing of the molecules is indicated in Fig. 2. The particular crystal studied here proved to be a racemic twin, as suggested by the Flack parameter (Flack, 1983) of 0.41 (2). During the refinement, the structure was treated as a racemic twin.

Compound (I) was oxidized by air to a cation radical in acetonitrile or on silica gel. The cation radical is blue and stable for weeks. Its visible spectrum shows a broad band with three peaks at 659, 733 and 818 nm (Nakano & Mori, 2005; Sawicki et al., 1963). The spectrum is very similar to that of the cation radical of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) [ABTS; systematic name: 2,2'-(hydrazine-1,2-diyledene)bis(3-ethyl-2,3-dihydrobenzo[d]thiazole-6- sulfonate)] which is a water-soluble analogue of the present compound (Henriquez & Lissi, 2002). Compound (I) was previously described in reaction with oxidants such as nitrite (Sawicki et al., 1963) and potassium ferricyanide (Bartsch et al., 1970). This electron-donating character to form the stable cation radical suggests that compound (I) would be useful for forming charge-transfer complexes with electron acceptors such as TCNQ (Guerin et al., 2002).

A recent point of concern regarding compounds with azine groups has appeared in the term `conjugate stopper', for heteroatoms in 1,3-diene systems including N atoms (Glaser et al., 1993; Zuman & Ludvik, 2000; Choytun et al., 2004). It was thought that the conjugation effect through the azine group was determined by the bond distances of ═N1—N2═and —C1═ N1— (—C9═N2—) and the torsion angle about the N—N bond of the >C═N—N═C< chain; the single-bond character of N—N and the double-bond character of C═N indicate a lack of delocalization of π electrons, while the planar structure of C═N—N═C indicates π conjugation.

The molecular geometry of compound (I) including >C═N—N═C< is completely planar (torsion angle of less than 1°; Table 1). It has a Z,Z-configuration, with angles of 111.0 and 110.2° for C1—N1—N2 and N1—N2—C9, respectively (Fig. 1). On the other hand, the bond distances of N1—N2 and C1═N1 (C9═N2) are 1.409 and 1.287 (1.294) Å, respectively (Table 1). The former indicates almost a single bond if compared with the value of 1.45 Å in NH₂NH₂ (Liminga & Olovsson, 1964), and the latter almost a double bond if compared with the value of 1.28 Å in imines (Allen et al., 1987). Additionally, these data are very similar to those of formaldehyde azine: the distances for N—N and C═N are 1.418 and 1.277 Å, respectively, and the angles for C—N—N and H—C—N are 111.4 and 120.7°, respectively (Lide, 1993). These bond distances suggests less delocalization of π electrons, while the molecule is completely flat, permitting interaction between π bonds of the C═N groups.

The packing of the molecules of (I) in the solid state (Fig. 2) indicates the lack of intra- and intermolecular hydrogen bonds, suggesting no hydrogen-bonding effect on the lone-pair electrons of the azine group.

The concept of the `conjugation stopper' of the azine group relating to distances and geometry has not been convincing to date and the present structural results contribute to the further detail of the study. The fact that the cation radical of compound (I) is stable gives additional information about the electronic structure of azine groups.

S2. Experimental

Compound (I) was prepared through the oxidation of 3-methyl-2-benzothiazolinone hydrazone (MBTH; systematic name: 2-hydrazino-3-methyl-2,3-dihydrobenzo[d]thiazole) (II) in air, catalyzed by a water-soluble iron porphyrin, FeTMPyPCl₅, [5,10,15,20-tetrakis(1-methyl-4-pyridino)-21H,23H-porphineiron(III) pentachloride] in a phosphate buffer solution (0.1 M; pH 7.0) (Nakano et al., 2005). Through the redox reaction of iron porphyrin, the superoxide anion radical was released and the porphyrin peripheral eventually decomposed after 30 min. Reagent (II) [Please define (II)] acted not only as a reducing one-electron donor, but was also oxidized to form compound (I), and dinitrogen was released from the system. In the present study, the reaction was performed under conditions of 7.0 × 10⁻⁴ M MBTH hydrochloride and a catalytic concentration of hemin (1 × 10⁻⁵ M). The product, (I), was extracted from the reaction mixture into dichloromethane, purified by column chromatography (silica gel, Eluent?) and then crystallized from a solution in dichloromethane–petroleum ether (Ratio?) by freely evaporating the solvents overnight. Crystals were collected on filter paper, washed with petroleum ether and dried. A single-crystal was selected and used for the data collection. Analysis: m/z = 326.0661; ¹H NMR (300 MHz, acetonitrile-d₃, δ, p.p.m.): 7.44 (2H), 7.27 (2H), 7.20 (4H), 3.48 (6H); sublimes at 500–503 K. (literature m.p. 534–535 K; Hünig & Quast, 1968).

S3. Refinement

H atoms were refined using a riding model, with C—H distances in the range 0.95–0.98 Å [Please check added text] and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the packing in the crystal of (I).

(1Z,2Z)-1,2-Bis(3-methyl-2,3-dihydro-1,3-benzothiazol-2-ylidene)hydrazine

Crystal data

C16H14N4S2	F(000) = 680.00
Mr = 326.43	Dx = 1.493 Mg m^−3
Monoclinic, C2	Melting point: 500-503 (sublimes) K
Hall symbol: C 2y	Cu Kα radiation, λ = 1.54187 Å
a = 16.0038 (17) Å	Cell parameters from 6970 reflections
b = 5.8679 (7) Å	θ = 5.7–68.2°
c = 15.9529 (18) Å	µ = 3.33 mm^−1
β = 104.235 (8)°	T = 93 K
V = 1452.1 (3) Å^3	Block, pale yellow
Z = 4	0.15 × 0.15 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	2352 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.039
ω scans	θmax = 68.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→19
Tmin = 0.597, Tmax = 0.717	k = −6→7
7214 measured reflections	l = −19→19
2506 independent reflections

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 2.2491P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.033	(Δ/σ)max < 0.001
wR(F^2) = 0.094	Δρmax = 0.35 e Å^−3
S = 1.10	Δρmin = −0.24 e Å^−3
2506 reflections	Absolute structure: Flack (1983), with 1044 Friedel pairs
203 parameters	Absolute structure parameter: 0.41 (2)
H-atom parameters constrained

Special details

Refinement. Refinement using reflections with F² > 2.0 σ(F²). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
S1	0.34069 (5)	0.46961 (12)	0.71348 (5)	0.01882 (18)
S2	0.68729 (4)	0.34559 (14)	0.78870 (5)	0.01911 (17)
N1	0.50491 (14)	0.3088 (4)	0.72824 (17)	0.0200 (6)
N2	0.52410 (14)	0.5063 (5)	0.77951 (16)	0.0200 (6)
N3	0.38844 (14)	0.1034 (4)	0.64617 (17)	0.0186 (6)
N4	0.64249 (16)	0.7063 (5)	0.86095 (17)	0.0200 (6)
C1	0.4231 (2)	0.2867 (5)	0.6977 (2)	0.0173 (7)
C2	0.26147 (19)	0.2869 (5)	0.65293 (19)	0.0172 (7)
C3	0.17275 (19)	0.3108 (6)	0.63575 (19)	0.0190 (7)
C4	0.1213 (2)	0.1435 (6)	0.5863 (2)	0.0212 (7)
C5	0.15866 (19)	−0.0415 (7)	0.55430 (19)	0.0202 (6)
C6	0.24774 (19)	−0.0655 (6)	0.57083 (18)	0.0195 (7)
C7	0.29865 (19)	0.0985 (5)	0.62110 (19)	0.0171 (6)
C8	0.4453 (2)	−0.0613 (6)	0.6202 (2)	0.0240 (7)
C9	0.60667 (19)	0.5277 (5)	0.80843 (19)	0.0178 (7)
C10	0.76810 (19)	0.5261 (6)	0.84878 (18)	0.0181 (7)
C11	0.85612 (19)	0.5034 (6)	0.86261 (18)	0.0202 (7)
C12	0.90876 (19)	0.6730 (6)	0.9102 (2)	0.0209 (7)
C13	0.87321 (18)	0.8554 (7)	0.94510 (18)	0.0199 (6)
C14	0.78423 (18)	0.8770 (7)	0.93171 (18)	0.0193 (7)
C15	0.73159 (19)	0.7119 (5)	0.8827 (2)	0.0190 (7)
C16	0.58713 (19)	0.8721 (6)	0.8894 (2)	0.0212 (7)
H1	0.1476	0.4379	0.6571	0.023*
H2	0.0603	0.1556	0.5743	0.025*
H3	0.1226	−0.1534	0.5205	0.024*
H4	0.2728	−0.1908	0.5483	0.023*
H5	0.4829	0.0174	0.5895	0.029*
H6	0.4108	−0.1754	0.5820	0.029*
H7	0.4807	−0.1366	0.6717	0.029*
H8	0.8805	0.3761	0.8405	0.024*
H9	0.9695	0.6633	0.9187	0.025*
H10	0.9101	0.9665	0.9785	0.024*
H11	0.7600	1.0018	0.9555	0.023*
H12	0.5665	0.9842	0.8435	0.025*
H13	0.6200	0.9499	0.9415	0.025*
H14	0.5378	0.7933	0.9024	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0136 (3)	0.0186 (4)	0.0222 (3)	0.0013 (3)	0.0005 (2)	−0.0035 (3)
S2	0.0139 (3)	0.0194 (4)	0.0220 (3)	0.0003 (3)	0.0006 (2)	−0.0019 (3)
N1	0.0146 (12)	0.0205 (17)	0.0227 (12)	0.0004 (11)	0.0006 (9)	−0.0018 (12)
N2	0.0166 (13)	0.0187 (17)	0.0228 (13)	−0.0035 (11)	0.0012 (9)	0.0019 (12)
N3	0.0113 (12)	0.0194 (16)	0.0234 (12)	0.0044 (11)	0.0009 (9)	−0.0021 (12)
N4	0.0162 (13)	0.0199 (17)	0.0216 (13)	−0.0001 (11)	0.0004 (10)	−0.0020 (12)
C1	0.0172 (15)	0.014 (2)	0.0200 (14)	−0.0002 (12)	0.0029 (11)	0.0032 (13)
C2	0.0193 (15)	0.015 (2)	0.0158 (14)	0.0028 (12)	0.0008 (11)	−0.0011 (12)
C3	0.0173 (15)	0.017 (2)	0.0219 (15)	0.0023 (13)	0.0033 (11)	−0.0009 (14)
C4	0.0153 (15)	0.023 (2)	0.0229 (15)	−0.0009 (13)	0.0013 (11)	0.0040 (15)
C5	0.0203 (15)	0.0179 (18)	0.0201 (14)	−0.0075 (14)	0.0008 (11)	0.0010 (16)
C6	0.0184 (15)	0.021 (2)	0.0174 (14)	0.0002 (13)	0.0006 (11)	0.0027 (14)
C7	0.0193 (16)	0.0152 (18)	0.0164 (14)	0.0029 (13)	0.0032 (11)	0.0031 (13)
C8	0.0180 (15)	0.027 (2)	0.0254 (15)	0.0018 (14)	0.0029 (12)	0.0002 (16)
C9	0.0167 (15)	0.019 (2)	0.0181 (14)	0.0021 (12)	0.0055 (11)	0.0017 (13)
C10	0.0180 (15)	0.019 (2)	0.0147 (14)	−0.0020 (13)	−0.0006 (11)	−0.0011 (13)
C11	0.0155 (14)	0.024 (2)	0.0189 (14)	0.0010 (13)	−0.0001 (11)	0.0040 (15)
C12	0.0130 (15)	0.026 (2)	0.0224 (15)	−0.0010 (13)	0.0012 (11)	0.0009 (15)
C13	0.0164 (15)	0.0224 (18)	0.0184 (13)	−0.0010 (16)	−0.0005 (10)	−0.0024 (16)
C14	0.0214 (15)	0.021 (2)	0.0156 (14)	−0.0004 (14)	0.0049 (11)	−0.0014 (15)
C15	0.0128 (15)	0.024 (2)	0.0179 (14)	0.0014 (13)	−0.0001 (11)	0.0044 (14)
C16	0.0177 (14)	0.0191 (19)	0.0265 (15)	0.0015 (14)	0.0051 (11)	−0.0040 (15)

Geometric parameters (Å, º)

S1—C1	1.765 (3)	C10—C15	1.407 (4)
S1—C2	1.757 (2)	C11—C12	1.400 (4)
S2—C9	1.762 (3)	C12—C13	1.391 (5)
S2—C10	1.762 (3)	C13—C14	1.393 (4)
N1—N2	1.409 (3)	C14—C15	1.391 (4)
N1—C1	1.287 (3)	C3—H1	0.950
N2—C9	1.294 (3)	C4—H2	0.950
N3—C1	1.384 (4)	C5—H3	0.950
N3—C7	1.394 (3)	C6—H4	0.950
N3—C8	1.456 (4)	C8—H5	0.980
N4—C9	1.375 (4)	C8—H6	0.980
N4—C15	1.383 (3)	C8—H7	0.980
N4—C16	1.462 (4)	C11—H8	0.950
C2—C3	1.385 (4)	C12—H9	0.950
C2—C7	1.408 (4)	C13—H10	0.950
C3—C4	1.394 (4)	C14—H11	0.950
C4—C5	1.396 (5)	C16—H12	0.980
C5—C6	1.392 (4)	C16—H13	0.980
C6—C7	1.383 (4)	C16—H14	0.980
C10—C11	1.378 (4)
S1···C11^i	3.594 (3)	C10···H11^viii	3.534
S1···C12^i	3.519 (3)	C10···H11^x	3.265
S2···C4^ii	3.594 (3)	C10···H13^x	3.413
N2···C8^iii	3.593 (4)	C11···H12^vii	3.455
C1···C11^i	3.496 (4)	C11···H13^x	3.069
C1···C12^i	3.517 (4)	C11···H14^vii	3.077
C2···C10^i	3.457 (4)	C12···H9^vi	2.939
C3···C9^i	3.591 (4)	C12···H10^vi	3.463
C4···C8^iv	3.460 (4)	C12···H12^vii	3.170
C6···C7^v	3.563 (4)	C12···H13^vii	3.545
C12···C12^vi	3.553 (3)	C12···H13^x	2.839
C12···C16^vii	3.441 (4)	C12···H14^vii	3.061
S1···H4^iii	3.269	C13···H8^iii	3.497
S1···H6^iii	3.339	C13···H9^vi	3.104
S1···H7^iii	3.397	C13···H10^vi	3.444
S1···H8^iv	3.093	C13···H13^x	2.975
S2···H1^vii	3.143	C13···H14^xii	3.584
S2···H11^viii	3.314	C14···H11^x	3.035
S2···H12^viii	3.136	C14···H13^x	3.346
N1···H1^vii	3.537	C15···H11^x	2.834
N1···H2^ii	3.468	C15···H13^x	3.549
N1···H7^iii	3.374	C16···H7^iii	3.474
N1···H9^i	3.336	C16···H8^iv	3.206
N1···H12^viii	2.662	C16···H9^iv	2.667
N2···H2^ii	3.571	C16···H10^x	3.171
N2···H7^iii	2.692	H1···H3^iii	3.199
N2···H8^iv	3.469	H1···H5^iv	2.633
N2···H9^i	3.271	H1···H7^iv	2.773
N2···H12^viii	3.248	H1···H12^i	3.536
N3···H3^ix	2.985	H2···H2^xi	2.664
N3···H8^i	3.405	H2···H3^xi	3.459
N4···H1^ii	3.544	H2···H5^iv	2.499
N4···H7^iii	3.582	H2···H5^ix	3.305
N4···H10^x	3.211	H2···H6^iv	2.621
N4···H11^x	3.194	H2···H6^ix	2.826
C1···H3^ix	3.394	H2···H7^iv	2.549
C1···H7^iii	3.558	H3···H4^ix	3.504
C1···H8^i	3.496	H3···H5^i	3.338
C1···H9^i	3.496	H3···H5^v	2.864
C1···H12^viii	3.347	H3···H6^v	3.452
C2···H4^iii	3.516	H3···H6^ix	3.224
C2···H4^ix	3.123	H4···H4^v	3.311
C3···H4^ix	3.261	H4···H4^ix	3.311
C3···H5^iv	3.185	H5···H5^xiii	3.036
C3···H6^ix	3.403	H7···H8^i	3.457
C3···H7^iv	3.277	H7···H12^viii	2.838
C4···H2^xi	3.369	H7···H14^viii	3.592
C4···H4^ix	3.196	H8···H10^viii	3.215
C4···H5^iv	3.127	H8···H12^vii	3.032
C4···H6^iv	3.517	H8···H13^x	3.507
C4···H6^ix	2.815	H8···H14^vii	2.516
C4···H7^iv	3.177	H9···H9^vi	2.537
C5···H1^viii	3.492	H9···H10^vi	2.831
C5···H4^ix	2.999	H9···H12^vii	2.422
C5···H6^ix	3.064	H9···H13^vii	2.659
C6···H4^ix	2.871	H9···H13^x	3.189
C7···H3^ix	3.196	H9···H14^vii	2.473
C7···H4^ix	2.935	H10···H10^vi	2.790
C8···H1^vii	3.144	H10···H13^x	3.369
C8···H2^vii	2.710	H10···H13^xii	3.195
C8···H2^v	3.502	H10···H14^ii	3.248
C8···H3^ix	3.279	H10···H14^xii	2.684
C9···H1^ii	3.581	H11···H11^x	3.309
C9···H7^iii	3.247	H11···H11^xii	3.309
C9···H10^x	3.493	H11···H13^xii	3.427
C9···H12^viii	3.328
C1—S1—C2	90.79 (14)	C13—C14—C15	118.5 (3)
C9—S2—C10	90.57 (15)	N4—C15—C10	112.6 (2)
N2—N1—C1	111.0 (2)	N4—C15—C14	127.0 (3)
N1—N2—C9	110.2 (2)	C10—C15—C14	120.3 (2)
C1—N3—C7	114.8 (2)	C2—C3—H1	120.8
C1—N3—C8	119.8 (2)	C4—C3—H1	120.8
C7—N3—C8	125.3 (2)	C3—C4—H2	119.7
C9—N4—C15	114.9 (2)	C5—C4—H2	119.7
C9—N4—C16	120.2 (2)	C4—C5—H3	119.3
C15—N4—C16	124.9 (2)	C6—C5—H3	119.3
S1—C1—N1	127.7 (2)	C5—C6—H4	121.0
S1—C1—N3	110.7 (2)	C7—C6—H4	121.0
N1—C1—N3	121.6 (3)	N3—C8—H5	109.5
S1—C2—C3	127.8 (2)	N3—C8—H6	109.5
S1—C2—C7	111.4 (2)	N3—C8—H7	109.5
C3—C2—C7	120.8 (2)	H5—C8—H6	109.5
C2—C3—C4	118.4 (3)	H5—C8—H7	109.5
C3—C4—C5	120.5 (2)	H6—C8—H7	109.5
C4—C5—C6	121.4 (3)	C10—C11—H8	120.9
C5—C6—C7	118.0 (3)	C12—C11—H8	120.9
N3—C7—C2	112.2 (2)	C11—C12—H9	119.6
N3—C7—C6	126.8 (3)	C13—C12—H9	119.6
C2—C7—C6	121.0 (2)	C12—C13—H10	119.6
S2—C9—N2	127.3 (2)	C14—C13—H10	119.6
S2—C9—N4	110.9 (2)	C13—C14—H11	120.7
N2—C9—N4	121.8 (3)	C15—C14—H11	120.7
S2—C10—C11	127.9 (2)	N4—C16—H12	109.5
S2—C10—C15	110.9 (2)	N4—C16—H13	109.5
C11—C10—C15	121.2 (2)	N4—C16—H14	109.5
C10—C11—C12	118.3 (3)	H12—C16—H13	109.5
C11—C12—C13	120.9 (2)	H12—C16—H14	109.5
C12—C13—C14	120.8 (3)	H13—C16—H14	109.5
C1—N1—N2—C9	−178.9 (3)	N2—N1—C1—N3	−179.2 (3)
N1—N2—C9—N4	−179.5 (3)	N2—N1—C1—S1	0.3 (4)
N1—N2—C9—S2	0.6 (4)

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x+1/2, y+1/2, z; (iii) x, y+1, z; (iv) x−1/2, y+1/2, z; (v) −x+1/2, y−1/2, −z+1; (vi) −x+2, y, −z+2; (vii) x+1/2, y−1/2, z; (viii) x, y−1, z; (ix) −x+1/2, y+1/2, −z+1; (x) −x+3/2, y−1/2, −z+2; (xi) −x, y, −z+1; (xii) −x+3/2, y+1/2, −z+2; (xiii) −x+1, y, −z+1.