N,N′-Bis(1,3-dimethyl­imidazolidin-2-yl­idene)-2,2′-dithio­dianiline

The mol­ecular structure of the title compound, C₂₂H₂₈N₆S₂, is the first crystallographically determined guanidine ligand containing sulfur. It shows two guanidyl groups bridged by a diphenyl­disulfanyl linker with localized C=N bonds. The C—S—S—C group has a folded nonplanar conformation like that found in H₂O₂ or H₂S₂, with a torsion angle of 84.65 (10)°. The S—S bond length is 2.0435 (7) Å. Molecules are linked by C—H...N hydrogen bonds. The crystal studied was an inversion twin with approximately 2:1 components.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.088
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro .          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.87
           From the CIF: _reflns_number_total               4209
           Count of symmetry unique reflns         2655
           Completeness (_total/calc)            158.53%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1554
           Fraction of Friedel pairs measured     0.585
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The synthesis and characterization of molecules containing nitrogen and sulfur as donor functions is important for biomimetic coordination chemistry. The use of this molecules as ligands in the synthesis of copper-complexes as mimics for active centres like the CuA in cytochrome-c-oxidase and N₂O-reductase is currently of considerable interest in bioinorganic chemistry. In search of multifunctional ligands we have extended our studies to guanidyl-type systems with N-donor functions. The first derivative, the ligand bis(tetramethyl-guanidino)propylene and its complexes with Cu, Fe, Ni and Mn have recently been investigated (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Wittmann et al., 2001; Herres et al., 2005, Neuba et al., 2007). We have now developed the title compound with disulfide group as novel ligand with redoxactivity for use in biomimetic copper-sulfur chemistry.

The most interesting feature are the torsion angles τ C–S1–S2–C' and C–C'–S1–S2 which indicate pπ-dπ interactions between the fully occupied pz orbital on the carbon C atom (part of the aromatic π system) with an empty d orbital on the S atom as reported for 2,2'-diaminodiphenyl disulfide (Lee & Bryant, 1970). The S–S bond length in disulfide compounds is correlated with the C–S–S–C torsion angles, being around 2.031 Å (τ = 75–105°) or 2.070 Å (t = 0–20°) (Allen et al., 1987). For (I) τ is 84.65 (10)° and the S1–S2 bond length 2.0435 (7) Å matching these ranges. As may be seen from the geometric bonding parameters (Table 1), the guanidyl double bonds C1═ N1 and C18═N14 are clearly localized.

The packing pattern shows intermolecular C–H···N hydrogen interactions (Table 2) with molecules stacked in [010] direction.

Related literature

For related literature, see: Allen et al. (1987); Gomes de Mesquita (1967); Harmjanz (1997); Herres et al. (2005); Kaitner & Pavlovic (1997); Lee & Bryant (1970); Neuba et al. (2007); Pohl et al. (2000); Schneider (2000); Waden (1999); Wittmann et al. (2001).

S2. Experimental

A solution of dimethylethylenechloroformamidinium chloride (5.07 g, 30 mmol) in dry MeCN was added dropwise to an ice-cooled solution of 2,2'-dithiodianiline (3.73 g, 15 mmol) and triethylamine (4.18 ml, 3.03 g, 30 mmol) in dry MeCN. After 3 h under reflux, a solution of NaOH (1.2 g, 30 mmol) in water was added. The solvents and NEt₃ were then evaporated under vacuum. In order to deprotonate the bis-hydrochloride, 50 wt% KOH (aqueous, 15 ml) was added and the free base was extracted into the THF phase (3 x 80 ml). The organic phase was dried with Na₂SO₄. After filtration, the solvent was evaporated under reduced pressure. Colourless crystals suitable for X-ray diffraction were obtained by diffusion of Et₂O into a cold saturated MeCN solution.

¹H NMR (500 MHz, CDCl₃): δ 2.65 (s, 12H, Me), 3.3 (s, 8H, CH₂), 6.79 (m, 4H, CH_arom), 6.95 (m, 2H, CH_arom), 7.45 (m, 2H, CH_arom); ¹³C NMR (125 MHz, CDCl₃): δ 43.8 (Me), 48.4 (CH₂), 121.1 (CH_arom), 122.0 (CH_arom), 125.2 (CH_arom), 125.8 (CH_arom), 128.9 (C_quart), 147.2 (C_quart), 155.5 (C_gua); IR (KBr, \v, cm^-1): 3035 (w), 2946 (m), 2858 (m), 1636 (versus, C═ N), 1613 (versus, C═N), 1568 (versus), 1441 (s), 1283 (s), 1034 (s), 966 (m), 740 (m). EI—MS: m/z (%) 440 (40) [M⁺], 344 (70), 248 (85), 220 (90), 165 (80), 124 (90), 80 (75), 44 (80), 28 (30); Elemental analysis (M = 440.63 g mol^-1): calcd. for C₂₂H₂₈N₆S₂: C: 59.97; H: 6.41; N: 19.07; found C: 60.05, H: 6.62, N: 19.00.

S3. Refinement

Hydrogen atoms located from difference Fourier maps were refined at idealized positions riding on the carbon atoms with isotropic displacement parameters U_iso(H) = 1.2U(Ceq) or 1.5U(CH₃). All CH₃ hydrogen atoms were allowed to rotate but not to tip. The crystal was refined as an inversion twin with the ratio of the two domains of 0.34 (6)/0.66 (6).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Molecular structure of I. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of I viewed along [010] with hydrogen bond indicated as dashed lines. H-atoms not involved are omitted.

N,N'-Bis(1,3-dimethylimidazolidin-2-ylidene)-2,2'-dithiodianiline

Crystal data

C22H28N6S2	F(000) = 468
Mr = 440.62	Dx = 1.317 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 913 reflections
a = 8.2794 (12) Å	θ = 2.5–28.2°
b = 10.1065 (14) Å	µ = 0.26 mm^−1
c = 13.7018 (19) Å	T = 120 K
β = 104.333 (3)°	Prism, colourless
V = 1110.8 (3) Å^3	0.42 × 0.39 × 0.36 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	4209 independent reflections
Radiation source: sealed tube	4074 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 27.9°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→9
Tmin = 0.898, Tmax = 0.912	k = −13→13
8801 measured reflections	l = −15→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.0758P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4209 reflections	Δρmax = 0.35 e Å^−3
276 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.34 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S1	0.55549 (6)	0.30126 (4)	0.67932 (4)	0.02459 (12)
S2	0.65522 (6)	0.12261 (4)	0.73258 (4)	0.02580 (12)
N1	0.4194 (2)	0.50987 (16)	0.54669 (13)	0.0256 (4)
N2	0.3726 (2)	0.72951 (16)	0.57965 (14)	0.0254 (4)
N3	0.5600 (2)	0.69499 (14)	0.49018 (14)	0.0263 (4)
N4	0.8884 (2)	−0.09539 (16)	0.77503 (14)	0.0272 (4)
N5	1.0402 (2)	−0.1713 (2)	0.94000 (15)	0.0329 (4)
N6	0.9051 (2)	−0.31590 (17)	0.82600 (16)	0.0338 (5)
C1	0.4521 (2)	0.63399 (19)	0.53619 (15)	0.0232 (4)
C2	0.2088 (3)	0.7044 (2)	0.5944 (2)	0.0382 (6)
H2A	0.2052	0.6150	0.6215	0.057*
H2B	0.1258	0.7120	0.5298	0.057*
H2C	0.1842	0.7692	0.6420	0.057*
C3	0.4088 (3)	0.86078 (19)	0.54545 (18)	0.0309 (5)
H3A	0.4261	0.9263	0.6008	0.037*
H3B	0.3179	0.8918	0.4886	0.037*
C4	0.5678 (3)	0.8371 (2)	0.51246 (18)	0.0310 (5)
H4A	0.5699	0.8899	0.4519	0.037*
H4B	0.6673	0.8591	0.5669	0.037*
C5	0.7065 (3)	0.6331 (2)	0.46938 (19)	0.0320 (5)
H5A	0.6830	0.6092	0.3979	0.048*
H5B	0.7348	0.5533	0.5106	0.048*
H5C	0.8003	0.6952	0.4855	0.048*
C6	0.4730 (2)	0.40803 (19)	0.49286 (16)	0.0243 (4)
C7	0.4507 (3)	0.4075 (2)	0.38863 (18)	0.0312 (5)
H7A	0.4041	0.4829	0.3506	0.037*
C8	0.4953 (3)	0.2983 (2)	0.33941 (18)	0.0343 (5)
H8A	0.4807	0.3001	0.2684	0.041*
C9	0.5613 (3)	0.1865 (2)	0.39408 (19)	0.0330 (5)
H9A	0.5916	0.1117	0.3606	0.040*
C10	0.5827 (3)	0.18485 (18)	0.49752 (18)	0.0282 (4)
H10A	0.6288	0.1088	0.5350	0.034*
C11	0.5374 (2)	0.29307 (17)	0.54681 (16)	0.0224 (4)
C12	0.8746 (3)	0.14206 (19)	0.75131 (15)	0.0246 (4)
C13	0.9518 (3)	0.2624 (2)	0.74463 (18)	0.0313 (5)
H13A	0.8864	0.3404	0.7290	0.038*
C14	1.1245 (3)	0.2698 (2)	0.76067 (19)	0.0378 (5)
H14A	1.1769	0.3522	0.7556	0.045*
C15	1.2188 (3)	0.1562 (3)	0.78401 (19)	0.0370 (5)
H15A	1.3365	0.1608	0.7949	0.044*
C16	1.1434 (3)	0.0360 (2)	0.79161 (17)	0.0317 (5)
H16A	1.2101	−0.0412	0.8077	0.038*
C17	0.9701 (3)	0.02614 (19)	0.77599 (15)	0.0249 (4)
C18	0.9436 (3)	−0.1845 (2)	0.84325 (17)	0.0268 (4)
C19	1.0216 (4)	−0.0560 (3)	1.0000 (2)	0.0419 (6)
H19A	0.9221	−0.0665	1.0259	0.063*
H19B	1.0099	0.0236	0.9580	0.063*
H19C	1.1201	−0.0473	1.0566	0.063*
C20	1.0484 (3)	−0.2999 (2)	0.9920 (2)	0.0411 (6)
H20A	0.9661	−0.3045	1.0335	0.049*
H20B	1.1613	−0.3165	1.0354	0.049*
C21	1.0063 (3)	−0.3963 (2)	0.9055 (2)	0.0383 (6)
H21A	1.1080	−0.4284	0.8873	0.046*
H21B	0.9428	−0.4729	0.9214	0.046*
C22	0.8467 (4)	−0.3676 (2)	0.7259 (2)	0.0429 (6)
H22A	0.9403	−0.4068	0.7041	0.064*
H22B	0.7980	−0.2959	0.6798	0.064*
H22C	0.7620	−0.4355	0.7253	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0266 (3)	0.0221 (2)	0.0259 (2)	0.00218 (18)	0.00804 (19)	0.00260 (18)
S2	0.0213 (2)	0.0223 (2)	0.0330 (3)	−0.00125 (17)	0.00521 (19)	0.00647 (19)
N1	0.0261 (9)	0.0233 (7)	0.0274 (9)	0.0044 (6)	0.0064 (7)	0.0029 (6)
N2	0.0258 (9)	0.0230 (7)	0.0263 (9)	0.0023 (6)	0.0047 (7)	−0.0028 (6)
N3	0.0282 (10)	0.0219 (7)	0.0296 (10)	0.0016 (6)	0.0088 (7)	0.0014 (6)
N4	0.0230 (9)	0.0245 (7)	0.0306 (9)	0.0001 (6)	−0.0001 (7)	0.0027 (7)
N5	0.0265 (10)	0.0428 (10)	0.0273 (10)	−0.0012 (8)	0.0025 (8)	0.0063 (8)
N6	0.0294 (10)	0.0259 (8)	0.0419 (12)	0.0045 (7)	0.0008 (9)	0.0063 (7)
C1	0.0196 (10)	0.0277 (9)	0.0197 (10)	0.0042 (7)	0.0000 (8)	0.0017 (7)
C2	0.0278 (12)	0.0357 (11)	0.0533 (17)	0.0040 (9)	0.0143 (11)	−0.0082 (10)
C3	0.0346 (12)	0.0245 (9)	0.0316 (12)	0.0037 (8)	0.0045 (9)	0.0000 (8)
C4	0.0332 (12)	0.0229 (9)	0.0346 (12)	−0.0009 (8)	0.0043 (9)	−0.0012 (8)
C5	0.0273 (11)	0.0335 (11)	0.0375 (12)	0.0011 (8)	0.0121 (9)	0.0009 (8)
C6	0.0199 (10)	0.0250 (8)	0.0275 (11)	0.0011 (7)	0.0049 (8)	0.0009 (7)
C7	0.0262 (11)	0.0344 (10)	0.0296 (11)	0.0053 (8)	0.0006 (9)	0.0037 (9)
C8	0.0327 (13)	0.0448 (12)	0.0244 (11)	−0.0012 (9)	0.0054 (9)	−0.0046 (9)
C9	0.0332 (13)	0.0322 (10)	0.0352 (13)	−0.0012 (8)	0.0117 (10)	−0.0105 (9)
C10	0.0259 (11)	0.0225 (8)	0.0365 (12)	0.0008 (7)	0.0085 (9)	−0.0012 (8)
C11	0.0172 (9)	0.0244 (8)	0.0255 (10)	−0.0021 (7)	0.0048 (7)	−0.0001 (7)
C12	0.0214 (10)	0.0276 (9)	0.0235 (10)	−0.0028 (7)	0.0029 (8)	0.0006 (7)
C13	0.0316 (12)	0.0257 (9)	0.0352 (12)	−0.0040 (8)	0.0055 (9)	0.0040 (8)
C14	0.0332 (13)	0.0407 (11)	0.0368 (13)	−0.0137 (9)	0.0038 (10)	0.0074 (9)
C15	0.0224 (11)	0.0543 (13)	0.0326 (12)	−0.0061 (10)	0.0036 (9)	0.0097 (10)
C16	0.0234 (11)	0.0409 (11)	0.0292 (11)	0.0032 (8)	0.0039 (8)	0.0061 (9)
C17	0.0250 (10)	0.0285 (9)	0.0198 (9)	−0.0021 (7)	0.0032 (7)	0.0014 (7)
C18	0.0182 (10)	0.0292 (9)	0.0311 (11)	0.0012 (7)	0.0025 (8)	0.0017 (7)
C19	0.0423 (14)	0.0529 (13)	0.0310 (13)	−0.0202 (11)	0.0100 (10)	−0.0038 (10)
C20	0.0300 (13)	0.0553 (14)	0.0368 (14)	0.0031 (10)	0.0060 (10)	0.0198 (11)
C21	0.0261 (12)	0.0350 (11)	0.0524 (16)	0.0036 (8)	0.0071 (10)	0.0190 (10)
C22	0.0491 (16)	0.0256 (10)	0.0465 (15)	−0.0001 (9)	−0.0020 (12)	−0.0008 (9)

Geometric parameters (Å, º)

S1—C11	1.786 (2)	C6—C11	1.409 (3)
S1—S2	2.0435 (7)	C7—C8	1.390 (3)
S2—C12	1.781 (2)	C7—H7A	0.9500
N1—C1	1.299 (3)	C8—C9	1.391 (3)
N1—C6	1.401 (3)	C8—H8A	0.9500
N2—C1	1.383 (3)	C9—C10	1.384 (3)
N2—C2	1.442 (3)	C9—H9A	0.9500
N2—C3	1.463 (3)	C10—C11	1.385 (3)
N3—C1	1.362 (3)	C10—H10A	0.9500
N3—C5	1.454 (3)	C12—C13	1.388 (3)
N3—C4	1.466 (2)	C12—C17	1.407 (3)
N4—C18	1.297 (3)	C13—C14	1.394 (3)
N4—C17	1.401 (3)	C13—H13A	0.9500
N5—C18	1.375 (3)	C14—C15	1.380 (4)
N5—C19	1.457 (3)	C14—H14A	0.9500
N5—C20	1.475 (3)	C15—C16	1.382 (3)
N6—C18	1.373 (3)	C15—H15A	0.9500
N6—C22	1.435 (3)	C16—C17	1.401 (3)
N6—C21	1.448 (3)	C16—H16A	0.9500
C2—H2A	0.9800	C19—H19A	0.9800
C2—H2B	0.9800	C19—H19B	0.9800
C2—H2C	0.9800	C19—H19C	0.9800
C3—C4	1.513 (3)	C20—C21	1.507 (4)
C3—H3A	0.9900	C20—H20A	0.9900
C3—H3B	0.9900	C20—H20B	0.9900
C4—H4A	0.9900	C21—H21A	0.9900
C4—H4B	0.9900	C21—H21B	0.9900
C5—H5A	0.9800	C22—H22A	0.9800
C5—H5B	0.9800	C22—H22B	0.9800
C5—H5C	0.9800	C22—H22C	0.9800
C6—C7	1.394 (3)
C11—S1—S2	104.29 (6)	C10—C9—H9A	120.2
C12—S2—S1	105.15 (7)	C8—C9—H9A	120.2
C1—N1—C6	123.32 (19)	C9—C10—C11	120.54 (19)
C1—N2—C2	120.12 (17)	C9—C10—H10A	119.7
C1—N2—C3	109.76 (19)	C11—C10—H10A	119.7
C2—N2—C3	118.61 (18)	C10—C11—C6	120.6 (2)
C1—N3—C5	124.81 (16)	C10—C11—S1	124.58 (16)
C1—N3—C4	110.31 (18)	C6—C11—S1	114.86 (15)
C5—N3—C4	117.79 (18)	C13—C12—C17	120.3 (2)
C18—N4—C17	121.27 (18)	C13—C12—S2	123.86 (17)
C18—N5—C19	120.3 (2)	C17—C12—S2	115.80 (15)
C18—N5—C20	109.09 (19)	C12—C13—C14	120.5 (2)
C19—N5—C20	115.5 (2)	C12—C13—H13A	119.8
C18—N6—C22	121.73 (19)	C14—C13—H13A	119.8
C18—N6—C21	110.3 (2)	C15—C14—C13	119.5 (2)
C22—N6—C21	120.65 (19)	C15—C14—H14A	120.3
N1—C1—N3	131.85 (19)	C13—C14—H14A	120.3
N1—C1—N2	119.5 (2)	C14—C15—C16	120.6 (2)
N3—C1—N2	108.66 (17)	C14—C15—H15A	119.7
N2—C2—H2A	109.5	C16—C15—H15A	119.7
N2—C2—H2B	109.5	C15—C16—C17	121.0 (2)
H2A—C2—H2B	109.5	C15—C16—H16A	119.5
N2—C2—H2C	109.5	C17—C16—H16A	119.5
H2A—C2—H2C	109.5	N4—C17—C16	122.52 (19)
H2B—C2—H2C	109.5	N4—C17—C12	119.12 (19)
N2—C3—C4	102.41 (16)	C16—C17—C12	118.11 (18)
N2—C3—H3A	111.3	N4—C18—N6	121.5 (2)
C4—C3—H3A	111.3	N4—C18—N5	130.2 (2)
N2—C3—H3B	111.3	N6—C18—N5	108.33 (18)
C4—C3—H3B	111.3	N5—C19—H19A	109.5
H3A—C3—H3B	109.2	N5—C19—H19B	109.5
N3—C4—C3	102.73 (17)	H19A—C19—H19B	109.5
N3—C4—H4A	111.2	N5—C19—H19C	109.5
C3—C4—H4A	111.2	H19A—C19—H19C	109.5
N3—C4—H4B	111.2	H19B—C19—H19C	109.5
C3—C4—H4B	111.2	N5—C20—C21	102.4 (2)
H4A—C4—H4B	109.1	N5—C20—H20A	111.3
N3—C5—H5A	109.5	C21—C20—H20A	111.3
N3—C5—H5B	109.5	N5—C20—H20B	111.3
H5A—C5—H5B	109.5	C21—C20—H20B	111.3
N3—C5—H5C	109.5	H20A—C20—H20B	109.2
H5A—C5—H5C	109.5	N6—C21—C20	101.97 (19)
H5B—C5—H5C	109.5	N6—C21—H21A	111.4
C7—C6—N1	124.29 (18)	C20—C21—H21A	111.4
C7—C6—C11	118.10 (18)	N6—C21—H21B	111.4
N1—C6—C11	117.25 (19)	C20—C21—H21B	111.4
C8—C7—C6	121.1 (2)	H21A—C21—H21B	109.2
C8—C7—H7A	119.4	N6—C22—H22A	109.5
C6—C7—H7A	119.4	N6—C22—H22B	109.5
C7—C8—C9	120.0 (2)	H22A—C22—H22B	109.5
C7—C8—H8A	120.0	N6—C22—H22C	109.5
C9—C8—H8A	120.0	H22A—C22—H22C	109.5
C10—C9—C8	119.7 (2)	H22B—C22—H22C	109.5
C11—S1—S2—C12	84.65 (10)	S1—S2—C12—C13	9.0 (2)
C6—N1—C1—N3	−12.6 (3)	S1—S2—C12—C17	−172.24 (15)
C6—N1—C1—N2	169.64 (18)	C17—C12—C13—C14	1.0 (4)
C5—N3—C1—N1	−21.9 (4)	S2—C12—C13—C14	179.77 (19)
C4—N3—C1—N1	−171.5 (2)	C12—C13—C14—C15	−0.4 (4)
C5—N3—C1—N2	156.0 (2)	C13—C14—C15—C16	0.0 (4)
C4—N3—C1—N2	6.4 (2)	C14—C15—C16—C17	−0.1 (4)
C2—N2—C1—N1	−28.6 (3)	C18—N4—C17—C16	45.6 (3)
C3—N2—C1—N1	−171.40 (18)	C18—N4—C17—C12	−140.4 (2)
C2—N2—C1—N3	153.2 (2)	C15—C16—C17—N4	174.7 (2)
C3—N2—C1—N3	10.4 (2)	C15—C16—C17—C12	0.6 (3)
C1—N2—C3—C4	−21.8 (2)	C13—C12—C17—N4	−175.4 (2)
C2—N2—C3—C4	−165.25 (19)	S2—C12—C17—N4	5.8 (3)
C1—N3—C4—C3	−19.5 (2)	C13—C12—C17—C16	−1.1 (3)
C5—N3—C4—C3	−171.50 (19)	S2—C12—C17—C16	−179.95 (17)
N2—C3—C4—N3	23.9 (2)	C17—N4—C18—N6	−156.8 (2)
C1—N1—C6—C7	−50.4 (3)	C17—N4—C18—N5	24.8 (4)
C1—N1—C6—C11	136.7 (2)	C22—N6—C18—N4	19.0 (4)
N1—C6—C7—C8	−174.8 (2)	C21—N6—C18—N4	169.2 (2)
C11—C6—C7—C8	−2.0 (3)	C22—N6—C18—N5	−162.3 (2)
C6—C7—C8—C9	0.9 (4)	C21—N6—C18—N5	−12.1 (3)
C7—C8—C9—C10	−0.2 (4)	C19—N5—C18—N4	34.9 (4)
C8—C9—C10—C11	0.6 (3)	C20—N5—C18—N4	171.7 (2)
C9—C10—C11—C6	−1.7 (3)	C19—N5—C18—N6	−143.7 (2)
C9—C10—C11—S1	178.80 (17)	C20—N5—C18—N6	−6.8 (3)
C7—C6—C11—C10	2.3 (3)	C18—N5—C20—C21	21.7 (3)
N1—C6—C11—C10	175.74 (19)	C19—N5—C20—C21	160.8 (2)
C7—C6—C11—S1	−178.12 (16)	C18—N6—C21—C20	25.1 (3)
N1—C6—C11—S1	−4.7 (2)	C22—N6—C21—C20	175.6 (2)
S2—S1—C11—C10	0.55 (19)	N5—C20—C21—N6	−27.1 (2)
S2—S1—C11—C6	−178.97 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···N2^i	0.95	2.54	3.463 (3)	165

Symmetry code: (i) x, −y+1, z−1/2.